DE4321430A1 - Dishwashing detergent with biodegradable builder component II - Google Patents

Description

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

The latest generation of low alkaline agents for mechanical rei dishes, in addition to oxygen-based bleaches, a combination of surfactants and enzymes water-soluble builders, which from complexing agents, e.g. B. citrate, from Alka carriers, e.g. B. soda, hydrogen carbonate or disilicate, and from Dispersants such as. B. polycarboxylates. More possible Builder components are organophosphonic acids, aminocarboxylic acids or kri stalline layered silicates; on the phosphates previously used, e.g. B. Pentasodium tripolyphosphate is widely used today for ecological reasons waived.

The polycarboxylates used in today's dishwashing detergents, e.g. B. Maleinate / acrylate copolymers prevent the build-up of limescale deposits residual water hardness too high in the cleaning and rinse cycle; with high salt loading the rinse liquor also improve the rinse aid effect.

However, the disadvantage of this type of polycarboxylates must be seen that they are difficult to biodegrade. There is therefore a need for ma rapid dishwashing detergents, the biodegradable builder components included, but at the same time the usual range of services from  show modern dishwashing detergents. Many biodegradable Builder components such as B. are oxidized starch or polyaspartic acid good dispersants for unusual calcium carbonate, however poor complexing agents for water hardness.

US Pat. No. 3,887,480 discloses dishes and textiles agents containing a polymer consisting of 35-70 mol% maleic acid, 20-45 mole% vinyl acetate and 2-40 mole% acrylic acid. The European Patent EP 0 193 360 B1 describes zeolite-containing textile detergents, the polycarboxylate polymers built up from a C₃-C₁₀ monocarboxylic acid, a C₄-C₆ dicarboxylic acid and a nonionic spacer, e.g. B. vinyl alcohol, included. U.S. Patent No. 3,755,264 discloses Copoly mere z. B. from 85 to 99 mol% maleic anhydride and 1 to 15 mol% a mixture of acrylic acid and vinyl acetate. The euro päische Offenlegungsschrift EP 0 076 992 A1 discloses u. a. the usage from 50-95% by weight acrylic acid, 0.5 to 5% by weight vinyl acetate and up to 49% by weight of maleic acid-built polymers as incrustation inhibitors in detergents and cleaning agents.

Surprisingly, it has now been found that copolymers which are in be agreed in the above Quantities not described in publications from (meth) acrylic acid or (meth) acrylate, maleic acid or maleate and Vi nyl alcohol and / or vinyl acetate are built, excellent as a builder components in machine dishwashing detergents.

The invention relates to a low alkaline agent for mechanical Cleaning 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 based on oxygen records that it ent a copolymer as a water-soluble builder component holds, the copolymer to 60-95 wt .-%, preferably 70-90 wt .-%, from (meth) acrylic acid or (meth) acrylate, preferably acrylic acid or Acrylate, and maleic acid or maleate and to 5-40 wt .-%, preferably 10-25 % By weight, vinyl alcohol and / or vinyl acetate is built up, the Weight ratio (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 based on the acids are, and a copolymer of the salts of acids and vinyl alcohol before are moving.

The copolymers used according to the invention can be after each of the produce known and conventional methods. In particular (Meth) acrylic acid, preferably acrylic acid, and maleic acid Implemented vinyl alcohol and / or vinyl acetate, whereupon optionally neutralization of the acids to preferably theirs Alkali salts such as the sodium or potassium salts or ammonium salts or Alkanolamine salts such as the monoethanolamine salt or the Triethanolamine salt, and optionally a partial or complete Cleavage of the vinyl acetate to vinyl alcohol is carried out.

Analogous to the known (co) polymeric polycarboxylic acids or polycarboxy latates such as the homo- or copolymeric acrylic acids or acrylates are sol che copolymers preferred, either completely or at least par tiell, especially more than 50%, based on the existing car boxyl groups are neutralized. A full is particularly preferred constantly neutralized copolymer, which is made from the salts of (meth) acrylic acid, preferably acrylic acid, and maleic acid, especially the Sodium or potassium salts, and vinyl alcohol. The copolymers white generally have a relative molecular mass between 1000 and 200,000, preferably between 2000 and 50,000, and in particular between 3000 and 10,000 on. They are preferably spray dried in powder form Form used. Particularly preferred copolymers are according to a Ver drive manufactured that in the older German patent application P 43 00 772.4 is described.

Preferred dishwashing detergents according to the invention contain the copolymer in Amounts of 0.5 to 30 wt .-%, preferably 2 to 20 wt .-%, further 0.5 up to 20% by weight, preferably 5 to 15% by weight, of a bleaching agent on sow erstoffbasis, in particular alkali perborate and / or percarbonate, and non-ionic surfactants in an amount of at most 5% by weight, preferably  maximum 2% by weight, the agents being free from anionic, cationic or amphoteric surfactants.

In a preferred embodiment, alkali metal carbonates are used as alkali carriers and / or bicarbonates, especially the sodium salts, in an amount of up to 60% by weight, preferably 5 to 50% by weight.

The dishwashing detergents according to the invention can be further water-soluble Builder components such as B. synthetic polymers, including the salts be understood by polymerization products of unsaturated carboxylic acids 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 to 30 wt .-%, preferably 2 to 20 % By weight. Suitable polyacrylates are e.g. B. Alcosperse® 102, 104, 106, 404, 406 from Alco, Acrysole® A N1, LMW 45 N, LMW 10 N der Norsohaas, Degapas® from Degussa; suitable copolymers Polyacrylic acid and maleic acid are e.g. B. Sokalan® CP 5, CP 7 from the company BASF, Acrysol® QR 1014 from Norsohaas, Alcosperse® 175 from the company Alco. In principle, phosphates or zeolites can also be present, however, the dishwashing agents are preferably free of zeolites and of phosphate-containing 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 nonionic ten side; 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 (EO) and / or 1 to 20 moles of propylene oxide (P0) with 1 mole of an aliphatic compound with 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxamides and Alkane sulfonamides of interest. In addition to the water-soluble non-ionic surfactants, non-or not fully water-soluble polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule are also important; these are preferably used 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 C atoms, G for a glycosyl unit 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 com plexer from the group of di- and multifunctional organic Carboxylic acids or their salts, e.g. B. nitrilotriacetic acid, in particular but 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 detergents Alkalizing agents used include alkali carbonates, hydro gene carbonates and alkali silicates with a molar ratio SiO₂ / M₂O (M = Al kaliatom) from 1.5: 1 to 2.5: 1. In the agents according to the invention preferred alkali metal carbonates and bicarbonates are Sodium carbonates and bicarbonates in those already mentioned above Amounts are included. On the use of highly alkaline metasilicates as an alkali carrier is preferably dispensed with. 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% by weight, based on the overall dishes detergent, used.

Among the compounds used as oxygen-based bleaching agents ha ben the sodium perborate tetrahydrate (NaBO₂ · H₂O₂ 3H₂O) the sodium per borate monohydrate (NaBO₂ · H₂O₂) and peroxycarbonate (Na₂CO₃ · 1.5 H₂O₂) special meaning. Other useful bleaches are e.g. B. Persaure Salts of organic acids, such as perbenzoates or salts of Diperdodecandi acid. 0.5 to 20% by weight is preferred, particularly preferably 5 to 15% % By weight of an oxygen-based bleaching agent, in particular alkali metal contain borates and / or percarbonates. In addition, the addition can be less Amounts of known bleach stabilizers such as borates or metaborates  and metasilicates and magnesium salts, e.g. B. magnesium sulfate be.

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′-tetraacetylethylenediamine (TAED). The agents according to the invention contain such conventional bleach activators in an amount of 0.1 to 10 % By weight, preferably 1 to 5% by weight. The agents according to the invention are preferably free of active chlorine-releasing agents such. B. Trichloroisocyanuric acid.

To better remove protein or starchy food residues, En enzymes such as proteases, amylases, lipases or cellulases are used, for example proteases such as BLAP® 140 from Henkel, Optimase® -M-440, Optimase® -M-330, Opticlean® -M-375, Opticlean® -M-250 the Solvay Enzymes, Maxacal® CX 450.000, Maxapem® from Ibis, Savinase® 4.0 T, 6.0 T, 8.0 T from Novo or Experase® T from Company Ibis; Amylases such as Termamyl® 60 T, 90 T from Novo, amylase LT® from Solvay Enzymes or Maxamyl® P 5000, CXT 5000 or CXT 2900 from the company Ibis; Lipases such as Lipolase® 30 T from Novo; Cellu read like Celluzym® 0.7 T from Novo Nordisk. Enzymes are in the Agents according to the invention in an amount of 0.1 to 5 wt .-%, preferably as 0.5 to 2 wt .-%, based on the total dishwashing detergent ent hold.

To prevent tarnishing of silver cutlery, Sil Protection means, as used in the older German patent application P 43 15 397.6 are described, in particular water-soluble Mn (II) salts, in one Amount of up to 2 wt .-%, preferably 0.1 to 0.5 wt .-%, contain his.

The dishwashing detergents according to the invention are preferably in powder form shaped, granular or tablet-like preparations, which in themselves usual way, for example by mixing, granulating, roller compact animals and / or can be produced by spray drying.  

For the production of cleaning agents according to the invention in tablet form one preferably proceeds in such a way that all components in a Mi shear mixed with each other and the mixture using conventional tablet tenpressen, for example eccentric presses or rotary presses with Press pressure in the range of 200 · 10⁵ Pa to 1500 · 10⁵ Pa pressed. Man thus easily gets unbreakable and yet under conditions of use sufficiently quickly soluble tablets with flexural strength from norma Usually over 150 N. Preferably, a tablet manufactured in this way has a weight of 15 g to 40 g, in particular from 20 g to 30 g, at a diameter of 35 mm to 40 mm.

The production of dishwasher detergents in the form of no jam emitting, storage-stable, free-flowing powders and / or granules with high Bulk densities in the range from 800 to 900 g / l are characterized by that in a first stage of the process with the builder components at least a proportion of liquid mixture components while increasing the Bulk density of this premix is mixed and subsequently - desired if after an intermediate drying - the other components of Ma Dishwashing detergent combined with the premix thus obtained.

Since the alkali carbonate content strongly influences the alkalinity of the product, 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 is as constant as possible). An additional one that arises from drying Sodium carbonate content should namely in the formulation of the granules Recipe are taken into account. Low drying temperatures work not only counteract the sodium bicarbonate decay, but also increase it also the solubility of the granulated detergent when used. It is therefore advantageous when drying a supply air temperature, on the one hand should be as low as possible to avoid bicarbonate decay and on the other hand, it must be as high as necessary to produce a product with good Preserve storage properties. A supply air is preferred during drying temperature of approx. 80 ° C. The granules themselves should not be at temperatures be heated above about 60 ° C.  

In the first stage of the mixing process, the builder is usually in admixture with at least one further component of the dishwasher by means of the liquid components. Comes into consideration here for example a precursor in which the builder component is mixed with perborate with the liquid nonionic surfactants and / or the solution the fragrances are applied and mixed intimately. Below will be the remaining components added and the total mixture in the mix device worked through and homogenized. The additional use Licher amounts of liquid, in particular the use of additional Water is usually not required here. The material incurred mixture then lies as a free-flowing, non-dusting powder wanted high bulk densities in the range of about 800 to 900 g / l.

The pre-granules are then with the missing components of the Ge Dishwasher detergent mixed into the finished product. The mixing time is in all cases shown here both in the preliminary stage of the compressing Mixing under the influence of liquid components as in the following Final mixing with the other components in a few minutes, for example in the range of 1 to 5 minutes.

In a particular embodiment, it can be used in the manufacture of fine Granules may be useful by powdering the surface of the gebil the granulate grain further stabilization and leveling adjust. Small proportions of what are particularly suitable for this purpose glass powder or powdered alkali carbonate.

Products are available with the automatic dishwashing agents according to the invention available, which besides their better biodegradability tional modern dishwashing detergents especially with regard to the toppings inhibition and the rinse aid effect on glasses and knife blades are laying.

The following examples are intended to explain the subject of the invention in more detail but without restricting it to this.

Examples

Granular dishwashing detergents of the following composition (he agent A according to the invention and comparative agent B and inventive agent Agent C) produced.

Agent A contained 10% by weight of the copolymer, which according to the disclosure of older German patent application P 43 00 772.4 from 80 wt .-% acrylic acid and maleic acid in a weight ratio of 7: 3 and from 20% by weight of vinyl acetate was produced and then completely neutralized.

Comparative example B contained 10% by weight of one from BASF under the Trade names Sokalan® CP5 acrylic-maleate copolymer sold.

Cleaning performance

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

The agent A according to the invention compared to that not according to the invention Agent B especially in the removal of starch, minced meat, fat stick and oatmeal soiling, but especially in the tea Soiling, a superior cleaning performance.

Scale inhibition

The formation of deposits of agents A and B was in a dishwasher Miele G 590 (Universal program 65 ° C) at doses of 20 g each 7.0 l water with 16 ° dH with the addition of 50 g 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 rinse effect ("spotting") was with ei ner scale from 1 (= very bad rinse aid effect) to 8 (= very good Rinse aid effect, no water stains). The results of the with the Agent A according to the invention and the comparative agent B on glasses, knives sound and porcelain plates can achieve rinse effects of the table 1 can be removed.  

Table 1

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

Agent C according to the invention showed with agent A according to the invention comparable cleaning and deposit inhibition services; due to the The presence of MnSO₄ showed it mainly in terms of prevention properties of tarnishing silver cutlery.

Claims (10)

1. Low alkaline agent for machine cleaning of dishes, the sen 1 wt .-% aqueous solution has a pH of 8 to 11.5, preferably 9 to 10.5, containing water-soluble builder components and bleaching agents based on oxygen, thereby 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 wt .-%, preferably 10-25 wt .-%, vinyl alcohol and / or vinyl acetate, the weight ratio (meth) acrylic acid or (meth) acrylate to maleic acid or maleate 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 are preferred. 2. Composition according to claim 1, characterized in that it is 0.5 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 an oxygen-based bleach, contains in particular alkali perborate and / or percarbonate and that it is free from anionic, cationic or amphoteric surfactants and the content of non-ionic surfactants max. 5% by weight, preferably max. 2 wt .-%, each based on the total agent. 3. Composition according to claim 1 and 2, characterized in that it is up to 60th % By weight, preferably 5 to 50% by weight, of alkali carbonate and / or hydro contains gen carbonate. 4. Composition according to claim 1 to 3, characterized in that it is complex formers from the group of di- and multifunctional organic car bonic acids or their salts, especially 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 composition, contains.   5. Composition according to claim 1 to 4, characterized in that it is up to 30% by weight, preferably 5 to 20% by weight, based on the total amount tel, alkali silicate with a molar ratio SiO₂ / M₂O (M = alkali atom) contains from 1.5: 1 to 2.5: 1. 6. Composition according to claim 1 to 5, characterized in that it is free of active chlorine-releasing agents. 7. Composition according to claim 1 to 6, characterized in that there are enzymes in an amount of 0.1 to 5 wt .-%, preferably 0.5 to 2 wt .-%, be moved to the entire medium, contains. 8. tablet-like composition according to claim 1 to 7, characterized in net that by mixing all of its components in a Mi shear and compress the mixture using a tablet press Press printing from 2 · 10⁷ Pa to 1.5 · 10⁸ Pa is available. 9. Powder or granular composition according to claim 1 to 7, characterized characterized in that it has a bulk density of 750 g / l to 1000 g / l having. 10. Use of the agent according to one of claims 1 to 9 for machine len cleaning dishes.