EP0703969B1 - Lower-buildup dish-washing detergents - Google Patents

Lower-buildup dish-washing detergents Download PDF

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Publication number
EP0703969B1
EP0703969B1 EP94918388A EP94918388A EP0703969B1 EP 0703969 B1 EP0703969 B1 EP 0703969B1 EP 94918388 A EP94918388 A EP 94918388A EP 94918388 A EP94918388 A EP 94918388A EP 0703969 B1 EP0703969 B1 EP 0703969B1
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EP
European Patent Office
Prior art keywords
weight
detergent
salts
free
carbonates
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EP94918388A
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German (de)
French (fr)
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EP0703969A1 (en
EP0703969A4 (en
Inventor
Willi Buchmeier
Hans Dolhaine
Birgit Burg
Jürgen Härer
Peter Jeschke
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids

Definitions

  • the invention relates to dishwashing detergents for the automatic cleaning of dishes, in particular low-alkaline dishwashing detergents with an application pH between 9 and 11, which contain glycine or its alkali metal or ammonium salts as alkali carrier.
  • the latest generation of low-alkaline agents for the automatic cleaning of dishes contain, in addition to water-soluble builders, oxygen-based bleaching agents, surface-active substances and enzymes, such as alkali carriers such as Soda, bicarbonate or disilicate.
  • the application pH is generally between 10 and 11.
  • these formulations have the disadvantage that with residual water hardness of 4 ° dH and greater, limescale deposits form on the items washed in the machine in the cleaning and rinse cycle.
  • the application pH can be reduced to 9 to 10, which increases the complexing effect of certain builder components, which can reduce the tendency to form limescale deposits.
  • very hard water above 16 ° dH
  • the inhibition of limescale formation is not completely satisfactory even at a lower application pH.
  • the object was therefore to find an alkali carrier system which does not have the disadvantages described above of the increased formation of limescale and which is compatible with the builder components normally used in automatic dishwashing detergents.
  • the alkali carriers are said to be readily biodegradable substances. It has now been found that glycine or its alkali metal or ammonium salts meet the requirements imposed on the new alkali metal carriers to a particular degree.
  • German laid-open documents DE 19 42 236 and DE 19 64 792 disclose textile detergents in which protein-dissolving enzymes are wholly or partly replaced by sulfur-free amino acids.
  • amino acids can be used as a substitute for conventional alkali carriers in machine dishwashing detergents.
  • EP 356 974 describes detergents and cleaning agents which contain 2 to 25% by weight of ⁇ -alanine-N, N-diacetic acid or its alkali metal or ammonium salts as softener.
  • DD 218 117 describes detergents for polyester fibers which, in addition to conventional detergent constituents, such as surfactants, builders, fat solvents and auxiliaries, contain a monoaminocarboxylic acid or a corresponding lactam
  • German published patent application DE 40 36 695 claims the use of substituted ⁇ -alanine derivatives as builders in machine dishwashing detergents.
  • the present invention relates to a
  • Agent for the automatic cleaning of dishes containing 1 to 60% by weight, preferably 20-50% by weight, water-soluble builder components, 0.5 to 20% by weight, preferably 5 to 12% by weight, of bleaching agent based on oxygen.
  • a certain desired pH value can be set just as easily as with the bicarbonate / carbonate system.
  • the alkali carrier system glycine / glycine salt is clearly superior to the hydrogen carbonate / carbonate system with regard to limescale inhibition.
  • carbonate and / or bicarbonates in particular alkali carbonates and / or bicarbonates, can be present in amounts of up to 15% by weight, based on the total dishwashing detergent.
  • the dishwashing detergents according to the invention are preferably free of carbonates and / or hydrogen carbonates.
  • highly alkaline metasilicates for example sodium metasilicate, is preferably also avoided; Disilicates with a molar SiO 2 / Na 2 O ratio of 1.5: 1 to 2.5 : 1, however, can optionally be contained in the form of their alkali salts in amounts of 0.1 to 20% by weight, based on the total dishwashing detergent.
  • builder components which have the actual function of complexing water hardness agents and keeping precipitated lime in dispersed form in the wash liquor, in order to prevent lime deposits, e.g. Organophosphonic acids or their salts, crystalline layered silicates, zeolites, di- and multifunctional organic carboxylic acids or their salts, oxidized starch and polycarboxylic acids or polycarboxylates as well as polyamino acids such as e.g. Polyaspartic acid in question.
  • phosphates previously used e.g. Pentasodium triphosphate, which may also be included in principle, is preferably avoided for ecological reasons.
  • Preferred builder components are di- or polyfunctional organic carboxylic acids or their salts, in particular citric acid or their salts and / or synthetic polycarboxylic acids or polycarboxylates, in a total amount of 1 to 60% by weight, preferably 20 to 50% by weight. , based on the total dishwashing detergent, are included.
  • Synthetic polycarboxylic acids or polycarboxylates are to be understood as meaning the synthetic polymers or their salts of the polymerization products of unsaturated carboxylic acids or their salts, to which e.g. Polyacrylic acid, polymethacrylic acid, polymaleic acids or copolymers of acrylic acid with maleic acid or maleic anhydride belong.
  • Suitable polyacrylates are, for example, Alcosperse (R) 102, 104, 106, 404, 406 from Alco, Acrysole (R) A N1, LMW 45 N, LMW 10 N from Norsohaas, Degapas (r) from Degussa; Suitable copolymers of polyacrylic acid and maleic acid are, for example, Sokalan (R) CP 5, CP 7 from BASF, Acrysol (R) QR 1014 from Norsohaas, Alcosperse (R) 175 from Alco.
  • the dishwashing detergents according to the invention furthermore necessarily contain oxygen-based bleaches, in particular perborates and / or percarbonates in an amount of 0.5 to 20 wt .-%, preferably 5 to 12 wt .-%, based on the total dishwashing detergent.
  • bleaching agents are, for example, peracidic salts of organic acids, such as perbenzoates or salts of diperdodecanedioic acid.
  • bleach activators are also included. Suitable bleach activators are in particular N-acyl and O-acyl compounds, preferably tetraacylated diamines such as N, N, N ', N'-tetraacetylethylene diamine (TAED).
  • the agents according to the invention contain such conventional bleach activators in an amount of 0.1 to 10% by weight, preferably 1 to 5% by weight.
  • the agents according to the invention can optionally also contain agents that release active chlorine, such as trichloroisocyanuric acid; however, they are preferably free of active chlorine-releasing agents.
  • the surfactants which can be used in the agents according to the invention their foaming behavior is decisive.
  • Low-foam connections are preferred because of the machine mechanics.
  • These are primarily nonionic surfactants;
  • the dishwashing detergents according to the invention can in principle also contain very small amounts of anionic, cationic or amphoteric surfactants, but are preferably free of these.
  • the content of nonionic surfactants is at most 5% by weight, preferably at most 2% by weight, based on the total dishwashing detergent.
  • nonionic surfactants can also Alkyl polyglycosides of the general formula RO- (G) X are used in which R is a primary, straight-chain or branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, G is a glycose unit with 5 or 6 carbon atoms and the degree of oligomerization x is between 1 and 10.
  • R is a primary, straight-chain or branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms
  • G is a glycose unit with 5 or 6 carbon atoms
  • the degree of oligomerization x is between 1 and 10.
  • Enzymes such as proteases, amylases, lipases or cellulases can preferably be used to better remove protein or starch-containing food residues, for example proteases such as BLAP (R) 140 from Henkel, Optimase (R) -M-440, Optimase (R) -M- 330, Opticlean (R) -M-375, Opticlean (R) -M-250 from Solvay Enzymes, Maxacal (R) CX 450,000, Maxapem (R) from Ibis, Savinase (R) 4.0 T, 6, 0 T, 8.0 T from Novo or Experase (R) T from Ibis; Amylases such as Termamyl (R) 60 T, 90 T from Novo, Amylase-LT (R) from Solvay Enzymes or Maxamyl (R) P 5000, CXT 5000 or CXT 2900 from Ibis; Lipases such as Lipolase (R) 30 T from Novo
  • the dishwashing detergents according to the invention are preferably in the form of powdery, granular or tablet-like preparations which can be prepared in a conventional manner, for example by mixing, granulating, roller compacting and / or by spray drying.
  • Another advantage of the alkali carrier system which consists primarily of organic raw materials, is that there are advantages in terms of packaging, particularly in the production of granules, tablets or extrudates.
  • the procedure is preferably such that all constituents are mixed with one another in a mixer and the mixture by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range from 200 ⁇ 10 5 Pa to 1500 ⁇ 10 5 Pa pressed.
  • a tablet produced in this way preferably has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter of 35 mm to 40 mm.
  • the machine dishwashing detergent is produced in the form of non-dusting, storage-stable, free-flowing powders and / or granules with high bulk densities in the range of preferably 750 to 1,000 g / l, for example by mixing the builder components with at least a portion of liquid mixture components while increasing the bulk density of this premix in a first process sub-stage and then - if desired after intermediate drying - combining the other components of the dishwasher detergent with the premix obtained in this way.
  • the liquid phase used in the first stage of the process in particular the surfactant compounds which are liquid under normal conditions - in particular the corresponding nonionic surfactants - and / or further liquid components of the overall formulation.
  • the fragrances dissolved in carrier liquids and / or limited amounts of water or aqueous solutions of mixture components of the desired dishwashing detergent come into consideration here.
  • the builder is generally mixed with at least one further component of the dishwashing detergent with the liquid components.
  • a precursor may be considered in which the builder component, mixed with perborate, is acted upon by the liquid nonionic surfactants and / or the solution of the fragrances and mixed intimately.
  • the remaining components are then added and the entire mixture is worked through and homogenized in the mixing device.
  • additional amounts of liquid in particular the use of additional water, is generally not necessary here.
  • the mixture of substances obtained is then in the form of a free-flowing, non-dusting powder of the desired high bulk densities, approximately in the range from 800 to 900 g / l.
  • the machine dishwashing detergents according to the invention which contain glycine and / or its salts as alkali carriers, provide products which, in addition to their good biodegradability, are superior to conventional modern dishwashing detergents, in which the alkali carrier system consists predominantly of carbonate and / or hydrogen carbonate, with regard to the inhibition of lime scale .
  • Granular dishwashing detergents of the following composition were produced.
  • Agent A contained 31.9% by weight of glycine and 17.2% by weight of sodium glycinate as the alkali carrier system, and the pH of a 1% by weight aqueous solution was 9.5.
  • Agent B contained 49.1% by weight of sodium glycinate as the alkali carrier system, and the pH of a 1% by weight aqueous solution was accordingly higher, at 10.9.
  • the comparative agent C contained 36.1% by weight of sodium hydrogen carbonate and 13.0% by weight of sodium carbonate as the alkali carrier system, and the pH of a 1% by weight aqueous solution was 9.5.
  • Agents D, E and F according to the invention contained 24.0% by weight glycine / 16.0% by weight sodium alycinate (D), 25.3% by weight glycine / 10.8% by weight sodium glycinate (E) and 37.5% by weight sodium glycinate (F).
  • Agent A according to the invention 1.0 Agent B According to the Invention 1.0 Comparative means C 0.2 Agent D according to the invention 2.2 Agent E according to the invention 2.6 Agent F according to the invention 2.6
  • agents A, B, D, E and F according to the invention are clearly superior to comparative agent C in terms of deposit formation.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Washing And Drying Of Tableware (AREA)

Abstract

The invention pertains to automatic dish-washing detergents containing, as good biodegradable alkali carriers, amino acids and their salts, especially short-chain alpha -amino acids, primarily glycine or glycinate. These dish-washing detergents containing amino acids show markedly better properties of inhibiting calcium buildup than conventional dish-washing detergents based on carbonate and/or hydrocarbonate.

Description

Die Erfindung betrifft Geschirrspülmittel für die maschinelle Reinigung von Geschirr, insbesondere niederalkalische Geschirrspülmittel mit einem Anwendungs-pH-Wert zwischen 9 und 11, die als Alkaliträger Glycin bzw. dessen Alkali- oder Ammoniumsalze enthalten.The invention relates to dishwashing detergents for the automatic cleaning of dishes, in particular low-alkaline dishwashing detergents with an application pH between 9 and 11, which contain glycine or its alkali metal or ammonium salts as alkali carrier.

Niederalkalische Mittel der neuesten Generation für die maschinelle Reinigung von Geschirr enthalten neben wasserlöslichen Buildern, Bleichmitteln auf Sauerstoffbasis, oberflächenaktiven Stoffen und Enzymen Alkaliträger wie z.B. Soda, Hydrogencarbonat oder Disilikat.The latest generation of low-alkaline agents for the automatic cleaning of dishes contain, in addition to water-soluble builders, oxygen-based bleaching agents, surface-active substances and enzymes, such as alkali carriers such as Soda, bicarbonate or disilicate.

Der Anwendungs-pH-Wert liegt dabei im allgemeinen zwischen 10 und 11. Diese Rezepturen weisen jedoch den Nachteil auf, daß sich bei Restwasserhärten von 4 °dH und größer im Reinigungs- und Klarspülgang Kalkbeläge auf dem in der Maschine gewaschenen Gut bilden. Durch den teilweisen Ersatz von Carbonat durch Hydrogencarbonat kann der Anwendungs-pH-Wert auf 9 bis 10 gesenkt werden, was die Komplexierwirkung von bestimmten Builderkomponenten erhöht, wodurch eine Verminderung der Neigung zur Bildung von Kalkbelägen erreicht werden kann. Bei Verwendung von sehr hartem Wasser (über 16 °dH) ist jedoch auch bei einem erniedrigten Anwendungs-pH-Wert die Inhibierung der Kalkbelagsbildung nicht voll zufriedenstellend.The application pH is generally between 10 and 11. However, these formulations have the disadvantage that with residual water hardness of 4 ° dH and greater, limescale deposits form on the items washed in the machine in the cleaning and rinse cycle. By partially replacing carbonate with hydrogen carbonate, the application pH can be reduced to 9 to 10, which increases the complexing effect of certain builder components, which can reduce the tendency to form limescale deposits. When using very hard water (above 16 ° dH), however, the inhibition of limescale formation is not completely satisfactory even at a lower application pH.

Es bestand daher die Aufgabe, ein Alkaliträgersystem zu finden, welches die oben geschilderten Nachteile der vermehrten Kalkbelagsbildung nicht besitzt und mit den üblicherweise in maschinellen Geschirrspülmitteln verwendeten Builderkomponenten kompatibel ist. Gleichzeitig sollen die Alkaliträger biologisch gut abbaubare Substanzen sein. Es wurde nun gefunden, daß Glycin bzw. dessen Alkali- oder Ammoniumsalze die an die neuen Alkaliträger gestellten Forderungen in besonderem Maße erfüllen.The object was therefore to find an alkali carrier system which does not have the disadvantages described above of the increased formation of limescale and which is compatible with the builder components normally used in automatic dishwashing detergents. At the same time, the alkali carriers are said to be readily biodegradable substances. It has now been found that glycine or its alkali metal or ammonium salts meet the requirements imposed on the new alkali metal carriers to a particular degree.

In den deutschen Offenlegungsschriften DE 19 42 236 und DE 19 64 792 werden Textilwaschmittel offenbart, in denen eiweißlösende Enzyme ganz oder teilweise durch schwefelfreie Aminosäuren ersetzt sind. Es finden sich jedoch keine Hinweise darauf, daß Aminosäuren als Ersatz für konventionelle Alkaliträger in Mitteln zum maschinellen Reinigen von Geschirr verwendet werden können.The German laid-open documents DE 19 42 236 and DE 19 64 792 disclose textile detergents in which protein-dissolving enzymes are wholly or partly replaced by sulfur-free amino acids. However, there is no evidence to suggest that amino acids can be used as a substitute for conventional alkali carriers in machine dishwashing detergents.

Die EP 356 974 beschreibt Wasch-und Reinigungsmittel, die als Enthärter 2 bis 25 Gew.-% β-Alanin-N,N-diessigsäure oder dessen Alkalimetall- oder Ammoniumsalze enthalten.EP 356 974 describes detergents and cleaning agents which contain 2 to 25% by weight of β-alanine-N, N-diacetic acid or its alkali metal or ammonium salts as softener.

Die DD 218 117 beschreibt Waschmittel für Polyesterfasern, die neben üblichen Waschmittelbestandteilen, wie Tensiden, Gerüststoffen, Fettlösern und Hilfsstoffen, eine Monoaminocarbonsäure, bzw. ein entsprechendes Lactam enthältDD 218 117 describes detergents for polyester fibers which, in addition to conventional detergent constituents, such as surfactants, builders, fat solvents and auxiliaries, contain a monoaminocarboxylic acid or a corresponding lactam

In der deutschen Offenlegungsschrift DE 40 36 695 wird die Verwendung von substituierten β-Alaninderivaten als Gerüstsubstanzen in maschinellen Geschirrspülmitteln beansprucht.German published patent application DE 40 36 695 claims the use of substituted β-alanine derivatives as builders in machine dishwashing detergents.

Gegenstand der vorliegenden Erfindung ist einThe present invention relates to a

Mittel zum maschinellen Reinigen von Geschirr, enthaltend 1 bis 60 Gew.-%, vorzugsweise 20 - 50 Gew.-%, wasserlösliche Builderkomponenten, 0,5 bis 20 Gew.-%, vorzugsweise 5 bis 12 Gew.-% Bleichmittel auf Sauerstoff-Basis, maximal 5 Gew.% bevorzugt schaumarme nichtionische Tenside und 0,1 bis 5 Gew.-% vorzugsweise 1 bis 3 Gew.-% Enzyme, dadurch gekennzeichnet, daß Glycin bzw. dessen Alkali- oder Ammoniumsalze in einer Menge enthalten sind, daß eine 1 Gew.-%ige wäßrige Lösung des Mittels einen pH-Wert von 8 bis 12, vorzugsweise 9 bis 11, aufweist, mindestens aber in einer Menge von 0,5 vorzugsweise 10 Gew.-%, und höchstens in einer Menge von 60 Gew.-%, vorzugsweise 50 Gew.-%, jeweils bezogen auf das gesamte Mittel.Agent for the automatic cleaning of dishes, containing 1 to 60% by weight, preferably 20-50% by weight, water-soluble builder components, 0.5 to 20% by weight, preferably 5 to 12% by weight, of bleaching agent based on oxygen. Basis, maximum 5% by weight, preferably low-foam, nonionic surfactants and 0.1 to 5% by weight, preferably 1 to 3% by weight, of enzymes, characterized in that glycine or its alkali metal or ammonium salts are present in an amount such that a 1% by weight aqueous solution of the composition has a pH of 8 to 12, preferably 9 to 11, but at least in an amount of 0.5, preferably 10% by weight, and at most in an amount of 60 % By weight, preferably 50% by weight, in each case based on the total composition.

Durch Variation des Verhältnisses des Glycins zu seinen Salzen läßt sich ebenso problemlos wie mit dem System Hydrogencarbonat/Carbonat ein bestimmter gewünschter pH-Wert einstellen. Hinsichtlich der Kalkbelagsinhibierung ist das Alkaliträger-System Glycin/Glycinsalz dem System Hydrogencarbonat/Carbonat jedoch deutlich überlegen.By varying the ratio of the glycine to its salts, a certain desired pH value can be set just as easily as with the bicarbonate / carbonate system. However, the alkali carrier system glycine / glycine salt is clearly superior to the hydrogen carbonate / carbonate system with regard to limescale inhibition.

Fakultativ können Carbonat und/oder Hydrogencarbonate, insbesondere Alkalicarbonate und/oder -hydrogencarbonate in Mengen von bis zu 15 Gew.-%, bezogen auf das gesamte Geschirrspülmittel, enthalten sein. Vorzugsweise sind die erfindungsgemäßen Geschirrspülmittel jedoch frei von Carbonaten und/oder Hydrogencarbonaten. Auch auf den Einsatz hochalkalischer Metasilikate, z.B. Natriummetasilikat, wird vorzugsweise verzichtet; Disilikate mit einem molaren Verhältnis SiO2/Na2O von 1,5 : 1 bis 2,5 : 1 hingegen können in Form ihrer Alkalisalze fakultativ in Mengen von 0,1 bis 20 Gew.-%, bezogen auf das gesamte Geschirrspülmittel, enthalten sein.Optionally, carbonate and / or bicarbonates, in particular alkali carbonates and / or bicarbonates, can be present in amounts of up to 15% by weight, based on the total dishwashing detergent. However, the dishwashing detergents according to the invention are preferably free of carbonates and / or hydrogen carbonates. The use of highly alkaline metasilicates, for example sodium metasilicate, is preferably also avoided; Disilicates with a molar SiO 2 / Na 2 O ratio of 1.5: 1 to 2.5 : 1, however, can optionally be contained in the form of their alkali salts in amounts of 0.1 to 20% by weight, based on the total dishwashing detergent.

Als Builderkomponenten, denen die eigentliche Funktion zukommt, Härtebildner des Wassers zu komplexieren und ausgefallenen Kalk in dispergierter Form in der Waschflotte zu halten, um so Kalkbeläge zu verhindern, kommen z.B. Organophosphonsäuren bzw. deren Salze, kristalline Schichtsilikate, Zeolithe, di- und mehrfunktionelle organische Carbonsäuren bzw. deren Salze, oxidierte Stärke und Polycarbonsäuren bzw. Polycarboxylate sowie Polyaminosäuren wie z.B. Polyasparaginsäure in Frage. Auf die früher verwendeten Phosphate, z.B. Pentanatriumtriphosphat, die prinzipiell ebenfalls enthalten sein können, wird aus ökologischen Gründen vorzugsweise verzichtet.As builder components, which have the actual function of complexing water hardness agents and keeping precipitated lime in dispersed form in the wash liquor, in order to prevent lime deposits, e.g. Organophosphonic acids or their salts, crystalline layered silicates, zeolites, di- and multifunctional organic carboxylic acids or their salts, oxidized starch and polycarboxylic acids or polycarboxylates as well as polyamino acids such as e.g. Polyaspartic acid in question. For the phosphates previously used, e.g. Pentasodium triphosphate, which may also be included in principle, is preferably avoided for ecological reasons.

Bevorzugte Builderkomponenten sind di- oder mehrfunktionelle organische Carbonsäuren bzw. deren Salze, insbesondere Zitronensäure bzw. deren Salze und/oder synthetische Polycarbonsäuren bzw. Polycarboxylate, die in einer Gesamtmenge von 1 bis 60 Gew.-%, vorzugsweise 20 bis 50 Gew.-%, bezogen auf das gesamte Geschirrspülmittel, enthalten sind.Preferred builder components are di- or polyfunctional organic carboxylic acids or their salts, in particular citric acid or their salts and / or synthetic polycarboxylic acids or polycarboxylates, in a total amount of 1 to 60% by weight, preferably 20 to 50% by weight. , based on the total dishwashing detergent, are included.

Unter synthetischen Polycarbonsäuren bzw. Polycarboxylaten sind die synthetischen Polymere bzw. deren Salze der Polymerisationsprodukte ungesättigter Carbonsäuren bzw. deren Salze zu verstehen, zu denen z.B. Polyacrylsäure, Polymethacrylsäure, Polymaleinsäuren oder Copolymere der Acrylsäure mit Maleinsäure bzw. Maleinsäureanhydrid gehören.Synthetic polycarboxylic acids or polycarboxylates are to be understood as meaning the synthetic polymers or their salts of the polymerization products of unsaturated carboxylic acids or their salts, to which e.g. Polyacrylic acid, polymethacrylic acid, polymaleic acids or copolymers of acrylic acid with maleic acid or maleic anhydride belong.

Geeignete Polyacrylate sind z.B. Alcosperse(R) 102, 104, 106, 404, 406 der Firma Alco, Acrysole(R) A N1, LMW 45 N, LMW 10 N der Firma Norsohaas, Degapas(r) der Firma Degussa; geeignete Copolymere aus Polyacrylsäure und Maleinsäure sind z.B. Sokalan(R) CP 5, CP 7 der Firma BASF, Acrysol(R) QR 1014 der Firma Norsohaas, Alcosperse(R) 175 der Firma Alco.Suitable polyacrylates are, for example, Alcosperse (R) 102, 104, 106, 404, 406 from Alco, Acrysole (R) A N1, LMW 45 N, LMW 10 N from Norsohaas, Degapas (r) from Degussa; Suitable copolymers of polyacrylic acid and maleic acid are, for example, Sokalan (R) CP 5, CP 7 from BASF, Acrysol (R) QR 1014 from Norsohaas, Alcosperse (R) 175 from Alco.

Die erfindungsgemäßen Geschirrspülmittel enthalten weiterhin zwingend Bleichmittel auf Sauerstoffbasis, insbesondere Perborate und/oder Percarbonate in einer Menge von 0,5 bis 20 Gew.-%, vorzugsweise 5 bis 12 Gew.-%, bezogen auf das gesamte Geschirrspülmittel.The dishwashing detergents according to the invention furthermore necessarily contain oxygen-based bleaches, in particular perborates and / or percarbonates in an amount of 0.5 to 20 wt .-%, preferably 5 to 12 wt .-%, based on the total dishwashing detergent.

Besondere Bedeutung haben das Natriumperborat-tetrahydrat (NaBO2 · H2O2 · 3H2O), das Natriumperborat-monohydrat (NaBO2 · H2O2) und das Peroxycarbonat (Na2CO3 · 1,5 H2O2). Weitere brauchbare Bleichmittel sind z.B. persaure Salze organischer Säuren, wie Perbenzoate oder Salze der Diperdodecandisäure. Außerdem sind fakultativ Bleichaktivatoren enthalten. Geeignete Bleichaktivatoren sind insbesondere N-Acyl- und O-Acyl-Verbindungen, vorzugsweise tetraacylierte Diamine wie N,N,N',N'-Tetraacetylethylendiamin (TAED). Die erfindungsgemäßen Mittel enthalten solche üblichen Bleichaktivatoren in einer Menge von 0,1 bis 10 Gew.-%, vorzugsweise 1 bis 5 Gew.-%. Die erfindungsgemäßen Mittel können fakultativ auch aktivchlorabspaltende Mittel wie z.B. Trichlorisocyanursäure enthalten; vorzugsweise sind sie jedoch frei von aktivchlorabspaltenden Mitteln.Of particular importance are sodium perborate tetrahydrate (NaBO 2 .H 2 O 2 · 3H 2 O), sodium perborate monohydrate (NaBO 2 .H 2 O 2) and the peroxy carbonate (Na 2 CO 3 · 1.5 H 2 O 2 ). Other usable bleaching agents are, for example, peracidic salts of organic acids, such as perbenzoates or salts of diperdodecanedioic acid. Optional bleach activators are also included. Suitable bleach activators are in particular N-acyl and O-acyl compounds, preferably tetraacylated diamines such as N, N, N ', N'-tetraacetylethylene diamine (TAED). The agents according to the invention contain such conventional bleach activators in an amount of 0.1 to 10% by weight, preferably 1 to 5% by weight. The agents according to the invention can optionally also contain agents that release active chlorine, such as trichloroisocyanuric acid; however, they are preferably free of active chlorine-releasing agents.

Bei den in den erfindungsgemäßen Mitteln einsetzbaren Tensiden ist deren Schaumverhalten ausschlaggebend. Wegen der Maschinenmechanik werden schaumarme Verbindungen bevorzugt. Dies sind vor allem nichtionische Tenside; die erfindungsgemäßen Geschirrspülmittel können prinzipiell zwar auch sehr geringe Mengen an anionischen, kationischen oder amphoteren Tensiden enthalten, sind aber vorzugsweise frei von diesen. Der Gehalt an nichtionischen Tensiden beträgt maximal 5 Gew.-%, vorzugsweise maximal 2 Gew.-% bezogen auf das gesamte Geschirrspülmittel. Als nichtionische Tenside sind vor allem Anlagerungsprodukte von 1 bis 20 Mol Ethylenoxid (EO) und/oder 1 bis 20 Mol Propylenoxid (PO) an 1 Mol einer aliphatischen Verbindung mit 10 bis 20 Kohlenstoffatomen aus der Gruppe der Alkohole, Carbonsäuren, Fettamine, Carbonsäureamide und Alkansulfonamide von Interesse. Wichtig sind neben den wasserlöslichen nichtionischen Tensiden aber auch nicht bzw. nicht vollständig wasserlösliche Polyglykolether mit 2 bis 7 Ethylenglykoletherresten im Molekül, vorzugsweise werden diese in Kombination mit wasserlöslichen nichtionischen Tensiden eingesetzt. Außerdem können als nichtionische Tenside auch Alkylpolyglycoside der allgemeinen Formel R-O-(G)X eingesetzt werden in der R einen primären, geradkettigen oder verzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet, G für eine Glykoseeinheit mit 5 oder 6 C-Atomen steht und der Oligomerisierungsgrad x zwischen 1 und 10 liegt.In the case of the surfactants which can be used in the agents according to the invention, their foaming behavior is decisive. Low-foam connections are preferred because of the machine mechanics. These are primarily nonionic surfactants; The dishwashing detergents according to the invention can in principle also contain very small amounts of anionic, cationic or amphoteric surfactants, but are preferably free of these. The content of nonionic surfactants is at most 5% by weight, preferably at most 2% by weight, based on the total dishwashing detergent. Addition products of 1 to 20 moles of ethylene oxide (EO) and / or 1 to 20 moles of propylene oxide (PO) with 1 mole of an aliphatic compound with 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxamides and Alkanesulfonamides of interest. In addition to the water-soluble nonionic surfactants, non-fully or not completely water-soluble polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule are also important; these are preferably used in combination with water-soluble nonionic surfactants. In addition, nonionic surfactants can also Alkyl polyglycosides of the general formula RO- (G) X are used in which R is a primary, straight-chain or branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, G is a glycose unit with 5 or 6 carbon atoms and the degree of oligomerization x is between 1 and 10.

Zur besseren Ablösung eiweiß- oder stärkehaltiger Speisereste können vorzugsweise Enzyme wie Proteasen, Amylasen, Lipasen oder Cellulasen eingesetzt werden, beispielsweise Proteasen wie BLAP(R) 140 der Firma Henkel, Optimase(R) -M-440, Optimase(R) -M-330, Opticlean(R) -M-375, Opticlean(R) -M-250 der Firma Solvay Enzymes, Maxacal(R) CX 450.000, Maxapem(R) der Firma Ibis, Savinase(R) 4,0 T, 6,0 T, 8,0 T der Firma Novo oder Experase(R) T der Firma Ibis; Amylasen wie Termamyl(R) 60 T, 90 T der Firma Novo, Amylase-LT(R) der Firma Solvay Enzymes oder Maxamyl(R) P 5000, CXT 5000 oder CXT 2900 der Firma Ibis; Lipasen wie Lipolase(R) 30 T der Firma Novo; Cellulasen wie Celluzym(R) 0,7 T der Firma Novo Nordisk. Enzyme sind in den erfindungsgemäßen Mitteln in einer Menge von 0,1 bis 5 Gew.-%, vorzugsweise 1 bis 3 Gew.-%, bezogen auf das gesamte Geschirrspülmittel, enthalten sein.Enzymes such as proteases, amylases, lipases or cellulases can preferably be used to better remove protein or starch-containing food residues, for example proteases such as BLAP (R) 140 from Henkel, Optimase (R) -M-440, Optimase (R) -M- 330, Opticlean (R) -M-375, Opticlean (R) -M-250 from Solvay Enzymes, Maxacal (R) CX 450,000, Maxapem (R) from Ibis, Savinase (R) 4.0 T, 6, 0 T, 8.0 T from Novo or Experase (R) T from Ibis; Amylases such as Termamyl (R) 60 T, 90 T from Novo, Amylase-LT (R) from Solvay Enzymes or Maxamyl (R) P 5000, CXT 5000 or CXT 2900 from Ibis; Lipases such as Lipolase (R) 30 T from Novo; Cellulases such as Celluzym (R) 0.7 T from Novo Nordisk. Enzymes are present in the agents according to the invention in an amount of 0.1 to 5% by weight, preferably 1 to 3% by weight, based on the total dishwashing detergent.

Die erfindungsgemäßen Geschirrspülmittel liegen vorzugsweise als pulverförmige, granulare oder tablettenförmige Präparate vor, die in an sich üblicher Weise, beispielsweise durch Mischen, Granulieren, Walzenkompaktieren und/oder durch Sprühtrocknung hergestellt werden können. Ein weiterer Vorteil des vornehmlich aus organischen Rohstoffen bestehenden Alkaliträger-System ist, daß sich Vorteile hinsichtlich der Konfektionierung, insbesondere bei der Herstellung von Granulaten, Tabletten oder Extrudaten bieten.The dishwashing detergents according to the invention are preferably in the form of powdery, granular or tablet-like preparations which can be prepared in a conventional manner, for example by mixing, granulating, roller compacting and / or by spray drying. Another advantage of the alkali carrier system, which consists primarily of organic raw materials, is that there are advantages in terms of packaging, particularly in the production of granules, tablets or extrudates.

Zur Herstellung von erfindungsgemäßen Reinigungsmitteln in Tablettenform geht man vorzugsweise derart vor, daß man alle Bestandteile in einem Mischer miteinander vermischt und das Gemisch mittels herkömmlicher Tablettenpressen, beispielsweise Exzenterpressen oder Rundläuferpressen, mit Preßdrucken im Bereich von 200 · 105 Pa bis 1500 · 105 Pa verpreßt. Man erhält so problemlos bruchfeste und dennoch unter Anwendungsbedingungen ausreichend schnell lösliche Tabletten mit Biegefestigkeiten von normalerweise über 150 N. Vorzugsweise weist eine derart hergestellte Tablette ein Gewicht von 15 g bis 40 g, insbesondere von 20 g bis 30 g auf, bei einem Durchmesser von 35 mm bis 40 mm.To produce cleaning agents according to the invention in tablet form, the procedure is preferably such that all constituents are mixed with one another in a mixer and the mixture by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range from 200 × 10 5 Pa to 1500 × 10 5 Pa pressed. In this way, one obtains unbreakable, but nevertheless under application conditions sufficiently rapidly soluble tablets with flexural strengths of normally more than 150 N. A tablet produced in this way preferably has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter of 35 mm to 40 mm.

Die Herstellung der Maschinengeschirrspülmittel in Form von nicht staubenden, lagerstabil rieselfähigen Pulvern und/oder Granulaten mit hohen Schüttdichten im Bereich von bevorzugt 750 bis 1.000 g/l erfolgt z.B. dadurch, daß man in einer ersten Verfahrensteilstufe die Builder-Komponenten mit wenigstens einem Anteil flüssiger Mischungskomponenten unter Erhöhung der Schüttdichte dieses Vorgemisches vermischt und nachfolgend - gewünschtenfalls nach einer Zwischentrocknung - die weiteren Bestandteile des Maschinengeschirrspülmittels mit dem so gewonnen Vorgemisch vereinigt.The machine dishwashing detergent is produced in the form of non-dusting, storage-stable, free-flowing powders and / or granules with high bulk densities in the range of preferably 750 to 1,000 g / l, for example by mixing the builder components with at least a portion of liquid mixture components while increasing the bulk density of this premix in a first process sub-stage and then - if desired after intermediate drying - combining the other components of the dishwasher detergent with the premix obtained in this way.

Als Flüssigphase werden in der ersten Verfahrensteilstufe, insbesondere die unter Normalbedingungen flüssigen Tensidverbindungen - insbesondere also die entsprechenden nichtionischen Tenside - und/oder weitere Flüssiganteile der Gesamtrezeptur eingesetzt. In Betracht kommen hier die in Trägerflüssigkeiten gelösten Duftstoffe und/oder begrenzte Mengen an Wasser bzw. wäßrigen Lösungen von Mischungskomponenten des angestrebten Geschirrspülmittels.The liquid phase used in the first stage of the process, in particular the surfactant compounds which are liquid under normal conditions - in particular the corresponding nonionic surfactants - and / or further liquid components of the overall formulation. The fragrances dissolved in carrier liquids and / or limited amounts of water or aqueous solutions of mixture components of the desired dishwashing detergent come into consideration here.

In der ersten Teilstufe des Mischverfahrens wird der Builder in der Regel in Abmischung mit wenigstens einer weiteren Komponente des Geschirrspülmittels mit den Flüssig komponenten beaufschlagt. In Betracht kommt hier beispielsweise eine Vorstufe, in der die Builder-Komponente in Abmischung mit Perborat mit den flüssigen nichtionoschen Tensiden und/oder der Lösung der Dufststoffe beaufschlagt und innig vermischt wird. Nachfolgend werden die restlichen Komponenten zugegeben und das Gesamtgemisch in der Mischvorrichtung durchgearbeitet und homogenisiert. Die Mitverwendung zusätzlicher Flüssigkeitsmengen, insbesondere also der Einsatz von zusätzlichem Wasser, ist hier in der Regel nicht erforderlich. Das angefallene Stoffgemisch liegt dann als rieselfähiges, nicht staubendes Pulver der gewünschten hohen Schüttdichten etwa im Bereich von 800 bis 900 g/l vor.In the first sub-stage of the mixing process, the builder is generally mixed with at least one further component of the dishwashing detergent with the liquid components. For example, a precursor may be considered in which the builder component, mixed with perborate, is acted upon by the liquid nonionic surfactants and / or the solution of the fragrances and mixed intimately. The remaining components are then added and the entire mixture is worked through and homogenized in the mixing device. The use of additional amounts of liquid, in particular the use of additional water, is generally not necessary here. The mixture of substances obtained is then in the form of a free-flowing, non-dusting powder of the desired high bulk densities, approximately in the range from 800 to 900 g / l.

Mit den erfindungsgemäßen als Alkaliträger Glycin und/oder dessen Salze enthaltende Maschinen-Geschirrspülmitteln stehen Produkte zur Verfügung, die neben ihrer guten biologischen Abbaubarkeit konventionellen modernen Geschirrspülmitteln, in denen das Alkaliträger-System überwiegend aus Carbonat und/oder Hydrogencarbonat besteht, hinsichtlich der Kalkbelagsinhibierung überlegen sind.The machine dishwashing detergents according to the invention, which contain glycine and / or its salts as alkali carriers, provide products which, in addition to their good biodegradability, are superior to conventional modern dishwashing detergents, in which the alkali carrier system consists predominantly of carbonate and / or hydrogen carbonate, with regard to the inhibition of lime scale .

BeispieleExamples

I. Es wurden granulare Geschirrspülmittel nachstehender Zusammensetzung (erfindungsgemäße Mittel A und B, Vergleichsmittel C sowie erfindungsgemäße Mittel D, E und F) hergestellt.I. Granular dishwashing detergents of the following composition (agents A and B according to the invention, comparative agents C and agents D, E and F according to the invention) were produced.

Mittel A enthielt als Alkaliträgersystem 31,9 Gew.-% Glycin und 17,2 Gew.-% Natriumglycinat, der pH-Wert einer 1 Gew.-%igen wäßrigen Lösung betrug 9,5. Mittel B enthielt als Alkaliträgersystem 49,1 Gew.-% Natriumglycinat, der pH-Wert einer 1 Gew.-%igen wäßrigen Lösung lag dementsprechend höher, bei 10,9. Das Vergleichsmittel C enthielt als Alkaliträgersystem 36,1 Gew.-% Natriumhydrogencarbonat und 13,0 Gew.-% Natriumcarbonat, der pH-Wert einer 1 Gew.-%igen wäßrigen Lösung lag bei 9,5.Agent A contained 31.9% by weight of glycine and 17.2% by weight of sodium glycinate as the alkali carrier system, and the pH of a 1% by weight aqueous solution was 9.5. Agent B contained 49.1% by weight of sodium glycinate as the alkali carrier system, and the pH of a 1% by weight aqueous solution was accordingly higher, at 10.9. The comparative agent C contained 36.1% by weight of sodium hydrogen carbonate and 13.0% by weight of sodium carbonate as the alkali carrier system, and the pH of a 1% by weight aqueous solution was 9.5.

Die erfindungsgemäßen Mittel D, E und F enthielten 24,0 Gew.-% Glycin / 16,0 Gew.-% Natriumalycinat (D), 25,3 Gew.-% Glycin / 10,8 Gew.-% Natriumglycinat (E) sowie 37,5 Gew.-% Natriumglycinat (F). A Gew.-% B Gew.-% C Gew.-% D Gew.-% E Gew.-% F Gew.-% Na-citrat 30,0 30,0 30,0 45,0 45,0 45,0 Sokalan® CP5 (Acrylat/Maleat-Copolymer der Fa. BASF) 10,0 10,0 10,0 - - - Na2CO3 - - 13,0 - - - NaHCO3 - - 36,1 - - - Glycin 31,9 - - 24,0 25,3 - Natriumglycinat 17,2 49,1 - 16,0 10,8 37,5 Na-perborat-Monohydrat 5,0 5,0 5,0 - - - Na-Percarbonat - - - 6,5 12,0 10,0 TAED 2,0 2,0 2,0 5,0 4,0 4,0 Amylase 1,5 1,5 1,5 1,0 1,0 1,0 Protease 1,5 1,5 1,5 1,0 1,0 1,0 Plurafac(R) LF 403 (C12-18-Fett-alkohol x EO x 4PO der Fa. BASF) 0,9 0,9 0,9 1,5 0,9 1,5 Agents D, E and F according to the invention contained 24.0% by weight glycine / 16.0% by weight sodium alycinate (D), 25.3% by weight glycine / 10.8% by weight sodium glycinate (E) and 37.5% by weight sodium glycinate (F). A% by weight B% by weight C% by weight D% by weight E% by weight F% by weight Na citrate 30.0 30.0 30.0 45.0 45.0 45.0 Sokalan ® CP5 (acrylate / maleate copolymer from BASF) 10.0 10.0 10.0 - - - Na 2 CO 3 - - 13.0 - - - NaHCO 3 - - 36.1 - - - Glycine 31.9 - - 24.0 25.3 - Sodium glycinate 17.2 49.1 - 16.0 10.8 37.5 Na perborate monohydrate 5.0 5.0 5.0 - - - Na percarbonate - - - 6.5 12.0 10.0 TAED 2.0 2.0 2.0 5.0 4.0 4.0 Amylase 1.5 1.5 1.5 1.0 1.0 1.0 Protease 1.5 1.5 1.5 1.0 1.0 1.0 Plurafac (R) LF 403 (C 12-18 fatty alcohol x EO x 4PO from BASF) 0.9 0.9 0.9 1.5 0.9 1.5

BelagsinhibierungScale inhibition

Die Kalkbelagsbildung der Mittel A, B und C wurde in einer Geschirrspülmaschine Miele G 590 (Programm Universal 65 °C) bei Dosierungen von jeweils 20 g in 6,2 l Wasser mit 16 °dH unter Zusatz von 50 g pumpbarer Anschmutzungen (Gemisch aus Ketchup, Bratensoße, Senf, Kartoffelstärke, Eigelb, Milch, Margarine) in Anwesenheit von 3,0 ml eines handelsüblichen Klarspülers über 10 Spülgänge getestet. Die Belagsbildung wurde mit einer Skala von 0 (= sehr starker Belag) bis 3 (= kein Belag) bewertet. Die Ergebnisse der mit den erfindungsgemäßen Mitteln A und B und dem Vergleichsmittel C erzielten Belagsprüfungen lauten wie folgt: Erfindungsgemäßes Mittel A 1,0 Erfindungsgemäßes Mittel B 1,0 Vergleichsmittel C 0,2 Erfindungsgemäßes Mittel D 2,2 Erfindungsgemäßes Mittel E 2,6 Erfindungsgemäßes Mittel F 2,6 Limescale formation of agents A, B and C was carried out in a Miele G 590 dishwasher (Universal 65 ° C program) at doses of 20 g each in 6.2 l water at 16 ° dH with the addition of 50 g pumpable soils (mixture of ketchup , Gravy, mustard, potato starch, egg yolk, milk, margarine) in the presence of 3.0 ml of a commercial rinse aid tested over 10 rinses. The deposit formation was rated on a scale from 0 (= very thick deposit) to 3 (= no deposit). The results of the covering tests achieved with agents A and B according to the invention and comparative agent C are as follows: Agent A according to the invention 1.0 Agent B According to the Invention 1.0 Comparative means C 0.2 Agent D according to the invention 2.2 Agent E according to the invention 2.6 Agent F according to the invention 2.6

Es zeigt sich, daß die erfindungsgemäßen Mittel A, B, D, E und F dem Vergleichsmittel C hinsichtlich der Belagsbildung deutlich überlegen sind.It can be seen that agents A, B, D, E and F according to the invention are clearly superior to comparative agent C in terms of deposit formation.

Claims (9)

  1. A machine dishwashing detergent containing 1 to 60% by weight and preferably 20 to 50% by weight of water-soluble builder components, 0.5 to 20% by weight and preferably 5 to 12% by weight of oxygen-based bleaching agents, at most 5% by weight of preferably low-foaming nonionic surfactants and 0.1 to 5% by weight and preferably 1 to 3% by weight of enzymes, characterized in that it contains glycine or alkali metal or ammonium salts thereof in such a quantity that a 1% by weight aqueous solution of the detergent has a pH value of 8 to 12 and preferably 9 to 11, but at least in a quantity of 0.5% by weight, preferably 10% by weight and at most in a quantity of 60% by weight and preferably 50% by weight, based on the detergent as a whole.
  2. A detergent as claimed in claim 1, characterized in that it contains no more than 15% by weight, based on the detergent as a whole, of carbonates and/or hydrogen carbonates.
  3. A detergent as claimed in claim 1, characterized in that it is free from carbonates and/or hydrogen carbonates.
  4. A detergent as claimed in claims 1 to 3, characterized in that it is free from metasilicates.
  5. A detergent as claimed in claims 1 to 4, characterized in that it contains dibasic or polybasic organic carboxylic acids or salts thereof, more particularly citric acid or salts thereof and/or synthetic polycarboxylic acids or polycarboxylates, as the water-soluble builder component.
  6. A detergent as claimed in claims 1 to 5, characterized in that it contains perborates and/or percarbonates as the oxygen-based bleaching agent.
  7. A detergent as claimed in claims 1 to 6, characterized in that it is free from anionic, cationic or amphoteric surfactants and contains no more than 2% by weight, based on the detergent as a whole, of nonionic surfactants.
  8. A tablet-form detergent as claimed in claims 1 to 7, characterized in that it is obtainable by mixing all its constituents in a mixer and tabletting the resulting mixture in a tablet press under pressures of 2·107 Pa to 1.5·108 Pa.
  9. A powder-form or granular detergent as claimed in claims 1 to 7, characterized in that it has an apparent density of 750 g/l to 1000 g/l.
EP94918388A 1993-06-15 1994-06-06 Lower-buildup dish-washing detergents Expired - Lifetime EP0703969B1 (en)

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DE4319798A DE4319798A1 (en) 1993-06-15 1993-06-15 Dishwashing detergent with reduced tendency to scale up
DE4319798 1993-06-15
PCT/EP1994/001830 WO1994029420A1 (en) 1993-06-15 1994-06-06 Lower-buildup dish-washing detergents

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DE4324396A1 (en) * 1993-07-21 1995-01-26 Henkel Kgaa Detergents with high wettability
US5531934A (en) * 1994-09-12 1996-07-02 Rohm & Haas Company Method of inhibiting corrosion in aqueous systems using poly(amino acids)
DE59704543D1 (en) * 1996-06-21 2001-10-11 Reckitt Benckiser Nv MGDA-BASED MACHINE DISHWASHER LOW ALKALITY
EP2305785A1 (en) 2009-10-02 2011-04-06 Unilever N.V. Use of a carboxylic or amino compound as cleaning aid for hard surfaces and method of cleaning such hard surfaces
JP5801941B1 (en) * 2014-11-21 2015-10-28 株式会社ニイタカ Cleaning composition, dishwashing method, liquid cleaning composition kit and cartridge cleaning
DE102015007403A1 (en) * 2015-06-08 2016-12-08 Sodasan Wasch- und Reinigungsmittel GmbH Phosphate and phosphonate-free machine dishwashing detergent
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GR3025871T3 (en) 1998-04-30
CZ286098B6 (en) 2000-01-12
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ATE160817T1 (en) 1997-12-15
CZ330395A3 (en) 1996-05-15

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