EP0706558A1 - Dishwasher agents with biodegradable builders - Google Patents

Dishwasher agents with biodegradable builders

Info

Publication number
EP0706558A1
EP0706558A1 EP94918884A EP94918884A EP0706558A1 EP 0706558 A1 EP0706558 A1 EP 0706558A1 EP 94918884 A EP94918884 A EP 94918884A EP 94918884 A EP94918884 A EP 94918884A EP 0706558 A1 EP0706558 A1 EP 0706558A1
Authority
EP
European Patent Office
Prior art keywords
acid
weight
composition according
agents
agent
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
EP94918884A
Other languages
German (de)
French (fr)
Inventor
Willi Buchmeier
Hans Andree
Peter Krings
Birgit Burg
Jürgen Härer
Peter Jeschke
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0706558A1 publication Critical patent/EP0706558A1/en
Ceased legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • C11D17/0065Solid detergents containing builders
    • C11D17/0073Tablets
    • C11D17/0091Dishwashing tablets
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065High-density particulate detergent compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3788Graft polymers

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 automatic cleaning of dishes contain not only bleaching agents based on oxygen, surface-active substances and enzymes, but also a combination of water-soluble builders which are derived from complexing agents, e.g. Citrate, from alkali carriers, e.g. Soda, hydrogecarbonate or disilicate, and from dispersants such as e.g. Polycarboxylates exist.
  • complexing agents e.g. Citrate
  • alkali carriers e.g. Soda
  • hydrogecarbonate or disilicate e.g. Polycarboxylates
  • Other possible builder components are organophosphonic acids, aminocarboxylic acids or crystalline phyllosilicates; to the phosphates previously used, e.g. Pentanatriu tripolyphi-sphat is largely avoided today for ecological reasons.
  • the polycarboxylates used in today's dishwashing detergents e.g. maleate / acrylate copolymers, prevent limescale deposits from accumulating when the residual water hardness is too high in cleaning and clearing agents. rinse cycle; if the rinsing liquor has a high salt load, they also improve the rinse aid effect.
  • the invention relates to a low-alkaline agent for mechanical 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 Oxygen base, characterized in that it contains, as a water-soluble builder component, a copolymer which is composed at least of the monomers of an onoethylenically unsaturated C3-C8 ⁇ carboxylic acid, a 2-A1-alkylallylsulfonic acid or 2-arylallylsulfonic acid and a carbohydrate .
  • the dishwashing detergents according to the invention also include those in which the copolymers are partially or wholly by the salts of the copolymers, that is to say those copolymers in which the carboxyl group were partially or completely converted to carboxylate groups, are replaced.
  • the copolymers used according to the invention contain two carboxylic acids and / or their salts and a carbohydrate as monomers.
  • the first acidic monomer or its salt is derived from an onoethylenically unsaturated C3-Cg-monocarboxylic acid and preferably from a C3-C4-monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt is a derivative of an allylsulfonic acid which, in the 2-position, has an alkyl radical, preferably a C 1 -C 6 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives. is substituted.
  • copolymers contain 40 to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate with particular preference for acrylic acid or acrylate, 10 to 30% by weight.
  • methallylsulfonic acid or methallylsulfonate preferably 15 to 25% by weight of methallylsulfonic acid or methallylsulfonate, where methallylsulfonic acid or methallylsulfonate can also be partially replaced by a methacrylic acid-polyethylene glycol ester formed by addition of 1 to 10 ethylene oxide units on methacrylic acid, the weight ratio then being between Methacrylic acid polyethylene glycol ester and methallylsulfonic acid or sulfonate is 1:10 to 10: 1, and 15 to 40% by weight, preferably 20 to 40% by weight, of a carbohydrate.
  • This carbohydrate can, for example, be a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred.
  • predetermined breaking points are built into the polymer, which are responsible for the degradability of the polymer.
  • sucrose is preferred as the carbohydrate.
  • the copolymers used according to the invention can be prepared by any of the known and customary processes.
  • the monomeric acids are reacted with the carbohydrate, whereupon the acids are then optionally neutralized to give preferably their alkali metal salts, such as the sodium or potassium salts, or ammonium salts or alkanolamine salts, such as the monoethanolamine salt or the triethanolamine salt.
  • copolymers Analogous to the known conventional (co) polymeric polycarboxylic acids or polycarboxylates such as the homo- or copolymeric acrylic acids or acrylates, those copolymers are also preferred which are either completely or at least partially, in particular more than 50%, based on the carboxyl groups present are neutralized.
  • a completely neutralized copolymer is particularly preferred, ie it consists of the salts of the monomeric acids, in particular the sodium or potassium salts of the monomeric acids, and a carbohydrate.
  • 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 powdery, spray-dried form. Particularly preferred copolymers are produced by a process which is described in the earlier German patent application P 4221 381.9.
  • 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, a bleaching agent based on oxygen, in particular alkali perborate and / or percarbonate, and nonionic surfactants in an amount of a maximum of 5% by weight, preferably a maximum of 2% by weight, the agents being free from anionic, cationic or amphoteric surfactants.
  • alkali carbonates and / or bicarbonates, in particular the sodium salts are used as alkali carriers.
  • ze in an amount of up to 60 wt .-%, preferably 5 to 50 wt .-%, contain.
  • the dishwashing detergents according to the invention can comprise 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, poly alylates or copolymers of acrylic acid with maleic acid or maleic anhydride Contain amount of 0.5 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, poly alylates or copolymers of acrylic acid with maleic acid or maleic anhydride Contain amount of 0.5 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 Norsohas, Degapas ( R ) from Degussa; Suitable copolymers of polyacrylic acid and maleic acid are, for example, Sokalan ( R ) CP 5, SP 7 from BASF, Acrysol ( R ) QR 1014 from Norsohaas, Alcosperse ( R ) 175 from Alco.
  • phosphates can also be present, but the dishwashing detergents are preferably free of phosphate-containing builder components.
  • 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 mechanical mechanics.
  • a 'ilem Weg ⁇ ionic surfactants; the dishwashing agents 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 having 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, are particularly suitable as nonionic surfactants.
  • water-soluble nonionic surfactants it is also important that the water is not or not completely water-soluble glycol ethers with 2 to 7 ethylene glycol ether residues in the molecule, preferably these are used in combination with water-soluble nonionic surfactants.
  • 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, carbon atoms, G represents a glycose 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 di- and honorally 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 di- and honorally 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.
  • Alkali carbonates and hydrogen carbonates used are the sodium carbonates and hydrogen carbonates, which are contained in the amounts already mentioned above.
  • the use of the highly alkaline metasilicates as alkali carriers is preferably avoided.
  • 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.
  • sodium perborate tetrahydrate (NaBÜ2 • H2O2 • 3H2O) has sodium perborate monohydrate (NaBÜ2 • H2O2) and peroxycarbonate (a2CÜ3 • 1.5 H2O2) special meaning.
  • Further bleaching agents which can be used are, for example, persic acid 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.
  • the addition of small amounts of known bleach stabilizers such as borates or metaborates and metasilicates and magnesium salts, for example magnesium sulfate, can be expedient.
  • 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 (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 of active chlorine-releasing agents such as e.g. Trichloroisocyanuric acid.
  • Enzymes such as proteases, amylases, lipases or cellulases can be used to better remove protein or starch-containing food residues, for example proteases such as BLAP ( R ) 140 from Henkel, 0ptimase ( R ) -M-440, 0ptimase ( R ) -M-330 , 0pticlean ( R ) -M-375, Opti- clean ( R ) -M-250 from Solvay Enzymes, Maxacal ( R ) CX 450,000, Maxapem ( R ) from Ibis, Savinase ( R ) 4.0 T, 6 , 0 T, 8.0 T from Novo or Experase ( R ) T from Ibis; Amylases such as Termamyl ( R ) 60 T, 90 T from Novo, Amylase-L ⁇ ( R ) from Solvay Enzymes or Maxamyl ( R ) P 5000, CXT 5000 or CX
  • 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.
  • optional silver protection agents as described in the older German patent application P 43 15 397.6, in particular water-soluble Mn (II) salts, can be used in an amount of up to 2% by weight, preferably 0.1 to 0.5% by weight.
  • the dishwashing detergents according to the invention are preferably in the form of pulverulent, granular or tablet-shaped 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 copolymers used according to the invention to be used in the form of a compound as an additive component to other granular constituents of the dishwashing detergent.
  • the procedure is preferably such that all the constituents are mixed with one another in a mixer and the mixture is produced by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressing pressures in the range from 200 • 10 ⁇ Pa to 1 500 • 10 ⁇ Pa pressed.
  • a tablet produced in this way preferably has a weight of 15 g to 40 g, in particular 20 g to 30 g, with one pass ⁇ knife from 35 mm to 40 mm.
  • the manufacture 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 stage of the process, the builder components are used with at least one portion liquid mixing com- 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 in such a way that the decomposition of the sodium bicarbonate into 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 granule formulation.
  • Low drying temperatures not only counteract the sodium bicarbonate disintegration, but also increase the solubility of the granulated cleaning agent 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.
  • a supply air temperature of approximately 80 ° C. is preferred during drying.
  • the granules themselves should not be heated to temperatures above about 60 ° C.
  • the builder is generally mixed with at least one further component of the dishwashing detergent with the liquid components.
  • a precursor comes into consideration, in which the builder component in admixture with perborate is acted upon by the liquid nonionic surfactants and / or the solution of the fragrances and intimately mixed.
  • the remaining components are then added, and the entire mixture is worked through and homogenized in the mixing device.
  • additional amounts of liquid in particular the use of additional water, is generally not necessary here.
  • the accumulated material The mixture is then in the form of a free-flowing, dust-free powder of the desired high bulk densities, in the range from 800 to 900 g / l.
  • the pre-granules are then mixed with the 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 from 1 to 5 minutes.
  • Granular dishwashing detergents of the following composition were produced.
  • Agent A contained 10% by weight of the copolymer which, according to the disclosure of the older German patent application P 42 21 381.9, consists of 50% by weight of acrylic acid, 33% by weight of sucrose and 17% by weight of 2-methallylsulfonic acid was produced and then completely neutralized.
  • Comparative Example B contained 10% by weight of an acrylate maleate sold by BASF under the trade name Sokalan ( R ) CP5.
  • the agent A according to the invention had a superior cleaning performance compared to the agent B not according to the invention, especially when removing the starch, grease stick and oatmeal stains, and showed one with the other stains - apart from the tea stain comparable cleaning performance.
  • 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 MnSÜ4, it showed superior properties, especially with regard to the prevention of tarnishing of silverware.

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

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 synthesized from the monomers of a monoethylenically unsaturated C3-C8 carboxylic acid, a 2-alkylallylsulphonic acid or 2-arylallylsulphonic acid and a carbohydrate, preferably saccharose.

Description

GescMrrspulmlttel mit biologisch abbaubarer Builderkomponente Dishwashing rinse with biodegradable builder component
Die Erfindung betrifft niederalkalische Geschirrspülmittel für die maschinelle 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 Reinigung von Geschirr enthalten neben Bleichmitteln auf Sauerstoff¬ basis, oberflächenaktiven Stoffen und Enzymen eine Kombination aus wasserlöslichen Buildern, die aus Komplexbildnern, z.B. Citrat, aus Alkaliträgern, z.B. Soda, Hydrogeπcarbonat oder Disilikat, und aus Dispergiermitteln wie z.B. Polycarboxylaten besteht. Weitere mögli¬ che Builderko ponenten sind Orgaπophosphonsäuren, Aminocarbonsäuren oder kristalline Schichtsilikate; auf die früher verwendeten Phos¬ phate, z.B. Pentanatriu tripolyphi-sphat, wird heute aus ökologischen Gründen weitgehend verzichtet.The latest generation of low-alkaline agents for the automatic cleaning of dishes contain not only bleaching agents based on oxygen, surface-active substances and enzymes, but also a combination of water-soluble builders which are derived from complexing agents, e.g. Citrate, from alkali carriers, e.g. Soda, hydrogecarbonate or disilicate, and from dispersants such as e.g. Polycarboxylates exist. Other possible builder components are organophosphonic acids, aminocarboxylic acids or crystalline phyllosilicates; to the phosphates previously used, e.g. Pentanatriu tripolyphi-sphat is largely avoided today for ecological reasons.
Die in den heutigen Geschirrspül itteln verwendeten Polycarboxylate, z.B. Maleinat/Acrylat-Copoly ere, verhindern die Ablagerung von Kalkbelägen bei zu hoher Restwasserhärte im Reinigungs- und Klar- spülgang; bei hoher Salzbelastung der Spülflotte verbessern sie außerdem den Klarspüleffekt.The polycarboxylates used in today's dishwashing detergents, e.g. maleate / acrylate copolymers, prevent limescale deposits from accumulating when the residual water hardness is too high in cleaning and clearing agents. rinse cycle; if the rinsing liquor has a high salt load, they also improve the rinse aid effect.
Als Nachteil dieser Polycarboxylate muß jedoch angesehen werden, daß sie schwer biologisch abbaubar sind. Es besteht daher Bedarf an ma¬ schinellen Geschirrspülmitteln, die biologisch abbaubare Builderkom- ponenten enthalten, gleichzeitig aber das gewohnte Leistungsspektrum von modernen Geschirrspülmitteln zeigen. Viele biologisch gut abbau¬ bare Builderkomponenten wie z.B. oxidierte Stärke oder Polyaspara- ginsäure sind zwar gute Dispergatoren für ausgefallenes fcalciumcar- bonat, jedoch schlechte Komplexbildner für Wasserhärte.A disadvantage of these polycarboxylates, however, must be considered 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 show the usual performance spectrum of modern dishwashing detergents. Many biodegradable builder components such as Oxidized starch or polyaspartic acid are good dispersants for unusual calcium carbonate, but are poor complexing agents for water hardness.
Überraschenderweise wurde nun gefunden, daß sich bestimmte aus we¬ nigstens drei Einzelbausteinen aufgebaute, biologisch gut abbaubare Copolymere hervorragend als Builderkomponenten in maschinellen Ge¬ schirrspülmitteln eignen.Surprisingly, it has now been found that certain copolymers which are built up from at least three individual building blocks and are readily biodegradable are eminently suitable as builder components in machine dishwashing detergents.
Gegenstand der Erfindung ist ein niederalkalisches Mittel zum ma¬ schinellen Reinigen von Geschirr, dessen 1 Gew.-%ige wäßrige Lösung einen pH-Wert von 8 bis 11,5 vorzugsweise 9 bis 10,5 aufweist, ent¬ haltend wasserlösliche Builderkomponenten und Bleichmittel auf Sau¬ erstoff-Basis, dadurch gekennzeichnet, daß es als wasserlösliche Builderkomponente ein Copolymer, das wenigstens aus den Monomeren einer onoethylenisch ungesättigten C3-C8~Carbonsäure, einer 2-A1- kylallylsulfonsäure oder 2-Arylallylsulfonsäure und einem Kohlenhy¬ drat aufgebaut ist, enthält.The invention relates to a low-alkaline agent for mechanical 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 Oxygen base, characterized in that it contains, as a water-soluble builder component, a copolymer which is composed at least of the monomers of an onoethylenically unsaturated C3-C8 ~ carboxylic acid, a 2-A1-alkylallylsulfonic acid or 2-arylallylsulfonic acid and a carbohydrate .
Zu den erfindungsgemäßen Geschirrspülmitteln zählen auch diejenigen, in denen die Copoly eren teilweise oder vollständig durch die Salze der Copolymeren, also solche Copolymeren, in denen die Carboxylgrup- pen teilweise oder vollständig zu Carboxylatgruppen umgesetzt wur¬ den, ersetzt sind.The dishwashing detergents according to the invention also include those in which the copolymers are partially or wholly by the salts of the copolymers, that is to say those copolymers in which the carboxyl group were partially or completely converted to carboxylate groups, are replaced.
Die erfindungsgemäß eingesetzten Copolymeren enthalten im einfach¬ sten Falle zwei Carbonsäuren und/oder deren Salze sowie ein Kohlen¬ hydrat als Monomere. Das erste saure Monomer bzw. dessen Salz leitet sich von einer onoethylenisch ungesättigten C3-Cg-Monocarbonsäure und vorzugsweise von einer C3-C4-Monocarbonsäure, insbesondere von der (Meth)-acrylsäure ab. Das zweite saure Monomer bzw. dessen Salz ist ein Derivat einer Allylsulfonsäure, die in 2-Stellung mit einem Alkylrest, vorzugsweise mit einem Ci-Czj-Alkylrest, oder einem aro¬ matischen Rest, der sich vorzugsweise von Benzol oder Benzolderi¬ vaten ableitet, substituiert ist. Desweiteren ist der Einbau weite¬ rer Monomer-Einheiten in das Copoly er nicht ausgeschlossen. Bevor¬ zugte Copoly ere enthalten dabei 40 bis 60 Gew.-%, insbesondere 45 bis 55 Gew.-% (Meth)-acrylsäure bzw. (Meth)-acrylat mit besonderer Bevorzugung von Acrylsäure bzw. Acrylat, 10 bis 30 Gew.-%, vorzugs¬ weise 15 bis 25 Gew.-% Methallylsulfonsäure bzw. Methallylsulfonat, wobei Methallylsulfonsäure bzw. Methallylsulfonat teilweise auch durch einen durch Anlagerung von 1 bis 10 Ethylenoxid-Einheiten an Methacrylsäure gebildeten Methacrylsäurepolyethylenglykolester er¬ setzt sein können, wobei dann das Gewichtsverhältnis zwischen Meth- acrylsäurepolyethylenglykolester und Methallylsulfonsäure bzw. -sul- fonat 1 : 10 bis 10 : 1 beträgt, und 15 bis 40 Gew.-%, vorzugsweise 20 bis 40 Gew.-% eines Kohlenhydrats. Dieses Kohlenhydrat kann bei¬ spielsweise ein Mono-, Di-, Oligo- oder Polysaccharid sein, wobei Mono-, Di- oder Oligo-saccharide bevorzugt sind. Durch den Einbau dieses Kohlenhydrats werden Sollbruchstellen in dem Polymer einge¬ baut, die für die Abbaubarkeit des Polymers verantwortlich sind. Insbesondere ist als Kohlenhydrat Saccharose bevorzugt. Die erfin¬ dungsgemäß eingesetzten Copolymeren lassen sich nach jedem der be¬ kannten und üblichen Verfahren herstellen. Dabei werden insbesondere die onomeren Säuren mit dem Kohlenhydrat umgesetzt, woraufhin im Anschluß gegebenenfalls eine Neutralisation der Säuren zu vorzugsweise ihren Alkalisalzen, wie den Natrium- oder Kaliumsalzen, oder Ammoniumsalzen oder Alkanolaminsalzen, wie dem Monoethanolaminsalz oder dem Triethanolaminsalz, durchgeführt wird.In the simplest case, the copolymers used according to the invention contain two carboxylic acids and / or their salts and a carbohydrate as monomers. The first acidic monomer or its salt is derived from an onoethylenically unsaturated C3-Cg-monocarboxylic acid and preferably from a C3-C4-monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt is a derivative of an allylsulfonic acid which, in the 2-position, has an alkyl radical, preferably a C 1 -C 6 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives. is substituted. Furthermore, the incorporation of further monomer units into the copoly is not excluded. Preferred copolymers contain 40 to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate with particular preference for acrylic acid or acrylate, 10 to 30% by weight. %, preferably 15 to 25% by weight of methallylsulfonic acid or methallylsulfonate, where methallylsulfonic acid or methallylsulfonate can also be partially replaced by a methacrylic acid-polyethylene glycol ester formed by addition of 1 to 10 ethylene oxide units on methacrylic acid, the weight ratio then being between Methacrylic acid polyethylene glycol ester and methallylsulfonic acid or sulfonate is 1:10 to 10: 1, and 15 to 40% by weight, preferably 20 to 40% by weight, of a carbohydrate. This carbohydrate can, for example, be a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. By incorporating this carbohydrate, predetermined breaking points are built into the polymer, which are responsible for the degradability of the polymer. In particular, sucrose is preferred as the carbohydrate. The copolymers used according to the invention can be prepared by any of the known and customary processes. In particular, the monomeric acids are reacted with the carbohydrate, whereupon the acids are then optionally neutralized to give preferably their alkali metal salts, such as the sodium or potassium salts, or ammonium salts or alkanolamine salts, such as the monoethanolamine salt or the triethanolamine salt.
Analog zu den bekannten üblichen (co-)polymeren Polycarbonsäuren bzw. Polycarboxylaten wie den homo- oder copolymeren Acrylsäuren bzw. Acrylaten sind auch solche Copoly ere bevorzugt, die entweder vollständig oder zumindest partiell, insbesondere zu mehr als 50 %, bezogen auf die vorhandenen Carboxylgruppen, neutralisiert sind. Besonders bevorzugt ist dabei ein vollständig neutralisiertes Co- polymer, das also aus den Salzen der monomeren Säuren, insbesondere den Natrium- oder Kaliumsalzen der monomeren Säuren, und einem Koh¬ lenhydrat besteht. Die Copolymeren weisen im allgemeinen eine rela¬ tive Molekülmasse zwischen 1000 und 200000, vorzugsweise zwischen 2000 und 50000 und insbesondere zwischen 3000 und 10000 auf. Sie werden vorzugsweise in pulverför iger, sprühgetrockneter Form ein¬ gesetzt. Insbesondere bevorzugte Copolymere werden nach einem Ver¬ fahren hergestellt, das in der älteren deutschen Patentanmeldung P 4221 381.9 beschrieben ist.Analogous to the known conventional (co) polymeric polycarboxylic acids or polycarboxylates such as the homo- or copolymeric acrylic acids or acrylates, those copolymers are also preferred which are either completely or at least partially, in particular more than 50%, based on the carboxyl groups present are neutralized. A completely neutralized copolymer is particularly preferred, ie it consists of the salts of the monomeric acids, in particular the sodium or potassium salts of the monomeric acids, and a carbohydrate. 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 powdery, spray-dried form. Particularly preferred copolymers are produced by a process which is described in the earlier German patent application P 4221 381.9.
Bevorzugte erfindungsgemäße Geschirrspülmittel enthalten das Copoly- mer 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 Sauerstoffbasis, insbesondere Alkaliperborat und/ oder Percarbonat, und nichtionische Tenside in einer Menge von maxi¬ mal 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, a bleaching agent based on oxygen, in particular alkali perborate and / or percarbonate, and nonionic surfactants in an amount of a maximum of 5% by weight, preferably a maximum of 2% by weight, the agents being free from anionic, cationic or amphoteric surfactants.
In einer bevorzugten Ausführungsform sind als Alkaliträger Alkali- carbonate und/oder -hydrogencarbonate, insbesondere die Natriumsal- ze, in einer Menge von bis zu 60 Gew.-%, vorzugsweise 5 bis 50 Gew.-%, enthalten.In a preferred embodiment, alkali carbonates and / or bicarbonates, in particular the sodium salts, are used as alkali carriers. ze, in an amount of up to 60 wt .-%, preferably 5 to 50 wt .-%, contain.
Die erfindungsgemäßen Geschirrspülmittel können weitere wasserlös¬ liche Builderkomponenten, wie z.B. synthetische Polymere, unter denen die Salze von Polymerisationsprodukten ungesättigter Carbon¬ säuren verstanden werden und zu denen beispielsweise Polyacrylate, Polymethacrylate, Poly aleinate 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 Norso- haas, Degapas(R) der Firma Degussa; geeignete Copolymere aus Poly- acrylsäure und Maleinsäure sind z.B. Sokalan(R) CP 5, SP 7 der Firma BASF, Acrysol(R) QR 1014 der Firma Norsohaas, Alcosperse(R) 175 der Firma Alco. Prinzipiell können auch Phosphate enthalten sein, vor¬ zugsweise sind die Geschirrspülmittel jedoch frei von phosphathal- tigen Builderkomponenten.The dishwashing detergents according to the invention can comprise 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, poly alylates or copolymers of acrylic acid with maleic acid or maleic anhydride Contain amount of 0.5 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 Norsohas, Degapas ( R ) from Degussa; Suitable copolymers of polyacrylic acid and maleic acid are, for example, Sokalan ( R ) CP 5, SP 7 from BASF, Acrysol ( R ) QR 1014 from Norsohaas, Alcosperse ( R ) 175 from Alco. In principle, phosphates can also be present, but the dishwashing detergents are preferably free of phosphate-containing builder components.
Bei den in den erfindungsgemäßen Mitteln einsetzbaren Tensiden ist deren Schaumverhalten ausschlaggebend. Wegen der Maschiπenmechanik werden schaumarme Verbindungen bevorzugt. Dies sind vor a'ilem nicht¬ ionische Tenside; die erfindungsgemäßen Geschirrspülmitte ) sind des¬ halb vorzugsweise frei von anionischen, kationischen oder amphoteren Tensiden. Der Gehalt an nichtionischen Tensiden beträgt maximal 5 Gew.-%, vorzugsweise maximal 2 Gew.-%. Als nichtioniscne Tenside sind vor allem Anlagerungsprodukte von 1 bis 20 Mol Ethylenoxid (E0) und/oder 1 bis 20 Mol Propylenoxid (PO) an 1 Mol einer aliphatisehen Verbindung mit 10 bis 20 Kohlenstoffatomen aus der Gruppe der Alko¬ hole, Carbonsäuren, Fettamine, Carbonsäureamide und Alkansulfona ide von Interesse. Wichtig sind neben den wasserlöslichen nichtionischen Tensiden aber auch nicht bzw. nicht vollständig wasserlösliche Poly- glykolether mit 2 bis 7 Ethylenglykoletherresten im Molekül, vor¬ zugsweise werden diese in Kombination mit wasserlöslichen nichtioni¬ schen 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 ali- phatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen be¬ deutet, G für eine Glykoseeinheit mit 5 oder 6 C-Atomen steht und der Oligomerisierungsgrad x zwischen 1 und 10 liegt.In the case of the surfactants which can be used in the agents according to the invention, their foaming behavior is decisive. Low-foam connections are preferred because of the mechanical mechanics. These are, a 'ilem nicht¬ ionic surfactants; the dishwashing agents 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 having 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, are particularly suitable as nonionic surfactants. Carboxamides and alkanesulfona ide of interest. In addition to the water-soluble nonionic surfactants, it is also important that the water is not or not completely water-soluble glycol ethers with 2 to 7 ethylene glycol ether residues in the molecule, preferably these are used in combination with water-soluble nonionic surfactants. 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, carbon atoms, G represents a glycose unit with 5 or 6 carbon atoms and the degree of oligomerization x is between 1 and 10.
Bevorzugte erfindungsgemäße Geschirrspülmittel enthalten außerdem Komplexbildner aus der Gruppe der di- und ehrfunktionellen organi¬ schen 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 di- and honorally 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 Geschirrspülmit¬ teln eingesetzten Alkalisierungsmitteln zählen Alkalicarbonate, -hydrogencarbonate und Alkalisilikate mit einem Molverhältnis Siθ2/M2θ (M = Alkaliatom) von 1,5 : 1 bis 2,5 : 1. Die in den er¬ findungsgemäßen Mitteln bevorzugt eingesetzten Alkalicarbonate und -hydrogencarbonate sind die Natriumcarbonate und -hydrogencarbonate, die in den bereits oben genannten Mengen enthalten sind. Auf den Einsatz der hochalkalischen Metasilikate als Alkaliträger wird vor¬ zugsweise 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 Geschirrspül¬ mittel, eingesetzt.The usual alkalizing agents used in low-alkaline machine dishwashing agents include alkali carbonates, bicarbonates and alkali silicates with a molar ratio SiO 2 / M 2 O (M = alkali atom) of 1.5: 1 to 2.5: 1. The agents preferred according to the invention Alkali carbonates and hydrogen carbonates used are the sodium carbonates and hydrogen carbonates, 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 Verbin¬ dungen haben das Natriumperborat-tetrahydrat (NaBÜ2 H2O2 • 3H2O) das Natriumperborat-monohydrat (NaBÜ2 H2O2) und das Peroxycarbonat ( a2CÜ3 1,5 H2O2) besondere Bedeutung. Weitere brauchbare Bleich¬ mittel sind z.B. persaure Salze organischer Säuren, wie Perbenzoate oder Salze der Diperdodecandisäure. Vorzugsweise sind 0,5 bis 20 Gew.-%, besonders bevorzugt 5 bis 15 Gew.-%, eines Bleichmittels auf Sauerstoffbasis, insbesondere Alkaliperborate und/oder -percarbonate enthalten. Überdies kann der Zusatz geringer Mengen bekannter Bleichmittelstabilisatoren wie Boraten bzw. Metaboraten und Metasi- likaten sowie Magnesiumsalzen, z.B. Magnesiumsulfat zweckdienlich sein.Among the compounds used as oxygen-based bleaches, sodium perborate tetrahydrate (NaBÜ2 H2O2 • 3H2O) has sodium perborate monohydrate (NaBÜ2 H2O2) and peroxycarbonate (a2CÜ3 1.5 H2O2) special meaning. Further bleaching agents which can be used are, for example, persic acid 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, can be expedient.
Geeignete Bleichaktivatoren für diese Oxidationsmittel sind insbe¬ sondere N-Acyl- und O-Acyl-Verbindungen, vorzugsweise tetraacylierte Diamine wie N,N,N' ,N'-Tetraacetylethylendiamin (TAED). Die erfin¬ dungsgemäßen 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 aktivchlorab- spaltenden 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 (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 of active chlorine-releasing agents such as e.g. Trichloroisocyanuric acid.
Zur besseren Ablösung eiweiß- oder stärkehaltiger Speisereste können Enzyme wie Proteasen, Amylasen, Lipasen oder Cellulasen eingesetzt werden, beispielsweise Proteasen wie BLAP(R) 140 der Firma Henkel, 0ptimase(R) -M-440, 0ptimase(R) -M-330, 0pticlean(R) -M-375, Opti- clean(R) -M-250 der Firma Solvay Enzymes, Maxacal(R) CX 450.000, Maxapem(R) der Firma Ibis, Savinase(R) 4,0 T, 6,0 T, 8,0 T der Firma Novo oder Experase(R) T der Firma Ibis; Amylasen wie Termamyl(R) 60 T, 90 T der Firma Novo, Amylase-Lτ(R) der Firma Solvay Enzymes oder Maxamyl(R) P 5000, CXT 5000 oder CXT 2900 der Firma Ibis; Lipasen wie Lipolase(R) 30 T der Firma Novo; Cellulasen wie Celluzym(R) 0,7 T der Firma Novo Nordisk. Enzyme sind in den erfindungsgemäßen Mit¬ teln in einer Menge von 0,1 bis 5 Gew.-%, vorzugsweise 0,5 bis 2 Gew.-%, bezogen auf das gesamte Geschirrspülmittel, enthalten. Zur Verhinderung des Anlaufens von Silberbesteck können fakultativ Silberschutzmittel, 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.Enzymes such as proteases, amylases, lipases or cellulases can be used to better remove protein or starch-containing food residues, for example proteases such as BLAP ( R ) 140 from Henkel, 0ptimase ( R ) -M-440, 0ptimase ( R ) -M-330 , 0pticlean ( R ) -M-375, Opti- clean ( R ) -M-250 from Solvay Enzymes, Maxacal ( R ) CX 450,000, Maxapem ( R ) from Ibis, Savinase ( R ) 4.0 T, 6 , 0 T, 8.0 T from Novo or Experase ( R ) T from Ibis; Amylases such as Termamyl ( R ) 60 T, 90 T from Novo, Amylase-Lτ ( 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. 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, can be used in an amount of up to 2% by weight, preferably 0.1 to 0.5% by weight.
Die erfindungsgemäßen Geschirrspülmittel liegen vorzugsweise als pul erförmige, granuläre oder tablettenför ige Präparate vor, die in an sich üblicher Weise, beispielsweise durch Mischen, Granulieren, Walzenkompaktieren und/oder durch Sprühtrocknung hergestellt werden können. Dabei ist es auch möglich, daß die erfindungsgemäß einge¬ setzten Copolymeren 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 pulverulent, granular or tablet-shaped 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 copolymers used according to the invention to be used in the form of a compound as an additive component to other granular constituents of the dishwashing detergent.
Zur Herstellung von erfindungsgemäßen Reinigungsmitteln in Tablet¬ tenform geht man vorzugsweise derart vor, daß man alle Bestandteile in einem Mischer miteinander vermischt und das Gemisch mittels her¬ kömmlicher Tablettenpressen, 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 normalerweise über 150 N. Vor¬ zugsweise weist eine derart hergestellte Tablette ein Gewicht von 15 g bis 40 g, insbesondere von 20 g bis 30 g auf, bei einem Durch¬ messer von 35 mm bis 40 mm.For the preparation of cleaning agents according to the invention in tablet form, the procedure is preferably such that all the constituents are mixed with one another in a mixer and the mixture is produced by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressing pressures in the range from 200 • 10 ^ Pa to 1 500 10 ^ Pa pressed. In this way, break-resistant tablets are obtained, which nevertheless dissolve sufficiently quickly under application conditions, with bending strengths of normally more than 150 N. A tablet produced in this way preferably has a weight of 15 g to 40 g, in particular 20 g to 30 g, with one pass ¬ knife from 35 mm to 40 mm.
Die Herstellung der Maschinengeschirrspül ittel in Form von nicht staubenden, 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 Buil- der-Komponenten mit wenigstens einem Anteil flüssiger Mischungskom- ponenten unter Erhöhung der Schüttdichte dieses Vorgemisches ver¬ mischt und nachfolgend - gewünschtenfalls nach einer Zwischentrock¬ nung - die weiteren Bestandteile des Maschinengeschirrspül ittels mit dem so gewonnenen Vorgemisch vereinigt.The manufacture 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 stage of the process, the builder components are used with at least one portion liquid mixing com- 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 be¬ einflußt, muß die Zwischen-Trocknung so durchgeführt werden, daß der Zerfall des Natriu bicarbonats zu Natriumcarbonat möglichst gering (oder zumindest möglichst konstant) ist. Ein zusätzlich durch die Trocknung entstehender Natriumcarbonat-Anteil müßte nämlich bei der Formulierung der Granulat-Rezeptur berücksichtigt werden. Niedrige Trocknungstemperaturen wirken dabei nicht nur dem Natriumbicarbo- nat-Zerfall entgegen, sondern erhöhen auch die Lösichkeit des gra¬ nulierten 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 Zulufttemperatur 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 in such a way that the decomposition of the sodium bicarbonate into 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 granule formulation. Low drying temperatures not only counteract the sodium bicarbonate disintegration, but also increase the solubility of the granulated cleaning agent 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. A supply air temperature of approximately 80 ° C. is preferred during drying. 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 Abmischung mit wenigstens einer weiteren Komponente des Geschirrspülmittels mit den Flüssigkomponenten beaufschlagt. In Be¬ tracht kommt hier beispielsweise eine Vorstufe, in der die Builder- Komponente in Abmischung mit Perborat mit den flüssigen nichtioni¬ schen Tensiden und/oder der Lösung der Duftstoffe beaufschlagt und innig vermischt wird. Nachfolgend werden die restlichen Komponenten zugegeben und das Gesamtgemisch in der Mischvorrichtung durchgear¬ beitet und homogenisiert. Die Mitverwendung zusätzlicher Flüssig¬ keitsmengen, insbesondere also der Einsatz von zusätzlichem Wasser, ist hier in der Regel nicht erforderlich. Das angefallene Stoffge- misch 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 mixed with at least one further component of the dishwashing detergent with the liquid components. Here, for example, a precursor comes into consideration, in which the builder component in admixture with perborate is acted upon by the liquid nonionic surfactants and / or the solution of the fragrances and intimately mixed. The remaining components are then added, and the entire mixture is worked through and homogenized in the mixing device. The use of additional amounts of liquid, in particular the use of additional water, is generally not necessary here. The accumulated material The mixture is then in the form of a free-flowing, dust-free powder of the desired high bulk densities, in the range from 800 to 900 g / l.
Die Vorgranulate werden dann mit den noch fehlenden Komponenten des Geschirrspülmittels 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 Be¬ reich weniger Minuten, beispielsweise im Bereich von 1 bis 5 Minu¬ ten.The pre-granules are then mixed with the 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 from 1 to 5 minutes.
In einer besonderen Ausführungsform kann es bei der Herstellung von feinen Granulatkörnern zweckmäßig sein, durch Abpudern der Oberflä¬ che des gebildeten Granulatkorns eine weiterführende Stabilisierung und Egalisierung einzustellen. Geeignet sind hierzu insbesondere geringe Anteile an Wasserglaspulver beziehungsweise pulverförmigem Alkalicarbonat.In a particular 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 amounts 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 Abbau- barkeit konventionellen modernen Geschirrspülmitteln vor allem hin¬ sichtlich der Belagsinhibierung und des Klarspüleffektes an Gläsern und Messerklingen überlegen 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 erläutern, 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 (erfindungsgemäßes Mittel A und Vergleichsmittel B sowie erfindungs¬ gemäßes Mittel C) hergestellt.Granular dishwashing detergents of 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 Offenba¬ rung der älteren deutschen Patentanmeldung P 42 21 381.9 aus 50 Gew.-% Acrylsäure, 33 Gew.-% Saccharose und 17 Gew.-% 2-Methallyl- sulfonsäure hergestellt und anschließend vollständig neutralisiert worden war.Agent A contained 10% by weight of the copolymer which, according to the disclosure of the older German patent application P 42 21 381.9, consists of 50% by weight of acrylic acid, 33% by weight of sucrose and 17% by weight of 2-methallylsulfonic acid was produced and then completely neutralized.
Vergleichsbeispiel B enthielt 10 Gew.-% eines von der Firma BASF unter dem Handelsnamen Sokalan(R) CP5 vertriebenen Acrylat-Maleat-Comparative Example B contained 10% by weight of an acrylate maleate sold by BASF under the trade name Sokalan ( R ) CP5.
Reiniqunqsleistunq Reiniqunqsleistunq
Die Reinigungsleistung der Mittel A und B wurde in einer Geschirr¬ spülmaschine Miele G 531 (Programm Universal 65°C) bei Dosierungen von jeweils 30 g in 7,0 1 Wasser mit 16° dH im Reinigungsgang ge¬ testet (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 Miele G 531 dishwasher (Universal 65 ° C program) at doses of 30 g each in 7.0 l water at 16 ° dH in the cleaning cycle (soiling as described 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 erfindungsge¬ mäßen Mittel B insbesondere bei der Entfernung der Stärke-, Fett¬ stift- und Haferflocken-Anschmutzungen eine überlegene Reinigungs¬ leistung auf und zeigte bei den übrigen Anschmutzungen - bis auf die Tee-Anschmutzung - eine vergleichbare Reinigungsleistung.The agent A according to the invention had a superior cleaning performance compared to the agent B not according to the invention, especially when removing the starch, grease stick and oatmeal stains, and showed one with the other stains - apart from the tea stain comparable cleaning performance.
BelaqsinhibierunqBelaqsinhibierunq
Die Belagsbildung der Mittel A und B wurde in einer Geschirrspülma¬ schine Miele G 590 (Programm Universal 65°C) bei Dosierungen von je¬ weils 20 g in 7,0 1 Wasser mit 16° dH unter Zusatz von 50 g pumpba¬ rer Anschmutzungen (Gemisch aus Ketchup, Bratensoße, Senf, Kartof¬ felstärke, Eigelb, Milch, Margarine) in Anwesenheit von 3,0 ml eines handelsüblichen Klarspülers über 10 Spülgänge getestet. Der Klar¬ spüleffekt ("spotting") wurde mit einer Skala von 1 (= sehr schlech¬ ter Klarspüleffekt) bis 8 (= sehr guter Klarspüleffekt, keine Was¬ serflecken) bewertet. Die Ergebnisse der mit dem erfindungsgemäßen Mittel A und dem Vergleichsmittel B an Gläsern, Messerklingen und Porzellantellern erzielten Klarspüleffekte können der Tabelle 1 ent¬ nommen werden. Tabelle 1The formation of deposits on 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) tested in the presence of 3.0 ml of a commercial rinse aid 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 found in Table 1. Table 1
Gläser 6Glasses 6
Messerklingen 5,5Knife blades 5.5
Porzellanteller 5Porcelain plate 5
Es zeigt sich, daß das erfindungsgemäße Mittel A dem Vergleichsmit¬ tel 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 Mit¬ tel A vergleichbare Reinigungs- und Belagsinhibierungsleistungen; aufgrund der Anwesenheit von MnSÜ4 zeigte es vor allem hinsichtlich der Verhinderung des Anlaufens von Silberbesteck überlegene Eigen¬ schaften. 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 MnSÜ4, it showed superior properties, especially with regard to the prevention of tarnishing of silverware.

Claims

Patentansprüche claims
1. 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, da¬ durch gekennzeichnet, daß es als wasserlösliche Builderkompo- nente ein Copolymer, das wenigstens aus den Monomeren einer monoethylenisch ungesättigten C3-C8-Carbonsäure, einer 2-Alkyl- allylsulfonsäure oder 2-Arylallylsulfonsäure und einem Kohlenhy¬ drat aufgebaut ist, enthält.1. 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 oxygen-based bleaching agents characterized in that it contains, as a water-soluble builder component, a copolymer which is composed at least of the monomers of a monoethylenically unsaturated C3-C8 carboxylic acid, a 2-alkylallylsulfonic acid or 2-arylallylsulfonic acid and a carbohydrate.
2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß das Copo¬ lymer zu 40 bis 60 Gew.-%, vorzugsweise 45 bis 55 Gew.-%, aus (Meth)acrylsäure, vorzugsweise Acrylsäure, zu 10 bis 30 Gew.-%, vorzugsweise 15 bis 25 Gew.-%, aus Methallylsulfonsäure, wobei Methallylsulfonsäure teilweise auch durch einen durch Anlagerung von 1 bis 10 Ethylenoxideinheiten an Methacrylsäure gebildeten Methacrylsäurepolyethylenglykolester ersetzt sein kann, wobei dann das Gewichtsverhältnis zwischen Methacrylsäurepolyethylen- glykolester und Methallylsulfonsäure 1 : 10 bis 10 : 1 beträgt, und zu 15 bis 40 Gew.-%, vorzugsweise 20 bis 40 Gew.-%, aus einem Kohlenhydrat, vorzugsweise Saccharose, besteht.2. Composition according to claim 1, characterized in that the copolymer is 40 to 60 wt .-%, preferably 45 to 55 wt .-%, of (meth) acrylic acid, preferably acrylic acid, 10 to 30 wt .-% , preferably 15 to 25% by weight, of methallylsulfonic acid, where methallylsulfonic acid can also be partially replaced by a methacrylic acid polyethylene glycol ester formed by the addition of 1 to 10 ethylene oxide units to methacrylic acid, the weight ratio between methacrylic acid polyethylene glycol ester and methallylsulfonic acid then being 1:10 to 10: 1, and 15 to 40 wt .-%, preferably 20 to 40 wt .-%, consists of a carbohydrate, preferably sucrose.
3. Mittel nach Anspruch 1 und 2, 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 -per- carbonat, 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 be¬ zogen auf das gesamte Mittel, beträgt.3. Composition according to claim 1 and 2, 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 .-% %, of 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 is max. 5% by weight, preferably max. 2% by weight, based in each case on the total agent.
4. Mittel nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß es bis 60 Gew.-%, vorzugsweise 5 bis 50 Gew.-%, Alkalicarbonat und/oder -hydrogencarbonat enthält.4. Composition according to claim 1 to 3, characterized in that it contains up to 60 wt .-%, preferably 5 to 50 wt .-%, alkali carbonate and / or bicarbonate.
5. Mittel nach Anspruch 1 bis 4, dadurch gekennzeichnet, daß es Komplexbildner aus der Gruppe der di- und mehrfunktionellen or¬ ganischen Carbonsäuren bzw. deren Salzen, insbesondere Citronen- säure bzw. deren Salze, in einer Menge von 0,5 bis 60 Gew.-%, vorzugsweise 20 bis 50 Gew.-%, bezogen auf das gesamte Mittel, enthält.5. Composition according to claim 1 to 4, characterized in that there are complexing agents from the group of 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.
6. Mittel nach Anspruch 1 bis 5, dadurch gekennzeichnet, daß es bis zu 30 Gew.-%, vorzugsweise 5 bis 20 Gew.-%, bezogen auf das gesamte Mittel, Alkalisilikat mit einem Molverhältnis Siθ2/ 2θ (M = Alkaliatom) von 1,5 : 1 bis 2,5 : 1 enthält.6. Composition according to claim 1 to 5, characterized in that it is up to 30 wt .-%, preferably 5 to 20 wt .-%, based on the total agent, alkali silicate with a molar ratio Siθ2 / 2θ (M = alkali atom) of 1.5: 1 to 2.5: 1 contains.
7. Mittel nach Anspruch 1 bis 6, dadurch gekennzeichnet, daß es frei von aktivchlorabspaltenden Mitteln ist.7. Composition according to claim 1 to 6, characterized in that it is free of active chlorine-releasing agents.
8. Mittel nach Anspruch 1 bis 7, dadurch gekennzeichnet, daß es Enzyme in einer Menge von 0,1 bis 5 Gew.-%, vorzugsweise 0,5 bis 2 Gew.-%, bezogen auf das gesamte Mittel, enthält.8. Composition according to claim 1 to 7, 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.
9. Tablettenförmiges Mittel nach Anspruch 1 bis 8, dadurch gekenn¬ zeichnet, daß es durch Vermischen aller seiner Bestandteile in einem Mischer und Verpressen des Gemisches mittels einer Tablet¬ tenpresse bei Preßdrucken von 2 • 10? Pa bis 1,5 10^ Pa er¬ hältlich ist. 9. tablet-like composition according to claim 1 to 8, characterized gekenn¬ characterized in that it by mixing all of its constituents in a mixer and pressing the mixture by means of a tablet press at press pressures of 2 • 10? Pa up to 1.5 10 ^ Pa is available.
10. Pulver- oder granulatförmiges Mittel nach Anspruch 1 bis 8, da¬ durch gekennzeichnet, daß es eine Schüttdichte von 750 g/1 bis 1000 g/1 aufweist.10. Powder or granular composition according to claim 1 to 8, da¬ characterized in that it has a bulk density of 750 g / 1 to 1000 g / 1.
11. Verwendung der Mittel, nach einem der Ansprüche 1 bis 10 zum ma¬ schinellen Reinigen von Geschirr. 11. Use of the agent according to one of claims 1 to 10 for machine cleaning of dishes.
EP94918884A 1993-06-28 1994-06-20 Dishwasher agents with biodegradable builders Ceased EP0706558A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19934321429 DE4321429A1 (en) 1993-06-28 1993-06-28 Dishwashing detergent with biodegradable builder component I
DE4321429 1993-06-28
PCT/EP1994/002001 WO1995000624A1 (en) 1993-06-28 1994-06-20 Dishwasher agents with biodegradable builders

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CA (1) CA2166277A1 (en)
CZ (1) CZ344395A3 (en)
DE (1) DE4321429A1 (en)
HU (1) HUT73203A (en)
PL (1) PL312473A1 (en)
WO (1) WO1995000624A1 (en)

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DE4417919A1 (en) * 1994-05-24 1995-11-30 Henkel Kgaa Rinse aid with biodegradable polymers
DE19503116A1 (en) * 1995-02-01 1996-08-08 Basf Ag Use of water-soluble grafted natural substances as an additive for dishwashing detergents
ES2264686T3 (en) 2000-03-29 2007-01-16 National Starch And Chemical Investment Holding Corporation POLYMERS THAT INHIBIT THE FORMATION OF INCRUSTATIONS OF CALCIUM PHOSPHATE AND CALCIUM CARBONATE IN DISHWASHER APPLICATIONS.
US6521576B1 (en) 2000-09-08 2003-02-18 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Polycarboxylic acid containing three-in-one dishwashing composition
US20070015674A1 (en) 2005-06-30 2007-01-18 Xinbei Song Low phosphate automatic dishwashing detergent composition
GB0522658D0 (en) 2005-11-07 2005-12-14 Reckitt Benckiser Nv Composition
WO2008017620A1 (en) 2006-08-10 2008-02-14 Basf Se Cleaning formulation for a dish washer
DE102007006628A1 (en) 2007-02-06 2008-08-07 Henkel Ag & Co. Kgaa cleaning supplies
DE102007042907A1 (en) * 2007-09-10 2009-03-12 Henkel Ag & Co. Kgaa cleaning supplies
DE502008002614D1 (en) * 2008-06-24 2011-03-31 Cognis Ip Man Gmbh Cleaning agent containing graft copolymers

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DE4003172A1 (en) * 1990-02-03 1991-08-08 Basf Ag PFROPOPOPOLYMERISATES OF MONOSACCHARIDES, OLIGOSACCHARIDES, POLYSACCHARIDES AND MODIFIED POLYSACCHARIDES, PROCESS FOR THEIR PREPARATION AND THEIR USE
FR2663948B1 (en) * 1990-07-02 1994-06-03 Rhone Poulenc Chimie DETERGENT COMPOSITION CONTAINING A BIODEGRADABLE GRAFT POLYSACCHARIDE.

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CA2166277A1 (en) 1995-01-05
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HU9503694D0 (en) 1996-02-28
HUT73203A (en) 1996-06-28
WO1995000624A1 (en) 1995-01-05

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