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WO2004013269A1 - Produits de lavage pour lave-vaisselle comprenant des agents d'inhibition du depot - Google Patents

Produits de lavage pour lave-vaisselle comprenant des agents d'inhibition du depot Download PDF

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Publication number
WO2004013269A1
WO2004013269A1 PCT/EP2003/007689 EP0307689W WO2004013269A1 WO 2004013269 A1 WO2004013269 A1 WO 2004013269A1 EP 0307689 W EP0307689 W EP 0307689W WO 2004013269 A1 WO2004013269 A1 WO 2004013269A1
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Prior art keywords
acid
weight
water
mol
preferred
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PCT/EP2003/007689
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German (de)
English (en)
Inventor
Christian Nitsch
Ulrich Pegelow
Maren Jekel
Markus Semrau
Arnd Kessler
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Henkel Kommanditgesellschaft Auf Aktien
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Priority to AU2003250963A priority Critical patent/AU2003250963A1/en
Publication of WO2004013269A1 publication Critical patent/WO2004013269A1/fr

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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
    • C11D3/3746—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
    • 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
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning 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
    • 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

Definitions

  • the present invention relates to automatic dishwashing agents which contain builders and scale-inhibiting polymers. Forms of supply which provide cleaning agents and rinse aid in one product are further objects of the present invention.
  • rinse aid is used successfully today.
  • the addition of rinse aid at the end of the wash program ensures that the water runs off the items to be washed as completely as possible, so that the different surfaces are residue-free and flawlessly shiny at the end of the wash program.
  • the automatic cleaning of dishes in household dishwashers usually comprises a pre-wash, a main wash and a rinse cycle, which are interrupted by intermediate wash cycles.
  • the pre-wash cycle for heavily soiled dishes can be activated, but is only selected by the consumer in exceptional cases, so that in most machines a main wash cycle, an intermediate rinse cycle with pure water and a rinse cycle are carried out.
  • 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 non-ionic surfactants as the main component. Such rinse aids are in liquid form and are widely described in the prior art. Your main task is to prevent limescale and deposits on the cleaned dishes. In addition to water and low-foaming nonionic surfactants, these rinse aids often also contain hydrotopes, pH adjusting agents such as citric acid or scale-inhibiting polymers.
  • the storage tank in the dishwasher must be filled with rinse aid at regular intervals, with one filling sufficient for 10 to 50 wash cycles, depending on the type of machine. If you forget to fill up the tank, glasses in particular become unsightly due to limescale and deposits. In the prior art there are therefore some proposed solutions for integrating a rinse aid into the detergent for machine dishwashing. "2in1" - Products that combine detergent and rinse aid are now also established on the market.
  • cleaners which combine the three functions of cleaning, rinsing and water softening in a single detergent formulation, so that the refill of salt with water hardness levels of 1 to 3 is no longer necessary for the consumer.
  • these cleaners usually contain sodium tripolyphosphate and / or polymers which act as softeners.
  • hardness deposits calcium and magnesium phosphate deposits
  • the object of the present invention was to provide cleaning agents for automatic dishwashing which can be formulated both as "normal” products and as “multifunctional cleaners", these products being said to show an improved deposit-inhibiting effect compared to conventional products of the prior art.
  • the present invention relates to machine dishwashing detergents containing 10 to 75% by weight of builder (s) and 1 to 25% by weight of a polymer which has monomer units of the formula I.
  • H 2 C CC-0-R 2 - [R 3 -0] n -R 4 (I),
  • R 2 for a chemical bond or a straight-chain or branched CC 6 -
  • R 3 for the same or different, straight-chain or branched C 2 -C 4 -
  • R 4 for a straight-chain or branched C 1 -C 6 -alkyl radical, ' . n stands for a natural number from 3 to 50.
  • the cleaning agents for machine dishwashing according to the invention are notable for their improved deposit-inhibiting action, in particular against deposits caused by the other constituents of the detergent formulation, such as deposits of calcium and magnesium phosphate, calcium and magnesium silicate and calcium and magnesium phosphonate, and deposits that come from the dirt components of the washing liquor, such as fat, protein and starch deposits, are effective.
  • the items of crockery treated with the agents according to the invention become significantly cleaner in subsequent cleaning operations than items of crockery that have been washed with conventional agents.
  • the effect is independent of whether the automatic dishwashing detergents are in liquid, powder or tablet form.
  • the invention is also characterized by an improved “cleanability” of the treated substrates in later cleaning processes and by a considerable reduction in the drying time compared to comparable agents without the use of the polymers mentioned.
  • drying time is generally understood to mean the meaning in words, i.e. the time which elapses until a dish surface treated in a dishwasher is dried, but in particular the time which elapses, up to 90% of one with a cleaning or Rinse aid is dried in a concentrated or diluted form treated surface.
  • the cleaning agents according to the invention for machine dishwashing contain 10 to 75% by weight of builders. They can contain all builders commonly used in washing and cleaning agents, in particular silicates, carbonates, zeolites, organic builders and cobuilders such as citrates or polycarboxylates and - if there are no ecological concerns about their use - also the phosphates.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x ⁇ 2 ⁇ + ⁇ 'H 2 0, 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 is 2, 3 or 4.
  • Preferred crystalline layered silicates of the The formula given are those in which M is sodium and x is 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 0 5 'yH 2 0 are preferred.
  • Preferred cleaning agents according to the invention for machine dishwashing have a content of crystalline layered silicate, preferably in amounts of 0.5 to 10% by weight, preferably 0.75 to 5% by weight and in particular 1 to 3% by weight, in each case based on the total mean.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the optionally usable fine crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water. It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry.
  • Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HP0 3 ) n and orthophosphoric acid H 3 P0 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in fabrics and also contribute to cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 P0 exists as a dihydrate (density 1.91, preferably “3 , melting point 60 °) and as a monohydrate (density 2.04, preferably " 3 ). Both salts are white powders, which are very easily soluble in water, lose the water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 0 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 0 9 ) and Maddrell's salt (see below).
  • NaH 2 P0 4 is acidic; it arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate primary or monobasic potassium phosphate, potassium biphosphate, KDP
  • KH 2 P0 4 is a white salt with a density of 2.33 "3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KP0 3 ) J and is easily soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HP0, is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly “3 , water loss at 95 °), 7 mol. (Density 1, 68 gladly “ 3 , melting point 48 ° with loss of 5 H 2 0) and 12 mol. Water ( Density 1, 52 like “3 , melting point 35 ° with loss of 5 H 2 0), becomes anhydrous at 100 ° and changes to diphosphate Na 4 P 2 0 7 when heated more.
  • Disodium hydrogen phosphate is lost by neutralizing phosphoric acid with soda solution Using phenolphthalein as an indicator Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HP0 4 , is an amorphous, white salt that is easily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 P0 4 are colorless crystals which, as dodecahydrate, have a density of 1.62 "3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 0 5 ) a melting point of 100 ° C and in anhydrous Form (corresponding to 39-40% P 2 0 5 ) have a density of 2.536 "3.
  • Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH.
  • Tripotassium phosphate (tertiary or three-base potassium phosphate), K 3 P0 4 , is a white, deliquescent, granular powder with a density of 2.56 "3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when Thomas slag is heated with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na P 2 0 7 , exists in anhydrous form (density 2.534 like “3 , melting point 988 °, also given 880 °) and as decahydrate (density 1, 815-1, 836 like " 3 , melting point 94 ° with water loss). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na 4 P 2 0 7 is formed by heating 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 formers and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 0 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33, preferably 3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.
  • NaH 2 P0 4 or KH 2 P0 produces higher mols.
  • Sodium and potassium phosphates in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's 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)
  • About 17 g of the salt of water free of water of crystallization dissolve in 100 g of water at room temperature, about 20 g at 60 ° and around 32 g at 100 °; after heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (> 23% p 2 0 5 , 25% K 2 0). The Kjaliumpolyphosphate are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:
  • these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.
  • Detergents according to the invention for automatic dishwashing which each contain 10 to 75% by weight, preferably 20 to 60% by weight, particularly preferably 30 to 50% by weight and in particular 35 to 45% by weight of phosphate (s) contain on the entire agent are preferred.
  • the agents according to the invention can also contain carbonates and / or hydrogen carbonates as builders.
  • the alkali metal salts particularly sodium carbonate
  • Preferred agents have a sodium carbonate content which is particularly preferably between 5 and 20% by weight, preferably between 7.5 and 17.5% by weight and in particular between 10 and 15% by weight, in each case based on the total Medium, lies.
  • s organic cobuilders can be used in the dishwasher detergents according to the invention, in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as 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, sugar acids and mixtures of these.
  • 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 cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • Polymeric polycarboxylates are also suitable as builders; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used.
  • GPC gel permeation chromatography
  • the measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard.
  • the molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 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 agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • Biodegradable polymers of more than two different monomer units are also particularly preferred, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers ,
  • copolymers are those which preferably have acrolein and acrylic acid / acrylic acid acids or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Polyaspartic acids or their salts and derivatives are particularly preferred which, in addition to cobuilder properties, also have a bleach-stabilizing effect.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from 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. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
  • 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 at C 6 of the saccharide ring can be particularly advantageous.
  • Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable cobuilders.
  • Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be 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 aminoalkane phosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably in the form of the neutral sodium salts, e.g. B.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, especially if the agents also contain bleach, it may be preferred to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • the agents according to the invention contain polymers which have monomer units of the formula (I). These polymers can either be homopolymers which have only monomer units of the formula (I) or copolymers which contain one or more other monomers in copolymerized form. Preferred special monomers which fall under the general formula (I) are described below, while further monomers which may be polymerized are described below.
  • the radical R 1 can stand for -H or -CH 3 , ie the monomer unit of the formula (I) contained in the polymers is based on acrylic acid or methacrylic acid.
  • the radical R 2 can represent a chemical bond or a straight-chain or branched CrC 6 alkylene radical.
  • monomer units of the formula (I) are preferred in which R 2 stands for a chemical bond or for a straight-chain, saturated alkenyl radical, units of the formula (I) in which R 2 stands for a chemical bond being preferred.
  • R 3 can each represent the same or different, straight-chain or branched C 2 -C 4 -alkylene radicals, units of the formula (I) in which R 3 represents -CH 2 -CH 2 - or -CH 2 -CH 2 -CH 2 - stands, are preferred.
  • R 4 represents a straight-chain or branched C r C 6 alkyl radical, units of the formula (I) in which R 4 represents -CH 3 or -CH 2 -CH 3 are preferred.
  • the number n in the monomer unit (I) stands for a natural number from 3 to 50, values from 5 to 40 being preferred and values from 10 to 30 being particularly preferred.
  • n of the compounds listed in the tables below are preferably 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26 , 27, 28, 29 or 30.
  • methoxypolyethylene glycol (meth) acrylate and methoxypolypropylene glycol (meth) acrylate are preferred and methoxypolyethylene glycol methacrylate is particularly preferred.
  • the polymers contained in the agents according to the invention are preferably copolymers.
  • the agents according to the invention particularly preferably contain polymers which, in addition to monomer units of the formula (I), also contain one or more monomers from the group of the unsaturated carboxylic acids. Acrylic acid, methacrylic acid and maleic acid are preferably used here.
  • Preferred automatic dishwashing agents according to the invention are characterized in that the polymer is a copolymer which contains one or more monomers (e) from the group consisting of acrylic acid and / or methacrylic acid and / or the water-soluble salts of acrylic and / or methacrylic acid.
  • Copolymers are particularly preferred which, in addition to the monomer units of the formula (I), contain both acrylic acid units and methacrylic acid units.
  • automatic dishwashing agents according to the invention are preferred, in which the polymer is a copolymer which
  • the proportion a) of polymerized acrylic acid is preferably 60 to 90 mol%, preferably 65 to 85 mol% and particularly preferably 65 to 75 mol%.
  • the proportion b) of polymerized methacrylic acid is preferably 10 to 27.5 mol%, preferably 12.5 to 25 mol% and particularly preferably 15 to 25 mol%.
  • the proportion c) of monomer units of the formula (I) is preferably 3 to 18 mol%, particularly preferably 5 to 15 mol% and in particular 5 to 10 mol%. All of the mol% stated above relate to the polymer contained in the agents according to the invention.
  • the copolymers contained in the agents according to the invention preferably have an average molecular weight M w of 3,000 to 50,000 gmol "1 , preferably from 10,000 to 30,000 gmol " 1 and particularly preferably from 15,000 to 25,000 gmol "1 .
  • the K value of the copolymers is preferably 15 to 40, in particular 20 to 35, especially 27 to 30 (measured in 1% strength by weight aqueous solution at 25 ° C.).
  • the agents according to the invention can contain further polymers.
  • the use of polymers containing sulfonic acid groups is particularly preferred.
  • preferred automatic dishwashing agents according to the invention are characterized in that they additionally contain 0.1 to 70% by weight.
  • 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 represents -COOH or - COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • H 2 C CH-X-S0 3 H (purple),
  • H 2 C C (CH 3 ) -X-S0 3 H (IIIb),
  • ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds.
  • the group III) monomer content of the above-mentioned sulfonic acid group-containing polymers is preferably less than 20% by weight, based on the polymer.
  • Particularly preferred polymers containing sulfonic acid groups consist only of monomers of groups i) and ii).
  • the agents according to the invention preferably contain other copolymers
  • 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 represents -COOH or - COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,
  • Particularly preferred agents according to the invention contain one or more copolymers
  • H 2 C CH-X-S0 3 H (purple),
  • H 2 C C (CH 3 ) -X-S0 3 H (IIIb),
  • R 6 and R 7 are independently selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -GH (CH 3 ) 2 and.
  • copolymers optionally contained in the agents according to the invention can contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives from group i) with all representatives from group ii) and all representatives from group iii) can be combined.
  • Particularly preferred polymers have certain structural units, which are described below.
  • automatic dishwashing agents according to the invention are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula IV
  • These polymers are produced by copolymerization of acrylic acid with an acrylic acid derivative containing sulfonic acid groups. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the agents according to the invention is also preferred and is characterized in that the agents according to the invention will contain one or more copolymers which have structural units of the formula V.
  • acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed.
  • Agents according to the invention which contain one or more copolymers, the structural units of the formula VI, are also preferred
  • a further preferred embodiment of the present invention are agents which contain one or more copolymers which have structural units of the formula VII
  • maleic acid can also be used as a particularly preferred monomer from group i).
  • preferred agents according to the invention are obtained which are characterized in that they contain one or more copolymers, the structural units of the formula VIII
  • All or part of the sulfonic acid groups in the polymers can be in neutralized form, i.e. that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions.
  • Corresponding agents according to the invention which are characterized in that the sulfonic acid groups in the copolymer are partially or fully neutralized, are preferred according to the invention.
  • the monomer distribution in the copolymers in copolymers which only contain monomers from groups i) and ii) is preferably in each case 5 to 95% by weight of i) or ii), particularly preferably 50 to 90% by weight of monomer from the Group i) and 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
  • those which contain 20 to 85% by weight of monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) are particularly preferred .
  • the molar mass of the polymers described above in the agents according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use.
  • Preferred uses are characterized in that the copolymers have molar masses 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 .
  • the content of one or more of the above-described copolymers containing sulfonic acid groups in the agents according to the invention can vary depending on the intended use and desired product performance, preferred agents according to the invention being characterized in that they contain the copolymer (s) containing sulfonic acid groups in amounts of 0.001 to 20% by weight, preferably from 0.01 to 15% by weight, particularly preferably from 0.1 to 10% by weight and in particular from 0.15 to 5% by weight, in each case based on the composition , contain.
  • agents according to the invention i.e. Agents which, in addition to 10 to 75% by weight of builder (s) and polymers which contain monomer units of the formula (I), also contain copolymers containing sulfonate groups.
  • the polymers which have the monomer units of the formula (I) may also contain copolymerized monomers containing sulfonic acid groups.
  • the polymers are quasi multifunctional.
  • Machine dishwashing detergents preferred according to the invention are characterized in that the polymer with monomer units of the formula (I) is a copolymer which contains one or more monomer (s) of the formula III containing sulfonic acid groups
  • polymers which contain both monomer units of the formula (I) and monomers of the formula (III) containing sulfonic acid groups
  • monomers (III) are: vinylsulfonic acid, 2-sulfoethyl (meth) acrylic acid, 2-sulfopropyl ( meth) acrylic acid, 3-sulfopropyl (meth) acrylic acid and 4-sulfobutyl (meth) acrylic acid and their salts, especially the sodium salts, vinyl sulfonic acid, 2-sulfoethyl methacrylic acid and 2-sulfopropyl methacrylic acid and their sodium salts being preferred, and 2-sulfoethyl methacrylic acid and its sodium salt being particularly preferred are.
  • Polymers which have both monomer units of the formula (I) and also contain monomers of the formula (III) in copolymerized form are preferably present in the agents according to the invention.
  • the monomer distribution in particularly preferred copolymers of the type mentioned above provides approximately equal proportions of monomer units of the formula (I) and monomers of the formula (III), copolymers which, in addition, predominantly containing copolymerized acrylic acid and / or methacrylic acid being preferred.
  • automatic dishwashing agents according to the invention are preferred, in which the polymer is a copolymer which
  • the proportion a) of polymerized acrylic acid and / or methacrylic acid and / or a water-soluble salt of these acids is preferably 50 to 90 mol%, preferably 55 to 85 mol% and particularly preferably 60 to 90 mol%.
  • the proportion b) of polymerized monomers of the formula (III) containing sulfonic acid groups is preferably 4 to 30 mol%, preferably 5 to 25 mol% and particularly preferably 5 to 20 mol%.
  • the proportion c) of monomer units of the formula (I) is preferably 3 to 30 mol%, particularly preferably 4 to 25 mol% and in particular 5 to 20 mol%. All of the mol% stated above relate to the polymer contained in the agents according to the invention.
  • the copolymers contained in the agents according to the invention preferably have an average molecular weight M w of 3,000 to 40,000 gmol "1 , preferably 10,000 to 30,000 gmol " 1 and particularly preferably 15,000 to 25,000 gmol "1 .
  • the K value of the copolymers is preferably 15 to 35, in particular 20 to 32, especially 27 to 30 (measured in a 1% strength by weight aqueous solution at 25 ° C.).
  • Machine dishwashing detergents which are particularly preferred according to the invention are characterized in that the additional polymer containing sulfonic acid groups and / or the copolymer with structural units of the formula (I) structural units of the formulas IV and and / or V and / or VI and / or VII and / or VIII and / or IX
  • the polymers or copolymers contained in the agents according to the invention can be used in varying amounts, machine dishwashing detergents are preferred which contain the polymer (s) or copolymer (s) in amounts of 2.5 to 22.5% by weight. %, preferably from 5 to 20% by weight, particularly preferably from 7.5 to 17.5% by weight and in particular from 8 to 15% by weight.
  • the agents according to the invention can also contain anionic, nonionic, cationic and / or amphoteric surfactants as the surfactant component, nonionic surfactants being preferred due to their foaming power.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Preferred surfactants of the sulfonate type are C 9-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and Disulfonates such as those obtained, for example, from C 12-18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids 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) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C 2 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • the C 2 -C 16 alkyl sulfates and C 2 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred for washing technology reasons.
  • 2,3-alkyl sulfates which can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C ⁇ 2-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulphosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred Sülfosuccinate contain C 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulphosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves (for a description, see below).
  • Sülfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are again particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • the preferred ethoxylated alcohols include, for example, C 2 - ⁇ l alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci 2 - ⁇ s alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C: 12 - ⁇ alcohol with 3 EO and C 12-18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula R ⁇ (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol for a glycose unit with 5 or 6 C-ato- Men, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • surfactants are polyhydroxy fatty acid amides of the formula (IX),
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 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 (X)
  • 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 is 2 to 8 carbon atoms
  • R 2 is a linear, branched or cyclic Alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1-4 alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives of this radical.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the cleaning agents according to the invention for machine dishwashing particularly preferably contain nonionic surfactants, in particular nonionic surfactants from the group of the aikoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ⁇ 2 . ⁇ 4 alcohol containing 3 EO and C 12- ⁇ 8 alcohol containing 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Dishwashing agents according to the invention which contain a nonionic surfactant which has a melting point above room temperature are particularly preferred. Accordingly, preferred dishwashing detergents are characterized in that they have nonionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43, 3 ° C.
  • Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature.
  • nonionic surfactants which are highly viscous at room temperature are used, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature originate from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more 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 with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.
  • a particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-2 alcohol), a C preferably 18 alcohol and at least 12 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide won.
  • C 16-2 alcohol straight chain fatty alcohol having 16 to 20 carbon atoms
  • C preferably 18 alcohol and at least 12 mole preferably at least 15 mol and in particular at least 20 moles of ethylene oxide won.
  • the so-called “narrow ranks ethoxylates” are particularly preferred.
  • particularly preferred dishwashing detergents according to the invention contain ethoxylated nonionic surfactant (s) which consist of C 6-2 o-monohydroxyalkanols or C 6 . 20 -alkylphenols or C 16-2 o-fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.
  • ethoxylated nonionic surfactant consist of C 6-2 o-monohydroxyalkanols or C 6 . 20 -alkylphenols or C 16-2 o-fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.
  • the nonionic surfactant which is solid at room temperature, preferably has additional propylene oxide units in the molecule.
  • Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant.
  • 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 makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70 wt .-% of the total molecular weight of such nonionic surfactants.
  • Preferred dishwashing detergents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule 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 Make up surfactants.
  • nonionic surfactants with melting points above room temperature which are to be used particularly preferably contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which comprises 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol 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 dishwashing detergent according to the invention contains nonionic surfactants of the formula
  • R 1 represents a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof
  • R 2 denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y stands for a value of at least 15.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
  • R 1 and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 3 represents H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical
  • x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ⁇ 2, each R 3 in the above formula can 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, where Residues with 8 to 18 carbon atoms are particularly preferred.
  • H, -CH 3 or - CH 2 CH 3 are particularly preferred for the radical R 3 .
  • 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 can be different if x> 2.
  • the value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x represents numbers 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 represents H and x assumes values from 6 to 15.
  • dishwashing detergents according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula
  • R 1 and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 3 represents H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical
  • x stands for values between 1 and 30
  • k and j stand for values between 1 and 12, preferably between 1 and 5, with surfactants of the type
  • weakly foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants.
  • surfactants with EO-AO-EO-AO blocks are preferred, one to ten EO or AO groups being bonded to one another before a block follows from the other groups.
  • automatic dishwashing agents according to the invention which contain surfactants of the general formula X as nonionic surfactant (s) are preferred
  • R 1 represents 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 represent integers from 1 to 6.
  • the preferred nonionic surfactants of the formula X can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in the above formula X can 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 generally not shown, 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, in the mixture, methyl-branched or linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • preferred dishwasher detergents according to the invention are those in which R 1 in formula I for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 is up to 11 carbon atoms.
  • butylene oxide is particularly suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit.
  • R 2 and R 3 are selected independently of one another from - CH 2 CH 2 -CH 3 or CH (CH 3 ) 2 are suitable.
  • Preferred automatic dishwashing agents are characterized in that R 2 or R 3 for a radical -CH 3 , w and x independently of one another stand for values of 3 or 4 and y and z independently of one another for values of 1 or 2.
  • nonionic surfactants which have a C 9-15 -alkyl radical with 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, are particularly preferred for use in the agents according to the invention.
  • These surfactants have the required low viscosity in aqueous solution and can be used with particular preference according to the invention.
  • the specified C chain lengths and degrees of ethoxylation or degrees of alkoxylation represent statistical mean values which can be an integer or a fractional number for a specific product. Due to the manufacturing process, commercial products of the formulas mentioned usually do not consist of an individual representative, but of mixtures, which can result in mean values and fractional numbers both for the C chain lengths and for the degrees of ethoxylation or alkoxylation.
  • cationic and / or amphoteric surfactants can also be used.
  • the agents according to the invention can contain, for example, cationic compounds of the formulas XI, XII or XIII as cationic active substances:
  • automatic dishwashing agents which contain surfactant (s), preferably nonionic surfactant (s) and in particular nonionic surfactant (s) from the group of the alkoxylated alcohols, in amounts of 0.1 to 60% by weight. %, preferably from 0; 5 to 50% by weight, particularly preferably from 1 to 40% by weight, and in particular from 2 to 30% by weight, in each case based on the composition.
  • Particularly preferred automatic dishwashing agents according to the invention are characterized in that they contain 5 to 25% by weight, preferably 6 to 22.5% by weight, particularly preferably 7.5 to 20% by weight and in particular 8 to 17.5% by weight.
  • -% non-ionic surfactant (s) contain.
  • automatic dishwashing detergents In addition to the builders, bleaches, bleach activators, enzymes, silver preservatives, dyes and fragrances, etc. are preferred ingredients of automatic dishwashing detergents. In addition, other ingredients may be present, with automatic dishwashing agents according to the invention being preferred which additionally contain one or more substances from the group of the acidifying agents or the chelating agents.
  • Both inorganic acids and organic acids are suitable as acidifiers, provided that these are compatible with the other ingredients.
  • the solid mono-, oligo- and polycarboxylic acids can be used in particular for reasons of consumer protection and handling safety. From this group, preference is again given to citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid.
  • the anhydrides of these acids can also be used as acidifying agents, maleic anhydride and succinic anhydride in particular being commercially available.
  • Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).
  • Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination point on a central atom, i. H. is at least "bidentate". In this case, normally elongated compounds are closed to form rings by complex formation via an ion. The number of ligands bound depends on the coordination number of the central ion.
  • Common chelate complexing agents preferred in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA).
  • Complex-forming polymers that is to say polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and generally react with suitable metal atoms to form chelate complexes, can be used according to the invention.
  • the polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or can belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.
  • Complexing groups (ligands) of conventional complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, Amidoxime, aminophosphoric acid, (cycl.) Polyamino, mercapto, 1, 3-dicarbonyl and crown ether residues with, for. T. very specific Activities against ions of different metals.
  • the base polymers of many commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided with further ligand functionalities by polymer-analogous conversions.
  • machine dishwashing detergents which contain one or more chelating complexing agents from the groups of
  • Hydroxyl groups is at least 5,
  • Dishwashing detergent in amounts above 0.1% by weight, preferably above 0.5% by weight, particularly preferably above 1% by weight and in particular above 2.5% by weight, in each case based on the weight of the Dishwashing detergent included.
  • polycarboxylic acids a) are understood to mean carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl groups and the hydroxyl groups contained in the molecule is at least 5.
  • Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. At the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is immaterial whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali, ammonium or alkylammonium salts, in particular sodium salts, are preferred.
  • the agents according to the invention can contain further customary ingredients of cleaning agents, bleaching agents, bleach activators, enzymes, silver protection agents, colorants and fragrances being particularly important. These substances are described below.
  • bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 0 2 -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • Cleaning agents according to the invention can also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as aikylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimoxyhexanoic acid [phthalimidhexanoic acid] (p-phthalimidoxythanoic acid) , o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyazela
  • Chlorine or bromine-releasing substances can also be used as bleaching agents in the cleaning agents according to the invention for machine dishwashing.
  • Suitable chlorine or bromine-releasing materials include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • Preferred automatic dishwashing detergents according to the invention additionally contain bleaching agents in amounts of 1 to 40% by weight, preferably 2.5 to 30% by weight and in particular 5 to 20% by weight, in each case based on the total agent.
  • Bleach activators which support the action of the bleaching agents can also be contained in the agents according to the invention.
  • Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of the anhydrides, the esters, the imides and the acylated imidazoles or oximes.
  • Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1, 5-diacetyl-2,2-dioxo-hexahydro-1, 3,5-triazine DADHT and isatoic anhydride ISA.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • Multi-acylated alkylenediamines in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), are preferred.
  • TAED tetraacetylethylene diamine
  • DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • TAGU tetraacetylglycoluril
  • N-acylimides especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso- NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate, ethylene glycol Diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), and enol esters as well as acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetacyl and undyloxylose acetylated, optionally N-alkylated glucamine
  • bleach activators are cationic nitriles of the formula (XIV)
  • R 1 is -H, -CH 3 , a C 2-2 -alkyl or -alkenyl radical, a substituted C 2-24 -alkyl or -alkenyl radical with 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 a substituted alkyl or ajkenylaryl 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 -CH
  • bleach catalysts can also be incorporated into the rinse aid particles.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts ,
  • Bleach activators from the group of multi-acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-Npnanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n-) or iso-n-iso, are preferred -Methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6 wt .-% based on the total agent used.
  • TAED tetraacetylethylenediamine
  • N-acylimides in particular N-Npnanoylsuccinimide (NOSI)
  • transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammin ) Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate are used in customary amounts, preferably in an amount up to 5 'wt .-%, more preferably from 0.0025 wt .-% to 1 wt .-% and particularly preferably of 0.01 wt .-% to 0.25 wt .-%, each based on the detergent as a whole , But in special cases, more bleach activator can be used.
  • Agents according to the invention can contain enzymes to increase the washing or cleaning performance, it being possible in principle to use all the enzymes established in the prior art for these purposes. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents and cleaning agents, which are accordingly preferred. Agents according to the invention preferably contain enzymes in total amounts of 1 ⁇ 10 " ⁇ to 5 percent by weight based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferred.
  • subtilisins BPN 'and Carlsberg the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and that which can no longer be assigned to the subtilisins in the narrower sense Proteases TW3 and TW7.
  • Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase ® from Novozymes A / S, Bagsvaerd, Denmark.
  • subtilisins 147 and 309 are sold under the trade names Esperase ®, or Savinase ® from Novozymes.
  • the variants listed under the name BLAP ® are derived from the protease from Bacillus lentus DSM 5483.
  • proteases are, for example, under the trade names Durazym ®, relase ®, Everlase® ®, Nafizym, Natalase ®, Kannase® ® and Ovozymes ® from Novozymes, under the trade names Purafect ®, Purafect ® OxP and Properase.RTM ® by the company Genencor, which is sold under the trade name Protosol ® by Advanced Biochemicals Ltd., Thane, India, which is sold under the trade name Wuxi ® by Wuxi Snyder Bioproducts Ltd., China, and in the trade name Proleather ® and Protease P ® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from ⁇ . amyloliquefaciens or from B. stearothermophilus and their further developments for use in detergents and cleaning agents.
  • the enzyme from ß; licheniformis is from Novozymes under the name Termamyl ® and from the company Qenencor is available under the name Purastar ® ST.
  • ⁇ - amylase Development products of this ⁇ - amylase are available from Novozymes under the trade names Duramyl ® and Termamyl ® ultra, from Genencor under the name Purastar® ® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ®.
  • Amyloliquefaciens is sold by Novozymes under the name BAN ® , and derived variants from the ⁇ -amylase from ⁇ . stearothermophiius under the names BSG ® and Novamyl ® , also from Novozymes.
  • Agents according to the invention can contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors.
  • lipases or cutinases include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ® , Lipolase ® Ultra, LipoPrime ® , Lipozyme ® and Lipex ® .
  • the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens.
  • lipases are available from Amano under the designations Lipase CE ®, Lipase P ®, Lipase B ®, or lipase CES ®, Lipase AKG ®, Bacillis sp. Lipase ® , Lipase AP ® , Lipase M-AP ® and Lipase AML ® available.
  • the Genencor company can use the lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • washing and cleaning agents according to the invention can contain oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) contain.
  • oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) contain.
  • Suitable commercial products are Denilite ® 1 and 2 from Novozymes.
  • organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the case of very different redox potentials between the oxidizing enzymes and the contaminants.
  • the enzymes used in agents according to the invention either originate from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological processes known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or filamentous fungi.
  • the enzymes in question are advantageously purified by methods which are in themselves established, for example by means of precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.
  • Agents according to the invention can be added to the enzymes in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers.
  • the enzymes can be encapsulated both for the solid and for the liquid administration form, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural, polymer or in the form of capsules, for example those in which the enzymes are enclosed in a solidified gel are or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals.
  • a protective layer impermeable to water, air and / or chemicals.
  • other active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, can be applied.
  • Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.
  • a protein and / or enzyme contained in an agent according to the invention can be protected, particularly during storage, against damage such as inactivation, denaturation or disintegration, for example by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or disintegration, for example by physical influences, oxidation or proteolytic cleavage.
  • the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases.
  • Agents according to the invention can contain stabilizers for this purpose; the provision of such agents is a preferred embodiment of the present invention.
  • a group of stabilizers are reversible protease inhibitors.
  • Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used, including above all derivatives with aromatic groups, for example ortho-substituted, meta-substituted and para-substituted phenylboronic acids, or their salts or esters.
  • Ovomucoid and leupeptin may be mentioned as peptide protease inhibitors; an additional option is the formation of fusion proteins from proteases and peptide inhibitors.
  • Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and their mixtures, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dlcarboxylic acids or salts of the acids mentioned. End-capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders can additionally stabilize an enzyme contained.
  • Lower aliphatic alcohols but above all polyols, such as, for example, glycerol, ethylene glycol, propylene glycol or sorbitol are further frequently used enzyme stabilizers.
  • enzyme stabilizers such as, for example, glycerol, ethylene glycol, propylene glycol or sorbitol are further frequently used enzyme stabilizers.
  • Calcium salts such as calcium acetate or calcium formate, and magnesium salts are also used.
  • Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or celulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation against physical influences or pH fluctuations, among other things.
  • Polyamine N- Oxide-containing polymers act as enzyme stabilizers.
  • Other polymeric stabilizers are the linear C 8 -C 8 polyoxyalkylenes.
  • Alkyl polyglycosides can stabilize the enzymatic components of the agent according to the invention and even increase their performance.
  • Crosslinked N-containing compounds also act as enzyme stabilizers.
  • a sulfur-containing reducing agent is, for example, sodium sulfite.
  • Combinations of stabilizers are preferably used, for example made of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.
  • the effect of peptide-aldehyde stabilizers is increased by the combination with boric acid and / or boric acid derivatives and polyols and is further enhanced by the additional use of divalent cations, such as calcium ions.
  • Preferred automatic dishwashing agents according to the invention are characterized in that they additionally contain one or more enzymes and / or enzyme preparations, preferably solid and / or liquid protease preparations and / or amylase preparations, in amounts of 1 to 5% by weight, preferably of 1 , 5 to 4.5 and in particular from 2 to 4 wt .-%, each based on the total agent.
  • Dyes and fragrances can be added to the automatic dishwashing agents according to the invention in order to improve the aesthetic impression of the resulting products and, in addition to the performance, to provide the consumer with a visually and sensorially "typical and unmistakable" product.
  • Individual fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl benzylatepylpropionate, stally.
  • the ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the jonones, ⁇ -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.
  • perfume oils can also contain natural fragrance mixtures, such as those obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • natural fragrance mixtures such as those obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • the fragrances can be incorporated directly into the cleaning agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which ensure a long-lasting fragrance due to a slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
  • the agents according to the invention can be colored with suitable dyes.
  • Preferred dyes the selection of which does not pose any problems for Fambamann, 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 agents, such as glass, ceramics or plastic dishes, so as not to stain them.
  • the cleaning agents according to the invention can contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents in particular being particularly important in the area of automatic dishwashing.
  • the known substances of the prior art can be used.
  • silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular.
  • Benzotriazole and / or alkylaminotriazole are particularly preferably to be used.
  • detergent formulations often contain agents containing active chlorine, which can significantly reduce the corroding of the silver surface.
  • oxygen- and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds.
  • Salt-like and complex-like inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used.
  • the transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate.
  • Zinc compounds can also be used to prevent corrosion on the wash ware.
  • Preferred agents which are able to provide corrosion protection for glassware during cleaning and / or rinsing operations of a dishwasher come from the group of the compounds of zinc, aluminum, silicon, tin, magnesium, calcium, strontium, titanium, zirconium, manganese and / or lanthanum. Of the compounds mentioned, the oxides are particularly preferred.
  • a preferred agent for providing corrosion protection for glassware during cleaning and / or rinsing operations of a dishwasher is zinc in oxidized form, i.e. Zinc compounds in which zinc is cationic.
  • Zinc compounds in which zinc is cationic are also preferred.
  • magnesium salts are also preferred.
  • both soluble and poorly or insoluble zinc or magnesium compounds can be incorporated into the agents according to the invention.
  • Preferred agents according to the invention contain one or more magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid.
  • the acids in question preferably originate from the group of unbranched saturated or unsaturated monocarboxylic acids, branched saturated or unsaturated monocarboxylic acids, saturated and unsaturated dicarboxylic acids, aromatic mono-, di- and tricarboxylic acids, sugar acids, hydroxy acids, oxo acids, etc.
  • magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids can be contained in the polymer matrix, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids are selected from the groups the unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids are preferred.
  • the acids mentioned below are again preferred within these groups:
  • benzoic acid 2-carboxybenzoic acid (phthalic acid), 3-carboxybenzoic acid (isophthalic acid), 4-C.arboxybenzoic acid (terephthalic acid), 3,4-dicarboxybenzoic acid (trimellitic acid), 3, 5- dicarboxybenzoic acid (trimesionic acid).
  • 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), hydroxysuccinic acid (malic acid), 2,3-
  • Dihydorxybutanedioic acid (tartaric acid), 2-hydroxy-1, 2,3-propanetricarboxylic acid (citric acid), ascorbic acid, 2-hydroxybenzoic acid (salicylic acid), 3,4,5-trihydroxybenzoic acid (gallic acid).
  • oxo acids 2-oxopropionic acid (pyruvic acid), 4-oxopentanoic acid (levulinic acid).
  • amino acids alanine, valine, leucine, isoleucine, proline, tryptophan, phenylalanine, methionine, glycine, serine, tyrosine, threonine, cysteine, asparagine, glutamine, apartic acid, glutamic acid, lysine, arginine, histidine.
  • polyacrylic acid polymethacrylic acid
  • alkyl acrylamide / acrylic acid copolymers alkyl acrylamide / methacrylic acid copolymers
  • Alkyl acrylamide / methyl methacrylic acid copolymers copolymers of unsaturated carboxylic acids, vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers.
  • the spectrum of the zinc salts of organic acids, preferably organic carboxylic acids preferred according to the invention, extends from salts which are sparingly or not soluble in water, ie have a solubility below 100 mg / L, preferably below 10 mg / L, in particular no solubility, up to such salts which have a solubility in water above 100 mg / L, preferably above 500 mg / L, particularly 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:
  • the agents according to the invention contain at least one zinc salt, but no magnesium salt of an organic acid, it preferably being at least one zinc salt of an organic carboxylic acid, particularly preferably a zinc salt from the group consisting of zinc stearate, zinc oleate, zinc gluconate and zinc acetate , Zinc lactate and / or zinc citrate.
  • Zinc ricinoleate, zinc abietate and zinc oxalate can also be used with preference
  • preferred automatic dishwashing detergents additionally contain one or more magnesium and / or zinc salts and / or magnesium and / or zinc complexes, preferably one or more magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid.
  • the cleaning agents according to the invention for machine dishwashing can be provided in all available forms known from the prior art, for example as powdered or granular detergents, as extrudates, pellets, flakes, etc. Irii in the area of machine dishwashing, in particular, tablets have been found to be easy to handle Offer form established in the market.
  • Another possibility of providing pre-portioned agents is packaging in water-soluble containers.
  • the agents according to the invention can be packaged in water-soluble packaging, for example pouches, so-called deep-drawn parts, injection molded parts, bottle blowing parts, etc.
  • Preferred dishwasher detergents according to the invention are characterized in that they are packaged in portions in a water-soluble envelope, the envelope preferably comprising one or more materials from the group consisting of acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polyurethane styrenesulfonates, polyurethanes, polyesters and polyethers and their mixtures, and preferably a wall thickness of 10 to 5000 ⁇ m, preferably from 20 to 3000 ⁇ m, particularly preferably from 25 to 2000 ⁇ m and in particular from 100 to 1500 ⁇ m.
  • Machine dishwashing detergents are particularly preferably characterized in that the water-soluble covering comprises a bag made of water-soluble film and / or an injection molded part and / or a blow molded part and / or a deep-drawn part, the covering preferably comprising one or more water-soluble polymer (s) , preferably a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose, and their derivatives and mixtures thereof, more preferably (optionally acetalized) polyvinyl alcohol (PVAL).
  • PVAL polyvinyl alcohol
  • PVAL polyvinyl pyrrolidone
  • Polyvinyl alcohols (abbreviation PVAL, occasionally also PVOH) is the name for polymers of the general structure
  • polyvinyl alcohols which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approximately 100 to 2500 (molar masses from approximately 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , therefore still contain a residual content of acetyl groups. They are characterized Polyvinyl alcohols on the part of the manufacturers by specifying the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.
  • polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils.
  • Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable.
  • the water solubility can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax.
  • the polyvinyl alcohol coatings are largely impervious to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • the bag made of water-soluble film comprises a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol -%.
  • Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the bags, it being preferred according to the invention that the bag made of water-soluble film comprises a polyvinyl alcohol, the molecular weight of which is in the range from 10,000 to 100,000 gmol "1 , preferably from 11,000 to 90,000 gmol " 1 , particularly preferably from 12,000 to 80,000 gmol "1 and in particular from 13,000 to 70,000 gmol " 1 .
  • dishwasher detergents according to the invention are preferably characterized in that the coating comprises a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%
  • Polyvinyl alcohols are preferred, the molecular weight of which is in the range from 10,000 to 100,000 gmol "1 , preferably from 11,000 to 90,000 gmol " 1 , particularly preferably from 12,000 to 80,000 gmol "1 and in particular from 13,000 to 70,000 gmol " 1 .
  • the degree of polymerization of such preferred polyvinyl alcohols is between approximately 200 to approximately 2100, preferably between approximately 220 to approximately 1890, particularly preferably between approximately 240 to approximately 1680 and in particular between approximately 260 to approximately 1500.
  • polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ® (Clariant). Particularly within the scope of the present invention suitable polyvinyl alcohols are, for example, Mowiol 3-83, Mowiol 4-88, Mowiol 5-88 and Mowiol ® 8-88.
  • ELVANOL 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont)
  • ALCOTEX ® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.)
  • Gohsenol ® NK- 05, A-300, AH-22, C- 500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (trademark of Nippon Gohsei KK) ,
  • the water solubility of PVAL can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization).
  • aldehydes acetalization
  • ketones ketalization
  • Polyvinyl alcohols which have been acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly preferred and particularly advantageous because of their extremely good solubility in cold water.
  • the reaction products made of PVAL and starch are extremely advantageous to use.
  • solubility in water can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus specifically adjusted to the desired values.
  • Films made of PVAL are largely impenetrable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • PVAL films examples include the PVAL films available from Syntana bottlesgesellschaft E. Harke GmbH & Co. under the name “SOLUBLON ® ". Their solubility in water can be adjusted to the degree, and they are films of this product range available which are soluble in all relevant temperature ranges in the aqueous phase.
  • PVP Polyvinylpyrrolidones
  • PVP are produced by radical polymerization of 1-vinyl pyrrolidone.
  • Commercial PVPs have molar masses in the range from approx. 2,500 to 750,000 g / mol and are offered as white, hygroscopic powders or as aqueous solutions.
  • Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula
  • Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions.
  • the amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance.
  • the use of gelatin as a water-soluble coating material is extremely widespread, particularly in pharmacy in the form of hard or soft gelatin capsules. In the form of films, gelatin is used only to a minor extent because of its high price in comparison to the abovementioned polymers.
  • Agents according to the invention are preferred within the scope of the present invention, their packaging consisting of at least partially water-soluble film made of at least one polymer the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof.
  • Starch is a homoglycan, with the glucose units linked ⁇ -glycosidically. Starch is made up of two components of different molecular weights: approx. 20 to 30% straight-chain amylose (MW. Approx. 50,000 to 150,000) and 70 to 80% branched-chain amylopectin (MW. Approx. 300,000 to 2,000,000). It also contains small amounts of lipids, phosphoric acid and cations. While the amylose forms long, helical, intertwined chains with about 300 to 1,200 glucose molecules due to the binding in the 1,4 position, the chain in the amylopectin branches after an average of 25 glucose units through 1
  • starch derivatives which are obtainable by polymer-analogous reactions from starch are also suitable for producing water-soluble coatings for the detergent, dishwashing detergent and cleaning agent portions.
  • Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives.
  • the group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches and amino starches.
  • Pure cellulose has the formal gross composition (C 6 H ⁇ o0 5 ) n and formally considered a ß-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
  • Suitable celluloses consist of approx. 500 to 5,000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
  • Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
  • the water-soluble film which forms the pouch has a thickness of 1 to 150 ⁇ m, preferably 2 to 100 ⁇ m, particularly preferably 5 to 75 ⁇ m and in particular from 10 to 50 ⁇ m.
  • These water-soluble films can be produced by various manufacturing processes. In principle, blowing, calendering and casting processes should be mentioned here. In a preferred method, the films are blown from a melt with air through a blow mandrel to form a tube. In the calendering process, which is also one of the preferred manufacturing processes, the raw materials plasticized by suitable additives are atomized to form the films. Here it may be necessary to connect drying to the atomization.
  • an aqueous polymer preparation is placed on a heatable drying roller; after the water has evaporated, cooling is optionally carried out and the film is removed as a film. If necessary, this film is additionally powdered off before or during the removal.
  • the polymer materials can particularly preferably be the groups (optionally partially acetalized) of polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and their derivatives, starch and their derivatives, in particular modified starches, and mixtures (polymer blends, composites, coextrudates etc.) materials mentioned - see above.
  • Gelatin and polyvinyl alcohols and the two materials mentioned are particularly preferred in each case in combination with starch or modified starch.
  • Inorganic salts and mixtures thereof can also be used as materials for the at least partially water-soluble coating.
  • an embodiment is preferred in which the bags as a whole are water-soluble, i.e. H. dissolves completely when used as intended for washing or machine cleaning, if the conditions for loosening have been reached.
  • a major advantage of this embodiment is that the bags can be at least partially detached in a practically relevant short time - as a non-limiting example, a few seconds to 5 inches - under precisely defined conditions in the cleaning liquor and thus, according to the requirements, the wrapped content, i.e. H. the active cleaning material or several materials into the fleet.
  • the water-soluble bag comprises areas which are less or not water-soluble or only water-soluble at a higher temperature and areas which are water-soluble or less Temperature water soluble areas.
  • the bags do not consist of a uniform material that has the same water solubility in all areas, but of materials of different water solubility. Areas of good water solubility are to be distinguished on the one hand from areas with less good water solubility, with poor or no water solubility or from areas in which water solubility is only at a higher temperature or at a different pH value or only at a changed electrolyte concentration the desired value achieved, on the other hand.
  • Bags can thus be provided in which a uniform polymer material comprises small areas of incorporated compounds (for example salts) which are more water-soluble than the polymer material.
  • incorporated compounds for example salts
  • several polymer materials with different water solubility can also be mixed (polymer blend), so that the more rapidly soluble polymer material is disintegrated faster under defined conditions by water or the liquor than the more slowly soluble.
  • water-soluble areas of the bags are areas made of a material which chemically essentially corresponds to that of the readily water-soluble areas or at lower temperatures water-soluble areas corresponds, but has a higher layer thickness and / or has a changed degree of polymerization of the same polymer and / or has a higher degree of crosslinking of the same polymer structure and / or has a higher degree of acetalization (in the case of PVAL, for example with saccharides, polysaccharides, such as starch) has uride / or has a content of water-insoluble salt components and / or a content of a water-insoluble polymer.
  • the water soluble bag material is preferably transparent.
  • transparency is understood to mean that the transmittance within the visible spectrum of light (410 to 800 nm) is greater than 20%, preferably greater than 30%, most preferably greater than 40% and in particular greater than 50%. As soon as a wavelength of the visible spectrum of light has a transmittance greater than 20%, it is to be regarded as transparent in the sense of the invention.
  • Portioned cleaning agents according to the invention which are packaged in transparent bags, can contain a stabilizing agent as an essential component.
  • Stabilizers in the sense of the invention are materials which protect the detergent components in their water-soluble, transparent bags from decomposition or deactivation by exposure to light. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.
  • Particularly suitable stabilizers in the sense of the invention are the antioxidants.
  • the formulations can contain antioxidants.
  • Phenols, bisphenols and thiobisphenols substituted by sterically hindered groups can be used as antioxidants.
  • Further examples are propyl gallate, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long-chain (C8-C22) esters of gallic acid, such as dodecyl gallate.
  • sweet dance classes are aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites, citric acids and citric acid derivatives, such as isopropyl citrate, compounds containing endiol groups, so-called reductones, such as ascorbic acid and its derivatives.
  • antioxidants such as ascorbic acid palmitate, organosulfur compounds, such as the esters of 3,3'-thiodipropionic acid with C 1-18 alkanols, in particular C 10-18 alkanols, metal ion deactivators which are able to metal ions which catalyze the autooxidation, such as, for example Copper to complex, such as nitrilotriacetic acid and its derivatives and their mixtures.
  • Antioxidants can be present in the formulations in amounts of up to 35% by weight, preferably up to 25% by weight, particularly preferably from 0.01 to 20 and in particular from 0.03 to 20% by weight.
  • UV absorbers can improve the lightfastness of the recipe components. These include organic substances (light protection filters) that are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, eg heat to deliver again. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position.
  • substituted benzotriazoles such as the water-soluble benzenesulfonic acid-3- (2H-benzotriazol-2-yl) - 4-hydroxy-5- (methylpropyl) monosodium salt (Ciba Fast ® H), 3-phenyl-substituted acrylates (cinnamic acid derivatives) , optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid.
  • biphenyl and especially stilbene derivatives which are commercially available as Tinosorb ® FD or Tinosorb ® FR ex Ciba.
  • 3-Benzylidene camphor or 3-benzylidene norcampher and its derivatives, for example 3- (4-methylbenzylidene) camphor may be mentioned as UV-B absorbers; 4-aminobenzoic acid derivatives, preferably 4-
  • esters of cinnamic acid preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-
  • esters of salicylic acid preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbenzyl ester, salicylic acid homomethyl ester;
  • benzophenone preferably 2 hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-
  • Dihydroxy-4-methoxybenzophenone Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate; Triazine derivatives, such as, for example, 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1, 3,5-triazine and octyl triazone or dioctyl butamido triazone (Uvasorb® HEB); P 'ropan-1, 3-diones, for example 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1, 3-dione; Ketotricyclo (5.2.1.0) decane derivatives.
  • Triazine derivatives such as, for example, 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1, 3,5-triazine and octy
  • 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts
  • Sulfonic acid derivatives of 3-benzylidene camphor such as 4- (2-oxo-3-bomylidene methyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.
  • Typical UV-A filters are, in particular, derivatives of benzoylmethane, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl -4'-meth-oxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds.
  • the UV-A and UV-B filters can of course also be used in mixtures.
  • insoluble light-protection pigments namely finely dispersed, preferably nanoized metal oxides or salts, are also suitable for this purpose.
  • suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof.
  • Silicates (talc), barium sulfate or zinc stearate can be used as salts become.
  • the oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
  • the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm.
  • the pigments can also be surface-treated, ie hydrophilized or hydrophobicized.
  • Typical examples are coated titanium dioxides, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents.
  • Micronized zinc oxide is preferably used.
  • UV absorbers can be present in the detergent or cleaning agent compositions in amounts of up to 5% by weight, preferably up to 3% by weight, particularly preferably from 0.01 to 2.0 and in particular from 0.03 to 1% by weight his.
  • fluorescent dyes include the 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methyl umbelliferones, coumarins, dihydroquinolinones, 1,3-darylpyrazolines, naphthalic imides, benzoxazole and benzisoxazole and Benzimidazole systems and the pyrene derivatives substituted by heterocycles.
  • fluorescent acids 4,4'-diamino-2,2'-stilbenedisulfonic acids
  • 4,4'-distyrylbiphenyls 4,4'-distyrylbiphenyls, methyl umbelliferones, coumarins, dihydroquinolinones, 1,3-darylpyrazolines, naphthalic imides, benzoxazole and benzisoxazole and Benzimidazole systems and the pyrene derivatives substitute
  • Fluorescent substances can be present in the formulations in amounts of up to 5% by weight, preferably up to 1% by weight, particularly preferably from 0.01 to 0.5 and in particular from 0.03 to 0.1% by weight.
  • the aforementioned stabilizing agents are used in any mixtures.
  • the stabilizing agents are used in amounts of up to 40% by weight, preferably up to 30% by weight, particularly preferably from 0.01 to 20% by weight, in particular from 0.02 to 5% by weight.
  • portioned detergent or cleaning agent compositions according to the invention can be provided in such a way that the packaging is water-soluble on the one hand and tightly closing on the other hand, ie sealed off from the environment.
  • Two embodiments can be implemented according to the invention: Sp it corresponds to a preferred embodiment of the invention that the bag (s) is / are and contain at least one water-free gas which does not react with the detergent or cleaning agent composition, more preferably in an amount that the total pressure within the / the sealed bag (s) is above the external pressure, more preferably is at least 1 r ⁇ bar above the external pressure.
  • Very particularly preferred embodiments of these portions according to the invention contain at least one anhydrous gas which does not react with the detergent or cleaning agent composition in such an amount that the total pressure inside the sealed bag is at least 5 mbar, more preferably at least 10 mbar, very particularly preferably is in the range from 10 mbar to 50 mbar above the external pressure.
  • the total pressure inside the sealed bag is at least 5 mbar, more preferably at least 10 mbar, very particularly preferably is in the range from 10 mbar to 50 mbar above the external pressure.
  • exital pressure is understood to mean the pressure which prevails on the surrounding side of the bags and acts on the outside of the bags, specifically at the time when the bags are filled with the respective at least one anhydrous gas.
  • the bags can either contain an anhydrous gas or can contain several anhydrous gases.
  • a gas in practice, it is preferred to apply a gas to the bags due to the associated lower costs.
  • water-free is understood to mean that the gas (s) are carefully dried in the portions according to the invention before use and thus contain no or virtually no water when used; a water content approaching zero is preferred.
  • the drying process can be carried out in any way known to the person skilled in the art for this purpose.
  • the aim is that the gases contain as little water as possible, which could react with the components in the detergent or cleaning agent compositions and thus lead to a deterioration in the quality of such components which are sensitive to moisture or water.
  • Preferred detergent or cleaning agent portions according to the invention comprise as gas (e) at least one anhydrous gas which is selected from the group N 2 , noble gas (s), C0 2 , N 2 0, 0 2 , H 2 , air, gaseous hydrocarbons, especially N 2 , which is available cheaply everywhere and can be completely “dried” by methods known per se.
  • gas (e) at least one anhydrous gas which is selected from the group N 2 , noble gas (s), C0 2 , N 2 0, 0 2 , H 2 , air, gaseous hydrocarbons, especially N 2 , which is available cheaply everywhere and can be completely “dried” by methods known per se.
  • the gases mentioned are advantageously inert to the components of the wash-active preparation and are therefore sometimes referred to as "inert gases" in the context of the present invention.
  • the bag (s) are / are closed and contain at least one substance which, when reacted with water, releases a gas which does not react with the detergent-active preparation (s) in an amount such that the total pressure is within the closed range Bag rises.
  • This embodiment is particularly advantageous in that its manufacture is greatly simplified compared to the embodiment in which the gas is contained in the sealed bag, since only the at least one substance has to be added, which at least when in contact with moisture / water in the sealed bag generates a gas. Furthermore, any moisture that has entered the bag is immediately absorbed and reacted by the substance capable of reacting with water and is therefore no longer available for a deterioration in the quality of the components of the detergent or cleaning agent composition. Mixed forms of the portions are also conceivable, in which from the beginning there is (at least) an anhydrous gas in the bag and also a substance capable of reacting with water. With this embodiment, the deterioration of the components of the agents according to the invention by an ingress of moisture or water can be prevented in a particularly good and efficient manner.
  • the water-releasing substance is a constituent of the detergent or cleaning agent composition and - more preferably - is a hygroscopic substance which is compatible with the components of the detergent or cleaning agent composition.
  • substances which are selected from the group consisting of bound hydrogen peroxide-containing substances, substances containing -OO groups, substances containing OCO groups, hydrides and carbides, more preferably a substance, which is selected from the group of percarbonates (particularly preferably sodium percarbonate), persulfates, perborates, peracids, M A M B H, where M A is an alkali metal (particularly preferably Li or Na) (for example LiAIH 4 , NaBH 4 , NaAIH 4 ) and M B is B or Al, or M 2 C 2 or M "c 2 , where M 1 is a monovalent metal and M 11 is a divalent metal (e.g. CaC 2 ).
  • anhydrous gas contained in the bag (s) with which the bags are directly applied is selected from the group N 2 , noble gas (s), C0 2 , N 2 0, 0 2 , H 2 , air, gaseous hydrocarbons or mixtures thereof.
  • the preferred gas - or at least one of the gases preferably used - is N 2 , because of the fact that nitrogen is available cheaply everywhere and can be dried well by conventional means or stored dry.
  • the at least one gas formed within the pouch by the water or moisture reactive substance is selected from the group C0 2 , N 2 , H 2 , 0 2 , gaseous hydrocarbons such as in particular methane, Ethane, propane or a mixture of several of the gases mentioned.
  • gaseous hydrocarbons such as in particular methane, Ethane, propane or a mixture of several of the gases mentioned.
  • the gases mentioned are advantageously inert to the components of the wash-active preparation and are therefore sometimes referred to as "inert gases" in the context of the present invention.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne des produits de lavage pour lave-vaisselle ayant une action d'inhibition du dépôt et comprenant 10 à 75 % en poids d'adjuvant(s) et 1 à 25 % en poids d'un polymère qui présente des unités monomériques de formule (I), dans laquelle R1 est -H ou -CH3, R2 est une liaison chimique ou un radical alkyle en C1-C6 linéaire ou ramifié, R3 représente des radicaux alkyle en C2-C4 linéaires ou ramifiés respectivement identiques ou différents, R4 est un radical alkyle en C1-C6 linéaire ou ramifié, et n est un nombre naturel qui vaut de 3 à 50.
PCT/EP2003/007689 2002-07-25 2003-07-16 Produits de lavage pour lave-vaisselle comprenant des agents d'inhibition du depot WO2004013269A1 (fr)

Priority Applications (1)

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AU2003250963A AU2003250963A1 (en) 2002-07-25 2003-07-16 Dishwasher rinse aid comprising scale inhibitors

Applications Claiming Priority (2)

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DE2002133834 DE10233834A1 (de) 2002-07-25 2002-07-25 Maschinelle Geschirrspülmittel mit Belagsinhibitoren
DE10233834.5 2002-07-25

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
US7858573B2 (en) 2007-08-16 2010-12-28 The Procter & Gamble Company Process for making a detergent composition containing a sulfonic acid/carboxylic acid copolymer and a hydrophobic silica
US8288333B2 (en) 2007-08-16 2012-10-16 The Procter & Gamble Company Process for making a detergent composition comprising a hydrophilic silica and a copolymer containing a carboxylic acid monomer and a sulfonic acid monomer
US8906837B2 (en) 2011-02-28 2014-12-09 Deb Ip Limited Skin and hand cleaning means containing super-absorbing particles
EP2963100A1 (fr) 2014-07-04 2016-01-06 Kolb Distribution Ltd. Compositions aqueuses de rinçage
EP2187796B2 (fr) † 2007-09-10 2021-03-24 Henkel AG & Co. KGaA Procédé de nettoyage

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US20050202995A1 (en) * 2004-03-15 2005-09-15 The Procter & Gamble Company Methods of treating surfaces using surface-treating compositions containing sulfonated/carboxylated polymers
US20050202996A1 (en) * 2004-03-15 2005-09-15 The Procter & Gamble Company Surface-treating compositions containing sulfonated/carboxylated polymers
DE102005026522B4 (de) * 2005-06-08 2007-04-05 Henkel Kgaa Verstärkung der Reinigungsleistung von Waschmitteln durch Polymer
DE102005041347A1 (de) * 2005-08-31 2007-03-01 Basf Ag Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophil modifizierte Polycarboxylate
DE102007019457A1 (de) 2007-04-25 2008-10-30 Basf Se Maschinengeschirrspülmittel mit ausgezeichneter Klarspülleistung
DE102007019458A1 (de) 2007-04-25 2008-10-30 Basf Se Phosphatfreies Maschinengeschirrspülmittel mit ausgezeichneter Klarspülleistung
WO2012098177A1 (fr) 2011-01-21 2012-07-26 Basf Se Utilisation d'alcooléthoxylates de suif en lavage en lave-vaisselle
US8840731B2 (en) 2011-12-09 2014-09-23 Basf Se Preparations, their production and use
CA2850127A1 (fr) 2011-12-09 2013-06-13 Basf Se Utilisation de preparations pour lavage en lave-vaisselle

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WO1999035234A1 (fr) * 1997-12-30 1999-07-15 Henkel Kommanditgesellschaft Auf Aktien Corps moules detergents pour lave-vaisselle, renfermant des polymeres anti-salissures
WO2001096514A1 (fr) * 2000-06-12 2001-12-20 Unilever Plc Compositions de lavage de vaisselle mecanique contenant des polymeres inhibiteurs de tartre
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7858573B2 (en) 2007-08-16 2010-12-28 The Procter & Gamble Company Process for making a detergent composition containing a sulfonic acid/carboxylic acid copolymer and a hydrophobic silica
US8288333B2 (en) 2007-08-16 2012-10-16 The Procter & Gamble Company Process for making a detergent composition comprising a hydrophilic silica and a copolymer containing a carboxylic acid monomer and a sulfonic acid monomer
EP2187796B2 (fr) † 2007-09-10 2021-03-24 Henkel AG & Co. KGaA Procédé de nettoyage
US8906837B2 (en) 2011-02-28 2014-12-09 Deb Ip Limited Skin and hand cleaning means containing super-absorbing particles
EP2963100A1 (fr) 2014-07-04 2016-01-06 Kolb Distribution Ltd. Compositions aqueuses de rinçage

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