EP2235153B1 - Détergents - Google Patents

Détergents Download PDF

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Publication number
EP2235153B1
EP2235153B1 EP08860636A EP08860636A EP2235153B1 EP 2235153 B1 EP2235153 B1 EP 2235153B1 EP 08860636 A EP08860636 A EP 08860636A EP 08860636 A EP08860636 A EP 08860636A EP 2235153 B1 EP2235153 B1 EP 2235153B1
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EP
European Patent Office
Prior art keywords
acid
tablet
weight
total weight
dishwashing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP08860636A
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German (de)
English (en)
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EP2235153A1 (fr
Inventor
Thomas Holderbaum
Nadine Warkotsch
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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 PL08860636T priority Critical patent/PL2235153T3/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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • 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
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase

Definitions

  • the present patent application describes detergents, in particular detergents for the machine cleaning of dishes.
  • the subject of this application are, in particular, citrate-containing automatic dishwashing detergent tablets.
  • Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. So the dishes after machine cleaning should not only be completely free of food particles free but also, for example, no whitish, based on water hardness or other mineral salts stains that come from lack of wetting agent from dried water drops.
  • Modern automatic dishwashing detergents meet these requirements by integrating cleansing, caring, water-softening and clear-rinsing active ingredients and are known to the consumer, for example, as “2in1" or "3in1" dishwashing detergents.
  • As essential for the cleaning as for the rinse aid success constituent intended for the private consumer dishwasher automatic dishwashing contain builders. On the one hand, these builders increase the alkalinity of the cleaning liquor, whereby fats and oils are emulsified and saponified with increasing alkalinity, and on the other hand reduce the water hardness of the cleaning liquor by complexing the calcium ions contained in the aqueous liquor.
  • Particularly effective builders have proved to be the alkali metal phosphates which, for this reason, form the main constituent of the vast majority of commercially available automatic dishwashing detergents.
  • phosphates are highly valued for their beneficial effect as a component of automatic dishwashing detergents, their use is not unproblematic from the environmental point of view, since a substantial portion of the phosphate enters the water via the domestic effluent and especially in stagnant waters (lakes , Barrages) plays a critical role in their over-fertilization.
  • eutrophication the use of pentasodium triphosphate in laundry detergents in a number of countries, e.g. USA, Canada, Italy, Sweden, Norway, significantly reduced by law and regulations. completely prohibited in Switzerland. In Germany, detergents since 1984 may contain no more than 20% of this builder.
  • nitrilotriacetic acid especially sodium aluminosilicates (zeolites) are used as phosphate substitutes or substitutes in textile detergents.
  • these substances are not suitable for use in automatic dishwashing detergents for various reasons.
  • alkali metal phosphates in automatic dishwashing detergents therefore, a number of substitutes are discussed in the literature, of which the citrates are particularly noteworthy.
  • Phosphate-free automatic dishwashing detergents which, in addition to a citrate, furthermore contain carbonates, bleaches and enzymes are described, for example, in the European patents EP 662 117 B1 (Henkel KGaA) and EP 692 020 B1 (Henkel KGaA).
  • the object of the present application was to provide a reduced-phosphate or phosphate-free automatic dishwashing detergent, which is comparable or even comparable with conventional phosphate-containing cleaning agents in terms of its cleaning performance as well as its rinse results and its performance in terms of scale inhibition surpasses and preferably in the form of convenience of the tablet for the consumer can be offered.
  • hydrophobically modified anionic polymers with a mixture of citrate and citric acid can provide automatic dishwashing detergent tablets with very good cleaning and rinse-off results with simultaneously improved hardness and disintegration properties.
  • the basis for the advantageous cleaning and rinsing performance of automatic dishwasher detergents according to the invention is their content of citrate a), citric acid b) and anionic polymer c).
  • the basis for the advantageous hardness and disintegration properties of the tablet phases A according to the invention is their content of a combination of citrate a), citric acid b) and anionic
  • the hardness and the disintegrating property of this tablet phase are improved by the addition of the copolymer c).
  • the observed improvement in phase hardness and phase decay is observed with the addition of anionic copolymers with nonionic monomers, but not with the addition of anionic copolymers containing no nonionic monomers.
  • Dishwashing detergent tablets according to the invention may have one or more phases.
  • Automatic dishwashing detergent tablets which are preferred according to the invention are characterized in that the tablet has two or more phases.
  • a "tablet phase” is therefore a body produced by tableting a particulate premix and, for example, not a granulate contained in the particulate premix.
  • These phases may, for example, be in the form of layers, inserts (e.g., cores in a well tablet) or inclusions.
  • a dishwasher tablet according to the invention has at least one layer, preferably two, three or more layers. At least one of these layers corresponds in composition to the abovementioned tablet phase A.
  • a first characteristic constituent of agents according to the invention is the citrate.
  • the term "citrate” includes the salts of citric acid, in particular their alkali metal salts.
  • Particularly preferred machine dishwasher detergents according to the invention contain citrate, preferably sodium citrate, in amounts of 10 to 45% by weight, preferably 15 to 40% by weight, in each case based on the total weight of the dishwashing tablet phase.
  • a second characteristic constituent of agents according to the invention is citric acid.
  • the term "citric acid” includes the citric acid itself and not its salts.
  • Particularly preferred machine dishwasher detergents according to the invention contain citric acid in amounts of from 2 to 15% by weight and in particular from 5 to 12% by weight, in each case based on the total weight of the dishwashing tablet phase.
  • such automatic dishwashing agents have proven particularly advantageous in which the weight ratio of citrate to citric acid in at least one of the tablet phases is 40: 1 to 2: 1, preferably 30: 1 to 2: 1 and especially 20 : 1 to 2: 1.
  • the automatic dishwashing compositions according to the invention contain anionic polymer (s) comprising acid group-containing monomer (s) and nonionic monomer (s).
  • the proportion by weight of this copolymer in the total weight of the tablet phase is preferably 0.2 to 20 wt .-%, preferably 0.5 to 15 wt .-% and in particular 1.0 to 10 wt .-%.
  • the monomer distribution of the copolymers c) used according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is in each case from 5 to 95% by weight i) or ii), preferably from 50 to 90% by weight, monomer from Group i) and 10 to 50 wt .-% monomer from group ii), each based on the polymer.
  • copolymers c) may vary in the chemical nature of their monomers.
  • further ionic or nonionic monomers may be present in the copolymer.
  • the copolymers c) comprise at least one unsaturated carboxylic acid as the acid group-containing monomer.
  • Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid, maleic anhydride, Fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • Dishwashing detergent tablet according to the invention characterized in that the anionic polymer c) is a copolymer of a carboxylic acid, preferably acrylic acid or methacrylic acid or maleic acid, are preferred according to the invention.
  • the carboxylic acid groups may be wholly or partially in neutralized form, i. in that the acidic carbon atom of the carboxylic acid group in some or all of the carboxylic 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.
  • partially or fully neutralized carboxylic acid group-containing copolymers is preferred according to the invention.
  • the molar mass of the carboxylic acid group-containing copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use.
  • the molecular weights of the copolymers are between 2000 and 200,000 gmol -1 , preferably between 4000 and 25,000 gmol -1 and in particular between 5000 and 15,000 gmol -1 .
  • the copolymers c) comprise at least one unsaturated sulfonic acid as acid group-containing monomer.
  • 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 mixtures of said acids or their water-soluble salt
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. in that the acidic acid 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.
  • partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred automatic dishwashing agents are characterized in that the copolymers have molar masses 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 .
  • preferred copolymers c) preferably comprise monomers ii) selected from the group of mono- or polyunsaturated hydrocarbon radicals having 2 to 26 carbon atoms.
  • R 3 (R 3 ) -XR 4 used, in which R 1 to R 3 independently of one another is -H, -CH 3 or -C 2 H 5 , X is an optional spacer group which is selected from -CH 2 -, -C (O) O- and -C (O) -NH-, and R 4 represents a straight or branched chain saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.
  • Particularly preferred unsaturated hydrocarbon radicals are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexene, 1-octene, ⁇ -olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecen
  • the anionic polymers c) used in tablet phases A according to the invention may also contain a combination of monomers containing carboxylic acid groups and monomers containing sulfonic acid groups.
  • dishwashing detergent tablets according to the invention may contain, in addition to the aforementioned ingredients, further washing or cleaning-active substances, preferably from the group of builders, surfactants, polymers, bleaches, bleach activators, enzymes, glass corrosion inhibitors, corrosion inhibitors, disintegration aids, fragrances and perfume carriers. These preferred ingredients will be described in more detail below.
  • the builders include in particular silicates, carbonates and organic cobuilders as well as the phosphates.
  • automatic dishwashing agents contain as builder crystalline layered silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4 where particularly preferred values for x are 2, 3 or 4 and y is a number from 0 to 33, preferably from 0 to 20.
  • 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 preferably delayed release and have secondary washing properties.
  • Machine dishwashing detergents preferred in the context of the present invention comprise from 2 to 15% by weight, preferably from 3 to 12% by weight and in particular from 4 to 8% by weight, of silicate (s).
  • Dishwashing detergent tablets according to the invention characterized in that the tablet, based in each case on its total weight, contains between 1 and 60% by weight, preferably between 5 and 55 and in particular between 10 and 50% by weight of carbonate, are preferred according to the invention.
  • Some example formulations for preferred carbonate-containing tablet phases A can be found in the following table: ingredient Recipe 17 Recipe 18 Recipe 19 Recipe 20 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] citrate 5 to 50 10 to 45 15 to 40 15 to 40 citric acid 2 to 15 2 to 15 2 to 15 5 to 12 Copolymer 1 0.1 to 40 0.2 to 20 0.5 to 15 1.0 to 10 Sodium carbonate / bicarbonate 1 to 60 5 to 55 10 to 50 10 to 50 Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 1 copolymer (s) comprising i) monomers containing acid groups ii) other nonionic monomers
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and other organic cobuilders. These classes of substances are described below.
  • Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function.
  • these are in addition to the above 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 environmental reasons, as well as mixtures of these.
  • the free acids also typically 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.
  • 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 lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • phosphates are the pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate).
  • the sodium potassium tripolyphosphates are also preferably used according to the invention.
  • preferred tablets comprise this phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or pentasodium). Potassium tripolyphosphate), in amounts of less than 20% by weight, preferably less than 10% by weight and in particular less than 5% by weight.
  • Particularly preferred machine dishwashing detergent tablets according to the invention are free of inorganic phosphates.
  • Some example formulations for preferred tablet phases A as a constituent of phosphate-free automatic dishwasher tablets can be found in the following table: ingredient Recipe 21 Recipe 22 Recipe 23 Recipe 24 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] citrate 5 to 50 10 to 45 15 to 40 15 to 40 citric acid 2 to 15 2 to 15 2 to 15 5 to 12 Copolymer 1 0.1 to 40 0.2 to 20 0.5 to 15 1.0 to 10 Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 1 copolymer (s) comprising i) monomers containing acid groups ii) other nonionic monomers
  • complexing agents preferably phosphonates
  • preferred dishwasher tablets are characterized in that the tablets contain at least one complexing agent, preferably 1-hydroxyethane-1,1-diphosphonic acid and / or methylglycine diacetic acid.
  • the complex-forming phosphonates comprise a number of different compounds such as, for example, diethylene triamine penta (methylene phosphonic acid) (DTPMP). Hydroxyalkane or aminoalkane phosphonates are particularly preferred in this application.
  • hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used.
  • 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.
  • automatic dishwashing detergents which contain as phosphonates 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP).
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepenta
  • the automatic dishwashing compositions of the invention may contain two or more different phosphonates.
  • the weight fraction of the phosphonate (s) in the total weight of the automatic dishwashing agent is less than the weight proportion of the polymer (s) b).
  • those agents are particularly preferred in which the ratio of the weight fraction of polymer b) to the weight fraction of the phosphonate is 200: 1 to 2: 1, preferably 150: 1 to 2: 1, particularly preferably 100: 1 to 2: 1, most preferably 80: 1 to 3: 1 and in particular 50: 1 to 5: 1.
  • the proportion by weight of these complexing agents in particular the sum of the proportions by weight of 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and methylglycinediacetic acid (MGDA) is preferably 0.5 to 14% by weight, preferably 1 to 12% by weight and in particular 2 to 8 wt .-%.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • MGDA methylglycinediacetic acid
  • preferred automatic dishwashing detergent tablets contain enzyme (s). These include in particular proteases, amylases, lipases, Hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly. Detergents or cleaning agents contain enzymes preferably in total amounts of 1 ⁇ 10 -6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferable.
  • these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger and A. oryzae, as well as the further developments of the aforementioned amylases which are improved for use in detergents and cleaners. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • DSM 12368 Bacillus sp. A 7-7
  • CTTase cyclodextrin glucanotransferase
  • lipases or cutinases are also usable according to the invention.
  • these include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L.
  • the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • Washing or cleaning-active enzymes such as proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations.
  • Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Preferred enzyme preparations according to the invention such as protease and amylase preparations, contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and in particular between 0.8 and 10% by weight of the enzyme protein.
  • Preferred dishwasher tablets are characterized in that the tablet, in each case based on their total weight, 0.2 to 5 wt .-%, preferably 0.5 to 5 wt .-% and in particular 0.1 to 4 wt .-% of one or more Enzyme preparation (s) contains.
  • Preferred automatic dishwashing agents according to the invention also contain one or more bleaching agents.
  • bleaching agents include sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaches 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 dishwashing detergent tablets according to the invention are characterized in that the tablet, based in each case on their total weight, contains 1 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 12% by weight of sodium percarbonate.
  • the automatic dishwashing detergent tablets according to the invention may additionally 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.
  • TAED tetraacetylethylenediamine
  • bleach activators in particular TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight and more preferably 2 to 6% by weight. , in each case based on the total weight of the bleach activator-containing agents used.
  • bleach catalysts can also be used.
  • 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.
  • complexes of manganese in the oxidation state II, III, IV or IV which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S.
  • ligands are used which have nitrogen donor functions.
  • bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1,4,7-triazacyclononane (Me / TACN).
  • Me-TACN 1,4,7-trimethyl-1,4,7-triazacyclononan
  • TACN 1,4,7-triazacyclononane
  • TACD 1,5,9-trimethyl-1,5,9-triazacyclododecane
  • Me-TACD 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane
  • 2-methyl-1,4,7-triazacyclononane
  • Automatic dishwasher tablets characterized in that it further comprises a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 -TACN ) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me 4 -TACN), are preferred according to the invention, since in particular the cleaning result can be significantly improved by the abovementioned bleach catalysts.
  • a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 -TACN ) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me 4 -TACN), are preferred according to the invention, since in particular the cleaning result can be significantly improved by the abovementi
  • the abovementioned bleach-enhancing transition metal complexes are used in customary amounts, preferably in an amount of up to 5% by weight.
  • Dishwashing detergent tablets characterized in that the tablet contains, based on their total weight, 0.01 to 2 wt .-%, preferably 0.02 to 1 wt .-% and in particular 0.05 to 0.8 wt .-% bleach catalyst are preferred according to the invention.
  • preferred dishwashing detergents according to the invention may contain surfactants.
  • surfactants has been found to be particularly advantageous in terms of cleaning performance and drying, the nonionic gave the best results from the group of non-ionic surfactants used with particular preference, anionic surfactants and amphoteric surfactants.
  • Anionic and amphoteric surfactants are preferably used in combination with defoamers or foam inhibitors.
  • nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art.
  • Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • 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.
  • washing or cleaning agents in particular automatic dishwashing detergents, contain nonionic surfactants from the group of the alkoxylated alcohols.
  • 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 is linear or preferably methyl-branched in the 2-position may contain or 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 moles of EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 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 stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of 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.
  • ethoxylated nonionic surfactants consisting of C 6-20 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 mol of ethylene oxide per mol Alcohol was used.
  • a particularly preferred 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 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide.
  • C 16-20 alcohol straight-chain fatty alcohol having 16 to 20 carbon atoms
  • C 18 -alcohol preferably a C 18 -alcohol
  • at least 12 mol preferably at least 15 mol and especially at least 20 mol of ethylene oxide.
  • the so-called “narrow range ethoxylates” are particularly preferred.
  • Nonionic surfactants which have a melting point above room temperature.
  • nonionic surfactants 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 nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa ⁇ s, preferably above 35 Pa ⁇ s and in particular above 40 Pa ⁇ s. Also, nonionic surfactants having waxy consistency at room temperature are preferred depending on their purpose.
  • Nonionic surfactants from the group of alkoxylated alcohols are also used with particular preference.
  • the nonionic surfactant solid at room temperature preferably 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 content of such nonionic surfactant molecules preferably makes up 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 agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.
  • surfactants come from the groups of 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).
  • 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.
  • 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 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.
  • nonionic surfactants of the general formula 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 stand for integers from 1 to 6.
  • the preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R'-OH and ethylene or alkylene oxide.
  • the radical R 1 in the above formula may vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
  • Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals.
  • nonionic surfactants in which R 1 in the above formula 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.
  • nonionic surfactants having a C 9-15 alkyl group 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.
  • These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.
  • R 1 -CH (OH) CH 2 O- (AO) w - (A'O) x - (A "O) y - (A"'O) z -R 2 in which R 1 and R 2 independently of one another represents a straight-chain or branched, saturated or mono- or polyunsaturated C 2-40 -alkyl or -alkenyl radical;
  • A, A ', A "and A"' independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 2 -CH 3 ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention
  • end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2 , in addition to a radical R 1 , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having from 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.
  • 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 , in which R 1 is a linear or branched aliphatic hydrocarbon radical with 4 R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15.
  • nonionic surfactants having a free hydroxyl group on one of the two terminal alkyl radicals By using the above-described nonionic surfactants having a free hydroxyl group on one of the two terminal alkyl radicals, the formation of deposits in machine dishwashing can be markedly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.
  • 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 R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 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.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.
  • nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,
  • the dishwashing tablet according to the invention contains, based on its total weight, nonionic surfactant in amounts of from 0.1 to 10% by weight, preferably from 0.2 to 8% by weight and in particular from 3 to 6% by weight.
  • Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses.
  • Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts and magnesium and zinc complexes.
  • the spectrum of the invention preferred zinc salts, preferably organic acids, particularly 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 below 0.01 have mg / l, to those salts which have 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.
  • glass corrosion inhibitor at least one zinc salt of an organic carboxylic acid, particularly preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, Zinc acetate, zinc lactate and zinc citrate used.
  • Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.
  • the content of zinc salt in detergents or cleaners is preferably between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight and in particular between 0.4 and 3% by weight.
  • the content of zinc in oxidized form (calculated as Zn 2+ ) between 0.01 to 1 wt .-%, preferably between 0.02 to 0.5 wt .-% and in particular between 0.04 to 0, 2 wt .-%, each based on the total weight of the glass corrosion inhibitor-containing agent.
  • Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants 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.
  • 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts preference is given to using 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts, these substances being particularly preferably used in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2 Wt .-%, particularly preferably 0.01 to 0.04 wt .-% are used.
  • Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric and succinic acid.
  • disintegration aids so-called tablet disintegrants
  • tablet disintegrants or disintegrants are meant excipients which ensure the rapid disintegration of tablets in water or other media and for the rapid release of the active ingredients.
  • Disintegration aids are preferably used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.
  • perfume oils or perfumes within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, 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.
  • the fragrances can be processed directly, but it can also be advantageous to apply the fragrances on carriers that provide a slower fragrance release for long-lasting fragrance.
  • carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the substrates to be treated with the dye-containing agents such as textiles, glass, ceramics or plastic dishes do not stain them.
  • the colorant When choosing the colorant, it must be taken into account that the colorants have a high storage stability and insensitivity to light. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to 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. In the case of readily water-soluble colorants, colorant concentrations in the range of a few 10 -2 to 10 -3 % by weight are typically selected. By contrast, in the case of the particularly preferred, but less readily water-soluble, pigment dyes due to their brilliance, the suitable concentration of the colorant in detergents or cleaners is typically about 10 -3 to 10 -4 % by weight.
  • Dyeing agents which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It has proven 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.
  • Preferred automatic dishwashing detergent tablets contain a binder in addition to the washing and cleaning-active substances. Particularly preferred is the integration of such a binder into the tablet phase A of the dishwasher tablet.
  • the group of preferred binders includes organic materials from the group of (modified) celluloses and starches.
  • particularly preferred binders are nonionic polymers, preferably polyethylene glycols or polyvinylpyrrolidones.
  • Dishwashing detergent tablets characterized in that the tablet phase A contains a nonionic polymer, preferably a nonionic polymer from the group polyalkylene glycols, are preferred according to the invention.
  • the proportion by weight of the polyethylene glycol in the total weight of the tablet phase A is preferably 0.1 to 10 wt .-%, preferably 0.1 to 5 wt .-% and in particular 0.1 to 3 wt .-%
  • Some example formulations for preferred binder-containing tablet phases A can be found in the following table: ingredient Recipe 25 Recipe 26 Recipe 27 Recipe 28 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] citrate 5 to 50 10 to 45 15 to 40 15 to 40 citric acid 2 to 15 2 to 15 2 to 15 5 to 12 Copolymer 1 0.1 to 40 0.2 to 20 0.5 to 15 1.0 to 10 polyethylene glycol 0.1 to 5 0.1 to 5 0.1 to 5 0.1 to 3 Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 1 copolymer (s) comprising i) monomers containing acid groups ii) other nonionic monomers
  • the manufacture of the dishwasher tablets preferably takes place in a manner known to the person skilled in the art by compressing particulate premixes.
  • the particulate premix has an average particle size between 0.4 and 3.0 mm, preferably between 0.6 and 2.5 mm and in particular between 0.8 and 2.0 mm.
  • the tabletting during which the particulate premix is compressed in a so-called matrix between two punches to form a solid compress, is divided into four sections: metering, compaction (elastic deformation), plastic deformation and expulsion.
  • the tabletting is preferably carried out on so-called rotary presses.
  • Plastic coatings, plastic inserts or plastic stamps are particularly advantageous.
  • Rotary punches have also proved to be advantageous, whereby upper and lower punches should, if possible, be rotatable. With rotating punches can be dispensed with a plastic insert usually.
  • the stamp surfaces should be electropolished.
  • Preferred processes in the context of the present invention are characterized in that the pressing takes place at pressing pressures of 0.01 to 50 kNcm -2 , preferably of 0.1 to 40 kNcm -2 and in particular of 1 to 25 kNcm -2 .
  • the density of dishwasher tablets preferred according to the invention is between 1.1 and 1.8 g / cm 3 , preferably between 1.2 and 1.7 cm 3 and in particular between 1.3 and 1.6 g / cm 3 .
  • Concentric presses can be provided to increase the throughput with two filling shoes, which only a semicircle must be run through to produce a tablet.
  • the tablets in the context of the present invention can also be multi-phase, in particular multi-layered.
  • the moldings can be made in a predetermined spatial form and predetermined size.
  • a form of space practically all useful manageable configurations come into consideration, for example, the training as a blackboard, the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section.
  • This last embodiment covers the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.
  • the detergent tablets After pressing, the detergent tablets have a high stability.
  • ⁇ is the diametrical fracture stress (DFS) in Pa
  • P is the force in N which results in the pressure applied to the molded article causing the breakage of the molded article
  • D is the molded article diameter in meters and t the height of the moldings.
  • the automatic dishwasher detergents according to the invention show their advantageous cleaning properties, in particular also low-temperature cleaning processes.
  • Preferred dishwashing processes using agents according to the invention are therefore characterized in that these processes are carried out at temperatures up to a maximum of 55 ° C., preferably up to a maximum of 50 ° C.
  • composition of the particulate premixes can be found in the following table: raw material V1 V2 E1 phosphonate 1.94 1.94 1.94 Nonionic surfactant 5.66 5.66 5.66 Sodium citrate dihydrate 22.39 22.39 22.39 Citric acid anhydrate 5.76 5.76 5.76 soda 32.36 32.36 32.36 sodium 17,04 17,04 17,04 TAED 4.17 4.17 4.17 Polyacrylic acid 1 9.06 - - Polysulfonic acid 2 - 9.06 - Anionic polymer 3 - - 9.06 Misc Add 100 Add 100 Add 100 Add 100 Add 100 1 polyacrylic acid, sodium salt 2 sulfonic acid-containing copolymer without nonionic monomers, sodium salt 3 anionic polymer, sodium salt, comprising i) monomers containing acid groups ii) other nonionic monomers

Abstract

L'invention concerne des tablettes de détergents pour lave-vaisselle à une ou plusieurs phases, constituées d'un matériau en forme de particules comprimées. Selon l'invention, au moins une phase A des tablettes comprend, relativement à son poids total : a) 5 à 50% en poids de citrate ; b) 1 à 20% en poids d'acide citrique ; c) 0,1 à 40% en poids de polymère(s) anionique(s) comprenant i) des monomères contenant des groupes acide, ii) d'autres monomères non ioniques. Ces tablettes se distinguent par de très bons résultats de lavage et de rinçage, avec en même temps une durée et des propriétés de dissociation améliorées.

Claims (15)

  1. Pastille monophasique ou polyphasique d'agent de lavage de la vaisselle constituée d'une matière particulaire comprimée, caractérisée en ce qu'au moins une phase A de la pastille comprend, rapportés à son poids total :
    a) de 5 à 50 % en poids de citrate ;
    b) de 1 à 20 % en poids d'acide citrique ;
    c) de 0,1 à 40 % en poids d'un ou de plusieurs polymères anioniques modifiés pour les rendre hydrophobes, comprenant :
    i) de 5 à 95 % en poids de monomères contenant des groupes acides ;
    ii) de 5 à 95 % en poids d'autres monomères non ioniques.
  2. Pastille d'agent de lavage de la vaisselle selon la revendication 1, caractérisée en ce que la phase A de la pastille contient, à chaque fois rapportés à son poids total, de 10 à 45 % en poids, et en particulier de 15 à 40 % en poids de citrate, de préférence de citrate de sodium.
  3. Pastille d'agent de lavage de la vaisselle selon l'une quelconque des revendications précédentes, caractérisée en ce que la phase A de la pastille contient, à chaque fois rapportés à son poids total, de 2 à 15 % en poids, et en particulier de 5 à 12 % en poids d'acide citrique.
  4. Pastille d'agent de lavage de la vaisselle selon l'une quelconque des revendications précédentes, caractérisée en ce que le rapport pondéral du citrate à l'acide citrique dans la phase A de la pastille s'élève de 40:1 à 2:1, de préférence de 30:1 à 2:1, et en particulier de 20:1 à 2:1.
  5. Pastille d'agent de lavage de la vaisselle selon l'une quelconque des revendications précédentes, caractérisée en ce que la phase A de la pastille contient, à chaque fois rapportés à son poids total, le polymère anionique c) dans des quantités de 0,2 à 20 % en poids, de préférence de 0,5 à 15 % en poids, et en particulier de 1,0 à 10 % en poids.
  6. Pastille d'agent de lavage de la vaisselle selon l'une quelconque des revendications précédentes, caractérisée en ce que, en ce qui concerne le polymère anionique c), il s'agit d'un copolymère d'un acide carboxylique, de préférence de l'acide acrylique ou de l'acide méthacrylique ou de l'acide maléique.
  7. Pastille d'agent de lavage de la vaisselle selon l'une quelconque des revendications précédentes, caractérisée en ce que, en ce qui concerne le polymère anionique c), il s'agit d'un copolymère :
    i) d'un monomère contenant des groupes d'acides carboxyliques ;
    ii) d'un monomère contenant des groupes d'acides sulfoniques ;
    iii) d'un monomère non ionogène.
  8. Pastille d'agent de lavage de la vaisselle selon l'une quelconque des revendications précédentes, caractérisée en ce que la phase A de la pastille contient, à chaque fois rapportés à son poids total, moins de 20 % en poids, de préférence moins de 10 % en poids, et en particulier moins de 5 % en poids de phosphate.
  9. Pastille d'agent de lavage de la vaisselle selon l'une quelconque des revendications précédentes, caractérisée en ce que la phase A de la pastille contient, à chaque fois rapportés à son poids total, entre 1 et 60 % en poids, de préférence entre 5 et 55, et en particulier entre 10 et 50 % en poids de carbonate.
  10. Pastille d'agent de lavage de la vaisselle selon l'une quelconque des revendications précédentes, caractérisée en ce que la pastille contient, à chaque fois rapportés à son poids total, de 0,2 à 5 % en poids, de préférence de 0,5 à 5 % en poids, et en particulier de 0,1 à 4 % en poids d'une ou de plusieurs préparations enzymatiques.
  11. Pastille d'agent de lavage de la vaisselle selon l'une quelconque des revendications précédentes, caractérisée en ce que la pastille contient, à chaque fois rapportés à son poids total, de 1 à 20 % en poids, de préférence de 2 à 15 % en poids, et en particulier de 4 à 12 % en poids de percarbonate de sodium.
  12. Procédé pour la production d'une pastille pour le lavage de la vaisselle selon l'une quelconque des revendications précédentes, caractérisé en ce qu'on prépare un prémélange particulaire comprenant :
    a) de 5 à 50 % en poids de citrate ;
    b) de 1 à 20 % en poids d'acide citrique ;
    c) de 0,1 à 40 % en poids d'un ou de plusieurs polymères anioniques
    et on le comprime pour obtenir une phase de pastille.
  13. Procédé selon la revendication 12, caractérisé en ce que le prémélange particulaire présente une granulométrie moyenne entre 0,4 et 3,0 mm, de préférence entre 0,6 et 2,5 mm, et en particulier entre 0,8 et 2,0 mm.
  14. Procédé pour le nettoyage de la vaisselle dans un lave-vaisselle, dans lequel on met en oeuvre un agent de lavage de la vaisselle en machine selon l'une quelconque des revendications 1 à 11.
  15. Procédé selon la revendication 14, caractérisé en ce que, au cours du processus de nettoyage, on n'introduit de manière dosée aucun adoucisseur d'eau supplémentaire et aucun agent de rinçage supplémentaire dans l'enceinte du lave-vaisselle.
EP08860636A 2007-12-10 2008-10-31 Détergents Revoked EP2235153B1 (fr)

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EP2235153A1 (fr) 2010-10-06
WO2009074398A1 (fr) 2009-06-18
KR20100106962A (ko) 2010-10-04
DE102007059677A1 (de) 2009-06-25
ES2386014T3 (es) 2012-08-07
PL2235153T3 (pl) 2012-11-30
US20100249008A1 (en) 2010-09-30

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