EP1004655A2 - Automatic dishwashing composition - Google Patents

Automatic dishwashing composition Download PDF

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Publication number
EP1004655A2
EP1004655A2 EP99120429A EP99120429A EP1004655A2 EP 1004655 A2 EP1004655 A2 EP 1004655A2 EP 99120429 A EP99120429 A EP 99120429A EP 99120429 A EP99120429 A EP 99120429A EP 1004655 A2 EP1004655 A2 EP 1004655A2
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EP
European Patent Office
Prior art keywords
weight
machine dishwashing
dishwashing detergent
detergent according
disilicate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP99120429A
Other languages
German (de)
French (fr)
Other versions
EP1004655A3 (en
Inventor
Günther Dr. Schimmel
Lothar Westermann
Harald Dr. Bauer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Produkte Deutschland GmbH
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Clariant GmbH
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Filing date
Publication date
Application filed by Clariant GmbH filed Critical Clariant GmbH
Publication of EP1004655A2 publication Critical patent/EP1004655A2/en
Publication of EP1004655A3 publication Critical patent/EP1004655A3/en
Ceased legal-status Critical Current

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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
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/755—Sulfoxides

Definitions

  • the invention relates to a liquid to pasty dishwasher detergent, a method for its manufacture and its use.
  • Liquid dishwashing detergents such as those used especially in the area of large-scale commercial consumption, are unsuitable for use in automatic household dishwashing machines in the household area, primarily because of their insufficiently low viscosity and high alkalinity, since these products come with must be labeled "caustic" and therefore pose a great security risk in the household. In addition, retention of the dishwashing liquid in the usual household dosing devices is not guaranteed in most cases.
  • the commercially available gel-like or thixotropic dishwashing detergents contain more or less large amounts of alkali silicates, generally in the form of aqueous solutions (water glass), for example in the ratio Na 2 O: SiO 2 of 1: 2 to 1: 3.3, to achieve the desired alkalinity and to serve as anti-corrosion agents for the glaze and decor of porcelain.
  • dishwashing detergents with such decorative and glaze protection have the disadvantage that they are on the rest of the dishes, preferably on glasses Deposits of different thicknesses form, which are initially in bright tarnish colors, later in whitish-cloudy, bluish-tinged, sticky toppings and only with extremely strong ones Acids, for example a hydrofluoric acid / sulfuric acid mixture, are removed can.
  • Such dishwashing detergents are therefore not suitable for long-term use.
  • the invention is therefore based on the object of a non-solid dishwasher detergent to make available that compared to the prior art with a good cleaning effect a reduced degree of corrosion, especially on glasses and porcelain plates as well results in a reduced level of deposits.
  • a dishwasher detergent of the type mentioned at the beginning characterized in that, in addition to the usual dishwasher detergent ingredients, it is a crystalline, layered silicate of the general formula a A 2 O ⁇ b BO ⁇ c C 2 O 3 ⁇ d D 2 O 5 ⁇ e SiO 2 ⁇ f H 2 O contains, in which A is an alkali metal and / or hydrogen, B is an alkaline earth metal, C is an element of the third main group of the periodic table and D is an element of the fifth main group of the periodic table and furthermore applies: 0 ⁇ a ⁇ 1; 0 ⁇ b ⁇ 0.5; 0 ⁇ c / e ⁇ 0.05; 0 ⁇ d / e ⁇ 0.25; 1.9 ⁇ e ⁇ 4; 0 ⁇ f ⁇ 20.
  • the machine dishwashing detergent particularly preferably contains 5 to 30% by weight of the crystalline layered silicate.
  • the crystalline layered silicate is preferably essentially Disodium disilicate.
  • the layered crystalline disodium disilicate is preferably present (the following information refer to% by weight) from 1 to 40% of alpha disodium disilicate:, 0 to 50% of beta disodium disilicate, 50 to 98% of delta disodium disilicate and 0 to 40% of non-layer silicate Sodium silicates.
  • layered crystalline disodium disilicate from 0 to 40% of alpha disodium disilicate, 20 to 98% of beta disodium disilicate, 0 to 40% of delta disodium disilicate and 0 to 50% of non-layer silicate Sodium silicates.
  • the layered crystalline disodium disilicate is present from 20 to 98% of alpha disodium disilicate, 0 to 40% of beta disodium disilicate, 0 to 50% of delta disodium disilicate and 0 to 50% of non-layer silicate Sodium silicates.
  • alpha, beta and delta disodium disilicate are known and can be used, for example can be found in EP 0 164 514.
  • the crystalline layered silicate in the dishwasher detergent according to the invention preferably contains up to 10 mol% boron, based on SiO 2 .
  • the crystalline layered silicate in the dishwasher detergent according to the invention preferably contains up to 50 mol% of phosphorus, based on SiO 2 .
  • the machine dishwashing detergent preferably also contains at least one surfactant and / or one Bleaching agent and / or a rheological additive and / or a dispersing agent and / or one Dispersion carrier.
  • the machine dishwashing detergent preferably contains long-chain block polymers as surfactants aliphatic alcohols with ethylene oxide or propylene oxide groups, modified fatty alcohol polyglycol ethers, Mono- and dialkyl sulfates, alkanesulfonates, amine oxides and / or fatty acid methyl polyglycol esters.
  • the machine dishwashing detergent preferably contains active chlorine carriers as bleaching agents and / or active oxygen carriers.
  • the machine dishwashing detergent preferably contains as a rheological additive and / or dispersant Carboxymethyl cellulose, polycarboxylates, phosphonates and / or synthetic Tone.
  • the machine dishwashing detergent preferably contains ethylene glycols as the dispersion carrier, Cooligo / copolymers of propylene oxide and ethylene oxide and / or water.
  • compositions mentioned above are sodium disilicate essentially disodium disilicate.
  • the machine dishwashing detergent according to the invention preferably has corrosion-inhibiting properties on.
  • the machine dishwashing detergent according to the invention particularly preferably has corrosion-inhibiting agents Properties especially on glasses.
  • the machine dishwashing detergent according to the invention preferably has an increased cleaning performance on.
  • the invention also relates to a method for producing a dishwasher detergent, characterized in that in a submitted aqueous medium and / or Dispersion carriers first dissolve alkali carriers, then rheological additives and / or dispersants admixed, cools to room temperature, adds the other components and on The crystalline layered silicate is added at the end of the mixing process.
  • the alkali carrier is preferably sodium carbonate, sodium hydroxide, potassium hydroxide and / or around water-soluble alkali silicates.
  • the components are preferably surfactants, bleaches, fillers, builders, Cobuilders, phosphates, organic complexing agents, foam inhibitors, perfumes and / or dyes and / or possibly other ingredients for machine dishwashing detergents.
  • the invention also relates to the use of the dishwasher detergent according to the invention for automatic dishwashing.
  • the layered silicate contained in the machine dishwashing detergent according to the invention which has the general formula as described above a A 2 O ⁇ b BO ⁇ c C 2 O 3 ⁇ d D 2 O 5 ⁇ e SiO 2 ⁇ f H 2 O in which A is an alkali metal and / or hydrogen, B is an alkaline earth metal, C is an element of the third main group of the periodic table and D is an element of the fifth main group of the periodic table (and the following also applies: 0 ⁇ a ⁇ 1; 0 ⁇ b ⁇ 0 , 5; 0 ⁇ c / e ⁇ 0.05; 0 ⁇ d / e ⁇ 0.25; 1.9 ⁇ e ⁇ 4; 0 ⁇ f ⁇ 20), may in particular also contain calcium and magnesium ions.
  • ions are those of the third and fifth main group of the periodic table, these include above all boron or phosphorus. This is especially true if a disodium disilicate as layered silicate, as described above and below is used.
  • the layered silicate can also be a sodium potassium disilicate, in which the Sodium to potassium ratio can be varied within a wide range.
  • layered silicates of the above formula which are essentially Contain alkali metals (Li, Na, K) and / or hydrogen, and in those low Shares in the above-mentioned alkaline earth metals (Be, Mg, Ca, Sr, Ba) and elements of third (B, Al, Ga, In, Tl) and fifth main group (P, As, Sb, Bi) of the periodic table are.
  • the aforementioned silicate is either used in a finely ground form, i.e. as a powder with an average particle diameter from 1 to 200 microns, or in easily dispersible form e.g. as pressed granules, that when working into the dishwashing dispersion into microscopic particles crushed.
  • Sodium disilicate with polycarboxylates are also particularly preferred Sodium disilicate with polycarboxylates, as described in DE-OS 197 19 888 are.
  • Preferred polycarboxylates are homo- or any combination of copolymers the monomers acrylic acid and / or maleic acid and / or vinyl acetate and / or methallylsulfonate.
  • the preferred compound of polycarboxylates and crystalline, layered Sodium disilicate consists of 50 to 98% by weight of said silicate and 2 to 50% by weight polycarboxylate.
  • dishwasher components some of which have already been mentioned above, such as Fillers, alkali carriers, surfactants, builders, bleaches, rheological additives and dispersants, Foam inhibitors and possibly perfumes and dyes and others can Substances that are already well known for these purposes.
  • Sodium sulfate can be used as a filler e.g. Sodium sulfate.
  • Oxides, hydroxides, carbonates and silicates of the alkali metals are preferred as alkali carriers Sodium carbonate and / or sodium hydroxide and / or potassium hydroxide or water soluble Called alkali silicates.
  • Chlorine-stable block polymers of long-chain aliphatic alcohols are also included as surfactants Ethylene oxide or propylene oxide groups or modified fatty alcohol polyglycol ethers or Mono- and di-alkyl sulfates or alkanesulfonates or amine oxides or fatty acid methyl polyglycol esters suitable.
  • alkali phosphates preferably Pentaalkali nitrate phosphate, anhydrous and / anhydrated and / or hexahydrate used become.
  • Organic complexing agents such as Mono-, di-, tri-, oligo- and / or polycarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids and phosphonic acids, preferably in the form of their water-soluble salts.
  • Preferred Oligocarboxylic acids are citric, tartaric, maleic, etc. These are preferred used together with the crystalline, layered silicate as press granulate.
  • Active chlorine carriers such as sodium dichloroisocyanurate or come as preferred bleaching agents
  • Sodium hypochlorite solution (chlorine bleach) and active oxygen carriers such as hydrogen peroxide, Alkali metal peroxides, alkaline earth metal peroxides, alkali perborate, persulfate, percarbonate, -perphosphate and peroxycarboxylic acids and their salts such as dodecane peroxidicarboxylic acid or magnesium peroxiphthalate.
  • Bleach activators or catalysts can also be used.
  • a common one Bleach activator is tetraacetylethylene diamine.
  • Common bleaching catalysts are complexes of Manganese with special ligands e.g. Derivatives of 1,4,7-triaminocyclononane.
  • Preferred rheological additives and dispersing agents are carboxymethyl cellulose, Polycarboxylates, phosphonates or synthetic clays.
  • Clays which can be used according to the invention are naturally occurring activated and partly modified Clay minerals such as Bentone grades from Rheox or synthetic clay minerals such as the Laponite grades from Laporte or synthetic hectorite from the SKS-21 type Hoechst and synthetic saponite type SKS-20 from Hoechst. More suitable Clays are known to the person skilled in the art and can be found in the manufacturer's catalogs.
  • Dissolved alkali silicates or mono-, oligo- and polyphosphates can be used in the dispersion act supportive.
  • Monomeric, oligomeric or polymeric can be used as the dispersion carrier (liquid component)
  • Ethylene glycol or cooligo / copolymers of propylene oxide and ethylene oxide and / or water be used.
  • Foam in dishwashers mostly caused by foam-producing surfactants or food residues containing protein causes a reduction in cleaning performance. Therefore, it is necessary to use a foam presser or foam damper to clean the dishes to add, for example chlorine-stable phosphoric acid esters, such as triisobutyl phosphate (Defoamer TIP from Clariant GmbH), or well-known silicones like the SP types from Wacker Chemie GmbH.
  • chlorine-stable phosphoric acid esters such as triisobutyl phosphate (Defoamer TIP from Clariant GmbH), or well-known silicones like the SP types from Wacker Chemie GmbH.
  • the aforementioned components can be used in the dishwasher detergent according to the invention individually or in mixtures in addition to the crystalline layered silicates, in particular Sodium disilicates (e.g. type SKS-6 from Clariant GmbH) may be included.
  • Sodium disilicates e.g. type SKS-6 from Clariant GmbH
  • the consistency of the mixtures according to the invention can be of low viscosity / liquid until pasty / gelatinous.
  • Machine dishwashing detergents according to the invention can contain phosphate as well be phosphate free.
  • alkali carriers such as sodium carbonate and / or sodium hydroxide and / or sodium water glass
  • rheological additives and / or dispersants preferably polycarboxylates and / or phosphonic acids
  • Components such as bleach, surfactant and builder (phosphate)
  • the crystalline layered silicate is added.
  • the mixing is preferably carried out under the action of strong shear forces e.g. With usual dispensers, high-shear mixers from Haake & Kunkel (Ultraturrax (TM)) or Impeller, propeller or turbine stirrers.
  • strong shear forces e.g. with usual dispensers, high-shear mixers from Haake & Kunkel (Ultraturrax (TM)) or Impeller, propeller or turbine stirrers.
  • the machine dishwashing detergents according to the invention are notable for good cleaning properties even with critical soiling such as burnt-on protein-containing food residues out. Furthermore, they show a high chlorine or active oxygen stability.
  • the dishwasher detergents according to the invention are preferably used in household dishwashers used, but can also be used in commercial dishwashers.
  • Standard tableware cleaner gels are used as a comparison based on phosphate and a test mixture without adding (according to the invention) crystalline layered silicate.
  • the pH value of the cleaning liquors became immediately after filtering off the contamination then determined using a glass electrode.
  • Example 1 formation of deposits on wash ware
  • compositions D to H according to the invention became shaped and shaped in comparison to the commercial products B and C checked for irreversible damage.
  • Porcelain plates and cups as well Stainless steel cutlery served as ballast for filling the prescribed amount of wash ware 12 place settings.
  • the test is carried out according to DIN V ENV 12875-1: April 1998, mechanical Dishwasher resistance of household goods, part 1.
  • the dosage of Test cleaner deviates from the pre-standard, there were 40 g of liquid test mixture in each Cleaning cycle and 3 ml of rinse aid dosed in the final rinse cycle of the test dishwasher.
  • Method 1 Determination of the deposits on the wash ware
  • the number of rinses is determined after which a visible cloudiness occurs for the first time.
  • grade daylight Black box " 0 no cloudiness no cloudiness 1 no cloudiness very slight turbidity / iridescence 2nd no cloudiness slight clouding / iridescence 3rd very slight turbidity / iridescence clear cloudiness 4th slight clouding / iridescence ------ 5 clear cloudiness ------
  • the arithmetic mean formed from the sum of the ratings and the number of glasses, gives the grade for the damage occurred.
  • the machine dishwashing detergents A to I were tested for their cleaning effect in three household dishwashers Miele G 688 SC based on DIN standard draft 44990 and the IKW method.

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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)
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  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

Liquid to pasty detergent for dishwashing machine contains a crystalline foliated silicate (I) besides usual components. Liquid to pasty detergent for dishwashing machine contains a crystalline foliated silicate of formula (I) besides usual components. A2O.bBO.cC2O3.dD2O5.eSiO2.fH2O (I) A = an alkali metal and/or hydrogen; B = an alkaline earth metal; C = a main group III element; D = a main group V element; a = 0-1; b = 0-0.5; c/e = 0-0.05; d/e = 0-0.25; e = 1.9-4; f = 0-20. An Independent claim is also included for the production of the detergent.

Description

Die Erfindung betrifft ein flüssiges bis pastöses Maschinengeschirrspülmittel, ein Verfahren zu seiner Herstellung und seine Verwendung.The invention relates to a liquid to pasty dishwasher detergent, a method for its manufacture and its use.

Feste Reinigungsmittel für das maschinelle Geschirrspülen werden überwiegend in Pulver- bzw. Granulatform (Agglomerate) angeboten. Ein gravierender Nachteil dieser Art fester Reinigungsmittel besteht darin, daß wegen der Hygroskopizität einzelner Rohstoffe bei Zutritt von geringen Mengen an Feuchtigkeit eine starke Neigung zum Verbacken oder Verklumpen besteht. Dies kann teilweise zu einem Verlust der Reinigungswirkung führen und wirkt zudem auf den Anwender aus optischen Gründen qualitätsmindernd.Solid detergents for automatic dishwashing are mainly used in powder or Granular form (agglomerates) offered. A serious disadvantage of this type of solid cleaning agent is that due to the hygroscopicity of individual raw materials upon entry from small amounts of moisture a strong tendency to cake or clump consists. This can sometimes lead to a loss of the cleaning effect and also works on the user for optical reasons quality-reducing.

Flüssige Geschirrspülmittel, wie sie speziell im Bereich des gewerblichen Großverbrauchs verwendet werden, sind vor allem wegen ihrer unzureichend geringen Viskosität und ihrer hohen Alkalität für den Einsatz in automatischen Haushaltsgeschirrspülmaschinen im Haushaltsbereich ungeeignet, da diese Produkte mit

Figure 00010001
ätzend" gekennzeichnet werden müssen und somit im Haushalt ein großes Sicherheitsrisiko darstellen. Daneben ist die Rückhaltung des Geschirrspülmittels in den haushaltsüblichen Dosiergeräten in den meisten Fällen nicht gewährleistet.Liquid dishwashing detergents, such as those used especially in the area of large-scale commercial consumption, are unsuitable for use in automatic household dishwashing machines in the household area, primarily because of their insufficiently low viscosity and high alkalinity, since these products come with
Figure 00010001
must be labeled "caustic" and therefore pose a great security risk in the household. In addition, retention of the dishwashing liquid in the usual household dosing devices is not guaranteed in most cases.

Die handelsüblichen gelförmigen oder thixotropen Geschirreinigungsmittel enthalten mehr oder weniger große Mengen Alkalisilikate, im allgemeinen in Form wäßriger Lösungen (Wasserglas), beispielsweise im Verhältnis Na2O: SiO2 von 1: 2 bis 1: 3,3, die zum Erreichen der gewünschten Alkalität und als Korrosionschutzmittel für die Glasur und das Dekor von Porzellan dienen sollen.The commercially available gel-like or thixotropic dishwashing detergents contain more or less large amounts of alkali silicates, generally in the form of aqueous solutions (water glass), for example in the ratio Na 2 O: SiO 2 of 1: 2 to 1: 3.3, to achieve the desired alkalinity and to serve as anti-corrosion agents for the glaze and decor of porcelain.

Es hat sich aber gezeigt, daß Geschirreinigungsmittel mit einem derartigen Dekor- und Glasurschutz den Nachteil haben, daß sie auf dem übrigen Geschirrgut, bevorzugt auf Gläsern unterschiedlich starke Ablagerungen bilden, die sich zunächst in bunten Anlauffarben, später in weißlich-trüben blaustichigen festhaftenden Belägen darstellen und nur mit extrem starken Säuren, beispielsweise einem Fluorwasserstoffsäure- / Schwefelsäure- Gemisch, entfernt werden können. Solche Geschirreinigungsmittel sind also für den Dauergebrauch nicht geeignet.However, it has been shown that dishwashing detergents with such decorative and glaze protection have the disadvantage that they are on the rest of the dishes, preferably on glasses Deposits of different thicknesses form, which are initially in bright tarnish colors, later in whitish-cloudy, bluish-tinged, sticky toppings and only with extremely strong ones Acids, for example a hydrofluoric acid / sulfuric acid mixture, are removed can. Such dishwashing detergents are therefore not suitable for long-term use.

Der Erfindung liegt daher die Aufgabe zugrunde, ein nichtfestes Maschinengeschirrspülmittel zur Verfügung zu stellen, das gegenüber dem Stand der Technik bei guter Reinigungswirkung ein verringertes Ausmaß von Korrosion, insbesondere an Gläsern und Porzellantellern sowie ein verringertes Ausmaß an Ablagerungen ergibt.The invention is therefore based on the object of a non-solid dishwasher detergent to make available that compared to the prior art with a good cleaning effect a reduced degree of corrosion, especially on glasses and porcelain plates as well results in a reduced level of deposits.

Diese Aufgabe wird gelöst durch ein Maschinengeschirrspülmittel der eingangs genannten Art; dadurch gekennzeichnet, daß es neben üblichen Maschinengeschirrspülmittelinhaltsstoffen ein kristallines, schichtförmiges Silikat der allgemeinen Formel a A2O · b BO · c C2O3 · d D2O5 · e SiO2 · f H2O enthält, in der A ein Alkalimetall und/oder Wasserstoff, B ein Erdalkalimetall, C ein Element der dritten Hauptgruppe des Periodensystems und D ein Element der fünften Hauptgruppe des Periodensystems bedeuten und weiterhin gilt: 0 ≤ a ≤ 1; 0 ≤ b ≤ 0,5; 0 ≤ c/e ≤ 0.05; 0 ≤ d/e ≤ 0,25; 1,9 ≤ e ≤ 4; 0 ≤ f ≤ 20.This object is achieved by a dishwasher detergent of the type mentioned at the beginning; characterized in that, in addition to the usual dishwasher detergent ingredients, it is a crystalline, layered silicate of the general formula a A 2 O · b BO · c C 2 O 3 · d D 2 O 5 · e SiO 2 · f H 2 O contains, in which A is an alkali metal and / or hydrogen, B is an alkaline earth metal, C is an element of the third main group of the periodic table and D is an element of the fifth main group of the periodic table and furthermore applies: 0 ≤ a ≤ 1; 0 ≤ b ≤ 0.5; 0 ≤ c / e ≤ 0.05; 0 ≤ d / e ≤ 0.25; 1.9 ≤ e ≤ 4; 0 ≤ f ≤ 20.

Bevorzugt enthält das Maschinengeschirrspülmittel 1 bis 50 Gew.-% des kristallinen schichtförmigen Silikats.The machine dishwashing detergent preferably contains 1 to 50% by weight of the crystalline layered Silicate.

Besonders bevorzugt enthält das Maschinengeschirrspülmittel 5 bis 30 Gew.-% des kristallinen schichtförmigen Silikats.The machine dishwashing detergent particularly preferably contains 5 to 30% by weight of the crystalline layered silicate.

Bevorzugt handelt es sich bei dem kristallinen schichtförmigen Silikat im wesentlichen um Dinatriumdisilikat.The crystalline layered silicate is preferably essentially Disodium disilicate.

Bevorzugt handelt es sich bei dem Dinatriumdisilikat um schichtförmiges kristallines Dinatriumdisilikat, das aus mindestens einer der polymorphen Phasen des Dinatriumdisilikates sowie aus Natriumsilikaten nicht schichtsilikatischer Natur besteht.The disodium disilicate is preferably a layered crystalline disodium disilicate, that from at least one of the polymorphic phases of the disodium disilicate and consists of sodium silicates of a non-phyllosilicate nature.

Bevorzugt besteht das schichtförmige kristalline Dinatriumdisilikat (die nachfolgenden Angaben beziehen sich auf Gew.-%) aus 1 bis 40% an alpha-Dinatriumdisilikat:, 0 bis 50% an beta-Dinatriumdisilikat, 50 bis 98% an delta-Dinatriumdisilikat und 0 bis 40% an nichtschichtsilikatischen Natriumsilikaten.The layered crystalline disodium disilicate is preferably present (the following information refer to% by weight) from 1 to 40% of alpha disodium disilicate:, 0 to 50% of beta disodium disilicate, 50 to 98% of delta disodium disilicate and 0 to 40% of non-layer silicate Sodium silicates.

In einer anderen Ausführungsform der Erfindung besteht das schichtförmige kristalline Dinatriumdisilikat aus 0 bis 40% an alpha-Dinatriumdisilikat, 20 bis 98% an beta-Dinatriumdisilikat, 0 bis 40% an delta-Dinatriumdisilikat und 0 bis 50% an nichtschichtsilikatischen Natriumsilikaten.In another embodiment of the invention there is the layered crystalline disodium disilicate from 0 to 40% of alpha disodium disilicate, 20 to 98% of beta disodium disilicate, 0 to 40% of delta disodium disilicate and 0 to 50% of non-layer silicate Sodium silicates.

In einer weiteren Ausführungsform der Erfindung besteht das schichtförmige kristalline Dinatriumdisilikat aus 20 bis 98% an alpha-Dinatriumdisilikat, 0 bis 40 % an beta-Dinatriumdisilikat, 0 bis 50% an delta-Dinatriumdisilikat und 0 bis 50% an nichtschichtsilikatischen Natriumsilikaten.In a further embodiment of the invention, the layered crystalline disodium disilicate is present from 20 to 98% of alpha disodium disilicate, 0 to 40% of beta disodium disilicate, 0 to 50% of delta disodium disilicate and 0 to 50% of non-layer silicate Sodium silicates.

Die Definitionen von alpha, beta- und delta-Dinatriumdisilkat sind bekannt und können beispielsweise der EP 0 164 514 entnommen werden.The definitions of alpha, beta and delta disodium disilicate are known and can be used, for example can be found in EP 0 164 514.

Bevorzugt enthält das kristalline schichtförmige Silikat im erfindungsgemäßen Maschinengeschirrspülmittel bis zu 10 Mol-% Bor, bezogen auf SiO2.The crystalline layered silicate in the dishwasher detergent according to the invention preferably contains up to 10 mol% boron, based on SiO 2 .

Bevorzugt enthält das kristalline schichtförmige Silikat im erfindungsgemäßen Maschinengeschirrspülmittel bis zu 50 Mol-% Phosphor, bezogen auf SiO2.The crystalline layered silicate in the dishwasher detergent according to the invention preferably contains up to 50 mol% of phosphorus, based on SiO 2 .

Bevorzugt enthält das Maschinengeschirrspülmittel mindestens noch ein Tensid und/oder ein Bleichmittel und/oder ein rheoligisches Additiv und/oder ein Dispergiermittel und/oder einen Dispersionsträger.The machine dishwashing detergent preferably also contains at least one surfactant and / or one Bleaching agent and / or a rheological additive and / or a dispersing agent and / or one Dispersion carrier.

Bevorzugt enthält das Maschinengeschirrspülmittel als Tenside Blockpolymerisate langkettiger aliphatischer Alkohole mit Ethylenoxid- oder Propylenoxidgruppen, modifizierte Fettalkoholpolyglykolether, Mono- und Dialkylsulfate, Alkansulfonate, Aminoxide und/oder Fettsäuremethylpolyglykolester.The machine dishwashing detergent preferably contains long-chain block polymers as surfactants aliphatic alcohols with ethylene oxide or propylene oxide groups, modified fatty alcohol polyglycol ethers, Mono- and dialkyl sulfates, alkanesulfonates, amine oxides and / or fatty acid methyl polyglycol esters.

Bevorzugt enthält das Maschinengeschirrspülmittel als Bleichmittel Aktivchlorträger und/oder Aktivsauerstoffträger. The machine dishwashing detergent preferably contains active chlorine carriers as bleaching agents and / or active oxygen carriers.

Bevorzugt enthält das Maschinengeschirrspülmittel als rheoligisches Additiv und/oder Dispergiermittel Carboxymethylcellulose, Polycarboxylate, Phosphonate und/oder synthetische Tone.The machine dishwashing detergent preferably contains as a rheological additive and / or dispersant Carboxymethyl cellulose, polycarboxylates, phosphonates and / or synthetic Tone.

Bevorzugt enthält das Maschinengeschirrspülmittel als Dispersionsträger Ethylenglykole, Cooligo-/Copolymere von Propylenoxid und Ethylenoxid und/oder Wasser.The machine dishwashing detergent preferably contains ethylene glycols as the dispersion carrier, Cooligo / copolymers of propylene oxide and ethylene oxide and / or water.

Bevorzugt enthält das Maschinengeschirrspülmittel neben den üblichen Maschinengeschirrspülmittelinhaltsstoffen

2,5 bis 50 Gew.-%
kristallines schichtförmiges Natriumdisilikat
0 bis 20 Gew. -%
Tensid
0 bis 40 Gew.-%
Natriumtripolyphosphat
0 bis 20 Gew.-%
Bleichmittel
0,1 bis 15 Gew. -%
rheologisches Additiv und /oder Dispergiermittel
50 bis 80 Gew.-%
Dispersionsträger
als weitere Inhaltsstoffe.The dishwasher detergent preferably contains, in addition to the usual dishwasher detergent ingredients
2.5 to 50% by weight
crystalline layered sodium disilicate
0 to 20% by weight
Surfactant
0 to 40% by weight
Sodium tripolyphosphate
0 to 20% by weight
Bleach
0.1 to 15% by weight
rheological additive and / or dispersant
50 to 80% by weight
Dispersion carrier
as additional ingredients.

Bevorzugt enthält das Maschinengeschirrspülmittel neben den üblichen Maschinengeschirrspülmittelinhaltsstoffen

5 bis 30 Gew.-%
kristallines schichtförmiges Natriumdisilikat
0 bis 20 Gew.-%
Tensid
15 bis 30 Gew.-%
Natriumtripolyphosphat
5 bis 15 Gew.-%
Bleichmittel
0,1 bis 10 Gew.-%
rheologisches Additiv und /oder Dispergiermittel
50 bis 70 Gew.-%
Dispersionsträger
als weitere Inhaltsstoffe.The dishwasher detergent preferably contains, in addition to the usual dishwasher detergent ingredients
5 to 30% by weight
crystalline layered sodium disilicate
0 to 20% by weight
Surfactant
15 to 30% by weight
Sodium tripolyphosphate
5 to 15% by weight
Bleach
0.1 to 10% by weight
rheological additive and / or dispersant
50 to 70% by weight
Dispersion carrier
as additional ingredients.

Bevorzugt enthält das Maschinengeschirrspülmittel neben den üblichen Maschinengeschirrspülmittelinhaltsstoffen

5 bis 30 Gew.-%
kristallines schichtförmiges Natriumdisilikat
5 bis 15 Gew.-%
Bleichmittel
0 bis 20 Gew.-%
Tensid
0,1 bis 10 Gew.-%
rheologisches Additiv und /oder Dispergiermittel
30 bis 70 Gew.-%
Dispersionsträger
als weitere Inhaltsstoffe.The dishwasher detergent preferably contains, in addition to the usual dishwasher detergent ingredients
5 to 30% by weight
crystalline layered sodium disilicate
5 to 15% by weight
Bleach
0 to 20% by weight
Surfactant
0.1 to 10% by weight
rheological additive and / or dispersant
30 to 70% by weight
Dispersion carrier
as additional ingredients.

Bevorzugt enthält das Maschinengeschirrspülmittel es neben den üblichen Maschinengeschirrspülmittelinhaltsstoffen

10 bis 40 Gew.-%
kristallines schichtförmiges Natriumdisilikat
0 bis 20 Gew.-%
Tensid
15 bis 30 Gew.-%
Natriumtripolyphosphat
0,1 bis 15 Gew.-%
rheologisches Additiv und /oder Dispergiermittel
30 bis 70 Gew.-%
Dispersionsträger
als weitere Inhaltsstoffe.The dishwasher detergent preferably contains it in addition to the usual dishwasher detergent ingredients
10 to 40% by weight
crystalline layered sodium disilicate
0 to 20% by weight
Surfactant
15 to 30% by weight
Sodium tripolyphosphate
0.1 to 15% by weight
rheological additive and / or dispersant
30 to 70% by weight
Dispersion carrier
as additional ingredients.

Bevorzugt enthält das Maschinengeschirrspülmittel neben den üblichen Maschinengeschirrspülmittelinhaltsstoffen

10 bis 50 Gew.-%
kristallines schichtförmiges Natriumdisilikat
0 bis 20 Gew.-%
Tensid
0,1 bis 15 Gew.-%
rheologisches Additiv und /oder Dispergiermittel
30 bis 70 Gew.-%
Dispersionsträger
als weitere Inhaltsstoffe.The dishwasher detergent preferably contains, in addition to the usual dishwasher detergent ingredients
10 to 50% by weight
crystalline layered sodium disilicate
0 to 20% by weight
Surfactant
0.1 to 15% by weight
rheological additive and / or dispersant
30 to 70% by weight
Dispersion carrier
as additional ingredients.

Bei den vorgenannten bevorzugten Zusammensetzungen handelt es sich bei dem Natriumdisilikat im wesentlichen um Dinatriumdisilikat.The preferred compositions mentioned above are sodium disilicate essentially disodium disilicate.

Bevorzugt weist das erfindungsgemäße Maschinengeschirrspülmittel korrosionhemmende Eigenschaften auf.The machine dishwashing detergent according to the invention preferably has corrosion-inhibiting properties on.

Besonders bevorzugt weist das erfindungsgemäße Maschinengeschirrspülmittel korrosionshemmende Eigenschaften an silikatischen Oberflächen des Spülgutes auf.The machine dishwashing detergent according to the invention particularly preferably has corrosion-inhibiting agents Properties on silicate surfaces of the wash ware.

Besonders bevorzugt weist das erfindungsgemäße Maschinengeschirrspülmittel korrosionshemmende Eigenschaften insbesondere an Gläsern auf. The machine dishwashing detergent according to the invention particularly preferably has corrosion-inhibiting agents Properties especially on glasses.

Bevorzugt weist das erfindungsgemäße Maschinengeschirrspülmittel eine erhöhte Reinigungsleistung auf.The machine dishwashing detergent according to the invention preferably has an increased cleaning performance on.

Bevorzugt weist das erfindungsgemäße Maschinengeschirrspülmittel ein geringeres Ausmaß an Ablagerungen, insbesondere an Gläsern auf.The machine dishwashing detergent according to the invention preferably has a smaller extent on deposits, especially on glasses.

Die Erfindung betrifft ebenfalls ein Verfahren zur Herstellung eines Maschinengeschirrspülmittels, dadurch gekennzeichnet, daß man in einem vorgelegten wäßrigen Medium und /oder Dispersionsträger zuerst Alkaliträger auflöst, dann rheologische Additive und/oder Dispergiermittel zumischt, auf Raumtemperatur abkühlt, die weiteren Komponenten zugibt und am Ende des Mischvorgangs das kristalline schichtförmige Silikat zusetzt.The invention also relates to a method for producing a dishwasher detergent, characterized in that in a submitted aqueous medium and / or Dispersion carriers first dissolve alkali carriers, then rheological additives and / or dispersants admixed, cools to room temperature, adds the other components and on The crystalline layered silicate is added at the end of the mixing process.

Bei dem Alkaliträger handelt es sich bevorzugt um Natriumcarbonat, Natriumhydroxid, Kaliumhydroxid und/oder um wasserlösliche Alkalisilkate.The alkali carrier is preferably sodium carbonate, sodium hydroxide, potassium hydroxide and / or around water-soluble alkali silicates.

Bei den Komponenten handelt es sich bevorzugt um Tenside, Bleichmittel, Füllstoffe, Builder, Cobuilder, Phosphate, organische Komplexbildner, Schauminhibitoren, Parfüme und/oder Farbstoffe und/oder gegebenenfalls um weitere Maschinengeschirrspülmittelinhaltsstoffe.The components are preferably surfactants, bleaches, fillers, builders, Cobuilders, phosphates, organic complexing agents, foam inhibitors, perfumes and / or dyes and / or possibly other ingredients for machine dishwashing detergents.

Die Erfindung betrifft auch die Verwendung des erfindungsgemäßen Maschinengeschirrspülmittels zum maschinellen Geschirrspülen.The invention also relates to the use of the dishwasher detergent according to the invention for automatic dishwashing.

Das im erfindungsgemäßen Maschinengeschirrspülmittel enthaltene schichtförmige Silikat, welches wie zuvor beschrieben der allgemeinen Formel a A2O · b BO· c C2O3 · d D2O5· e SiO2 · f H2O entspricht, in der A ein Alkalimetall und/oder Wasserstoff, B ein Erdalkalimetall, C ein Element der dritten Hauptgruppe des Periodensystems und D ein Element der fünften Hauptgruppe des Periodensystems bedeuten (und weiterhin gilt: 0 ≤ a ≤ 1; 0 ≤ b ≤ 0,5; 0 ≤ c/e ≤ 0,05; 0 ≤ d/e ≤ 0,25; 1,9 ≤ e ≤ 4; 0 ≤ f ≤ 20), kann insbesondere noch Calcium- und Magnesiumionen enthalten. The layered silicate contained in the machine dishwashing detergent according to the invention, which has the general formula as described above a A 2 O · b BO · c C 2 O 3 · d D 2 O 5 · e SiO 2 · f H 2 O in which A is an alkali metal and / or hydrogen, B is an alkaline earth metal, C is an element of the third main group of the periodic table and D is an element of the fifth main group of the periodic table (and the following also applies: 0 ≤ a ≤ 1; 0 ≤ b ≤ 0 , 5; 0 ≤ c / e ≤ 0.05; 0 ≤ d / e ≤ 0.25; 1.9 ≤ e ≤ 4; 0 ≤ f ≤ 20), may in particular also contain calcium and magnesium ions.

Weitere, bevorzugt enthaltene Ionen sind solche der dritten und fünften Hauptgruppe des Periodensystems, hierzu zählen vor allem Bor bzw. Phosphor. Dies trifft inbesondere dann zu, wenn als schichtförmiges Silikat ein Dinatriumdisilikat, wie es weiter oben und nachfolgend beschrieben ist, eingesetzt wird.Further, preferably contained ions are those of the third and fifth main group of the periodic table, these include above all boron or phosphorus. This is especially true if a disodium disilicate as layered silicate, as described above and below is used.

Das schichtförmige Silikat kann aber auch ein Natriumkaliumdisilikat sein, in welchem das Natrium- zu Kalium-Verhältnis in einem weiten Bereich variiert werden kann.The layered silicate can also be a sodium potassium disilicate, in which the Sodium to potassium ratio can be varied within a wide range.

Erfindungsgemäß sind ebenfalls schichtförmige Silikate der vorgenannten Formel, die im wesentlichen Alkalimetalle (Li, Na, K) und/oder Wasserstoff enthalten, und bei denen geringe Anteile an den oben erwähnten Erdalkalimetallen (Be, Mg, Ca, Sr, Ba) sowie Elemente der dritten (B, Al, Ga, In, Tl) bzw. fünften Hauptgruppe (P, As, Sb, Bi) des Periodensystem enthalten sind.According to the invention are also layered silicates of the above formula, which are essentially Contain alkali metals (Li, Na, K) and / or hydrogen, and in those low Shares in the above-mentioned alkaline earth metals (Be, Mg, Ca, Sr, Ba) and elements of third (B, Al, Ga, In, Tl) and fifth main group (P, As, Sb, Bi) of the periodic table are.

Für das erfindungsgemäße Maschinengeschirrspülmittel wird das vorgenannte Silikat entweder in einer feingemahlenen Form eingesetzt, d.h. als Pulver mit einem mittleren Teilchendurchmesser von 1 bis 200 Mikrometer, oder in leicht dispergierbarer Form z.B. als Preßgranulat, das beim Einarbeiten in die Geschirreinigerdispersion zu mikroskopisch kleinen Teilchen zerfüllt.For the machine dishwasher detergent according to the invention, the aforementioned silicate is either used in a finely ground form, i.e. as a powder with an average particle diameter from 1 to 200 microns, or in easily dispersible form e.g. as pressed granules, that when working into the dishwashing dispersion into microscopic particles crushed.

Bevorzugt geeignet sind auch leicht dispergierbare Compounds von kristallinem, schichtförmigem Natriumdisilikat mit Polycarboxylaten, wie sie in der DE-OS 197 19 888 beschrieben sind. Bevorzugte Polycarboxylate sind Homo- bzw beliebige Kombinationen von Copolymeren der Monomere Acrylsäure und/oder Maleinsäure und/oder Vinylacetat und/oder Methallylsulfonat. Das bevorzugte Compound von Polycarboxylaten und kristallinem, schichtförmigem Natriumdisilikat besteht dabei zu 50 bis 98 Gew.-% aus besagtem Silikat und 2 bis 50 Gew.-% Polycarboxylat.Easily dispersible compounds of crystalline, layered are also particularly preferred Sodium disilicate with polycarboxylates, as described in DE-OS 197 19 888 are. Preferred polycarboxylates are homo- or any combination of copolymers the monomers acrylic acid and / or maleic acid and / or vinyl acetate and / or methallylsulfonate. The preferred compound of polycarboxylates and crystalline, layered Sodium disilicate consists of 50 to 98% by weight of said silicate and 2 to 50% by weight polycarboxylate.

Die übrigen Geschirrspülkomponenten, die teilweise bereits weiter oben genannt wurden, wie Füllstoffe, Alkaliträger, Tenside, Builder, Bleichmittel, rheologische Additive und Dispergiermittel, Schauminhibitoren sowie gegebenfalls Parfüme und Farbstoffe und andere, können Stoffe sein, die für diese Zwecke bereits hinreichend bekannt sind. The other dishwasher components, some of which have already been mentioned above, such as Fillers, alkali carriers, surfactants, builders, bleaches, rheological additives and dispersants, Foam inhibitors and possibly perfumes and dyes and others can Substances that are already well known for these purposes.

Als Füllstoff kann z.B. Natriumsulfat eingesetzt werden.As a filler e.g. Sodium sulfate can be used.

Als Alkaliträger seien die Oxide, Hydroxide, Carbonate und Silikate der Alkalimetalle, bevorzugt Natriumcarbonat und/oder Natriumhydroxid und/oder Kaliumhydroxid oder wasserlösliche Alkalisilikate genannt.Oxides, hydroxides, carbonates and silicates of the alkali metals are preferred as alkali carriers Sodium carbonate and / or sodium hydroxide and / or potassium hydroxide or water soluble Called alkali silicates.

Als Tenside sind chlorstabile Blockpolymerisate langkettiger aliphatischer Alkohole mit Ethylenoxid- oder Propylenoxidgruppen oder modifizierte Fettalkoholpolyglykolether oder Mono- und Di-alkylsulfate oder Alkansulfonate oder Aminoxide oder Fettsäuremethylpolyglykolester geeignet.Chlorine-stable block polymers of long-chain aliphatic alcohols are also included as surfactants Ethylene oxide or propylene oxide groups or modified fatty alcohol polyglycol ethers or Mono- and di-alkyl sulfates or alkanesulfonates or amine oxides or fatty acid methyl polyglycol esters suitable.

Als Builder können monomere, dimere, oligomere oder polymere Alkaliphosphate, vorzugsweise Pentaalkalitriphosphat, wasserfrei und/anhydratisiert und/oder Hexahydrat eingesetzt werden.As builders, monomeric, dimeric, oligomeric or polymeric alkali phosphates, preferably Pentaalkali nitrate phosphate, anhydrous and / anhydrated and / or hexahydrate used become.

Desweiteren kommen als erfindungsgemäßer Bestandteil organische Komplexbildner, wie Mono-, Di-, Tri-, Oligo- und/oder Polycarbonsäuren, Hydroxycarbonsäuren, Aminocarbonsäuren und Phosphonsäuren, vorzugsweise in Form ihrer wasserlöslichen Salze in Frage. Bevorzugte Oligocarbonsäuren sind Citronen-, Wein-, Maleinsäure usw. Diese werden bevorzugt zusammen mit dem kristallinen, schichtförmigen Silikat als Preßgranulat eingesetzt.Organic complexing agents such as Mono-, di-, tri-, oligo- and / or polycarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids and phosphonic acids, preferably in the form of their water-soluble salts. Preferred Oligocarboxylic acids are citric, tartaric, maleic, etc. These are preferred used together with the crystalline, layered silicate as press granulate.

Als bevorzugte Bleichmittel kommen Aktivchlorträger, wie Natriumdichlorisocyanurat oder Natriumhypochlorit-Lösung (Chlorbleichlauge) und Aktivsauerstoffträger, wie Wasserstoffperoxid, Alkalimetallperoxide, Erdalkalimetallperoxide, Alkaliperborat, -persulfat, -percarbonat, -perphosphat sowie Peroxycarbonsäuren und deren Salze wie Dodecanperoxidicarbonsäure oder Magnesiumperoxiphthalat in Betracht.Active chlorine carriers such as sodium dichloroisocyanurate or come as preferred bleaching agents Sodium hypochlorite solution (chlorine bleach) and active oxygen carriers, such as hydrogen peroxide, Alkali metal peroxides, alkaline earth metal peroxides, alkali perborate, persulfate, percarbonate, -perphosphate and peroxycarboxylic acids and their salts such as dodecane peroxidicarboxylic acid or magnesium peroxiphthalate.

Weiterhin können Bleichaktivatoren oder -katalysatoren eingesetzt werden. Ein üblicher Bleichaktivator ist Tetraacetylethylendiamin. Übliche Bleichkatalysatoren sind Komplexe des Mangans mit speziellen Liganden z.B. Derivate des 1,4,7-Triaminocyclononans.Bleach activators or catalysts can also be used. A common one Bleach activator is tetraacetylethylene diamine. Common bleaching catalysts are complexes of Manganese with special ligands e.g. Derivatives of 1,4,7-triaminocyclononane.

Bevorzugte rheologische Additive und Dispergierhilfsmittel sind Carboxymethylcellulose, Polycarboxylate, Phosphonate oder synthetische Tone. Preferred rheological additives and dispersing agents are carboxymethyl cellulose, Polycarboxylates, phosphonates or synthetic clays.

Erfindungsgemäß einsetzbare Tone sind natürlich vorkommende aktivierte und zum Teil modifizierte Tonmineralien wie Bentone-Typen der Fa. Rheox oder auch synthetische Tonminerale wie die Laponite-Typen der Fa. Laporte oder synthetischer Hectorit der Type SKS-21 der Fa. Hoechst und synthetischer Saponit der Type SKS-20 der Fa. Hoechst. Weitere, geeignete Tone sind dem Fachmann bekannt und den Herstellerkatalogen zu entnehmen.Clays which can be used according to the invention are naturally occurring activated and partly modified Clay minerals such as Bentone grades from Rheox or synthetic clay minerals such as the Laponite grades from Laporte or synthetic hectorite from the SKS-21 type Hoechst and synthetic saponite type SKS-20 from Hoechst. More suitable Clays are known to the person skilled in the art and can be found in the manufacturer's catalogs.

Bei der Dispergierung können gelöste Alkalisilikate bzw. Mono-, Oligo- und Polyphosphate unterstützend wirken.Dissolved alkali silicates or mono-, oligo- and polyphosphates can be used in the dispersion act supportive.

Als Dispersionsträger (flüssige Komponente) können monomeres, oligomeres oder polymeres Ethylenglykol oder Cooligo-/Copolymere von Propylenoxid und Ethylenoxid und/oder Wasser eingesetzt werden.Monomeric, oligomeric or polymeric can be used as the dispersion carrier (liquid component) Ethylene glycol or cooligo / copolymers of propylene oxide and ethylene oxide and / or water be used.

Schaum in Geschirrspülmaschinen, meistens hervorgerufen durch schaumproduzierende Tenside oder einweißhaltige Speiserückstände bewirkt eine Verringerung der Reinigungsleistung. Deshalb ist es notwendig, den Geschirreinigungsmitteln einen Schaumdrücker oder Schaumdämpfer zuzusetzen, beispielsweise chlorstabile Phosphorsäureester, wie etwa Triisobutylphosphat (Entschäumer TIP der Clariant GmbH), oder bekannte Silikone wie die SP-Typen der Fa. Wacker Chemie GmbH.Foam in dishwashers, mostly caused by foam-producing surfactants or food residues containing protein causes a reduction in cleaning performance. Therefore, it is necessary to use a foam presser or foam damper to clean the dishes to add, for example chlorine-stable phosphoric acid esters, such as triisobutyl phosphate (Defoamer TIP from Clariant GmbH), or well-known silicones like the SP types from Wacker Chemie GmbH.

Die vorgenannten Komponenten können im erfindungsgemäßen Maschinengeschirrspülmittel einzeln oder in Gemischen neben den kristallinen schichtförmigen Silikaten, insbesondere Natriumdisilikaten (z.B. Type SKS-6 der Clariant GmbH) enthalten sein.The aforementioned components can be used in the dishwasher detergent according to the invention individually or in mixtures in addition to the crystalline layered silicates, in particular Sodium disilicates (e.g. type SKS-6 from Clariant GmbH) may be included.

Die Konsistenz der erfindungsgemäßen Mischungen kann je nach Feststoffanteil niedrigviskos/flüssig bis pastös/gallertig eingestellt werden.Depending on the solids content, the consistency of the mixtures according to the invention can be of low viscosity / liquid until pasty / gelatinous.

Erfindungsgemäße Maschinengeschirrspülmittel können sowohl Phosphat enthalten als auch phosphatfrei sein. Machine dishwashing detergents according to the invention can contain phosphate as well be phosphate free.

Die Herstellung sollte bevorzugt nach folgendem Verfahren erfolgen:
In einem vorgelegten wäßrigen Medium oder einem anderen Dispersionsträger werden zuerst Alkaliträger, wie z.B. Natriumcarbonat und/oder Natriumhydroxid und/oder Natriumwasserglas, aufgelöst, dann rheologische Additive und/oder Dispergiermittel (bevorzugt Polycarboxylate und/oder Phosphonsäuren) zugemischt, auf Raumtemperatur abgekühlt und die weiteren Komponenten (etwa Bleichmittel, Tensid und Builder (Phosphat)) zugefügt. Am Ende des Mischvorgangs wird das kristalline schichtförmige Silikat zugesetzt.The production should preferably be carried out according to the following procedure:
In a submitted aqueous medium or another dispersion carrier, alkali carriers, such as sodium carbonate and / or sodium hydroxide and / or sodium water glass, are first dissolved, then rheological additives and / or dispersants (preferably polycarboxylates and / or phosphonic acids) are mixed in, cooled to room temperature and the others Components (such as bleach, surfactant and builder (phosphate)) added. At the end of the mixing process, the crystalline layered silicate is added.

Die Untermischung erfolgt bevorzugt unter Einwirkung von starken Scherkräften z.B. mit üblichen Dispensoren, High-Shear-Mixern der Fa. Haake&Kunkel (Ultraturrax(TM)) oder Impeller-, Propeller- bzw. Turbinenrührern.The mixing is preferably carried out under the action of strong shear forces e.g. With usual dispensers, high-shear mixers from Haake & Kunkel (Ultraturrax (TM)) or Impeller, propeller or turbine stirrers.

Die Maschinengeschirrspülmittel gemäß der Erfindung zeichnen sich durch ein gutes Reinigungsvermögen auch bei kritischen Anschmutzungen wie angebrannten eiweißhaltigen Speiserückständen aus. Des Weiteren zeigen sie eine hohe Chlor- oder Aktivsauerstoffstabilität.The machine dishwashing detergents according to the invention are notable for good cleaning properties even with critical soiling such as burnt-on protein-containing food residues out. Furthermore, they show a high chlorine or active oxygen stability.

Die Schädigung von Gläsern und dekorierten Porzellantellern durch Ablagerungen und durch Korosion ist viel bis sehr geringer als bei handelsüblichen Geschirrreinigern, die dem Stand der Technik entsprechen. Dies ist aus den nachfolgenden Beispielen leicht ersehbar.The damage to glasses and decorated porcelain plates by deposits and by Corrosion is much to very low than with standard dishwashers that stand correspond to the technology. This can easily be seen from the examples below.

Die erfindungsgemäßen Maschinengeschirrspülmittel werden vorzugsweise in Haushaltsgeschirrspülmaschinen eingesetzt, können aber auch in Gewerbegeschirrspülern verwendet werden.The dishwasher detergents according to the invention are preferably used in household dishwashers used, but can also be used in commercial dishwashers.

Folgende Beispiele sollen die vorteilhaften Eigenschaften des erfindungsgemäßen Maschinengeschirrspülmittels unter Beweis stellen. Als Vergleich gelten marktübliche Geschirreiniger-Gels auf Phosphatbasis und eine Versuchsmischung ohne Zusatz von (erfindungsgemäßem) kristallinem schichtförmigem Silikat.The following examples are intended to illustrate the advantageous properties of the dishwasher detergent according to the invention prove. Standard tableware cleaner gels are used as a comparison based on phosphate and a test mixture without adding (according to the invention) crystalline layered silicate.

Der pH-Wert der Reinigungsflotten wurde nach Abfiltrieren der Schmutzbelastung unmittelbar danach mit Hilfe einer Glaselektrode ermittelt. The pH value of the cleaning liquors became immediately after filtering off the contamination then determined using a glass electrode.

Eingesetzte MaschinengeschirrspülmittelMachine dishwashing detergent used

  • A Handelsprodukt 1A commercial product 1
  • B Handelsprodukt 2B Commercial product 2
  • C Handelsprodukt 3C commercial product 3
  • D Vergleich
    22,20 Gew%
    Natriumtripolyphosphat, teilhydratisiert
    9,00 Gew%
    Natriumhypochlorit-Lösung (Chlorbleichlauge, 15 % Aktivchlor)
    0,10 Gew%
    Verdickungsmittel
    0,04 Gew%
    Silikonentschäumer
    49,50 Gew%
    Natriumsilikat (Wasserglas, 45,5 Gew%, Siliciumdioxid zu Dinatriumoxid Verhältnis 2,0)
    1,50 Gew%
    Natriumalkansulfonat (®Hostapur SAS 60 der Clariant GmbH)
    0,80 Gew%
    Natriumpolyacrylat
    0,60 Gew%
    Phosphonat (43 % Wirksubstanz)
    3,96 Gew%
    Natriumcarbonat
    12,30 Gew%
    Wasser
    D comparison
    22.20% by weight
    Sodium tripolyphosphate, partially hydrated
    9.00% by weight
    Sodium hypochlorite solution (chlorine bleach, 15% active chlorine)
    0.10% by weight
    Thickener
    0.04% by weight
    Silicone defoamer
    49.50% by weight
    Sodium silicate (water glass, 45.5% by weight, silicon dioxide to disodium oxide ratio 2.0)
    1.50% by weight
    Sodium alkane sulfonate (®Hostapur SAS 60 from Clariant GmbH)
    0.80% by weight
    Sodium polyacrylate
    0.60% by weight
    Phosphonate (43% active substance)
    3.96% by weight
    sodium
    12.30% by weight
    water
  • E Vergleich
    1,0 Gew%
    kristallines schichtförmiges Natriumdisilikat (SKS-6 der Clariant GmbH)
    25,0 Gew%
    Natriumtripolyphosphat-Granulat
    9,0 Gew%
    Natriumhypochlorit-Lösung
    0,2 Gew%
    Entschäumer
    1,5 Gew%
    Natriumalkylsulfat
    1,1 Gew%
    Natriumpolyacrylat
    0,3 Gew%
    Phosphonsäure (60 % Wirksubstanz)
    0,5 Gew%
    Natriumhydroxid
    6,0 Gew%
    Natriumcarbonat
    46,5 Gew%
    Natriumwasserglas (wie bei D)
    8,9 Gew%
    Wasser
    E comparison
    1.0% by weight
    crystalline layered sodium disilicate (SKS-6 from Clariant GmbH)
    25.0% by weight
    Sodium tripolyphosphate granules
    9.0% by weight
    Sodium hypochlorite solution
    0.2% by weight
    Defoamer
    1.5% by weight
    Sodium alkyl sulfate
    1.1% by weight
    Sodium polyacrylate
    0.3% by weight
    Phosphonic acid (60% active substance)
    0.5% by weight
    Sodium hydroxide
    6.0% by weight
    sodium
    46.5% by weight
    Sodium water glass (like D)
    8.9% by weight
    water
  • F Erfindung
    5,5 Gew%
    kristallines schichtförmiges Natriumdisilikat (SKS-6 der Clariant GmbH)
    22,2 Gew%
    Natriumtripolyphosphat, wasserfrei
    9,0 Gew%
    Natriumhypochlorit-Lösung
    0,4 Gew%
    Entschäumer (®Entschäumer TIP der Clariant GmbH)
    49,50 Gew%
    Natriumsilikat (Wasserglas, 45,5 Gew%, Siliciumdioxid zu Dinatriumoxid Verhältnis 2,0)
    1,0 Gew%
    Natriumalkansulfonat
    2,0 Gew%
    Natriumpolyacrylat
    0,6 Gew%
    Phosphonsäure (50 % Wirksubstanz)
    1,0 Gew%
    Natriumhydroxid
    4,0 Gew%
    Natriumcarbonat
    17,3 Gew%
    Wasser
    F invention
    5.5% by weight
    crystalline layered sodium disilicate (SKS-6 from Clariant GmbH)
    22.2% by weight
    Sodium tripolyphosphate, anhydrous
    9.0% by weight
    Sodium hypochlorite solution
    0.4% by weight
    Defoamer (® defoamer TIP from Clariant GmbH)
    49.50% by weight
    Sodium silicate (water glass, 45.5% by weight, silicon dioxide to disodium oxide ratio 2.0)
    1.0% by weight
    Sodium alkane sulfonate
    2.0% by weight
    Sodium polyacrylate
    0.6% by weight
    Phosphonic acid (50% active substance)
    1.0% by weight
    Sodium hydroxide
    4.0% by weight
    sodium
    17.3% by weight
    water
  • G Erfindung
    17,5 Gew%
    kristallines schichtförmiges Natriumdisilikat /Copolymer-Compound auf Basis Acrylsäure/Maleinsäure (SKS-6 HD der Clariant GmbH)
    20,0 Gew%
    Natriumtripolyphosphat, wasserfrei
    10,0 Gew%
    Natriumpercarbonat
    1,4 Gew%
    Fettsäurepolyglykolester
    0,6 Gew%
    Entschäumer
    49,50 Gew%
    Natriumsilikat (Wasserglas, 45,5 Gew%, Siliciumdioxid zu Dinatriumoxid Verhältnis 2,0)
    0,2 Gew%
    Verdickungsmittel Bentonit
    18,3 Gew%
    Wasser
    G invention
    17.5% by weight
    crystalline layered sodium disilicate / copolymer compound based on acrylic acid / maleic acid (SKS-6 HD from Clariant GmbH)
    20.0% by weight
    Sodium tripolyphosphate, anhydrous
    10.0% by weight
    Sodium percarbonate
    1.4% by weight
    Fatty acid polyglycol esters
    0.6% by weight
    Defoamer
    49.50% by weight
    Sodium silicate (water glass, 45.5% by weight, silicon dioxide to disodium oxide ratio 2.0)
    0.2% by weight
    Bentonite thickener
    18.3% by weight
    water
  • H Erfindung
    10,0 Gew%
    kristallines schichtförmiges Natriumdisilikat
    10,0 Gew%
    Natriumperborat-Monohydrat
    0,1 Gew%
    Silikonentschäumer
    0,9 Gew%
    Natriumalkansulfonat
    5,0 Gew%
    Natriumcarbonat
    15,0 Gew%
    Natriumtripolyphosphat, teilhydratisiert
    15,0 Gew%
    Natriumtripolyphosphat-Hexahydrat
    1,5 Gew%
    Bentonit
    42,5 Gew%
    Wasser
    H invention
    10.0% by weight
    crystalline layered sodium disilicate
    10.0% by weight
    Sodium perborate monohydrate
    0.1% by weight
    Silicone defoamer
    0.9% by weight
    Sodium alkane sulfonate
    5.0% by weight
    sodium
    15.0% by weight
    Sodium tripolyphosphate, partially hydrated
    15.0% by weight
    Sodium tripolyphosphate hexahydrate
    1.5% by weight
    Bentonite
    42.5% by weight
    water
  • I Erfindung
    30,0 Gew%
    kristallines schichtförmiges Natriumdisilikat -Granulat
    4,0 Gew%
    Natriumcarbonat
    1,0 Gew%
    Natriumhydroxid
    0,5 Gew%
    Phosphonsäure, 50 %ig
    1,0 Gew%
    Natriumcopolymer (Sokalan CP5, BASF)
    1,5 Gew%
    Blockpolymerisat (Genapol 2909, Clariant GmbH)
    1,5 Gew%
    Protease-Enzym
    1,5 Gew%
    Amylase-Enzym
    10,0 Gew%
    Natriumperborat-Monohydrat
    49,0 Gew%
    Wasser
    I invention
    30.0% by weight
    crystalline layered sodium disilicate granules
    4.0% by weight
    sodium
    1.0% by weight
    Sodium hydroxide
    0.5% by weight
    Phosphonic acid, 50%
    1.0% by weight
    Sodium copolymer (Sokalan CP5, BASF)
    1.5% by weight
    Block polymer (Genapol 2909, Clariant GmbH)
    1.5% by weight
    Protease enzyme
    1.5% by weight
    Amylase enzyme
    10.0% by weight
    Sodium perborate monohydrate
    49.0% by weight
    water

    • Beispiel 1 (Bildung von Ablagerungen auf Spülgut)Example 1 (formation of deposits on wash ware)

    An Gläsern und dekorierten Porzellantellern verschiedener Provenienz, Zusammensetzung und Form wurde die erfindungsgemäßen Mischungen D bis H im Vergleich zu den Handelsprodukten B und C auf irreversible Schädigung geprüft. Porzellanteller und -tassen sowie Edelstahlbestecke dienten als Ballast zur Auffüllung der vorgeschriebenen Spülgutmenge von 12 Maßgedecken. Das Prüfverfahren erfolgt nach DIN V ENV 12875-1: April 1998, Mechanische Geschirrspülmaschinenbeständigkeit von Haushaltswaren, Teil 1. Die Dosierung der Testreiniger weicht von der Vornorm ab, es wurden jeweils 40 g flüssige Testmischung im Reinigungsgang und 3 ml Klarspüler im Klarspülgang der Prüf-Geschirrspülmaschine dosiert.On glasses and decorated porcelain plates of various origins, composition The mixtures D to H according to the invention became shaped and shaped in comparison to the commercial products B and C checked for irreversible damage. Porcelain plates and cups as well Stainless steel cutlery served as ballast for filling the prescribed amount of wash ware 12 place settings. The test is carried out according to DIN V ENV 12875-1: April 1998, mechanical Dishwasher resistance of household goods, part 1. The dosage of Test cleaner deviates from the pre-standard, there were 40 g of liquid test mixture in each Cleaning cycle and 3 ml of rinse aid dosed in the final rinse cycle of the test dishwasher.

    Methode 1: Bestimmung der Ablagerungen auf dem SpülgutMethod 1: Determination of the deposits on the wash ware

    Nach 125 Spülgängen wird das Geschirr mit Hilfe untengenannter Punktebewertungstabelle visuell bei Tageslicht und in einer sogen. Black Box" (schwarzer Kasten mit diffusem Kunstlicht) beurteilt.After 125 rinse cycles, the dishes are visually checked in daylight and in a so-called. Black Box "(black box with diffuse artificial light).

    Methode 2: Bestimmung der Korrosion an GläsernMethod 2: Determination of corrosion on glasses

    Man bestimmt die Anzahl von Spülgängen nach denen erstmalig eine sichtbare Trübung auftritt. Note Tageslicht Black Box" 0 keine Trübung keine Trübung 1 keine Trübung sehr schwache Trübung/Irisieren 2 keine Trübung schwache Trübung/Irisieren 3 sehr schwache Trübung/Irisieren deutliche Trübung 4 schwache Trübung/Irisieren ------ 5 deutliche Trübung ------ The number of rinses is determined after which a visible cloudiness occurs for the first time. grade daylight Black box " 0 no cloudiness no cloudiness 1 no cloudiness very slight turbidity / iridescence 2nd no cloudiness slight clouding / iridescence 3rd very slight turbidity / iridescence clear cloudiness 4th slight clouding / iridescence ------ 5 clear cloudiness ------

    Der arithmetische Mittelwert, gebildet aus der Summe der Bewertungen und Anzahl der Gläser, ergibt die Note für den eingetretenen Schaden.The arithmetic mean, formed from the sum of the ratings and the number of glasses, gives the grade for the damage occurred.

    Methode 1Method 1

    Stand der TechnikState of the art Gemäß der ErfindungAccording to the invention Produktproduct BB CC. DD EE FF GG HH pH(10g/l)pH (10g / l) 11,511.5 11,711.7 11,311.3 11,411.4 11,711.7 11,411.4 11,211.2 Benotung der Ablagerungen auf GläsernGrading of deposits on glasses 5,05.0 5,05.0 5,05.0 4,04.0 1,01.0 0,50.5 0,00.0

    Methode 2Method 2

    Stand der TechnikState of the art Gemäß der ErfindungAccording to the invention Produktproduct BB CC. DD EE FF GG HH Zahl der SpülgängeNumber of rinses 2020th 2525th 2525th 3030th 125125 375375 >400> 400

    Ein Vergleich von erfindungsgemäßen Maschinengeschirrspülmittel mit Handelsprodukten nach dem Stand der Technik bzw. dem Testprodukt nach dem Stand der Technik hinsichtlich der Benotungen nach den Methoden 1 und 2 zeigt, daß die erfindungsgemäßen Produkte wesentlich geringere Schädigung durch Ablagerungen und durch Korrosion ergeben.A comparison of dishwasher detergents according to the invention with commercial products according to the prior art or the test product according to the prior art with regard to The marks according to methods 1 and 2 show that the products according to the invention are essential less damage due to deposits and corrosion.

    Beispiel 2 (Reinigungswirkung)Example 2 (cleaning effect)

    Die Maschinengeschirrspülmittel A bis I wurden in Anlehnung an DIN-Norm-Entwurf 44990 und der IKW-Methode in drei Haushaltsgeschirrspülmaschinen Miele G 688 SC auf ihre Reinigungswirkung geprüft. Die erfindungsgemäßen Testprodukte, das Vergleichsprodukt nach dem Stand der Technik und die Handelsprodukte nach dem Stand der Technik wurden mit gleicher Dosierung von 40 g Geschirrspülmittel und 3 ml Klarspüler eingesetzt. Die Auswertung erfolgt nach dem Spülen durch visuelle Abmusterung des Spülgutes. Das Prüfergebnis wird in Prozent dargestellt (100%= sauber). In folgender Tabelle sind die Ergebnisse der Versuche und die pH-Werte der Spülflotte zusammengestellt. Geschirrspülmittel A B C D E F G H I pH-Spülflotte 10,1 10,6 10,6 10,4 10,5 10,5 10,5 10,2 10,5 % Reinigungswirkung bei 50°C Spültemperatur 79 76 74 76 79 86 89 86 92 The machine dishwashing detergents A to I were tested for their cleaning effect in three household dishwashers Miele G 688 SC based on DIN standard draft 44990 and the IKW method. The test products according to the invention, the comparative product according to the prior art and the commercial products according to the prior art were used with the same dosage of 40 g of dishwashing detergent and 3 ml of rinse aid. After washing, the evaluation is carried out by visual inspection of the items to be washed. The test result is shown in percent (100% = clean). The results of the tests and the pH values of the washing liquor are summarized in the following table. Dishwashing liquid A B C. D E F G H I. pH rinse liquor 10.1 10.6 10.6 10.4 10.5 10.5 10.5 10.2 10.5 % Cleaning effect at 50 ° C rinsing temperature 79 76 74 76 79 86 89 86 92

    Die Ergebnisse zeigen, daß die erfindungsgemäßen Maschinengeschirrspülmittel eine deutliche Steigerung der Reinigungswirkung gegenüber solchen aus dem Stand der Technik aufweisen.The results show that the machine dishwashing detergents according to the invention clearly Have an increase in the cleaning effect compared to those from the prior art.

    Claims (29)

    Flüssiges bis pastöses Maschinengeschirrspülmittel, dadurch gekennzeichnet, daß es neben üblichen Maschinengeschirrspülmittelinhaltsstoffen ein kristallines, schichtförmiges Silikat der allgemeinen Formel a A2O · b BO · c C2O3 · d D2O5 · e SiO2· f H2O enthält, in der A ein Alkalimetall und/oder Wasserstoff B ein Erdalkalimetall, C ein Element der dritten Hauptgruppe des Periodensystems und D ein Element der fünften Hauptgruppe des Periodensystems bedeuten und weiterhin gilt: 0 ≤ a ≤ 1; 0 ≤ b ≤ 0,5; 0 ≤ c/e ≤ 0,05; 0 ≤ d/e ≤ 0,25; 1,9 ≤ e ≤ 4; 0 ≤ f ≤ 20.Liquid to pasty machine dishwashing detergent, characterized in that it contains, in addition to conventional machine dishwashing detergent ingredients, a crystalline, layered silicate of the general formula a A 2 O · b BO · c C 2 O 3 · d D 2 O 5 · e SiO 2 · f H 2 O. , in which A is an alkali metal and / or hydrogen B is an alkaline earth metal, C is an element of the third main group of the periodic table and D is an element of the fifth main group of the periodic table and the following also applies: 0 ≤ a ≤ 1; 0 ≤ b ≤ 0.5; 0 ≤ c / e ≤ 0.05; 0 ≤ d / e ≤ 0.25; 1.9 ≤ e ≤ 4; 0 ≤ f ≤ 20. Maschinengeschirrspülmittel nach Anspruch 1, dadurch gekennzeichnet, daß es 1 bis 50 Gew.-% des kristallinen schichtförmigen Silikats enthält.Machine dishwashing detergent according to claim 1, characterized in that it is 1 to 50 % By weight of the crystalline layered silicate. Maschinengeschirrspülmittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß es 5 bis 30 Gew.-% des kristallinen schichtförmigen Silikats enthält.Machine dishwashing detergent according to claim 1 or 2, characterized in that it is 5 contains up to 30 wt .-% of the crystalline layered silicate. Maschinengeschirrspülmittel nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es sich bei dem kristallinen schichtförmigen Silikat im wesentlichen um Dinatriumdisilikat handelt.Machine dishwashing detergent according to one or more of claims 1 to 3, characterized characterized in that it is essentially in the crystalline layered silicate is disodium disilicate. Maschinengeschirrspülmittel nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es sich bei dem Dinatriumdisilikat um schichtförmiges kristallines Dinatriumdisilkat handelt, das aus mindestens einer der polymorphen Phasen des Dinatriumdisilikates sowie aus Natriumsilikaten nicht schichtsilikatischer Natur besteht.Machine dishwashing detergent according to one or more of claims 1 to 4, characterized characterized in that the disodium disilicate is layered crystalline Disodium disilicate, which consists of at least one of the polymorphic phases of the disodium disilicate and consists of sodium silicates of a non-phyllosilicate nature. Maschinengeschirrspülmittel nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das schichtförmige kristalline Dinatriumdisilikat aus 1 bis 40% an alpha-Dinatriumdisilikat:, 0 bis 50% an beta-Dinatriumdisilikat, 50 bis 98% an delta-Dinatriumdisilikat und 0 bis 40% an nichtschichtsilikatischen Natriumsilikaten besteht.Machine dishwashing detergent according to one or more of claims 1 to 5, characterized characterized in that the layered crystalline disodium disilicate from 1 to 40% alpha disodium disilicate:, 0 to 50% of beta disodium disilicate, 50 to 98% of delta disodium disilicate and 0 to 40% of non-layer silicate sodium silicates. Maschinengeschirrspülmittel nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das schichtförmige kristalline Dinatriumdisilikat aus 0 bis 40% an alpha-Dinatriumdisilikat:, 20 bis 98% an beta-Dinatriumdisilikat, 0 bis 40% an delta-Dinatriumdisilikat und 0 bis 50% an nichtschichtsilikatischen Natriumsilikaten besteht.Machine dishwashing detergent according to one or more of claims 1 to 5, characterized characterized in that the layered crystalline disodium disilicate from 0 to 40% alpha disodium disilicate:, 20 to 98% of beta disodium disilicate, 0 to 40% of delta disodium disilicate and 0 to 50% of non-layer silicate sodium silicates. Maschinengeschirrspülmittel nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das schichtförmige kristalline Dinatriumdisilikat aus 20 bis 98% an alpha-Dinatriumdisilikat, 0 bis 40 % an beta-Dinatriumdisilikat, 0 bis 50% an delta-Dinatriumdisilikat und 0 bis 50% an nichtschichtsilikatischen Natriumsilikaten besteht.Machine dishwashing detergent according to one or more of claims 1 to 5, characterized characterized in that the layered crystalline disodium disilicate from 20 to 98% alpha disodium disilicate, 0 to 40% beta disodium disilicate, 0 to 50% delta disodium disilicate and 0 to 50% of non-layer silicate sodium silicates. Maschinengeschirrspülmittel nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß kristalline schichtförmige Silikat bis zu 10 Mol-% Bor, bezogen auf SiO2 enthält.Machine dishwashing detergent according to one or more of claims 1 to 8, characterized in that crystalline layered silicate contains up to 10 mol% boron, based on SiO 2 . Maschinengeschirrspülmittel nach einem oder mehreren der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß kristalline schichtförmige Silikat bis zu 50 Mol-% Phosphor, bezogen auf SiO2 enthält.Machine dishwashing detergent according to one or more of claims 1 to 9, characterized in that crystalline layered silicate contains up to 50 mol% of phosphorus, based on SiO 2 . Maschinengeschirrspülmittel nach einem oder mehreren der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß es mindestens noch ein Tensid und/oder ein Bleichmittel und/oder ein rheoligisches Additiv und/oder ein Dispergiermittel und/oder einen Dispersionsträger enthält.Machine dishwashing detergent according to one or more of claims 1 to 10, characterized characterized in that there is at least one more surfactant and / or a bleach and / or a rheological additive and / or a dispersant and / or a dispersion carrier contains. Maschinengeschirrspülmittel nach einem oder mehreren der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß es als Tenside Blockpolymerisate langkettiger aliphatischer Alkohole mit Ethylenoxid- oder Propylenoxidgruppen, modifizierte Fettalkoholpolyglykolether, Mono- und Dialkylsulfate, Alkansulfonate, Aminoxide und/oder Fettsäuremethylpolyglykolester enthält. Machine dishwashing detergent according to one or more of claims 1 to 11, characterized characterized in that it is a surfactant block polymers of long-chain aliphatic alcohols with ethylene oxide or propylene oxide groups, modified fatty alcohol polyglycol ethers, Mono- and dialkyl sulfates, alkanesulfonates, amine oxides and / or fatty acid methyl polyglycol esters contains. Maschinengeschirrspülmittel nach einem oder mehreren der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß es als Bleichmittel Aktivchlorträger und/oder Aktivsauerstoffträger enthält.Machine dishwashing detergent according to one or more of claims 1 to 12, characterized characterized in that it is a bleaching agent containing active chlorine and / or active oxygen contains. Maschinengeschirrspülmittel nach einem oder mehreren der Ansprüche 1 bis 13, dadurch gekennzeichnet, daß es als rheoligisches Additiv und/oder Dispergiermittel Carboxymethylcellulose, Polycarboxylate, Phosphonate und/oder synthetische Tone enthält.Machine dishwashing detergent according to one or more of claims 1 to 13, characterized characterized in that it is a rheolitic additive and / or dispersant carboxymethyl cellulose, Contains polycarboxylates, phosphonates and / or synthetic clays. Maschinengeschirrspülmittel nach einem oder mehreren der Ansprüche 1 bis 14, dadurch gekennzeichnet, daß es als Dispersionsträger Ethylenglykole, Cooligo-/Copolymere von Propylenoxid und Ethylenoxid und/oder Wasser enthält.Machine dishwashing detergent according to one or more of claims 1 to 14, characterized characterized in that it is used as a dispersion carrier ethylene glycols, cooligo / copolymers of Contains propylene oxide and ethylene oxide and / or water. Maschinengeschirrspülmittel nach einem oder mehreren der Ansprüche 1 bis 15, dadurch gekennzeichnet, daß es neben den üblichen Maschinengeschirrspülmittelinhaltsstoffen
    2,5 bis 50 Gew.-%
    kristallines schichtförmiges Natriumdisilikat
    0 bis 20 Gew.-%
    Tensid
    0 bis 40 Gew.-%
    Natriumtripolyphosphat
    0 bis 20 Gew.-%
    Bleichmittel
    0,1 bis 15 Gew.-%
    rheologisches Additiv und /oder Dispergiermittel
    50 bis 80 Gew.-%
    Dispersionsträger
    als weitere Inhaltsstoffe enthält.    Machine dishwashing detergent according to one or more of claims 1 to 15, characterized in that it contains, in addition to the usual machine dishwashing detergent ingredients
    2.5 to 50% by weight
    crystalline layered sodium disilicate
    0 to 20% by weight
    Surfactant
    0 to 40% by weight
    Sodium tripolyphosphate
    0 to 20% by weight
    Bleach
    0.1 to 15% by weight
    rheological additive and / or dispersant
    50 to 80% by weight
    Dispersion carrier
    contains as additional ingredients.         Maschinengeschirrspülmittel nach einem oder mehreren der Ansprüche 1 bis 15, dadurch gekennzeichnet daß es neben den üblichen Maschinengeschirrspülmittelinhaltsstoffen
    5 bis 30 Gew.-%
    kristallines schichtförmiges Natriumdisilikat
    0 bis 20 Gew.-%
    Tensid
    15 bis 30 Gew.-%
    Natriumtripolyphosphat
    5 bis 15 Gew.-%
    Bleichmittel
    0,1 bis 10 Gew.-%
    rheologisches Additiv und /oder Dispergiermittel
    50 bis 70 Gew.-%
    Dispersionsträger
    als weitere Inhaltsstoffe enthält.     Machine dishwashing detergent according to one or more of claims 1 to 15, characterized in that it is in addition to the usual machine dishwashing detergent ingredients
    5 to 30% by weight
    crystalline layered sodium disilicate
    0 to 20% by weight
    Surfactant
    15 to 30% by weight
    Sodium tripolyphosphate
    5 to 15% by weight
    Bleach
    0.1 to 10% by weight
    rheological additive and / or dispersant
    50 to 70% by weight
    Dispersion carrier
    contains as additional ingredients.         Maschinengeschirrspülmittel nach einem oder mehreren der Ansprüche 1 bis 15, dadurch gekennzeichnet, daß neben den üblichen Maschinengeschirrspülmittelinhaltsstoffen
    5 bis 30 Gew.-%
    kristallines schichtförmiges Natriumdisilikat
    5 bis 15 Gew.-%
    Bleichmittel
    0 bis 20 Gew.-%
    Tensid
    0,1 bis 10 Gew.-%
    rheologisches Additiv und /oder Dispergiermittel
    30 bis 70 Gew.-%
    Dispersionsträger
    als weitere Inhaltsstoffe enthält.    Machine dishwashing detergent according to one or more of claims 1 to 15, characterized in that in addition to the usual machine dishwashing detergent ingredients
    5 to 30% by weight
    crystalline layered sodium disilicate
    5 to 15% by weight
    Bleach
    0 to 20% by weight
    Surfactant
    0.1 to 10% by weight
    rheological additive and / or dispersant
    30 to 70% by weight
    Dispersion carrier
    contains as additional ingredients.         Maschinengeschirrspülmittel nach einem oder mehreren der Ansprüche 1 bis 15, dadurch gekennzeichnet, daß es neben den üblichen Maschinengeschirrspülmittelinhaltsstoffen
    10 bis 40 Gew.-%
    kristallines schichtförmiges Natriumdisilikat
    0 bis 20 Gew.-%
    Tensid
    15 bis 30 Gew.-%
    Natriumtripolyphosphat
    0,1 bis 15 Gew.-%
    rheologisches Additiv und /oder Dispergiermittel
    30 bis 70 Gew.-%
    Dispersionsträger
    als weitere Inhaltsstoffe enthält.    Machine dishwashing detergent according to one or more of claims 1 to 15, characterized in that it contains, in addition to the usual machine dishwashing detergent ingredients
    10 to 40% by weight
    crystalline layered sodium disilicate
    0 to 20% by weight
    Surfactant
    15 to 30% by weight
    Sodium tripolyphosphate
    0.1 to 15% by weight
    rheological additive and / or dispersant
    30 to 70% by weight
    Dispersion carrier
    contains as additional ingredients.         Maschinengeschirrspülmittel nach einem oder mehreren der Ansprüche 1 bis 15, dadurch gekennzeichnet, daß es neben den üblichen Maschinengeschirrspülmittelinhaltsstoffen
    10 bis 50 Gew.-%
    kristallines schichtförmiges Natriumdisilikat
    0 bis 20 Gew.-%
    Tensid
    0,1 bis 15 Gew.-%
    rheologisches Additiv und /oder Dispergiermittel
    30 bis 70 Gew.-%
    Dispersionsträger
    als weitere Inhaltsstoffe enthält.    Machine dishwashing detergent according to one or more of claims 1 to 15, characterized in that it contains, in addition to the usual machine dishwashing detergent ingredients
    10 to 50% by weight
    crystalline layered sodium disilicate
    0 to 20% by weight
    Surfactant
    0.1 to 15% by weight
    rheological additive and / or dispersant
    30 to 70% by weight
    Dispersion carrier
    contains as additional ingredients.         Maschinengeschirrspülmittel nach einem oder mehreren der Ansprüche 1 bis 20, dadurch gekennzeichnet, daß es korrosionhemmende Eigenschaften aufweist.Machine dishwashing detergent according to one or more of claims 1 to 20, characterized characterized in that it has corrosion-inhibiting properties. Maschinengeschirrspülmittel nach einem oder mehreren der Ansprüche 1 bis 21, dadurch gekennzeichnet, daß es korrosionshemmende Eigenschaften an silikatischen Oberflächen des Spülgutes aufweist. Machine dishwashing detergent according to one or more of claims 1 to 21, characterized characterized in that it has anti-corrosive properties on silicate surfaces of the wash ware. Maschinengeschirrspülmittel nach einem oder mehreren der Ansprüche 1 bis 22, dadurch gekennzeichnet, daß es korrosionshemmende Eigenschaften insbesondere an Gläsern aufweist.Machine dishwashing detergent according to one or more of claims 1 to 22, characterized characterized in that it has corrosion-inhibiting properties, in particular on glasses. Maschinengeschirrspülmittel nach einem oder mehreren der Ansprüche 1 bis 23 dadurch gekennzeichnet, daß es eine erhöhte Reinigungsleistung aufweist.Dishwasher detergent according to one or more of claims 1 to 23 thereby characterized in that it has an increased cleaning performance. Maschinengeschirrspülmittel nach einem oder mehreren der Ansprüche 1 bis 24, dadurch gekennzeichnet, daß es ein geringeres Ausmaß an Ablagerungen, insbesondere an Gläsern aufweist.Machine dishwashing detergent according to one or more of claims 1 to 24, characterized characterized in that there is a lower level of deposits, especially on glasses having. Verfahren zur Herstellung eines Maschinengeschirrspülmittels nach einem oder mehreren der Ansprüche 1 bis 25, dadurch gekennzeichnet, daß man in einem vorgelegten wäßrigen Medium und /oder Dispersionsträger zuerst Alkaliträger auflöst, dann rheologische Additive und/oder Dispergiermittel zumischt, auf Raumtemperatur abkühlt, die weiteren Komponenten zugibt und am Ende des Mischvorgangs das kristalline schichtförmige Silikat zusetzt.Method of manufacturing a dishwasher detergent according to one or more of claims 1 to 25, characterized in that in a submitted aqueous Medium and / or dispersion carrier first dissolves alkali carrier, then rheological additives and / or dispersant mixed, cooled to room temperature, the other components admits and at the end of the mixing process the crystalline layered silicate adds. Verfahren nach Anspruch 26, dadurch gekennzeichnet, daß daß es sich bei dem Alkaliträger um Nariumcarbonat, Natriumhydroxid, Kaliumhydroxid und/oder um wasserlösliche Alkalisilkate handelt.A method according to claim 26, characterized in that it is the alkali carrier sodium carbonate, sodium hydroxide, potassium hydroxide and / or water-soluble Alkali silicates. Verfahren nach Anspruch 26 oder 27, dadurch gekennzeichnet, daß es sich bei den Komponenten um Tenside, Bleichmittel, Füllstoffe, Builder, Cobuilder, Phosphate, organische Komplexbildner, Schauminhibitoren, Parfüme und/oder Farbstoffe und/oder gegebenenfalls weitere Maschinengeschirrspülmittelinhaltsstoffe handelt.A method according to claim 26 or 27, characterized in that the components to surfactants, bleaches, fillers, builders, cobuilders, phosphates, organic Complexing agents, foam inhibitors, perfumes and / or dyes and / or optionally other machine dishwashing detergent ingredients. Verwendung des Maschinengeschirrspülmittels nach einem oder mehreren der Ansprüche 1 bis 25 zum maschinellen GeschirrspülenUse of the dishwasher detergent according to one or more of the claims 1 to 25 for automatic dishwashing
    EP99120429A 1998-11-29 1999-10-14 Automatic dishwashing composition Ceased EP1004655A3 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE19854960A DE19854960A1 (en) 1998-11-29 1998-11-29 Dishwasher detergent
    DE19854960 1998-11-29

    Publications (2)

    Publication Number Publication Date
    EP1004655A2 true EP1004655A2 (en) 2000-05-31
    EP1004655A3 EP1004655A3 (en) 2002-09-25

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    EP (1) EP1004655A3 (en)
    CA (1) CA2291419C (en)
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    WO2015070976A1 (en) * 2013-11-15 2015-05-21 Weylchem Wiesbaden Gmbh Dishwashing composition and use thereof

    Also Published As

    Publication number Publication date
    EP1004655A3 (en) 2002-09-25
    US6539954B1 (en) 2003-04-01
    CA2291419A1 (en) 2000-05-29
    CA2291419C (en) 2003-06-10
    DE19854960A1 (en) 2000-05-31

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