WO2001046377A1 - Agent pour traiter des substrats - Google Patents

Agent pour traiter des substrats Download PDF

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Publication number
WO2001046377A1
WO2001046377A1 PCT/EP2000/012581 EP0012581W WO0146377A1 WO 2001046377 A1 WO2001046377 A1 WO 2001046377A1 EP 0012581 W EP0012581 W EP 0012581W WO 0146377 A1 WO0146377 A1 WO 0146377A1
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Prior art keywords
acid
agents
agent
weight
sodium
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PCT/EP2000/012581
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German (de)
English (en)
Inventor
Hans-Jürgen Riebe
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Henkel Kommanditgesellschaft Auf Aktien
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Priority to AU25107/01A priority Critical patent/AU2510701A/en
Publication of WO2001046377A1 publication Critical patent/WO2001046377A1/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
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts

Definitions

  • the present invention relates to agents for the treatment of substrates which can be used for the pretreatment or aftertreatment of soiled textiles or as a washing additive or also for the treatment of hard surfaces, and to a pretreatment or aftertreatment process for textile washing.
  • Textiles often have stubborn stains that cannot be completely removed by washing with a commercially available detergent. These stains are usually treated directly in the home with a so-called pretreatment agent. These are usually surfactant compositions that are offered in the form of sprays, pastes or liquids. Such agents are applied directly to the stains and left there until they are washed. The stains are pre-dissolved by this pretreatment and finally removed in the main washing process.
  • pretreatment agent usually surfactant compositions that are offered in the form of sprays, pastes or liquids. Such agents are applied directly to the stains and left there until they are washed. The stains are pre-dissolved by this pretreatment and finally removed in the main washing process.
  • Common pretreatment agents are pastes containing surfactants, which show good cleaning performance on greasy stains, but whose cleaning effect is not always satisfactory compared to bleachable stains such as tea or coffee.
  • Products containing bleach which are known from the prior art as low-viscosity products, are more expedient for the removal of pliable soils.
  • Commercial products have a viscosity of up to approximately 1,200 mPa * s.
  • the object of the present invention was to provide an agent for treating substrates which can be used as a pre-treatment and / or after-treatment agent in textile washing, for treating stains on textile surfaces and for treating stains on hard surfaces.
  • the agent should have a good cleaning effect against both greasy and bleachable soiling and at the same time be easy to apply to the soiling and also be suitable for mechanical stain pretreatments.
  • compositions which contain bleaching agents and / or surfactants and, if appropriate, other customary constituents, have a good cleaning action against fatty and bleachable stains and can also be used well for mechanical pretreatment of stains if they have a shear-thinning behavior.
  • the composition liquefies so that it can be easily distributed and can also penetrate into textile fabrics.
  • the viscosity increases again, i.e. the fluidity decreases and the composition remains on the treated substrate without flowing.
  • the present invention accordingly relates to an agent for the treatment of substrates containing surfactants and / or bleaching agents and optionally solvents, which is characterized in that it exhibits a shear-thinning behavior.
  • substrates are textiles, textile surfaces and any hard surfaces, such as floor coverings, wall and furniture surfaces and any surfaces of household objects, e.g. Metal, plastic and porcelain.
  • the agent exhibits shear thinning behavior. This means that the viscosity of the agent is reduced when exposed to shear.
  • the shear thinning behavior can be pseudoplastic or thixotropic, ie as soon as the action stops from shear forces, the original viscosity is restored immediately (pseudoplastic behavior) or with a time delay (thixotropic behavior).
  • the agents according to the invention are used for the pretreatment of soiled textiles or as a washing additive.
  • they can also be used as a heavy-duty detergent, for washing in a washing machine or by hand, as a detergent booster and as a household cleaner for hard surfaces, such as in wet rooms or in the kitchen, as a dishwashing detergent, as a toilet cleaner or for carpet cleaning.
  • pretreatment of soiled textiles means that the aqueous composition is applied to the soiled fiber and is left there before the textile fiber is washed.
  • the soiling can also be treated mechanically, for example by Rubbing and distributing the composition according to the invention, if appropriate in aqueous dilution, with a sponge or a brush or by simply rubbing textile surfaces against one another
  • the aqueous composition can also be applied to the textile substrate together with sufficient water to moisten the textile.
  • washing here means the usual cleaning process for textiles with at least one surfactant using a washing machine or simply by hand.
  • treatment of hard surfaces means that customary of the above-mentioned surfaces, as they usually occur in the home, can be (pre) treated with the agent according to the invention in order to remove stubborn stains.
  • the pretreatment can be carried out with a sponge or a brush or other auxiliary means.
  • the treatment with the composition according to the invention can be followed by a conventional cleaning.
  • the agents contain bleaching agents and / or surfactants as essential components.
  • Preferred bleaching agents are H 2 O and compounds which provide H 2 O 2 in water, such as sodium perborate tetrahydrate, sodium perborate monohydrate, sodium percarbonate or ent speaking percarbonate salts, persilicate, peroxypyrophosphates, persulfates, such as monopersulfate, urea peroxyhydrate, citrate perhydrates, organic peroxides and peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperoxyazelaic acid, phthalimino acids or diperoxydodecandis.
  • H 2 0 2 is particularly preferably used.
  • the bleaching agent component can be present in the agents according to the invention in an amount of 0.1 to 35% by weight, based on the total agent, preferably 0.5 to 15% by weight and particularly preferably 1 to 10% by weight his.
  • acylated alkylenediamines in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1, 5-diacetyl-2,4-dioxohexahydro-1, 3,5-triazine (DADHT), acylated glycolurils, in particular 1, 3,4.6 - Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), acylated hydroxycarboxylic acids (acetyl) -AC, such as triethyl-acetic acid such as triethyl , Carboxylic anhydrides and their derivatives, in particular phthalic anhydride, isatoic anhydr
  • Hydrophilically substituted acyl acetates and acyl lactams can also be used.
  • Nitride derivatives such as cyanopyridines, nitrile quats and / or cyanamide derivatives can also be used.
  • the preferred bleach activators are sodium 4- (octanoyloxy) benzol sulfonate, undecenoyloxy benzene sulfonate (UDOBS), sodium dodecanoyloxy benzene sulfonate (DOBS) and / or decanoyloxy benzoic acid (DOBA, OBC 10 patent) Formanidinium salts can also be mentioned.
  • a mixture of several bleach activators can also be used. Such bleach activators are in the usual range of 0.01 to 20% by weight, preferably 0.1 to 15% by weight, in particular 1% by weight. % to 10% by weight, based on the total composition
  • transition metal compounds in question include in particular the manganese-iron, cobalt, ruthenium or molybdenum-salt complexes known from German patent application DE-A-195 29905 and their N-analog compounds known from German patent application DE-A-196 20 267, the from the German patent application DE-A-195 36 082 known manganese, iron-cobalt, ruthenium or molybdenum-carbonyl complexes, the manganese, iron, cobalt, ruthenium described in German patent application DE-A-196 05 688 -, Molybdenum, titanium, vanadium and copper complexes with nitrogen-containing Tnpod ligand
  • surfactants are in liquid form, they can also serve as the sole solvent.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical has a methyl or linear branching in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 . 14 alcohols with 3 EO to 7 EO, C alcohol with 7 EO, C 13 . ⁇ 5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 .i 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci 2 - ⁇ alcohol with 3 EO and C ⁇ 2 - ⁇ 8 alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention.
  • block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
  • mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not distributed in blocks but rather statistically. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18, C-atoms, in particular in 2-division, and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or preferably according to that in the international patent application Patent application WO-A-90/13533 can be prepared.
  • Nonionic surfactants of the amine oxide type for example N-coco-alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, the fatty acid alkanolamides and the fatty amine alkoxylates may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula I,
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 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 formula II
  • R 2 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 3 is a linear, branched or cyclic alkyl radical or an aryl radical is 2 to 8 carbon atoms
  • R 4 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, 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 propylated derivatives of this residue.
  • [Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose
  • a sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Suitable surfactants of the sulfonate type are preferably C 8- thereby ⁇ 3 - alkylbenzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C 12 _ ⁇ 8 monoolefins with terminal or internal double bond by sulfonation obtained with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products suitable are alkanesulfonates, which are from C ⁇ 2 . ⁇ 8 alkanes, for example by Sulfochlo ⁇ réelle or sulfoxidation and subsequent hydrolysis or neutralization obtained.
  • the alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of the d 2 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, my ⁇ styl, cetyl or stearyl alcohol or the C 10 -C 20 -Oxo alcohols and those half esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis.
  • the Cj 2 -C 6 alkyl sulfates and C 12 -C 5 alkyl sulfates and C 1 - ds alkyl sulfates are preferred from a washing-technical point of view.
  • 2,3-alkyl sulfates which are produced for example according to U.S. Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
  • Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • 2 ⁇ -alcohols such as 2-methyl-branched Cg.n-alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 - ⁇ 8 fatty alcohols with 1 to 4 EO, are suitable. Because of their high foaming behavior, they are used in surfactant compositions or cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yi chain or salts thereof.
  • Other anionic surfactants that are particularly suitable are soaps that are used in particular at higher pH values.
  • the anionic surfactants can be present in the form of the free acids or their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine
  • Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO ( ⁇ or -SO ⁇ group in the molecule.
  • Particularly suitable zwitterionic surfactants are so-called betaines such as N-alkyl-N, N-dimethylammonium.
  • glyc ⁇ nate for example, the cocoalkyl-dimethylammonium glycinate, N-acylaminopropyl-N N-dimethylammonium glycinate, for example the cocoacylaminopropyl-dimethylammonium glycinate and 2-alkyl-3-carboxymethyl-3-hydroxyethyl- ⁇ m ⁇ dazol ⁇ ne each with 8 to 18 C-atoms in the - or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylgiycinat
  • a preferred zwitterionic surfactant is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine
  • Ampholytic surfactants are surface-active compounds which, in addition to a C 8 18 -alkyl or -acyl group, contain at least one free ammo group and at least one -COOH or -S0 3 H group in the molecule and are capable of forming internal salts.
  • Suitable examples of surfactants containing amino groups are the fatty amine alkoxylates Suitable examples are quaternary ammonium compounds of the formulas (III) and (IV)
  • R 5 is an acychic alkyl radical having 12 to 24 carbon atoms
  • R 6 is a saturated C 1 -C 8 alkyl or hydroxyalkyl radical
  • R 7 is either R 5 or R 6
  • COR 8 is an aliphatic acyl radical having 12 to 22 carbon atoms 0, 1, 2 or 3 double bonds
  • R 9 is H or OH
  • n is 1, 2 or 3
  • X is either a halide, methosulfate, methophosphate or phosphate ion, and mixtures of these compounds are particularly preferred
  • R 10 is a saturated alkyl group having 12 to 18 carbon atoms
  • R 11 is an alkyl group having 1 to 4 carbon atoms or H
  • Z is an NH group or oxygen and A is an anion.
  • R 12 each independently represents a C M alkyl, alkenyl or hydroxyalkyl group
  • R 13 each independently represents a C 8-28 alkyl group
  • n is a number between 0 and 5.
  • short-chain, water-soluble, quaternary ammonium compounds can also be used, such as trihydroxyethyl methylammonium methosulfate or the alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride.
  • Protonated alkylamine compounds which have a plasticizing effect and the non-quaternized, protonated precursors of the cationic emulsifiers are also suitable
  • the quaternized protein hydrolyzates are further cationic compounds which can be used according to the invention.
  • cationic silicone cones such as, for example, the commercially available products Q2-7224 (manufacturer Dow Corning, a stabilized methylmethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone) SM-2059 (Manufacturer General Electric), SLM-55067 (manufacturer Wacker) and Ab ⁇ l ® -Quat 3270 and 3272 (manufacturer Th Goldschmidt, diquatemare polydimethylsiloxane Quaternium- 80)
  • Alkylamidoamines especially fatty acid amidoamines such as the stearylamidopropyldimethylamine available under the name Tego Am ⁇ d ® S 18, are characterized not only by a good conditioning effect but also by their good biodegradability
  • estersquats such as the Methylhy- marketed under the trade Stepantex® ® are droxyalkyldialkoyloxyalkylammoniummethosulfate
  • quaternary sugar derivative that can be used as a cationic surfactant is the commercial product Glucquat ® 100, according to the CTFA nomenclature a "lauryl methyl gluceth-10 hydroxypropyl dimonium chloride"
  • the agent according to the invention shows a shear thinning behavior, which means that the agents are still partially flowable under strong shear and can therefore be easily dosed from a tube or a suitable dispenser and can be distributed well on the substrate to be treated the original viscosity returns and the composition remains on the substrate without running.
  • the shear thinning behavior also shows great advantages in the production and filling of the products.
  • the viscosity of the agents according to the invention is preferably above 5,000 mPa * s, particularly preferably above 6,000 mPa * s and ins- especially over 10,000 mPa * s and can be adjusted with suitable theological additives.
  • the viscosity can be measured using standard methods, such as the Brookfield RVD-VII viscometer at 20 rpm and 20 ° C., spindle 4).
  • Suitable theological additives are inorganic or polymeric organic compounds. Mixtures of several additives can also be used.
  • the organic theological additives come from the groups of natural polymers, modified natural polymers and fully synthetic polymers.
  • Polymers originating from nature and used as theological additives are, for example, agar agar, carrageenan, tragacanth, acacia, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein.
  • Modified natural products mainly come from the group of modified starches and celluloses, examples include carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and corn flour ether.
  • a large group of theological additives that are widely used in a wide variety of applications are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.
  • the theological additives can be contained in an amount of up to 10% by weight, preferably from 0.05 to 5% by weight, and particularly preferably from 0.1 to 3% by weight, based on the finished composition.
  • Rheological additives from the substance classes mentioned are commercially available and are sold, for example, under the trade names Acusol ® -820 (methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ® - GT-282-S (alkyl polyglycol ether, Akzo), Deutero ⁇ ® polymer 11 (Dicarboxylic acid copolymer, Schoener GmbH), Deuteron ® -XG (anionic heteropolysaccharide based on ß-D-glucose, D-manose, D-glucuronic acid, Schoener GmbH), Deuteron ® -XN (non-ionic polysaccharide, Schoener GmbH), Dicryla ⁇ ® thickener-0 (ethylene oxide adduct, 50% in water / isopropanol, Pfersse Chemie), EMA ® -81 and EMA ®
  • xanthan a microbial anionic heteropolysaccharide that is produced by Xanthomonas campestris and some other species under aerobic conditions and has a molecular weight of 2 to 15 million daltons.
  • Xanthan is formed from a chain with ß-1, 4-bound glucose (cellulose) with side chains.
  • the structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan.
  • Xanthan can be described by the following formula:
  • Polyurethanes are produced by polyaddition from dihydric and higher alcohols and isocyanates and can be described by the general formula VII
  • TDI 2,4- or 2,6-toluenediisocyanate
  • MDI C 6 H 4 -CH 2 -C 6 H 4
  • Modified polyacrylates which can be used in the context of the present invention are derived, for example, from acrylic acid or methacrylic acid and can be described by the general formula VIII
  • R 16 represents H or a branched or unbranched C 1-4 alk (en) yl radical
  • X represents N- R 18 or O
  • R 19 represents an optionally alkoxylated branched or unbranched, possibly substituted C 8 . 22 -alk (en) yl radical
  • R 18 is H or R 17 and n is a natural number.
  • modified polyacrylates are generally esters or amides of acrylic acid or an ⁇ -substituted acrylic acid. Preferred among these polymers are those in which R 16 represents H or a methyl group.
  • Modified polyacrylates to be preferably used in the context of the present invention are polyacrylate-polymethacrylate copolymers which satisfy the formula Villa
  • R 7 is a preferably unbranched, saturated or unsaturated C 8-22 alk (en) yl radical
  • R 19 and R 20 independently of one another are H or CH 3
  • the degree of polymerization n is a natural number
  • the degree of aikoxylation a is a natural number is between 2 and 30, preferably between 10 and 20.
  • Products of the formula IIa are commercially available for example under the name Acusol ® 820 (Rohm & Haas) in the form of 30 wt -% ⁇ ger dispersions available
  • Acusol ® 820 Rohm & Haas
  • R 19 is a hydrogen atom
  • R 20 is H or CH 3 and the degree of ethoxy a is 20
  • a further increase in viscosity can also be achieved by adding electrolytes (neutral salts).
  • electrolytes neutral salts
  • alkali halides in particular chlorides, alkali metal bicarbonates, alkane sulfates and alkali metal phosphates, sodium chloride and sodium sulfate being particularly preferred
  • compositions according to the invention can contain further ingredients which further improve the application technology and / or aesthetic properties of the composition.
  • preferred compositions can additionally contain one or more substances from the group of builders, cobuilders, enzymes, pH regulators, fragrances , Perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, soil release compounds, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, color transfer agents inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, swelling and anti-slip agents, abrasives, complexing agents and UV absorbers.
  • the individual ingredients can be present as solids. These solids are preferably in particle sizes as are customary in the detergent and cleaning agent sector, and nanoscale particles can also be present.
  • the solids present particularly preferably have, at least in part, a particle size between 1 and 1000 nm.
  • the builders that can be contained in the compositions according to the invention include, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x 0 2x + ⁇ H 2 0, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ß- and ⁇ -
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • Compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • Fine-crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
  • the zeolite can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 1 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups, C 12 -C 4 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of the greatest importance in the detergent and cleaning agent industry.
  • Alkali metal phosphates is the general term for the aicali metal (especially sodium and potassium) salts of the various phosphoric acids, in which metaphosphoric acids (HP0 3 ) n and orthophosphoric acid H 3 P0 4 in addition to higher molecular weight distinctive representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts or lime incrustations in tissues and also contribute to cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 P0 4 exists as a dihydrate (density 1, 91 like “3 , melting point 60 °) and as a monohydrate (density 2.04 like “ 3 ). Both salts are white powders that are very easily soluble in water, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 0 7 ) at 200 ° C, and at higher temperature in sodium trimetaphosphate (Na 3 P 3 0 9 ) and Maddrell's salt (see below).
  • NaH 2 P0 is acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate primary or monobasic potassium phosphate, potassium biphosphate, KDP
  • KH 2 P0 4 is a white salt with a density of 2.33 "3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KP0 3 ) x ] and is easily soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HP0 4 , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 like “3 , water loss at 95 °), 7 moles (density 1, 68 like “ 3 , melting point 48 ° with loss of 5 H 2 0) and 12 moles of water (density 1, 52 like "3 , melting point 35 ° with loss of 5 H 2 0), becomes anhydrous at 100 ° and changes to diphosphate Na 4 P 2 0 when heated.
  • Disodium hydrogen phosphate is obtained by neutralizing phosphoric acid with soda solution using Phenolphthalein produced as an indicator Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HP0, is an amorphous, white salt that is easily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 P0 are colorless crystals which, as dodecahydrate, have a density of 1.62 "3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 0 5 ) has a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 0 5) having a density of 2.536 like.
  • 3 trisodium phosphate is readily soluble in water with an alkaline reaction and is disodium phosphate by evaporating a solution of exactly 1 mole and 1 mol of NaOH.
  • Tetranate diphosphate sodium pyrophosphate
  • Na P 2 0 7 exists in anhydrous form (density 2.534, preferably 3 , melting point 988 °, also given 880 °) and as decahydrate (density 1, 815-1, 836, preferably 3 , melting point 94 ° with loss of water ) Both substances are colorless crystals which are soluble in water with an alkaline reaction.
  • Na 4 P 2 0 7 is formed when dinate phosphate is heated to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating the solution by spraying.
  • the decahydrate complexes heavy metal salts and hard formers and therefore reduces the hardness of the water potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 "3 , which is soluble in water , the pH of the 1% solution at 25 ° being 10.4
  • pentasodium phosphate In the production of pentasodium phosphate, phosphoric acid is reacted with sodium hydroxide solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying, similar to Graham's salt and sodium diphosphate, pentanatium phosphate, and many insoluble metal compounds, as well as many insoluble metal compounds - phosphate, K 5 P 3 O ⁇ 0 (potassium tripolyphosphate), for example in the form of a 50 wt .-% solution (> 23% P 2 0 5 , 25% K 2 0) on the market.
  • the potassium polyphosphates are widely used in the detergent and cleaning agent industry.
  • sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimethosphate with KOH:
  • these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.
  • Organic cobuilders which can be used in the detergent tablets according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid and derivatives thereof, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA) and their derivatives, as long as such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to establish a lower and milder pH value of Detergents or cleaning agents
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned
  • Polymeric polycarboxyates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol
  • the molar masses specified for polymeric polycarboxyates are weight-average molar masses M w of the particular acid form, which were generally determined by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. This information differs significantly from the molecular weight data for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights specified in this document
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates can in turn have a molecular weight of 2,000 to 10,000 g / mol, and particularly preferably 3,000 to 5,000 g / mol. mol, are preferred.
  • copolymeric polycarboxyates especially those of acrylic acid with methacrylic acid and 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
  • Molecular mass, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol
  • the (co) polymeric polycarboxyates can be used either as a powder or as an aqueous solution.
  • the amount of (co) polymeric polycarboxylates in the compositions is preferably 0 5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • copolymers are those which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
  • DE dextrose equivalent
  • Ethylenediamine-N, N '- disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycerol trisuccinates are also preferred in this context.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned are suitable. All these hydrolases are useful in washing for removing stains such as stains containing protein, fat or starch and Graying in cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxireductases can also be used to bleach or inhibit color transfer.
  • pH adjusting agents may be indicated. All known acids or alkalis can be used here, provided their use is not normally prohibited for application-related or ecological reasons or for reasons of consumer protection The amount of these adjusting agents does not exceed 2% by weight of the total formulation.
  • suitable dyes Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to textile fibers in order not to stain them
  • Foam inhibitors that can be used in the compositions according to the invention are, for example, soaps, paraffins or silicone oils
  • Suitable soil release compounds are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether and those from the Polymers of phthalic acid and / or terephthalic acid or their derivatives known in the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid. Poiymere
  • Optical brighteners can be added to the compositions according to the invention in order to eliminate graying and yellowing of the treated textiles. These substances absorb on the fiber and bring about a brightening and a pretreated bleaching effect by converting invisible ultraviolet radiation into visible long-wave light, whereby the white from the sunlight aosorbATOR ultraviolet light as a pale bluish fluorescence is emitted and pure for the yellow shade of the grayed or yellowed washing results
  • Suitable compounds originate for example from the substance classes of the 4,4 '-D ⁇ am ⁇ no-2,2' - stilbendisulfonsauren (Flavesauren) 4,4 '-D ⁇ styryl-b ⁇ phenylen, Methylumbelhferone, Cumanne, dihydroquino none, 1, 3-D ⁇ arylpyrazol'ne, Naphthalsaureimide, benzoxazole, benzisoxazole and benzimidazole systems, and the Pyrendenvate
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of (co) polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose.
  • Soluble starch preparations and other starch products than those mentioned above can also be used, e.g. B. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 10% by weight, based on the Means used.
  • compositions according to the invention can contain synthetic anti-crease agents.
  • the compositions according to the invention can contain antimicrobial active ingredients.
  • antimicrobial active ingredients Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc.
  • Important substances from these groups are, for example, organic cationic compounds such as cationic surfactants, eg. B. benzalkonium chlorides, alkylarlylsulfonates, halophenols and phenol mercuric acetate, it being possible to dispense entirely with these compounds in the compositions according to the invention.
  • silicone condensates can be used in the compositions according to the invention. These additionally improve the rinsing behavior of the compositions according to the invention due to their foam-inhibiting properties the alkyl groups have one to five carbon atoms and are partially or completely fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which may or may not have been de ⁇ vated and then amino-functional! or are quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
  • the viscosities of the preferred silicones range from 100 to 100,000 mPas at 25 ° C., the silicones in amounts between 0 2 and 5% by weight, based on the total composition, can be used
  • agents for cleaning hard surfaces can contain so-called abrasives, such as quartz flours, micro glass balls, plastic flours and wood flours
  • Suitable heavy metal complexing agents are, for example, ethylenediaminetetraacetic acid (EDTA) or nitinotinyl acetic acid (NTA) in the form of the free acids or as alkali metal salts of the foregoing and derivatives as well as alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates
  • a preferred class of complexing agents are the phosphonates, which in preferred compositions are present in amounts of 0.01 to 2.0% by weight, preferably 0.05 to 1.5 % By weight and in particular from 0.1 to 1.0% by weight are included.
  • These preferred compounds include, in particular, organophosphonates such as, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotronic (methylenephosphonic acid) (ATMP), dimethyltriamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1, 2,4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts.
  • organophosphonates such as, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotronic (methylenephosphonic acid) (ATMP), dimethyltriamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1
  • Suitable complexing agents are low molecular weight hydroxycarboxylic acids, which also have builder properties , such as citric acid, tartaric acid, malic acid, or gluconic acid or salts thereof, citric acid or sodium citrate being particularly preferred.
  • the complexing agents can be used in an amount of 1 to 25% by weight, preferably 3.0 to 10.0% by weight and in particular 4 , 0 to 5.0% by weight, based on the finished composition
  • compositions according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the lightfastness of the fibers.
  • UV absorbers which absorb onto the treated textiles and improve the lightfastness of the fibers.
  • Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone with substituents in 2- and / / which are effective through radiation-free deactivation. or 4-position Also substituted benzotazoles, in the 3-position phenyl-substituted acrylates (cinnamon acid redevines), optionally with cyano groups in the 2-position, stilbene derivatives, biphenyls, sahcylates, organic Ni complexes and natural substances such as umbelhferone and the body's own urocanoic acid are also suitable
  • the composition according to the invention contains 1 to 10% by weight of bleach, up to 15% by weight of nonionic surfactant, up to 15% by weight of anionic surfactant, up to 15% by weight of further surfactants, 0.01 to 5% by weight.
  • % rheological additives 0.01 to 3% by weight of complexing agent, 0.1 to 10% by weight of citrate and water and, if appropriate, further conventional detergent ingredients
  • the agents according to the invention can be produced continuously or in batches in a manner known per se.
  • the finished agents can be packaged in any desired forms using which the substrate can be treated, for example in bottles, tubes or as pens
  • the composition according to the invention is usually applied to the fiber over a period of up to 24 hours, in particular from one minute to one hour and particularly preferably from five minutes to 30 minutes.
  • the textiles are usually contaminated with dried-on stains or dirt, which are usually very difficult to remove.
  • the compositions can simply be applied to the textiles and left there, the dirt removal can also be done by mechanical support, e.g. B. be supported by rubbing or by treatment with a sponge or a brush.
  • the agents according to the invention can be applied to the soiling and left there for a longer period of time.
  • the non-textile substrates are also usually contaminated with dried-on stains or dirt, which can be easily removed if it is treated over a longer period of time, the agent according to the invention optionally being diluted with water.

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Textile Engineering (AREA)
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Abstract

L'invention concerne un agent utilisé pour traiter des substrats, qui contient des agents de blanchiment et/ou des tensioactifs, ainsi qu'éventuellement des solvants. Cet agent se caractérise en ce qu'il présente un comportement à effet diluant sous l'action du cisaillement.
PCT/EP2000/012581 1999-12-21 2000-12-12 Agent pour traiter des substrats WO2001046377A1 (fr)

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AU25107/01A AU2510701A (en) 1999-12-21 2000-12-12 Agent for treating substrates

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DE19961659.0 1999-12-21
DE19961659A DE19961659A1 (de) 1999-12-21 1999-12-21 Mittel zur Behandlung von Substraten

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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4130501A (en) * 1976-09-20 1978-12-19 Fmc Corporation Stable viscous hydrogen peroxide solutions containing a surfactant and a method of preparing the same
US4339235A (en) * 1979-12-06 1982-07-13 Economics Laboratory, Inc. Methods and compositions for bleaching of mycological stain
US4648987A (en) * 1985-02-13 1987-03-10 The Clorox Company Thickened aqueous prewash composition
US4800036A (en) * 1985-05-06 1989-01-24 The Dow Chemical Company Aqueous bleach compositions thickened with a viscoelastic surfactant
EP0314050A2 (fr) * 1987-09-29 1989-05-03 Colgate-Palmolive Company Composition détergente liquide aqueuse thixotropique pour le lavage automatique de la vaisselle
US5102573A (en) * 1987-04-10 1992-04-07 Colgate Palmolive Co. Detergent composition
EP0598693A1 (fr) * 1992-11-16 1994-05-25 The Procter & Gamble Company Emulsions stables d'agents tensioactifs non-ioniques contenant un agent de contrôle de la viscosité
WO1995031523A1 (fr) * 1994-05-17 1995-11-23 S.C. Johnson & Son, Inc. Compositions pre-detachantes pour lessives avec epaississant polymere associe
DE19535082A1 (de) * 1995-09-21 1997-03-27 Henkel Ecolab Gmbh & Co Ohg Pastenförmiges Wasch- und Reinigungsmittel
EP0842605A1 (fr) * 1996-11-13 1998-05-20 The Procter & Gamble Company Compositions vaporisables et leur utilisation pour désinfecter les surfaces
DE19824708A1 (de) * 1998-06-03 1999-12-09 Henkel Kgaa Strukturviskoses wäßriges Bleichmittel
WO2000004119A1 (fr) * 1998-07-16 2000-01-27 Reckitt Benckiser Inc Compositions de nettoyage et leur utilisation pour le nettoyage de taches sur des vetements et des textiles

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4130501A (en) * 1976-09-20 1978-12-19 Fmc Corporation Stable viscous hydrogen peroxide solutions containing a surfactant and a method of preparing the same
US4339235A (en) * 1979-12-06 1982-07-13 Economics Laboratory, Inc. Methods and compositions for bleaching of mycological stain
US4648987A (en) * 1985-02-13 1987-03-10 The Clorox Company Thickened aqueous prewash composition
US4800036A (en) * 1985-05-06 1989-01-24 The Dow Chemical Company Aqueous bleach compositions thickened with a viscoelastic surfactant
US5102573A (en) * 1987-04-10 1992-04-07 Colgate Palmolive Co. Detergent composition
EP0314050A2 (fr) * 1987-09-29 1989-05-03 Colgate-Palmolive Company Composition détergente liquide aqueuse thixotropique pour le lavage automatique de la vaisselle
EP0598693A1 (fr) * 1992-11-16 1994-05-25 The Procter & Gamble Company Emulsions stables d'agents tensioactifs non-ioniques contenant un agent de contrôle de la viscosité
WO1995031523A1 (fr) * 1994-05-17 1995-11-23 S.C. Johnson & Son, Inc. Compositions pre-detachantes pour lessives avec epaississant polymere associe
DE19535082A1 (de) * 1995-09-21 1997-03-27 Henkel Ecolab Gmbh & Co Ohg Pastenförmiges Wasch- und Reinigungsmittel
EP0842605A1 (fr) * 1996-11-13 1998-05-20 The Procter & Gamble Company Compositions vaporisables et leur utilisation pour désinfecter les surfaces
DE19824708A1 (de) * 1998-06-03 1999-12-09 Henkel Kgaa Strukturviskoses wäßriges Bleichmittel
WO2000004119A1 (fr) * 1998-07-16 2000-01-27 Reckitt Benckiser Inc Compositions de nettoyage et leur utilisation pour le nettoyage de taches sur des vetements et des textiles

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AU2510701A (en) 2001-07-03

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