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EP3877493B1 - Détergents et produits de nettoyage d'efficacité améliorée - Google Patents

Détergents et produits de nettoyage d'efficacité améliorée Download PDF

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Publication number
EP3877493B1
EP3877493B1 EP19801245.2A EP19801245A EP3877493B1 EP 3877493 B1 EP3877493 B1 EP 3877493B1 EP 19801245 A EP19801245 A EP 19801245A EP 3877493 B1 EP3877493 B1 EP 3877493B1
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EP
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Prior art keywords
washing
acid
agents
stains
general formula
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EP19801245.2A
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German (de)
English (en)
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EP3877493A1 (fr
Inventor
Christian Kropf
Sascha Schaefer
Christian Umbreit
Mareile Job
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/34—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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0084—Antioxidants; Free-radical scavengers

Definitions

  • the present invention relates to the use of catechol disulfonamides in washing and cleaning agents to improve the washing or cleaning performance.
  • the polymerizable substances are primarily polyphenolic dyes, preferably flavonoids, in particular from the class of anthocyanidins or anthocyanins.
  • the soiling can be caused in particular by food products or drinks that contain corresponding dyes.
  • the soiling can in particular be stains from fruit or vegetables or even red wine stains, which in particular contain polyphenolic dyes, in particular those from the class of anthocyanidins or anthocyanins.
  • the EN 10 2007 008656 A1 relates to detergents and cleaning agents containing urea derivatives, as well as the use of these detergents and cleaning agents for cleaning textiles and surfaces.
  • the bleachable stains usually contain polymerizable substances, in particular polymerizable dyes, the polymerizable dyes preferably being polyphenolic dyes, in particular flavonoids, especially anthocyanidins or anthocyanins or oligomers of these compounds.
  • polymerizable dyes preferably being polyphenolic dyes, in particular flavonoids, especially anthocyanidins or anthocyanins or oligomers of these compounds.
  • the removal of stains in intermediate colors in particular violet, purple, brown, purple or pink
  • stains that have a green, yellow, red, violet, purple, brown, purple, pink or blue tint without essentially consisting entirely of this color themselves can also be light or dark.
  • stains in particular stains from grass, fruit or vegetables, and in particular stains from food products such as spices, sauces, chutneys, curries, purees and jams, or drinks such as coffee, tea, wines and juices which contain corresponding green, yellow, red, violet, purple, brown, purple, pink and/or blue dyes.
  • the soiling to be removed according to the invention can be caused in particular by cherries, morello cherries, grapes, apples, pomegranates, aronia, plums, sea buckthorn, açai, kiwi, mango, grass or berries, in particular by red or black currants, elderberries, blackberries, raspberries, blueberries, cranberries, lingonberries, strawberries or blueberries, by coffee, tea, red cabbage, blood orange, aubergine, tomato, carrot, beetroot, spinach, peppers, red-fleshed or blue-fleshed potatoes, or red onions.
  • R 1 and R 3 and/or R 2 and R 4 are preferably the same.
  • the preferred compounds of the general formula (I) also include those in which R 1 , R 2 , R 3 and R 4 are selected independently of one another from hydrogen, the methyl group, the ethyl group, the n-propyl group and the isopropyl group. If R 1 and R 2 and/or R 3 and R 4 are part of a heterocycle formed from them and the N atom, this is preferably a piperidine ring.
  • the use according to the invention of the compound of the general formula (I) in washing or cleaning agents is preferably carried out by using it in an amount of 0.001% by weight to 20% by weight, in particular in an amount of 0.01% by weight to 10% by weight, where here and below the information on "% by weight” refers in each case to the weight of the entire washing or cleaning agent.
  • a further subject of the invention is therefore a washing or cleaning agent containing surfactant and 0.001% by weight to 20% by weight of a compound of the general formula (I) defined above in an amount of preferably 0.01% by weight to 10% by weight, the preferred embodiments of the use according to the invention described above or below also applying mutatis mutandis to this subject of the invention.
  • Such an agent is used in conventional washing or cleaning processes carried out mechanically or manually, in which soiled laundry or a soiled hard surface is exposed to an aqueous liquor containing the agent with the aim of removing the soiling from the textile or hard surface.
  • the washing or cleaning agent can be in any dosage form established according to the state of the art and/or any appropriate dosage form.
  • dosage form established according to the state of the art and/or any appropriate dosage form.
  • These include, for example, solid, powdered, liquid, gel-like or pasty dosage forms, possibly also consisting of several phases; furthermore, they include, for example: extrudates, granulates, tablets or pouches, both in bulk containers and packaged in portions.
  • the use according to the invention takes place in a washing and cleaning agent that does not contain any oxidative bleaching agents.
  • the agent does not contain any oxidative bleaching agents in the narrower sense, which include hypochlorites, hydrogen peroxide or substances that provide hydrogen peroxide and peroxoacids; it also preferably does not contain any bleach activators and/or bleach catalysts.
  • the washing or cleaning agent which contains a compound according to general formula (I) may well contain such oxidative bleaching agents, since the presence of the compound according to general formula (I) also results in an increase in the bleaching performance after storage of such agents.
  • the compound according to general formula (I) may possibly stabilize the bleaching agent by complexing redox-active metal ions and thus also contribute to increasing the washing or cleaning performance of such agents against bleachable stains.
  • the detergent is a liquid textile detergent.
  • the detergent is a powdered or liquid color detergent, i.e. a textile detergent for colored textiles.
  • the washing or cleaning agents can contain other usual constituents of washing or cleaning agents, in particular textile detergents, in particular selected from the group of builders and preferably polymers, enzymes, disintegration aids, fragrances and perfume carriers.
  • the builders include in particular zeolites, silicates, carbonates, organic cobuilders and - provided there are no ecological prejudices against their use - also phosphates.
  • the finely crystalline, synthetic zeolite containing bound water is preferably zeolite A and/or zeolite P.
  • Zeolite MAPO (a commercial product from Crosfield) is an example of a suitable zeolite P.
  • zeolite X and mixtures of zeolite A, X and/or P are also suitable.
  • Commercially available and usable in the context of the present invention is, for example, a co-crystallizate of zeolite X and zeolite A (approx.
  • zeolite X which is represented by the formula n Na 2 O ⁇ (1-n)K 2 O ⁇ Al 2 O 3 ⁇ (2 - 2.5) SiO 2 ⁇ (3.5 - 5.5) H 2 O
  • the zeolite can be used both as a builder in a granular compound and as a kind of "powdering" of a granular mixture, preferably a mixture to be pressed, whereby both methods are usually used to incorporate the zeolite into the premix.
  • Zeolites can have an average particle size of less than 10 ⁇ m (volume distribution; measuring method: Coulter Counter) and preferably contain 18 wt.% to 22 wt.%, in particular 20 wt.% to 22 wt.% of bound water.
  • Crystalline layered silicates of the general formula NaMSi x O 2x+1 ⁇ y H 2 O can also be used, in which M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values for x being 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
  • the crystalline layered silicates of the formula NaMSi x O 2x+1 ⁇ y H 2 O are sold, for example, by Clariant GmbH (Germany) under the trade name Na-SKS.
  • silicates Na-SKS-1 (Na 2 Si 22 O 45 ⁇ x HzO, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 ⁇ x HzO, magadiite), Na-SKS-3 (Na 2 SisO 17 ⁇ x H 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 ⁇ x H 2 O, Makatite).
  • crystalline layered silicates of the formula NaMSi x O 2x+1 ⁇ y HzO in which x is 2.
  • Detergents or cleaning agents preferably contain a weight proportion of the crystalline layered silicate of the formula NaMSi x O 2x+1 ⁇ y H 2 O of 0.1 wt.% to 20 wt.%, preferably of 0.2 wt.% to 15 wt.% and in particular of 0.4 wt.% to 10 wt.%.
  • Amorphous sodium silicates with a NazO:SiOz modulus of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and in particular 1:2 to 1:2.6, which preferably have a delayed dissolution and secondary washing properties, can also be used.
  • the delayed dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compaction/densification or by overdrying.
  • the term "amorphous" means that the silicates do not produce sharp X-ray reflections in X-ray diffraction experiments, as is typical for crystalline substances, but at most produce one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • X-ray amorphous silicates can be used, the silicate particles of which produce blurred or even sharp diffraction maxima in electron diffraction experiments. This can be interpreted as meaning that the products have microcrystalline regions of a size of ten to several hundred nm, with values of up to a maximum of 50 nm and in particular up to a maximum of 20 nm being preferred.
  • Such X-ray amorphous silicates also have a dissolution delay compared to conventional water glasses. Particularly preferred are compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • silicate(s) preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, are, if present, used in washing or cleaning agents in amounts of 3 wt.% to 60 wt.%, preferably from 8 wt.% to 50 wt.% and in particular from 20 wt.% to 40 wt.%.
  • alkali metal phosphates are the most important in the detergent and cleaning agent industry, with particular preference given to pentasodium and pentapotassium triphosphate (sodium and potassium tripolyphosphate).
  • Alkali metal phosphates is the collective term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, of which metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 can be distinguished alongside higher molecular weight representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts or limescale incrustations in fabrics and also contribute to the cleaning performance.
  • Technically particularly important phosphates are pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate).
  • Sodium potassium tripolyphosphates are still preferred.
  • phosphates are used in washing or cleaning agents
  • preferred agents contain these phosphate(s), preferably alkali metal phosphate(s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of from 5% by weight to 80% by weight, preferably from 15% by weight to 75% by weight and in particular from 20% by weight to 70% by weight.
  • Alkali carriers can also be used.
  • alkali carriers include alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, the alkali silicates mentioned, alkali metasilicates and mixtures of the aforementioned substances, with alkali carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, being used preferably.
  • a builder system containing a mixture of tripolyphosphate and sodium carbonate can be particularly preferred.
  • alkali metal hydroxides are usually only used in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, particularly preferably below 4% by weight and in particular below 2% by weight. Agents which contain less than 0.5% by weight of their total weight and in particular no alkali metal hydroxides are particularly preferred. Preference is given to the use of carbonate(s) and/or hydrogen carbonate(s), preferably alkali carbonate(s), particularly preferably sodium carbonate, in amounts of from 2% by weight to 50% by weight, preferably from 5% by weight to 40% by weight and in particular from 7.5% by weight to 30% by weight.
  • Organic builders include, in particular, polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins and phosphonates.
  • useful polycarboxylic acids are those that can be used in the form of the free acid and/or their sodium salts, whereby polycarboxylic acids are understood to be carboxylic acids that have more than one acid function. Examples include citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these.
  • NTA nitrilotriacetic acid
  • the free acids typically also have the property of an acidifying component and are therefore also used to set a lower and milder pH value for washing or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these are particularly suitable.
  • Polymeric polycarboxylates are also suitable as builders. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular mass of 500 g/mol to 70,000 g/mol. Polyacrylates which preferably have a molecular mass of 2,000 g/mol to 20,000 g/mol are particularly suitable.
  • the short-chain polyacrylates from this group which have molecular masses of 2,000 g/mol to 10,000 g/mol, and particularly preferably 3,000 g/mol to 5,000 g/mol, may be preferred.
  • Copolymeric polycarboxylates are also suitable, particularly 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% by weight to 90% by weight of acrylic acid and 50% by weight to 10% by weight of maleic acid have proven to be particularly suitable.
  • the relative molecular mass, based on free acids, is generally 2000 g/mol to 70000 g/mol, preferably 20000 g/mol to 50000 g/mol and in particular 30000 g/mol to 40000 g/mol.
  • the polymers can also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • the (co)polymeric polycarboxylates can be used as a solid or in aqueous solution.
  • the content of (co)polymeric polycarboxylates in washing or cleaning agents is preferably 0.5% by weight to 20% by weight and in particular 3% by weight to 10% by weight.
  • Biodegradable polymers made from more than two different monomer units are also particularly preferred, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or which contain salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives as monomers.
  • Other preferred copolymers are those which contain acrolein and acrylic acid/acrylic acid salts or acrolein and vinyl acetate as monomers.
  • Other preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids and/or their salts are particularly preferred.
  • Phosphonates represent another class of substances with builder properties. These are the salts of hydroxyalkane or aminoalkanephosphonic acids in particular. Of the hydroxyalkanephosphonic acids, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) is of particular importance. It is used in particular as a sodium salt, with the disodium salt reacting neutrally and the tetrasodium salt alkaline. Ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP) and their higher homologues are particularly suitable as aminoalkanephosphonic acids.
  • ETMP Ethylenediaminetetramethylenephosphonic acid
  • DTPMP diethylenetriaminepentamethylenephosphonic acid
  • their higher homologues are particularly suitable as aminoalkanephosphonic acids.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as gluconic acid and/or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by conventional methods, for example acid- or enzyme-catalyzed methods. These are preferably hydrolysis products with average molecular weights in the range from 400 g/mol to 500,000 g/mol.
  • DE dextrose equivalent
  • Maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molecular weights in the range of 2000 g/mol to 30000 g/mol are suitable.
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are able to oxidize at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Ethylenediamine-N,N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts used if desired are 3% to 15% by weight, particularly in zeolite-containing and/or silicate-containing formulations.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups.
  • the detergents and cleaning agents may contain non-ionic, anionic, cationic and/or amphoteric surfactants.
  • nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants. Washing or cleaning agents particularly preferably contain nonionic surfactants from the group of alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with 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 can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals from alcohols of native origin with 12 to 18 carbon atoms, e.g. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 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 5 EO.
  • the stated degrees of ethoxylation represent statistical averages which can correspond to a whole or a fractional number 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 these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO(G) x can also be used as further non-ionic surfactants, in which R corresponds to a primary straight-chain or methyl-branched, in particular methyl-branched in the 2-position, aliphatic radical with 8 to 22, preferably 12 to 18 C atoms and G is the symbol that stands for a glycose unit with 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; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are 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 with 1 to 4 carbon atoms in the alkyl chain.
  • Non-ionic surfactants of the amine oxide type for example N-coconut alkyl-N,N-dimethylamine oxide and N-tallow alkyl-N,N-dihydroxyethylamine oxide, and fatty acid alkanolamides can also be used.
  • the amount of these non-ionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of that.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula in which R is 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.
  • 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 in which 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] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst.
  • nonionic surfactants from the group of alkoxylated alcohols particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO/AO/EO nonionic surfactants, or PO/AO/PO nonionic surfactants, especially PO/EO/PO nonionic surfactants, are particularly preferred.
  • Such PO/EO/PO nonionic surfactants are characterized by good foam control.
  • anionic surfactants used are sulfonates and sulfates.
  • sulfonate-type surfactants are C 9-13 alkylbenzenesulfonates, olefinsulfonates, i.e. mixtures of alkene and hydroxyalkanesulfonates, and disulfonates, such as those obtained from C 12-18 monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • sulfated fatty acid glycerol esters are understood to mean the mono-, di- and triesters as well as mixtures thereof, 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.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Preferred alk(en)yl sulfates are the alkali metal and especially the sodium salts of the sulfuric acid half esters of the C 12 -C 18 fatty alcohols, for example from 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.
  • alk(en)yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis and which have a degradation behavior similar to that of the corresponding compounds based on oleochemical raw materials.
  • the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C 14 -C 15 alkyl sulfates are preferred.
  • the sulfuric acid monoesters of straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12-18 fatty alcohols with 1 to 4 EO, are also suitable. Due to their high foaming behavior, they are only used in relatively small amounts in cleaning agents, for example in amounts of 1% to 5% by weight.
  • Suitable anionic surfactants are the salts of alkyl sulfosuccinic acid, which are also referred to as sulfosuccinates or sulfosuccinic acid esters and are 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 which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants.
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk(en)ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk(en)yl chain or salts thereof.
  • anionic surfactants that may be considered include soaps.
  • Saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and particularly soap mixtures derived from natural fatty acids, e.g. coconut, palm kernel or tallow fatty acids, are suitable.
  • the anionic surfactants can 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 in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • Cationic and/or amphoteric surfactants can also be used instead of the surfactants mentioned or in combination with them.
  • subtilisins those of the subtilisin type are preferred.
  • these are the subtilisins BPN' and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the proteases TW3 and TW7, which are classified as subtilases but no longer as subtilisins in the narrower sense.
  • amylases examples include the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the further developments of the aforementioned amylases that have been improved for use in washing and cleaning products. Furthermore, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) are particularly noteworthy for this purpose.
  • Lipases or cutinases can be used because of their triglyceride-splitting activity. These include, for example, lipases originally obtained from Humicola lanuginosa (Thermomyces lanuginosus) or further developed from these, especially those with the amino acid exchange D96L. Cutinases that were originally isolated from Fusarium solani pisi and Humicola insolens can also be used. Lipases and/or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii can also be used.
  • oxidoreductases for example oxidases, oxygenases, catalases, peroxidases such as halo-, chloro-, bromo-, lignin-, glucose- or manganese-peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used to increase the bleaching effect.
  • organic compounds, particularly aromatic ones, which interact with the enzymes are also added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons when the redox potentials between the oxidizing enzymes and the soiling differ greatly (mediators).
  • the enzymes can be used in any form established according to the state of the art. These include, for example, solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and/or mixed with stabilizers.
  • the enzymes can be encapsulated for both the solid and liquid dosage forms, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as if in a solidified gel or in those of the core-shell type in which an enzyme-containing core is covered with a protective layer that is impermeable to water, air and/or chemicals.
  • Additional active ingredients for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can also be applied in superimposed layers.
  • Such capsules are applied using methods known per se, for example by shaking or rolling granulation or in fluid bed processes.
  • Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable in storage due to the coating. It is also possible to package two or more enzymes together so that a single granulate has several enzyme activities.
  • one or more enzymes and/or enzyme preparations are used in amounts of from 0.1% by weight to 5% by weight, preferably from 0.2% by weight to 4.5% by weight and in particular from 0.4% by weight to 4% by weight.
  • fragrance compounds e.g. synthetic products such as esters, ethers, aldehydes, ketones, alcohols and hydrocarbons
  • perfume oils or fragrances can be used as perfume oils or fragrances.
  • mixtures of different fragrances are preferred, which together produce an appealing scent.
  • perfume oils can also contain natural fragrance mixtures, such as those available from plant sources, such as pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • a fragrance In order to be perceptible, a fragrance must be volatile, whereby the molecular mass plays an important role alongside the nature of the functional groups and the structure of the chemical compound.
  • Most fragrances have molecular masses of up to around 200 g/mol, while molecular masses of 300 g/mol and above are rather the exception.
  • the smell of a perfume or fragrance composed of several odorants changes during evaporation, with the odor impressions being divided into "top note”, “middle note, body” and “end note, dry out”. Since the perception of smell is also largely based on the intensity of the smell, the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note consists mainly of less volatile, i.e. more adherent odorants. When composing perfumes, more volatile odorants can be bound to certain fixatives, for example, which prevents them from evaporating too quickly.
  • the fragrances can be processed directly, but it can also be advantageous to apply the fragrances to carriers that ensure a long-lasting fragrance through a slower release of the fragrance.
  • Cyclodextrins for example, have proven to be suitable carrier materials, although the cyclodextrin perfume complexes can also be coated with other excipients.
  • the dye When choosing the dye, it is important to ensure that the dye has a high storage stability and insensitivity to light and does not have too strong an affinity to textile surfaces, particularly synthetic fibers. At the same time, it must also be taken into account that colorants can have different levels of stability with regard to oxidation. In general, water-insoluble colorants are more stable against oxidation than water-soluble colorants. The concentration of the colorant in the washing or cleaning agent varies depending on the solubility and therefore also on the sensitivity to oxidation. For colorants that are easily soluble in water, colorant concentrations in the range of a few 10 -2 % to 10 -3 % by weight are typically selected.
  • the suitable concentration of the colorant in washing or cleaning agents is typically a few 10 -3 % to 10 -4 % by weight. Colorants that can be destroyed by oxidation in the washing process are preferred, as are mixtures of these with suitable blue dyes, so-called blue tinters. It has proven advantageous to use dyes that are soluble in water or in liquid organic substances at room temperature. Anionic dyes, such as anionic nitroso dyes, are suitable.
  • the washing or cleaning agents can contain other ingredients that further improve the application and/or aesthetic properties of these agents.
  • Preferred agents contain one or more substances from the group of electrolytes, pH adjusters, fluorescent agents, hydrotropes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, shrinkage inhibitors, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids, phobic and waterproofing agents, swelling and slip-resistant agents and UV absorbers.
  • a wide range of different salts from the group of inorganic salts can be used as electrolytes.
  • Preferred cations are alkali and alkaline earth metals, preferred anions are halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl 2 in washing or cleaning agents is preferred.
  • pH adjusters In order to bring the pH value of washing or cleaning agents into the desired range, the use of pH adjusters may be indicated. All known acids or alkalis can be used here, provided their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. The amount of these adjusters usually does not exceed 1% by weight of the total formulation.
  • Suitable foam inhibitors are soaps, oils, fats, paraffins or silicone oils, which can optionally be applied to carrier materials.
  • Suitable carrier materials include, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the aforementioned materials.
  • Preferred materials in the context of the present application Agents contain paraffins, preferably unbranched paraffins (n-paraffins) and/or silicones, preferably linear polymer silicones, which are structured according to the scheme (R 2 SiO) x and are also referred to as silicone oils.
  • silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids with a molecular weight between 1000 g/mol and 150,000 g/mol and viscosities between 10 mPa ⁇ s and 1,000,000 mPa ⁇ s.
  • Suitable soil repellents are the polymers of phthalic acid and/or terephthalic acid and their derivatives known from the prior art, in particular polymers of ethylene terephthalate and/or polyethylene glycol terephthalate or anionically and/or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of the phthalic acid and terephthalic acid polymers are particularly preferred.
  • Optical brighteners can be added to detergents in particular to eliminate greying and yellowing of the treated textiles. These substances absorb into the fibres and cause a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible, longer-wave light. The ultraviolet light absorbed from sunlight is emitted as a weak bluish fluorescence and, together with the yellow tone of the greyed or yellowed laundry, produces pure white.
  • Suitable compounds come, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyryl-biphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole and benzimidazole systems as well as pyrene derivatives substituted by heterocycles.
  • fluor acids 4,4'-diamino-2,2'-stilbenedisulfonic acids
  • 4,4'-distyryl-biphenyls 4,4'-distyryl-biphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole and benzimidazo
  • the purpose of greying inhibitors is to keep the dirt that has been detached from the fiber suspended in the liquor and thus prevent the dirt from being reabsorbed.
  • Water-soluble colloids usually of an organic nature, are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of 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 can also be used, for example degraded starch and aldehyde starches.
  • Polyvinylpyrrolidone can also be used.
  • Cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof can also be used as greying inhibitors.
  • synthetic anti-crease agents can be used. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.
  • Repellents and impregnating processes are used to equip textiles with substances that prevent dirt from settling or make it easier to wash out.
  • Preferred repellents and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum and zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol components or polymerizable compounds coupled with perfluorinated acyl or sulfonyl residues.
  • Antistatic agents can also be included. Dirt-repellent treatment with repellents and impregnating agents is often classified as easy-care treatment. The penetration of the impregnating agents in the form of solutions or emulsions of the active ingredients in question can be facilitated by adding wetting agents that reduce the surface tension.
  • hydrophobic agents used for hydrophobic treatment coat textiles, leather, paper, wood, etc. with a very thin layer of hydrophobic groups, such as long alkyl chains or siloxane groups. Suitable hydrophobic agents include paraffins, waxes, metal soaps, etc.
  • Antimicrobial agents can be used to combat microorganisms. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, and so on. Substances from these groups include benzalkonium chlorides, alkylarylsulfonates, halogen phenols and phenol mercuriacetate, although these compounds can also be dispensed with entirely.
  • the agents contain antioxidants.
  • This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
  • Antistatic agents increase surface conductivity and thus enable charges to flow away more easily.
  • External antistatic agents are usually substances with at least one hydrophilic molecular ligand and form a more or less hygroscopic film on the surface.
  • These antistatic agents which are mostly surface-active, can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulphur-containing (alkyl sulphonates, alkyl sulphates) antistatic agents.
  • Lauryl (or stearyl) dimethylbenzylammonium chlorides are also suitable as antistatic agents for textiles or as an additive to detergents, where an additional conditioning effect is achieved.
  • Silicone derivatives can be used in textile detergents to improve the water absorption capacity, the rewettability of the treated textiles and to make ironing the treated textiles easier. These also improve the rinsing behavior of washing or cleaning agents through their foam-inhibiting properties.
  • Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes, in which the alkyl groups have one to five carbon atoms and are fully or partially fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and/or Si-Cl bonds.
  • Other preferred silicones are polyalkylene oxide-modified polysiloxanes, i.e. polysiloxanes which contain, for example, polyethylene glycols, and polyalkylene oxide-modified dimethylpolysiloxanes.
  • UV absorbers can also be used, which are absorbed onto the treated textiles and improve the light resistance of the fibers.
  • Compounds that have these desired properties are, for example, compounds that are effective through radiation-free deactivation and derivatives of benzophenone with substituents in the 2- and/or 4-position.
  • Substituted benzotriazoles, acrylates substituted by phenyl in the 3-position (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid are also suitable.
  • Protein hydrolysates are other suitable active substances due to their fiber-care effect. Protein hydrolysates are product mixtures that are obtained by acidic, basic or enzymatically catalyzed degradation of proteins. Protein hydrolysates of both plant and animal origin can be used. Animal protein hydrolysates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolysates, which can also be present in the form of salts. The use of protein hydrolysates of plant origin is preferred. Origin, for example soy, almond, rice, pea, potato and wheat protein hydrolysates.
  • protein hydrolysates as such is preferred, amino acid mixtures obtained from other sources or individual amino acids such as arginine, lysine, histidine or pyroglutamic acid can also be used instead.
  • amino acid mixtures obtained from other sources or individual amino acids such as arginine, lysine, histidine or pyroglutamic acid can also be used instead.
  • derivatives of protein hydrolysates is also possible, for example in the form of their fatty acid condensation products.
  • Washing tests were carried out at 30 °C on cotton fabrics with various standardised stains based on polyphenolic natural dyes as shown in Table 1 below.
  • a commercially available liquid detergent (FWM) containing no bleach and surfactants was used for the washing tests and washing liquors with a pH of 8.5 were prepared, consisting of 15 g FWM and, if necessary, 0.225 g of the active ingredient prepared in Example 1.B to 17 l of water at 16 °dH.
  • the evaluation was carried out by measuring the colour difference according to the L*a*b* values and the Y values calculated from them as a measure of the brightness.
  • dY values when an active ingredient used according to the invention was added were always higher than the values achieved with the FWM without additive, which corresponds to a higher degree of whiteness and thus improved stain removal.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Detergent Compositions (AREA)

Claims (10)

  1. Utilisation de composés de formule générale (I),
    Figure imgb0011
     où R1, R2, R3 et R4 représentent indépendamment les uns des autres l'hydrogène ou un radical hydrocarboné cyclique ou acyclique, linéaire ou ramifié, aliphatique ou aromatique, comportant 1 à 20, de préférence 1 à 10 atomes de carbone, dans des agents de lavage ou de nettoyage pour l'amélioration de la performance de lavage ou de nettoyage vis-à-vis de salissures pouvant être blanchies.
  2. Utilisation selon la revendication 1, caractérisée en ce que les salissures contiennent des substances polymérisables choisies parmi des colorants polyphénoliques, en particulier parmi des flavonoïdes, particulièrement parmi des colorants de la classe des anthocyanidines ou anthocyanes ou oligomères desdits composés.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que la performance de lavage ou de nettoyage améliorée consiste en une élimination améliorée de salissures de couleur verte, jaune, rouge, bleue, violette, mauve, brune, pourpre ou rose, en particulier de taches d'herbe, fruits ou légumes, en particulier de salissures causées par des produits alimentaires, tels qu'épices, sauces, chutneys, currys, purées et confitures, ou par des boissons, telles que café, thé, vins et jus qui contiennent des colorants verts, jaunes, rouges, violets, mauves, bruns, pourpres, roses et/ou bleus correspondants.
  4. Utilisation selon l'une des revendications 1 à 3, caractérisée en ce que les salissures sont choisies parmi des salissures causées par de la cerise, morelle, raisin, pomme, grenade, aronia, prune, argousier, açaï, kiwi, mangue, herbe ou baies, en particulier causées par des groseilles ou cassis, baies de sureau, mûres, framboises, bleuets, airelles, canneberges, fraises ou myrtilles, par du café, thé, chou rouge, orange sanguine, aubergine, tomate, carotte, betterave rouge, épinard, poivron, pomme de terre à chair rouge ou bleue, ou oignon rouge.
  5. Agent de lavage ou de nettoyage, contenant un tensioactif et 0,001 % en poids à 20 % en poids d'un composé de formule générale (I),
    Figure imgb0012
     où R1, R2, R3 et R4 représentent indépendamment les uns des autres l'hydrogène ou un radical hydrocarboné cyclique ou acyclique, linéaire ou ramifié, aliphatique ou aromatique, comportant 1 à 20 atomes de carbone.
  6. Agent selon la revendication 5, caractérisé en ce qu'il contient 0,01 % en poids à 10 % en poids d'un composé de formule générale (I).
  7. Agent selon la revendication 5 ou 6, caractérisé en ce qu'il ne contient aucun agent de blanchiment oxydant au sens strict, c'est-à-dire hypochlorites, peroxyde d'hydrogène ou substances générant du peroxyde d'hydrogène et acides peroxyliques.
  8. Agent selon l'une des revendications 5 à 7, caractérisé en ce qu'il est un agent de lavage pour textiles liquide, en particulier un agent de lavage pour couleurs liquide, ou un agent de lavage pour couleurs en poudre.
  9. Agent selon l'une des revendications 5 à 8, caractérisé en ce qu'il contient, outre le composé de formule générale (I), d'autres composants d'agents de lavage pour textiles choisis dans le groupe des adjuvants, polymères, enzymes, auxiliaires de désintégration, matières odorantes et supports de parfum.
  10. Utilisation selon l'une des revendications 1 à 4 ou agent selon l'une des revendications 5 à 9, caractérisé en ce que, dans les composés de formule générale (I), R1 et R3 et/ou R2 et R4 sont identiques, et/ou en ce que R1, R2, R3 et R4 sont choisis indépendamment les uns des autres parmi l'hydrogène, le groupe méthyle, le groupe éthyle, le groupe n-propyle et le groupe iso-propyle.
EP19801245.2A 2018-11-06 2019-11-04 Détergents et produits de nettoyage d'efficacité améliorée Active EP3877493B1 (fr)

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