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 relates to automatic dishwashing detergents and rinse aids. More particularly, the invention relates to automatic dishwashing detergents and rinse aids, as well as to dosage forms which provide detergents and rinse aids in a product containing certain polymers. These agents are hereinafter summarized under the generic term "detergent for machine dishwashing” or "automatic dishwashing detergent”.
• Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. So even a completely cleaned of leftovers dishes is then rated as not flawless if it has after dishwasher washing whitish, based on water hardness or other mineral salts stains that come from lack of wetting agent from dried water droplets.
• rinse aid In order to obtain glossy and spotless dishes, it is therefore successfully used today rinse aid.
• the addition of rinse aid at the end of the wash program ensures that the water runs as completely as possible from the items to be washed, so that the different surfaces at the end of the wash program are residue-free and flawless gloss.
• the automatic cleaning of dishes in household dishwashers usually includes a pre-wash, a main wash, and a rinse cycle interrupted by intermediate rinses.
• the pre-rinse for heavily soiled dishes is switchable, but is selected only in exceptional cases by the consumer, so that in most machines a main rinse, an intermediate rinse with pure water and a rinse cycle are performed.
• the temperature of the main wash cycle varies between 40 and 65 ° C, depending on the machine type and program level selection.
• rinse aids are added from a dosing tank in the machine, which usually contain nonionic surfactants as the main constituent. Such rinse aids are in liquid form and are widely described in the art. Your task consists primarily in limescale. and to prevent deposits on the cleaned dishes. In addition to water and low-foaming nonionic surfactants, these rinse aids often also contain hydrotopes, pH regulators such as citric acid or scale-inhibiting polymers.
• EP-B1 0 197 434 discloses liquid rinse aids which contain mixed ethers as nonionic surfactants.
• the dishwasher is a variety of different Materials (glass, metal, silver, plastic, porcelain) cleaned. This variety of materials must be wetted as well as possible in the rinse cycle.
• Rinse aid formulations which contain exclusively mixed ethers as surfactant component, do not meet these requirements or only to a small extent, so that the rinse effect or drying effect is not satisfactory especially for plastic surfaces.
• the storage tank in the dishwasher must be filled with rinse aid at regular intervals, with a filling sufficient for 10 to 50 rinses, depending on the machine type. If the filling of the tank is forgotten, then glasses in particular by lime stains and coverings become unsightly. In the prior art, therefore, there are some solutions proposed to integrate a rinse aid in the detergent for machine dishwashing. These proposed solutions are tied to the offer form of the compact molded article.
• European Patent Application EP-A-0 851 024 (Unilever) describes two-layer detergent tablets whose first layer contains peroxy bleach, builder and enzyme, while the second layer contains acidifying agent and a continuous medium having a melting point between 55 and 70 ° C and scale inhibitors contains. Due to the high-melting continuous medium, the acid (s) and scale inhibitor (s) are to be released with a delay and bring about a clear rinse effect. Powdered automatic dishwashing or surfactant-containing rinse systems are not mentioned in this document.
• the object of the present invention was to provide new rinse aid, which provide at least the same results in terms of performance properties as marketable rinse aid and also provide further performance benefits.
• the new rinse aid should be used both as conventional rinse aid and in the form of combination products and develop their advantageous properties regardless of the formulation.
• Last but not least, the use of the new rinse aids should also be possible in conventional automatic dishwashing detergents, i. the funds should also provide performance benefits as an additional component.
• the present invention therefore relates, in a first embodiment, to a machine dishwashing detergent comprising at least one polymer which is modified with phosphorus-containing groups, wherein the polymer in 1% strength by weight solution in distilled water at 20 ° C. has a pH of 20%. Value below 6.
• the compositions comprise at least one polymer which has P-containing groups and has a pH of less than 6 in 1% strength by weight solution in distilled water at 20 ° C.
• These polymers can come from different groups. Preference is given to polymers which have, in addition to unsaturated carboxylic acids, P-group-containing monomers as monomer building blocks. Preference is given to polymers which additionally contain further ionic or nonionic monomers.
• Preferred automatic dishwasher detergents according to the invention comprise a polymer of i) unsaturated carboxylic acids ii) monomers containing phosphate groups iii) optionally further ionic or nonionic monomers.
• unsaturated carboxylic acids of the formula I are preferred as the monomer
• R 1 to R 3 independently of one another are -H-CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
• the phosphate group-containing monomers can be described by the formula II,
• Preferred among these monomers are those of the formulas Ha, Mb and / or IIc,
• H 2 C CH-X-PO 4 H (Ha).
• H 2 C C (CH 3 ) -X-PO 4 H (Mb)
• H0 4 PX- (R 6 ) C C (R 7 ) -X-PO 4 H (IIc) in which R 6 and R 7 are independently selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2
• the polymers may contain further ionic or nonionic monomers.
• suitable compounds are vinylpyrrolidones, vinyl esters, vinyl acetate, alkylacrylamide, alkylaminoalkyl (meth) acrylic acid, cationically derivatized unsaturated carboxylic acids, acrylamidoalkyltrialkylammonium chloride, methacroylethylbetaine, crotonic acid, N-tert-butylacrylamide.
• the phosphate groups can 'be present wholly or partially in neutralized form, ie the acidic hydrogen atom of the phosphate group in some or all of phosphate groups against metal ions, preferably alkali metal ions and in particular with sodium ions can be exchanged. It is of course to pay attention to the observance of the pH value criterion.
• the monomer distribution in the copolymers in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight of i) or ii), particularly preferably from 50 to 90% by weight of monomer Group i) and 10 to 50 wt .-% monomer from group ii), each based on the polymer.
• terpolymers particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,
• the molecular weight of the polymers can be varied to match the properties of the polymers to the desired use.
• Preferred copolymers have molar masses of 2000 to 200,000 gmol “1 , preferably from 4000 to 25,000 gmol “ 1 and in particular from 5000 to 15,000 gmol "1 .
• a further preferred automatic dishwashing agent according to the invention is characterized in that it comprises a polymer of i) unsaturated carboxylic acids ii) monomers containing phosphonate groups iii) optionally further ionic or nonionogenic monomers.
• the phosphonate groups may be wholly or partially in neutralized form, i. the acidic hydrogen atom of the phosphonate group in some or all of the phosphonate groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. It is of course to pay attention to the observance of the pH value criterion.
• the monomer distribution in the copolymers in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight of i) or ii), particularly preferably from 50 to 90% by weight of monomer Group i) and 10 to 50 wt .-% monomer from group ii), each based on the polymer.
• terpolymers particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,
• the molecular weight of the polymers can be varied to match the properties of the polymers to the desired use.
• Preferred copolymers have molecular weights of 2000 to 200,000 gmol “1 , preferably from 4000 to 25,000 gmol " 1 and in particular from 5000 to 15,000 gmol "1 on.
• Another preferred machine dishwashing detergent according to the invention is characterized in that it comprises a polymer of i) unsaturated carboxylic acids ii) phosphite-containing monomers iii) optionally further ionic or non-ionogenic monomers.
• the phosphite groups may be wholly or partially in neutralized form, i. in that the acidic hydrogen atom of the phosphite group in some or all of the phosphite groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. It is of course to pay attention to the observance of the pH value criterion.
• the monomer distribution in the copolymers in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight of i) or ii), particularly preferably from 50 to 90% by weight of monomer Group i) and 10 to 50 wt .-% monomer from group ii), each based on the polymer.
• terpolymers particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,
• the molecular weight of the polymers can be varied to match the properties of the polymers to the desired use.
• Preferred copolymers have molar masses of 2000 to 200,000 gmol “1 , preferably from 4000 to 25,000 gmol “ 1 and in particular from 5000 to 15,000 gmol "1 .
• a further preferred automatic dishwashing agent according to the invention is characterized in that it comprises a polymer of i) unsaturated carboxylic acids ii) monomers containing phosphine oxide groups iii) optionally further ionic or nonionogenic monomers.
• R 5 (R 6 ) C C (R 7 ) -XP (0)
• Preferred among these monomers are those of the formulas Va, Vb and / or Vc,
• Particularly preferred machine dishwasher detergents according to the invention are characterized in that the polymer modified with phosphorus-containing groups has at least partially terminal phosphorus-containing groups.
• the agents of the invention may contain varying amounts of said polymers.
• Preferred automatic dishwashing agents according to the invention are characterized in that they contain the polymer (s) modified with phosphorus-containing groups, preferably in amounts of from 0.1 to 20% by weight, particularly preferably from 0.2 to 10% by weight. -% and in particular from 0.5 to 7.5 wt .-%, each based on the total agent included.
• automatic dishwasher detergents according to the invention are preferred in which the polymer (s) modified with phosphorus-containing groups have average molecular weights of from 1000 to 10 000 000 gmol -1 , preferably from 1500 to 1000 .000 gmol "1 , particularly preferably from 2000 to 100,000 gmol " 1 and in particular from 2500 to 50,000 gmol "1 .
• the polymer (s) modified with phosphorus-containing groups has a degree of polymerization of from 10 to 10000, preferably from 20 to 5000, particularly preferably from 40 to 2000 and in particular from 80 to 1000.
• the molar ratio of the monomers i) to ii) is 1: 1 to 200: 1, preferably 1: 1 to 100: 1 and in particular 1: 1 to 10: 1.
• Particularly preferred machine dishwasher detergents according to the invention are characterized in that the phosphorus-containing group-modified polymer (s) has a phosphorus content of from 0.5 to 5.0% by weight, preferably from 0.7 to 4.0 Wt .-% and in particular from 0.9 to 3.0 wt .-%, each based on the total weight of the / the phosphorus-containing polymer (s) s, have.
• machine dishwashing agents are preferred in which the content of the polymers in monomers iii) is at most 20 mol%, preferably at most 10 mol% and in particular maximum 5 mol.%.
• the automatic dishwashing compositions according to the invention may contain further polymers.
• automatic dishwasher detergents are preferred which additionally contain one or more cationic and / or amphoteric polymer (s), preferably in amounts of from 0.1 to 20% by weight, particularly preferably from 0.2 to 10% by weight .-% and in particular from 0.5 to 7.5 wt .-%, each based on the total agent included.
• Preferred amphoteric polymers are from the group of
• Preferred zwitterionic polymers are selected from the group of
• Preferred water-soluble cationic polymers are preferably selected from the group of
• a particularly preferred ingredient for automatic dishwashing agents is a polymer containing sulfonic acid groups.
• Preferred compositions according to the invention are therefore characterized in that they comprise at least one copolymer of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers
• Preferred automatic dishwasher detergents according to the invention are therefore characterized in that they additionally comprise one or more polymer (s) of i) unsaturated carboxylic acids ii) monomers containing sulfonic acid groups iii) optionally further ionic or nonionogenic monomers preferably in amounts of 0.1 to 20 wt .-%, particularly preferably from 0.2 to 10% by weight and in particular from 0.5 to 7.5 wt .-%, each based on the total agent.
• unsaturated carboxylic acids of the formula I as monomer are also preferred for the polymers containing sulfonic acid groups,
• R 1 to R 3 independently of one another are -H-CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
• R 5 to R 7 independently of one another are -H-CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or.
• Preferred among these monomers are those of the formulas Via, Vlb and / or Vlc,
• Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts of said acids.
• Suitable further ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds.
• the content of the monomers used according to the invention to monomers of group iii) is preferably less than 20% by weight, based on the polymer.
• Particularly preferred polymers to be used consist only of monomers of groups i) and ii).
• copolymers are made of
• R 1 to R 3 independently of one another are -H-CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,
• Particularly preferred copolymers consist of i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid ii) one or more monomers containing sulfonic acid groups of the formulas Via, Vlb and / or Vlc:
• H 2 C CH-X-SO 3 H (Via)
• H 2 C C (CH 3 ) -X-SO 3 H (VIb)
• H0 3 SX- (R 6 ) C C (R 7 ) - X-S0 3 H (Vlc)
• the copolymers may contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii).
• Particularly preferred polymers have certain structural units, which are described below.
• compositions according to the invention which are characterized in that they contain one or more copolymers which contain structural units of the formula VII
• compositions contain one or more copolymers which contain structural units of the formula VIII
• Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed.
• compositions according to the invention which comprise one or more copolymers which are structural units of the formula IX
• maleic acid can also be used as a particularly preferred monomer from group i).
• preferred compositions which are characterized in that they contain one or more copolymers, the structural units of the formula X.
• compositions according to the invention which contain one or more copolymers which contain structural units of the formulas VI and / or VII and / or VIII and / or IX and / or X and / or XI are preferred.
• the sulfonic acid groups may be wholly or partially in neutralized form, i. in that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
• metal ions preferably alkali metal ions and in particular for sodium ions.
• Corresponding compositions which are characterized in that the sulfonic acid groups are partially or fully neutralized in the copolymer are preferred according to the invention.
• the monomer distribution of the copolymers used in the compositions according to the invention in the case of copolymers containing only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight. % Of monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
• terpolymers particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,
• compositions according to the invention can be varied in order to adapt the properties of the polymers to the desired use.
• Preferred compositions are thereby characterized in that the copolymers have molar masses of 2000 to 200,000 gmol "1 , preferably from 4000 to 25,000 gmol " 1 and in particular from 5000 to 15,000 gmol "1 .
• Preferred automatic dishwashing agents according to the invention additionally contain one or more surfactants, preferably nonionic surfactant (s), preferably in amounts of from 0.1 to 20% by weight, more preferably from 0.2 to 15% by weight and in particular of 0.5 to 12% by weight, in each case based on the total agent.
• surfactants preferably nonionic surfactant (s)
• s preferably in amounts of from 0.1 to 20% by weight, more preferably from 0.2 to 15% by weight and in particular of 0.5 to 12% by weight, in each case based on the total agent.
• nonionic surfactants being clearly preferred in the context of automatic dishwashing and the surfactants from the other groups being used only in minor amounts or preferably not at all.
• anionic surfactants for example, those of the sulfonate type and sulfates are used.
• Suitable surfactants of the sulfonate type are preferably C 9-13 alkyl benzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example from C ⁇ 2- i8 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
• alkanesulfonates which are obtained from C 2-18 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 Taigfettcicren are suitable.
• sulfated fatty acid glycerol esters are sulfated fatty acid glycerol esters.
• Fatty acid glycerol esters are the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
• Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
• Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 0 -C 20 -oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length which are synthetic, petrochemical Basis produced straight-chain alkyl radical containing an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
• sulfuric monoesters of ethoxylated with 1 to 6 moles of ethylene oxide straight-chain or branched C 7-2 - ⁇ -alcohols such as 2-methyl-branched C 9 . ⁇ alcohols having an average of 3.5 moles of ethylene oxide (EO) or C 12-8 Fatty alcohols containing 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
• Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
• alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
• Preferred sulfosuccinates contain C 8- i 8 fatty alcohol radicals or mixtures thereof.
• Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
• Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
• alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
• anionic surfactants are particularly soaps into consideration.
• Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
• the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
• the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
• nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical is linear or preferred may be methyl branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
• EO ethylene oxide
• alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
• the preferred ethoxylated alcohols include, for example, C- ⁇ 2- ⁇ 4 - alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13 - ⁇ 5 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 ⁇ 8 alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-1 linear alcohol with 3 EO and C 12-i 8 alcohol containing 5 EO.
• the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
• Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
• NRE narrow rank ethoxylates
• 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.
• nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.
• alkyl polyglycosides Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG).
• APG alkyl polyglycosides
• Usable Alkypolyglycoside meet the general formula RO (G) z , in which R is a linear or branched, especially in the 2-position methyl branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Symbol that represents a glycose unit having 5 or 6 C atoms, preferably glucose.
• the degree of glycosidation z is between 1, 0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1, 1 and 1.4.
• Preference is given to using linear alkyl polyglucosides, that is to say alkyl polyglycosides which consist of a glucose residue and an n-alkyl chain.
• nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
• nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylaminoxid and N-tallow alkyl-N, N-dihydroxyethylaminoxid, and the fatty acid alkanolamides may be suitable.
• the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
• surfactants are polyhydroxy fatty acid amides of the formula (XII)
• RCO is an aliphatic acyl group having 6 to 22 carbon atoms
• R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms
• [Z] is a linear or branched polyhydroxyalkyl group 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 (XIII)
• 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
• R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C ⁇ -4 -alkyl or phenyl radicals are 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 this rest.
• [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 then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
• detergents and cleaners for automatic dishwashing come as surfactants in general all surfactants in question.
• the nonionic surfactants described above and, above all, the low-foaming nonionic surfactants are preferred for this purpose.
• alkoxylated alcohols especially the ethoxylated and / or propoxylated alcohols.
• the person skilled in the art generally means, under alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the context of the present invention, the longer-chain alcohols (C 10 to C 18 , preferably between C 12 and C 16 , such as, for example, C 1) -, C 12 -. C 13 -, -C -, C 15 -, C 16 - .C ⁇ - and C 18 - alcohols).
• n moles of ethylene oxide and one mole of alcohol form a complex mixture of addition products of different degrees of ethoxylation.
• a further embodiment consists in the use of mixtures of alkylene oxides, preferably of the mixture of ethylene oxide and propylene oxide.
• the substance class of "closed" alcohol ethoxylates reach, which can also be used in the context of the invention.
• Very particularly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or mixtures thereof with end-capped fatty alcohol ethoxylates.
• nonionic surfactants have been low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
• surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
• Machine dishwashing detergents according to the invention which contain surfactants of the general formula XIV as nonionic surfactant (s) are preferred here
• each group R 2 or R 3 is independently selected from -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH (CH 3 ) 2 and the indices w, x, y, z independently of one another are integers from 1 to 6.
• the preferred nonionic surfactants of formula III can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
• the radical R 1 in the formula I above may vary depending on the origin of the alcohol. Become native sources used, the radical R 1 has an even number of carbon atoms and is usually not shown, wherein the linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, are preferred are.
• Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position in the mixture, as they are usually present in oxo alcohol radicals.
• R 1 in formula I is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.
• alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
• R 2 or R 3 are independently selected from - CH 2 CH 2 -CH 3 or -CH (CH 3 ) 2 are suitable.
• Preferred automatic dishwashing agents are characterized in that R 2 and R 3 are each a residue -CH 3 , w and x independently of one another for values of 3 or 4 and y and z independently of one another represent values of 1 or 2.
• nonionic surfactants are particularly preferred for use in the inventive compositions, the C 9 . 15 alkyl having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed byi to 4 ethylene oxide units, followed byi to 4 propylene oxide units.
• the automatic dishwasher detergents according to the invention contain a nonionic surfactant which has a melting point above room temperature.
• preferred agents are characterized by containing nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C, and most preferably between 26.6 and 43, 3 ° C, included.
• Suitable nonionic surfactants in addition to the nonionic surfactants according to the invention which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If high-viscosity nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.
• Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
• Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
• the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
• a particularly preferred nonionic surfactant which is solid at room temperature is selected from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 6-2 o-alcohol), preferably a C 18 -alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol of ethylene oxide won.
• C 6-2 o-alcohol straight-chain fatty alcohol having 16 to 20 carbon atoms
• C 18 -alcohol preferably a C 18 -alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol of ethylene oxide won.
• the so-called “narrow rank ethoxylates" are particularly preferred.
• compositions according to the invention contain ethoxylated nonionic surfactant (s) comprising C 6-20 monohydroxyalkanols or C 6-2 o-alkylphenols or C 6-20 fatty alcohols and more than 12 mol, preferably more than 15 Mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was won (n).
• ethoxylated nonionic surfactant comprising C 6-20 monohydroxyalkanols or C 6-2 o-alkylphenols or C 6-20 fatty alcohols and more than 12 mol, preferably more than 15 Mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was won (n).
• the nonionic surfactant preferably additionally has propylene oxide units in the molecule.
• such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
• Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
• the alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
• Preferred automatic dishwashing detergents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule contain up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant. Further particularly preferably used nonionic surfactants with melting points.
• above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of Polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
• Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ® SLF-18 from Olin Chemicals.
• a further preferred machine dishwashing detergent according to the invention contains nonionic surfactants of the formula
• R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof
• R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y is a value of at least 15.
• nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
• R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
• R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical
• x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x> 2, each R 3 in the above formula may be different.
• R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
• R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
• Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
• each R 3 in the above formula may be different if x ⁇ 2.
• the alkylene oxide unit in the square bracket can be varied.
• the value 3 for x has been selected here by way of example and may well be greater, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
• R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
• dishwashing agents according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula
• R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
• R 3 is H or a methyl, ethyl, n-propyl, iso-propyl
• x is n-butyl, 2-butyl or 2-methyl-2-butyl
• x are values between 1 and 30
• k and j are values between 1 and 12, preferably between 1 and 5
• x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.
• anionic, cationic and / or amphoteric surfactants in conjunction with the surfactants mentioned, these having only secondary importance owing to their foaming behavior in automatic dishwashing detergents and in most cases only in Amounts below 10 wt .-%, usually even below 5 wt .-%, for example, from 0.01 to 2.5 wt .-%, each based on the agent used.
• the agents according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as surfactant component.
• Preferred automatic dishwashing agents according to the invention contain, in addition to the ingredients mentioned above, one or more substances from the group of builders, co-builders, bleaches, bleach activators, enzymes, dyes, fragrances, corrosion inhibitors, polymers, or another common constituent of detergents and cleaners , These ingredients are described below.
• all builders commonly used in detergents and cleaners in particular silicates, carbonates, organic cobuilders and also the phosphates, may be incorporated in the detergents and cleaners.
• Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 H 2 O, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are.
• Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 "yH 2 O are preferred.
• amorphous sodium silicates with a Na 2 O: SiO 2 modulus of 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 Delayed and have secondary washing properties.
• the dissolution delay compared to conventional amorphous sodium silicates may be caused in various ways, for example by surface treatment, compounding, grain pakt réelle / compression or by overdrying.
• the term "amorphous" is also understood to mean "X-ray amorphous”.
• the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values up to max. 50 nm and in particular up to max. 20 nm are preferred. Especially preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
• both the monoalkali metal salts and the dialkali metal salts of carbonic acid as well as sesquicarbonates can be contained in the compositions.
• Preferred alkali metal ions are sodium and / or potassium ions.
• Compounds of, for example, carbonate, silicate and optionally other auxiliaries such as, for example, anionic surfactants or other, in particular organic builders, may be present as a separate component in the finished compositions.
• the alkali metal phosphates with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.
• Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids in which metaphosphoric acids (HP0 3 ) n and orthophosphoric H 3 P0 4 can distinguish in addition to higher molecular weight representatives.
• the phosphates combine several advantages: they act as alkali carriers, prevent limescale deposits on machine parts or limescale deposits on the items to be washed and also contribute to the cleaning performance.
• Sodium dihydrogen phosphate, NaH 2 P0 4 exists as dihydrate (density 1, 91 like “3 , melting point 60 °) and as monohydrate (density 2.04 like “ 3 ). Both salts are white powders which are very slightly soluble in water and which lose the water of crystallization on heating and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 0 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 0 9 ) and Maddrell's salt (see below).
• NaH 2 P0 is acidic; It is formed when phosphoric acid is adjusted to pH 4.5 with narcotic eye and the mash is sprayed.
• Potassium dihydrogen phosphate (potassium phosphate primary or monobasic phosphate, potassium biphosphate, KDP), KH 2 P0, is a white salt of density 2.33 "3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KP0 3 ) ⁇ ] and is readily soluble in water.
• Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt.
• Disodium hydrogen phosphate is by neutralization of phosphoric acid with sodium carbonate solution under Use of phenolphthalein as an indicator Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HP0 4 , is an amorphous, white salt that is readily soluble in water.
• Trisodium phosphate, tertiary sodium phosphate, Na 3 P0 4 are colorless crystals which have a density of 1, 62 "3 and a melting point of 73-76 ° C (decomposition) as dodecahydrate, as decahydrate (corresponding to 19-20% P 2 0 5 ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 ⁇ s ) aufeisen a density of 2.536 like "3 .
• Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
• Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 P0 4 , is a white, deliquescent, granular powder with a density of 2.56 "3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction Heating of Thomas slag with coal and potassium sulfate Despite the higher price, in the detergent industry, the more soluble, hence highly effective, potassium phosphates are often preferred over corresponding sodium compounds.
• Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O, exists in anhydrous form (density 2.534 like “3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 like " 3 , melting point 94 ° with loss of water).
• decahydrate Density 1.815-1.836 like " 3 , melting point 94 ° with loss of water.
• Na P 2 0 7 is formed when heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and the solution is dehydrated by spraying.
• the decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
• Potassium diphosphate (potassium pyrophosphate), KP 2 0 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 "3 ", which is soluble in water, the pH of the 1% solution at 25 ° is 10.4.
• Sodium and potassium phosphates where one can distinguish cyclic representatives, the sodium or Kaliummetaphoshate and chain types, the sodium or potassium polyphosphates. Especially for the latter, a variety of names are in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
• pentasodium triphosphate Na 5 P 3 O ⁇ 0 (sodium tripolyphosphate)
• n 3.
• 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate.
• pentasodium triphosphate In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K 5 P O ⁇ 0 (potassium tripolyphosphate), for example in the form of a 50 wt .-% - solution (> 23% P 2 0 5 , 25% K 2 0) in the trade. Potassium polyphosphates are widely used in the detergents and cleaners industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:
• Automatic dishwashing detergents preferred in the context of the present invention contain no sodium and / or potassium hydroxide.
• a waiver of sodium and / or potassium hydroxide as the alkali source has proved to be particularly advantageous if zinc gluconate, zinc formate and zinc acetate are used as zinc salts.
• organic cobuilders in the detergents in the context of the present invention in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and Phosphonates are used.
• the polymers may also be part of the active ingredient-containing matrix, but they may also be contained completely independently of these in the inventive compositions. The mentioned classes of substances are described below.
• Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, 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), if such use is not objectionable for ecological reasons, and mixtures of these.
• Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, methylglycinediacetic acid, sugar acids and mixtures thereof.
• the acids themselves can also be used.
• the acids typically also have the property of an acidifying component and thus also serve for setting a lower and milder pH of detergents or cleaners, in particular citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures thereof ,
• polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
• the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
• Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1000 to 20 000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and more preferably from 1,200 to 4,000 g / mol, may again be preferred from this group. Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers are particularly preferably used in the compositions according to the invention. The sulfonic acid-containing copolymers will be described in detail below.
• the sulfonic acid group-containing polymers described above may also be present in the agents according to the invention, without necessarily having to be part of the active ingredient-containing matrix zuu.
• polyacrylates As already mentioned above, in the agents according to the invention it is particularly preferable to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers.
• the polyacrylates were described in detail above. Particularly preferred are combinations of the above-described sulfonic acid-containing copolymers with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons.
• Such polyacrylates are commercially available under the trade name Sokalan ® PA15 and PA25 Sohimlan ® (BASF).
• 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 which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
• Their molecular weight relative to free acids is generally from 2000 to 100,000 g / mol, preferably from 20,000 to 90,000 g / mol and in particular from 30,000 to 80,000 g / mol.
• the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
• the content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
• the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
• biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives .
• Other preferred copolymers have as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
• polymeric aminodicarboxylic acids their salts or their precursors.
• polyaspartic acids or their salts and derivatives are particularly preferred.
• polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 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 carried out by customary, for example acid or enzyme catalyzed processes.
• it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
• a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
• DE dextrose equivalent
• 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.
• a product oxidized to C 6 of the saccharide ring may be particularly advantageous.
• Oxydisuccinates and other derivatives of disuccinates are further suitable co-builders.
• 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 are in zeolithissen and / or silicate-containing formulations at 3 to 15 wt .-%.
• 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 hydroxyl group and a maximum of two acid groups.
• phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
• hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder.
• HEDP 1-hydroxyethane-1,1-diphosphonate
• Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
• the builder used here is preferably HEDP from the class of phosphonates.
• the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
• agents according to the invention are characterized in that they comprise builders, preferably from the group of silicates, carbonates, organic cobuilders and / or phosphates, in amounts of from 0.1 to 99.5% by weight, preferably from 1 to 95% Wt .-%, particularly preferably from 5 to 90 wt .-% and in particular from 10 to 80 wt .-%, each based on the composition.
• Bleaching agents and bleach activators are important constituents of detergents and cleaners, and a washing and cleaning agent may in the context of the present invention contain one or more substances from the groups mentioned.
• sodium percarbonate has particular significance.
• Other useful bleaching agents are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate .
• Na 2 C0 3 -3 H 2 0 2 The commercial commodity has the average composition 2 Na 2 C0 3 -3 H 2 0 2 and is therefore no peroxycarbonate.
• Sodium percarbonate forms a white, water-soluble powder of density 2.14 "3 , which readily decomposes into sodium carbonate and bleaching or oxidizing oxygen.
• the industrial production of sodium percarbonate is predominantly produced by precipitation from aqueous solution (so-called wet process).
• aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium by salting-out agent (mainly sodium chloride), Kristallisierangesstoff (for example, polyphosphates, polyacrylates) and stabilizers (for example, Mg 2+ ions).
• the precipitated salt which still contains 5 to 12 wt .-% mother liquor, is then removed by centrifugation and dried in fluid bed dryers at 90 ° C.
• the bulk density of the finished product may vary between 800 and 1200 g / l, depending on the manufacturing process.
• the percarbonate is stabilized by an additional coating. Coating methods and materials used for coating are widely described in the patent literature. In principle, all commercially available percarbonate types can be used according to the invention, as offered for example by the companies Solvay Interox, Degussa, Kemira or Akzo.
• Dishwashing detergents may also contain bleaches from the group of organic bleaches.
• Typical organic bleaches that can be used as ingredients in the present invention are the diacyl peroxides such as dibenzoyl peroxide.
• Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
• Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP )], o- Carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid,
• Diperoxybrassylic acid the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.
• chlorine or bromine releasing substances can also be used according to the present invention.
• suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration.
• DICA dichloroisocyanuric acid
• Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
• Advantageous agents in the context of the present invention comprise one or more bleaching agents, preferably from the group of the oxygen or halogen bleaches, in particular the chlorine bleach, with particular preference of sodium percarbonate and / or sodium perborate monohydrate, in amounts of from 0.5 to 40 Wt .-%, preferably from 1 to 30 wt .-%, particularly preferably from 2.5 to 25 wt .-% and in particular from 5 to 20 wt .-%, each based on the total agent.
• bleaching agents preferably from the group of the oxygen or halogen bleaches, in particular the chlorine bleach, with particular preference of sodium percarbonate and / or sodium perborate monohydrate, in amounts of from 0.5 to 40 Wt .-%, preferably from 1 to 30 wt .-%, particularly preferably from 2.5 to 25 wt .-% and in particular from 5 to 20 wt .-%, each based on the total agent.
• cleaning agents in the context of the present invention may contain bleach activators.
• bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
• Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
• polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydro drofuran.
• TAED t
• bleach catalysts can also be incorporated into the detergents according to the present invention.
• These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
• Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
• agents which comprise one or more substances from the group of bleach activators, in particular from the groups of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, in particular Nonanoyl or Isononanoyloxybenzolsulfonat (n- or iso-NOBS) and n-methyl-morpholinium acetonitrile methyl sulfate (MMA), in amounts of 0.1 to 20 wt .-%, preferably from 0.5 to 15 wt. -% and in particular from 1 to 10 wt .-%, each based on the total agent included.
• TAED tetraacetylethylenediamine
• N-acylimides in particular N-nonanoylsuccinimide (NOSI)
• the bleach activators preferred in the context of the present invention furthermore include the "nitrile quats", cationic nitriles of the formula (XV),
• R 1 is -H, -CH 3 , a C 2-24 -alkyl or -alkenyl radical, a substituted C 2-24 -alkyl or -alkenyl radical having at least one substituent from the group - Cl, -Br, - OH, -NH 2 , -CN, an alkyl or Alkenylarylrest with a -24- alkyl group, or represents a substituted alkyl or Alkenylarylrest with a -24- alkyl group and at least one further substituent on the aromatic ring
• R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3, -CH 2 - CH 2 -CH 2 -OH,
• the general formula (XXI) includes a variety of cationic nitriles useful in the present invention.
• the detergent tablets according to the invention contain cationic nitriles in which R 1 represents methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl ,. n-dodecyl, n-tetradecyl, n- Hexadecyl or n-octadecyl stands.
• R 2 and R 3 are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, wherein one or both radicals may advantageously also be a Cyanomethylenrest.
• radicals R 1 to R 3 are identical, for example (CH 3 ) 3 N (+) CH 2 -CN X “ , (CH 3 CH 2 ) 3 N (+) CH 2 -CN X “ , (CH 3 CH 2 CH 2 ) 3 N (+) CH 2 -CN X “ , (CH 3 CH (CH 3 )) 3 N (+) CH 2 -CN X “ , or (HO -CH 2 -CH 2 ) 3 N (+) CH 2 -CN X " , where X " is preferably an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is selected.
• Detergents and cleaning agents which are preferred in the context of the present invention are characterized in that they contain the cationic nitrile of the formula (XXI) in amounts of from 0.1 to 20% by weight, preferably from 0.25 to 15% by weight, and in particular from 0.5 to 10 wt .-%, each based on the molding weight.
• Particularly suitable enzymes are those from the classes of hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer.
• Bacillus subtilis Bacillus subtilis
• Bacillus licheniformis Bacillus licheniformis
• Streptomyceus griseus Streptomyceus griseus
• Coprinus cinereus and Humicola insolens
• enzymatically-derived variants derived from their genetically modified variants e.g., Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens
• subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
• enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
• lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases.
• Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.
• As cellulases are preferably cellobiohydrolases, endoglucanases and - glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
• the enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation.
• Preferred agents according to the invention contain enzymes, preferably in the form of liquid and / or solid enzyme preparations, in amounts of from 0.1 to 10% by weight, preferably from 0.5 to 8% by weight and in particular from 1 to 5% by weight. , in each case based on the total mean.
• Dyes which are preferred in the context of the present invention and whose selection does not present any difficulty to a person skilled in the art have a high storage stability and insensitivity to the other ingredients of the compositions and to light and no pronounced substantivity to textile fibers so as not to stain them.
• Preferred for use in the detergents and cleaning agents according to the invention are all colorants which can be oxidatively destroyed in the cleaning process and mixtures thereof with suitable blue dyes, so-called blue toners. It has proved to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe.
• One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020)., That is as a commercial product, for example as Basacid ® Green 970 from BASF, Ludwigshafen available, as well as mixtures thereof with suitable blue dyes.
• Pigmosol come ® Blue 6900 (CI 74160), Pigmosol ® Green 8730 (CI 74260), Basonyl ® Red 545 FL (CI 45170), Sandolan® ® rhodamine EB400 (CI 45100), Basacid® ® Yellow 094 (CI 47005) Sicovit ® Patentblau 85 e 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, Cl Acidblue 183), pigment Blue 15 (Cl 74160), Supranol Blue ® GLW (CAS 12219-32- 8, Cl Acidblue 221 )), Nylosan Yellow ® N-7GL SGR (CAS 61814-57-1, Cl Acidyellow 218) and / or Sandolan Blue ® (Cl Acid Blue 182, CAS 12219-26-0) is used.
• the colorant When choosing the colorant, it must be taken into account that the colorants do not have too high an affinity for the textile surfaces and, in particular, for synthetic fibers. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. For highly soluble dyes, for example, the above-mentioned Basacid ® Green or the above-mentioned Sandolan Blue ®, are typically selected dye concentrations in the range of some 10 "2 to 10" 3 wt .-%.
• the appropriate concentration of the colorant is in washing or cleaning agents, however, typically a few 10 "3 to 10" 4 wt .-% ,
• fragrance compounds e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used.
• Fragrance compounds of the ester type are known e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate,
• DMBCA Dimethylbenzylcarbinylacetate
• phenylethylacetate benzylacetate
• the ethers include, for example, benzyl ethyl ether and ambroxane, to the aldehydes e.g. the linear alkanals having 8-18 C atoms, citral, citronellal, citronellyloxy-acetaldehyde, cyclamen aldehyde, lilial and bourgeonal, to the ketones e.g.
• the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol;
• the hydrocarbons mainly include the terpenes such as limonene and pinene.
• mixtures of different fragrances are used, which together produce an attractive fragrance.
• perfume oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are Muskateller sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, Cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil, and orange blossom oil, neroliol, orange peel oil and sandalwood oil.
• fragrance To be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role , For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception.
• the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note", “middle note or body”
• the top note of a perfume or fragrance consists not only of volatile compounds, while the base note for the most part from less volatile
• more volatile fragrances may be bound to certain fixatives, thereby preventing them from evaporating too quickly
• the embodiment of the present invention described above in which the more volatile fragrances are based on the water-insoluble fragrances support material low density is one such method of fragrance fixation.
• Adhesive-resistant fragrances which can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, amicaceous oil, basil oil, bay oil, bergamot oil, Champacablütenöl, Edeltannöl, Edeltannenzapfenapfen, Elemiöl, eucalyptus oil, fennel oil, spruce algae oil, galbanum oil, geranium oil, gingergrass oil, Guaiac wood oil, gurdy balm oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine oil, copa ⁇ va balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil, Moisturizer Oil, Myrrh
• fragrances can be used in the context of the present invention as adherent fragrances or fragrance mixtures, ie fragrances.
• These compounds include the following compounds and mixtures thereof: ambrettolide, ⁇ -amyl cinnamic aldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, Benzyl valerate, borneol, bornyl acetate, ⁇ -bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalypto
• the more volatile fragrances include in particular the lower-boiling fragrances natural or synthetic origin, which can be used alone or in mixtures.
• Examples of more readily volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.
• Detergents for automatic dishwashing may contain corrosion inhibitors to protect the items to be washed or the machine, with silver protectants in particular being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which corrode the Silver surface can significantly reduce.
• chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
• transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate and the manganese complexes tMe-TACN) Mn , V (m-0) 3 Mn JV (Me-TACN)] 2+ (PF 6 -) 2 >
• Me-MeTACN Mn I, I (m-O) (m-OAc) 2 Mn , II (Me-MeTACN)] 2+ (PF 6 " ) 2 , wherein Me-TACN is 1,4,7-trimethyl 1, 4,7-triazacyclononane and Me-MeTACN are 1, 2,4,7-tetramethyl-1, 4,7-triazacyclononane.
• zinc compounds can be used to prevent corrosion on the dishes.
• a preferred agent for providing anticorrosive protection to glassware during dishwashing and / or rinsing operations of a dishwashing machine is zinc in oxidized form, i. Zinc compounds in which zinc is cationic. Similarly, magnesium salts are also preferred. Both soluble and non-soluble zinc or magnesium compounds can be used here. Preferred inventive
• Compositions contain one or more magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid.
• the acids in question preferably originate from the group of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the Amino acids and / or the polymeric carboxylic acids, the unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acids having at least 8 carbon atoms and / or resin acids.
• magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids may be present according to the invention, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids from the Groups of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids are preferred. Within these groups, the acids mentioned below are again preferred in the context of the present invention:
• hydroxy acids From the group of hydroxy acids: hydroxyphenylacetic acid (mandelic acid), 2-hydroxypropionic acid (lactic acid), malic acid (malic acid), 2,3-
• Dihydorxybutanedioic acid (tartaric acid), 2-hydroxy-1,2,3-propanetricarboxylic acid (citric acid), ascorbic acid, 2-hydroxybenzoic acid (salicylic acid), 3,4,5-trihydroxybenzoic acid (gallic acid).
• oxo acids 2-oxopropionic acid (pyruvic acid), 4-oxopentanoic acid (levulinic acid).
• polyacrylic acid polymethacrylic acid
• alkylacrylamide / acrylic acid copolymers alkylacrylamide / methacrylic acid copolymers
• Alkylacrylamide / methylmethacrylic acid copolymers copolymers of unsaturated carboxylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers.
• inventively preferred zinc salts of organic acids preferably organic carboxylic acids, ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / L, preferably below 10 mg / L, in particular have no solubility, to such salts having a solubility in water above 100 mg / L, preferably above 500 mg / L, more preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C water temperature).
• the first group of zinc salts includes, for example, the zinc nitrate, the zinc oleate and the zinc stearate;
• the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate:
• compositions according to the invention contain at least one zinc salt but no magnesium salt of an organic acid, which is preferably at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt selected from zinc stearate, zinc oleate, zinc gluconate, zinc acetate , Zinc lactate and / or Zinkeitrat acts.
• zinc ricinoleate, zinc abietate and zinc oxalate are also preferably used.

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