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EP1468068B1 - Agent conditionneur menageant les textiles - Google Patents

Agent conditionneur menageant les textiles Download PDF

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Publication number
EP1468068B1
EP1468068B1 EP03704400A EP03704400A EP1468068B1 EP 1468068 B1 EP1468068 B1 EP 1468068B1 EP 03704400 A EP03704400 A EP 03704400A EP 03704400 A EP03704400 A EP 03704400A EP 1468068 B1 EP1468068 B1 EP 1468068B1
Authority
EP
European Patent Office
Prior art keywords
weight
range
conditioning
composition according
substrate
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.)
Revoked
Application number
EP03704400A
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German (de)
English (en)
Other versions
EP1468068A1 (fr
Inventor
Tatiana Schymitzek
Berthold Schreck
Rainer Jeschke
Joseph Penninger
Pavel Gentschev
Maren Jekel
Karl-Heinz Scheffler
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Publication date
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Priority claimed from DE2002103192 external-priority patent/DE10203192A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1468068A1 publication Critical patent/EP1468068A1/fr
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/047—Arrangements specially adapted for dry cleaning or laundry dryer related applications
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • 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
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3753—Polyvinylalcohol; Ethers or esters 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
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • 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
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
    • 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
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam

Definitions

  • the invention relates to a conditioning agent for textile care and the use of the conditioning agent in a washing or textile drying process. Furthermore, the invention relates to a conditioning substrate containing a conditioning agent and a conditioning method using the conditioning substrate in a textile drying process. Conditioner and conditioning substrate are used to reduce the formation of lint and the pill.
  • the conditioners contain cationic surfactants for setting a comfortable fabric softening and optionally Textilkonditionierzusatz für, such as wrinkling agents, deodorizing substances and perfume.
  • the conditioners are applied by melting to the carrier cloths so that they can be released at the temperatures usually present in a household dryer.
  • WO 00/24853 describes liquid softener formulations having wrinkle reducing components selected from silicone derivatives and sulphated or sulphonated vegetable oils, and dryer sheets containing one of these wrinkle reducing components.
  • EP 255 711 describes a conditioning cloth provided with a fabric conditioner containing cationic surfactants and polydiorganosiloxanes, wherein the fabric conditioner has a melting point above 38 ° C.
  • US 5,174,911 describes a fabric conditioning article for a tumble dryer wherein the conditioning agent applied to the article comprises a plasticizer component and an aminosilicone component.
  • EP 317 135 discloses an aqueous fabric softener formulation containing a cationic and a nonionic softening component.
  • the nonionic plasticizer component is a special siloxane which carries at least one C 6 -C 22 -alkyl group.
  • EP 544 493 describes highly concentrated fabric softeners which comprise from 60 to 99% by weight of a fabric softening component and from 1 to 40% by weight of an emulsified mixture of silicone oil and silicone emulsifier.
  • a phase separation of the components is avoided and achieved a uniform coating of dryer sheets.
  • the conditioner composition for the dryer cloths have a melting point of 25 to 150 ° C and thus are not in liquid form at room temperature.
  • WO-A-99/14295 discloses detergent compositions containing cellulosic polymers to reduce pilling.
  • the conditioners and conditioning wipes described in the prior art do not take into account the protection of the textile.
  • the modern textile care makes high demands on the laundry.
  • the washing of garments in a washing machine and the subsequent drying in a tumble dryer is associated with a high mechanical stress on the fabric.
  • the frictional forces often lead to damage to the textile fabric, recognizable by a fluff and pilling.
  • a further abrasion and / or breakage of tiny fibers takes place on the surface of the textile surface fabrics.
  • the conventional conditioning and fabric care agents are unable to reduce this damage to the fabric.
  • the object of the present invention is therefore to reduce the fluffing and pilling of textile fabrics, in particular the reduction of this formation during a textile washing or drying process.
  • the present invention is therefore in a first embodiment, a conditioning agent containing at least one lint reduction component.
  • conditioning is to be understood as the avivating treatment of textile fabrics, fabrics, yarns and fabrics.
  • the textiles are given positive properties, such as an improved softness, increased gloss and color brilliance, a fragrance refreshment, reduction of creasing and static charge and a relieved Ironing behavior.
  • the conditioning in the context of this invention leads to a textile protection, detectable at a reduced lint and Pillê.
  • the conditioning agents according to the invention contain at least one lint reduction component.
  • Fluff reduction components are present in the liquid conditioners according to the invention as finely divided polymer particles or polymer emulsions or polymer dispersions which have a substantivity to textile fabrics or textile fibers.
  • these are water-insoluble polymers.
  • biological polymers are also polymers which are only partially of biological or biotechnological origin.
  • biological polymers in which at least 60%, preferably at least 80% and in particular at least 90% of the molecular weight is of biological or biotechnological origin.
  • Particularly preferred biological polymers are selected from the group of celluloses. Microcrystalline cellulose of natural origin, for example, Arbocel® BE 600-10, 600-20 and Arbocel® BE Arbocel ® BE 600-30 ex Rettenmaier or biotechnological origin, for example Cellulon ® ex Kelco are highly preferred.
  • Biotechnologically fermented celluloses as described, for example, in US Pat. No. 6,329,192 B1, are likewise suitable for use as a lint reduction component.
  • Cellulose derivatives are also suitable for use as lint reduction components.
  • examples are the alkylated and / or hydroxyalkylated polysaccharides, cellulose ethers, for example hydroxypropylmethylcellulose (HPMC), ethyl (hydroxyethyl) cellulose (EHEC), hydroxypropylcellulose (HPC), methylcellulose (MC), propylcellulose (PC), carboxymethylmethylcellulose (CMMC), hydroxybutylcellulose (HBC ), Hydroxybutylmethylcellulose (HBMC), hydrdoxyethylcellulose (HEC), hydroxyethylcarboxymethylcellulose (HECMC), hydroxyethylethylcellulose (HEEC), hydroxypropylcellulose (HPC), hydroxypropylcarboxymethylcellulose (HPCMC), hydroxyethylmethylcellulose (HEMC), methylhydroxyethylcellulose (MHEC), methylhydroxyethylpropylcellulose (MHEPC) and mixtures thereof, methylcellulose, methyl
  • At least 90% of the particles have a particle size less than 100 microns, preferably less than 50 microns, more preferably less than 20 microns.
  • hydrogels of biological polymers are water-containing systems based on hydrophilic but water-insoluble polymers, which are present as a three-dimensional network, the particles on the textile surface after the drying process are substantially smaller and are usually only one tenth or less of their original volume.
  • Suitable hydrogel dispersions are all hydrogels which are present in finely particulate form.
  • Particularly suitable are hydrogels in which at least 90% of the particles have a particle size of less than 100 ⁇ m, preferably less than 50 ⁇ m, particularly preferably less than 20 ⁇ m.
  • Hydrogels in which at least 90% of the particles have a particle size less than 500 nm, are particularly suitable.
  • Suitable hydrogels are natural polymers such as agarose, gelatin, curdlan, alginates, pectinates, carageenans, chitosans, etc.
  • An improved Aufzieh the hydrogel particles can be achieved in addition by their cationic modification.
  • Nanoscale hydrogel particles can be effected by microemulsion polymerization of a water / oil emulsion stabilized in most cases with emulsifiers by homogenization by means of high-pressure homogenizers or rotor-stator homogenizers.
  • the aqueous phase contains the dispersed polymers or monomers.
  • synthetic polymers such as. Polyacrylates, polymethacrylates, polyacrylamides or polymethacrylamides, polyurethanes, polyvinylpyrrolidones, polyvinyl alcohols, polyvinyl acetate and / or their partial hydrolysates or copolymers thereof can be used.
  • the synthetic polymers can be added as finely divided powders or dispersions to the conditioning agents according to the invention or, in a preferred embodiment, they can also be present as hydrogels.
  • the polycarboxylates have proven to be particularly suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 500 to 1,000,000 g / mol, preferably 1,000 to 70,000 g / mol.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 12,000 to 30,000 g / mol.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid or of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molar mass, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 15,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. Commercially available are the preferred products either in the form of aqueous solutions with solids contents of z. B.
  • At least 90% of the particles preferably have a particle size of less than 100 ⁇ m, preferably less than 50 ⁇ m, particularly preferably less than 20 ⁇ m.
  • the conditioning agents according to the invention contain the lint components in amounts of from 0.005 to 15% by weight, preferably from 0.01 to 10% by weight, particularly preferably from 0.1 to 7% by weight and in particular from 0.5 to 5% by weight. , in each case based on the total mean.
  • the conditioning agents according to the invention contain at least one additional plasticizer component.
  • fabric softening components are quaternary ammonium compounds, cationic polymers and emulsifiers, such as those used in hair care products and also in textile saliva.
  • Suitable examples are quaternary ammonium compounds of the formulas (I) and (II), wherein in (I) R and R 1 is an acyclic alkyl radical having 12 to 24 carbon atoms, R 2 is a saturated C 1 -C 4 alkyl or hydroxyalkyl radical, R 3 is either R, R 1 or R 2 or is a aromatic residue stands.
  • X - is either a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof.
  • Examples of cationic compounds of the formula (I) are didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.
  • Ester quats are so-called ester quats. Esterquats are characterized by excellent biodegradability.
  • R 4 is an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds
  • R 5 is H, OH or O (CO)
  • R 7 is independently of R 5 is H, OH or O (CO) R 8 , wherein R 7 and R 8 are each independently an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds.
  • m, n and p can each independently be 1, 2 or 3.
  • X - may be either a halide, methosulfate, methophosphate or phosphate ion, as well as mixtures of these.
  • Examples of compounds of the formula (II) are methyl N- (2-hydroxyethyl) -N, N-di (tallowacyl-oxyethyl) ammonium methosulfate, bis (palmitoyl) -ethyl-hydroxyethyl-methyl-ammonium methosulfate or methyl -N, N-bis (acyloxy-ethyl) -N- (2-hydroxyethyl) ammonium methosulfate.
  • acyl groups whose corresponding fatty acids have an iodine number between 5 and 80, preferably between 10 and 60 and in particular between 15 and 45 and which have a cis / trans isomer ratio are preferred (in wt .-%) of greater than 30: 70, preferably greater than 50: 50 and in particular greater than 70: 30 have.
  • Commercial examples are sold by Stepan under the tradename Stepantex ® methylhydroxyalkyldialkoyloxyalkylammonium or those known under Dehyquart ® Cognis products known under or Rewoquat ® manufactured by Goldschmidt-Witco.
  • Further preferred compounds are the diester quats of the formula (III), which are named Rewoquat® W 222 LM or CR 3099 are available and provide in addition to the softness for stability and color protection.
  • R 21 and R 22 are each independently an aliphatic radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds.
  • quaternary imidazolinium compounds of the formula (IV) where R 9 is H or a saturated alkyl radical having 1 to 4 carbon atoms, R 10 and R 11 are each independently an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, R 10 may alternatively be O (CO) R 20 wherein R 20 is an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, and Z is an NH group or oxygen and X - is an anion.
  • q can take integer values between 1 and 4.
  • R 12 , R 13 and R 14 independently represent a C 1-4 alkyl, alkenyl or hydroxyalkyl group, each of R 15 and R 16 independently represents a C 8-28 alkyl group and r is a number between 0 and 5 is.
  • short-chain, water-soluble, quaternary ammonium compounds may also be used, such as trihydroxyethylmethylammonium methosulfate or the alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. Cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetylmethyl ammonium chloride.
  • trihydroxyethylmethylammonium methosulfate or the alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides e.g. Cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chlor
  • Protonated alkylamine compounds which have a softening effect as well as the non-quaternized, protonated precursors of the cationic emulsifiers are also suitable.
  • cationic compounds which can be used according to the invention are the quaternized protein hydrolysates.
  • Suitable cationic polymers include the polyquaternium polymers as described in the CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry and Fragrance, Inc., 1997), in particular the Polyquaternium-6, Polyquaternium-7, Polyquaternium, also known as Merquats. 10 polymers (Ucare Polymer IR 400; Amerchol), polyquaternium-4 copolymers such as graft copolymers having a cellulose backbone and quaternary ammonium groups bonded via allyldimethylammonium chloride, cationic cellulose derivatives such as cationic guar such as guar hydroxypropyltriammonium chloride, and similar quaternized guar gum.
  • cationic quaternary sugar derivatives for example the commercial product Glucquat ® 100, according to CTFA nomenclature a "lauryl methyl Gluceth-10 hydroxypropyl Dimonium Chloride", copolymers of PVP and dimethylaminomethacrylate, copolymers of vinylimidazole and vinylpyrrolidone, aminosilicone polymers and copolymers re.
  • Polyquaternized polymers for example Luviquat Care from BASF
  • cationic biopolymers based on chitin and derivatives thereof for example, under the trade designation chitosan ® (manufacturer: Cognis) polymer obtainable.
  • cationic silicone oils such as the commercially available products Q2-7224 (manufacturer: Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified Silicone, which is also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) Abil ® -Quat 3270 and 3272 (manufacturer: Goldschmidt-Rewo; diquaternary polydimethylsiloxanes, quaternium-80), Silicone Quat and Rewoquat ® SQ 1 (Tegopren ® 6922, manufacturer: Goldschmidt-Rewo).
  • the alkylamidoamines may be in their quaternized or, as shown, their quaternized form.
  • R 17 may be an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds. s can take values between 0 and 5.
  • R 18 and R 19 are each independently H, C 1-4 alkyl or hydroxyalkyl.
  • Preferred compounds are fatty acid amidoamines such as Stearylamidopropyldimethylamin available under the name Tego Amid ® S 18 or 3-Talgamidopropyl-trimethylammonium methosulfate available under the name Stepantex ® X 9124, which in addition to a good conditioning effect by color transfer inhibiting effect and especially by their good distinguish biodegradability.
  • alkylated quaternary ammonium compounds of which at least one alkyl chain is interrupted by an ester group and / or amido group, in particular N-methyl-N (2-hydroxyethyl) -N, N- (ditalgacyloxyethyl) ammonium methosulfate and / or N-methyl -N (2-hydroxyethyl) -N, N- (palmitoyloxyethyl) ammonium methosulfate.
  • nonionic plasticizers are especially Polyoxyalkylenglycerolalkanoate, as described in British Patent GB 2,202,244, polybutylenes, as described in British Patent GB 2,199,855, long-chain fatty acids, as in EP 13 780, ethoxylated fatty acid ethanolamides, as described in EP 43 547, Alkylpolyglycosides, in particular sorbitan mono-, di- and triesters, as described in EP 698 140 and fatty acid esters of polycarboxylic acids, as described in German Patent DE 2,822,891.
  • the conditioning agent according to the invention can plasticizer components in amounts of up to 50 wt .-%, preferably from 0.1 to 45 wt .-%, particularly preferably from 5 to 40 wt .-% and in particular from 11 to 35 wt.%, Each based on the total agent included.
  • the conditioning agent according to the invention additionally comprises at least one ironing facilitator component.
  • easy-iron facilitating components are to be understood as substances which, by acting on textile fabrics, ensure that the textiles have a low frictional resistance during ironing. Silicone oils have proven to be a particularly suitable ironing component.
  • partially oxidized polyethylene is meant predominantly linear polyethylene waxes, which are relatively low molecular weight products in the range of 500 to 50,000.
  • the polyethylene waxes are generally prepared by direct low-pressure polymerization or, preferably, high-pressure polymerization of the monomers or by specific depolymerization of products of relatively high molecular weights.
  • the modified polyethylene waxes used herein may be obtained by polymerization of ethylene, preferably in the absence of a catalyst with premature termination of polymerization and subsequent oxidation, e.g. by introducing air, or by copolymerization of ethylene with suitable other monomers such as acrylic acid, wherein the proportion of the acrylic acid units preferably does not exceed 20%, in particular 10%.
  • the ironing relief component (s) may be present in amounts of up to 10% by weight, preferably 0.1 to 8% by weight and in particular 0.5 to 5% by weight, based in each case on the entire composition.
  • the conditioning agents according to the invention comprise at least one spreading agent.
  • the spreading agent has a wetting function and causes an optimal distribution of the remaining components over a large area. It is achieved by not being too partial on the textile surface Overconcentrations come, which would be visible as stains.
  • the use of spreading agents is particularly recommended when conditioning substrates impregnated with the conditioning agent according to the invention are brought into effect in a textile drying process.
  • the spreading agent can be used in amounts of up to 10% by weight, preferably from 0.01 to 5% by weight, particularly preferably from 0.05 to 2% by weight and in particular from 0.1 to 1% by weight, in each case in relation to the entire remedy.
  • the conditioning agents according to the invention are in liquid form. To achieve a liquid consistency, the use of both liquid organic solvents, as well as being indicated by water.
  • the conditioning agents according to the invention therefore optionally contain solvents.
  • Solvents that can be used in the compositions according to the invention originate, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the concentration range indicated.
  • the solvents are selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether , Diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, butoxy-propoxy-propanol (BPP), dipropylene glycol monomethyl, or ethyl ether, di-isopropylene glycol monomethyl, or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1 Butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol,
  • glycol ethers are available under the trade name Arcosolv ® (Arco Chemical Co.) or Cellosolve ®, carbitol ® or Propasol ® (Union Carbide Corp.); this includes for example ButylCarbitol® ®, hexyl carbitol ®, MethylCarbitol® ®, and carbitol ® itself, (2- (2-ethoxy) ethoxy) ethanol.
  • Arcosolv ® Arco Chemical Co.
  • Cellosolve ® Cellosolve ®
  • Carbitol ® or Propasol ® Union Carbide Corp.
  • ButylCarbitol® ® hexyl carbitol ®
  • MethylCarbitol® ® MethylCarbitol®
  • carbitol ® itself, (2- (2-ethoxy) ethoxy) ethanol.
  • the choice of glycol ether can be readily made by one skilled in the art on the
  • Pyrrolidone solvents such as N-alkylpyrrolidones, for example N-methyl-2-pyrrolidone or NC 8 -C 12 -alkylpyrrolidone, or 2-pyrrolidone, may also be used.
  • N-alkylpyrrolidones for example N-methyl-2-pyrrolidone or NC 8 -C 12 -alkylpyrrolidone, or 2-pyrrolidone
  • glycerol derivatives in particular glycerol carbonate.
  • alcohols which can be used as cosolvents in the present invention are low molecular weight liquid polyethylene glycols, for example, polyethylene glycols having a molecular weight of 200, 300, 400 or 600.
  • suitable cosolvents are other alcohols, for example (a) lower Alcohols such as ethanol, propanol, isopropanol and n-butanol, (b) ketones such as acetone and methyl ethyl ketone, (c) C 2 -C 4 polyols such as a diol or a triol, for example ethylene glycol, propylene glycol, glycerol or mixtures thereof.
  • 1,2-octanediol from the class of diols.
  • the conditioning agent according to the invention may contain one or more water-soluble organic solvents and / or water.
  • Water-soluble is understood to mean that the organic solvent is soluble in the amount contained in an optionally aqueous agent.
  • the conditioning agent according to the invention contains one or more solvents from the group comprising C 1 to C 4 monoalcohols, C 2 to C 6 glycols, C 3 to C 12 glycol ethers and glycerol, in particular ethanol.
  • the C 3 - to C 12 glycol ethers according to the invention contain alkyl or alkenyl groups having less than 10 carbon atoms, preferably up to 8, in particular up to 6, more preferably 1 to 4 and most preferably 2 to 3 carbon atoms.
  • Preferred C 1 to C 4 monohydric alcohols are ethanol, n- propanol, iso- propanol and tert- butanol.
  • Preferred C 2 to C 6 glycols are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,5-pentanediol, neopentyl glycol and 1,6-hexanediol, in particular ethylene glycol and 1,2-propylene glycol.
  • Preferred C 3 - to C 12 glycol ethers are di-, tri-, tetra- and pentaethylene glycol, di-, tri- and tetrapropylene glycol, propylene glycol monotertiary butyl ether and propylene glycol monoethyl ether and the solvents designated according to INCI butoxydiglycol, butoxyethanol, butoxyisopropanol, butoxypropanol, butyloctanol, ethoxydiglycol, Ethoxyethanol, ethyl hexanediol, isobutoxypropanol, isopentyldiol, 3-methoxybutanol, methoxyethanol, methoxyisopropanol and methoxymethylbutanol.
  • Particularly preferred solvents are ethanol, 1,2-propylene glycol and dipropylene glycol and mixtures thereof, in particular ethanol and isopropanol.
  • the agent according to the invention optionally contains one or more solvents and / or in particular water in an amount of usually up to 95% by weight, preferably 20 to 90% by weight and in particular 50 to 80% by weight, in each case based on the total Medium.
  • the conditioning agents according to the invention may additionally contain nonionic surfactants.
  • the nonionic surfactants show excellent emulsifier properties, especially in the presence of cationic surfactants.
  • nonionic surfactants are preferably alkoxylated, advantageously ethoxylated and / or propoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) and / or 1 to 10 moles of propylene oxide (PO) per mole of alcohol used.
  • EO ethylene oxide
  • PO propylene oxide
  • C 8 -C 16 -alcohol alkoxylates advantageously ethoxylated and / or propoxylated C 10 -C 15 -alcohol alkoxylates, in particular C 12 -C 14 -alcohol alkoxylates, having a degree of ethoxylation of between 2 and 10, preferably between 3 and 8, and / or a degree of propoxylation between 1 and 6, preferably between 1.5 and 5.
  • the alcohol radical may preferably be linear or more preferably methyl-branched in the 2-position or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the indicated degrees of ethoxylation and propoxylation represent statistical averages which may be an integer or a fractional number for a particular product.
  • Preferred alcohol ethoxylates and propoxylates have a narrow homolog distribution (narrow range ethoxylates / propoxylates, NRE / NRP).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkoxylated amines advantageously ethoxylated and / or propoxylated, in particular primary and secondary amines having preferably 1 to 18 carbon atoms per alkyl chain and an average of 1 to 12 moles of ethylene oxide (EO) and / or 1 to 10 moles of propylene oxide (PO) per Mole of amine.
  • EO ethylene oxide
  • PO propylene oxide
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x for example as compounds, especially with anionic surfactants, are used in which R is a primary straight-chain or methyl-branched, especially methyl-branched in the 2-position aliphatic radical having 8 to 22 , preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as they are for example, in Japanese Patent Application JP 58/217598, or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • Other suitable surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated by a so-called “spacer.” This spacer is usually a carbon chain, which should be long enough that the hydrophilic groups have a sufficient distance so that they can act independently of each other In general, however, the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to the German patent application DE-A-43 21 022 or dimer alcohol bis- and trimeralcohol tris-sulfates and ether sulfates according to the international patent application WO-A-96/23768.
  • End-capped dimeric and trimeric mixed ethers according to the German patent application DE-A-195 13 391 are distinguished in particular by their bi-and multifunctionality.
  • the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides as described in international patent applications WO-A-95/19953, WO-A-95119954 and WO-A-95119955.
  • surfactants are polyhydroxy fatty acid amides of the following formula
  • RCO is an aliphatic acyl radical having 6 to 22 carbon atoms
  • R 5 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
  • [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the following formula R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 6 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 7 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides according to the teaching of international application WO-A-95/07331, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the nonionic surfactants can usually in amounts of up to 20 wt .-%, preferably from 0.5 to 10 wt .-% and particularly preferably from 0.8 to 5 wt .-%, each based on the total agent, before.
  • the conditioning agents according to the invention optionally additionally contain electrolytes.
  • Electrolytes serve to regulate the viscosity (viscosity regulator) and can usually be used in amounts of up to 15% by weight, preferably up to 10% by weight, particularly preferably from 0.5 to 8% by weight and in particular from 1 to 6% by weight. %, in each case based on the total mean.
  • electrolytes from the group of inorganic salts a wide number of different salts can be used.
  • Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl, CaCl 2 or MgCl 2 in the agents according to the invention is preferred.
  • pH adjusting agents In order to bring the pH of the agents according to the invention in the desired range, the use of pH adjusting agents may be indicated. All known acids can be used here.
  • Figure 1 Course of the contact angles with time or alkalis, unless their use is prohibited for application-related or ecological reasons or for reasons of consumer protection. Usually, the amount of these adjusting agents does not exceed 2% by weight of the total formulation.
  • the conditioning agents according to the invention have a pH of from 2 to 7, preferably from 2.2 to 5 and in particular from 2.4 to 3.
  • compositions according to the invention may optionally contain one or more customary auxiliaries and additives, in particular from the group of builders, enzymes, complexing agents, fragrances, perfume carriers, fluorescers, dyes, thickeners, foam inhibitors, grayness inhibitors, anti-crease agents, antimicrobial Active ingredients, germicides, fungicides, antioxidants, antistatic agents, UV absorbers, optical brighteners, anti-redeposition agents, pearlescers, color transfer inhibitors, anti-shrinkage agents, corrosion inhibitors, preservatives, repellents and impregnating agents and hydrotropes.
  • customary auxiliaries and additives in particular from the group of builders, enzymes, complexing agents, fragrances, perfume carriers, fluorescers, dyes, thickeners, foam inhibitors, grayness inhibitors, anti-crease agents, antimicrobial Active ingredients, germicides, fungicides, antioxidants, antistatic agents, UV absorbers, optical brighteners, anti-redeposition agents, pearlescers, color transfer inhibitors, anti-
  • the agent according to the invention may optionally additionally contain one or more complexing agents.
  • INCI chelating agents also called sequestrants, are ingredients that are capable of complexing and inactivating metal ions to prevent their detrimental effects on the stability or appearance of the agents, such as clouding. On the one hand, it is important to complex the incompatible with numerous ingredients calcium and magnesium ions of water hardness. The complexation of the ions of heavy metals such as iron or copper retards the oxidative decomposition of the finished agents.
  • Suitable examples are the following according to INCI described complexing agents, which are described in the International Cosmetic Ingredient Dictionary and Handbook : Aminotrimethylene Phosphonic Acid, Beta Alanine Diacetic Acid, Calcium Disodium EDTA, Citric Acid, Cyclodextrin, Cyclohexanediamine Tetraacetic Acid, Diammonium Citrate, Diammonium EDTA , Diethylenetriamine Pentamethylene Phosphonic Acid, Dipotassium EDTA, Disodium Azacycloheptane Diphosphonate, Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactic Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonate, Pentasodium Ethylenediamine Tetramethylene Phosphonate, Pentaso
  • Preferred complexing agents are tertiary amines, in particular tertiary alkanolamines (amino alcohols).
  • the alkanolamines have both amino and hydroxy and / or ether groups as functional groups.
  • Particularly preferred tertiary alkanolamines are triethanolamine and tetra-2-hydroxypropylethylenediamine (N, N, N ', N'-tetrakis- (2-hydroxypropyl) ethylenediamine).
  • a particularly preferred complexing agent is etidronic acid (1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxy-ethane-1,1-diphosphonic acid, HEDP, acetophosphonic acid, INCl etidronic acid), including their salts.
  • the agent according to the invention accordingly contains etidronic acid and / or one or more of its salts as complexing agent.
  • the agent according to the invention contains a complexing agent combination of one or more tertiary amines and one or more further complexing agents, preferably one or more complexing acids or salts thereof, in particular triethanolamine and / or tetra-2-hydroxypropylethylenediamine and etidronic acid and / or one or more several of their salts.
  • the agent according to the invention contains complexing agents in an amount of usually 0 to 20% by weight, preferably 0.1 to 15% by weight, in particular 0.5 to 10% by weight, particularly preferably 1 to 8% by weight, most preferably 1.5 to 6 wt .-%, for example, 1.5, 2.1, 3 or 4.2 wt .-%.
  • the agent optionally contains one or more thickening agents.
  • the viscosity of the optionally liquid agents can be measured by conventional standard methods (for example Brookfield Viscometer RVD-VII at 20 rpm and 20 ° C., spindle 3) and is preferably in the range from 10 to 5000 mPas.
  • Preferred liquid to gel compositions have viscosities of 20 to 4000 mPas, with values between 40 and 2000 mPas being particularly preferred. If the conditioning agents according to the invention are used as impregnating liquids for the conditioning substrates according to the invention, advantageously a viscosity below 150 mPas, preferably between 10 and 100 mPas and in particular between 20 and 80 mPas is indicated.
  • Suitable thickeners are inorganic or polymeric organic compounds. It is also possible to use mixtures of several thickeners.
  • the agent optionally contains one or more enzymes.
  • enzymes are in particular those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other Glykosylhydrolasen and mixtures of said enzymes in question. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying.
  • the conditioning agents according to the invention additionally contain cellulases and / or other glycosyl hydrolases.
  • these enzymes can contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils.
  • Oxireductases can also be used for bleaching or inhibiting color transfer.
  • Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens derived enzymatic agents.
  • Bacillus subtilis Bacillus subtilis
  • Bacillus licheniformis Bacillus licheniformis
  • Streptomyceus griseus and Humicola insolens derived enzymatic agents.
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • As cellulases are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes may be adsorbed as a shaped body to carriers or embedded coated to protect against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.12 to about 2 wt .-%.
  • the agent optionally contains one or more perfumes in an amount of usually up to 10 wt .-%, preferably 0.01 to 5 wt .-%, in particular 0.05 to 3 wt .-%, particularly preferably 0, 2 to 2 wt .-%, most preferably 0.3 to 1.8 wt .-%.
  • perfume oils or fragrances individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, ⁇ -isomethylionone and methyl cedrylketone , the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • Dyes may optionally be used in the composition according to the invention, wherein the amount of one or more dyes is to be chosen so small that remain after application of the agent no visible residues.
  • the agent according to the invention is free of dyes.
  • composition according to the invention may optionally contain one or more antimicrobial agents or preservatives in an amount of usually 0.0001 to 3% by weight, preferably 0.0001 to 2% by weight, in particular 0.0002 to 1% by weight, especially preferably 0.0002 to 0.2% by weight, most preferably 0.0003 to 0.1% by weight.
  • the conditioning agent according to the invention is used as an impregnating liquid for the conditioning substrates according to the invention
  • the use of antimicrobial agents for germ killing the bacteria located on the substrates may be indicated.
  • Antimicrobial agents or preservatives are differentiated depending on the antimicrobial spectrum and mechanism of action between bacteriostats and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenol mercuriacetate.
  • the terms antimicrobial action and antimicrobial active ingredient in the context of the teaching according to the invention have the usual meaning, which is described, for example, by K. H.
  • Suitable antimicrobial agents are preferably selected from the groups of the alcohols, amines, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazolines , Phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propyl-butyl-carbamate, iodine, iodophores, peroxo compounds, halogen compounds and any mixtures of above.
  • the antimicrobial agent may be selected from ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, benzoic acid, salicylic acid, dihydracetic acid, o-phenylphenol, N-methylmorpholine.
  • acetonitrile MMA
  • 2-benzyl-4-chlorophenol 2,2'-methylenebis (6-bromo-4-chlorophenol), 4,4'-dichloro-2'-hydroxydiphenyl ether (dichlosan), 2,4 , 4'-trichloro-2'-hydroxydiphenyl ether (trichlosan), chlorhexidine, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) -urea, N, N '- (1,10-decandiyldi-1) pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis (4-chlorophenyl) -3,12-dinimino-2,4,11,13-tetraaza-tetradecane diimidamide, glucoprotamines, antimicrobial surface-active quaternary compounds, guanidines including the bi- and polyguanidine
  • halogenated xylene and cresol derivatives such as p-chlorometacresol or p-chloro-meta-xylene, as well as natural antimicrobial agents of plant origin (eg from spices or herbs), animal and microbial origin.
  • antimicrobial surface-active quaternary compounds a natural antimicrobial agent of plant origin and / or a natural antimicrobial agent of animal origin, most preferably at least one natural antimicrobial agent of plant origin from the group comprising caffeine, theobromine and theophylline and essential oils such as eugenol, thymol and geraniol, and / or at least one natural antimicrobial agent of animal origin from the group comprising enzymes such as protein from milk, lysozyme and lactoperoxidase, and / or at least one antimicrobial surface-active quaternary compound having an ammonium, sulfonium, phosphonium, iodonium or arsonium group, peroxo compounds and chlorine compounds.
  • bacteriocins substances of microbial origin, so-called bacteriocins.
  • Glycine, glycine derivatives, formaldehyde, compounds which readily split off formaldehyde, formic acid and peroxides are preferably used.
  • the conditioner according to the invention is used as the impregnating liquid for the conditioning substrates according to the invention, in particular the dehydraacetic acid and the glycolic acid are suitable.
  • the quaternary ammonium compounds (QAV) suitable as antimicrobial agents have the general formula (R 1 ) (R 2 ) (R 3 ) (R 4 ) N + X, in which R 1 to R 4 are the same or different C 1 -C 22 -Alkyl radicals, C 7 -C 28 -aralkyl radicals or heterocyclic radicals, where two or, in the case of an aromatic inclusion as in pyridine, even three radicals together with the nitrogen atom form the heterocycle, eg a pyridinium or imidazolinium compound, and X - halide ions, Sulfate ions, hydroxide ions or similar anions are.
  • at least one of the radicals has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.
  • QACs are prepared by reacting tertiary amines with alkylating agents, e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • the alkylation of tertiary amines with a long alkyl radical and two methyl groups succeeds particularly easily, and the quatern
  • Suitable QAVs are benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B ( m, p- dichlorobenzyl-dimethyl-C 12 -alkylammonium chloride, CAS No. 58390-78 6), benzoxonium chloride (benzyl-dodecyl-bis- (2-hydroxyethyl) -ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide, CAS No.
  • benzetonium chloride N, N-dimethyl-N- [2- [2- [ p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzyl ammonium chloride, CAS No. 121-54-0
  • dialkyldimethylammonium chlorides such as di-n-decyl dimethyl ammonium chloride (CAS No. 7173-51-5-5) Didecyldi-methylammoniumbromid (CAS No. 2390-68-3), dioctyl-dimethylammoniumchloric , 1-cetylpyridinium chloride (CAS No.
  • QACs are the benzalkonium chlorides having C 8 -C 18 -alkyl radicals, in particular C 12 -C 14 -alkyl-benzyl-dimethyl-ammonium chloride.
  • Benzalkonium halides and / or substituted benzalkonium halides are for example commercially available as Barquat ® ex Lonza, Marquat® ® ex Mason, Variquat ® ex Witco / Sherex and Hyamine ® ex Lonza and as Bardac ® ex Lonza.
  • antimicrobial agents are N- (3-chloroallyl) hexaminium chloride such as Dowicide and Dowicil ® ® ex Dow, benzethonium chloride such as Hyamine ® 1622 ex Rohm & Haas, methylbenzethonium as Hyamine ® 10X ex Rohm & Haas, cetylpyridinium chloride such as Cepacol ex Merrell Labs ,
  • the agents may further optionally contain UV absorbers which are applied to the treated fabrics and improve the lightfastness of the fibers and / or the lightfastness of the other formulation ingredients.
  • UV absorber are organic substances (sunscreen) to understand, which are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, eg heat to give back.
  • Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position.
  • substituted benzotriazoles such as the water-soluble benzenesulfonic acid-3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Ciba ® Fast H), phenyl substituted in the 3-position acrylates (cinnamic acid derivatives) , optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's urocanic acid suitable.
  • the biphenyl and, above all, stilbene derivatives as described for example in EP 0728749 A are described and commercially available as Tinosorb FD ® ® or Tinosorb FR ex Ciba.
  • 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts
  • Sulfonic acid derivatives of 3-Benzylidencamphers such as 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.
  • UV-A filter in particular derivatives of benzoylmethane are suitable, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1,3-dione and also enamine compounds as described in DE 19712033 A1 (BASF).
  • the UV-A and UV-B filters can also be used in mixtures.
  • insoluble photoprotective pigments namely finely dispersed, preferably nano-metal oxides or salts
  • suitable metal oxides are in particular zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof.
  • salts silicates (talc), barium sulfate or zinc stearate can be used.
  • the oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
  • the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm.
  • the pigments may also be surface-treated, ie hydrophilized or hydrophobized.
  • Typical examples are coated titanium dioxides, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck).
  • Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones.
  • micronized zinc oxide is used.
  • UV light protection filters can be found in the review by P. Finkel in S ⁇ FW Journal 122, 543 (1996).
  • the UV absorbers are usually used in amounts of from 0.01% by weight to 5% by weight, preferably from 0.03% by weight to 1% by weight.
  • the invention in a second embodiment is the use of the conditioning agent according to the invention, for the conditioning of textile fabrics in a textile drying process or in a washing process.
  • the use according to the invention of the conditioning agents according to the invention can be carried out directly in a washing process, for example by integration of the conditioning agent according to the invention into a detergent formulation and / or preferably in a rinse cycle following the washing process.
  • the conditioning agents according to the invention can be used in a textile drying process in a device for drying textiles, preferably in a household tumble dryer.
  • the conditioning agent according to the invention is brought into contact with the textiles to be conditioned via the dispensing chamber of a washing machine in the final rinse cycle.
  • a third object of the invention is a conditioning substrate, which is a substrate which is impregnated and / or impregnated with the conditioning agent according to the invention.
  • the substrate material is made of porous materials capable of reversibly adding and dispensing an impregnating liquid.
  • Eligible for this purpose are three-dimensional structures, for example sponges, but preferably porous flat sheets. They may consist of a fibrous or cellular flexible material which has sufficient thermal stability for use in the dryer and which can retain sufficient quantities of impregnating or coating agent to effectively condition fabrics without significant bleeding or bleeding during storage By means of done.
  • These cloths include woven cloths and nonwoven synthetic and natural fibers, felt, paper or foam, such as hydrophilic polyurethane foam.
  • conventional cloths of nonwoven material are used here.
  • Nonwovens are generally defined as adhesively bonded fibrous products having a mat or layered fibrous structure, or those comprising fibrous mats in which the fibers are randomly or randomly distributed.
  • the fibers may be natural such as wool, silk, jute, hemp, cotton, flax, sisal or ramie; or synthetic, such as rayon, cellulose esters, polyvinyl derivatives, polyolefins, polyamides, viscose or polyesters. In general, any fiber diameter or titer is suitable for the present invention.
  • Preferred conditioning substrates according to the invention consist of a nonwoven material which contains cellulose.
  • nonwoven fabrics employed herein tend not to rupture or disintegrate due to the random or random arrangement of fibers in the nonwoven material which impart excellent strength in all directions when used, for example, in a household tumble dryer.
  • nonwoven fabrics suitable as substrates in the present invention are known, for example, from WO 93/23603.
  • Preferred porous and flat conditioning cloths consist of one or different fiber materials, in particular of cotton, refined cotton, polyamide, polyester or mixtures of these.
  • the conditioning substrates in fabric form preferably have an area of from 0.2 to 0.005 m 2 , preferably from 0.15 to 0.01 m 2 , in particular from 0.1 to 0.03 cm 2 and particularly preferably from 0.09 to 0, 06 m 2 up.
  • the grammage of the material is usually between 20 and 500 g / m 2 , preferably from 25 to 200 g / m 2 , in particular from 30 to 100 g / m 2 and particularly preferably from 40 to 80 g / m 2 .
  • the fourth subject of the invention is a conditioning method for conditioning wet textiles by means of the conditioning substrate according to the invention.
  • the conditioning process is carried out by using the conditioning substrate according to the invention together with moist textiles, for example obtained from a previous washing process, in a textile drying process.
  • the textile drying process usually takes place in a device for drying textiles, preferably in a household tumble dryer.
  • the fifth subject of the invention is therefore the use of the agents according to the invention and / or of the conditioning substrates according to the invention for reducing the linting of textile fabric.
  • Another object is the use of the agents according to the invention and / or the conditioning substrates according to the invention for reducing the pilling of textile fabric.
  • Fluffs are formed when fibers break on textile surfaces. In a household dryer with lint filter then find the fiber fragments again. The fiber particles are transported by the air flow to the lint filter. The pilling is similar. Pills are more or less spherical structures that are connected to the fabric by anchor fibers and whose density is such that no light penetrates and a shadow is thrown. This change can occur both during the washing process and during use. Pills are formed when fibers from a textile fabric work out and become tangled in use. Such surface changes are undesirable. In general, the amount of pilling is determined by the speed of the following parallel processes: a) fiber entanglement leading to pilling; b) formation of further surface fibers and c) abrasion of fibers and pills.
  • Conditioners according to the invention are, for example, E1 and E2, a comparative formulation is V1 whose compositions are given in Table 1.
  • Table 1 ⁇ / b> Composition in% by weight V2 E1 E2 E3 V1 Rewoquat WE 18 [a] 22.5 22.5 22.5 22.5 22.5 Silicone oil [b] 5 --- --- --- Tegopren 5843 [c] 0.75 0.75 0.75 0.75 --- MgCl 2 .6H 2 O 0.5 0.5 0.5 0.5 + Plexophore Eco [d] --- --- --- Arbocel ® BE 600-10 [e] --- --- --- Cellulon® [f] --- --- --- 0.4 --- Perfume 1.6 1.6 1.6 1.6 + dye + + + + + + Water, demineralized ad 100 ad 100 ad 100 ad 100 ad 100 [a] N-Methyl-N (2-hydroxye
  • the formulations E1 to E4 were prepared by melting the esterquat in water. The molten esterquat is then stirred with a high dispersing device and the remaining active substances added. The perfume addition was carried out after cooling the mixture to below 30 ° C.
  • nonwovens made of cellulose were impregnated with 20 g each of one of the conditioners E1 to E4 according to the invention.
  • a comparison substrate with formulation V1 was produced.
  • the weight of the fluff was determined after each drying cycle and added over the 10 cycles. It showed for a) 7.58 g, for b) 8.39 g, c) 4.05 g, d) 5.51 g, e) 4.17 and f) 6.21 g.
  • the 140mm diameter abrasive discs are clamped over the scrubbing tables underlaid with standard felt discs.
  • the test specimens (diameter 140 mm) are fixed in special specimen holders and placed with the right side to the counter-textile.
  • the guide plate of the device is placed above and spindles loaded with weights are inserted through the guide plate into the underlying sample holders.
  • the drive mechanism consists of two outer and one inner drive, which forces the sample holder guide plate to describe a Lissajous figure.
  • the Lissajous movement changes into a circular motion to gradually narrowing ellipses until it becomes a straight line from which progressively expanding ellipses develop in a diagonally opposite direction before repeating the pattern. Pill grade is determined by comparing the sample to prepared photographs of standard items.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Detergent Compositions (AREA)

Claims (22)

  1. Agent de conditionnement liquide, contenant
    a) au moins un composant de réduction des peluches choisi dans le groupe des celluloses, des hydrogels et des polymères synthétiques et
    b) au moins un agent d'étalement, qui est un siloxane modifié par un polyéther.
  2. Agent selon la revendication 1, caractérisé en ce que le composant de réduction de peluches est une cellulose microcristalline, de préférence une cellulose microcristalline provenant d'un processus de fermentation microbiologique.
  3. Agent selon la revendication 1, caractérisé en ce que le composant de réduction des peluches est un hydrogel, choisi dans le groupe formé par les polymères naturels, de préférence l'agarose, la gélatine, le curdlan, les alginates, les pectinates, le carrageenan ainsi que les mélanges quelconques de ceux-ci.
  4. Agent selon la revendication 1, caractérisé en ce que le composant de réduction des peluches est choisi dans le groupe formé par les polymères synthétiques, de préférence les polyacrylates, les polyméthacrylates, les polyacrylamides, les polyméthacrylamides, les polyuréthanes, les polyvinylpyrrolidones, les poly(alcools vinyliques), le poly(acétate de vinyle) et/ou leurs hydrolysats partiels ou leurs copolymères, en particulier les copolymères de l'acide acrylique-acide maléique ainsi que les mélanges quelconques de ceux-ci.
  5. Agent selon la revendication 4, caractérisé en ce que les polymères synthétiques se trouvent sous forme d'hydrogels.
  6. Agent selon l'une quelconque des revendications 2 à 4, caractérisé en ce que 90% des particules du composant de réduction des peluches présentent une grosseur de particules inférieure à 100 µm, de préférence inférieure à 50 µm, de manière particulièrement préférée inférieure à 30 µm et en particulier inférieure à 20 µm.
  7. Agent selon l'une quelconque des revendications 1 à 6, caractérisé en ce que la teneur en composant de réduction de peluches est de 0,005 à 15% en poids, de préférence de 0,01 à 10% en poids, de manière particulièrement préférée de 0,1 à 7% en poids et en particulier de 0,5 à 5% en poids, à chaque fois par rapport à l'agent total.
  8. Agent selon l'une quelconque des revendications 1 à 7, caractérisé en ce que l'agent contient en outre au moins un composant assouplissant.
  9. Agent selon la revendication 8, caractérisé en ce qu'il contient comme composant assouplissant des agents tensioactifs cationiques, de préférence des composés d'ammonium quaternaire alkylés, dont au moins une chaîne alkyle est interrompue par un groupe ester et/ou amido, en particulier le méthosulfate de N-méthyl-N(2-hydroxyéthyl)-N,N-(disuifacyloxyéthyl)ammonium ou le méthosulfate de N-méthyl-N(2-hydroxyéthyl)-N,N-(dipalmitoyléthyl)ammonium.
  10. Agent selon l'une quelconque des revendications 8 ou 9, caractérisé en ce qu'il contient le composant assouplissant en une quantité allant jusqu'à 50% en poids, de préférence de 0,1 à 45% en poids, de manière particulièrement préférée de 5 à 40% en poids et en particulier de 11 à 35% en poids, à chaque fois par rapport à l'agent total.
  11. Agent selon l'une quelconque des revendications 1 à 10, caractérisé en ce qu'il contient en outre des agents tensioactifs non ioniques, en particulier des alcools en C8-C18 comprenant 1 à 12 OE.
  12. Agent selon l'une quelconque des revendications 1 à 11, caractérisé en ce qu'il contient jusqu'à 95% en poids, de manière particulièrement préférée 20 à 90% en poids et en particulier 50 à 80% en poids d'un ou de plusieurs solvants, de préférence des solvants solubles dans l'eau et en particulier de l'eau.
  13. Agent selon la revendication 1, caractérisé en ce que l'agent d'étalement se trouve en des quantités allant jusqu'à 10% en poids, de préférence de 0,01 à 5% en poids, de manière particulièrement préférée de 0,05 à 2% en poids et en particulier de 0,1 à 1 % en poids.
  14. Utilisation d'un agent selon l'une quelconque des revendications 1 à 13 pour le conditionnement de tissus textiles dans un procédé de séchage de textiles ou dans un procédé de lavage.
  15. Substrat de conditionnement, caractérisé en ce qu'il s'agit d'un substrat imprégné et/ou imbibé d'un agent selon l'une quelconque des revendications 1 à 13.
  16. Substrat de conditionnement selon la revendication 15, caractérisé en ce que le substrat contient un matériau non-tissé, de préférence un non-tissé en cellulose.
  17. Substrat de conditionnement selon l'une quelconque des revendications 15 ou 16, caractérisé en ce que le substrat présente un poids surfacique de 20 à 500 g/m2, de préférence de 25 à 200 g/m2, de manière particulièrement préférée de 30 à 100 g/m2 et en particulier de 40 à 80 g/m2.
  18. Substrat de conditionnement selon l'une quelconque des revendications 15 à 17, caractérisé en ce que le substrat présente une taille de 0,2 à 0,005 m2, de préférence de 0,15 à 0,01, de manière particulièrement préférée de 0,1 à 0,03 m2 et en particulier de 0,09 à 0,06 m2.
  19. Procédé de conditionnement de textiles, caractérisé en ce qu'on utilise un ou plusieurs substrats de conditionnement selon l'une quelconque des revendications 15 à 18 dans un procédé de séchage de textiles.
  20. Utilisation d'un agent selon l'une quelconque des revendications 1 à 13 et/ou d'un substrat de conditionnement selon l'une quelconque des revendications 15 à 18 pour diminuer la formation de peluches de structures planes textiles.
  21. Utilisation d'un agent selon l'une quelconque des revendications 1 à 13 et/ou d'un substrat de conditionnement selon l'une quelconque des revendications 15 à 18 pour diminuer la formation de bouloches de structures planes textiles.
  22. Utilisation selon l'une quelconque des revendications 20 ou 21, caractérisée en ce que l'agent et/ou le substrat de conditionnement est utilisé dans un procédé de séchage de textiles.
EP03704400A 2002-01-25 2003-01-15 Agent conditionneur menageant les textiles Revoked EP1468068B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US35187802P 2002-01-25 2002-01-25
DE10203192 2002-01-25
US351878P 2002-01-25
DE2002103192 DE10203192A1 (de) 2002-01-25 2002-01-25 Konditioniermittel zur Textilschonung
PCT/EP2003/000323 WO2003062361A1 (fr) 2002-01-25 2003-01-15 Agent conditionneur menageant les textiles

Publications (2)

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EP1468068A1 EP1468068A1 (fr) 2004-10-20
EP1468068B1 true EP1468068B1 (fr) 2007-05-16

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EP (1) EP1468068B1 (fr)
AT (1) ATE362513T1 (fr)
DE (1) DE50307290D1 (fr)
ES (1) ES2285093T3 (fr)
WO (1) WO2003062361A1 (fr)

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DE10215602A1 (de) 2002-04-10 2003-10-30 Henkel Kgaa Textilschonendes Textilreinigungsmittel
US8772359B2 (en) 2006-11-08 2014-07-08 Cp Kelco U.S., Inc. Surfactant thickened systems comprising microfibrous cellulose and methods of making same
US9045716B2 (en) 2006-11-08 2015-06-02 Cp Kelco U.S., Inc. Surfactant thickened systems comprising microfibrous cellulose and methods of making same
CA2715652C (fr) 2008-02-15 2014-08-12 The Procter & Gamble Company Composition detergente liquide comprenant une structure externe constituee d'un reseau de cellulose bacterienne
WO2013032480A1 (fr) 2011-09-01 2013-03-07 Colgate-Palmolive Company Procédé permettant de faciliter le repassage
WO2013032479A1 (fr) 2011-09-01 2013-03-07 Colgate-Palmolive Company Procédé pour réaliser un séchage rapide d'un tissu
WO2013032481A1 (fr) 2011-09-01 2013-03-07 Colgate-Palmolive Company Procédé pour augmenter la libération d'une fragrance pendant le repassage
US9758927B2 (en) 2011-09-01 2017-09-12 Colgate-Palmolive Company Method for ease of ironing
EP3339408B1 (fr) 2016-12-22 2020-01-29 The Procter & Gamble Company Composition d'adoucissant textile présentant de meilleures propriétés de distribution
EP3339409B1 (fr) 2016-12-22 2020-04-15 The Procter & Gamble Company Composition d'adoucissant textile présentant une meilleure stabilité aux cycles gel-dégel
US10676694B2 (en) 2016-12-22 2020-06-09 The Procter & Gamble Company Fabric softener composition having improved detergent scavenger compatibility
EP3339411B1 (fr) 2016-12-22 2019-12-11 The Procter & Gamble Company Composition d'adoucissant textile à stabilité de viscosité améliorée
EP3375855B1 (fr) 2017-03-16 2021-04-21 The Procter & Gamble Company Composition d'adoucissant textile comprenant un agent bénéfique encapsulé
EP3375856B1 (fr) 2017-03-16 2021-09-01 The Procter & Gamble Company Composition d'adoucissant textile comprenant un agent bénéfique encapsulé

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Publication number Priority date Publication date Assignee Title
DE2631419A1 (de) * 1975-07-16 1977-02-03 Procter & Gamble Europ Zusammensetzungen fuer die textilbehandlung
GB8817961D0 (en) * 1988-07-28 1988-09-01 Dow Corning Ltd Compositions & process for treatment of textiles
GB9011785D0 (en) * 1990-05-25 1990-07-18 Unilever Plc Fabric treatment compositions
AU641014B2 (en) * 1990-06-01 1993-09-09 Unilever Plc Liquid fabric conditioner and dryer sheet fabric conditioner containing compatible silicones
AU9389598A (en) * 1997-09-15 1999-04-05 Procter & Gamble Company, The Laundry detergent compositions with anionically modified, cyclic amine based polymers
BR0013690A (pt) * 1999-09-02 2002-05-07 Colgate Palmolive Co Composição aquosa para o cuidado de tecido, método de tratamento de tecido, e, folha secadora para proporcionar benefìcios de cuidado de tecido as roupas secas em uma secadora elétrica
DE10112318A1 (de) * 2001-02-05 2002-08-14 Henkel Kgaa Konditioniermittel

Also Published As

Publication number Publication date
ATE362513T1 (de) 2007-06-15
WO2003062361A1 (fr) 2003-07-31
DE50307290D1 (de) 2007-06-28
ES2285093T3 (es) 2007-11-16
EP1468068A1 (fr) 2004-10-20

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