EP2732015B1 - Utilisation d'une combinaison d'un sulfonate de paraffine secondaire et d'amylase pour augmenter le pouvoir détergent de lessives liquides - Google Patents

Utilisation d'une combinaison d'un sulfonate de paraffine secondaire et d'amylase pour augmenter le pouvoir détergent de lessives liquides Download PDF

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EP2732015B1
EP2732015B1 EP12735211.0A EP12735211A EP2732015B1 EP 2732015 B1 EP2732015 B1 EP 2732015B1 EP 12735211 A EP12735211 A EP 12735211A EP 2732015 B1 EP2732015 B1 EP 2732015B1
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Prior art keywords
acid
weight
alkyl
amylase
pigment
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EP12735211.0A
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German (de)
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EP2732015A1 (fr
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Johannes Himmrich
Barbara Duecker
Joachim Erbes
Stefan RIEGELBECK
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Weylchem Switzerland AG
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Weylchem Switzerland AG
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    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3463—Organic compounds containing sulfur containing thio sulfate or sulfite groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38618—Protease or amylase in liquid compositions only

Definitions

  • the invention relates to the use of a combination of secondary paraffin sulfonate and amylase for increasing the cleaning power of liquid detergents against starch-containing stains on textiles.
  • liquid detergents can be increased over starch-containing stains on fabrics when amylase is combined with one or more secondary paraffin sulfonates having 8 to 22 carbon atoms.
  • the present invention therefore relates to the use of a combination of one or more secondary Paraffinsulfonaten having 8 to 22 carbon atoms and amylase to increase the cleaning power of liquid detergents against starch-containing stains on textiles.
  • the use according to the invention has the advantage, for example, that with comparable cleaning performance, the amount of liquid detergent can be lowered, which offers ecological advantages. In addition, it can be cleaned at low temperatures, which can reduce energy consumption.
  • the secondary paraffin sulfonates may be prepared under photochemical conditions by sulfoxidation of paraffins, and are, for example, on the market under the trade name Hostapur ® SAS at concentrations of 30 wt .-%, wt .-% and 93 60 wt .-% available.
  • At least 95%, more preferably at least 97%, by weight of the one or more secondary paraffin sulfonates contain from 14 to 17 carbon atoms.
  • the counterions of the one or more secondary paraffin sulfonates are selected from the group consisting of Na + , K + , Mg 2+ and Ca 2+ .
  • the counterion of the one or more secondary paraffin sulfonates is Na + .
  • from 99.5 to 100% by weight of the one or more secondary paraffin sulfonates contains a saturated paraffin portion and from 0 to 0.5% by weight of the one or more secondary paraffin sulfonates comprises an unsaturated paraffin portion. More preferably, 100% by weight of the one or more secondary paraffin sulfonates contain a saturated paraffin moiety and no unsaturated moieties.
  • second paraffin sulfonate means that the sulfonate groups are attached to the non-terminal paraffin moiety.
  • the sulfonate groups are randomly distributed throughout the non-terminal paraffin portion of the one or more secondary paraffin sulfonates, and more preferably, from 75 to 95 weight percent of the one or more secondary paraffin sulfonates carry a sulfonate group and from 5 to 25 weight percent one or more secondary paraffin sulfonates two or more sulfonate groups.
  • Steinzyme are example of amylases available ® Plus 12L, Termamyl ®, amylase ® LT, Maxamyl ®, Duramyl ® and / or Pruafect ® Ox.
  • the liquid detergents may contain one or more common ingredients such as other surfactants (different from the secondary paraffin sulfonates), emulsifiers, builders, bleach catalysts and activators, sequestering agents, soil release polymers , Graying inhibitors, color transfer inhibitors, color fixing agents, complexing agents, optical brighteners, softening components, dyes and / or fragrances.
  • the total amount of surfactants in the liquid detergents may preferably be from 1 to 99% by weight, more preferably from 5 to 80% by weight, especially preferably from 10 to 70% by weight and most preferably from 20 to 60% by weight. %, in each case based on the total weight of the finished liquid detergent.
  • the surfactants used in the liquid detergents may be anionic, nonionic, amphoteric or cationic. It is also possible to use mixtures of the surfactants mentioned.
  • Preferred liquid detergents contain anionic and / or nonionic surfactants and mixtures thereof with other surfactants.
  • anionic surfactants z.
  • anionic surfactants are of particular interest: ester sulfonates, sulfates, ether sulfates, substituted benzenesulfonates, sulfonates and soaps.
  • Preferred ester sulfonates are compounds of the formula wherein R 1 is a C 8 -C 20 hydrocarbon radical, preferably alkyl, and R is a C 1 -C 6 hydrocarbon radical, preferably alkyl.
  • M is a cation that forms a water-soluble salt with the ester sulfonate.
  • Suitable cations are Sodium, potassium, lithium or ammonium cations, such as monoethanolamine, diethanolamine and triethanolamine.
  • Particularly preferred are methyl ester sulfonates in which R 1 is C 10 -C 16 -alkyl and R is methyl.
  • Sulfates are here water-soluble salts or acids of the formula ROSO 3 M, wherein R is a. C 10 -C 24 -hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical with C 10 -C 20 -alkyl component, more preferably a C 12 -C 18 -alkyl or hydroxyalkyl radical.
  • M is hydrogen or a cation, e.g. As an alkali metal cation (eg, sodium, potassium, lithium) or ammonium or substituted ammonium.
  • Ether sulfates are water-soluble salts or acids of the formula RO (A) m SO 3 M, where R is an unsubstituted C 10 -C 24 -hydrocarbon radical, preferably C 10 -C 24 -alkyl radical, or a hydroxyl-substituted C 10 -C 24 - Hydrocarbon radical, preferably C 10 -C 24 hydroxyalkyl, particularly preferably a C 12 -C 20 alkyl or hydroxyalkyl radical, more preferably C 12 -C 18 alkyl or hydroxyalkyl.
  • R is an unsubstituted C 10 -C 24 -hydrocarbon radical, preferably C 10 -C 24 -alkyl radical, or a hydroxyl-substituted C 10 -C 24 - Hydrocarbon radical, preferably C 10 -C 24 hydroxyalkyl, particularly preferably a C 12 -C 20 alkyl or hydroxyalkyl radical, more preferably C 12 -C 18 al
  • A is an ethoxy (EO) or propoxy (PO) unit
  • m is a number greater than 0, preferably between 0.5 and 6, more preferably between 0.5 and 3
  • M is a hydrogen atom or a cation such as For example, sodium, potassium, lithium, calcium, magnesium, ammonium or a substituted ammonium cation.
  • Examples C 12 were - to C 18 fatty alcohol ether sulfates called, wherein the content of EO is 1, 2, 2.5, 3, or 4 mol per mol of fatty alcohol ether sulfate, and in which M is sodium or potassium.
  • alkenyl or alkylbenzenesulfonates are alkenyl or alkylbenzenesulfonates.
  • the alkenyl or alkyl group may be branched or linear and optionally substituted with a hydroxyl group.
  • the preferred alkylbenzenesulfonates contain linear alkyl chains of 9 to 25 carbon atoms, preferably 10 to 13 carbon atoms, the cation being sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium, magnesium or a mixture thereof.
  • magnesium is preferred as a cation
  • sodium is preferred for standard washing applications. The same applies to alkenylbenzenesulfonates.
  • the primary sulfonates are preferably alkane or alkene sulfonates, where the alkyl or alkenyl group may be either branched or linear and optionally substituted with one hydroxyl group.
  • the preferred primary sulfonates contain linear alkyl or alkenyl chains of 9 to 25 carbon atoms, preferably 10 to 20 carbon atoms, and more preferably 13 to 17 carbon atoms.
  • the cation is, for example, sodium, potassium, ammonium, mono-, di- or triethanolammonium, magnesium, or a mixture thereof. Sodium is preferred as a cation.
  • anionic surfactants also includes olefin sulfonates obtained by sulfonation of C 12 -C 24 , preferably C 14 -C 16, ⁇ -olefins with sulfur trioxide and subsequent neutralization. Due to the preparation process, these olefin sulfonates may contain minor amounts of hydroxyalkanesulfonates and alkanedisulfonates. Specific mixtures of ⁇ -olefin sulfonates are in US 3,332,880 described.
  • anionic surfactants are carboxylates, eg. B. fatty acid soaps and comparable surfactants.
  • the soaps may be saturated or unsaturated and may contain various substituents such as hydroxyl groups or ⁇ -sulfonate groups.
  • Preferred are linear saturated or unsaturated hydrocarbon radicals as hydrophobic moiety having 6 to 30 and preferably 10 to 18 carbon atoms.
  • alkylphenols having a C 6 to C 20 alkyl group which may be either linear or branched, with alkene oxides.
  • alkylphenol alkoxylates e.g. B. Alkylphenolethoxylate called.
  • the alkyl or alkenyl chain of the aliphatic alcohols may be linear or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms. Particularly preferred are the condensation products of C 10 - to C 20 -alcohols with 2 to 18 moles of ethylene oxide per mole of alcohol.
  • the alcohol ethoxylates may have a narrow range (“narrow range ethoxylates") or a broad homolog distribution of the ethylene oxide ("Broad Range Ethoxylates").
  • Tergitol ® 15-S-9 the condensation product of a linear secondary C 11 -C 15 -Atkohols with 9 moles ethylene oxide
  • Tergitol ® 24-L-NMW the condensation product of a linear primary C 12 -C 14- alcohol with 6 moles of ethylene oxide with a narrow molecular weight distribution
  • This product class also includes the Genapol ® brands from Clariant.
  • the hydrophobic part of these compounds preferably has a molecular weight between 1500 and 1800.
  • the addition of ethylene oxide to this hydrophobic part leads to an improvement in water solubility.
  • the product is liquid up to a polyoxyethylene content of about 50% of the total weight of the condensation product, which corresponds to a condensation with up to about 40 moles of ethylene oxide.
  • Commercially available examples of this product class are the Pluronic ® brands from BASF and the Genapol ® PF brands from Clariant. Condensation products of ethylene oxide with a reaction product of propylene oxide and ethylenediamine.
  • the hydrophobic moiety of these compounds consists of the reaction product of ethylenediamine with excess propylene oxide and generally has a molecular weight of 2500 to 3000. Ethylene oxide is added to this hydrophobic unit to a content of 40 to 80 wt .-% polyoxyethylene and a molecular weight of 5000 to 11000.
  • this class of compounds are the Tetronic ® brands of BASF and Genapol ® PN brands of Clariant.
  • This category of nonionic compounds includes water-soluble amine oxides of the formula
  • R here is an alkyl, hydroxyalkyl or alkylphenol group having a chain length of 8 to 22 carbon atoms
  • R 2 is an alkylene or hydroxyalkylene group having 2 to 3 carbon atoms or mixtures thereof
  • each R 1 is an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms or a polyethylene oxide group having 1 to 3 ethylene oxide units
  • x represents a number from 0 to 10.
  • Fatty acid amides have the formula wherein R is an alkyl group having 7 to 21, preferably 9 to 17 carbon atoms and each R 1 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl or (C 2 H 4 O) x H, wherein x varies from 1 to 3.
  • R is an alkyl group having 7 to 21, preferably 9 to 17 carbon atoms and each R 1 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl or (C 2 H 4 O) x H, wherein x varies from 1 to 3.
  • Preferred are C 8 -C 20 amides, - monoethanolamides, -diethanolamide and -isopropanolamide.
  • nonionic surfactants are alkyl and Alkenyloligoglycoside and Fettchurepolyglykolester or Fettaminpolyglykolester having in each case 8 to 20, preferably 12 to 18 carbon atoms in the fatty alkyl radical, Alkyloligoglycoside, Alkenyloligoglycoside and fatty acid N-alkylglucamide.
  • amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidbetaines, aminopropionates, aminoglycinates or amphoteric imidazolinium compounds of the formula wherein R 1 is C 8 -C 22 alkyl or alkenyl, R 2 is hydrogen or CH 2 CO 2 M, R 3 is CH 2 CH 2 OH or CH 2 CH 2 OCH 2 CH 2 CO 2 M, R 4 is hydrogen, CH 2 CH 2 OH or CH 2 CH 2 COOM, Z is CO 2 M or CH 2 CO 2 M, n is 2 or 3, preferably 2, M is hydrogen or a cation such as alkali metal, alkaline earth metal, ammonium or alkanolammonium.
  • Preferred amphoteric surfactants of this formula are monocarboxylates and dicarboxylates. Examples of these are cocoamphocarboxypropionate, Cocoamidocarboxypropionic acid, cocoamphocarboxyglycinate (also referred to as cocoamphodiacetate) and cocoamphoacetate.
  • amphoteric surfactants are alkyl dimethyl betaines and alkyl dipolyethoxy betaines having an alkyl group of 8 to 22 carbon atoms, which may be linear or branched, preferably having 8 to 18 carbon atoms and more preferably having 12 to 18 carbon atoms. These compounds are z. B. marketed by Clariant under the trade name Genagen ® LAB.
  • Suitable cationic surfactants are substituted or unsubstituted straight-chain or branched quaternary ammonium salts of the type R 1 N (CH 3 ) 3 ⁇ X ⁇ , R 1 R 2 N (CH 3 ) 2 ⁇ X ⁇ , R 1 R 2 R 3 N (CH 3 ) ⁇ X ⁇ or R 1 R 2 R 3 R 4 N ⁇ X ⁇ .
  • the radicals R 1 , R 2 , R 3 and R 4 may preferably be, independently of one another, unsubstituted alkyl having a chain length between 8 and 24 C atoms, in particular between 10 and 18 C atoms, hydroxyalkyl having 1 to 4 C atoms, phenyl, C 2 - to C 18 alkenyl, C 7 - to C 24 aralkyl, (C 2 H 4 O) X H, where x is from 1 to 3, one or more ester group-containing alkyl groups or cyclic quaternary ammonium salts.
  • X is a suitable anion.
  • Suitable emulsifiers are adducts of 0 to 30 moles of alkylene oxide, in particular ethylene, propylene and / or butylene oxide, to linear or branched, saturated or unsaturated fatty alcohols having 8 to 22 C atoms, to fatty acids having 12 to 22 C atoms, on alkylphenols having 8 to 15 C atoms in the alkyl group and on sorbitan esters; (C 12 -C 18 ) fatty acid mono- and diesters of addition products of 0 to 30 moles of ethylene oxide with glycerol; Glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and optionally their ethylene oxide addition products; Addition products of 5 to 60 mol, preferably 15 to 60 mol, of ethylene oxide with castor oil and / or hydrogenated castor oil; Polyol and in particular polyglycerol esters, such as. Polygly
  • anionic emulsifiers such as ethoxylated and nonethoxylated mono-, di- or tri-phosphoric esters
  • cationic emulsifiers such as mono-, di- and tri-alkyl quats and their polymeric derivatives.
  • liquid detergents include inorganic and / or organic builders to reduce the degree of hardness of the water.
  • Inorganic builders include, for example, alkali, ammonium and alkanolammonium salts of polyphosphates such as tripolyphosphates, pyrophosphates and glassy polymeric metaphosphates, phosphonates, silicates, carbonates including bicarbonates and sesquicarbonates, sulfates and aluminosilicates.
  • silicate builders are the alkali metal silicates, in particular those having a SiO 2 : Na 2 O ratio of between 1.6: 1 and 3.2: 1, and also phyllosilicates, for example sodium layer silicates, as described in US Pat US 4,664,839 , available from Clariant under the trademark SKS ® .
  • SKS- 6® is a particularly preferred phyllosilicate builder.
  • Aluminosilicate builders are particularly preferred. These are, in particular, zeolites of the formula Na z [(AlO 2 ) z (SiO 2 ) y ] .xH 2 O, where z and y are integers of at least 6, the ratio of z to y is 1.0 is 0.5 and x is an integer of 15 to 264.
  • Suitable aluminosilicate-based ion exchangers are commercially available. These aluminosilicates may be of crystalline or amorphous structure, and may be naturally occurring or synthetically produced.
  • zeolite A zeolite A
  • zeolite P zeolite P (B) (including those described in US Pat EP-A-0 384 070 disclosed)
  • zeolite X zeolite X
  • Suitable organic builders include polycarboxylic compounds such as, for example, ether polycarboxylates and oxydisuccinates, such as in U.S. Pat US 3,128,287 and US 3,635,830 described. Likewise on “TMS / TDS" equipment from US 4,663,071 to get expelled.
  • Suitable builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, the alkali, ammonium and substituted ammonium salts of polyacetic acids such as e.g. Ethylenediaminetetraacetic acid and nitrilotriacetic acid, and polycarboxylic acids such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and their soluble salts.
  • polyacetic acids such as e.g. Ethylenediaminetetraacetic acid and nitrilotriacetic acid
  • polycarboxylic acids such as mellitic acid, succinic acid, oxydisuccinic acid
  • Citrate-based builders e.g., citric acid and its soluble salts, in particular the sodium salt, are preferred polycarboxylic acid, which can also be used in granulated formulations, in particular together with zeolites and / or phyllosilicates.
  • phosphorus based builders can be used, various alkali metal phosphates such as sodium tripolyphosphate, sodium pyrophosphate, and sodium orthophosphate can be used.
  • alkali metal phosphates such as sodium tripolyphosphate, sodium pyrophosphate, and sodium orthophosphate can be used.
  • phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates can be used as described, for example, in U.S. Pat US 3,159,581 . US 3,213,030 . US 3,422,021 . US 3,400,148 and US 3,422,137 are disclosed.
  • the liquid detergents may optionally contain one or more conventional bleaching agents, as well as activators or stabilizers, in particular peroxyacids.
  • the peroxyacid may be either a free peroxyacid or a combination of an inorganic persalt, for example, sodium perborate or sodium percarbonate and an organic peroxyacid precursor, which is converted to a peroxyacid when the combination of the persalt and the peroxyacid precursor is dissolved in water.
  • organic peroxyacid precursors are often referred to as bleach activators.
  • peroxyacids which are preferred include peroxydodecanedioic acid (DPDA), nonylamide of peroxysuccinic acid (NAPSA), nonylamide of peroxyadipic acid (NAPAA) and decyldiperoxysuccinic acid (DDPSA).
  • DPDA peroxydodecanedioic acid
  • NAPSA nonylamide of peroxysuccinic acid
  • NAPAA nonylamide of peroxyadipic acid
  • DDPSA decyldiperoxysuccinic acid
  • the peroxyacid-containing bleaching agent is used in amounts in which it is usually used in liquid detergents.
  • Suitable amounts of peroxyacid bleach based on a unit dose of a liquid detergent used for a typical wash liquor comprising about 10-15 liters of water from 5 to 60 ° C, will produce from about 1 ppm to about 150 ppm of available oxygen , preferably from about 2 ppm to about 20 ppm of available oxygen.
  • the wash liquor should have a pH of preferably 7 to 12, and more preferably 8 to 11, to achieve a sufficient bleaching result.
  • the bleach composition may contain a suitable organic peroxyacid precursor which produces one of the above peroxyacids when reacted with hydrogen peroxide in aqueous alkaline solution.
  • the source of hydrogen peroxide may be any inorganic peroxide that releases hydrogen peroxide in aqueous solution, such as sodium perborate (monohydrate and tetrahydrate) and sodium percarbonate.
  • N, N, N ', N'-tetraacetylethylenediamine (TAED), glucose pentaacetate (GPA), xylose tetraacetate (TAX), sodium 4-benzoyloxy-benzenesulphonate (SBOBS), sodium trimethylhexanoyloxybenzenesulphonate (STHOBS), tetraacetylglucoluril (TAGU) are available on bleach activators.
  • TACA Tetraacetylcyanoic acid
  • ADMG di-N-acetyldimethylglyoxine
  • PAH 1-phenyl-3-acetylhydantoin
  • APES nonanoylcaprolactam phenylsulfonate esters
  • NOPS nonanoylphenylsulphonate esters
  • NTA nitrilotriacetate
  • Sequestering agents available are sodium tripolyphosphate (STPP), ethylenediaminetetraacetic acid (EDTA), salts, nitrilotriacetic acid (NTA), polyacrylate, phosphonate, oxalic acid, salt, citric acid, zeolite, condensed phosphates, carbonates, polycarbonates.
  • STPP sodium tripolyphosphate
  • EDTA ethylenediaminetetraacetic acid
  • NTA nitrilotriacetic acid
  • polyacrylate phosphonate
  • oxalic acid salt
  • citric acid citric acid
  • zeolite zeolite
  • condensed phosphates carbonates, polycarbonates.
  • Suitable for soil release polymers are polyesters obtainable by polymerization of the components selected from one or more sulfo-free aromatic dicarboxylic acids and / or their salts, one or more sulfo-containing dicarboxylic acids, one or more compounds of the formula R 1 O (CHR 2 CHR 3 O) n H, where R 1 is a linear or branched alkyl or alkenyl group having 1 to 22 C atoms, preferably C 1 -C 4 alkyl and particularly preferably methyl, R 2 and R 3 are independently Are hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably hydrogen and / or methyl, and n is a number from 1 to 100, one or more compounds of the formula H- (OCH 2 CH 2 ) m -SO 3 X, wherein m is a number from 1 to 100 and X is hydrogen or an alkali metal ion, and one or more crosslinking polyfunctional compounds.
  • SRPs soil release polymers
  • the SRPs can be present in amounts of from 0.1 to 10% by weight and preferably in amounts of from 0.2 to 3% by weight, based on the finished liquid detergents.
  • Suitable graying inhibitors are carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose, methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and polyvinyl pyrrolidone.
  • color transfer inhibitors for example polyamine N-oxides such as poly (4-vinylpyridine-N-oxide), eg Chromabond S-400, Fa. ISP; Polyvinylpyrrolidone, eg Sokalan ® HP 50, Fa. BASF, and copolymers of N-vinylpyrrolidone with N-vinylimidazole, and optionally other monomers.
  • polyamine N-oxides such as poly (4-vinylpyridine-N-oxide), eg Chromabond S-400, Fa. ISP; Polyvinylpyrrolidone, eg Sokalan ® HP 50, Fa. BASF, and copolymers of N-vinylpyrrolidone with N-vinylimidazole, and optionally other monomers.
  • the liquid detergents may also contain color fixing agents as active substances, for example color fixing agents obtained by reacting diethylenetriamine, dicyandiamide and amidosulfuric acid, amines with epichlorohydrin, for example dimethylaminopropylamine and epichlorohydrin or dimethylamine and epichlorohydrin or dicyandiamide, formaldehyde and ammonium chloride, or dicyandiamide, ethylenediamine and formaldehyde or cyanamide with amines and formaldehyde or polyamines with cyanamides and amidosulfuric acid or cyanamides with aldehydes and ammonium salts, but also polyamine N-oxides such as poly (4-vinylpyridine-N-oxide), for.
  • color fixing agents obtained by reacting diethylenetriamine, dicyandiamide and amidosulfuric acid, amines with epichlorohydrin, for example dimethylaminopropylamine and epichlorohydrin or
  • Chromabond S-400, Fa. ISP Polyvinylpyrrolidone, e.g. B. Sokalan ® HP 50, BASF and copolymers of N-vinylpyrrolidone with N-vinylimidazole and optionally other monomers.
  • Polyvinylpyrrolidone e.g. B. Sokalan ® HP 50, BASF and copolymers of N-vinylpyrrolidone with N-vinylimidazole and optionally other monomers.
  • the liquid detergents may complexing agents, for example, aminocarboxylates such as ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediamine tetrapropionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate, cyclohexanediaminetetraacetate, phosphonates, for example Azacycloheptane diphosphonate, Na salt, pyrophosphates, etidronic acid (1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, acetophosphonic acid) and their salts, aminophosphonates such as ethylenediaminetetrakis (methylenephosphonate), diethylenetriaminepentakis (methylenephosphonate), aminetrimethylenephosphonic acid , Cyclodextrins, as well as polyfunctionally substituted aromatic complex
  • Cyclic hydrocarbons such as distyrylbenzenes, distyrylbiphenyls, diphenylstilbenes, triazinylaminostilbenes, stilbenyl-2H-triazoles, for example stilbenzyl-2H-naphthol [1,2-d] triazoles and bis (1,2,3-triazole-2 -yl) stilbenes, benzoxazoles, for example stilbenylbenzoxazole and bis (benzoxazole), furans, benzofurans and benzimidazoles, for example bis (benzo [b] furan-2-yl) biphenyl and cationic benzimidazoles, 1,3-diphenyl-2-pyrazoline, coumarin , Naphthalimides, 1,3,5-2-yl derivatives, methine cyanine and dibenzothiophene-5,5-oxide.
  • stilbenyl-2H-triazoles for example stilbenzyl-2H-naph
  • anionic optical brighteners in particular sulfonated compounds.
  • triazinylaminostilbenes distyrylbiphenyls, and mixtures thereof, 2- (4-styrylphenyl) -2H-naphtho [1,2-d] triazole, 4,4'-bis (1,2,3-triazole-2-) yl) stilbene, aminocoumarin, 4-methyl-7-ethylaminocoumarin, 1,2-bis (benzimidazol-2-yl) ethylene, 1,3-diphenylphrazoline, 2,5-bis (benzooxazol-2-yl) thiophene, 2- Strylnaphtho [1,2-d] oxazole, 2- (4-styryl-3-sulfophenyl) -2H-naphtho [1,2-d] triazole and 2- (stilben-4-yl) -2H-naphthol [ 1,2-d] triazole
  • the liquid detergents may contain optical brightener in amounts of 0.001 to 2 wt .-%, preferably in amounts of 0.002 to 0.8 wt .-% and particularly preferably in amounts of 0.003 to 0.4 wt .-%.
  • Examples thereof are distearyldimethylammonium chloride, ditallowalkyldimethylammonium chloride, ditallowalkylmethylhydroxypropylammonium chloride, cetyltrimethylammonium chloride or else the corresponding benzyl derivatives such as dodecyldimethylbenzylammonium chloride. Cyclic quaternary ammonium salts such as alkyl morpholine derivatives can also be used.
  • ester quats are reaction products of alkanolamines and fatty acids, which are then quaternized with conventional alkylating or hydroxyalkylating agents.
  • esterquats are compounds of the formulas: wherein RCO is derived from C 8 -C 24 fatty acids, which may be saturated or unsaturated. n is in the range of 0 to 10, preferably in the range of 0 to 3, and more preferably in the range of 0 to 1.
  • quaternization of the tertiary amino group may additionally be a radical R 3 , which may be C 1 -C 4 alkyl, preferably methyl, and a counterion X, which may be chloride, bromide, iodide or methyl sulfate, are introduced.
  • R 3 which may be C 1 -C 4 alkyl, preferably methyl
  • a counterion X which may be chloride, bromide, iodide or methyl sulfate, are introduced.
  • the liquid detergents preferably contain dyes and fragrances or perfumes.
  • Preferred as dyes are Acid Red 18 (CI 16255), Acid Red 26, Acid Red 27, Acid Red 33, Acid Red 51, Acid Red 87, Acid Red 88, Acid Red 92, Acid Red 95, Acid Red 249 (CI) 18134, Acid Red 52 (Cl45100), Acid Violet 126, Acid Violet 48, Acid Violet 54, Acid Yellow 1, Acid Yellow 3 (CI 47005), Acid Yellow 11, Acid Yellow 23 (CI 19140).
  • Acid Yellow 3 Direct Blue 199 (CI 74190), Direct Yellow 28 (CI 19555), Food Blue 2 (CI 42090), Food Blue 5: 2 (CI 42051: 2), Food Red 7 (CI 16255), Food Yellow 13 (CI 47005), Food Yellow 3 (CI 15985), Food Yellow 4 (CI 19140), Reactive Green 12, Solvent Green 7 (CI 59040).
  • Particularly preferred dyes are water-soluble acid dyes, for example, Food Yellow 13 (Acid Yellow 3, CI 47005), Food Yellow 4 (Acid Yellow 23, CI 19140), Food Red 7 (Acid Red 18, CI 16255), Food Blue 2 (Acid Blue 9, CI 42090), Food Blue 5 (Acid Blue 3, CI 42051), Acid Red 249 (CI 18134), Acid Red 52 (CI 45100), Acid Violet 126, Acid Violet 48, Acid Blue 80 (CI 61585), Acid Blue 182, Acid Blue 182, Acid Green 25 (CI 61570), Acid Green 81.
  • Food Yellow 13 Acid Yellow 3, CI 47005
  • Food Yellow 4 Acid Yellow 23, CI 19140
  • Food Red 7 Acid Red 18, CI 16255
  • Food Blue 2 Acid Blue 9, CI 42090
  • Food Blue 5 Acid Blue 3, CI 42051
  • Acid Red 249 CI 18134
  • Acid Red 52 CI 45100
  • Acid Violet 126 Acid Violet 48
  • Acid Blue 80 CI 61585
  • Acid Blue 182 Acid
  • Water-soluble direct dyes for example Direct Yellow 28 (CI 19555), Direct Blue 199 (CI 74190) and water-soluble reactive dyes, for example Reactive Green 12, as well as the dyes Food Yellow 3 (CI 15985), Acid Yellow 184 can also be used with preference ,
  • the concentration of the dye dispersions used for dyeing solutions or dispersions being in the range from 0.1 to 50% by weight, preferably in the range from 1 to 45% by weight, especially preferably in the range of 5 to 40 wt .-% and particularly preferably in the range of 10 to 35 wt .-% is.
  • aqueous pigment dispersions contain, in addition to the pigments, dispersants and optionally further auxiliaries, for example biocides.
  • Suitable pigment dyes are Pigment Black 7 (CI 77266), Pigment Blue 15 (CI 74160), Pigment Blue 15: 1 (CI 74160), Pigment Blue 15: 3 (CI 74160), Pigment Green 7 (CI 74260). , Pigment Orange 5, Pigment Red 112 (CI 12370), Pigment Red 112 (CI 12370), Pigment Red 122 (CI 73915), Pigment Red 179 (CI 71130), Pigment Red 184 (CI 12487), Pigment Red 188 (CI 12467), Pigment Red 4 (CI 12085), Pigment Red Pigment Yellow 3 (CI 11680), Pigment Yellow 1 (CI 11680), Pigment Yellow 13 (CI 21100), Pigment Yellow 154, Pigment Yellow 3 (CI 11710), Pigment Yellow 74, Pigment Yellow 83 (CI 21108), Pigment Yellow 97.
  • the following pigment dyes are used in the form of dispersions: Pigment Yellow 1 (CI 11680), Pigment Yellow 3 (CI 11710), Pigment Red 112 (CI 12370), Pigment Red 5 (CI 12490), Pigment Red 181 (CI 73360 ), Pigment Violet 23 (CI 51319), Pigment Blue 15: 1 (CI 74160), Pigment Green 7 (CI 74260), Pigment Black 7 (CI 77266).
  • water-soluble polymer dyes for example Liquitint.RTM., Liquitint Blue HP.RTM., Liquitint Blue 65.RTM., Liquitint Patent Blue.RTM., Liquitint Royal Blue.RTM., Liquitint Experimental Yellow 8949-43.RTM , Liquitint Green HMC.RTM., Liquitint Yellow II.RTM. and mixtures thereof.
  • fragrance or perfume individual fragrance compounds, eg.
  • ethers, aldehydes, ketones, alcohols and hydrocarbons are used.
  • Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, benzylformate, ethyl-methylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate.
  • the ethers include, for example, benzyl ethyl ether to the aldehydes z.
  • the linear alkanals having 8 to 18 carbon atoms citral, citronellal, citronellyloxyacetaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z.
  • the alcohols include anethole, citronellol, eugenol, geranion, linalool, phenylethyl alcohol and terpineol
  • the hydrocarbons include mainly the terpenes and balsams.
  • Perfume oils may also contain natural fragrance mixtures, such as those available from plant or animal sources, e.g. Pine, citrus, jasmine, lily, rose or ylang-ylang oil. Also essential oils of lower volatility, which are mostly used as aroma components, are suitable as perfume oils, eg. B. sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon oil, lime blossom oil and juniper berry oil.
  • solutions or emulsions of the abovementioned fragrances and perfume oils which can be prepared by customary methods.
  • the liquid detergents contain, in addition to the one or more secondary paraffin sulfonates and the amylase, one or more surfactants (different from the secondary paraffin sulfonates).
  • the washing temperature when using the liquid detergent for cleaning the starch-containing stains on textiles is preferably from 5 to 60 ° C, more preferably from 10 to 50 ° C and particularly preferably from 20 to 40 ° C.
  • the cleaning power of the liquid detergents against starch-containing stains on textiles is thus increased when using said liquid laundry detergents for textiles preferably at wash temperatures of 5 to 60 ° C, particularly preferably from 10 to 50 ° C and particularly preferably from 20 to 40 ° C. ,
  • the use according to the invention preferably takes place at a pH of 7 to 12 and more preferably at a pH of 8 to 11.
  • the amount of the one or more used according to the invention secondary Paraffinsulfonate preferably from 5 to 30 wt .-%, particularly preferably from 7 to 25 wt .-% and particularly preferably from 10 to 20 wt .-%, each based on the total weight of the finished liquid detergent.
  • the amount of amylase is preferably at least 0.001% by weight, more preferably from 0.001 to 8% by weight, more preferably from 0.01 to 3% by weight and most preferably from 0.1 to 2 wt .-%, each based on the total weight of the finished liquid detergent.
  • the total surfactant concentration in the wash liquor is preferably from 0.08 to 0.30 wt .-%, particularly preferably from 0.09 to 0.20 wt .-%, particularly preferably from 0.10 to 0.15 wt .-% and most preferably from 0.11 to 0.13 wt .-%, each based on the total weight of the wash liquor.
  • composition % By weight (active substance) A Edenor K 12-18 2 coconut fatty acid water ad 100 B triethanolamine 2 C HostapurTM ® SAS 60 15 Sec. Sodium paraffin sulfonate Genapol ® OX 070 (Clariant) 18 C 12 , 15 -oxoalcohol, 7 EO Cublen ® BIT 121 2 phosphonate Tri-sodium citrate dihydrate 3 propanediol 8th ethanol 4 Leucophore ® BSB 0.5 Optical brightener D Liquanase Ultra 2.0 XL 3.0 protease Stainzyme Plus 12 L 1.5 amylase Mannaway 4.0 L 0.6 mannose Lipex 100L 0.5 lipase Endolase 5000L 0 , 6 Endolase
  • Hostapur ® SAS 60 in Formulation I 15 wt .-% of active substance of Marlon ® A 360 (linear alkylbenzene sulfonate, Na-salt) were added.
  • Hostapur ® SAS 60 is a composition of secondary sodium paraffin sulfonate (about 60 wt .-%) in water.
  • the secondary paraffin sulfonate used contains about 97% by weight of paraffin sulfonates having 14 to 17 carbon atoms.
  • the n-paraffin content of the secondary paraffin sulfonate is> 98% by weight.
  • the secondary paraffin sulfonate is 100% saturated. It consists of about 90 wt .-% of monosulfonated and about 10 wt .-% of disulfonated and higher sulfonated Paraffinsulfonaten.
  • washing tests were carried out under the following conditions: Washing machine: Siemens S 16-79 Program: Standard / Color Loading: 3 kg Temperature: 20 ° C Fling: 1400 revolutions / minute Amount of water: 12 liters
  • the differences in the remission values ⁇ R 457 nm from washed to unwashed textiles were measured.
  • the measured soiled textiles are available for purchase.
  • the following 17 textiles / stains were measured: WFK 20 PF pigment / vegetable fat, WFK 10 N whole egg / pigment, CS 6 salad dressing with natural black, CS 73 locust bean gum / pigment, CS 10 butterfat stained, CS 27 potato starch stained, CS 28 rice starch stained, CS 8 grass, PC 3 chocolate / milk / soot, C 3 chocolate / milk / soot, CS 1 blood aged, C 5 blood / milk / India ink, EMPA 162 starch, EMPA 164 grass, EMPA 112 cocoa, EMPA 117 blood / milk / Ink and EMPA 116 blood / milk / ink.
  • formulations A 'and B' without enzyme can be prepared like the formulations A, B, I and II, but the preparation is then terminated after step II.
  • the formulations A and B used for the measurements contain several enzymes. It is known to those skilled in the art that amylase polysaccharides such as e.g. Strength degrades.
  • the percentage changes in remission values ⁇ R 457 nm ( ⁇ R -%) indicate a measure of the increase in the cleaning power of a combination of SAS with enzyme versus SAS without enzyme or for increasing the cleaning power of a combination of LAS with enzyme versus LAS without enzyme.

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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)
  • Detergent Compositions (AREA)

Claims (10)

  1. Utilisation d'une combinaison d'un ou de plusieurs sulfonates de paraffine secondaires ayant de 8 à 22 atomes de carbone et d'amylase pour augmenter le pouvoir détergent de lessives liquides contre de petites salissures contenant de l'amidon sur des textiles.
  2. Utilisation selon la revendication 1, caractérisée en ce qu'au moins 95 % en poids des un ou plusieurs sulfonates de paraffine secondaires contiennent de 14 à 17 atomes de carbone.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que de 95 à 100 % en poids des un ou plusieurs sulfonates de paraffine secondaires contiennent une partie de paraffine linéaire et de 0 à 5 % en poids des un ou plusieurs sulfonates de paraffine secondaires contiennent une partie de paraffine ramifiée.
  4. Utilisation selon une ou plusieurs des revendications 1 à 3, caractérisée en ce que les contre-ions des un ou plusieurs sulfonates de paraffine secondaires sont sélectionnés parmi le groupe constitué de Na+, K+, Mg2+ et Ca2+.
  5. Utilisation selon la revendication 4, caractérisée en ce que le contre-ion des un ou plusieurs sulfonates de paraffine secondaires est Na+.
  6. Utilisation selon une ou plusieurs des revendications 1 à 5, caractérisée en ce que 100 % en poids des un ou plusieurs sulfonates de paraffine secondaires contiennent une partie de paraffine saturée.
  7. Utilisation selon une ou plusieurs des revendications 1 à 6, caractérisée en ce que les groupements sulfonates sont répartis de manière aléatoire sur la partie de paraffine non terminale des un ou plusieurs sulfonates de paraffine secondaires et de 75 à 95 % en poids des un ou plusieurs sulfonates de paraffine secondaires portent un groupement sulfonate et de 5 à 25 % en poids des un ou plusieurs sulfonates de paraffine secondaires portent deux groupements sulfonates ou plus.
  8. Utilisation selon une ou plusieurs des revendications 1 à 7, caractérisée en ce que le pouvoir détergent de la lessive liquide est accru à des températures de lavage comprises entre 5 et 60 °C.
  9. Utilisation selon une ou plusieurs des revendications 1 à 8, caractérisée en ce que la quantité des un ou plusieurs sulfonates de paraffine secondaires dans les lessives liquides va de 5 à 30% en poids.
  10. Utilisation selon une ou plusieurs des revendications 1 à 9, caractérisée en ce que la quantité d'amylase dans les lessives liquides va de 0,001 à 8 % en poids.
EP12735211.0A 2011-07-12 2012-07-07 Utilisation d'une combinaison d'un sulfonate de paraffine secondaire et d'amylase pour augmenter le pouvoir détergent de lessives liquides Not-in-force EP2732015B1 (fr)

Applications Claiming Priority (2)

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PCT/EP2012/002869 WO2013007366A1 (fr) 2011-07-12 2012-07-07 Utilisation d'une association d'un sulfonate de paraffine secondaire et d'amylase pour augmenter le pouvoir détergent de liquides lessiviels

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EP2732015B1 true EP2732015B1 (fr) 2015-09-09

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DE102012204270A1 (de) * 2012-03-19 2013-09-19 Henkel Ag & Co. Kgaa Flüssiges Waschmittel mit erhöhter Reinigungsleistung
JP6157970B2 (ja) * 2013-07-26 2017-07-05 花王株式会社 衣料用液体洗浄剤組成物
WO2016010474A1 (fr) * 2014-07-18 2016-01-21 Sophia Morgan Kit de détachage

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CA777769A (en) 1963-03-18 1968-02-06 H. Roy Clarence Substituted methylene diphosphonic acid compounds and detergent compositions
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ES2554243T3 (es) 2015-12-17
WO2013007366A1 (fr) 2013-01-17
US20140189960A1 (en) 2014-07-10
JP2014522896A (ja) 2014-09-08
EP2732015A1 (fr) 2014-05-21

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