DE4321429A1 - Dishwashing detergent with biodegradable builder component I - Google Patents

Description

The invention relates to alkaline dishwashing detergents for machine cleaning of dishes with a biodegradable Builder component.

The latest generation of low alkaline agents for mechanical Dishwashing items contain bleach on oxygen base, surfactants and enzymes a combination of water-soluble builders, which from complexing agents, e.g. B. citrate Alkali carriers, e.g. B. soda, hydrogen carbonate or disilicate, and from Dispersants such as. B. polycarboxylates. More possible Che builder components are organophosphonic acids, aminocarboxylic acids or crystalline layered silicates; to the previously used Phos phate, e.g. B. pentasodium tripolyphosphate, is now ecological Reasons largely waived.

The polycarboxylates used in today's dishwashing detergents, e.g. B. maleate / acrylate copolymers prevent the deposition of Limescale deposits when the residual water hardness is too high in the cleaning and clear  rinse cycle; they improve when there is a high salt load in the washing liquor also the rinse aid effect.

A disadvantage of these polycarboxylates must be seen, however, that they are difficult to biodegrade. There is therefore a need for ma rapid dishwashing detergents, the biodegradable builder com components, but at the same time the usual range of services of modern dishwashing detergents. Many biodegradable bare builder components such. B. oxidized starch or polyaspara Gic acid are good dispersants for unusual calcium car bonat, but poor complexing agent for water hardness.

Surprisingly, it has now been found that certain of we at least three individual building blocks that are easily biodegradable Copolymers are excellent as builder components in machine tools Dishwashing detergents are suitable.

The invention relates to a lower alkaline agent for ma rapid cleaning of dishes, its 1% by weight aqueous solution has a pH of 8 to 11.5, preferably 9 to 10.5 holding water-soluble builder components and bleach on sow erstoff basis, characterized in that it is water-soluble Builder component is a copolymer consisting at least of the monomers a monoethylenically unsaturated C₃-C₈ carboxylic acid, a 2-Al kylallylsulfonic acid or 2-arylallylsulfonic acid and a kohlhy is built up contains.

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  pen was partially or completely converted to carboxylate groups that are replaced.

The copolymers used according to the invention contain simple Most cases two carboxylic acids and / or their salts and a carbon hydrate as monomers. The first acidic monomer or its salt conducts yourself from a monoethylenically unsaturated C₃-C₈ monocarboxylic acid and preferably of a C₃-C₄ monocarboxylic acid, in particular of the (meth) acrylic acid. The second acidic monomer or its salt is a derivative of an allylsulfonic acid that is in the 2-position with a Alkyl radical, preferably with a C₁-C₄ alkyl radical, or an aro Matic residue, which is preferably from benzene or benzol di vaten derives, is substituted. Furthermore, the installation is wide rer monomer units in the copolymer not excluded. Before drawn copolymers contain 40 to 60% by weight, in particular 45 up 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, whereby methallylsulfonic acid or methallylsulfonate also partially by adding 1 to 10 ethylene oxide units He formed methacrylic acid polyethylene glycol ester sets can be, then the weight ratio between meth acrylic acid polyethylene glycol ester and methallylsulfonic acid or sul formate is 1:10 to 10: 1, and 15 to 40% by weight, preferably 20 to 40% by weight of a carbohydrate. This carbohydrate can help with for example, be a mono-, di-, oligo- or polysaccharide, where Mono-, di- or oligosaccharides are preferred. By installation of this carbohydrate are predetermined breaking points in the polymer builds, which are responsible for the degradability of the polymer. In particular, sucrose is preferred as the carbohydrate. The invent Copolymers used according to the invention can be after each of the be known and usual methods.  

In particular, the monomeric acids with the carbohydrate implemented, whereupon a neutralization if necessary the acids to preferably their alkali salts, such as the sodium or Potassium salts, or ammonium salts or alkanolamine salts such as that Monoethanolamine salt or the triethanolamine salt.

Analogous to the known customary (co) polymeric polycarboxylic acids or polycarboxylates such as the homo- or copolymeric acrylic acids or acrylates are also preferred copolymers which either completely or at least partially, in particular more than 50%, based on the carboxyl groups present, are neutralized. A completely neutralized Co is particularly preferred polymer, that is, from the salts of the monomeric acids, in particular the sodium or potassium salts of the monomeric acids, and a Koh lenhydrate exists. The copolymers generally have a rela tive molecular weight between 1000 and 200,000, preferably between 2000 and 50,000 and in particular between 3000 and 10,000. she are preferably in powdered, spray-dried form set. Particularly preferred copolymers are according to a Ver drive manufactured that in the older German patent application P 42 21 381.9 is described.

Preferred dishwashing detergents according to the invention contain the copoly mer in amounts of 0.5 to 30% by weight, preferably 2 to 20% by weight, further 0.5 to 20% by weight, preferably 5 to 15% by weight, of one Oxygen-based bleaching agents, in particular alkali perborate and / or percarbonate, and nonionic surfactants in an amount of maxi times 5 wt .-%, preferably a maximum of 2 wt .-%, the agents free of anionic, cationic or amphoteric surfactants.

In a preferred embodiment, the alkali carriers are alkali carbonates and / or hydrogen carbonates, especially the sodium salt  ze, in an amount of up to 60 wt .-%, preferably 5 to 50 % By weight.

The dishwashing detergents according to the invention can be further water-soluble Liche builder components such. B. synthetic polymers, under which are the salts of polymerization products of unsaturated carbon acids are understood and to which, for example, polyacrylates, Polymethacrylates, polymaleinates or copolymers of acrylic acid with Maleic acid or maleic anhydride belong in an amount of 0.5 Contain up to 30 wt .-%, preferably 2 to 20 wt .-%. Suitable Polyacrylates are e.g. B. Alcosperse® 102, 104, 106, 404, 406 of Alco, Acrysole® A N1, LMW 45 N, LMW 10 N from Norso haas, Degapas® from Degussa; suitable copolymers of poly acrylic acid and maleic acid are e.g. B. Sokalan® CP 5, SP 7 from the company BASF, Acrysol® QR 1014 from Norsohaas, Alcosperse® 175 from Alco company. In principle, phosphates can also be present however, the dishwashing detergents are preferably free from phosphate builder components.

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 non-ionic 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, carboxamides are the main nonionic surfactants and alkanesulfonamides of interest. In addition to the water-soluble nonionic surfactants, non-fully or not completely water-soluble polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule are also important, preferably in combination with water-soluble nonionic surfactants. In addition, alkyl polyglycosides of the general formula RO- (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 for a glycose unit is 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 multifunctional organi 's carboxylic acids or their salts, e.g. B. 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.

To the usual in lower alkaline automatic dishwashing Alkalizing agents used include alkali carbonates, -hydrogen carbonates and alkali silicates with a molar ratio SiO₂ / M₂O (M = alkali atom) from 1.5: 1 to 2.5: 1. The in which he Alkali carbonates and agents preferably used according to the invention bicarbonates are sodium carbonates and bicarbonates, which are contained in the amounts already mentioned. On the The use of highly alkaline metasilicates as alkali carriers is planned preferably waived. Instead of the metasilicates are preferred Alkali silicates, preferably sodium silicates with a molar ratio SiO₂ / Na₂O from 1.5: 1 to 2.5: 1, in amounts of up to 30% by weight, preferably 5 to 20 wt .-%, based on the total dishwashing medium, used.

Among the compounds used as oxygen-based bleach dung have sodium perborate tetrahydrate (NaBO₂ · H₂O₂ · 3H₂O) the sodium perborate monohydrate (NaBO₂ · H₂O₂) and the peroxycarbonate  (Na₂CO₃ · 1.5 H₂O₂) special meaning. More useful bleach means are z. B. peracidic salts of organic acids, such as perbenzoates or salts of diperdodecanedioic acid. Preferably 0.5 to 20 % By weight, particularly preferably 5 to 15% by weight, of a bleaching agent Oxygen base, especially alkali perborates and / or percarbonates contain. In addition, the addition of small amounts can be known Bleach stabilizers such as borates or metaborates and metasi Liquates and magnesium salts, e.g. B. Magnesium sulfate useful his.

Suitable bleach activators for these oxidizing agents are in particular special N-acyl and O-acyl compounds, preferably tetraacylated Diamines such as N, N, N ′, N′-tetraacetylethylenediamine (TAED). The invent 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 splitting agents such. B. trichloroisocyanuric acid.

For better detachment of protein or starchy food residues Enzymes such as proteases, amylases, lipases or cellulases are used proteases such as BLAP® 140 from Henkel, Optimase® -M-440, Optimase® -M-330, Opticlean® -M-375, Opti clean® -M-250 from Solvay Enzymes, Maxacal® CX 450,000, Maxapem® from the company Ibis, Savinase® 4.0 T, 6.0 T, 8.0 T from the company Novo or Experase® T from the company Ibis; Amylases like Termamyl® 60 T, 90 T from Novo, Amylase-LT® from Solvay Enzymes or Maxamyl® P 5000, CXT 5000 or CXT 2900 from Ibis; Lipases such as Lipolase® 30 T from Novo; Cellulases such as Celluzym® 0.7 T from Novo Nordisk. Enzymes are in 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 silver cutlery can be optional Silver protection agents, as in the older German patent application P 43 15 397.6 are described, in particular water-soluble Mn (II) - salts, 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 powdery, granular or tablet-like preparations, which in in a conventional manner, for example by mixing, granulating, Roll compacting and / or by spray drying can.

For the production of cleaning agents according to the invention in tablets tenform is preferably carried out in such a way that all components mixed together in a mixer and the mixture by means of conventional tablet presses, for example eccentric presses or Rotary presses, with pressures in the range of 200 · 10⁵ Pa to 1500 · 10⁵ Pa pressed. You get unbreakable and so easily nevertheless sufficiently quickly soluble under application conditions Tablets with flexural strengths usually above 150 N. Vor preferably a tablet produced in this way has a weight of 15 g to 40 g, in particular from 20 g to 30 g, in one go knife from 35 mm to 40 mm.

Production of dishwasher detergents in the form of not dusty, storage-stable, free-flowing powders and / or granules with high bulk densities in the range of 800 to 900 g / l by the fact that the Buil the components with at least a portion of liquid mixing comm components while increasing the bulk density of this premix mixes and then - if necessary after an intermediate drying - the other components of the dishwasher detergent combined with the premix obtained in this way.  

Since the alkali carbonate content strongly affects the alkalinity of the product influences, the intermediate drying must be carried out so that the Disintegration of the sodium bicarbonate to sodium carbonate as low as possible (or at least as constant as possible). An additional through the Drying sodium carbonate content should namely at Formulation of the granulate recipe are taken into account. Low Drying temperatures do not only affect sodium bicarbo nat decay, but also increase the solubility of the gra detergent in use. It is therefore advantageous when drying a supply air temperature, on the one hand to avoid bicarbonate decay should be as low as possible and On the other hand, it must be as high as necessary to produce a product with good Preserve storage properties. When drying is preferred Supply air temperature of approx. 80 ° C. The granules themselves shouldn't be on Temperatures above about 60 ° C are heated.

In the first stage of the mixing process, the builder in the Usually mixed with at least one other component of the Dishwasher detergent with the liquid components. In Be for example, here comes a preliminary stage in which the builder Component mixed with perborate with the liquid nonioni acted upon tensides and / or the solution of the fragrances and is intimately mixed. Below are the remaining components added and the entire mixture in the mixing device processed and homogenized. The use of additional liquid quantities, in particular the use of additional water, is usually not necessary here. The material incurred The mixture then lies as a free-flowing, dust-free powder desired high bulk densities in the range of 800 to 900 g / l in front.  

The pre-granules are then filled with the missing components of the Dishwashing detergent mixed into the finished product. The mixing time is in both cases in the preliminary stage of the compacting mixture under the influence of liquid components as in the subsequent final mixing with the other components in the Be rich few minutes, for example in the range of 1 to 5 minutes ten.

In a particular embodiment, it can be used in the production of fine granules may be useful by powdering the surface surface of the granules formed further stabilization and adjust equalization. Are particularly suitable for this small proportions of water glass powder or powdered Alkali carbonate.

Stand with the automatic dishwashing detergents according to the invention Products available in addition to their better biodegradation Ability to conventional modern dishwashing detergents obviously the deposit inhibition and the rinse aid effect on glasses and knife blades are superior.

The following examples are intended to illustrate the subject matter of the invention explain, but without restricting him to this.  

Examples

Granular dishwashing detergents of the following composition were used (Agent A according to the invention and comparative agent B and fiction according to means C).

Agent A contained 10 wt .-% of the copolymer, which according to Offenba tion of the older German patent application P 42 21 381.9 from 50 % By weight of acrylic acid, 33% by weight of sucrose and 17% by weight of 2-methallyl sulfonic acid produced and then completely neutralized had been.

Comparative Example B contained 10% by weight of one from BASF Acrylate maleate sold under the trade name Sokalan® CP5 Copolymers.

Cleaning performance

The cleaning performance of agents A and B was in a dish Miele G 531 dishwasher (Universal 65 ° C program) for dosing of 30 g each in 7.0 l water with 16 ° dH in the cleaning cycle tests (soiling as in "Th. Altenschöpfer, SÖFW, 98 (1972), 763-765 ": tea, milk, minced meat, pudding, fat stick, Starch, oatmeal).

The agent A according to the invention has not compared to the Invention moderate means B especially in the removal of starch, fat stick and oatmeal stains a superior cleaning performance and showed the other stains - except for the Tea soiling - a comparable cleaning performance.

Scale inhibition

The formation of deposits on agents A and B was carried out in a dishwasher Schine Miele G 590 (Universal program 65 ° C) with doses of each because 20 g in 7.0 l water with 16 ° dH with the addition of 50 g pumpba 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 clear rinsing effect ("spotting") was on a scale of 1 (= very bad ter rinse aid effect) to 8 (= very good rinse aid effect, no what stains). The results of the with the invention Means A and the comparative means B on glasses, knife blades and Porcelain plates achieved rinse effects can be found in Table 1 be taken.  

Table 1

It can be seen that agent A according to the invention is the comparative agent tel B especially with regard to the rinse aid effect on glasses and Knife blades is superior.

Agent C according to the invention showed with the Mit according to the invention tel A comparable cleaning and deposit inhibition services; due to the presence of MnSO₄ it showed mainly in terms of superior in preventing silver tarnish from tarnishing create.

Claims (11)

1. 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, as characterized by that it contains a copolymer as a water-soluble builder component, which is composed at least of the monomers of a monoethylenically unsaturated C₃-C₈ carboxylic acid, a 2-alkyl allylsulfonic acid or 2-arylallylsulfonic acid and a carbohydrate. 2. Composition according to claim 1, characterized in that the copo lymer to 40 to 60 wt .-%, preferably 45 to 55 wt .-% (Meth) acrylic acid, preferably acrylic acid, at 10 to 30% by weight, preferably 15 to 25 wt .-%, of methallylsulfonic acid, wherein Methallylsulfonic acid partly also by an addition from 1 to 10 ethylene oxide units formed on methacrylic acid Methacrylic acid polyethylene glycol ester can be replaced, wherein then the weight ratio between methacrylic acid polyethylene glycol ester and methallylsulfonic acid is 1:10 to 10: 1, and 15 to 40% by weight, preferably 20 to 40% by weight a carbohydrate, preferably sucrose. 3. Composition according to claim 1 and 2, characterized in that it is 0.5 up to 30% by weight, preferably 2 to 20% by weight of copolymer and 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 per contains carbonate 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 be drawn on the total mean. 4. Composition according to claim 1 to 3, characterized in that it is up to 60% by weight, preferably 5 to 50% by weight, of alkali carbonate and / or - contains hydrogen carbonate. 5. Composition according to claim 1 to 4, characterized in that it Complexing agents from the group of di- and multifunctional or ganic carboxylic acids or their salts, especially lemons acid or its salts, in an amount of 0.5 to 60% by weight, preferably 20 to 50% by weight, based on the total agent, contains. 6. Composition according to claim 1 to 5, characterized in that it up to 30 wt .-%, preferably 5 to 20 wt .-%, based on the total agent, alkali silicate with a molar ratio SiO₂ / M₂O (M = alkali atom) from 1.5: 1 to 2.5: 1. 7. Composition according to claim 1 to 6, characterized in that it is free of active chlorine-releasing agents. 8. Composition according to claim 1 to 7, characterized in that it Enzymes in an amount of 0.1 to 5 wt .-%, preferably 0.5 to Contains 2 wt .-%, based on the total agent. 9. tablet-like composition according to claim 1 to 8, characterized records that by mixing all of its components in a mixer and pressing the mixture using a tablet tenpress at pressures from 2 · 10⁷ Pa to 1.5 · 10⁸ Pa er is stable.   10. Powder or granular agent according to claim 1 to 8, there characterized in that it has a bulk density of 750 g / l to 1000 g / l. 11. Use of the agent according to one of claims 1 to 10 to ma Fast cleaning of dishes.