EP2075326A1 - Textilwaschzusammensetzungen mit Oxazolenen - Google Patents

Textilwaschzusammensetzungen mit Oxazolenen Download PDF

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Publication number
EP2075326A1
EP2075326A1 EP08171692A EP08171692A EP2075326A1 EP 2075326 A1 EP2075326 A1 EP 2075326A1 EP 08171692 A EP08171692 A EP 08171692A EP 08171692 A EP08171692 A EP 08171692A EP 2075326 A1 EP2075326 A1 EP 2075326A1
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EP
European Patent Office
Prior art keywords
oxazoline
fabric
polymer
composition
rinse
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.)
Withdrawn
Application number
EP08171692A
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English (en)
French (fr)
Inventor
Andrew Philip Parker
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 EP08171692A priority Critical patent/EP2075326A1/de
Publication of EP2075326A1 publication Critical patent/EP2075326A1/de
Withdrawn legal-status Critical Current

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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
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/28Heterocyclic compounds containing nitrogen in the ring
    • 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
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776Heterocyclic compounds, e.g. lactam
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35Heterocyclic compounds
    • D06M13/352Heterocyclic compounds having five-membered heterocyclic rings
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3562Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen

Definitions

  • the present invention relates to fabric care compositions, such as laundry detergent compositions and laundry rinse compositions, which comprise an oxazoline-ring functionalised material.
  • the invention also relates to a method of treating fabric using the compositions of the invention and to the use of oxazoline-ring functionalised materials in the treatment of fabric which comprises oxidised cellulose to provide a colour care benefit to the fabric.
  • Oxidising species are present in the laundering process due to the wide-ranging inclusion of oxidation sources (such as bleaches) in detergents, or oxidising species present in the water supply (such as chlorine based disinfectants added as part of the water treatment process).
  • oxidation sources such as bleaches
  • oxidising species present in the water supply such as chlorine based disinfectants added as part of the water treatment process.
  • Oxidising species are able to oxidise the hydroxyl groups present in cellulose to produce carboxylic acids/carboxylate groups. This is disadvantageous because cellulose oxidation leads to the weakening of the fibres in the cellulosic fabric, which in turns leads to pilling, fuzzing and/or fibrillation of the fabric and manifests as a fading of colour due to poorer light scattering from the fabric (see for example " The Kinetics of Cellulose Fibre Degradation and Correlation with some Tensile Properties", G. Testa, A. Sardella, E. Rossi, C. Bozzi, A. Seves, Acta Polymer 45 47-49 1994 ).
  • Cellulose oxidation also leads to enhanced complexation with transition metals such as copper, which catalyses further cellulose oxidation, and iron which causes yellowing of white fabrics (see “ Catalytic Effects in the Alkaline Oxidation of Cellulose", W.A. Bell, Nature 186 963-964 18 June 1960 and " The Complexation of Fe(III)-ions in Cellulose Fibres: A Fundamental Property", A. Kongdee, T. Bechtold, Carbohydrate Polymers 56 2004 47-53 ).
  • Poly(2-ethyl-2-oxazoline) is known in the laundry field as a dye transfer inhibitor, i.e. in that it will bind to dye released during the laundry process to prevent the dye being transferred from one part of the fabric to another.
  • compositions which comprise low molecular weight modified and unmodified amines which provide enhanced fabric care benefits.
  • the compositions may additionally comprise a polymer comprising poly(2-ethyl-2-oxazoline) for use as a fabric abrasion polymer and dye transfer inhibitor.
  • EP 0 668 902 relates to compositions and processes useful for inhibiting the transfer of dyes, released into laundering solution from coloured fabrics, from one fabric to another.
  • Poly(2-ethyl-2-oxazoline is an example of one such material.
  • these poly(2-ethyl-2-oxazoline) materials lose their oxazoline ring functionality during polymerisation, so they do not comprise oxazoline in the form of a ring.
  • the present invention arises from the surprising finding that treatment of fabrics with an oxazoline material which is included in a polymer having at least two oxazoline-ring moieties provides a colour benefit to laundered fabrics.
  • the present invention provides a laundry treatment composition comprising:
  • the detersive surfactant is chosen from anionic and/or nonionic surfactants.
  • the rinse conditioner is a quaternary ammonium compound.
  • the polymer has a glass transition temperature of less than 30°C.
  • the polymer is an oxazoline ring-functionalised poly(styrene-acrylic) polymer.
  • a further aspect of the present invention provides a method of treating fabric comprising:
  • a yet further aspect of the invention relates to the use of an oxazoline material which is included in a polymer having at least two oxazoline-ring moieties in the treatment of fabric which comprises oxidised cellulose to provide a colour care benefit to the fabric.
  • the laundry treatment composition may take many varied forms, for example a main wash detergent composition, or a rinse conditioner.
  • the composition may alternatively be in the form of a spray or a foaming product, for application before or after the laundry process.
  • the laundry treatment composition is a main wash composition or a rinse conditioner composition.
  • the oxazoline material is included in a polymer having at least two oxazoline-ring moieties.
  • the oxazoline material may be copolymerised as part of a polymer chain.
  • a polymer chain For example a long chain polymer comprising side chains which in turn comprise oxazoline rings. Therefore the oxazoline material still bears at least two oxazoline-ring moieties, and preferably more.
  • these materials are oxazoline ring-functionalised poly(styrene-acrylic) polymers, available from Nippon Shokubai as EPOCROS(Trademark).
  • oxazoline polymers which do not contain any oxazoline ring moieties are outside the scope of this invention.
  • the material is a polymer having at least two oxazoline groups with a glass transition temperature of below 30°C, examples being Epocros TM K-2020E and Epocros TM K-2010E.
  • compositions of the invention when applied to fabric, can be cured at ambient temperature (full curing taking between 1 and 14 days) or at elevated temperature, for example a tumble dryer (curing taking between 30 minutes and 4 hours) or by ironing (curing taking between 1 and 10 minutes) or a combination of these methods.
  • the level of oxazoline material present in the laundry treatment composition is from 0.1 to 30 wt.%.
  • the inclusion levels are based on actual oxazoline comprising material actives, as the material can be provided as an emulsion, or dispersion of solids in a liquid.
  • the laundry compositions may be in concentrated form, whereby the aforementioned inclusion levels are appropriate, or it may take a dilute form, whereby preferred inclusion levels of the oxazoline material are 0.01 to 10 wt.%.
  • the oxazoline ring moiety is believed to function as a reactive agent for oxidised cellulose, by ring-opening reaction of the oxazoline ring with a carboxylic acid (or carboxylate) present in oxidised cellulose. The reaction forms an amide ester link between the oxidised cellulose and the oxazoline material.
  • This reaction reduces the amount of oxidised cellulose present in the fabric, so reducing the amount of associated oxidative damage to the fabric and thus reducing the colour negative.
  • the site of the damage is effectively masked from further chemical processes.
  • the reaction also removes any propensity for the site to bind transition metals such as iron(III), thus reducing yellowing.
  • the oxazoline material has two or more oxazoline moieties and can be used to crosslink oxidised cellulose.
  • the fabric treated may be any cellulose-fibre containing fabric. These encompass cotton, cotton-rich fabrics and polyester-cotton fabric mixes. Preferably the fabric comprises at least 50% cellulosic fibres.
  • the method of treating fabric comprises the following steps:
  • the drying step of the method starts the curing process of the polymer.
  • the fabrics can be cured at ambient temperature (full curing taking between 1 and 14 days) or at elevated temperature, for example a tumble dryer (curing taking between 30 minutes and 4 hours) or by ironing (curing taking between 1 and 10 minutes) or a combination of these methods.
  • the curing process occurs such that the oxazoline groups react with the carboxylate groups present on the oxidatively-damaged cellulose of the fabric.
  • the aqueous medium provided in part a) of the method is a main wash or rinse liquor from a laundering process.
  • Laundering process used herein refers solely to the wash and rinse process. This process may be done by machine (automatic, semi-automatic or manual), or by hand.
  • compositions of the invention may be used outside this defined laundry process (either by a pre- or post treatment in reference to the main wash and rinse), but preferably the composition is applied as part of the laundry process as defined.
  • oxazoline material which is included in a polymer having at least two oxazoline-ring moieties in the treatment of fabric which comprises oxidised cellulose to provide a colour care benefit to the fabric can be achieved in various ways.
  • the oxazoline material which is included in a polymer having at least two oxazoline-ring moieties can be part of a cellulosic textile substantive material, which binds to one surface of the cellulosic textile, and allows reaction with oxidised cellulose to take place via an oxazoline ring moiety. Having at least two oxazoline rings to enable cellulosic crosslinking to occur via each oxazoline ring.
  • the colour care benefit provided to the fabric can be the reduction in colour fading of the fabric, or dye transfer inhibition.
  • the colour care benefit is the reduction in colour fading of the fabric.
  • the term "textile compatible carrier” includes a component which can assist in the interaction of the cellulose cross-liking agent with a textile.
  • the carrier is selected from a detersive surfactant or a rinse conditioner compound.
  • the textile compatible carrier is a detersive surfactant, then preferably it is selected from anionic, nonionic, cationic, zwitterionic or amphoteric detersive surfactants.
  • the detersive surfactant is an anionic and/or nonionic surfactant.
  • the composition comprises between 2 to 70 wt% of a detersive surfactant, most preferably 10 to 30 wt %.
  • the detersive surfactant may be chosen from the surfactants described " 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 22 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 C 8 to C 18 primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.
  • Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing 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 C 8 to C 18 alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C 9 to C 20 benzene sulphonates, particularly sodium linear secondary alkyl C 10 to C 15 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 preferred anionic detergent compounds are sodium C 11 to C 15 alkyl benzene sulphonates and sodium C 12 to C 18 alkyl sulphates.
  • 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.
  • Suitable amphoteric surfactants are amine oxides or betaines.
  • Preferred surfactant systems are mixtures of anionic with nonionic detergent active materials, in particular the groups and examples of anionic and nonionic surfactants pointed out in EP-A-346 995 (Unilever).
  • surfactant system that is a mixture of an alkali metal salt of a C 16 to C 18 primary alcohol sulphate together with a C 12 to C 15 primary alcohol 3 to 7 EO ethoxylate.
  • the nonionic detergent is preferably present in amounts greater than 10%, e.g. 25 to 90 wt % of the surfactant system.
  • Anionic surfactants can be present, for example, in amounts in the range from about 5% to about 40 wt % of the surfactant system.
  • the textile compatible carrier is a rinse conditioner compound, then preferably the textile compatible carrier is a cationic compound.
  • Preferred cationic compounds are quaternary ammonium compounds.
  • the quaternary ammonium compound is a quaternary ammonium compound having at least one C 12 to C 22 alkyl chain.
  • the quaternary ammonium compound has the following formula: in which R 1 is a C 12 to C 22 alkyl or alkenyl chain; R 2 , R 3 and R 4 are independently selected from C 1 to C 4 alkyl chains and X - is a compatible anion.
  • R 1 is a C 12 to C 22 alkyl or alkenyl chain; R 2 , R 3 and R 4 are independently selected from C 1 to C 4 alkyl chains and X - is a compatible anion.
  • a preferred compound of this type is the quaternary ammonium compound cetyl trimethyl quaternary ammonium bromide.
  • a second class of materials for use with the present invention are the quaternary ammonium of the above structure in which R 1 and R 2 are independently selected from C 12 to C 22 alkyl or alkenyl chain; R 3 and R 4 are independently selected from C 1 to C 4 alkyl chains and X - is a compatible anion.
  • the cationic compound may be present from 1.5 wt % to 50 wt % of the total weight of the composition.
  • the cationic compound may be present from 2 wt % to 25 wt %, a more preferred composition range is from 5 wt % to 20 wt %.
  • compositions suitable for delivery during the rinse cycle may also be delivered to the textile in the tumble dryer if used in a suitable form.
  • another product form is a composition (for example, a paste) suitable for coating onto, and delivery from, a substrate e.g. a flexible sheet or sponge or a suitable dispenser during a tumble dryer cycle.
  • the composition may comprise one or more builders.
  • Such materials may suitably be aluminosilicates, silicates, carbonates, citrates, polycarboxylates, complexing agents, and phosphates.
  • compositions may suitably contain from 10 to 70 wt.% of detergency builder.
  • the total level of builder is less than 20 wt.%.
  • zeolites examples include: zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070 .
  • composition may also comprise a complexing agent such as: ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid, or, mixtures thereof.
  • a complexing agent such as: ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid, or, mixtures thereof.
  • phosphate builders may be used.
  • 'phosphate' embraces diphosphate, triphosphate, and phosphonate species.
  • Other forms of builder include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst).
  • carbonate including bicarbonate and sesquicarbonate
  • citrate may be employed as builders.
  • the composition may comprise one or more polymers. Examples are: carboxymethylcellulose, poly(ethylene glycol), poly(vinyl alcohol), poly(vinylpyridine-N-oxide), polycarboxylates (such as polyacrylates, maleic/ acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers), and mixtures thereof.
  • the composition may additionally comprise soil release polymers such as block copolymers of polyethylene oxide and terephthalate.
  • the composition may additionally comprise a dye transfer inhibition agent.
  • a dye transfer inhibition agent These prevent migration of dyes, especially during long soak times.
  • Such agents are preferably selected from polyvinylpyrridine N-oxide (PVNO), polyvinyl pyrrolidone (PVP), polyvinyl imidazole, N-vinylpyrrolidone and N-vinylimidazole copolymers (PVPVI), and copolymers thereof, and/or mixtures thereof.
  • the amount of dye transfer inhibition agent if present, in the composition will be from 0.01 to 10 %, preferably from 0.02 to 5 %, more preferably from 0.03 to 2 %, by weight of the composition.
  • Enzymes contemplated for use in laundry detergent compositions include proteases, alpha-amylases, cellulases, lipases, peroxidases/oxidases, pectate lyases, mannanases, or mixtures thereof.
  • compositions of the invention may also contain optional colour care benefit agents.
  • Preferred colour care benefit agents are polysaccharides.
  • the wash/rinse liquor will comprise around 0.01 g/L of a polysaccharide colour care benefit agent.
  • the polysaccharide is a beta 1-4 polysaccharide; more preferably a cellulose derivative, such as a hydroxy C2-C4 alkyl derivative. More preferably the hydroxy C2-C4 alkyl derivative is a hydroxy ethyl derivative.
  • the degree of substitution (DS) of the polysaccharide is 1.5-2.25.
  • the molecular weight of the polysaccharide is 100,000 to 500,000 Dalton.
  • composition may also contain other conventional detergent ingredients such as e.g. fabric conditioners including clays or silicones, foam boosters, anti-corrosion agents, soil-suspending agents, anti-soil redeposition agents, dyes, anti-abrasion agents, anti-microbials, stabilisers, tarnish inhibitors, or perfumes.
  • fabric conditioners including clays or silicones, foam boosters, anti-corrosion agents, soil-suspending agents, anti-soil redeposition agents, dyes, anti-abrasion agents, anti-microbials, stabilisers, tarnish inhibitors, or perfumes.
  • Further optional ingredients include non-aqueous solvents, perfume carriers, fluorescers, colourants, hydrotropes, antifoaming agents and opacifiers.
  • compositions may comprise one or more of anti-shrinking agents, anti-wrinkle agents, anti-spotting agents, germicides, fungicides, anti-oxidants, UV absorbers (sunscreens), heavy metal sequestrants, chlorine scavengers, dye fixatives, anti-abrasion agents, anti-corrosion agents, drape imparting agents, antistatic agents and ironing aids.
  • a load comprising 4 panels of each of the following were washed 10 times in a front loading washing machine (Whirlpool Electronic AWM6100-6K, 40°C cotton cycle) using Prenton water and 100g Persil Performance to generate damage on the cloth.
  • the fabrics were tumble dried (Miele Novotronic T430) after every wash.
  • Cotton interlock knitted fabric 1. BP1-K 2% Indanthrene Blue RS 2. BP2-K 4% Remazol Brilliant Orange 3R 3. BP3-K 3.85% Procion Yellow H-EXL 1.35% Procion Crimson H-EXL 2.41% Procion Navy H-EXL 4. BP4-K 1.6% Remazol Brilliant Yellow RNL 1.2% Remazol Red RB 1.2% Remazol Blue BB 5.
  • the fabrics were cut into 100 x 50cm pieces, folded into 50 x 50cm double panels and overlocked around the three remaining edges. Four pieces of each cloth were used (total 32 pieces, weight 2.1kg).
  • the fabrics were tumble dried (Miele Novotronic T430) after each wash cycle.
  • the fabrics were measured after the 9 tn wash using the Spectraflash spectrometer using the same conditions as before.
  • the parameter ⁇ L* (Delta Delta L*) is measured on a reflectance spectrophotometer. After calibrating the machine using the standard black trap and white tile, the colour coordinates of the white tile are measured and used as the reference standard. The coloured fabrics used in the test are then measured against this standard. The measurements are known as the CIELAB space coordinate system based around the theory of the three opponent pairs of colour vision:
  • the polymer can be incorporated into main wash powders or liquids (most preferably those based around cationic surfactants) or rinse conditioner products.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP08171692A 2007-12-18 2008-12-15 Textilwaschzusammensetzungen mit Oxazolenen Withdrawn EP2075326A1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08171692A EP2075326A1 (de) 2007-12-18 2008-12-15 Textilwaschzusammensetzungen mit Oxazolenen

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EP07123479 2007-12-18
EP08171692A EP2075326A1 (de) 2007-12-18 2008-12-15 Textilwaschzusammensetzungen mit Oxazolenen

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012010531A1 (de) * 2010-07-23 2012-01-26 Henkel Ag & Co. Kgaa Verhinderung von textilschäden beim waschen

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EP0070074A2 (de) 1981-07-13 1983-01-19 THE PROCTER & GAMBLE COMPANY Schäumende, oberflächenaktive Verbindungen enthaltende Zusammensetzungen
EP0239910A2 (de) 1986-04-02 1987-10-07 The Procter & Gamble Company Biologisch abbaubare Gewebeweichmacher
EP0328177A2 (de) 1988-02-10 1989-08-16 Unilever N.V. Flüssige Reinigungsmittel
EP0346995A2 (de) 1988-06-13 1989-12-20 Unilever N.V. Flüssige Reinigungsmittel
EP0384070A2 (de) 1988-11-03 1990-08-29 Unilever Plc Zeolith P, sein Herstellungsverfahren und seine Verwendung in Waschmitteln
EP0668902A1 (de) 1992-11-16 1995-08-30 Procter & Gamble Gewebeweichspülzusammensetzungen mit farbstofftrabsferinhibitoren zwecks verbessertem gewebeerscheinungsbild.
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"Tenside-Taschenbuch", 1981, CARL HAUSER VERLAG
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