WO1994029420A1 - Lower-buildup dish-washing detergents - Google Patents

Lower-buildup dish-washing detergents Download PDF

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Publication number
WO1994029420A1
WO1994029420A1 PCT/EP1994/001830 EP9401830W WO9429420A1 WO 1994029420 A1 WO1994029420 A1 WO 1994029420A1 EP 9401830 W EP9401830 W EP 9401830W WO 9429420 A1 WO9429420 A1 WO 9429420A1
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WO
WIPO (PCT)
Prior art keywords
composition according
weight
amino acids
total
agent
Prior art date
Application number
PCT/EP1994/001830
Other languages
German (de)
French (fr)
Inventor
Willi Buchmeier
Hans Dolhaine
Birgit Burg
Jürgen Härer
Peter Jeschke
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP94918388A priority Critical patent/EP0703969B1/en
Priority to DE59404733T priority patent/DE59404733D1/en
Priority to PL94312248A priority patent/PL178743B1/en
Priority to JP7501300A priority patent/JPH10508042A/en
Priority to DK94918388T priority patent/DK0703969T3/en
Publication of WO1994029420A1 publication Critical patent/WO1994029420A1/en
Priority to GR980400044T priority patent/GR3025871T3/en

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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 machine washing of dishes, in particular low-alkaline dishwashing detergents with an application pH between 9 and 11, which contain amino acids, preferably lower oc-amino acids, as alkali carriers.
  • low-alkaline agents for the mechanical cleaning of dishes contain, in addition to water-soluble builders, oxygen-based bleaching agents, surface-active substances and enzymes, such as e.g. Soda, bicarbonate or disilicate.
  • the application pH is generally between 10 and 11. However, these formulations have the night 1 that with residual water hardness of 4 ° dH and greater, limescale deposits on the machine-washed in the cleaning and rinse cycle Make good. By partially replacing carbonate with bicarbonate, the application pH can be reduced to 9 to 10, which increases the complexing effect of certain builder components, as a result of which the tendency to form lime deposits can be reduced. When using very hard water (above 16 ° dH), however, the inhibition of limescale formation is not completely satisfactory even at a lower application pH.
  • 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 an agent for the mechanical cleaning of dishes, the 1% by weight aqueous solution of which has a pH of 8 to 12, preferably 9 to 11, containing water-soluble builder components and bleaching agents for oxygen.
  • Basis characterized in that 0.5 to 60% by weight, preferably 10 to 50% by weight, based on the total composition, of one or more amino acids or their alkali metal or ammonium salts are contained as alkali carriers.
  • Amino acids in the sense of the invention are those amino acids whose amino function is not substituted, i.e. whose amino functions only carry hydrogens.
  • Suitable amino acids are synthetic or naturally occurring amino acids, which e.g. can be obtained by hydrolysis from vegetable or animal proteins such as collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein.
  • ⁇ -amino acids for example serine, threonine, ornithine, arginine, lysine, asparagine, glutin, phenylalanine or tyrosine, but especially glycine, alanine, valine, leucine and isoleucine.
  • Glycine or its alkali metal or ammonium salts for example sodium glycinate, is particularly preferred.
  • their alkali metal, alkaline earth metal or ammonium salts can also be used in the dishwashing detergents according to the invention, in particular the sodium salts.
  • the amino acids or their salts can be in powder form or as granules, optionally together with auxiliaries such as. B. Na citrate, can be used.
  • Amino acids or amino acid salts are contained in the agents according to the invention in amounts of 0.5 to 60% by weight, preferably 10 to 50% by weight. Mixtures of different amino acids or amino acid salts can also be used.
  • carbonate and / or hydrogen carbonates in particular alkali carbonates and / or hydrogen carbonates, 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. Also on the use of highly alkaline metasilicates, e.g.
  • Organophosphonic acids or their salts Organophosphonic acids or their salts, crystalline phyllosilicates, zeolites, di-and Honorary functional organic carboxylic acids or their salts, oxidized starch and polycarboxylic acids or polycarboxylates as well as polyamino acids such as polyaspartic acid in question.
  • phosphates used earlier for example pentasodium triphosphate, which in principle also may be included, is preferably omitted for ecological reasons.
  • Preferred builder components are di- or honor-functional 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, poly ethacrylic 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 Nl, 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 () 175 from Alco.
  • the dishwashing detergents according to the invention furthermore necessarily contain oxygen-based bleaching agents, in particular perborates and / or percarbonates in an amount of 0.5 to 20% by weight, preferably 5 to 12% by weight, based on the total dishwashing detergent.
  • bleaching agents which can be used are, for example, peracidic salts of organic acids, such as perbenzoates or salts of diperdodecadic acid.
  • bleach activators are also included. Suitable bleach activators are in particular N-acyl and 0-acyl compounds, preferably tetraacylated diamines such as N, N, N ', N'-tetraacetylethylenediamine (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. Above all, these are nonionic surfactants;
  • the dishwashing detergents according to the invention can in principle also contain very small amounts of anionic, cationic or a photonic surfactants, but are preferably free of these.
  • the content of nonionic surfactants is a maximum of 5% by weight, preferably a maximum of 2% by weight, based on the total dishwashing detergent.
  • Addition products of 1 to 20 moles of ethylene oxide (EO) and / or 1 to 1 are particularly suitable as nonionic surfactants 20 moles of propylene oxide (PO) to 1 mole of an aliphatic compound having 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxylic acid amides and alkanesulfonamides of interest.
  • nonionic surfactants non-or not completely water-soluble polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule are also important, and are preferably used in combination with water-soluble nonionic surfactants.
  • nonionic surfactants can also be alkyl polyglycosides of the general formula R-0- (G) x , in which R is a primary, straight-chain or branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, G represents a glycose unit with 5 or 6 carbon atoms and 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 () 140 from Henkel, Optimase ( R ) -M-440, 0ptimase ( R ) -M-330, 0pticlean ( R ) -M-375, 0 ⁇ ticlean ( R ) -M-250 from Solvay Enzy es, Maxacal ( R ) CX 450,000, Maxapem ( R ) from Ibis, Savinase ( R ) 4.0 T, 6.0 T, 8.0 T from Novo or Experise ( 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
  • 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.
  • a further advantage of the alkali carrier system, which consists primarily of organic raw materials, is that there are advantages with regard to assembly, particularly in the production of granules, tablets or extrudates.
  • a tablet produced in this way has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter from 35 mm to 40 mm.
  • the machine dishwashing detergents are 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, in that in a first process sub-stage the builder components are mixed with at least a portion of liquid mixture components are mixed while increasing the bulk density of this premix and then - if desired after an intermediate drying - the further components of the dishwasher detergent are combined 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 other 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 agent 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 intimately mixed.
  • 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 material mixture 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.
  • dishwasher detergents according to the invention containing amino acids and / or their salts, products are available which, in addition to their good biodegradability, are conventional modern dishwashing detergents in which the alkali carrier system consists predominantly of carbonate and / or hydrogen carbonate , are superior in terms of lime scale inhibition.
  • Granular dishwashing detergents with 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, 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; 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 allycinate (D), 25.3% by weight glycine / 10.8% by weight sodium glycinate (E ) and 37.5% by weight sodium glycinate (F).
  • Na glycinate can be used in powder form or as granules.
  • Granule production can e.g. in the following way:
  • Na glycinate or a mixture of Na glycinate and Na citrate (90:10) produced in a Lödige mixer customary in the industry were pressed into slugs in a roller press at a roller temperature of 20 ° C. and a line pressure of 17 kN / cm .
  • the slugs were then ground and sieved from a fraction of ⁇ 1.6 mm.
  • This fraction was then placed in a batch-operated stainless steel fluidized bed apparatus and sprayed over a period of 30 minutes with a paraffin wax (S p 42-45 ° C.) which was introduced into the fluidized bed via a two-component nozzle.
  • the vortex air was kept at 30 ° C.
  • a ratio of roller compactate: paraffin wax of 9: 1 slightly sticky granules were formed, however due to the hydrophobized layer applied on the outside, they are also stable in formulations containing vagrant water.
  • Agent A according to the invention 1.0
  • Agent B according to the invention: 1.0 Comparative agent C: 0.2
  • agents A, B, D, E and F according to the invention are clearly superior to comparative agent C with regard to the formation of deposits.

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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 α-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

"Geschirrspülmittel mit verringerter Belaqsbildunqsneiqunq" "Dishwashing detergent with reduced washing capacity"
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 Aminosäuren, vorzugsweise niedere oc-Aminosäuren, enthalten.The invention relates to dishwashing detergents for machine washing of dishes, in particular low-alkaline dishwashing detergents with an application pH between 9 and 11, which contain amino acids, preferably lower oc-amino acids, as alkali carriers.
Niederalkalische Mittel der neuesten Generation für die maschinelle Rei¬ nigung von Geschirr enthalten neben wasserlöslichen Buildern, Bleichmit¬ teln auf Sauerstoffbasis, oberflächenaktiven Stoffen und Enzymen Alkali¬ träger wie z.B. Soda, Hydrogencarbonat oder Disilikat.The latest generation of low-alkaline agents for the mechanical cleaning of dishes contain, in addition to water-soluble builders, oxygen-based bleaching agents, surface-active substances and enzymes, such as e.g. Soda, bicarbonate or disilicate.
Der Anwendungs-pH-Wert liegt dabei im allgemeinen zwischen 10 und 11. Die¬ se Rezepturen weisen jedoch den Nachte l auf, daß sich bei Restwasserhär¬ ten 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 Builderkompo- nenten erhöht, wodurch eine Verminderung der Neigung zur Bildung von Kalk¬ belägen 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 night 1 that with residual water hardness of 4 ° dH and greater, limescale deposits on the machine-washed in the cleaning and rinse cycle Make good. By partially replacing carbonate with bicarbonate, the application pH can be reduced to 9 to 10, which increases the complexing effect of certain builder components, as a result of which the tendency to form lime deposits can be reduced. 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 ver¬ wendeten Builderkomponenten kompatibel ist. Gleichzeitig sollen die Alka- liträger biologisch gut abbaubare Substanzen sein. Es wurde nun gefunden, daß Aminosäuren, insbesondere niedere α-Aminosäuren, die an die neuen Al- kaliträger gestellten Forderungen in besonderem Maße erfüllen. In den deutschen Offenlegungsschriften DE 19 42 236 und DE 19 64 792 wer¬ den 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 konventio¬ nelle Alkaliträger in Mitteln zum maschinellen Reinigen von Geschirr ver¬ wendet werden können.It was therefore an object 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 amino acids, in particular lower α-amino acids, meet the requirements imposed on the new alkali carriers to a particular degree. Textile detergents in which protein-dissolving enzymes are replaced in whole or in part by sulfur-free amino acids are disclosed in the German patent applications DE 19 42 236 and DE 19 64 792. However, there is no evidence that amino acids can be used as a substitute for conventional alkali carriers in agents for the automatic cleaning of dishes.
In der deutschen Offenlegungsschrift DE 40 36 695 wird die Verwendung von substituierten ß-Alaninderivaten als Gerüstsubstanzen in maschinellen Ge¬ schirrspülmitteln 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 ein Mittel zum maschinellen Rei¬ nigen von Geschirr, dessen 1 Gew.-%ige wäßrige Lösung einen pH-Wert von 8 bis 12, vorzugsweise 9 bis 11, aufweist, enthaltend wasserlösliche Buil- derkomponenten und Bleichmittel auf Sauerstoff-Basis, dadurch gekennzeich¬ net, daß als Alkaliträger 0,5 bis 60 Gew.- , vorzugsweise 10 bis 50 Gew.-%, bezogen auf das gesamte Mittel, eine oder mehrere Aminosäuren bzw. deren Alkali- oder Ammoniumsalze enthalten sind.The present invention relates to an agent for the mechanical cleaning of dishes, the 1% by weight aqueous solution of which has a pH of 8 to 12, preferably 9 to 11, containing water-soluble builder components and bleaching agents for oxygen. Basis, characterized in that 0.5 to 60% by weight, preferably 10 to 50% by weight, based on the total composition, of one or more amino acids or their alkali metal or ammonium salts are contained as alkali carriers.
Aminosäuren im Sinne der Erfindung sind solche Aminosäuren, deren Amino- funktion nicht substituiert ist, d.h. deren Aminofunktionen nur Wasser¬ stoffe tragen.Amino acids in the sense of the invention are those amino acids whose amino function is not substituted, i.e. whose amino functions only carry hydrogens.
Als Aminosäuren kommen synthetische oder natürlich vorkommende Aminosäuren in Frage, die z.B. durch Hydrolyse aus pflanzlichen oder tierischen Pro¬ teinen wie Kollagen, Keratin, Casein, Elastin, Sojaprotein, Weizengluten oder Mandelprotein erhältlich sind.Suitable amino acids are synthetic or naturally occurring amino acids, which e.g. can be obtained by hydrolysis from vegetable or animal proteins such as collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein.
Bevorzugt sind α-Aminosäuren, z.B. Serin, Threonin, Ornithin, Arginin, Lysin, Asparagin, Gluta in, Phenylalanin oder Tyrosin, insbesondere jedoch Glycin, Alanin, Valin, Leucin und Isoleucin. Besonders bevorzugt ist Gly¬ cin bzw. dessen Alkali- oder Ammoniumsalze, z.B. Natriumglycinat. Neben den Aminosäuren können in den erfindungsgemäßen Geschirrspülmitteln auch deren Alkali-, Erdalkali- oder Ammoniumsalze eingesetzt werden, ins¬ besondere die Natriumsalze.Preferred are α-amino acids, for example serine, threonine, ornithine, arginine, lysine, asparagine, glutin, phenylalanine or tyrosine, but especially glycine, alanine, valine, leucine and isoleucine. Glycine or its alkali metal or ammonium salts, for example sodium glycinate, is particularly preferred. In addition to the amino acids, their alkali metal, alkaline earth metal or ammonium salts can also be used in the dishwashing detergents according to the invention, in particular the sodium salts.
Die Aminosäuren bzw. deren Salze können dabei in Pulverform oder als Gra¬ nulat, gegebenenfalls gemeinsam mit Hilfsmitteln wie z. B. Na-citrat, ein¬ gesetzt werden.The amino acids or their salts can be in powder form or as granules, optionally together with auxiliaries such as. B. Na citrate, can be used.
Durch Variation des Verhältnisses der Aminosäuren zu ihren Salzen läßt sich ebenso problemlos wie mit dem System Hydrogencarbonat/Carbonat ein bestimmter gewünschter pH-Wert einstellen. Hinsichtlich der Kalkbelagsin- hibierung ist das Alkaliträger-System Aminosäure/Aminosäuresalz dem System Hydrogencarbonat/Carbonat jedoch deutlich überlegen.By varying the ratio of the amino acids to their salts, a certain desired pH value can be set just as easily as with the bicarbonate / carbonate system. However, the alkali carrier system amino acid / amino acid salt is clearly superior to the bicarbonate / carbonate system with regard to limescale inhibition.
Aminosäuren bzw. Aminosäuresalze sind in den erfindungsgemäßen Mitteln in Mengen von 0,5 bis 60 Gew.-%, vorzugsweise 10 bis 50 Gew.-%, enthalten. Dabei können auch Mischungen verschiedener Aminosäuren bzw. Aminosäure¬ salze verwendet werden. Fakultativ können Carbonat und/oder Hydrogencarbo- nate, insbesondere Alkalicarbonate und/oder -hydrogencarbonate in Mengen von bis zu 15 Gew.-%, bezogen auf das gesamte Geschirrspülmittel, enthal¬ ten sein. Vorzugsweise sind die erfindungsgemäßen Geschirrspülmittel je¬ doch frei von Carbonaten und/oder Hydrogencarbonaten. Auch auf den Einsatz hochalkalischer Metasilikate, z.B. Natriummetasilikat, wird vorzugsweise verzichtet; Disilikate mit einem molaren Verhältnis Siθ2/Na2Ü 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, enthal¬ ten sein.Amino acids or amino acid salts are contained in the agents according to the invention in amounts of 0.5 to 60% by weight, preferably 10 to 50% by weight. Mixtures of different amino acids or amino acid salts can also be used. Optionally, carbonate and / or hydrogen carbonates, in particular alkali carbonates and / or hydrogen carbonates, 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. Also on the use of highly alkaline metasilicates, e.g. Sodium metasilicate, is preferably avoided; Disilicates with a molar ratio of SiO 2 / Na 2 O of 1.5: 1 to 2.5: 1, on the other hand, 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, Härtebild¬ ner 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 ehrfunktionelle organische Carbonsäuren bzw. deren Sal¬ ze, oxidierte Stärke und Polycarbonsäuren bzw. Polycarboxylate sowie Poly- aminosäuren wie z.B. Polyasparaginsäure in Frage. Auf die früher verwende¬ ten Phosphate, z.B. Pentanatriumtriphosphat, die prinzipiell ebenfalls enthalten sein können, wird aus ökologischen Gründen vorzugsweise verzich¬ tet.Organophosphonic acids or their salts, crystalline phyllosilicates, zeolites, di-and Honorary functional organic carboxylic acids or their salts, oxidized starch and polycarboxylic acids or polycarboxylates as well as polyamino acids such as polyaspartic acid in question. On the phosphates used earlier, for example pentasodium triphosphate, which in principle also may be included, is preferably omitted for ecological reasons.
Bevorzugte Builderkomponenten sind di- oder ehrfunktionelle 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 honor-functional 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 syn¬ thetischen Polymere bzw. deren Salze der Polymerisationsprodukte ungesät¬ tigter Carbonsäuren bzw. deren Salze zu verstehen, zu denen z.B. Poly- acrylsäure, Poly ethacrylsäure, 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, poly ethacrylic 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 Nl, 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( ) 175 der Firma Alco.Suitable polyacrylates are, for example, Alcosperse ( R ) 102, 104, 106, 404, 406 from Alco, Acrysole ( R ) A Nl, 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 () 175 from Alco.
Die erfindungsgemäßen Geschirrspülmittel enthalten weiterhin zwingend Bleichmittel auf Sauerstoffbasis, insbesondere Perborate und/oder Percar- bonate 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 bleaching agents, in particular perborates and / or percarbonates in an amount of 0.5 to 20% by weight, preferably 5 to 12% by weight, based on the total dishwashing detergent.
Besondere Bedeutung haben das Natriumperborat-tetrahydrat (NaBθ2 • H2O2 • 3H2O), das Natriumperborat-monohydrat (NaB02 • H2O2) und das Peroxycar- bonat (Na2CÜ3 • 1,5 H2O2). Weitere brauchbare Bleichmittel sind z.B. per¬ saure Salze organischer Säuren, wie Perbenzoate oder Salze der Diperdode- candisäure. Außerdem sind fakultativ Bleichaktivatoren enthalten. Geeig¬ nete Bleichaktivatoren sind insbesondere N-Acyl- und 0-Acyl-Verbindungen, vorzugsweise tetraacylierte Diamine wie N,N,N' ,N'-Tetraacetylethylendiamin (TAED). Die erfindungsgemäßen Mittel enthalten solche üblichen Bleichak¬ tivatoren in einer Menge von 0,1 bis 10 Gew.-%, vorzugsweise 1 bis 5 Gew.-%. Die erfindungsgemäßen Mittel können fakultativ auch aktivchlorab- spaltende Mittel wie z.B. Trichlorisocyanursäure enthalten; vorzugsweise sind sie jedoch frei von aktivchlorabspaltenden Mitteln.Sodium perborate tetrahydrate (NaBθ2 • H2O2 • 3H2O), sodium perborate monohydrate (NaB02 • H2O2) and peroxycarbonate (Na2CÜ3 • 1.5 H2O2) are of particular importance. Other bleaching agents which can be used are, for example, peracidic salts of organic acids, such as perbenzoates or salts of diperdodecadic acid. Optional bleach activators are also included. Suitable bleach activators are in particular N-acyl and 0-acyl compounds, preferably tetraacylated diamines such as N, N, N ', N'-tetraacetylethylenediamine (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 Ten- side; die erfindungsgemäßen Geschirrspülmittel können prinzipiell zwar auch sehr geringe Mengen an anionischen, kationischen oder a photeren Ten¬ siden 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 Ten- side sind vor allem Anlagerungsprodukte von 1 bis 20 Mol Ethylenoxid (EO) und/oder 1 bis 20 Mol Propylenoxid (PO) an 1 Mol einer aliphatischen Ver¬ bindung mit 10 bis 20 Kohlenstoffatomen aus der Gruppe der Alkohole, Car¬ bonsäuren, Fettamine, Carbonsäurea ide 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 Kombina¬ tion mit wasserlöslichen nichtionischen Tensiden eingesetzt. Außerdem kön¬ nen als nichtionische Tenside auch Alkylpolyglycoside der allgemeinen For¬ mel R-0-(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. Above all, these are nonionic surfactants; The dishwashing detergents according to the invention can in principle also contain very small amounts of anionic, cationic or a photonic surfactants, but are preferably free of these. The content of nonionic surfactants is a maximum of 5% by weight, preferably a maximum of 2% by weight, based on the total dishwashing detergent. Addition products of 1 to 20 moles of ethylene oxide (EO) and / or 1 to 1 are particularly suitable as nonionic surfactants 20 moles of propylene oxide (PO) to 1 mole of an aliphatic compound having 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxylic acid amides and alkanesulfonamides of interest. In addition to the water-soluble nonionic surfactants, non-or not completely water-soluble polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule are also important, and are preferably used in combination with water-soluble nonionic surfactants. In addition, nonionic surfactants can also be alkyl polyglycosides of the general formula R-0- (G) x , in which R is a primary, straight-chain or branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, G represents 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 vor¬ zugsweise Enzyme wie Proteasen, Amylasen, Lipasen oder Cellulasen einge¬ setzt werden, beispielsweise Proteasen wie BLAP( ) 140 der Firma Henkel, Optimase(R) -M-440, 0ptimase(R) -M-330, 0pticlean(R) -M-375, 0ρticlean(R) -M-250 der Firma Solvay Enzy es, 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 Expera- se(R) T der Firma Ibis; Amylasen wie Termamyl(R) 60 T, 90 T der Firma No¬ vo, 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 kön¬ nen 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 () 140 from Henkel, Optimase ( R ) -M-440, 0ptimase ( R ) -M-330, 0pticlean ( R ) -M-375, 0ρticlean ( R ) -M-250 from Solvay Enzy es, Maxacal ( R ) CX 450,000, Maxapem ( R ) from Ibis, Savinase ( R ) 4.0 T, 6.0 T, 8.0 T from Novo or Experise ( 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 the company Novo; Cellulases such as Celluzym ( R ) 0.7 T from Novo Nordisk. Enzymes can be present in the detergents 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 pulver- förmige, granuläre oder tablettenförmige Präparate vor, die in an sich üblicher Weise, beispielsweise durch Mischen, Granulieren, Walzenkompak¬ tieren und/oder durch Sprühtrocknung hergestellt werden können. Ein wei¬ terer Vorteil des vornehmlich aus organischen Rohstoffen bestehenden Al- kaliträger-System ist, daß sich Vorteile hinsichtlich der Konfektionie¬ rung, insbesondere bei der Herstellung von Granulaten, Tabletten oder Ex- trudaten 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. A further advantage of the alkali carrier system, which consists primarily of organic raw materials, is that there are advantages with regard to assembly, 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 Mi¬ scher miteinander vermischt und das Gemisch mittels herkömmlicher Tablet¬ tenpressen, beispielsweise Exzenterpressen oder Rundläuferpressen, mit Preßdrucken im Bereich von 200 • IO5 Pa bis 1500 • 105 Pa verpreßt. Man erhält so problemlos bruchfeste und dennoch unter Anwendungsbedingungen ausreichend schnell lösliche Tabletten mit Biegefestigkeiten von norma¬ lerweise 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.For the preparation of the inventive cleaning compositions in tablet form is preferably such procedure is to shear-mixing all ingredients in a Mi¬ together and the mixture using conventional Tablet¬ tenpressen, for example eccentric presses or rotary presses with press pressures in the range of 200 • IO 5 Pa to 1500 • 10 5 Pa pressed. In this way, break-resistant tablets are obtained which, under application conditions, dissolve sufficiently quickly, with bending strengths of normally over 150 N. Preferably, a tablet produced in this way has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter from 35 mm to 40 mm.
Die Herstellung der Maschinengeschirrspülmittel in Form von nicht stauben¬ den, lagerstabil rieselfähigen Pulvern und/oder Granulaten mit hohen Schüttdichten im Bereich von bevorzugt 750 bis 1.000 g/1 erfolgt z.B. da¬ durch, daß man in einer ersten Verfahrensteilstufe die Builder-Komponenten mit wenigstens einem Anteil flüssiger Mischungskomponenten unter Erhöhung der Schüttdichte dieses Vorgemisches vermischt und nachfolgend - gewünsch- tenfalls nach einer Zwischentrocknung - die weiteren Bestandteile des Ma- schinengeschirrspülmittels mit dem so gewonnen Vorgemisch vereinigt. Als Flüssigphase werden in der ersten Verfahrensteilstufe, insbesondere die unter Normalbedingungen flüssigen Tensidverbindungen - insbesondere also die entsprechenden nichtionischen Tenside - und/oder weitere Flüs¬ siganteile der Gesamtrezeptur eingesetzt. In Betracht kommen hier die in Trägerflüssigkeiten gelösten Duftstoffe und/oder begrenzte Mengen an Was¬ ser bzw. wäßrigen Lösungen von Mischungskomponenten des angestrebten Ge¬ schirrspülmittels.The machine dishwashing detergents are 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, in that in a first process sub-stage the builder components are mixed with at least a portion of liquid mixture components are mixed while increasing the bulk density of this premix and then - if desired after an intermediate drying - the further components of the dishwasher detergent are combined 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 other 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 Geschirrspül¬ mittels mit den Flüssigkomponenten 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 Misch¬ vorrichtung durchgearbeitet und homogenisiert. Die Mitverwendung zusätz¬ licher Flüssigkeitsmengen, insbesondere also der Einsatz von zusätzlichem Wasser, ist hier in der Regel nicht erforderlich. Das angefallene Stoff¬ gemisch liegt dann als rieselfähiges, nicht staubendes Pulver der ge¬ wünschten hohen Schüttdichten etwa im Bereich von 800 bis 900 g/1 vor.In the first part of the mixing process, the builder is generally mixed with at least one further component of the dishwashing agent 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 intimately mixed. 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 material mixture 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 Aminosäuren und/oder deren Sal¬ ze enthaltende Maschinen-Geschirrspülmitteln stehen Produkte zur Verfü¬ gung, die neben ihrer guten biologischen Abbaubarkeit konventionellen mo¬ dernen Geschirrspülmitteln, in denen das Alkaliträger-System überwiegend aus Carbonat und/oder Hydrogencarbonat besteht, hinsichtlich der Kalkbe- lagsinhibierung überlegen sind. With the dishwasher detergents according to the invention containing amino acids and / or their salts, products are available which, in addition to their good biodegradability, are conventional modern dishwashing detergents in which the alkali carrier system consists predominantly of carbonate and / or hydrogen carbonate , are superior in terms of lime scale inhibition.
B e i s p i e l eB e i s p i e l e
Es wurden granuläre Geschirrspülmittel nachstehender Zusammensetzung (erfindungsgemäße Mittel A und B, Vergleichsmittel C sowie erfindungs¬ gemäße Mittel D, E und F) hergestellt.Granular dishwashing detergents with 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.-% Na¬ triumglycinat, der pH-Wert einer 1 Gew.-%igen wäßrigen Lösung lag dem¬ entsprechend höher, bei 10,9. Das Vergleichsmittel C enthielt als Al- kaliträgersystem 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, 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; 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.-% Natriu alycinat (D), 25,3 Gew.-% Glycin / 10,8 Gew.-% Natriumglycinat (E) sowie 37,5 Gew.-% Natriumglycinat (F).Agents D, E and F according to the invention contained 24.0% by weight glycine / 16.0% by weight sodium allycinate (D), 25.3% by weight glycine / 10.8% by weight sodium glycinate (E ) and 37.5% by weight sodium glycinate (F).
Na-glycinat kann dabei in Pulverform oder als Granulat eingesetzt wer¬ den. Die Granulatherstellung kann z.B. auf folgende Weise erfolgen:Na glycinate can be used in powder form or as granules. Granule production can e.g. in the following way:
Na-Glycinat bzw. ein in einem technikumsüblichen Lödige Mischer herge¬ stelltes Gemisch aus Na-Glycinat und Na-Citrat (90:10) wurden in einer Walzenpresse bei einer Walzentemperatur von 20°C und einem Liniendruck von 17 kN/cm zu Schülpen verpreßt. Die Schülpen wurden anschließend gemahlen und einer Fraktion von < 1,6 mm abgesiebt.Na glycinate or a mixture of Na glycinate and Na citrate (90:10) produced in a Lödige mixer customary in the industry were pressed into slugs in a roller press at a roller temperature of 20 ° C. and a line pressure of 17 kN / cm . The slugs were then ground and sieved from a fraction of <1.6 mm.
Diese Fraktion wurde nun in eine batchweise betriebene Niro-Aero- matic-Wirbelschichtapparatur verbracht und über einen Zeitraum von 30 min mit einem Paraffinwachs (S p 42-45°C), welches über eine Zwei¬ stoffdüse in die Wirbelschicht eingetragen wurde, bedüst. Die Wirbel¬ luft wurde auf 30°C gehalten. Bei einem Verhältnis Walzenkompaktat : Paraffinwachs von 9:1 entstanden leicht klebrige Granulate, die jedoch aufgrund der außen aufgetragenen hydrophobierten Schicht auch in Re¬ zepturen, die vagabundierendes Wasser enthalten, stabil sind. This fraction was then placed in a batch-operated stainless steel fluidized bed apparatus and sprayed over a period of 30 minutes with a paraffin wax (S p 42-45 ° C.) which was introduced into the fluidized bed via a two-component nozzle. The vortex air was kept at 30 ° C. With a ratio of roller compactate: paraffin wax of 9: 1, slightly sticky granules were formed, however due to the hydrophobized layer applied on the outside, they are also stable in formulations containing vagrant water.
A B C D E FA B C D E F
Gew.-% Gew.-% Gew.-% Gew.-% Gew.-% Gew.-%% By weight% by weight% by weight% by weight% by weight
Na-citrat 30,0 30,0 30,0 45,0 45,0 45,0Na citrate 30.0 30.0 30.0 45.0 45.0 45.0
Sokalan(R) CP5 (Acrylat/Sokalan ( R ) CP5 (acrylate /
Maleat-Copolymer der Fa.Maleate copolymer from
BASF) 10,0 10,0 10,0 - - -BASF) 10.0 10.0 10.0 - - -
Na2C03 - - 13,0 - - -Na2C03 - - 13.0 - - -
NaHC03 - - 36,1 - - -NaHC03 - - 36.1 - - -
Glycin 31,9 - - 24,0 25,3 -Glycine 31.9 - - 24.0 25.3 -
Natriumglycinat 17,2 49,1 - 16,0 10,8 37,5Sodium glycinate 17.2 49.1 - 16.0 10.8 37.5
Na-perborat-Monohydrat 5,0 5,0 5,0 - - -Na perborate monohydrate 5.0 5.0 5.0 - - -
Na-Percarbonat - - - 6,5 12,0 10,0Na percarbonate - - - 6.5 12.0 10.0
TAED 2,0 2,0 2,0 5,0 4,0 4,0TAED 2.0 2.0 2.0 5.0 4.0 4.0
Amylase 1,5 1,5 1,5 1,0 1,0 1,0Amylase 1.5 1.5 1.5 1.0 1.0 1.0
Protease 1,5 1,5 1,5 1,0 1,0 1,0Protease 1.5 1.5 1.5 1.0 1.0 1.0
Plurafac(R) LF 403Plurafac ( R ) LF 403
(Cl2-18-Fett-alkohol x(Cl2-18 fatty alcohol x
EO x 4P0 der Fa. BASF) 0,9 0,9 0,9 1,5 0,9 1,5EO x 4P0 from BASF) 0.9 0.9 0.9 1.5 0.9 1.5
BeiaqsiπhibierunqBeiaqsiπhibierunq
Die Kalkbelagsbildung der Mittel A, B und C wurde in einer Geschirr¬ spülmaschine Miele G 590 (Programm Universal 65 °C) bei Dosierungen von jeweils 20 g in 6,2 1 Wasser mit 16 °dH unter Zusatz von 50 g pumpbarer Anschmutzungen (Gemisch aus Ketchup, Bratensoße, Senf, Kar¬ toffelstärke, Eigelb, Milch, Margarine) in Anwesenheit von 3,0 ml ei¬ nes handelsüblichen Klarspülers über 10 Spülgänge getestet. Die Be¬ lagsbildung 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: 1,0The 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 of water with 16 ° dH with the addition of 50 g of pumpable soiling (mixture from ketchup, gravy, mustard, potato starch, egg yolk, milk, margarine) in the presence of 3.0 ml of a commercial rinse aid over 10 rinse cycles. The formation of deposits 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
Erfindungsgemäßes Mittel B: 1.0 Vergleichsmittel C: 0,2Agent B according to the invention: 1.0 Comparative agent C: 0.2
Erfindungsgemäßes Mittel D 2,2Agent D 2.2 according to the invention
Erfindungsgemäßes Mittel E 2,6Agent E 2.6 according to the invention
Erfindungsgemäßes Mittel F 2,6Agent F 2.6 according to the invention
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 with regard to the formation of deposits.

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Mittel zum maschinellen Reinigen von Geschirr, dessen 1 Gew.-%ige wä߬ rige Lösung einen pH-Wert von 8 bis 12, vorzugsweise 9 bis 11, auf¬ weist, enthaltend wasserlösliche Builderkomponenten und Bleichmittel auf Sauerstoff-Basis, dadurch gekennzeichnet, daß als Alkaliträger 0,5 bis 60 Gew.-%, vorzugsweise 10 bis 50 Gew.- , bezogen auf das gesamte Mittel, eine oder mehrere Aminosäuren bzw. deren Alkali- oder Ammo¬ niumsalze enthalten sind.1. Means for machine cleaning of dishes, the 1 wt .-% aqueous solution has a pH of 8 to 12, preferably 9 to 11, containing water-soluble builder components and bleaching agents on an oxygen basis, characterized that 0.5 to 60% by weight, preferably 10 to 50% by weight, based on the total composition, of one or more amino acids or their alkali metal or ammonium salts are present as alkali carriers.
2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß die Aminosäuren α-Aminosäuren sind.2. Composition according to claim 1, characterized in that the amino acids are α-amino acids.
3. Mittel nach Anspruch 2, dadurch gekennzeichnet, daß die α-Aminosäuren ausgewählt sind aus Glycin, Alanin, Valin, Leucin und Isoleucin.3. Composition according to claim 2, characterized in that the α-amino acids are selected from glycine, alanine, valine, leucine and isoleucine.
4. Mittel nach Anspruch 2, dadurch gekennzeichnet, daß die α-Aminosäure Glycin ist.4. Composition according to claim 2, characterized in that the α-amino acid is glycine.
5. Mittel nach Anspruch 1 bis 4, dadurch gekennzeichnet, daß nicht mehr als 15 Gew.-%, bezogen auf das gesamte Mittel, Carbonate und/oder Hy- drogencarbonate, enthalten sind.5. Composition according to claim 1 to 4, characterized in that not more than 15 wt .-%, based on the total composition, carbonates and / or hydrogen carbonates are contained.
6. Mittel nach Anspruch 1 bis 5, dadurch gekennzeichnet, daß es frei von Carbonaten und/oder Hydrogencarbonaten ist.6. Composition according to claim 1 to 5, characterized in that it is free of carbonates and / or bicarbonates.
7. Mittel nach Anspruch 1 bis 6, dadurch gekennzeichnet, daß es frei von Metasilikaten ist.7. Composition according to claim 1 to 6, characterized in that it is free of metasilicates.
8. Mittel nach Anspruch 1 bis 7, dadurch gekennzeichnet, daß als wasser¬ lösliche Builderkomponenten insgesamt 1 bis 60 Gew.- , vorzugsweise 20 bis 50 Gew.-% di- oder mehrfunktionelle organische Carbonsäuren, bzw. deren Salze, insbesondere Zitronensäure bzw. deren Salze und/oder syn¬ thetische Polycarbonsäuren bzw. Polycarboxylate, enthalten sind. 8. Composition according to claim 1 to 7, characterized in that as water-soluble builder components a total of 1 to 60 wt .-%, preferably 20 to 50 wt .-% di- or polyfunctional organic carboxylic acids, or their salts, especially citric acid or the salts and / or synthetic polycarboxylic acids or polycarboxylates are included.
9. Mittel nach Anspruch 1 bis 8, dadurch gekennzeichnet, daß als Bleich¬ mittel auf Sauerstoff-Basis 0,5 bis 20 Gew.-%, vorzugsweise 5 bis 12 Gew.-%, bezogen auf das gesamte Mittel, Perborate und/oder Percarbo- nate enthalten sind.9. Composition according to claim 1 to 8, characterized in that as an oxygen-based bleaching agent 0.5 to 20 wt .-%, preferably 5 to 12 wt .-%, based on the total agent, perborates and / or Percarbonates are included.
10. Mittel nach Anspruch 1 bis 9, dadurch gekennzeichnet, daß es frei von anionischen, kationischen oder amphoteren Tensiden ist und nicht mehr als 5 Gew.-%, vorzugsweise nicht mehr als 2 Gew.- , bezogen auf das gesamte Mittel, nichtionische Tenside enthält.10. Composition according to claim 1 to 9, characterized in that it is free of anionic, cationic or amphoteric surfactants and not more than 5% by weight, preferably not more than 2% by weight, based on the total composition, of nonionic surfactants contains.
11. Mittel nach Anspruch 1 bis 10, dadurch gekennzeichnet, daß es Enzyme in einer Menge von 0,1 bis 5 Gew.-%, vorzugsweise 1 bis 3 Gew.-%, be¬ zogen auf das gesamte Mittel, enthält.11. Agent according to claim 1 to 10, characterized in that it contains enzymes in an amount of 0.1 to 5 wt .-%, preferably 1 to 3 wt .-%, based on the total agent.
12. Tablettenför iges Mittel nach Anspruch ,1 bis 11, dadurch gekennzeich¬ net, daß es durch Vermischen aller seiner Bestandteile in einem Mi¬ scher und Verpressen des Gemisches mittels einer Tablettenpresse bei Preßdrucken von 2 • 107 Pa bis 1,5 • IO8 Pa erhältlich ist.12. tablet agent according to claim 1 to 11, characterized gekennzeich¬ net that it by mixing all its components in a mixer and pressing the mixture by means of a tablet press at pressures of 2 • 10 7 Pa to 1.5 • IO 8 Pa is available.
13. Pulver- oder granulatförmiges Mittel nach Anspruch 1 bis 11, dadurch gekennzeichnet, daß es eine Schüttdichte von 750 g/1 bis 1000 g/1 auf¬ weist. 13. Powder or granular composition according to claim 1 to 11, characterized in that it has a bulk density of 750 g / 1 to 1000 g / 1.
PCT/EP1994/001830 1993-06-15 1994-06-06 Lower-buildup dish-washing detergents WO1994029420A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP94918388A EP0703969B1 (en) 1993-06-15 1994-06-06 Lower-buildup dish-washing detergents
DE59404733T DE59404733D1 (en) 1993-06-15 1994-06-06 DISHWASHER WITH A REDUCED TILAGE PREPARATION
PL94312248A PL178743B1 (en) 1993-06-15 1994-06-06 Dish washing up agent of reduced tarnish forming tendency
JP7501300A JPH10508042A (en) 1993-06-15 1994-06-06 Low film-forming dishwashing detergent
DK94918388T DK0703969T3 (en) 1993-06-15 1994-06-06 Detergents with reduced propensity for coating formation
GR980400044T GR3025871T3 (en) 1993-06-15 1998-01-12 Lower-buildup dish-washing detergents

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4319798A DE4319798A1 (en) 1993-06-15 1993-06-15 Dishwashing detergent with reduced tendency to scale up
DEP4319798.1 1993-06-15

Publications (1)

Publication Number Publication Date
WO1994029420A1 true WO1994029420A1 (en) 1994-12-22

Family

ID=6490376

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/001830 WO1994029420A1 (en) 1993-06-15 1994-06-06 Lower-buildup dish-washing detergents

Country Status (12)

Country Link
EP (1) EP0703969B1 (en)
JP (1) JPH10508042A (en)
AT (1) ATE160817T1 (en)
CA (1) CA2165285A1 (en)
CZ (1) CZ286098B6 (en)
DE (2) DE4319798A1 (en)
DK (1) DK0703969T3 (en)
ES (1) ES2109704T3 (en)
GR (1) GR3025871T3 (en)
HU (1) HU216096B (en)
PL (1) PL178743B1 (en)
WO (1) WO1994029420A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
EP3103859A3 (en) * 2015-06-08 2017-01-04 Sodasan Wasch- und Reinigungsmittel GmbH Phosphate-free and phosphonate-free dishwasher detergent
US20220403295A1 (en) * 2019-11-15 2022-12-22 Basf Se Cleaning compositions and their use

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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)
ES2160355T3 (en) * 1996-06-21 2001-11-01 Reckitt Benckiser Nv LOW-ALCALINITY WASHING AGENT, FOR DISHWASHERS, CONTAINING METHYLGLYCINDIACETIC ACID.
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

Citations (2)

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Publication number Priority date Publication date Assignee Title
DD218117A1 (en) * 1983-08-24 1985-01-30 Bitterfeld Chemie DETERGENT FOR TEXTILES
EP0356974A2 (en) * 1988-09-02 1990-03-07 BASF Aktiengesellschaft Cleaning and washing composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD218117A1 (en) * 1983-08-24 1985-01-30 Bitterfeld Chemie DETERGENT FOR TEXTILES
EP0356974A2 (en) * 1988-09-02 1990-03-07 BASF Aktiengesellschaft Cleaning and washing composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
EP3103859A3 (en) * 2015-06-08 2017-01-04 Sodasan Wasch- und Reinigungsmittel GmbH Phosphate-free and phosphonate-free dishwasher detergent
US20220403295A1 (en) * 2019-11-15 2022-12-22 Basf Se Cleaning compositions and their use

Also Published As

Publication number Publication date
HU9503574D0 (en) 1996-02-28
DE59404733D1 (en) 1998-01-15
CA2165285A1 (en) 1994-12-22
PL312248A1 (en) 1996-04-01
DK0703969T3 (en) 1998-08-10
EP0703969B1 (en) 1997-12-03
DE4319798A1 (en) 1994-12-22
HUT75585A (en) 1997-05-28
ATE160817T1 (en) 1997-12-15
PL178743B1 (en) 2000-06-30
ES2109704T3 (en) 1998-01-16
EP0703969A1 (en) 1996-04-03
HU216096B (en) 1999-04-28
GR3025871T3 (en) 1998-04-30
CZ330395A3 (en) 1996-05-15
CZ286098B6 (en) 2000-01-12
EP0703969A4 (en) 1995-08-28
JPH10508042A (en) 1998-08-04

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