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EP1664257B1 - Detergents pour lave-vaisselle contenant un melange polymere special - Google Patents

Detergents pour lave-vaisselle contenant un melange polymere special Download PDF

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Publication number
EP1664257B1
EP1664257B1 EP04764845A EP04764845A EP1664257B1 EP 1664257 B1 EP1664257 B1 EP 1664257B1 EP 04764845 A EP04764845 A EP 04764845A EP 04764845 A EP04764845 A EP 04764845A EP 1664257 B1 EP1664257 B1 EP 1664257B1
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EP
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Prior art keywords
acid
oil
preferred
polymer
weight
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EP04764845A
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German (de)
English (en)
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EP1664257A1 (fr
Inventor
Rolf BAYERDÖRFER
Arnd Kessler
Silke Menke
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL04764845T priority Critical patent/PL1664257T3/pl
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3742—Nitrogen containing silicones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • 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 washing 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 washing 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 is primarily to prevent limescale and deposits on the cleaned dishes. In addition to water and low-foaming nonionic surfactants these rinse aids often include hydrotopes, pH adjusters such as citric acid or scale-inhibiting polymers.
  • 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.
  • EP-A-0 851 024 Unilever
  • the first layer of which contains peroxy bleach, builder and enzyme while the second layer contains acidifying agents and a continuous medium with a melting point of between 55 and 70 ° C and scale inhibitors. 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.
  • anionic polymers modified with S-containing groups brings about advantageous effects in automatic dishwashing detergents. It is particularly advantageous if the polymers are used in the rinse cycle.
  • the present invention therefore relates to a machine dishwashing detergent according to claim 1.
  • Preferred machine dishwashing detergents according to the invention are characterized in that the polymer comprising cationic monomer units is a cationic polymer.
  • “Cationic polymers” in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups present in the polymer chain or other positively charged groups.
  • Particularly preferred cationic polymers originate from the groups of the quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCl designations Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.
  • polymer has not only cationic groups but also anionic ones.
  • Corresponding polymers are derived from the groups of zwitterionic or amphoteric polymers.
  • Preferred automatic dishwashing agents according to the invention are therefore characterized in that the polymer which has cationic monomer units is an amphoteric polymer.
  • Preferred usable amphoteric polymers are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylfaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methylmethacrytic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate Copolymers and copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or nonionic
  • Preferably usable zwitterionic polymers are selected from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.
  • amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers, methacrylamidoalkyltrialkylammonium chloride and dimethyl (diallyl) ammonium chloride.
  • Particularly preferred amphoteric polymers are selected from the group consisting of the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid Copolymers and their alkali metal and ammonium salts.
  • amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers and their alkali metal and ammonium salts.
  • compositions of the invention contain at least one anionic polymer according to claim 1 which is modified with sulfur-containing groups, wherein the pH of a 1 wt .-% - solution of the anionic polymer in distilled water at 20 ° C less than pH 6.
  • 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 (R 6 ) C C (R 7 ) -X-SO 3 H (VI)
  • H 2 C CH-X-SO 3 H (VIa)
  • H 2 C C (CH 3 ) -X-SO 3 H (VIb)
  • HO 3 SX- (R 6 ) C C (R 7 ) -X-SO 3 H (VIc)
  • 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-propene-1-sulfonic 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).
  • 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.
  • 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 - [CH 2 -CHCOOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - (VI), - [CH 2 -C (CH 3 ) COOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - (VII) - [CH 2 -CHCOOH] m - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] p - (VIII), - [CH 2 -C (CH 3 ) COOH] m - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] p - (IX), - [HOOCCH-CHCOOH] m m
  • 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.
  • 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) ,
  • the molecular weight of the above-described sulfo-copolymers used in the compositions according to the invention can be varied in order to adapt the properties of the polymers to the desired use.
  • Preferred compositions are characterized in that the copolymers have molecular weights of from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • Machine dishwashing detergents according to the invention are preferred in which the polymer modified with sulfur-containing groups has at least partially terminal sulfur-containing groups.
  • automatic dishwashing agents which contain the sulfur-containing group-modified polymer (s), preferably in amounts of from 0.1 to 20% by weight, more 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 automatic dishwasher detergents according to the invention are characterized in that the sulfur-containing group (s) modified polymer (s) average molecular weights of 1000 to 10,000,000 gmol -1 , preferably from 1500 to 1,000,000 gmol -1 , more preferably from 2000 to 100,000 gmol -1 and especially from 2500 to 50,000 gmol -1 .
  • Particularly preferred automatic dishwasher detergents according to the invention are furthermore characterized in that 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.
  • terpolymers can be prepared and used from the abovementioned monomers i) to iii). However, it is preferred to limit the content of monomers iii).
  • Machine dishwashing agents according to the invention 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 not more than 5 mol%.
  • Automatic dishwashing detergents according to the invention additionally comprise from 0.01 to 5% by weight of one or more nonionic surfactant (s).
  • nonionic surfactants are therefore limited.
  • Other surfactants are used in automatic dishwashing detergents only in awakegordneten amounts - well below 1 wt .-%, based on the agent - used.
  • the amount of surfactant can be reduced without loss of performance, whereby further advantageous properties, such as, for example, better tabletability in detergent tablets, can be achieved.
  • Machine dishwashing detergents according to the invention which have a content of nonionic surfactants below 4% by weight and in particular between 0.01 and 2% by weight, based in each case on the total weight of the automatic dishwashing detergent, are preferred.
  • the surfactants are described below. They come from the groups of anionic, nonionic, cationic and / or amphoteric surfactants, nonionic surfactants being imperative 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.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates which are 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 are suitable.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 -oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which can be obtained as commercial products of Shell Oil Company under the name DAN ® , are suitable anionic surfactants.
  • EO ethylene oxide
  • Fatty alcohols with 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 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • 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.
  • the nonionic surfactants used 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 can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, 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 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants 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 Is a symbol which 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 of the amine oxide type for example, N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide can 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.
  • polyhydroxy fatty acid amides of the formula (XII) wherein 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 and [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) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C 1-4 alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an ary
  • [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.
  • nonionic surfactants in 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.
  • Particularly preferred are the alkoxylated alcohols, especially the ethoxylated and / or propoxylated 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 11 -, C 12 -, C 13 -, C 14 -, C 15 -, C 16 - C 17 - and C 18 -alcohols).
  • the longer-chain alcohols C 10 to C 18 , preferably between C 12 and C 16 , such as, for example, C 11 -, C 12 -, C 13 -, C 14 -, C 15 -, C 16 - C 17 - and C 18 -alcohols.
  • a further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Also, if desired, by a final etherification with short-chain alkyl groups, such as preferably the butyl group, 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 which contain surfactants of the general formula XIV as nonionic surfactant (s) are preferred here in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; 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. When native sources are used, the radical R 1 has an even number of carbon atoms and is usually undisplayed, 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.
  • 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 which have a C 9-15 -alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 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 room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called “narrow range ethoxylates" (see above) are particularly preferred.
  • compositions according to the invention contain ethoxylated nonionic surfactants which are prepared from C 6-2o monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 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 recovered (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.
  • More particularly preferred nonionic surfactants having melting points above room temperature contain from 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 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (OH) R 2 ],
  • 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 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which 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.
  • 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, with the variation width 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 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j R 2 in which 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, surfactants of the type R 1 O [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 in which 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 may also be used in conjunction with the surfactants mentioned, these having only minor importance because of their foaming behavior in dishwasher detergents and usually only in amounts below 10% by weight, in most cases even below 5% by weight .-%, 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 with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification 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, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Particularly preferred are compacted / compacted amorphous silicates, com pounded 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 one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 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.
  • NaH 2 PO 4 Sodium dihydrogen phosphate, NaH 2 PO 4 , exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
  • NaH 2 PO 4 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 PO 4 , is a white salt of density 2.33 gcm -3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm -3 , loss of water at 95 °), 7 moles (density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 moles water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na 4 P 2 O 7 .
  • Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which have a density of 1.62 gcm -3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) aufeisen a density of 2.536 gcm -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 PO 4 , is a white, deliquescent, granular powder of density 2.56 gcm -3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals.
  • Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
  • the decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.
  • Sodium and potassium phosphates where one can distinguish cyclic representatives, the sodium or Kaliummetaphoshate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names 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 10 (sodium tripolyphosphate)
  • sodium tripolyphosphate 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 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning 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: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
  • 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 an alkali source has proved to be particularly advantageous if zinc gluconate, zinc formate and zinc acetate are used as zinc salts.
  • the organic cobuilders used may in particular be polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and also phosphonates.
  • 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 to set a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • 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.
  • compositions of the invention may be included in the compositions of 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 Sokalan ® PA25 (BASF).
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Particularly suitable copolymers of acrylic acid with maleic acid have proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid.
  • 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 containing as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or the monomers as the salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives contain.
  • copolymers preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • 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 other 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% % By weight, more preferably from 5 to 90% by weight and in particular from 10 to 80% by weight, based in each case 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.
  • Further useful bleaching agents are, for example, sodium perborate tetrahydrate and the sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • Sodium percarbonate is a term used in unspecified form for sodium carbonate peroxohydrates, which strictly speaking are not “percarbonates” (ie salts of percarbonic acid) but hydrogen peroxide adducts of sodium carbonate.
  • the commercial product has the average composition 2 Na 2 CO 3 ⁇ 3 H 2 O 2 and is therefore no peroxycarbonate.
  • Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm -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) like.
  • the precipitated salt which still contains 5 to 12 wt .-% mother liquor is then removed by centrifugation and dried in fluidized bed driers 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 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-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid,
  • 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.
  • 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 bleaches, with particular preference of sodium percarbonate and / or sodium perborate monohydrate, in amounts of from 0.5 to 40% by weight. %, 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 bleaches, with particular preference of sodium percarbonate and / or sodium perborate monohydrate, in amounts of from 0.5 to 40% by weight. %, 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, especially n-nonanoyl or Isononanoyloxybenzolsulfonat (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-dihydrofuran.
  • TAED tetraacety
  • 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 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 alkenylaryl radical having a C 1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C 1-24 -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
  • the general formula (XXI) includes a variety of cationic nitriles useful in the present invention.
  • the detergent tablets according to the invention comprise cationic nitriles in which R 1 represents methyl, ethyl, Propyl, isopropyl or n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
  • 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)) N (+) CH 2 -CN X -, or (HO- CH 2 -CH 2 ) 3 N (+) CH 2 -CN X - , wherein X - preferably represents an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is.
  • 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), which as a commercial product ® for example as Basacid Green 970 from BASF, Ludwigshafen, is, 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 colorants do not have too high an affinity for the textile surfaces and, in particular, for synthetic fibers.
  • 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.
  • 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, citronellyloxyacetaldehyde, cyclamen aldehyde, lilial and bourgeonal
  • the ketones e.g. the ionones, ⁇ -isomethylionone and methyl cedryl ketone
  • the alcohols 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 such as are available from vegetable sources, e.g. 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 , That's how most people own it Perfumes up to about 200 daltons, while molar masses of 300 daltons and more are an exception. Due to the different volatility of fragrances, 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” and “base note” (end note or dry out).
  • the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note consists for the most part of less volatile, ie adherent Riehcstoffen.
  • more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly.
  • the above-described embodiment of the present invention wherein the more-volatile fragrances are applied to the water-insoluble low-density support materials is one such fragrance-fixing method.
  • the subsequent classification of the fragrances in "more volatile” or "adherent" fragrances so nothing about the olfactory impression and whether the corresponding fragrance is perceived as a head or middle note, nothing said.
  • 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, arnica blossom oil, basil oil, bay oil, bergamot oil, Champacablütenöl, Edeltannöl, Edeltannenzapfenapfen, Elemiöl, eucalyptus oil, fennel oil, spruce alder 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, kanga oil, cardamom oil, cassia oil, pine oil, copaia balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil, Musk Grain 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, ⁇ -amylcinnamaldehyde, 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, eucalyptol,
  • 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 machine 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 can markedly reduce the corrosion of the silver surface.
  • 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 (amrin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate, as well as the manganese complexes [Me-TACN) Mn IV (m-0) 3 Mn IV (Me-TACN)] 2+ (PF 6 - ) 2 [Me-MeTACN) Mn IV (m-0) 3 Mn IV (Me-MeTACN)] 2+ (PF 6 - ) 2 , [Me-TACN) Mn III (mO) (m-OAc) 2 Mn III (Me-TACN)] 2+ (PF 6 - ) 2 and [Me-MeTACN) Mn III (m-0) (m-0A
  • 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 compositions according to the invention comprise one or more magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid.
  • the acids in question are preferably derived. from the group of unbranched saturated or unsaturated monocarboxylic acids, branched saturated or unsaturated monocarboxylic acids, saturated and unsaturated dicarboxylic acids, aromatic mono-, di- and tricarboxylic acids, sugar acids, hydroxy acids, oxo acids, amino acids and / or 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 contained according to the invention, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids are selected from the groups of unbranched saturated or unsaturated monocarboxylic acids, branched saturated or unsaturated monocarboxylic acids, saturated and unsaturated dicarboxylic acids, aromatic mono-, di- and tricarboxylic acids, sugar acids, hydroxy acids, oxo acids, amino acids and / or polymeric carboxylic acids. Within these groups, the acids mentioned below are again preferred in the context of the present invention:
  • benzoic acid 2-carboxybenzoic acid (phthalic acid), 3-carboxybenzoic acid (isophthalic acid), 4-carboxybenzoic acid (terephthalic acid), 3,4-dicarboxybenzoic acid (trimellitic acid), 3,5-dicarboxybenzoic acid (Trimesionklare).
  • sugar acids galactonic acid, mannonic acid, fructonic acid, arabinonic acid, xylonic acid, ribonic acid, 2-deoxy-ribonic acid, alginic acid.
  • hydroxy acids From the group of hydroxy acids: hydroxyphenylacetic acid (mandelic acid), 2-hydroxypropionic acid (lactic acid), malic acid (malic acid), 2,3-dihydroxybutanedioic 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).
  • amino acids From the group of amino acids: alanine, valine, leucine, isoleucine, proline, tryptophan, phenylalanine, methionine, glycine, serine, tyrosine, threonine, cysteine, asparagine, glutamine, aspartic acid, glutamic acid, lysine, arginine, histidine.
  • polymeric carboxylic acids polyacrylic acid, polymethacrylic acid, alkylacrylamide / acrylic acid copolymers, alkylacrylamide / methacrylic acid copolymers, alkylacrylamide / methylmethacrylic acid copolymers, copolymers of unsaturated carboxylic acids, vinylacetate / crotonic acid copolymers, vinylpyrrolidone-nylacrylate copolymers.
  • the spectrum of the inventively preferred zinc salts of organic 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, zinc citrate, zinc oleate and 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 comprise 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 zinc citrate.
  • zinc ricinoleate, zinc abietate and zinc oxalate are also preferably used

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Claims (10)

  1. Produit pour le lavage mécanique de la vaisselle, comprenant :
    a) au moins un polymère qui présente des unités monomères cationiques ; et
    b) au moins un polymère anionique qui a été modifié avec des groupes sulfurés, caractérisé en ce que le polymère modifié avec des groupes sulfurés comprend, à titre d'unités monomères
    i) des acides carboxyliques insaturés
    ii) des monomères contenant des groupes d'acides sulfoniques
    iii) le cas échéant, d'autres monomères ioniques ou non ionogènes.
    la valeur de pH d'une solution à 1 % en poids du polymère anionique dans de l'eau distillée à 20 °C étant inférieure à 6 ; et
    c) un agent tensioactif non ionique à concurrence de 0,01 à 5 % en poids.
  2. Produit pour le lavage mécanique de la vaisselle selon la revendication 1, caractérisé en ce qu'il s'agit, en ce qui concerne le polymère qui présente des unités monomères cationiques, d'un polymère cationique.
  3. Produit pour le lavage mécanique de la vaisselle selon la revendication 1, caractérisé en ce qu'il s'agit, en ce qui concerne le polymère qui présente des unités monomères cationiques, d'un polymère amphotère.
  4. Produit pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le polymère modifié avec des groupes sulfurés présente au moins en partie des groupes sulfurés terminaux.
  5. Produit pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'il contient le/les polymère(s) modifié(s) avec des groupes sulfurés dans des quantités de 0,1 à 20 % en poids, de manière particulièrement préférée de 0,2 à 10 % en poids et en particulier de 0,5 à 7,5 % en poids, chaque fois rapportés au produit dans sa totalité.
  6. Produit pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le produit vaisselle présente une teneur en agents tensioactifs non ioniques qui est inférieure à 4 % en poids et en particulier entre 0,01 et 2 % en poids, chaque fois rapportés au poids total du produit pour le lavage mécanique de la vaisselle.
  7. Produit pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le/les polymère(s) modifié(s) avec des groupes sulfurés présente(nt) des masses molaires moyennes de 1000 à 10.000.000 gmol-1, de préférence de 1500 à 1.000.000 gmol-1, de manière particulièrement préférée de 2000 à 100.000 gmol-1 et en particulier de 2500 à 50.000 gmol-1.
  8. Produit pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 1 à 7, caractérisé en ce que le rapport molaire des monomères i) à ii) s'élève de 1 : 1 à 200 : 1, de préférence de 1 : 1 à 100 : 1 et en particulier de 1 : 1 à 10 : 1.
  9. Produit pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 1 à 8, caractérisé en ce que la teneur des polymères en monomères iii) s'élève au maximum à 20 mol %, de préférence au maximum à 10 mol % et en particulier au maximum à 5 mol %.
  10. Procédé de lavage mécanique de la vaisselle en mettant en oeuvre un produit pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications précédentes.
EP04764845A 2003-09-15 2004-09-04 Detergents pour lave-vaisselle contenant un melange polymere special Revoked EP1664257B1 (fr)

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Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0522658D0 (en) 2005-11-07 2005-12-14 Reckitt Benckiser Nv Composition
DE102005060431A1 (de) * 2005-12-15 2007-06-21 Henkel Kgaa Maschinelles Geschirrspülmittel
GB0607562D0 (en) * 2006-04-18 2006-05-24 Reckitt Benckiser Nv Method, composition and use
CA2681676C (fr) 2007-05-04 2015-12-29 Ecolab Inc. Compositions nettoyantes contenant un compose au magnesium soluble a l'eau et procedes d'utilisation correspondants
MX2010003825A (es) * 2007-10-18 2010-04-27 Ecolab Inc Composiciones de limpieza solidas, auto-solidificables, comprimidas, y metodos para hacerlas.
JP5503545B2 (ja) * 2007-11-09 2014-05-28 ザ プロクター アンド ギャンブル カンパニー モノカルボン酸単量体、ジカルボン酸単量体、およびスルホン酸基含有単量体を含む洗浄用組成物
CA2720346C (fr) * 2008-03-31 2015-05-05 The Procter & Gamble Company Composition automatique pour laver la vaisselle contenant un copolymere sulfone
DE102008028229A1 (de) * 2008-06-16 2009-12-17 Fit Gmbh Zusammensetzung zur Herstellung von Reinigungsmitteln, Tablettiermischung, Polymerkombination, Reinigunsmittel-Formkörper und Verfahren zur deren Herstellung
DE102008060471A1 (de) * 2008-12-05 2010-06-10 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
US8852353B2 (en) * 2008-12-10 2014-10-07 Michael Oberlander Solid dishmachine detergent not requiring a separate rinse additive
DE102009027158A1 (de) * 2009-06-24 2010-12-30 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
ES2565192T3 (es) * 2010-04-23 2016-04-01 The Procter & Gamble Company Método para perfumar
EP2571972A1 (fr) * 2010-05-20 2013-03-27 Arkema Inc. Compositions nettoyantes au peroxyde activé

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2811010A1 (de) * 1977-03-15 1978-09-28 Oreal Mittel und verfahren zur behandlung von keratinmaterialien mit kationischen und anionischen polymeren

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI823446L (fi) * 1981-10-16 1983-04-17 Unilever Nv Foerbaettrad komposition foer maskinell diskning och skoeljning
DE3418496A1 (de) 1984-05-18 1985-11-21 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von mischpolymerisaten aus vinylphosphonsaeure und (meth-)acrylsaeure in waessriger loesung und ihre verwendung
DE3664480D1 (en) 1985-04-03 1989-08-24 Henkel Kgaa Rinsing agents for use in mechanical dish washing
US5077361A (en) 1989-06-26 1991-12-31 Rohm And Haas Company Low molecular weight water soluble phosphinate and phosphonate containing polymers
US5451644A (en) * 1994-01-14 1995-09-19 Rohm And Haas Company Aqueous process for preparing water soluble polymers of monoethylenically unsaturated dicarboxylic acids
EP0664334A1 (fr) 1994-01-19 1995-07-26 The Procter & Gamble Company Détergents avec additifs pour éviter le transfert de colorant
DE19532542B4 (de) * 1995-09-04 2008-12-18 Henkel Ag & Co. Kgaa Klarspülmittel mit kationischen Polymeren
EP0824145A1 (fr) 1996-08-12 1998-02-18 The Procter & Gamble Company Compositions de blanchiment
EP0835925A3 (fr) * 1996-09-09 1999-01-27 Unilever N.V. Compositions pour lave-vaisselle contenant des polymères amphotères
US5783540A (en) 1996-12-23 1998-07-21 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing tablets delivering a rinse aid benefit
US5866664A (en) * 1997-02-03 1999-02-02 Rohm And Haas Company Process for preparing phosphonate-terminated polymers
DE69819593T2 (de) * 1997-05-09 2004-09-16 Rohm And Haas Co. Detergensformulierungen
EP0998548B1 (fr) * 1997-07-23 2004-09-29 Unilever N.V. Compositions pour lave-vaisselle renfermant des polymeres cationiques ou amphoteres solubles dans l'eau
US6200937B1 (en) * 1998-06-09 2001-03-13 Neutrogena Corporation Anti-residue shampoo and liquid toiletry production method
US6367487B1 (en) 1999-08-11 2002-04-09 Diversey Lever, Inc. Anti-etch and cleaning composition for glass bottles
AU2001273988A1 (en) 2000-05-11 2001-11-20 Unilever Plc Machine dishwashing compositions containing bleaching agents and polymers
DE10050622A1 (de) * 2000-07-07 2002-05-02 Henkel Kgaa Klarspülmittel II a
DE10032612A1 (de) 2000-07-07 2002-02-14 Henkel Kgaa Klarspülmittel II
US6326343B1 (en) * 2000-09-08 2001-12-04 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Three-in-one composition for dishwashing machines
US20030162679A1 (en) * 2002-01-15 2003-08-28 Rodrigues Klein A. Hydrophobically modified polymer formulations
FR2839977B1 (fr) * 2002-05-27 2005-08-12 Rhodia Chimie Sa Utilisation, dans une composition lavante et rincante de la vaisselle en machine, d'un copolymere amphotere comme agent anti-redeposition des salissures
US7012048B2 (en) * 2003-02-11 2006-03-14 National Starch And Chemical Investment Holding Corporation Composition and method for treating hair containing a cationic ampholytic polymer and an anionic benefit agent

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2811010A1 (de) * 1977-03-15 1978-09-28 Oreal Mittel und verfahren zur behandlung von keratinmaterialien mit kationischen und anionischen polymeren

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ES2308224T3 (es) 2008-12-01
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PL1664257T3 (pl) 2008-12-31
WO2005026305A1 (fr) 2005-03-24
ATE400636T1 (de) 2008-07-15
DE10342631A1 (de) 2005-04-28
US7462588B2 (en) 2008-12-09
DE502004007574D1 (de) 2008-08-21

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