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
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3784—(Co)polymerised monomers containing phosphorus

Definitions

• the present invention is related to the use of polymers comprising phosphono groups in washing and cleaning agents to improve their cleaning performance, in particular with regard to bleach-sensitive stains.
• stains containing polymerizable dyes are mostly red- to blue-colored stains.
• the polymerizable substances are above all polyphenolic dyes, preferably flavonoids, in particular from the class of anthocyanidins or anthocyanins.
• the stains can be caused in particular by food products or drinks containing corresponding dyes.
• the stains can be marks from fruit or vegetables or red wine marks containing red and/or blue dyes, in particular polyphenolic dyes, above all those from the class of anthocyanidins or anthocyanins.
• the present invention firstly provides the use of polymers, obtainable by radical induced polymerization of monomers according to formula I, in which, independently from each other, R 1 , R 2 and R 3 is H or an alkyl group with 1 to 4 C-atoms with the proviso that at least one of R 1 and R 2 is H, or by radical induced copolymerization of monomers of said formula I with co-monomers selected from the group consisting of compounds according to formula II, in which
• the present invention secondly provides for washing and cleaning detergents comprising said polymers and/or copolymers.
• “Bleach-sensitive stains” are understood to be stains which normally are removed, at least partially, by the action of conventional bleaching agents or bleaching agent systems, such as sodium perborate or sodium percarbonate, often used as a system in combination with so-called bleach activators such as tetraacetylethylenediamine or sodium nonanoyloxy benzene sulfonate, commonly used in detergents.
• Red- to blue-colored stains are understood to be stains which can have a color from the red to blue color spectrum.
• stains in the colors red or blue they include in particular stains in intermediate colors, in particular violet, lilac, purple or pink, in other words stains having a red, violet, lilac, purple, pink or blue tone, without themselves essentially consisting entirely of that color.
• the specified colors can in particular also be light or dark, i.e. possible colors include in particular light and dark red and light and dark blue.
• the stains to be preferably removed according to the invention can be caused in particular by cherries, red grapes, pomegranate, chokeberry, plums, sea buckthorn, acai or berries, in particular by redcurrants or blackcurrants, elderberries, blackberries, raspberries, blueberries, lingonberries, cowberries, strawberries or bilberries, red cabbage, blood orange, eggplant, black carrot, red- or blue-fleshed potatoes or red onions.
• both R 1 and R 2 are H, and/or R 3 is H.
• R 4 is H and R 5 is -C(O)-O-R 12 or -O-C(O)-R 13
• R 12 is H or a linear alkyl group with 1, 8 or 18 C-atoms
• R 13 is a methyl group.
• preferred monomers according to formula III are terpenes such as 1,3 butadiene and isoprene and their mixtures, preferably R 6 is a methyl group and R 7 is an ethenyl group.
• the polymers and copolymers used according to the invention are obtainable by free-radical polymerization of the ethylenically unsaturated monomers of the general formula I, if one so wishes with the co-monomers defined above. If they are not homopolymers, they may contain the units stemming from said monomers and said co-monomers in random distribution or they may comprise blocks each made up of one of the different monomeric units. Preferably, the copolymers used according to the invention consist only of monomeric units stemming from monomers and co-monomers defined above, apart from portions originating from customary radical chain initiators and terminators.
• the polymer or copolymer used according to the invention preferably has an average molar mass in the range from 1000 g/mol to 500,000 g/mol, in particular from 1000 g/mol to 250,000 g/mol.
• the average molar masses specified here and below, optionally for other polymers, are number-average molar masses M n , which can be determined in principle by gel permeation chromatography using an RI detector, the measurement conveniently being performed against an external standard. It preferably comprises units stemming from monomers according to formula I and units stemming from co-monomers defined above in molar ratios in the range of from 100:0 to 60:40, preferably from 90:10 to 70:30.
• the polymers and copolymers defined above are preferably used in washing or cleaning detergents in an amount in a range of from 0.01 wt.% to 5 wt.%, in particular in a range of from 0.1 wt.% to 2 wt.%, wherein here and below the figures given as "wt.%" refer in each case to the weight of the total washing or cleaning detergent.
• the washing or cleaning detergent can be present in any presentation form that is established according to the prior art and/or any convenient presentation form.
• presentation forms include for example solid, powdered, liquid, gel or paste presentation forms, optionally also consisting of a plurality of phases, compressed or not compressed; they also include, for example: extrudates, granules, tablets or pouches, packed both in bulk containers and in portions.
• the use according to the invention occurs in a washing or cleaning detergent containing no bleaching agent.
• the detergent according to the invention contains no bleaching agent in the narrower sense, in other words hydrogen peroxide or substances yielding hydrogen peroxide in aqueous systems; it preferably also contains no bleach activators and/or bleach catalysts.
• the detergent according to the invention is a liquid detergent for washing textiles.
• the detergent according to the invention is a powdered color detergent, in other words a powdered detergent for washing colored textiles.
• washing and cleaning detergents according to the invention can moreover contain other conventional constituents of washing and cleaning agents, in particular textile washing agents, selected in particular from the group of builders, surfactants, polymers, enzymes, disintegrating agents, scents and perfume carriers.
• the builders include in particular zeolites, silicates, carbonates, organic cobuilders and - provided there are no ecological prejudices against their use - phosphates.
• the finely crystalline, synthetic zeolite containing bound water is preferably zeolite A and/or zeolite P.
• zeolite A and/or zeolite P are zeolite MAP® (a commercial product from Crosfield).
• Zeolite X and mixtures of zeolite A, X and/or P are also suitable, however.
• a co-crystallisate of zeolite X and zeolite A (approx.
• 80 wt.% zeolite X for example, which can be described by the formula nNa 2 O ⁇ (1-n)K 2 O ⁇ Al 2 O 3 ⁇ (2 - 2.5)SiO 2 ⁇ (3.5 - 5.5)H 2 O is commercially available and can be used in the context of the present invention.
• the zeolite can be used both as a builder in a granular compound and also to achieve a type of "powdering" of a granular mixture, preferably of a compressible mixture, wherein both methods of incorporating the zeolite into the pre-mixture are conventionally used.
• Zeolites can have an average particle size of less than 10 ⁇ m (volume distribution; measurement 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 ⁇ yH 2 O can also be used, in which M denotes sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, more preferred values for x being 2, 3 or 4, and y denotes a number from 0 to 33, preferably from 0 to 20.
• the crystalline layered silicates of the formula NaMSi x O 2x+1 ⁇ yH 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 ⁇ xH 2 O, kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 ⁇ xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 ⁇ x H 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 ⁇ xH 2 O, makatite).
• Crystalline phyllosilicates of the formula NaMSi x O 2x+1 ⁇ yH 2 O in which x denotes 2 are preferred.
• both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 ⁇ yH 2 O and moreover above all Na-SKS-5 ( ⁇ -Na 2 Si 2 O 5 ), Na-SKS-7 ( ⁇ -Na 2 Si 2 O 5 , natrosilite), Na-SKS-9 (NaHSi 2 O 5 ⁇ H 2 O), Na-SKS-10 (NaHSi 2 O 5 ⁇ 3H 2 O, kanemite), Na-SKS-11 (t-Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ) are suitable, but in particular Na-SKS-6 ( ⁇ -Na 2 Si 2 O 5 ).
• Washing or cleaning agents preferably contain a proportion by weight of the crystalline layered silicate of the formula NaMSi x O 2x+1 ⁇ yH 2 O from 0.1 wt.% to 20 wt.%, preferably from 0.2 wt.% to 15 wt.% and in particular from 0.4 wt.% to 10 wt.%.
• Amorphous sodium silicates having an Na 2 O : SiO 2 modulus from 1:2 to 1:3.3, preferably from 1:2 to 1:2.8 and in particular from 1:2 to 1:2.6, which preferably have a delayed solubility and secondary washing properties, can also be used.
• the delayed solubility in comparison to conventional amorphous sodium silicates can be brought about in various ways, for example by surface treatment, compounding, compacting/compression or by overdrying.
• the term "amorphous" is understood to mean that in X-ray diffraction experiments the silicates do not yield sharp X-ray reflexes, as is typical of crystalline substances, but rather at most give rise to one or more maxima of the scattered X-ray radiation having a width of several degree units of the diffraction angle.
• X-ray-amorphous silicates can be used whose silicate particles yield intergrown or even sharp diffraction maxima in electron diffraction experiments. This should be interpreted to mean that the products have microcrystalline regions of ten to some hundred nm in size, with values of up to max. 50 nm and in particular up to max. 20 nm being preferred.
• Such X-ray-amorphous silicates likewise have a delayed solubility in comparison to the conventional water glasses. Compressed/compacted amorphous silicates, compounded amorphous silicates and overdried X-ray-amorphous silicates are preferred in particular.
• this (these) silicate(s), preferably alkali silicates, more preferably crystalline or amorphous alkali disilicates, are included in washing or cleaning agents in amounts from 3 wt.% to 60 wt.%, preferably from 8 wt.% to 50 wt.% and in particular from 20 wt.% to 40 wt.%.
• phosphates as builder substances are also possible, provided that such a use is not to be avoided on ecological grounds.
• alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest significance in the washing and cleaning agents industry.
• Alkali metal phosphates is the summary term for the alkali metal (in particular sodium and potassium) salts of the various phosphoric acids, among which it is possible to differentiate between metaphosphoric acids (HPO 3 ) n and orthophosphoric acids H 3 PO 4 and higher-molecular-weight representatives.
• the phosphates combine several advantages: they act as alkali carriers, prevent limescale deposits on machine parts or limescale encrustations in fabrics and in addition contribute to the cleaning performance.
• Particularly important phosphates in industry 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 also preferably used. If phosphates are used in washing or cleaning agents, preferred agents contain this (these) phosphate(s), preferably alkali metal phosphate(s), more preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts from 5 wt.% to 80 wt.%, preferably from 15 wt.% to 75 wt.% and in particular from 20 wt.% to 70 wt.%.
• phosphate(s) preferably alkali metal phosphate(s), more preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate)
• 5 wt.% to 80 wt.% preferably from 15 wt.% to 75 wt.% and in particular from 20 wt.% to 70 wt.%.
• Alkali carriers can also be used.
• Alkali carriers include for example alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, the cited alkali silicates, alkali metasilicates and mixtures of the aforementioned substances, with alkali carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, preferably being used.
• a builder system containing a mixture of tripolyphosphate and sodium carbonate can be more preferred.
• the alkali metal hydroxides are conventionally used in only small amounts, preferably in amounts below 10 wt.%, preferably below 6 wt.%, more preferably below 4 wt.% and in particular below 2 wt.%. Agents containing relative to their total weight less than 0.5 wt.% and in particular no alkali metal hydroxides are more preferred.
• Polycarboxylates/polycarboxylic acids polymeric polycarboxylates, aspartic acid, polyacetals, dextrins and phosphonates can be mentioned in particular as organic cobuilders.
• the polycarboxylic acids which can be used in the form of the free acid and/or its sodium salts, polycarboxylic acids being understood to be those carboxylic acids carrying more than one acid function, can be used for example.
• citric acid for example 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 a use is not to be opposed on ecological grounds, and mixtures thereof.
• NTA nitrilotriacetic acid
• the free acids typically also have the characteristic of an acidifying component and are thus also used to establish a lower and milder pH in washing or cleaning agents.
• Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof are to be cited here in particular.
• polymeric polycarboxylates such as for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molar mass from 500 g/mol to 70,000 g/mol.
• Polyacrylates which preferably have a molar mass from 2000 g/mol to 20,000 g/mol, are suitable in particular. Of this group, owing to their superior solubility, preference can in turn be given to the short-chain polyacrylates having molar masses from 2000 g/mol to 10,000 g/mol and more preferably from 3000 g/mol to 5000 g/mol.
• copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
• Copolymers of acrylic acid with maleic acid containing 50 wt.% to 90 wt.% of acrylic acid and 50 wt.% to 10 wt.% of maleic acid have proved to be particularly suitable.
• Their relative molar mass, relative to free acids is generally 2000 g/mol to 70,000 g/mol, preferably 20,000 g/mol to 50,000 g/mol and in particular 30,000 g/mol to 40,000 g/mol.
• the polymers can also contain allyl sulfonic acids, such as for example allyloxybenzenesulfonic acid and methallyl sulfonic 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 wt.% to 20 wt.% and in particular 3 wt.% to 10 wt.%.
• Biodegradable polymers consisting of more than two different monomer units are also preferred in particular, for example those containing as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or those containing as monomers salts of acrylic acid and 2-alkyl allyl sulfonic acid and sugar derivatives.
• Further preferred copolymers are those having acrolein and acrylic acid/acrylic acid salts or acrolein and vinyl acetate as monomers.
• Also to be mentioned as further preferred builder substances are polymeric amino dicarboxylic acids, the salts thereof or the precursor substances thereof. Polyaspartic acids or salts thereof are more preferred.
• polyacetals which can be obtained by reacting dialdehydes with polyol carboxylic acids having 5 to 7 C atoms and at least 3 hydroxyl groups.
• Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic 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 performed by conventional methods, for example acid- or enzyme-catalyzed methods.
• the hydrolysis products preferably have average molar masses in the range from 400 g/mol to 500,000 g/mol.
• DE dextrose equivalent
• Both maltodextrins having a DE of between 3 and 20 and dry glucose syrups having a DE of between 20 and 37 and also yellow dextrins and white dextrins having elevated molar masses in the range from 2000 g/mol to 30,000 g/mol can be used.
• the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
• Ethylenediamine-N,N'-disuccinate (EDDS) is preferably used here in the form of its sodium or magnesium salts.
• glycerol disuccinates and glycerol trisuccinates are also preferred in this context.
• suitable amounts to be used, in particular in formulations containing zeolites and/or silicates are 3 wt.% to 15 wt.%.
• organic cobuilders which can be used are for example acetylated hydroxycarboxylic acids or salts thereof which can optionally also be present in the lactone form and which contain at least four carbon atoms and at least one hydroxyl group as well as a maximum of two acid groups.
• Washing and cleaning agents can contain non-ionic, anionic, cationic and/or amphoteric surfactants.
• non-ionic surfactants known to the person skilled in the art can be used as non-ionic surfactants. Washing or cleaning agents contain to particular advantage non-ionic surfactants from the group of alkoxylated alcohols.
• Alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 C atoms and on average 1 to 12 mol of ethylene oxide (EO) per mol of alcohol are preferably used as non-ionic surfactants, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched residues in the mixture, such as are conventionally present in oxoalcohol residues.
• alcohol ethoxylates having linear residues obtained from alcohols of native origin having 12 to 18 C atoms, for example from coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 mol of EO per mol of alcohol are preferred in particular.
• the preferred ethoxylated alcohols include, for example, C 12-14 alcohols having 3 EO or 4 EO, C 9-11 alcohol having 7 EO, C 13-15 alcohols having 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols having 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol having 3 EO and C 12-18 alcohol having 5 EO.
• the specified degrees of ethoxylation are statistical averages which for an individual product can correspond to a whole number or a fraction.
• Preferred alcohol ethoxylates have a narrow homolog distribution (narrow-range ethoxylates, NRE).
• fatty alcohols having more than 12 EO can also be used. Examples thereof are tallow fatty alcohol having 14 EO, 25 EO, 30 EO or 40 EO.
• Alkyl glycosides of the general formula RO(G) x can moreover be used as further non-ionic surfactants, in which R corresponds to a primary straight-chain or methyl-branched aliphatic residue, in particular one methyl-branched in the 2-position, having 8 to 22, preferably 12 to 18 C atoms, and G is the symbol denoting 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; x is preferably 1.2 to 1.4.
• non-ionic surfactants which are used either as the only non-ionic surfactant or in combination with other non-ionic surfactants, is alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain.
• Non-ionic surfactants of the amine oxide type for example N-cocoalkyl-N,N-dimethyl amine oxide and N-tallow alkyl-N,N-dihydroxyethyl amine oxide, and of the fatty acid alkanol amide type can also be used.
• the amount of these non-ionic surfactants is preferably no more than that of the ethoxylated fatty alcohols, in particular no more than half that.
• polyhydroxy fatty acid amides of the formula in which R denotes an aliphatic acyl residue having 6 to 22 carbon atoms, R 1 denotes hydrogen, an alkyl or hydroxyalkyl residue having 1 to 4 carbon atoms and [Z] denotes a linear or branched polyhydroxyalkyl residue having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
• the polyhydroxy fatty acid amides are known substances which can conventionally be obtained by reductive amination of a reducing sugar with ammonia, an alkyl amine or an alkanol amine 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 denotes a linear or branched alkyl or alkenyl residue having 7 to 12 carbon atoms, R 1 denotes a linear, branched or cyclic alkyl residue or an aryl residue having 2 to 8 carbon atoms and R 2 denotes a linear, branched or cyclic alkyl residue or an aryl residue or an oxyalkyl residue having 1 to 8 carbon atoms, C 1-4 alkyl or phenyl residues being preferred, and [Z] denotes a linear polyhydroxyalkyl residue, whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.
• [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• the N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
• Non-ionic surfactants from the group of alkoxylated alcohols are preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO/AO/EO non-ionic surfactants, or PO/AO/PO non-ionic surfactants, especially PO/EO/PO non-ionic surfactants, are more preferred in cleaning agents.
• Such PO/EO/PO non-ionic surfactants are characterized by good foam control.
• Surfactants of the sulfonate and sulfate type for example are used as anionic surfactants.
• Suitable surfactants of the sulfonate type are preferably C 9-13 alkylbenzene sulfonates, olefin sulfonates, i.e. mixtures of alkene and hydroxyalkane sulfonates, and disulfonates, such as are obtained for example from C 12-18 monoolefins having a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products.
• alkane sulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
• esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
• Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
• Fatty acid glycerol esters are understood to be the mono-, di- and triesters and mixtures thereof, such as are obtained in the production by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the interesterification of triglycerides with 0.3 to 2 mol of glycerol.
• Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example of hexanoic acid, octanoic acid, decanoic acid, myristic acid, lauric acid, palmitic acid, stearic acid or docosanoic acid.
• alkali and in particular the sodium salts of the sulfuric acid semi-esters of C 12 -C 18 fatty alcohols for example of coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or of C 10 -C 20 oxoalcohols and the semi-esters of secondary alcohols of those chain lengths are preferred as alk(en)yl sulfates.
• alk(en)yl sulfates of the specified chain length containing a synthetic, straight-chain alkyl residue produced on a petrochemical basis which have an analogous degradation behavior to the appropriate compounds based on fat chemistry raw materials. From a detergent perspective the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
• the sulfuric acid monoesters of 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 mol of ethylene oxide (EO) or C 12-18 fatty alcohols having 1 to 4 EO, are also suitable. Owing to their high foaming characteristics they are used in cleaning agents in only relatively small amounts, for example in amounts from 1 wt.% to 5 wt.%.
• Suitable anionic surfactants are also the salts of alkyl sulfosuccinic acid, which are also known as sulfosuccinates or 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 thereof.
• Sulfosuccinates that are preferred in particular contain a fatty alcohol residue derived from ethoxylated fatty alcohols which are non-ionic surfactants in their own right.
• sulfosuccinates whose fatty alcohol residues derive from ethoxylated fatty alcohols having a narrow homolog distribution are more preferred. It is likewise also possible to use alk(en)yl succinic acid having preferably 8 to 18 carbon atoms in the alk(en)yl chain or salts thereof.
• Suitable anionic surfactants are in particular soaps.
• Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and docosanoic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
• the anionic surfactants including the soaps can be present 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 their sodium salts.
• Cationic and/or amphoteric surfactants can also be used in place of or in conjunction with the specified surfactants.
• Textile-softening compounds can be used to care for the textiles and to improve textile properties such as a softer "touch” (finishing) and reduced electrostatic charge (increased wear comfort).
• the active ingredients of these formulations are quaternary ammonium compounds having two hydrophobic residues, such as for example distearyl dimethyl ammonium chloride, which, however, because of its unsatisfactory biodegradability is increasingly being replaced by quaternary ammonium compounds containing in their hydrophobic residues ester groups as predetermined breaking points for biodegradation.
• esterquats having improved biodegradability are obtainable for example by esterifying mixtures of methyl diethanolamine and/or triethanolamine with fatty acids and then quaternizing the reaction products in a manner known per se with alkylating agents.
• Dimethylol ethylene urea is also suitable as a finishing agent.
• Enzymes can be used to increase the washing or cleaning performance of washing or cleaning agents. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are of natural origin in principle; starting from the natural molecules, improved variants are available for use in washing and cleaning agents which accordingly are preferably used. Washing or cleaning agents preferably contain enzymes in total amounts of 1 x 10 -6 wt.% to 5 wt.%, relative to active protein. The protein concentration can be determined with the aid of known methods, for example the BCA method or the Biuret method.
• subtilisins those of the subtilisin type are preferred.
• subtilisins BPN' and Carlsberg and the developed forms thereof 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 can be assigned to the subtilases but no longer in the narrower sense to the subtilisins.
• amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae, and the further developments of the aforementioned amylases improved for use in washing and cleaning agents. Furthermore, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) can be mentioned for this purpose.
• Lipases or cutinases can be used because of their triglyceride-cleaving activity. These include for example the lipases obtainable originally from Humicola lanuginosa (Thermomyces lanuginosus) or the further developments thereof, in particular those with the amino acid exchange D96L. Furthermore, the cutinases that were originally isolated from Fusarium solani pisi and Humicola insolens can also be used, for example. Lipases 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 (phenoloxidases, polyphenoloxidases) can be used if desired.
• organic, more preferably aromatic compounds which interact with the enzymes are advantageously additionally added to strengthen the activity of the oxidoreductases concerned (enhancers) or to ensure the flow of electrons in the case of very differing redox potentials between the oxidizing enzymes and the stains (mediators).
• the enzymes can be used in any form established according to the prior art. These include for example the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of agents in liquid or gel form, solutions of the enzymes, advantageously as concentrated as possible, with a low water content and/or mixed with stabilizers.
• the enzymes can alternatively be encapsulated, 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 in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer which is impermeable to water, air and/or chemicals.
• Further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, can additionally be applied in superimposed layers.
• Such capsules are applied by methods known per se, for example by vibrating or roll granulation or in fluidized-bed processes.
• Such granules are advantageously low in dust, for example through the application of polymeric film formers, and stable in storage because of the coating. It is also possible to make up two or more enzymes together so that a single granulated product has multiple enzyme activities.
• One or more enzymes and/or enzyme preparations are preferably used in amounts from 0.1 wt.% to 5 wt.%, preferably from 0.2 wt.% to 4.5 wt.% and in particular from 0.4 wt.% to 4 wt.%.
• fragrance compounds for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or scents. Mixtures of different fragrances which together generate an attractive scent note are preferably used, however. Such perfume oils can also contain natural fragrance mixtures, such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
• a fragrance In order to be perceptible, a fragrance must be volatile, wherein in addition to the nature of the functional groups and the structure of the chemical compound, the molar mass also plays an important role. Thus, most fragrances have molar masses of up to approx. 200 g/mol, whereas molar masses of 300 g/mol and above constitute an exception.
• the odor of a perfume or scent composed of a plurality of fragrances changes as it evaporates, wherein the odor impressions are divided into “top note”, “middle note” or “body”, and “end note” or “dry-out”.
• the top note of a perfume or scent does not consist solely of highly volatile compounds, whereas the end note consists largely of less volatile, i.e. fixative, fragrances.
• more highly volatile fragrances can be bound for example to certain fixatives, thus preventing their too rapid evaporation.
• fragrances into "more highly volatile” or “fixative” fragrances says nothing about the odor impression or whether the corresponding fragrance is perceived as a top note or middle note.
• the scents can be processed directly, but it can also be advantageous to apply the scents to carriers, which through a slower release of the scent ensure a long-lasting scent.
• Cyclodextrins for example have proved effective as such carrier materials, wherein the cyclodextrin perfume complexes can also additionally be layered with further auxiliary agents.
• coloring agents can have a high storage stability and photostability and not too strong an affinity to textile surfaces and in particular to synthetic fibers.
• coloring agents can exhibit differing levels of oxidation stability.
• non-water-soluble coloring agents have a greater oxidation stability than water-soluble coloring agents.
• concentration of the coloring agent in the washing or cleaning agents varies, depending on the solubility and hence also on the oxidation sensitivity. In the case of readily water-soluble coloring agents, coloring agent concentrations in the range from a few 10 -2 wt.% to 10 -3 wt.% are typically chosen.
• the suitable concentration of the coloring agent in washing or cleaning agents is typically a few 10 -3 wt.% to 10 -4 wt.%.
• Coloring agents which can be broken down by oxidation in the washing process and mixtures thereof with suitable blue dyes known as blue toners are preferred. It has proved advantageous to use coloring agents that are soluble in water or at room temperature in liquid organic substances.
• anionic coloring agents e.g. anionic nitroso dyes, are suitable.
• the washing or cleaning agents can contain further ingredients which further improve the applicational and/or aesthetic properties of said 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, anti-shrink agents, anti-crease agents, dye transfer inhibitors, antimicrobial active ingredients, germicides, fungicides, antioxidants, antistatics, ironing aids, phobing and impregnating agents, non-swelling and anti-slip agents and UV absorbers.
• a large number of the most diverse salts can be used as electrolytes from the group of inorganic salts.
• Preferred cations are the alkali and alkaline-earth metals, while preferred anions are the halides and sulfates. From a manufacturing perspective the use of NaCl or MgCl 2 in the washing or cleaning agents is preferred.
• pH adjusters can be indicated in order to bring the pH of washing or cleaning agents into the desired range. All known acids or bases can be used here, provided that their use is not prohibited on applicational or ecological grounds or for reasons of consumer protection. The amount of these adjusters does not usually exceed 1 wt.% of the total formulation.
• Inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the aforementioned materials, for example, are suitable as carrier materials.
• preferred agents contain paraffins, preferably unbranched paraffins (n-paraffins) and/or silicones, preferably linear-polymer silicones, which are structured in accordance with the scheme (R 2 SiO) x and are also known as silicone oils.
• silicone oils are usually clear, colorless, neutral, odor-free, hydrophobic liquids having a molecular weight of between 1000 g/mol and 150,000 g/mol and viscosities of between 10 mPa ⁇ s and 1,000,000 mPa ⁇ s.
• Suitable anti-redeposition agents are for example non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose having a methoxy group content of 15 to 30 wt.% and a hydroxypropyl group content of 1 to 15 wt.%, relative in each case to the non-ionic cellulose ethers.
• polymers of phthalic acid and/or terephthalic acid and derivatives thereof in particular polymers of ethylene terephthalate and/or polyethylene glycol terephthalate, or anionically and/or non-ionically modified derivatives thereof, known from the prior art are suitable as soil repellents.
• the sulfonated derivatives of phthalic acid and terephthalic acid polymers are preferred in particular.
• Optical brighteners can be added to washing agents in particular to eliminate graying and yellowing of the treated textiles. These substances attach to the fibers and bring about a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible light of a longer wavelength, wherein the ultraviolet light absorbed from sunlight is radiated as a weakly bluish fluorescence and forms pure white with the yellow tone of grayed or yellowed laundry.
• Suitable compounds are derived for example from the substance classes of 4,4'-diamino-2,2'-stilbene disulfonic acids (flavonic acids), 4,4'-distyryl biphenylene, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diaryl pyrazolines, naphthalic acid imides, benzoxazole, benzisoxazole and benzimidazole systems and the pyrene derivatives substituted by heterocyclic compounds.
• flavonic acids 4,4'-diamino-2,2'-stilbene disulfonic acids
• 4,4'-distyryl biphenylene methylumbelliferones
• coumarins dihydroquinolinones
• 1,3-diaryl pyrazolines 1,3-diaryl pyrazolines
• naphthalic acid imides benzoxazole, benzisoxazole and benzimidazole systems
• graying inhibitors The role of graying inhibitors is to hold the dirt released by the fibers suspended in the liquor and thus to prevent the dirt from reattaching.
• Water-soluble colloids mostly 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 acid sulfuric acid esters of cellulose or starch.
• Water-soluble polyamides containing acid groups are also suitable for this purpose. Soluble starch preparations can moreover be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
• cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof can be used as graying inhibitors.
• synthetic anti-crease agents can be used. These include for example synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty alkylol esters, fatty alkylol amides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.
• Phobing and impregnating methods serve to treat textiles with substances which prevent dirt from being deposited or make it easier to wash out.
• Preferred phobing and impregnating agents are perfluorinated fatty acids, also in the form of the aluminum and zirconium salts thereof, organic silicates, silicones, polyacrylic acid esters with a perfluorinated alcohol component or polymerizable compounds coupled with a perfluorinated acyl or sulfonyl residue.
• Antistatics can also be included.
• the dirt-repellent treatment with phobing and impregnating agents is often classed as an easy-care treatment.
• hydrophobing and impregnating agents are used for hydrophobing coat textiles, leather, paper, wood, etc. with a very thin layer of hydrophobic groups, such as relatively long alkyl chains or siloxane groups.
• Suitable hydrophobing agents are for example paraffins, waxes, metal soaps, etc., with additions of aluminum or zirconium salts, quaternary ammonium compounds having long-chain alkyl residues, urea derivatives, fatty acid-modified melamine resins, chromium complex salts, silicones, organotin compounds and glutardialdehyde as well as perfluorinated compounds.
• the hydrophobed materials do not feel greasy, but - as on greased materials - water droplets roll off them without wetting them.
• silicone-impregnated textiles for example have a soft feel and are water- and dirt-repellent; marks from ink, wine, fruit juices and the like are easier to remove.
• Antimicrobial active ingredients can be used to combat microorganisms.
• Substances from these groups are, for example, benzalkonium chlorides, alkylaryl sulfonates, halogen phenols and phenol mercuriacetate, wherein these compounds can also be dispensed with entirely.
• the agents can contain antioxidants to prevent undesirable changes to the washing and cleaning agents and/or to the treated textiles caused by exposure to atmospheric oxygen and by other oxidative processes.
• This class of compounds includes for example substituted phenols, hydroquinones, catechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
• Antistatics increase the surface conductivity and thus allow an improved discharge of charges that are formed.
• External antistatics are generally substances having at least one hydrophilic molecule ligand and they form a more or less hygroscopic film on the surfaces. These mostly interfacially active antistatics can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatics. Lauryl (or stearyl) dimethyl benzyl ammonium chlorides are likewise suitable as antistatics for textiles or as an addition to washing agents, with a finishing effect additionally being achieved.
• Silicone derivatives can be used in textile washing agents to improve the water absorbency and the rewettability of the treated textiles and to make it easier to iron the treated textiles. Through their foam-inhibiting properties they additionally improve the rinsing behavior of washing or cleaning agents.
• Preferred silicone derivatives are for example polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five C atoms and are wholly or partially fluorinated.
• Preferred silicones are polydimethyl siloxanes, which can optionally be derivatized and are then amino-functional or quaternized or which have Si-OH, Si-H and/or Si-Cl bonds.
• Further preferred silicones are the polyalkylene oxide-modified polysiloxanes, in other words polysiloxanes, which for example contain polyethylene glycols, and the polyalkylene oxide-modified dimethyl polysiloxanes.
• UV absorbers which attach to the treated textiles and improve the light resistance of the fibers
• Compounds having these desired properties are for example the compounds and derivatives of benzophenone having substituents in the 2- and/or 4-position which act by non-radiative deactivation.
• substituted benzotriazoles, acrylates substituted with phenyl in the 3-position (cinnamic acid derivatives), optionally having cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and urocanic acid, which is produced naturally in the body, are also suitable.
• protein hydrolysates are further suitable active substances.
• Protein hydrolysates are mixtures of products which are obtained by acidically, basically or enzymatically catalyzed breakdown 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 hydrolysates, which can also be present in the form of salts.
• protein hydrolysates as such is preferred, amino acid mixtures obtained by other means or individual amino acids such as for example arginine, lysine, histidine or pyroglutamic acid can optionally be used in their place.
• amino acid mixtures obtained by other means or individual amino acids such as for example arginine, lysine, histidine or pyroglutamic acid can optionally be used in their place.
• derivatives of protein hydrolysates for example in the form of their fatty acid condensation products, is likewise possible.
• the values obtained with the detergents comprising the polymers according to invention are greater than those obtained using only the liquid detergent; this corresponds to a higher degree of whiteness and hence to an improved stain removal.

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• 2018
  • 2018-07-27 EP EP18185930.7A patent/EP3599273A1/fr active Pending

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