EP2134826B1 - Agent de lavage anti-gris - Google Patents

Agent de lavage anti-gris Download PDF

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Publication number
EP2134826B1
EP2134826B1 EP08735743.0A EP08735743A EP2134826B1 EP 2134826 B1 EP2134826 B1 EP 2134826B1 EP 08735743 A EP08735743 A EP 08735743A EP 2134826 B1 EP2134826 B1 EP 2134826B1
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EP
European Patent Office
Prior art keywords
alkyl
stands
groups
alkylene
weight
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EP08735743.0A
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German (de)
English (en)
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EP2134826A2 (fr
Inventor
Nadine Warkotsch
Birgit Middelhauve
Marc-Steffen Schiedel
Thomas Eiting
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority claimed from DE102007016382A external-priority patent/DE102007016382A1/de
Priority claimed from DE200710023872 external-priority patent/DE102007023872A1/de
Priority claimed from DE200710038451 external-priority patent/DE102007038451A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2134826A2 publication Critical patent/EP2134826A2/fr
Application granted granted Critical
Publication of EP2134826B1 publication Critical patent/EP2134826B1/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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3742—Nitrogen containing silicones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3726—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones

Definitions

  • the invention relates to a surfactant-containing detergent which contains a compound with certain reactive groups as graying-inhibiting active ingredient
  • Graying inhibitors have the task of keeping the fabric removed from the fiber during washing of the fiber suspended in the liquor and thus prevent the re-raising of the dirt on the textile.
  • water-soluble colloids are usually suitable organic nature, such as glue.
  • Gelatin salts of starch or cellulose ether sulphonic acids or salts of acid sulphate esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • soluble starch preparations and starch products other than those mentioned above can be used, for example degraded starch, strong aldehydes, etc. Polyvinylpyrrolidone is also useful.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methyl-carboxymethylcellulose and mixtures thereof in amounts of normally 0.1 to 5 wt .-%, based on the detergent used
  • EP1541568 describes the stain-resistant properties of the polyurethane and polycarbonate compounds. It discloses the surface treatment of fibers with aqueous solutions of polyurethane and polycarbonate compounds of formula IV.
  • Reactive cyclic carbonates and ureas processes for their preparation and their reaction with polymeric substrates are described in the international patent application WO 2005/058863 described. Surprisingly, it has now been found that the reactive carbonyl carbonates themselves or from these polymers obtainable by reaction with polymeric substrates have the desired effect.
  • polymeric substrates suitable in connection with the latter aspect of the invention include in particular polyvinyl alcohols, polyalkyleneamines such as polyethyleneimines, polyvinylamines, polyallylamines, polyethylene glycols, chitosan, polyamide-epichlorohydrin resins, polyamino-styrenes, aminoalkyl-terminated or pendant polysiloxanes such as polydimethylsiloxanes, peptides, Polypeptides, and proteins and mixtures thereof.
  • polyvinyl alcohols polyalkyleneamines such as polyethyleneimines, polyvinylamines, polyallylamines, polyethylene glycols, chitosan, polyamide-epichlorohydrin resins, polyamino-styrenes, aminoalkyl-terminated or pendant polysiloxanes such as polydimethylsiloxanes, peptides, Polypeptides, and proteins and mixtures thereof.
  • the compound of formula IV is preferably selected from 4-phenyloxycarbonyloxymethyl-2-oxo-1,3-dioxolane, 4- (4-Phenyloxycarbonyloxy) butyl-2-oxo-1,3-dioxolane, 2-oxo-1,3-dioxolan-4-yl-methyl, 2-oxo-1,3-dioxolan-4-yl-methyl, 4- (2-oxo-1,3-dioxolan-4-yl) butyl acrylate, 4- (2-oxo-1,3-dioxolan-4-yl) -butyl methacrylate and 4- (Vinylsulfonylethyloxy) butyl-2-oxo-1,3-dioxolane.
  • An agent of the invention preferably contains from 0.01% to 5%, more preferably from 0.1% to 1% by weight of the graying-inhibiting active ingredient described herein.
  • the invention also relates to the use of said active substances in detergents, in particular in aqueous liquid detergents, for improving the grayness inhibition when washing textile fabrics with the detergent.
  • a liquid detergent according to the invention contains, in addition to said graying-inhibiting active ingredient or mixtures thereof and surfactants described in more detail below, water in amounts of up to 85% by weight, and in particular from 40% by weight to 75%, of the total composition. %, which, if desired, can also be exchanged proportionally for a water-soluble solvent component.
  • Non-aqueous solvents that can be used in the liquid agents for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible in the specified concentration range with water.
  • the solvents are preferably selected from ethanol, n- or i-propanol, the butanols, ethylene glycol, butanediol, glycerol, diethylene glycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl , ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene Glycol t-butyl ether and mixtures of these.
  • the detergents according to the invention contain at least one surfactant, wherein anionic, nonionic, cationic and / or amphoteric surfactants can be used. Preference is given to the presence of anionic surfactants, mixtures of anionic and nonionic surfactants being particularly advantageous from an application point of view.
  • the total surfactant content of the particular liquid agent is preferably in the range of 10 wt .-% to 60 wt .-%, in particular 15 wt .-% to 50 wt .-%, each based on the total liquid agent.
  • the nonionic surfactants used are preferably alcohol alkoxylates, ie alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferably 2- Position may be methyl branched or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 carbon atoms for example, coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred among the preferred ethoxylated Alcohols include, for example, C 12-14 alcohols with 3 EO, 4 EO or 7 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -18- alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants containing 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.
  • nonionic surfactants and alkyl glycosides in particular of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethyl-amine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the alcohol alkoxylates, especially not more than half thereof.
  • Nonionic surfactants are polyhydroxy fatty acid amides of the formula (VI) in the R-CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.
  • 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 (VII) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical
  • [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.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the content of nonionic surfactants in the particularly liquid detergents is preferably 5 wt .-% to 30 wt .-%, in particular 7 wt .-% to 20 wt .-% and particularly preferably 9 wt .-% to 15 wt .-% , in each case based on the total mean.
  • the nonionic surfactant is selected from alcohol alkoxylate and alkyl polyglycoside and mixtures thereof.
  • anionic surfactants for example, those of the sulfonate type and sulfates can be used.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization can be recovered.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation 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.
  • Preferred sulfated 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.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, 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) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which may for example be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • the sulfuric acid monoesters of the above-mentioned alcohol alkoxylates for example the straight-chain or branched C 7-21 -alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 9-11 -alcohols having on average 3.5 moles of ethylene oxide (EO) or C. 12-18 fatty alcohols with 1 to 4 EO are suitable. These are often referred to as ether sulfates.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Preferred anionic surfactants are soaps. Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
  • the detergent contains 2 wt .-% to 20 wt .-%, in particular 3 wt .-% to 15 wt .-% and particularly preferably 5 wt .-% to 10 wt .-% fatty acid soap.
  • Fatty acid soaps are in particular an important constituent for the washing power of a liquid, in particular aqueous, washing and cleaning agent. Surprisingly, it has been shown that clear and stable liquid detergents are obtained when using the low-methylated carboxymethylcellulose also in the presence of high amounts of fatty acid soap. Typically, the use of high levels ( ⁇ 2% by weight) of fatty acid soap in such systems results in cloudy and / or unstable products.
  • the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the content of preferred detergents to anionic surfactants is 5 wt .-% to 35 wt .-%, in particular 8 wt .-% to 30 wt .-% and particularly preferably 10 wt .-% to 25 wt .-%, each based on the entire remedy. It is particularly preferred that the amount of fatty acid soap is at least 2% by weight, more preferably at least 3% by weight and in particular from 4% by weight to 10% by weight. In a further preferred embodiment, the compositions contain at least 2, in particular 3, different anionic surfactants selected from alkylbenzenesulfonate, ether sulfate and fatty acid soap.
  • the detergent may contain a co-builder and optionally also a thickener-acting polyacrylate.
  • polyacrylates include polyacrylate or polymethacrylate thickeners, such as, for example, the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to the International Dictionary of Cosmetic Ingredients, The Cosmetic, Toiletry and Fragrance Association (CTFA) ": carbomer), also referred to as carboxyvinyl polymers.
  • CTFA Cosmetic, Toiletry and Fragrance Association
  • Such polyacrylic acids are available, inter alia, from 3V Sigma under the trade name Polygel®, for example Polygel DA, and from Noveon under the trade name Carbopol®, for example Carbopol 940 (molecular weight about 4,000,000), Carbopol 941 (molecular weight approx 1. 250,000) or Carbopol 934 (molecular weight about 3,000,000).
  • Polygel® for example Polygel DA
  • Carbopol® for example Carbopol 940 (molecular weight about 4,000,000), Carbopol 941 (molecular weight approx 1. 250,000) or Carbopol 934 (molecular weight about 3,000,000).
  • acrylic acid copolymers are included: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, esters (INCI Acrylates Copolymer) preferably formed with C 1-4 -alkanols, for example the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS designation according to Chemical Abstracts Service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and which are available, for example, from Rohm & Haas under the trade names Aculyn® and Acusol® and from Degussa (Goldschmidt) under the trade name Tego® Polymer, for example the anionic non-associative polymers Aculyn 22, Aculyn 28, Aculyn 33 (cross-linked), Acusol 810, Acusol 823 and Acusol 830 (CAS 25852-37-3); (ii) crosslinked high mole
  • Preferred detergents in particular those in liquid form, contain the polyacrylate in an amount of up to 5% by weight, in particular from 0.1% by weight to 2.5% by weight. It is advantageous if the polyacrylate is a copolymer of an unsaturated mono- or dicarboxylic acids and one or more C 1 -C 30 -alkyl esters of (meth) acrylic acid.
  • the viscosity of liquid detergents and cleaning agents can be measured by conventional standard methods (for example Brookfield LVT-II viscosimeter at 20 rpm and 20 ° C., spindle 3) and is preferably in the range from 150 mPas to 5000 mPas.
  • Preferred liquid agents have viscosities in the range from 500 mPas to 4000 mPas, with values in the range from 1000 mPas to 3500 mPas being particularly preferred.
  • detergents may contain other ingredients that further improve their performance and / or aesthetic properties.
  • preferred agents comprise one or more substances from the group of builders, bleaches, bleach activators, enzymes, electrolytes, pH adjusters, fragrances, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, additional antiredeposition agents or grayness inhibitors, optical brighteners, Anti-shrinkage agents, anti-wrinkling agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents and UV absorbers.
  • Suitable builders which may be present in the compositions are, for example, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.
  • the usable finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P.
  • zeolite P zeolite MAP ® commercial product from Crosfield
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • the zeolite can be used as a spray-dried powder or, in particular in water-containing liquid agents, also as undried, still moist, stabilized suspension of its preparation.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • phosphates As builders, if such use is not to be avoided for ecological reasons.
  • Particularly suitable enzymes are those from the classes of hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. Oxireductases can also be used for bleaching or inhibiting color transfer.
  • hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying.
  • Bacillus subtilis Bacillus licheniformis, Streptomyceus griseus and Humicola insolens derived enzymatic agents.
  • Bacillus subtilis Bacillus subtilis
  • Bacillus licheniformis Bacillus licheniformis
  • Streptomyceus griseus and Humicola insolens derived enzymatic agents.
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • Enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing Mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • As cellulases are preferably Cellobiohydrolaseh, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes can be adsorbed and / or coated on carriers to protect against premature degradation.
  • the proportion of enzymes, enzyme liquid formulations, enzyme mixtures or enzyme granules may, for example, about 0.1 wt .-% to 5 wt .-%, preferably 0.12 wt .-% to about 2.5 wt .-%, each based on the total agent , amount.
  • electrolytes from the group of inorganic salts a wide number of different salts can be used.
  • Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl 2 in the compositions is preferred.
  • the proportion of electrolytes in the particular liquid agents is usually not more than 8 wt .-%, in particular 0.5 wt .-% to 5 wt .-%.
  • pH adjusters In order to bring the pH of liquid agents in the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited. Usually, the amount of these adjusting agents does not exceed 10% by weight of the total formulation.
  • liquid agents of the invention is a hydrotrope.
  • Preferred hydrotropes include the sulfonated hydrotropes such as the alkylarylsulfonates or alkylarylsulfonic acids.
  • Preferred hydrotropes are selected from xylene, toluene, cumene, naphthalenesulfonate or sulfonic acid and mixtures thereof.
  • Counterions are preferably selected from sodium, calcium and ammonium.
  • the liquid agents may comprise up to 20% by weight of a hydrotrope, in particular from 0.05% to 10% by weight.
  • dyes In order to improve the aesthetic impression of the agents, they or at least one of their components can be dyed with suitable dyes.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to textile fibers so as not to stain them.
  • Suitable foam inhibitors which can be used in the detergents and cleaners are, for example, soaps, paraffins or silicone oils which, if appropriate, may have been applied to support materials.
  • Suitable antiredeposition agents which are also referred to as "soil repellents" are, for example, the polymers of phthalic acid and / or terephthalic acid known from the prior art or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified Derivatives of these. Especially preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers.
  • Optical brighteners can be added to the detergents and cleaners to eliminate yellowing of the treated fabrics. These fabrics attract and cause lightening by converting ultraviolet radiation invisible to the human eye into visible longer wavelength light, emitting the ultraviolet light absorbed from the sunlight as faint bluish fluorescence and turning the yellowish yellowed laundry to pure white.
  • Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems as well as heterocyclic substituted pyrene derivatives.
  • Optical brighteners are normally used in amounts of up to 0.5% by weight, in particular from 0.03% by weight to 0.3% by weight, based on the finished composition.
  • compositions may contain synthetic crease inhibitors.
  • detergents and cleaning agents may contain antimicrobial agents.
  • antimicrobial agents Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistatics and fungicides, etc.
  • Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate, and the compounds according to the invention can be completely dispensed with.
  • the compositions may contain antioxidants.
  • This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
  • antioxidants When such antioxidants are used, the agents according to the invention are free from oxidizing bleaches.
  • Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges.
  • External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents.
  • External antistatic agents are, for example, lauryl (or stearyl) dimethylbenzylammonium chlorides, which are suitable as antistatic agents for textile fabrics or as an additive to detergents, in which case additionally a finishing effect is achieved.
  • silicone derivatives can be used in the detergents and cleaners. These additionally improve the rinsing behavior of the agents by their foam-inhibiting properties.
  • Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
  • the viscosities of the preferred silicones are in the range between 100 and 100,000 mPas at 25 ° C, wherein the silicones in amounts between 0.2 and 5 wt .-%, based on the total agent can be used.
  • the detergents and cleaners may also contain UV absorbers which wick onto the treated fabrics and improve the lightfastness of the fibers.
  • Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, in the 3-position phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and urocanic acid.
  • Suitable heavy metal complexing agents are, for example, the alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.
  • EDTA ethylenediaminetetraacetic acid
  • NTA nitrilotriacetic acid
  • 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 from 0.01% to 2.5%, preferably from 0.02% to 2%, by weight, and most preferably 0.03 wt .-% to 1.5 wt .-% are included.
  • These preferred compounds include in particular organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2 , 4-tricarboxylic acid (PBS-AM), which are used mostly in the form of their ammonium or alkali metal salts.
  • organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobut
  • Liquid detergents according to the invention are preferably clear, ie they have no sediment and are transparent or at least translucent.
  • the liquid detergents and cleaners without addition of a dye preferably have a transmission of the visible light (410 to 800 nm) of at least 30%, preferably at least 50% and especially preferably at least 75%.
  • Aqueous detergents and cleaners can be inexpensively and easily produced in conventional mixing and bottling plants.
  • the acidic components such as, for example, the linear alkyl sulfonates, citric acid, boric acid, phosphonic acid, the fatty alcohol ether sulfates, and the nonionic surfactants are preferably initially introduced.
  • the solvent component is preferably also added at this time, but the addition may also be made at a later time.
  • the complexing agent is added. Subsequently, a base such as NaOH, KOH, triethanolamine or monoethanolamine followed by the fatty acid, if present, is added.
  • the remaining ingredients and optionally, adding the remaining solvents of the aqueous liquid agent to the mixture and adjusting the pH to the desired value.
  • the particles to be dispersed can be added and distributed homogeneously in the aqueous liquid agent by mixing.
  • Table 1 shows the composition (ingredients in percent by weight, in each case based on the total agent) of a detergent M1 according to the invention.
  • Table 1 M1 C 9-13 alkyl benzene sulfonate, Na salt 10 Sodium lauryl ether sulfate with 2 EO 5 C 12-18 fatty alcohol with 7 EO 10 C 12-14 alkyl polyglycoside 2 C 12-18 fatty acid, Na salt 8th glycerin 5 trisodium citrate 1 polyacrylate 2 active substance 1
  • the agent was tested under the following conditions: Washer: Washing machine Washing temperature: 40 ° C Number of washes: 10 Water hardness: 16 ° dH Soil carrier: 6,7 g mixed dirt (eg clay, dust-skin fat, soot) Dosage: 75 g of the medium / 17L

Claims (7)

  1. Agent de lavage, qui est liquide et qui contient jusqu'à 85% en poids d'eau, comportant un tensioactif et facultativement d'autres ingrédients classiques d'agents de lavage et de nettoyage, l'agent contenant un composé d'inhibition de grisonnement de la formule générale IV,
    Figure imgb0008
     dans laquelle
    R représente des alkyles en C1 à C12;
    k est un nombre supérieur à 0,
    X représente CO-CH=CH2, CO-C(CH3)=CH2, CO-O-aryle, alkylène en C6 à C6-SO2CH=CH2 ou CO-NH-R1 ; R1 représente alkyle en C1 à C30, halogénoalkyle en C1 à C30, hydroxyalkyle en C1 à C30, alkyloxy en C1 à C6-alkyle en C1 à C30, alkyl en C1 à C6-carbonyloxy-alkyle en C1 à C30, amino-alkyle en C1 à C30, mono- ou di-alkyle en C1 à C6-amino-alkyle en C1 à C30, ammonio-alkyle en C1 à C30, polyoxyalkylène-alkyle en C1 à C30, polysiloxanyl-alkyle en C1 à C30, (méth)acryloyloxy-alkyle en C1 à C30, sulfono-alkyle en C1 à C30, phosphono-alkyle en C1 à C30, di-alkyl en C1 à C6-phosphono-alkyle en C1 à C30, phosphonato-alkyle en C1 à C30, di-alkyle en C1 à 6-phosphonato-alkyle en C1 à C30 ou un résidu saccharide, où X n'a ce sens que lorsque k vaut 1, ou
    X représente
    (i) le résidu d'une polyamine auquel la formule entre crochets est liée par des groupes (CO)NH-, ou
    (ii) un squelette polymérique auquel la formule entre crochets est liée par des groupes (CO)-, NH-C2-alkylène en C2 à C5-O(CO)- ou - CO)-O-alkylène en C2 à C5-O(CO), ou
    (iii) un squelette polymérique auquel la formule entre crochets est liée par des groupes (CO)-polysiloxanyl-alkyle en C1 à C30,,
    si k est un nombre supérieur à 1,
    et/ou un polymère qui peut être obtenu par réaction d'un substrat polymère qui présente des groupes fonctionnels qui sont choisis parmi des groupes hydroxy, des groupes amino primaires et secondaires, avec un composé de la formule générale IV.
  2. Agent selon la revendication 1, caractérisé en ce qu'il contient 10% en poids à 60% en poids, en particulier 15% en poids à 50% en poids de tensioactif.
  3. Agent selon la revendication 1 ou 2, caractérisé en ce qu'il contient un tensioactif anionique et en particulier un savon d'acide gras.
  4. Agent selon l'une des revendications 1 à 3, caractérisé en ce qu'elle contient au moins deux tensioactifs anioniques différents choisis parmi le sulfonate d'alcoylbenzène, un sulfate d'éther et un savon.
  5. Agent selon l'une des revendications 1 à 4, caractérisé en ce qu'il contient un tensioactif non ionique, choisi en particulier parmi un alcoxylat d'alcool et un polyglycoside d'alkyle et leurs mélanges.
  6. Agent selon l'une des revendications 1 à 5, caractérisé en ce qu'il comprend de 40% en poids à 75% en poids d'eau.
  7. Utilisation de composés de la formule générale IV,
    Figure imgb0009
     dans laquelle
    R représente des alkyles en C1 à C12 ;
    k est un nombre supérieur à 0,
    X représente CO-CH=CH2, CO-C(CH3)=CH2, CO-O-aryle, alkylène en C6 à C6-SO2CH=CH2 ou CO-NH-R1 ; R1 représente alkyle en C1 à C30, halogénoalkyle en C1 à C30, hydroxyalkyle en C1 à C30, alkyloxy en C1 à C6-alkyle en C1 à C30, alkyl en C1 à C6-carbonyloxy-alkyle en C1 à C30, amino-alkyle en C1 à C30, mono- ou di-alkyle en C1 à C6-amino-alkyle en C1 à C30, ammonio-alkyle en C1 à C30, polyoxyalkylène-alkyle en C1 à C30, polysiloxanyl-alkyle en C1 à C30, (méth)acryloyloxy-alkyle en C1 à C30, sulfono-alkyle en C1 à C30, phosphono-alkyle en C1 à C30, di-alkyl en C1 à C6-phosphono-alkyle en C1 à C30, phosphonato-alkyle en C1 à C30, di-alkyle en C1 à 6-phosphonato-alkyle en C1 à C30 ou un résidu saccharide, où X n'a ce sens que lorsque k vaut 1, ou
    X représente
    (i) le résidu d'une polyamine auquel la formule entre crochets est liée par des groupes (CO)NH-, ou
    (ii) un squelette polymérique auquel la formule entre crochets est liée par des groupes (CO)-, NH-C2-alkylène en C2 à C5-O(CO)- ou - CO)-O-alkylène en C2 à C5-O(CO), ou
    (iii) un squelette polymérique auquel la formule entre crochets est liée par des groupes (CO)-polysiloxanyl-alkyle en C1 à C30,
    si k est un nombre supérieur à 1,
    et/ou un polymère qui peut être obtenu par réaction d'un substrat polymère qui présente des groupes fonctionnels qui sont choisis parmi des groupes hydroxy, des groupes amino primaires et secondaires, avec un composé de la formule générale IV,
    dans des agents de lavage, en particulier des agents de lavage liquides aqueux, pour améliorer l'inhibition du grisonnement lors du lavage de surfaces textiles.
EP08735743.0A 2007-04-03 2008-04-03 Agent de lavage anti-gris Not-in-force EP2134826B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102007016382A DE102007016382A1 (de) 2007-04-03 2007-04-03 Vergrauungsinhibierendes Waschmittel
DE200710023872 DE102007023872A1 (de) 2007-05-21 2007-05-21 Vergrauungsinhibierendes Waschmittel
DE200710038451 DE102007038451A1 (de) 2007-08-14 2007-08-14 Vergrauungsinhibierendes Waschmittel
PCT/EP2008/053994 WO2008119831A2 (fr) 2007-04-03 2008-04-03 Agent de lavage anti-gris

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EP2134826A2 EP2134826A2 (fr) 2009-12-23
EP2134826B1 true EP2134826B1 (fr) 2015-11-04

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KR20090128448A (ko) 2007-04-03 2009-12-15 헨켈 아게 운트 코. 카게아아 발오 성분을 함유하는 세제
WO2008119834A1 (fr) 2007-04-03 2008-10-09 Henkel Ag & Co. Kgaa Détergents
WO2008141858A2 (fr) 2007-04-03 2008-11-27 Henkel Ag & Co. Kgaa Détergents contenant des principes actifs améliorant la détergence primaire
US8354478B2 (en) * 2007-09-12 2013-01-15 Alzo International, Inc. Silicone polyurethane blends

Also Published As

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US20100022428A1 (en) 2010-01-28
US8044016B2 (en) 2011-10-25
US8324145B2 (en) 2012-12-04
WO2008119831A2 (fr) 2008-10-09
ES2554983T3 (es) 2015-12-28
US20120004155A1 (en) 2012-01-05
WO2008119831A3 (fr) 2009-02-05
KR20090128443A (ko) 2009-12-15
EP2134826A2 (fr) 2009-12-23

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