EP0171008A2 - Dish cleaning agent - Google Patents

Abstract

The agents can be used in machines at low temperatures. They contain alkali metal di- or triphosphates, zeolites or organic complexing agents for calcium, alkali metal metasilicate, sodium carbonate, sodium bicarbonate, waterglass, compounds which release active oxygen, a low-foam, non-ionic surfactant, 0.1 to 5% by weight of a hydrolase enzyme (amylases, proteases, lipases) and as cleaning enhancer 0.1 to 5% by weight of high molecular weight terminal or non-terminal epoxyalkanes which are reacted with 1 mole of mono- or diethanolamine per mole of alkane and are optionally alkoxylated with 1 to 5 mole of ethylene oxide or propylene oxide.

Description

The invention relates to dishwashing detergents, in particular for the automatic washing of dishes at low temperatures, which are distinguished by a high level of cleaning ability, in particular also in relation to stubborn and normally difficult to remove soiling, such as sebum / grease soiling, and by an extraordinarily low foaming ability.

It is known that alkaline cleaning agent mixtures are used for the automatic cleaning of dishes, which essentially consist of inorganic salts such as alkali phosphates, alkali silicates and alkali carbonates and of active chlorine carriers and which, in order to improve the wetting effect, may also contain minor additions of a low-foaming nonionic surfactant. These mixtures have a good cleaning ability against all stains at generally normal working temperatures of 55 to 65 ° C. In order to prevent thin deposits, which can settle over time on the surface of the dishes, which consist essentially of starch and possibly traces of protein and which may significantly impair the appearance of the washed dishes, improved, enzyme-containing dishwashing detergents have been used, as described, for example, in DE-OS 17 67 567 are described.

Following the pressure to save energy, many manufacturers have already launched dishwashers on the market as energy-saving models in which the water consumption of the cleaning fleet has not only been reduced from 10 to 6 to 7 liters, but also offer a savings program with a greatly reduced temperature. For example, a "Favorit de Luxe Elektronik i" household dishwashing machine put on the market by AEG only needs about 6 liters of water for the cleaning liquor. The power consumption of the "40 ° C Normal" program (rinse aid temperature: 55 ° C) is only 1.1 kW / h, in contrast to the usual consumption of 1.9 to 2.2 kW / h at 65 ° C . When working with this machine, however, it has been shown that the cleaning performance of - as usual - 30 g standard cleaner (~ 5 g / l) during the transition from the 65 ° C program to the 40 C program with 8 test stains by an average 1.4 evaluation points dropped.

While adding 1% of an amylase-protease mixture in the cleaning cycle improved the removal of oatmeal and starch residues, adding a lipase to the cleaner to increase fat removal was not very effective. Sebum grease stains were difficult to remove at temperatures around 40 ° C.

Surprisingly, it has now been found that the removal of particularly stubborn grease stains, such as. B. beef tallow at cleaning temperatures by 40 ° C above the normal known 65 ° C result is also improved if the dishwashing detergent, in addition to an enzyme mixture as a cleaning enhancer, has higher molecular weight end-oc internal epoxyalkanes which have been reacted with mono- or diethanolamine and optionally also alkoxylated , adds.

The invention therefore relates to agents for the mechanical cleaning of dishes based on polymeric alkali phosphates and / or their substitutes, alkali silicates, alkali carbonates and, where appropriate, compounds which release active oxygen and low-foaming nonionic surfactants, which are characterized in that they contain enzymes and higher molecular weight terminal or internal epoxyalkanes, which have been reacted with mono- or diethanolamine and optionally alkoxylated.

• O bis 50, vorzugsweise 10 bis 40 Gew.-%, eines poly-- meren Alkaliphosphates aus der Gruppe der Alkalidiphosphate und Alkalitriphosphate,
• 0 bis 60, vorzugsweise 5 bis 50 Gew.-% an wasserunlöslichen, komplexbildenden Zeolithen vom Typ NaA oder NaX bzw. deren Gemischen oder wasserlöslichen organischen Komplexierungsmitteln für Calcium, wobei wenigstens eine dieser Verbindungen oder eines der polymeren Alkaliphosphate anwesend sein muß,
• 10 bis 60, vorzugsweise 20 bis 50 Gew.-% Alkalimetasilikat,
• 2 bis 40, vorzugsweise 5 bis 30 Gew.-% Natriumcarbonat,
• O bis 20, vorzugsweise 5 bis 20 Gew.-% Natriumhydrogencarbonat,
• 1 bis 20, vorzugsweise 1 bis 15 Gew.-% Wasserglas,
• 0,1 bis 5, vorzugsweise 0,5 bis 3 Gew.-% eines Enzyms oder Enzymgemisches aus der Gruppe der Hydrolasen, vorzugsweise Amylasen, Proteasen und Lipasen,
• 0,1 bis 10, vorzugsweise 0,5 bis 5 Gew.-% an höhermolekularen end- oder innenständigen Epoxyalkanen, die mit 1 Mol Mono- oder Diethanolamin pro Mol Alkan umgesetzt und gegebenenfalls noch mit jeweils 1 bis 5, vorzugsweise 1 bis 4 Mol Ethylen- oder Propylenoxid alkoxyliert sein können,
• 0 bis 10, vorzugsweise 0,5 bis 5 Gew.-% an aktivsauerstoffabspaltenden Verbindungen, gegebenenfalls auch Aktivatoren für diese, und
• O bis 5, vorzugsweise 0,5 bis 5 Gew.-% eines schwachschäumenden nichtionogenen Tensids aus der Gruppe der Alkylenoxidaddukte an C₁₂-C₁₈-Alkanole, Nonylphenol oder an Polypropylenglykole der Molgewichte 900 bis 4 000.

The cleaning agents according to the invention consist of a combination of

• 0 to 50, preferably 10 to 40% by weight of a polymeric alkali metal phosphate from the group of alkali metal diphosphates and alkali metal triphosphates,
• 0 to 60, preferably 5 to 50% by weight of water-insoluble, complex-forming zeolites of the NaA or NaX type or their mixtures or water-soluble organic complexing agents for calcium, at least one of these compounds or one of the polymeric alkali metal phosphates must be present,
• 10 to 60, preferably 20 to 50% by weight alkali metasilicate,
• 2 to 40, preferably 5 to 30% by weight sodium carbonate,
• 0 to 20, preferably 5 to 20% by weight sodium hydrogen carbonate,
• 1 to 20, preferably 1 to 15% by weight of water glass,
• 0.1 to 5, preferably 0.5 to 3% by weight of an enzyme or enzyme mixture from the group of the hydrolases, preferably amylases, proteases and lipases,
• 0.1 to 10, preferably 0.5 to 5% by weight of higher molecular weight terminal or internal epoxyalkanes which are reacted with 1 mole of mono- or diethanolamine per mole of alkane and optionally also with 1 to 5, preferably 1 to 4, moles Ethylene or propylene oxide can be alkoxylated,
• 0 to 10, preferably 0.5 to 5% by weight of active oxygen-releasing compounds, optionally also activators for these, and
• 0 to 5, preferably 0.5 to 5% by weight of a low-foaming nonionic surfactant from the group of the alkylene oxide adducts with C ₁₂ -C ₁₈ -alkanols, nonylphenol or with polypropylene glycols with a molecular weight of 900 to 4,000.

Suitable polymeric alkali metal phosphates are the condensed phosphates which are customarily used in washing-up and cleaning agent mixtures and which can be present in the form of their alkaline neutral or acidic sodium or potassium salts. Examples include: tetrasodium pyrophosphate, disodium dihydrogen pyrophosphate, pentasodium triphosphate, sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.

As is well known, the phosphate content of detergents in general is increasingly being made responsible for water reutrophication by experts and the public and is therefore regarded as a disadvantage. _M an has therefore proposed a number of substances as replacements for the previously common detergent phosphates. Sodium aluminum silicates in the form of the synthetically produced zeolites of the NaA and NaX type, as described, for example, in US Pat. Nos. 2,882,243 and 2,882,244, have apparently proven to be the best and have become established. The zeolites are used in their hydrated form.

The water-soluble organic complexing agents for calcium are essentially found among the polycarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, carboxyalkyl ethers, polyanionic polymeric carboxylic acids and the phosphonic acids, these compounds mostly being used in the form of their water-soluble salts. Specific but not exhaustive examples are citric acid, carboxymethyl tartronic acid, mellitic acid, polyacrylic acid, poly-c4-hydroxyacrylic acid, carboxymethyl malic acid, nitrilotriacetic acid and 1-hydroxyethane-1,1-diphosphonic acid.

Water-soluble sodium or potassium metasilicates are used as alkali metal silicates. You can free of water, or anhydrate kristallwasserhalti ^g and containing from 5 to 9 moles of water.

Water glass is understood as meaning water-soluble sodium or potassium silicates in which the ratio of alkali oxide to silicon dioxide is approximately 1: 2 to 1: 4. They can be used as anhydrous solid substances or as liquid, approximately 50% solutions.

Such enzymes are those of animal and vegetable origin, in particular active substances obtained from digestive ferment, yeast and bacterial strains. They usually represent a complex mixture of different enzymatic active ingredients. Of particular interest are starch, protein or fat-cleaving enzymes, such as amylases, proteases and lipases. The enzymes are obtained from a variety of processes from bacterial strains, fungi, yeasts or animal organs and are sold under different names. Most of these are enzyme mixtures that have a combined effect on starch, protein and fats have. The enzyme preparations obtained from Bacilius subtilis have the particular advantage for practical use that they are relatively resistant to alkalis. The temperature sensitivity of the enzymes no longer plays a significant role here.

The manufacturers set the enzymes to a certain degree of activity, optionally with the addition of blending agents such as sodium sulfate, sodium chloride, alkali phosphates or alkali polyphosphates. The data in LVE / g (Löhlein-Volhard units per gram), IU (international units) and DE / g (Delft units per gram) are common for proteolytic enzymes. Because of the simple analysis method, the activity is often stated in LVE / g. In the dishwashing detergents according to the invention, the proteolytic enzyme activity should be 100 to 5,000, preferably 200 to 2,000 LVE / g. Amylolytic activity is generally reported in SKB / g (Sandstedt-Kneen-Blish units per gram). It should be about 5 to 1,000, preferably 15 to 250, SKB / g in the detergent mixture. The amount of the enzymes to be used in the dishwashing detergents depends on these values.

The products used together with the enzymes as cleaning enhancers are produced in a known manner by reacting higher molecular weight terminal or internal epoxyalkanes with a linear C ₁₀ -C ₂₀ alkyl chain, preferably a C ₁₀ -C ₁₅ alkyl chain, with 1 mol of diethanolamine and then 3rd to 20, preferably 5 to 12 moles of ethylene oxide, which is preferably at elevated temperatures of about 50 to 200 ° C. under normal pressure or happens under increased pressure. The reaction is generally accelerated by basic or acidic catalysts. The epoxyalkanes used as starting materials for the preparation of the hydroxyamines are obtained in a manner known per se from the corresponding olefins or olefin mixtures. The alpha or 1,2-epoxyalkanes are obtained via alpha monoolefins, which are obtained, for example, by polymerizing ethylene with organic aluminum compounds as catalysts or by thermal cracking of paraffin wax. Of the terminal monoolefins, those with chain lengths in the range of C ₁₀ -C ₁₈ were preferably used. The internal epoxyalkanes are obtained, for example, by preparing them from linear aliphatic olefins having 10 to 20 carbon atoms and internal, statistically distributed double bonds by epoxidation using peracids or hydrogen peroxide and lower carboxylic acids forming peracids, or by epoxidation of olefin mixtures which are produced by catalytic dehydrogenation or by chlorination / dehydrochlorination of linear paraffins and selective extraction of the monoolefins. Monoolefins with an internal double bond can also be prepared by isomerizing alpha-olefins.

• C_11-C₁₄-Fraktion: C₁₁-Olefine _ca. 22 Gew.-% C12-Olefine _ca. ₃0 Gew.-% C13-Olefine ca. 26 Gew.-% C -Olefine ca. 22 Gew.-% 14

Internal monoolefins of a C ₁₁ -C ₁₄ fraction with statistical distribution of the double bond which were preferably used had the following chain length distribution:

• C _11- C ₁₄ fraction: C ₁₁ -olefins _approx . 22% by weight of C12 olefins _approx . ₃ 0 wt .-% C13 olefins about 26 wt .-% C olefins about 22 wt .-% 14

• C₁₂/C₁₄-Fraktion: _C12-Olefine _ca. 70 Gew.-% C14-Olefine ca. 30 Gew.-%.

Terminal monoolefins had the following chain length distribution:

• C ₁₂ / C ₁₄ fraction: _C12 olefins _approx . 70% by weight of C14 olefins approx. 30% by weight.

• 1 Mol C₁₁-C₁₄-i-Epoxyalkan + 1 Mol Diethanolamin + 1 Mol Ethylenoxid (= Produkt I),
• 1 Mol C₁₂/C₁₄-alpha-Epoxyalkan + 1 Mol Diethanolamin (= Produkt II),
• 1 Mol C₁₂/C₁₄-alpha-Epoxyalkan + 1 Mol Diethanolamin + 4 Mol Ethylenoxid (= Produkt III),
• 1 Mol C₁₂/C₁₄-alpha-Epoxyalkan + 1 Mol Diethanolamin + 1 Mol Propylenoxid (= Produkt IV),
• 1 Mol C₁₂/C₁₄-alpha-Epoxyalkan + 1 Mol Diethanolamin + 2 Mol Propylenoxid (= Produkt V),
• 1 Mol C₁₂/C₁₄-alpha-Epoxyalkan + 1 Mol Monoethanolamin (= Produkt VI),
• 1 Mol C₁₂/C₁₄-alpha-Epoxyalkan + 1 Mol Monoethanolamin + 1 Mol Propylenoxid (= Produkt VII),
• 1 Mol C₁₂/C₁₄-alpha-Epoxyalkan + 1 Mol Monoethanolamin + 2 Mol Propylenoxid (= Produkt VIII).

The products used as cleaning enhancers were obtained as follows:

• 1 mol of C ₁₁ -C ₁₄ -i-epoxyalkane + 1 mol of diethanolamine + 1 mol of ethylene oxide (= product I),
• 1 mol of C ₁₂ / C ₁₄ -alpha-epoxyalkane + 1 mol of diethanolamine (= product II),
• 1 mol C ₁₂ / C ₁₄ -alpha-epoxyalkane + 1 mol diethanolamine + 4 mol ethylene oxide (= product III),
• 1 mol of C ₁₂ / C ₁₄ -alpha-epoxyalkane + 1 mol of diethanolamine + 1 mol of propylene oxide (= product IV),
• 1 mol of C ₁₂ / C ₁₄ -alpha-epoxyalkane + 1 mol of diethanolamine + 2 mol of propylene oxide (= product V),
• 1 mol of C ₁₂ / C ₁₄ -alpha-epoxyalkane + 1 mol of monoethanolamine (= product VI),
• 1 mol of C ₁₂ / C ₁₄ -alpha-epoxyalkane + 1 mol of monoethanolamine + 1 mol of propylene oxide (= product VII),
• 1 mol of C ₁₂ / C ₁₄ -alpha-epoxyalkane + 1 mol of monoethanolamine + 2 mol of propylene oxide (= product VIII).

The known alkali perborates, persulfates and percarbonate, which can be activated by activators such as tetraacetylethylenediamine, tetraacetylglycoluril, pentaacetylglucose, but also compounds such as magnesium monoperphthalate, can be used as compounds which release active oxygen, but also compounds such as magnesium monoperphthalate, it being possible to dispense with the addition of activator.

Suitable nonionic low-foaming surfactants are preferably ethylene oxide adducts with higher molecular weight polypropylene glycols with a molecular weight of 900 to 4,000, and ethylene oxide or ethylene oxide and propylene oxide adducts with C ₁₂ -C ₁₈ alkanols and nonylphenol. The preparation is carried out in a known manner by addition of the alkylene oxides in question in the presence of mostly alkaline catalysts, if appropriate under pressure and at elevated temperatures, it being possible to add up to three times the amount by weight of the starting compounds on alkylene oxides. Examples of suitable addition products are the adduct of 10% by weight of ethylene oxide with a polyoxypropylene glycol of molecular weight 1750, and the adduct of 9 mol of ethylene oxide and 10 mol of propylene oxide with nonylphenol, and the like.

The useful nonionic surfactants also include the surface-active amine oxides, which are usually derived from tertiary amines with a hydrophobic C ₁₀ -C ₂₀ alkyl group and two shorter alkyl and / or alkylol groups each containing up to 4 C atoms. Typical representatives are, for example, the compounds N-dodecyl-N, N-dimethylamine oxide, N-tetradecyl-N, N-dihydroxyethylamine oxide or N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) amine oxide.

In addition to the constituents mentioned, the claimed mixtures may contain further components, in particular inorganic salts such as sodium sulfate, as a blending agent. In addition, acidic or alkaline or buffering inorganic or organic compounds can be used to establish a pH value which is advantageous for the enzyme action. For this purpose, the organic hydroxycarhonic acids, such as citric acid or tartaric acid, such as phosphoric acid or acidic alkali orthophosphates, are also preferred. Generally lie The pH values - depending on the type of enzyme - between 4 and 12. Finally, enzyme-activating additives such as ammonium chloride, sodium chloride, dyes, perfumes and the like can also be added to the mixtures.

The claimed agents are generally used as mixtures of granular or powdery individual substances or as granulated, agglomerated or prilled products.

The claimed Reinigunrsmittelkombinationen are characterized by a high wetting effect and a very good low-temperature cleaning power, especially against stubborn stains such as fat, protein and Stärkebelä ^g s-off.

The application is carried out by addition of the powdered, granulated, agglomerated or prilled means by hand into the Geschirreinigun sflotte ^g or, preferably, by means of automatic dosing devices. The application concentrations in the cleaning liquor should be about 2 to 7 g / 1, temperatures of about 40 to 45 ° C being used.

To test the cleaning result of the inventive detergents plate with potato starch and Haferbreianschmutzungen and with Fettstift- and Rindertalgbelägen, bowls of milk, pudding and Hackfleischanschmutzungen and continue cups were cleaned with ^dix etrock- Neten Teeresten. The tests were carried out in a household dishwashing machine (HGSM) of the type AEG "Favorit de Luxe Elektronik i" with Düsseldorf city water (16 ° d), which had the following program steps:

30 g of detergent, corresponding to 5 g / 1 liquor, were used in the cleaning cycle. No rinse aid was added in the rinse aid in order not to falsify the cleaning results. At the end of the entire program, the cleaning ability of the cleaning agents used was visually assessed. The individual evaluations were carried out according to a point system which ranged from 0 to 10, with 0 points meaning "without a recognizable cleaning effect" and 10 points meaning "complete removal of the test soiling".

This resulted in a number of intermediate values that made it possible to make a differentiated statement. The results represent mean values from 4 parallel assessments by 4 test subjects.

The test soils consisted of oatmeal porridge and starch in the form of mashed potatoes, which were placed on plates and scraped off. The dishes were then left to stand in the air for 6 hours at room temperature and then placed in the dishwasher. In the Rindertalganschmutzung following procedure was gen ^g Toggle: O, from 5 to 0.8 g of beef tallow were heated until liquefied and stirred for about 2% of titanium dioxide. Then the still warm mass was spread evenly onto red plastic plates using a brush. First, a conventional standard cleaning agent (A) was used, which had the following composition:

Cleaner A:

• 40% by weight sodium triphosphate, anhydrous,
• 45% by weight sodium metasilicate, anhydrous, 5% by weight sodium carbonate, anhydrous,
• Rest of water

There have been other detergent compositions using other inorganic complexing agents, such as. B. sodium aluminum silicates of the type zeolite NaA or NaX or organic complexing agents, such as. B. the sodium salt of nitrilotriacetic acid as a partial or full phosphate substitute included in the studies. These cleaners had the following compositions:

Cleaner B:

• 20% by weight sodium triphosphate, anhydrous,
• 20 G _ew .-% zeolite NaA, (calculated as anhydrous substance),
• 45% by weight sodium metasilicate, anhydrous, 5% by weight sodium carbonate, anhydrous,
• Rest of water

Cleaner C:

• 40% by weight of zeolite NaA (calculated as anhydrous substance),
• 45% by weight sodium metasilicate, anhydrous, 5% by weight sodium carbonate, anhydrous,
• Rest of water

Cleaner D:

• 20% by weight sodium triphosphate, anhydrous,
• 20% by weight nitrilotriacetic acid, sodium salt,
• 45% by weight sodium metasilicate, anhydrous, 5% by weight sodium carbonate, anhydrous,
• Rest of water
• Cleaner E:
• 40% by weight nitrilotriacetic acid, sodium salt,
• 45% by weight sodium metasilicate, anhydrous, 5% by weight sodium carbonate, anhydrous
• Rest of water

The cleaning results are shown in Table 1 below. It shows that the use of cleaning agents of the conventionally varied recipes given above leads to a considerably reduced cleaning performance when the cleaning temperature is reduced by 25 ° C.

In the following examples, 4% by weight, corresponding to 1.2 g, of the sodium metasilicate of standard formulation A was replaced by 1% by weight, corresponding to 0.3 g, of a 1: 1 mixture of amylase and protease (Maxamyl (R) or Maxatase (R) from Koninklijke Nederlandsche Gist en Spiritus-Fabriek NV, Delft) and 3% by weight, corresponding to 0.9 g, of the products listed in the table below.

Claims (2)

1. Dishwashing detergent based on polymeric alkali phosphates and / or their substitutes, alkali silicates, alkali carbonates and optionally active oxygen-releasing compounds and low-foaming nonionic surfactants, characterized in that they contain enzymes and higher molecular weight terminal or internal epoxyalkanes which are reacted with mono- or diethanolamine and were optionally alkoxylated. 2. Composition according to claim 1, characterized in that it consists of a combination of 0 to 50, preferably 10 to 40% by weight of a polymeric alkali metal phosphate from the group of the alkali metal diphosphates and alkali metal triphosphates, 0 to 60, preferably 5 to 50% by weight of water-insoluble, complex-forming zeolites of the NaA or NaX type or their mixtures or water-soluble organic complexing agents for calcium, at least one of these compounds or one of the polymeric alkali metal phosphates must be present, 10 to 60, preferably 20 to 50% by weight alkali metasilicate, 2 to 40, preferably 5 to 30% by weight sodium carbonate, 0 to 20, preferably 5 to 20% by weight sodium hydrogen carbonate, 1 to 20, preferably 1 to 15% by weight of water glass, 0.1 to 5, preferably 0.5 to 3% by weight of an enzyme or enzyme mixture from the group of the hydrolases, preferably amylases, proteases and lipases, 0.1 to 10, preferably 0.5 to 5% by weight of higher molecular weight terminal or internal epoxyalkanes which are reacted with 1 mole of mono- or diethanolamine per mole of alkane and optionally also with 1 to 5, preferably 1 to 4, moles Ethylene or propylene oxide have been alkoxylated, 0 to 10, preferably 0.5 to 5% by weight of compounds which release active oxygen, optionally also activators for these, and O to 5, preferably 0.5 to 2 wt .-% of a low-foaming nonionic surfactant from the group of alkylene oxide adducts with C ₁₂ -C ₁₈ -A1- canoles, nonylphenol or with polypropylene glycols with a molecular weight of 900 to 4,000.