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WO1995000623A1 - Dishwasher agent with biodegradable builders - Google Patents

Dishwasher agent with biodegradable builders Download PDF

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Publication number
WO1995000623A1
WO1995000623A1 PCT/EP1994/002000 EP9402000W WO9500623A1 WO 1995000623 A1 WO1995000623 A1 WO 1995000623A1 EP 9402000 W EP9402000 W EP 9402000W WO 9500623 A1 WO9500623 A1 WO 9500623A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
composition according
meth
agent
salts
Prior art date
Application number
PCT/EP1994/002000
Other languages
German (de)
French (fr)
Inventor
Willi Buchmeier
Hans Andree
Peter Krings
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 EP94918883A priority Critical patent/EP0706557A1/en
Publication of WO1995000623A1 publication Critical patent/WO1995000623A1/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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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

Definitions

  • the invention relates to alkaline dishwashing detergents for the mechanical cleaning of dishes with a biodegradable bath component.
  • the latest generation of low-alkaline agents for the mechanical cleaning of dishes contain, in addition to bleaching agents based on oxygen, surface-active substances and enzymes, a combination of water-soluble builders which are derived from complexing agents, e.g. Citrate, from alkali carriers, e.g. Soda, bicarbonate or disilicate, and from dispersants such as e.g. Polycarboxylates exist.
  • complexing agents e.g. Citrate
  • alkali carriers e.g. Soda, bicarbonate or disilicate
  • dispersants such as e.g. Polycarboxylates
  • Other possible binder components are organophosphonic acids, aminocarboxylic acids or crystalline layered silicates; on the phosphates previously used, e.g. Pentasodium tripolyphosphate is largely dispensed with today for ecological reasons.
  • the polycarboxylates used in today's dishwashing detergents e.g. Maleinat / Acrylat-Copoly ere, prevent limescale deposits when the residual water hardness is too high in the cleaning and rinse cycle; with a high salt load in the washing liquor, they also improve the rinse aid effect.
  • US Pat. No. 3,887,480 discloses dishwashing and textile cleaning agents which contain a polymer which consists of 35-70 mol% maleic acid, 20-45 mol% vinyl acetate and 2-40 mol% acrylic acid.
  • the European patent EP 0 193 360 B1 describes zeolite-containing textile detergents, the polycarboxylate poly ere composed of a C3-Cio-onocarboxylic acid, a C ⁇ -Cß-dicarboxylic acid and a nonionic spacer, for. B. vinyl alcohol included.
  • the US Pat. No. 3,755,264 discloses copolymers which, for. B.
  • EP 0 076 992 AI discloses u. a. the use of polymers composed of 50-95% by weight of acrylic acid, 0.5 to 5% by weight of vinyl acetate and up to 49% by weight of maleic acid as incrustation inhibitors in washing and cleaning agents.
  • the invention relates to a low-alkaline agent for machine cleaning of dishes, the 1% by weight aqueous solution of which has a pH of 8 to 11.5, preferably 9 to 10.5, containing water-soluble builder components and bleaching agents based on oxygen, characterized in that it contains a copoly as water-soluble builder component, the copolymer comprising 60-95% by weight, preferably 70-90% by weight, of (meth) acrylic acid or (meth) acrylate , preferably acrylic acid or acrylate, and maleic acid or maleate and 5-40% by weight, preferably 10-25% by weight, of vinyl alcohol and / or vinyl acetate, the weight ratio being (meth) acrylic acid or (meth) acrylate to maleic acid or Maleate is between 1.5: 1 and 4: 1, preferably between 2: 1 and 2.5: 1, both the amounts and the weight ratios are based on the acids, and a copolymer of the salts of the acids and vinyl alcohol is preferred are moving.
  • the copolymers used according to the invention can be prepared by any of the known and customary processes.
  • (meth) acrylic acid, preferably acrylic acid, and maleic acid are reacted with vinyl alcohol and / or vinyl acetate, whereupon the acids may then be neutralized to preferably their alkali metal salts, such as the sodium or potassium salts or ammonium salts or alkanolamine salts, such as the monoethanol insole the triethanolamine salt, and optionally a partial or complete cleavage of the vinyl acetate to the vinyl alcohol is carried out.
  • alkali metal salts such as the sodium or potassium salts or ammonium salts or alkanolamine salts, such as the monoethanol insole the triethanolamine salt
  • copolymers which are either completely or at least partially, in particular to more than 50%, based on the existing carboxyl groups are neutralized.
  • a completely neutralized copolymer is particularly preferred, ie it consists of the salts of (meth) acrylic acid, preferably acrylic acid, and maleic acid, in particular the sodium or potassium salts, and vinyl alcohol.
  • the copolymers generally have a relative molecular mass between 1000 and 200000, preferably between 2000 and 50,000, and in particular between 3000 and 10,000. They are preferably used in powder-sprayed form. Particularly preferred copolymers are produced by a process which is described in the earlier German patent application P 43 00 772.4.
  • Preferred dishwashing detergents according to the invention contain the copolymer in amounts of 0.5 to 30% by weight, preferably 2 to 20% by weight, furthermore 0.5 to 20% by weight, preferably 5 to 15% by weight, of a bleaching agent based on oxygen, in particular alkali perborate and / or percarbonate, and nonionic surfactants in an amount of at most 5% by weight, preferably at most 2% by weight, the agents being free from anionic, cationic or amphoteric surfactants.
  • a bleaching agent based on oxygen in particular alkali perborate and / or percarbonate
  • nonionic surfactants in an amount of at most 5% by weight, preferably at most 2% by weight, the agents being free from anionic, cationic or amphoteric surfactants.
  • alkali metal carbonates and / or hydrogen carbonates, in particular the sodium salts are present as alkali carriers in an amount of up to 60% by weight, preferably 5 to 50% by weight.
  • the dishwashing detergents according to the invention can contain further water-soluble builder components, such as synthetic polymers, which include the salts of polymerization products of unsaturated carboxylic acids and which include, for example, polyacrylates, polymethacrylates, polymaleinates or copolymers of acrylic acid with maleic acid or maleic anhydride, in an amount of 0.5 Contain up to 30 wt .-%, preferably 2 to 20 wt .-%.
  • synthetic polymers which include the salts of polymerization products of unsaturated carboxylic acids and which include, for example, polyacrylates, polymethacrylates, polymaleinates or copolymers of acrylic acid with maleic acid or maleic anhydride, in an amount of 0.5 Contain up to 30 wt .-%, preferably 2 to 20 wt .-%.
  • 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 ( R ) 175 from Alco.
  • phosphates or zeolites can also be present, but the dishwashing detergents are preferably free from zeolites and from phosphate-containing bath components.
  • nonionic surfactants 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 are therefore preferably free of anionic, cationic or amphoteric surfactants.
  • the content of nonionic surfactants is at most 5% by weight, preferably at most 2% by weight.
  • Addition products of 1 to 20 moles of ethylene oxide (E0) and / or 1 to 20 moles of propylene oxide (PO) with 1 mole of an aliphatic compound with 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines and carboxamides are the nonionic surfactants and alkanesulfonamides of interest.
  • polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule, which are not or not completely water-soluble are also important, preferably in combination with water-soluble nonionic ones Surfactants used.
  • alkyl polyglycosides of the general formula R-0- (G) x can also be used as nonionic surfactants, in which R denotes a primary, straight-chain or branched aliphatic radical having 8 to 22, preferably 12 to 18 C atoms, G for a glyco - Se unit with 5 or 6 carbon atoms and the degree of oligomerization x is between 1 and 10.
  • Preferred dishwashing detergents according to the invention also contain complexing agents from the group of the di- and honorically functional organic carboxylic acids or their salts, e.g. Nitrilotriacetic acid, but especially citric acid or its salts, in an amount of 0.5 to 60% by weight, preferably 20 to 50% by weight.
  • complexing agents from the group of the di- and honorically functional organic carboxylic acids or their salts, e.g. Nitrilotriacetic acid, but especially citric acid or its salts, in an amount of 0.5 to 60% by weight, preferably 20 to 50% by weight.
  • M alkali metal
  • alkali silicates preferably sodium silicates, with a SiO 2 Na 2 O molar ratio of 1.5: 1 to 2.5: 1, in amounts of up to 30% by weight, preferably 5 to 20% by weight, based on the entire dishwashing detergent used.
  • bleaching agents that can be used are, for example, peracidic salts of organic acids, such as perbenzoates or salts of diperdodecanedioic acid. It preferably contains 0.5 to 20% by weight, particularly preferably 5 to 15% by weight, of an oxygen-based bleach, in particular alkali perborates and / or percarbonates.
  • bleach stabilizers such as borates or metaborates and metasilicates and magnesium salts, for example magnesium sulfate.
  • Suitable bleach activators for these oxidizing agents are in particular N-acyl and O-acyl compounds, preferably tetraacylated diamines such as N, N, N '.N'-tetraacetylethylene diamine in (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 are preferably free from agents that release active chlorine, e.g. Trichloroisocyanuric acid.
  • Enzymes such as proteases, aylases, lipases or cellulases can be used to better remove protein or starch-containing food residues, for example proteases such as BLAP () 140 from Henkel, 0ptimase ( R ) -M-440, 0ptimase ( R ) -M -330, 0pticlean ( R ) -M-375, 0pticlean ( 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 Experase ( R ) T from Ibis; Amylases such as Termamyl ( R ) 60 T, 90 T from Novo, A ylase-LT ( R ) from Solvay Enzymes or Maxamyl ( R ) P 5000, CXT 5000 or C
  • silver protection agents as described in the older German patent application P 43 15 397.6, in particular water-soluble Mn (II) salts, in an amount of up to 2% by weight, preferably 0. 1 to 0.5 wt .-%, may be included.
  • 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. It is also possible for the polymers used according to the invention to be in the form of a compound can be used as an additive component to other granular components of the dishwashing detergent.
  • the procedure is preferably such that all constituents are mixed with one another in a mixer and the mixture is used by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range from 200 ⁇ 10 ⁇ Pa to 1 500 • 10 ⁇ Pa pressed.
  • 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 m to 40 mm.
  • the production of machine dishwashing detergents in the form of non-dusting, storage-stable, free-flowing powders and / or granules with high bulk densities in the range from 800 to 900 g / 1 is characterized in that in a first process stage, the builder components are at least partially liquid Mixing components are mixed while increasing the bulk density of this premix and subsequently - if desired - after an intermediate drying - the further components of the dishwasher detergent are combined with the premix obtained in this way.
  • the intermediate drying must be carried out so that the decomposition of the sodium bicarbonate to sodium carbonate is as low as possible (or at least as constant as possible).
  • An additional sodium carbonate portion resulting from the drying would have to be taken into account when formulating the ⁇ granulate recipe.
  • Low drying temperatures not only counteract sodium bicarbonate decay, but also increase the solubility of the granulated detergent during use. It is therefore advantageous for drying to have a supply air temperature which, on the one hand, should be as low as possible to avoid bicarbonate decomposition and, on the other hand, must be as high as necessary in order to obtain a product with good storage properties. When drying, a supply air is preferred. te temperature of approx. 80 ° C. The granules themselves should not be heated to temperatures above about 60 ° C.
  • the builder is generally acted upon 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 mixed intimately.
  • the remaining components are then added and the entire mixture is worked through and homogenized in the mixing device.
  • additional amounts of liquid in particular the use of additional water, is generally not necessary here.
  • the mixture of substances obtained is then in the form of a free-flowing, dust-free powder of the desired high bulk densities, approximately in the range from 800 to 900 g / l.
  • the pre-granules are then mixed with the still missing components of the dishwashing detergent to form the finished product.
  • the mixing time is both in the preliminary stage of the compacting mixture under the influence of liquid components and in the subsequent final mixture with the other components in the range of a few minutes, for example in the range of 1 to 5 minutes.
  • Granular dishwashing detergents with the following composition were produced.
  • Agent A contained 10% by weight of the copolymer which, according to the disclosure of the earlier German patent application P 43 00 772.4, was prepared from 80% by weight of acrylic acid and maleic acid in a weight ratio of 7: 3 and from 20% by weight of vinyl acetate and then completely neutralized had been.
  • Comparative Example B contained 10% by weight of an acrylate-maleate copolymer sold by BASF under the trade name Sokalan ( R ) CP5.
  • Agent A according to the invention had a superior cleaning performance compared to agent B not according to the invention, particularly when removing the starch, minced meat, fat stick and oatmeal stains, but in particular when staining tea.
  • agents A and B were carried out in a Miele G 590 dishwasher (Universal 65 ° C program) at doses of 20 g each in 7.0 l of water at 16 ° dH with the addition of 50 g of pumpable soiling (mixture of ketchup, gravy , Mustard, potato starch, egg yolk, milk, margarine) in the presence of 3.0 ml of a commercial rinse aid tested over 10 rinse cycles.
  • agent A according to the invention is superior to comparative agent B above all with regard to the rinse aid effect on glasses and knife blades.
  • Agent C according to the invention showed cleaning and deposit inhibition performances comparable to agent A according to the invention; due to the presence of MnSÜ, it showed superior properties especially in preventing silver tarnishing from tarnishing.

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Abstract

The invention concerns low-alkaline agents for use in dishwashing machines, the agents containing builders which are readily biodegradable. These readily biodegradable builders are copolymers of [meth]acrylic acid or [meth]acrylate, maleic acid or maleate and vinyl alcohol and/or vinyl acetate.

Description

Gesch1rrspulm1ttel mit biologisch abbaubarer bullderko ponente Dishwashing liquid with biodegradable bullder component
Die Erfindung betrifft niederalkalische Geschirrspülmittel für die ma¬ schinelle Reinigung von Geschirr mit einer biologisch abbaubaren Bui1derkomponente.The invention relates to alkaline dishwashing detergents for the mechanical cleaning of dishes with a biodegradable bath component.
Niederalkalische Mittel der neuesten Generation für die maschinelle Rei¬ nigung von Geschirr enthalten neben Bleichmitteln auf Sauerstoffbasis, oberflächenaktiven Stoffen und Enzymen eine Kombination aus wasserlöslichen Buildern, die aus Komplexbildnern, z.B. Citrat, aus Alka- liträgern, z.B. Soda, Hydrogencarbonat oder Disilikat, und aus Dispergiermitteln wie z.B. Polycarboxylaten besteht. Weitere mögliche Bui lderkomponenten sind Organophosphonsäuren, Aminocarbonsäuren oder kri¬ stalline Schichtsilikate; auf die früher verwendeten Phosphate, z.B. Pentanatriumtripolyphosphat, wird heute aus ökologischen Gründen weitge¬ hend verzichtet.The latest generation of low-alkaline agents for the mechanical cleaning of dishes contain, in addition to bleaching agents based on oxygen, surface-active substances and enzymes, a combination of water-soluble builders which are derived from complexing agents, e.g. Citrate, from alkali carriers, e.g. Soda, bicarbonate or disilicate, and from dispersants such as e.g. Polycarboxylates exist. Other possible binder components are organophosphonic acids, aminocarboxylic acids or crystalline layered silicates; on the phosphates previously used, e.g. Pentasodium tripolyphosphate is largely dispensed with today for ecological reasons.
Die in den heutigen Geschirrspülmitteln verwendeten Polycarboxylate, z.B. Maleinat/Acrylat-Copoly ere, verhindern die Ablagerung von Kalkbelägen bei zu hoher Restwasserhärte im Reinigungs- und Klarspülgang; bei hoher Salz¬ belastung der Spülflotte verbessern sie außerdem den Klarspüleffekt.The polycarboxylates used in today's dishwashing detergents, e.g. Maleinat / Acrylat-Copoly ere, prevent limescale deposits when the residual water hardness is too high in the cleaning and rinse cycle; with a high salt load in the washing liquor, they also improve the rinse aid effect.
Als Nachteil dieser Art von Polycarboxylaten muß jedoch angesehen werden, daß sie schwer biologisch abbaubar sind. Es besteht daher Bedarf an ma¬ schinellen Geschirrspülmitteln, die biologisch abbaubare Builderkomponen¬ ten enthalten, gleichzeitig aber das gewohnte Leistungsspektrum von modernen Geschirrspülmitteln zeigen. Viele biologisch gut abbaubare Builderkomponenten wie z.B. oxidierte Stärke oder Polyasparaginsäure sind zwar gute Dispergatoren für ausgefallenes Calciumcarbonat, jedoch schlechte Komplexbildner für Wasserhärte.However, a disadvantage of this type of polycarboxylates is that they are difficult to biodegrade. There is therefore a need for machine dishwashing detergents which contain biodegradable builder components but at the same time the usual range of services from show modern dishwashing detergents. Many biodegradable builder components such as oxidized starch or polyaspartic acid are good dispersants for failed calcium carbonate, but poor complexing agents for water hardness.
Die US-Patentschrift US 3,887,480 offenbart Geschirr- und Textilreini- gungsmittel, die ein Polymer enthalten, das aus 35-70 Mol% Maleinsäure, 20-45 Mol% Vinylacetat und 2-40 Mol% Acrylsäure besteht. Die europäische Patentschrift EP 0 193 360 Bl beschreibt zeolithhaltige Textilwasch ittel , die Polycarboxylatpoly ere aufgebaut aus einer C3-Cιo- onocarbonsäure, einer C^-Cß-Dicarbonsäure und einem nichtionischen Spacer, z. B. Vinyl- alkohol, enthalten. Die US-Patentschrift US 3,755,264 offenbart Copoly- mere, die z. B. aus 85 bis 99 Mol% Maleinsäureanhydrid und 1 bis 15 Mol% einer Mischung aus Acrylsäure und Vinylacetat aufgebaut sind. Die euro¬ päische Offenlegungsschrift EP 0 076 992 AI offenbart u. a. die Verwendung von aus 50-95 Gew.-% Acrylsäure, 0,5 bis 5 Gew.-% Vinylacetat und bis zu 49 Gew.-% Maleinsäure aufgebauten Polymeren als Inkrustationsinhibitoren in Wasch- und Reinigungsmitteln.US Pat. No. 3,887,480 discloses dishwashing and textile cleaning agents which contain a polymer which consists of 35-70 mol% maleic acid, 20-45 mol% vinyl acetate and 2-40 mol% acrylic acid. The European patent EP 0 193 360 B1 describes zeolite-containing textile detergents, the polycarboxylate poly ere composed of a C3-Cio-onocarboxylic acid, a C ^ -Cß-dicarboxylic acid and a nonionic spacer, for. B. vinyl alcohol included. The US Pat. No. 3,755,264 discloses copolymers which, for. B. from 85 to 99 mol% of maleic anhydride and 1 to 15 mol% of a mixture of acrylic acid and vinyl acetate. The European patent application EP 0 076 992 AI discloses u. a. the use of polymers composed of 50-95% by weight of acrylic acid, 0.5 to 5% by weight of vinyl acetate and up to 49% by weight of maleic acid as incrustation inhibitors in washing and cleaning agents.
Überraschenderweise wurde nun gefunden, daß sich Copolymere, die in be¬ stimmten, in o.g. Druckschriften nicht beschriebenen Mengenverhältnissen aus (Meth)acrylsäure bzw. (Meth)acrylat, Maleinsäure bzw. Maleat und Vi- nylalkohol und/oder Vinylacetat aufgebaut sind, hervorragend als Builder¬ komponenten in maschinellen Geschirrspülmitteln eignen.Surprisingly, it has now been found that copolymers, which in certain, can be found in the abovementioned. The quantitative ratios not described in (meth) acrylic acid or (meth) acrylate, maleic acid or maleate and vinyl alcohol and / or vinyl acetate are outstandingly suitable as builder components in automatic dishwashing detergents.
Gegenstand der Erfindung ist ein niederalkalisches Mittel zum maschinellen Reinigen von Geschirr, dessen 1 Gew.-%ige wäßrige Lösung einen pH-Wert von 8 bis 11,5 vorzugsweise 9 bis 10,5 aufweist, enthaltend wasserlösliche Builderkomponenten und Bleichmittel auf Sauerstoff-Basis, dadurch gekenn¬ zeichnet, daß es als wasserlösliche Builderko ponente ein Copoly er ent¬ hält, wobei das Copolymer zu 60 - 95 Gew.-%, vorzugsweise 70 - 90 Gew.-%, aus (Meth)acrylsäure bzw. (Meth)acrylat, vorzugsweise Acrylsäure bzw. Acrylat, und Maleinsäure bzw. Maleat und zu 5 - 40 Gew.- , vorzugsweise 10 - 25 Gew.-%, Vinylalkohol und/oder Vinylacetat aufgebaut ist, wobei das Gewichtsverhältnis (Meth)acrylsäure bzw. (Meth)acrylat zu Maleinsäure bzw. Maleat zwischen 1,5:1 und 4:1, vorzugsweise zwischen 2:1 und 2,5:1 liegt, sowohl die Mengen als auch die Gewichtsverhältnisse auf die Säuren bezogen sind, und ein Copolymer aus den Salzen der Säuren und Vinylalkohol bevor¬ zugt sind.The invention relates to a low-alkaline agent for machine cleaning of dishes, the 1% by weight aqueous solution of which has a pH of 8 to 11.5, preferably 9 to 10.5, containing water-soluble builder components and bleaching agents based on oxygen, characterized in that it contains a copoly as water-soluble builder component, the copolymer comprising 60-95% by weight, preferably 70-90% by weight, of (meth) acrylic acid or (meth) acrylate , preferably acrylic acid or acrylate, and maleic acid or maleate and 5-40% by weight, preferably 10-25% by weight, of vinyl alcohol and / or vinyl acetate, the weight ratio being (meth) acrylic acid or (meth) acrylate to maleic acid or Maleate is between 1.5: 1 and 4: 1, preferably between 2: 1 and 2.5: 1, both the amounts and the weight ratios are based on the acids, and a copolymer of the salts of the acids and vinyl alcohol is preferred are moving.
Die erfindungsgemäß eingesetzten Copolymeren lassen sich nach jedem der bekannten und üblichen Verfahren herstellen. Dabei werden insbesondere (Meth)acrylsäure, vorzugsweise Acrylsäure, und Maleinsäure mit Vinylalkohol und/oder Vinylacetat umgesetzt, woraufhin im Anschluß gegebenenfalls eine Neutralisation der Säuren zu vorzugsweise ihren Alkalisalzen wie den Natrium- oder Kaliumsalzen oder Ammoniumsalzen oder Alkanolaminsalzen, wie dem Monoethanola insalz ^der dem Triethanolaminsalz, sowie gegebenenfalls eine partielle oder vollständige Spaltung des Vinylacetats zum Vinylalkohol durchgeführt wird.The copolymers used according to the invention can be prepared by any of the known and customary processes. In particular, (meth) acrylic acid, preferably acrylic acid, and maleic acid are reacted with vinyl alcohol and / or vinyl acetate, whereupon the acids may then be neutralized to preferably their alkali metal salts, such as the sodium or potassium salts or ammonium salts or alkanolamine salts, such as the monoethanol insole the triethanolamine salt, and optionally a partial or complete cleavage of the vinyl acetate to the vinyl alcohol is carried out.
Analog zu den bekannten (co)polymeren Polycarbonsäuren bzw. Polycarboxy¬ laten wie den ho o- oder copolymeren Acrylsäuren bzw. Acrylaten sind sol¬ che Copolymeren bevorzugt, die entweder vollständig oder zumindest par¬ tiell, insbesondere zu mehr als 50 %, bezogen auf die vorhandenen Car- boxylgruppen, neutralisiert sind. Besonders bevorzugt ist dabei ein voll¬ ständig neutralisiertes Copolymer, das also aus den Salzen der (Meth)- acrylsäure, vorzugsweise Acrylsäure, und Maleinsäure, insbesondere den Natrium- oder Kaliumsalzen, und Vinylalkohol besteht. Die Copolymeren wei¬ sen im allgemeinen eine relative Molekülmasse zwischen 1000 und 200000, vorzugsweise zwischen 2000 und 50000, und insbesondere zwischen 3000 und 10000 auf. Sie werden vorzugsweise in p lverför iger sprühgetrockneter Form eingesetzt. Insbesondere bevorzugte Copolymere werden nach einem Ver¬ fahren hergestellt, das in der älteren deutschen Patentanmeldung P 43 00 772.4 beschrieben ist.Analogous to the known (co) polymeric polycarboxylic acids or polycarboxylates such as the ho- or copolymeric acrylic acids or acrylates, preference is given to copolymers which are either completely or at least partially, in particular to more than 50%, based on the existing carboxyl groups are neutralized. A completely neutralized copolymer is particularly preferred, ie it consists of the salts of (meth) acrylic acid, preferably acrylic acid, and maleic acid, in particular the sodium or potassium salts, and vinyl alcohol. The copolymers generally have a relative molecular mass between 1000 and 200000, preferably between 2000 and 50,000, and in particular between 3000 and 10,000. They are preferably used in powder-sprayed form. Particularly preferred copolymers are produced by a process which is described in the earlier German patent application P 43 00 772.4.
Bevorzugte erfindungsgemäße Geschirrspülmittel enthalten das Copolymer in Mengen von 0,5 bis 30 Gew.-%, vorzugsweise 2 bis 20 Gew.-%, weiterhin 0,5 bis 20 Gew.-%, vorzugsweise 5 bis 15 Gew.-%, eines Bleichmittels auf Sau¬ erstoffbasis, insbesondere Alkaliperborat und/ oder Percarbonat, und nichtionische Tenside in einer Menge von maximal 5 Gew.-%, vorzugsweise maximal 2 Gew.-%, wobei die Mittel frei von anionischen, kationischen oder amphoteren Tensiden sind.Preferred dishwashing detergents according to the invention contain the copolymer in amounts of 0.5 to 30% by weight, preferably 2 to 20% by weight, furthermore 0.5 to 20% by weight, preferably 5 to 15% by weight, of a bleaching agent based on oxygen, in particular alkali perborate and / or percarbonate, and nonionic surfactants in an amount of at most 5% by weight, preferably at most 2% by weight, the agents being free from anionic, cationic or amphoteric surfactants.
In einer bevorzugten Ausführungsform sind als Alkaliträger Alkalicarbonate und/oder -hydrogencarbonate, insbesondere die Natriumsalze, in einer Menge von bis zu 60 Gew.-%, vorzugsweise 5 bis 50 Gew.-%, enthalten.In a preferred embodiment, alkali metal carbonates and / or hydrogen carbonates, in particular the sodium salts, are present as alkali carriers in an amount of up to 60% by weight, preferably 5 to 50% by weight.
Die erfindungsgemäßen Geschirrspülmittel können weitere wasserlösliche Builderkomponenten, wie z.B. synthetische Polymere, unter denen die Salze von Polymerisationsprodukten ungesättigter Carbonsäuren verstanden werden und zu denen beispielsweise Polyacrylate, Polymethacrylate, Polymaleinate oder Copolymere der Acrylsäure mit Maleinsäure bzw. Maleinsäureanhydrid gehören, in einer Menge von 0,5 bis 30 Gew.-%, vorzugsweise 2 bis 20 Gew.-% enthalten. 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(R) 175 der Firma Alco. Prinzipiell können auch Phosphate oder Zeolithe enthalten sein, vorzugsweise sind die Geschirrspülmittel jedoch frei von Zeolithen und von phosphatha11igen Bui1derkomponenten.The dishwashing detergents according to the invention can contain further water-soluble builder components, such as synthetic polymers, which include the salts of polymerization products of unsaturated carboxylic acids and which include, for example, polyacrylates, polymethacrylates, polymaleinates or copolymers of acrylic acid with maleic acid or maleic anhydride, in an amount of 0.5 Contain up to 30 wt .-%, preferably 2 to 20 wt .-%. 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 ( R ) 175 from Alco. In principle, phosphates or zeolites can also be present, but the dishwashing detergents are preferably free from zeolites and from phosphate-containing bath components.
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 sind deshalb vorzugsweise frei von anionischen, kationischen oder amphoteren Tensiden. Der Gehalt an nichtionischen Tensiden beträgt maximal 5 Gew.- , vorzugsweise maximal 2 Gew.-%. Als nichtionische Tenside sind vor allem Anlagerungsprodukte von 1 bis 20 Mol Ethylenoxid (E0) und/oder 1 bis 20 Mol Propylenoxid (PO) an 1 Mol einer aliphatischen Verbindung mit 10 bis 20 Kohlenstoffato en aus der Gruppe der Alkohole, Carbonsäuren, Fettamine, Carbonsäureamide und Alkan- sulfonamide von Interesse. Wichtig sind neben den wasserlöslichen nicht- ionischen Tensiden aber auch nicht bzw. nicht vollständig wasserlösliche Polyglykolether mit 2 bis 7 Ethylenglykoletherresten im Molekül, vorzugs¬ weise werden diese in Kombination mit wasserlöslichen nichtionischen Tensiden eingesetzt. Außerdem können als nichtionische Tenside auch Alkylpolyglycoside der allgemeinen Formel 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 Glyko- seeinheit mit 5 oder 6 C-Atomen steht und der Oligo erisierungsgrad 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 are therefore preferably free of anionic, cationic or amphoteric surfactants. The content of nonionic surfactants is at most 5% by weight, preferably at most 2% by weight. Addition products of 1 to 20 moles of ethylene oxide (E0) and / or 1 to 20 moles of propylene oxide (PO) with 1 mole of an aliphatic compound with 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines and carboxamides are the nonionic surfactants and alkanesulfonamides of interest. In addition to the water-soluble nonionic surfactants, polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule, which are not or not completely water-soluble, are also important, preferably in combination with water-soluble nonionic ones Surfactants used. In addition, alkyl polyglycosides of the general formula R-0- (G) x can also be used as nonionic surfactants, in which R denotes a primary, straight-chain or branched aliphatic radical having 8 to 22, preferably 12 to 18 C atoms, G for a glyco - Se unit with 5 or 6 carbon atoms and the degree of oligomerization x is between 1 and 10.
Bevorzugte erfindungsgemäße Geschirrspülmittel enthalten außerdem Kom¬ plexbildner aus der Gruppe der di- und ehrfunktionellen organischen Carbonsäuren bzw. deren Salzen, z.B. Nitrilotriessigsäure, insbesondere aber Citronensäure bzw. deren Salze, in einer Menge von 0,5 bis 60 Gew.-%, vorzugsweise 20 bis 50 Gew.-%.Preferred dishwashing detergents according to the invention also contain complexing agents from the group of the di- and honorically functional organic carboxylic acids or their salts, e.g. Nitrilotriacetic acid, but especially citric acid or its salts, in an amount of 0.5 to 60% by weight, preferably 20 to 50% by weight.
Zu den üblichen in niederalkalischen maschinellen Geschirrspülmitteln eingesetzten Alkalisierungs itteln zählen Alkalicarbonate, -hydro- gencarbonate und Alkalisilikate mit einem Molverhältnis Siθ2/M2θ (M = Al- kaliatom) von 1,5 : 1 bis 2,5 : 1. Die in den erfindungsgemäßen Mitteln bevorzugt eingesetzten Alkalicarbonate und -hydrogencarbonate sind die Natriu carbonate und -hydrogencarbonate, die in den bereits oben genannten Mengen enthalten sind. Auf den Einsatz der hochalkalischen Metasilikate als Alkaliträger wird vorzugsweise verzichtet. Anstelle der Metasilikate werden bevorzugt Alkalisilikate, vorzugsweise Natriumsilikate mit einem MolVerhältnis Siθ2 Na2θ von 1,5 : 1 bis 2,5 : 1, in Mengen von bis zu 30 Gew.-%, vorzugsweise 5 bis 20 Gew.-%, bezogen auf das gesamte Geschirr¬ spülmittel, eingesetzt.The usual alkalizing agents used in low-alkaline machine dishwashing detergents include alkali carbonates, hydrogen carbonates and alkali silicates with a molar ratio SiO 2 / M2 O (M = alkali metal) of 1.5: 1 to 2.5: 1 alkali carbonates and bicarbonates preferably used are the sodium carbonates and bicarbonates which are contained in the amounts already mentioned above. The use of the highly alkaline metasilicates as alkali carriers is preferably avoided. Instead of the metasilicates, preference is given to alkali silicates, preferably sodium silicates, with a SiO 2 Na 2 O molar ratio of 1.5: 1 to 2.5: 1, in amounts of up to 30% by weight, preferably 5 to 20% by weight, based on the entire dishwashing detergent used.
Unter den als Bleichmittel auf Sauerstoffbasis dienenden Verbindungen ha¬ ben das Natriumperborat-tetrahydrat (NaBÜ2 • H2O2 • 3H2O) das Natriumper- borat-monohydrat ( aBÜ2 • H2O2) und das Peroxycarbonat (Na2C03 • 1,5 H2O2) besondere Bedeutung. Weitere brauchbare Bleichmittel sind z.B. persaure Salze organischer Säuren, wie Perbenzoate oder Salze der Diperdodecandi- säure. Vorzugsweise sind 0,5 bis 20 Gew.-%, besonders bevorzugt 5 bis 15 Gew.-%, eines Bleichmittels auf Sauerstoffbasis, insbesondere Alkaliper¬ borate und/oder -percarbonate enthalten. Überdies kann der Zusatz geringer Mengen bekannter Bleichmittelstabilisatoren wie Boraten bzw. Metaboraten und Metasilikaten sowie Magnesiumsalzen, z.B. Magnesiumsulfat, zweckdien¬ lich sein.Among the compounds serving as oxygen-based bleaching agents, sodium perborate tetrahydrate (NaBÜ2 • H2O2 • 3H2O), sodium perborate monohydrate (aBÜ2 • H2O2) and peroxycarbonate (Na2C03 • 1.5 H2O2) are of particular importance. Other bleaching agents that can be used are, for example, peracidic salts of organic acids, such as perbenzoates or salts of diperdodecanedioic acid. It preferably contains 0.5 to 20% by weight, particularly preferably 5 to 15% by weight, of an oxygen-based bleach, in particular alkali perborates and / or percarbonates. In addition, the addition of small amounts of known bleach stabilizers such as borates or metaborates and metasilicates and magnesium salts, for example magnesium sulfate.
Geeignete Bleichaktivatoren für diese Oxidationsmittel sind insbesondere N-Acyl- und O-Acyl-Verbindungen, vorzugsweise tetraacylierte Diamine wie N,N,N' .N'-Tetraacetylethylendia in (TAED). Die erfindungsgemäßen Mittel enthalten solche üblichen Bleichaktivatoren in einer Menge von 0,1 bis 10 Gew.-%, vorzugsweise 1 bis 5 Gew.-%. Die erfindungsgemäßen Mittel sind vorzugsweise frei von aktivchlorabspaltenden Mitteln wie z.B. Trichlorisocyanursäure.Suitable bleach activators for these oxidizing agents are in particular N-acyl and O-acyl compounds, preferably tetraacylated diamines such as N, N, N '.N'-tetraacetylethylene diamine in (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 are preferably free from agents that release active chlorine, e.g. Trichloroisocyanuric acid.
Zur besseren Ablösung eiweiß- oder stärkehaltiger Speisereste können En¬ zyme wie Proteasen, A ylasen, Lipasen oder Cellulasen eingesetzt werden, beispielsweise Proteasen wie BLAP( ) 140 der Firma Henkel, 0ptimase(R) -M-440, 0ptimase(R) -M-330, 0pticlean(R) -M-375, 0pticlean(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 Experase(R) T der Firma Ibis; Amylasen wie Termamyl(R) 60 T, 90 T der Firma Novo, A ylase- 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; Cellu¬ lasen wie Celluzym(R) 0,7 T der Firma Novo Nordisk. Enzyme sind in den erfindungsgemäßen Mitteln in einer Menge von 0,1 bis 5 Gew.-%, vorzugs¬ weise 0,5 bis 2 Gew.-%, bezogen auf das gesamte Geschirrspülmittel, ent¬ halten.Enzymes such as proteases, aylases, lipases or cellulases can be used to better remove protein or starch-containing food residues, for example proteases such as BLAP () 140 from Henkel, 0ptimase ( R ) -M-440, 0ptimase ( R ) -M -330, 0pticlean ( R ) -M-375, 0pticlean ( 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 Experase ( R ) T from Ibis; Amylases such as Termamyl ( R ) 60 T, 90 T from Novo, A ylase-LT ( R ) from Solvay Enzymes or Maxamyl ( R ) P 5000, CXT 5000 or CXT 2900 from Ibis; Lipases such as Lipolase ( R ) 30 T from Novo; Cellulases such as Celluzym ( R ) 0.7 T from Novo Nordisk. Enzymes are contained in the agents according to the invention in an amount of 0.1 to 5% by weight, preferably 0.5 to 2% by weight, based on the total dishwashing detergent.
Zur Verhinderung des Anlaufens von Silberbesteck können fakultativ Sil¬ berschutzmittel, wie sie in der älteren deutschen Patentanmeldung P 43 15 397.6 beschrieben sind, insbesondere wasserlösliche Mn(II)-salze, in einer Menge von bis zu 2 Gew.-%, vorzugsweise 0,1 bis 0,5 Gew.-%, enthalten sein.To prevent tarnishing of silver cutlery, optional silver protection agents, as described in the older German patent application P 43 15 397.6, in particular water-soluble Mn (II) salts, in an amount of up to 2% by weight, preferably 0. 1 to 0.5 wt .-%, may be included.
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. Dabei ist es auch möglich, daß die erfindungsgemäß eingesetzten Polymeren in Form eines Compounds als Zumischkomponente zu anderen granulären Bestandteilen der Geschirrspülmittel eingesetzt werden.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. It is also possible for the polymers used according to the invention to be in the form of a compound can be used as an additive component to other granular components of the dishwashing detergent.
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 • 10^ Pa bis 1 500 • 10^ 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 m bis 40 mm.To produce cleaning agents according to the invention in tablet form, the procedure is preferably such that all constituents are mixed with one another in a mixer and the mixture is used by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range from 200 · 10 ^ Pa to 1 500 • 10 ^ 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 m to 40 mm.
Die Herstellung der Maschinengeschirrspülmittel in Form von nicht stau¬ benden, lagerstabil rieselfähigen Pulvern und/oder Granulaten mit hohen Schüttdichten im Bereich von 800 bis 900 g/1 kennzeichnet sich dadurch, daß man in einer ersten Verfahrensteilstufe die Builder-Komponenten mit wenigstens einem Anteil flüssiger Mischungskomponenten unter Erhöhung der Schüttdichte dieses Vorgemisches vermischt und nachfolgend - cewünschten- falls nach einer Zwischentrocknung - die weiteren Bestandteile des Ma- schinengeschirrspülmittels mit dem so gewonnenen Vorgemisch vereinigt.The production of machine dishwashing detergents in the form of non-dusting, storage-stable, free-flowing powders and / or granules with high bulk densities in the range from 800 to 900 g / 1 is characterized in that in a first process stage, the builder components are at least partially liquid Mixing components are mixed while increasing the bulk density of this premix and subsequently - if desired - after an intermediate drying - the further components of the dishwasher detergent are combined with the premix obtained in this way.
Da der Alkalicarbonat-Gehalt die Alkalität des Produktes stark beeinflußt, muß die Zwischen-Trocknung so durchgeführt werden, daß der Zerfall des Natriumbicarbonats zu Natriumcarbonat möglichst gering (ode>- zumindest möglichst konstant) ist. Ein zusätzlich durch die Trocknung entstehender Natriumcarbonat-Anteil müßte nämlich bei der Formulierung derΛ Granulat- Rezeptur berücksichtigt werden. Niedrige Trocknungstemperaturen wirken dabei nicht nur dem Natriumbicarbonat-Zerfall entgegen, sondern erhöhen auch die Löslichkeit des granulierten Reinigungsmittels bei der Anwendung. Vorteilhaft ist daher beim Trocknen eine Zulufttemperatur, die einerseits zur Vermeidung des Bicarbonat-Zerfalls so gering wie möglich sein sollte und die andererseits so hoch wie nötig sein muß, um ein Produkt mit guten Lagereigenschaften zu erhalten. Bevorzugt ist beim Trocknen eine Zuluft- te peratur von ca. 80°C. Das Granulat selbst sollte nicht auf Temperaturen über etwa 60°C erhitzt werden.Since the alkali carbonate content strongly influences the alkalinity of the product, the intermediate drying must be carried out so that the decomposition of the sodium bicarbonate to sodium carbonate is as low as possible (or at least as constant as possible). An additional sodium carbonate portion resulting from the drying would have to be taken into account when formulating the Λ granulate recipe. Low drying temperatures not only counteract sodium bicarbonate decay, but also increase the solubility of the granulated detergent during use. It is therefore advantageous for drying to have a supply air temperature which, on the one hand, should be as low as possible to avoid bicarbonate decomposition and, on the other hand, must be as high as necessary in order to obtain a product with good storage properties. When drying, a supply air is preferred. te temperature of approx. 80 ° C. The granules themselves should not be heated to temperatures above about 60 ° C.
In der ersten Teilstufe des Mischverfahrens wird der Builder in der Regel in Ab ischung 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 nichtionischen Tensiden und/oder der Lösung der Duftstoffe 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 sub-stage of the mixing process, the builder is generally acted upon 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 mixed intimately. The remaining components are then added and the entire mixture is worked through and homogenized in the mixing device. The use of additional amounts of liquid, in particular the use of additional water, is generally not necessary here. The mixture of substances obtained is then in the form of a free-flowing, dust-free powder of the desired high bulk densities, approximately in the range from 800 to 900 g / l.
Die Vorgranulate werden dann mit den noch fehlenden Komponenten des Ge¬ schirrspülmittels zum Fertigprodukt abgemischt. Die Mischzeit liegt in allen hier dargestellten Fällen sowohl in der Vorstufe der verdichtenden Abmischung unter Einfluß von Flüssigkomponenten wie in der nachfolgenden Endabmischung mit den weiteren Komponenten im Bereich weniger Minuten, beispielsweise im Bereich von 1 bis 5 Minuten.The pre-granules are then mixed with the still missing components of the dishwashing detergent to form the finished product. In all the cases shown here, the mixing time is both in the preliminary stage of the compacting mixture under the influence of liquid components and in the subsequent final mixture with the other components in the range of a few minutes, for example in the range of 1 to 5 minutes.
In einer besonderen Ausführungsform kann es bei der Herstellung von feinen Granulatkörnern zweckmäßig sein, durch Abpudern der Oberfläche des gebil¬ deten Granulatkorns eine weiterführende Stabilisierung und Egalisierung einzustellen. Geeignet sind hierzu insbesondere geringe Anteile an Was¬ serglaspulver beziehungsweise pulverförmigem Alkalicarbonat.In a special embodiment, it may be expedient in the production of fine granules to set further stabilization and leveling by powdering the surface of the granules formed. Small portions of water glass powder or powdered alkali carbonate are particularly suitable for this purpose.
Mit den erfindungsgemäßen maschinellen Geschirrspülmitteln stehen Produkte zur Verfügung, die neben ihrer besseren biologischen Abbaubarkeit konven¬ tionellen modernen Geschirrspülmitteln vor allem hinsichtlich der Belags- inhibierung und des Klarspüleffektes an Gläsern und Messerklingen über¬ legen sind.With the automatic dishwashing agents according to the invention, products are available which, in addition to their better biodegradability, are superior to conventional modern dishwashing agents above all with regard to the deposit inhibition and the rinse aid effect on glasses and knife blades.
Die nachfolgenden Beispiele sollen den Erfindungsgegenstand näher erläu¬ tern, ohne ihn jedoch hierauf zu beschränken. B e i s p i e l eThe following examples are intended to explain the subject of the invention in more detail, but without restricting it thereto. Examples
Es wurden granuläre Geschirrspülmittel nachstehender Zusammensetzung (er¬ findungsgemäßes Mittel A und Vergleichsmittel B sowie erfindungsgemäßes Mittel C) hergestellt.Granular dishwashing detergents with the following composition (agent A according to the invention and comparative agent B and agent C according to the invention) were produced.
Mittel A enthielt 10 Gew.-% des Copolymeren, das gemäß der Offenbarung der älteren deutschen Patentanmeldung P 43 00 772.4 aus 80 Gew.-% Acrylsäure und Maleinsäure im Gewichtsverhältnis 7:3 sowie aus 20 Gew.-% Vinylacetat hergestellt und anschließend vollständig neutralisiert worden war.Agent A contained 10% by weight of the copolymer which, according to the disclosure of the earlier German patent application P 43 00 772.4, was prepared from 80% by weight of acrylic acid and maleic acid in a weight ratio of 7: 3 and from 20% by weight of vinyl acetate and then completely neutralized had been.
Vergleichsbeispiel B enthielt 10 Gew.-% eines von der Firma BASF unter dem Handelsnamen Sokalan(R) CP5 vertriebenen Acrylat-Maleat-Copolymers.Comparative Example B contained 10% by weight of an acrylate-maleate copolymer sold by BASF under the trade name Sokalan ( R ) CP5.
A B CA B C
Gew.-% Gew.-% Gew.-%% By weight% by weight% by weight
Na-citrat 30,0 30,0 40,0Na citrate 30.0 30.0 40.0
Sokalan CP5 — 10,0 — o.g. Copolymer 10,0 — 5,0Sokalan CP5 - 10.0 - above Copolymer 10.0 - 5.0
Na2C03 13,0 13,0 6,0Na2C03 13.0 13.0 6.0
NaHC03 35,5 35,5 30,1NaHC03 35.5 35.5 30.1
Na-perborat 5,0 5,0 —Na perborate 5.0 5.0 -
Na-percarbonat — — 12,0Na percarbonate - - 12.0
TAED 2,0 2,0 3,0TAED 2.0 2.0 3.0
Amylase 1,5 1,5 1,0Amylase 1.5 1.5 1.0
Protease 1.5 1,5 1,0Protease 1.5 1.5 1.0
Plurafac LF403 der Fa. BASFPlurafac LF403 from BASF
(C^/iβ-Fettalkohol x E0 x 4 PO) 0,9 0,9 0,9 Parfümöl 0,6 0,6 0,6(C ^ / iβ-fatty alcohol x E0 x 4 PO) 0.9 0.9 0.9 perfume oil 0.6 0.6 0.6
MnSθ4 0,4 ReiπiqunosleistunqMnSθ4 0.4 Reiπiqunosleistunq
Die Reinigungsleistung der Mittel A und B wurde in einer Geschirrspülma¬ schine Miele G 531 (Programm Universal 65°C) bei Dosierungen von jeweils 30 g in 7,0 1 Wasser mit 16° dH im Reinigungsgang getestet (Anschmutzungen wie in "Th. Altenschöpfer, SÖFW, 98 (1972) 763 - 765" beschrieben: Tee, Milch, Hackfleisch, Pudding, Fettstift, Stärke, Haferflocken).The cleaning performance of agents A and B was tested in a dishwasher Miele G 531 (program Universal 65 ° C) at doses of 30 g each in 7.0 l water with 16 ° dH in the cleaning cycle (soiling as in "Th. Altenschöpfer , SÖFW, 98 (1972) 763-765 ": tea, milk, minced meat, pudding, fat stick, starch, oatmeal).
Das erfindungsgemäße Mittel A wies gegenüber dem nicht erfindungsgemäßen Mittel B insbesondere bei der Entfernung der Stärke-, Hackfleisch-, Fett¬ stift- und Haferflocken-Anschmutzungen, insbesondere aber bei der Tee- Anschmutzung, eine überlegene Reinigungsleistung auf.Agent A according to the invention had a superior cleaning performance compared to agent B not according to the invention, particularly when removing the starch, minced meat, fat stick and oatmeal stains, but in particular when staining tea.
BelaqsinhibierunqBelaqsinhibierunq
Die Belagsbildung der Mittel A und B wurde in einer Geschirrspülmaschine Miele G 590 (Programm Universal 65°C) bei Dosierungen von jeweils 20 g in 7,0 1 Wasser mit 16° dH unter Zusatz von 50 g pumpbarer Anschmutzungen (Gemisch aus Ketchup, Bratensoße, Senf, Kartoffelstärke, Eigelb, Milch, Margarine) in Anwesenheit von 3,0 ml eines handelsüblichen Klarspülers über 10 Spülgänge getestet. Der Klarspüleffekt ("spotting") wurde mit ei¬ ner Skala von 1 (= sehr schlechter Klarspüleffekt) bis 8 (= sehr guter Klarspüleffekt, keine Wasserflecken) bewertet. Die Ergebnisse der mit dem erfindungsgemäßen Mittel A und dem Vergleichsmittel B an Gläsern, Messer¬ klingen und Porzellantellern erzielten Klarspüleffekte können der Tabelle 1 entnommen werden. The buildup of agents A and B was carried out in a Miele G 590 dishwasher (Universal 65 ° C program) at doses of 20 g each in 7.0 l of water at 16 ° dH with the addition of 50 g of pumpable soiling (mixture of ketchup, gravy , Mustard, potato starch, egg yolk, milk, margarine) in the presence of 3.0 ml of a commercial rinse aid tested over 10 rinse cycles. The rinsing effect ("spotting") was rated on a scale from 1 (= very bad rinsing effect) to 8 (= very good rinsing effect, no water stains). The results of the rinsing effects achieved with agent A according to the invention and comparative agent B on glasses, knife blades and porcelain plates can be seen in Table 1.
Tabelle 1Table 1
GläserGlasses
MesserklingenKnife blades
PorzellantellerPorcelain plate
Es zeigt sich, daß das erfindungsgemäße Mittel A dem Vergleichsmittel B vor allem hinsichtlich des Klarspüleffektes an Gläsern und Messerklingen überlegen ist.It can be seen that agent A according to the invention is superior to comparative agent B above all with regard to the rinse aid effect on glasses and knife blades.
Das erfindungsgemäße Mittel C zeigte mit dem erfindungsgemäßen Mittel A vergleichbare Reinigungs- und Belagsinhibierungsleistungen; aufgrund der Anwesenheit von MnSÜ zeigte es vor allem hinsichtlich der Verhinderung des Anlaufens von Silberbesteck überlegene Eigenschaften. Agent C according to the invention showed cleaning and deposit inhibition performances comparable to agent A according to the invention; due to the presence of MnSÜ, it showed superior properties especially in preventing silver tarnishing from tarnishing.

Claims

Patentansprüche claims
1. Niederalkalisches Mittel zum maschinellen Reinigen von Geschirr, des¬ sen 1 Gew.-%ige wäßrige Lösung einen pH-Wert von 8 bis 11,5 vorzugs¬ weise 9 bis 10,5 aufweist, enthaltend wasserlösliche Builderkomponen¬ ten und Bleichmittel auf Sauerstoff-Basis, dadurch gekennzeichnet, daß als wasserlösliche Builderkomponente ein Copolymer enthalten ist, das zu 60-95 Gew.-%, vorzugsweise 70-90 Gew.-%, aus (Meth)acrylsäure bzw. (Meth)acrylat, vorzugsweise Acrylsäure bzw. Acrylat, und Maleinsäure bzw. Maleat und zu 5-40 Gew.-%, vorzugsweise 10-25 Gew.-%} Vinylalko¬ hol und/oder Vinylacetat aufgebaut ist, wobei das Gewichtsverhältnis (Meth)acrylsäure bzw. (Meth)acrylat zu Maleinsäure bzw. Maleat zwi¬ schen 1,5:1 und 4:1, vorzugsweise zwischen 2:1 und 2,5:1 liegt, sowohl die Mengen als auch die Gewichtsverhältnisse auf die Säuren bezogen sind, und ein Copolymer aus den Salzen der Säuren und Vinylalkohol bevorzugt sind.1. Low-alkaline agent for machine cleaning of dishes, whose 1% by weight aqueous solution has a pH of 8 to 11.5, preferably 9 to 10.5, containing water-soluble builder components and bleaching agents for oxygen -Base, characterized in that a copolymer is present as the water-soluble builder component which comprises 60-95% by weight, preferably 70-90% by weight, of (meth) acrylic acid or (meth) acrylate, preferably acrylic acid or Acrylate, and maleic acid or maleate and 5-40% by weight, preferably 10-25% by weight, of vinyl alcohol and / or vinyl acetate, the weight ratio of (meth) acrylic acid or (meth) acrylate being increased Maleic acid or maleate is between 1.5: 1 and 4: 1, preferably between 2: 1 and 2.5: 1, both the amounts and the weight ratios are based on the acids, and a copolymer of the salts of Acids and vinyl alcohol are preferred.
2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß es 0,5 bis 30 Gew.-%, vorzugsweise 2 bis 20 Gew.-% Copolymer und 0,5 bis 20 Gew.-%, vorzugsweise 5 bis 15 Gew.-%, eines Bleichmittels auf Sauerstoffbasis, insbesondere Alkaliperborat und/oder -percarbonat, enthält und daß es frei von anionischen, kationischen oder amphoteren Tensiden ist und der Gehalt an nichtionischen Tensiden max. 5 Gew.-%, vorzugsweise max. 2 Gew.-%, jeweils bezogen auf das gesamte Mittel, beträgt.2. Composition according to claim 1, characterized in that it is 0.5 to 30 wt .-%, preferably 2 to 20 wt .-% copolymer and 0.5 to 20 wt .-%, preferably 5 to 15 wt .-% , an oxygen-based bleach, in particular alkali perborate and / or percarbonate, and that it is free of anionic, cationic or amphoteric surfactants and the content of nonionic surfactants max. 5% by weight, preferably max. 2 wt .-%, each based on the total agent.
3. Mittel nach Anspruch 1 und 2, dadurch gekennzeichnet, daß es bis 60 Gew.-%, vorzugsweise 5 bis 50 Gew.-%, Alkalicarbonat und/oder -hydro- gencarbonat enthält.3. Composition according to claim 1 and 2, characterized in that it contains up to 60 wt .-%, preferably 5 to 50 wt .-%, alkali carbonate and / or hydrogen carbonate.
4. Mittel nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß es Komplex¬ bildner aus der Gruppe der di- und mehrfunktionellen organischen Car¬ bonsäuren bzw. deren Salzen, insbesondere Citronensäure bzw. deren Salze, in einer Menge von 0,5 bis 60 Gew.-%, vorzugsweise 20 bis 50 Gew.-%, bezogen auf das gesamte Mittel, enthält. 5. Mittel nach Anspruch 1 bis 4, dadurch gekennzeichnet, daß es bis zu 30 Gew.-%, vorzugsweise 5 bis 20 Gew.-%, bezogen auf das gesamte Mit¬ tel, Alkalisilikat mit einem Molverhältnis Siθ2/ 2θ (M = Alkaliatom) von 1,5:1 bis 2,4. Composition according to claim 1 to 3, characterized in that there are complexing agents from the group of the di- and polyfunctional organic carboxylic acids or their salts, in particular citric acid or their salts, in an amount of 0.5 to 60 % By weight, preferably 20 to 50% by weight, based on the total agent. 5. Composition according to claim 1 to 4, characterized in that it is up to 30 wt .-%, preferably 5 to 20 wt .-%, based on the total Mit¬ tel, alkali silicate with a molar ratio Siθ2 / 2θ (M = alkali atom ) from 1.5: 1 to 2,
5:1 enthält, ι5: 1 contains, ι
6. Mittel nach Anspruch 1 bis 5, dadurch gekennzeichnet, daß es frei von aktivchlorabspaltenden Mitteln ist.6. Composition according to claim 1 to 5, characterized in that it is free of active chlorine-releasing agents.
7. Mittel nach Anspruch 1 bis 6, dadurch gekennzeichnet, daß es Enzyme in einer Menge von 0,1 bis 5 Gew.-%, vorzugsweise 0,5 bis 2 Gew.-%, be¬ zogen auf das gesamte Mittel, enthält.7. Composition according to claim 1 to 6, characterized in that it contains enzymes in an amount of 0.1 to 5 wt .-%, preferably 0.5 to 2 wt .-%, based on the total agent.
8. Tablettenförmiges Mittel nach Anspruch 1 bis 7, 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 • 108 Pa erhältlich ist.8. Tablet-like composition according to claim 1 to 7, characterized gekennzeich¬ net that it by mixing all of 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 • 10 8 Pa is available.
9. Pulver- oder granulatförmiges Mittel nach Anspruch 1 bis 7, dadurch gekennzeichnet, daß es eine Schüttdichte von 750 g/1 bis 1000 g/1 aufweist.9. Powder or granular composition according to claim 1 to 7, characterized in that it has a bulk density of 750 g / 1 to 1000 g / 1.
10. Verwendung der Mittel nach einem der Ansprüche 1 bis 9 zum maschinel¬ len Reinigen von Geschirr. 10. Use of the agent according to one of claims 1 to 9 for mechanically cleaning dishes.
PCT/EP1994/002000 1993-06-28 1994-06-20 Dishwasher agent with biodegradable builders WO1995000623A1 (en)

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CN107083287A (en) * 2017-04-20 2017-08-22 合肥酷睿网络科技有限公司 A kind of novel mechanical processing cleaning agent and its production technology
WO2020086257A1 (en) * 2018-10-22 2020-04-30 Dow Global Technologies Llc Automatic dishwashing composition with dispersant polymer

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JP7039587B2 (en) 2016-12-16 2022-03-22 ローム アンド ハース カンパニー Additives for controlling spot formation in automated dishwashing systems

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EP0504091A1 (en) * 1991-03-15 1992-09-16 Cleantabs A/S A phosphate-free automatic dishwashing composition
WO1992017565A1 (en) * 1991-03-30 1992-10-15 Henkel Kommanditgesellschaft Auf Aktien Low-alkaline, chlorine and phosphate-free dishwasher detergents in the form of heavy powders and granulates

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US20130050056A1 (en) * 2011-08-31 2013-02-28 Qualcomm Incorporated Wireless device with 3-d antenna system
CN107083287A (en) * 2017-04-20 2017-08-22 合肥酷睿网络科技有限公司 A kind of novel mechanical processing cleaning agent and its production technology
WO2020086257A1 (en) * 2018-10-22 2020-04-30 Dow Global Technologies Llc Automatic dishwashing composition with dispersant polymer
CN112739806A (en) * 2018-10-22 2021-04-30 陶氏环球技术有限责任公司 Automatic dishwashing composition with dispersant polymer
JP2022503862A (en) * 2018-10-22 2022-01-12 ダウ グローバル テクノロジーズ エルエルシー Automatic dishwashing composition containing dispersant polymer
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CZ342395A3 (en) 1996-06-12
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HU9503693D0 (en) 1996-02-28
HUT73202A (en) 1996-06-28
DE4321430A1 (en) 1995-01-05

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