DE3428833A1 - DISHWASHER - 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

4000 Düsseldorf, August 2nd, 1984 HENKELKGaA

Henkelstrasse 67 ZR-FE / Patents

Dr. Wf / Ne - 3. ·

Patent application D 7133

"Dishwasher detergent"

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The invention relates to dishwashing detergents, in particular: for machine washing of dishes when never- ' low temperatures, which are characterized by a high cleaning power, especially with regard to stubborn and normally difficult to remove soiling such as such as sebum - grease soiling, as well as being characterized by an extremely low foaming capacity.

For machine cleaning of dishes, alkaline cleaning agent mixtures are known to be used, which essentially consist of inorganic salts such as alkali phosphates, alkali silicates and alkali carbonates as well as active chlorine carriers and which may contain small additions of a low-foaming nonionic surfactant to improve the wetting effect. These mixtures have a good cleaning ability against all soiling at generally usual working temperatures of 55 to 65 ⁰ C. To prevent thin deposits that over time on the surface

2c can deposit the surface that is essentially consist of starch and possibly traces of protein and which may significantly affect the appearance of the washed dishes affect, improved, enzyme-containing dishwashing detergents were used, for example in DE-OS 17 67 567 are described.

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In response to the need to save energy, many manufacturers have already brought dishwashers onto the market as energy-saving models in which the water consumption of the cleaning solution has not only been reduced from 10 to 6 liters, but also offer a savings program with a greatly reduced temperature. A household dishwasher of the "Favorit de Luxe Electronics i" type marketed by the AEG company requires, for example, only about 6 liters of water for the cleaning liquor. The power consumption of the program "40 ° C Normal" (rinse temperature: 55 ° C) is, in contrast to the previously usual consumption of 1.9 to 2.2 kW / h at 6 5 ⁰ C, only 1.1 kW / H. When working with this machine, however, it has been shown that the cleaning performance of - as previously usual - 30 g standard cleaner (^^ 5 g / l) with the transition from the 65 C program to the 40 C program with 8 test soils by an average of 1 , 4 rating points fell off.

While an addition of 1% of an amylase-protease mixture Although the cleaning process improved the removal of oat flakes and starch residues, a lipase was added not very effective as a cleaner to increase grease removal. Sebum fat stains left Temperatures around 40 C can only be removed with difficulty.

Surprisingly, it has now been found that the distance especially from stubborn grease soiling, such as B. Beef tallow at cleaning temperatures around 40 C above The normal known 65 C result is also improved if the dishwashing detergent is used except for an enzyme mixture as a torture intensifier higher molecular weight terminal or internal epoxyalkanes, those with mono- or diethanolamine reacted and optionally also alkoxylated, added.

Patent application D 7133 -3 "- HENKELKGaA

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The invention therefore relates to agents for the machine cleaning of dishes based on polymeric alkali metal phosphates and / or their substitutes, alkali metal silicates, alkali metal carbonates and optionally active oxygen-releasing compounds 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 contain.

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

to 50, preferably 10 to 40 wt .-%, of a polymer Alkali phosphates from the group of alkali metal diphosphates and alkali metal triphosphates,

T5 0 to 60, preferably 5 to 50 wt -.% Of water-insoluble, complexing zeolites mixtures thereof or water-soluble organic complexing agents for calcium, at least one of these compounds or one of the polymeric alkali phosphates having to be present from the NaA or NaX type or until 60 , preferably 20 to 50% by weight alkali metasilicate,
to 40, preferably 5 to 30 wt .-% of sodium carbonate ^nat f

up to 20, preferably 5 to 20% by weight sodium hydrogen

carbonate,

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

3Q or enzyme mixture from the group of

Hydrolases, preferably amylases, proteases and lipases.

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0.1 to 10, preferably 0.5 to 5 wt .-% of higher molecular weight terminal or internal epoxyalkanes,

which can be reacted with 1 mole of mono- or diethanolamine per mole of alkane and optionally also alkoxylated with 1 to 5, preferably 1 to 4 moles of ethylene or propylene oxide , 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 alkylene oxide adducts with C ₁ ^ -C ₁₀ alkenols, nonylphenol or polypropylene glycols with a molecular weight of 9CO to 4,000.

The polymeric alkali metal phosphates usually come in Dishwashing and cleaning agent mixtures used condensed phosphates into consideration, in the form of their alkaline neutral or acidic sodium or potassium salts can be present. Examples are: 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, experts and the general public are increasingly making the phosphate content of detergents responsible for water eutrophication and are therefore viewed as a disadvantage. A number of substances have therefore been proposed as replacements for the detergent phosphates that have hitherto been customary.Sodium aluminum silicates in the form of the synthetically produced zeolites of the NaA and NaX types, such as those described, for example, in US Pat and 2,882,244. The zeolites are used in their hydrated form. ,,,

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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 in Form of their water-soluble salts are used. Specific but not exhaustive examples are Citric acid, carboxymethyltartronic acid, mellitic acid, Polyacrylic acid, poly-eC-hydroxyacrylic acid, carboxymethyl malic acid, Nitrilotriacetic acid and 1-hydroxy-ethane-1,1-diphosphonic acid.

The alkali metasilicates used are water-soluble sodium or Potassium metasilicates used. They can be anhydrous, anhydrated or contain water of crystallization and 5 contain up to 9 moles of water.

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

The enzymes used are those of animal and vegetable origin, in particular from digestive enzymes, yeasts and Active ingredients obtained from bacterial strains in question. They usually represent a complex mixture of different of enzymatic active ingredients. Of particular interest are starch, protein or fat-splitting enzymes, like amy lasen, proteases and lipases. The enzymes are produced from bacterial strains using a wide variety of methods, Obtained from mushrooms, yeast or animal organs and sold under different names. Most of these are mixtures of enzymes that have a combined effect on starch, protein and fats

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own. The enzyme preparations obtained from Bacillus subtilis have the special ones for practical use Advantage that they are relatively resistant to alkalis. The temperature sensitivity of the enzymes plays a role no longer a significant role here.

The enzymes are used by the manufacturers, if necessary with the addition of diluents such as sodium sulfate, sodium chloride, Alkali phosphates or alkali polyphosphates, adjusted to a certain level of activity. Common are the data in LVE / g (Löhlein-Volhard units per gram), IU (international units) and DE / g (Delft Units per gram) for proteolytic enzymes. Because of the In a simple analytical method, the activity is often given in LVU / g. In the dishwashing detergents according to the invention the proteolytic enzyme activity should be 100 to 5,000, preferably 200 to 2,000 LVU / g. the amylolytic activity is generally given 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 cleaning agent mixture. The amount that goes in the dish detergent The enzymes to be used depend 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 ^ g-C20-alkyl chain, preferably C ₁₀ -C 15 -alkyl chain, with 1 mol of diethanolamine and then reacting 3 to 20, preferably 5 to 12 mol of ethylene oxide is added, which is preferably at elevated temperatures of about 50 to 200 ⁰ C at normal pressure or

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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, preference was given to using chain lengths in the range C, _Q - ^ ₁₈ . 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 bond by epoxidation using peracids or lower carboxylic acids forming hydrogen peroxide and peracids, or by epoxidation of olefin mixtures produced by catalytic dehydrogenation or obtained by chlorination / dehydrochlorination of linear paraffins and selective extraction of the monoolefins. Monoolefins with an internal double bond can also be produced by isomerizing alpha-olefins.

Internal monoolefins of a C ₁₁ -C - ^ fraction with statistical distribution of the double bond used with preference had the following chain length distribution:

Cj ^ ^ -CJ fraction: C _{i; L} -01ef ine about 22 wt -%.

C ₁₂ -01efine approx. 30 wt. Cjj-olefins approx. 26% by weight

C-olefins about 22 wt -.% 14

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Terminal monoolefins had the following chain length distribution:

C ₁₂ / C ₁₄ fraction: C ₁₂ olefins approx. 70% by weight

C ₁₄ olefins approx. 30% by weight . 5

The products used as cleaning enhancers were obtained as follows:

1 mole of C _n -C ₁₄ -i-epoxyalkane + 1 mole of diethanolamine + 1 mole of ethylene oxide (= product I),
1 mol of C ₁₂ / C ₁₄ -alpha-epoxyalkane + 1 mol of diethanolamine (= product II),

1 mol of C ₁₂ / C ₁₄ -alpha-epoxyalkane + 1 mol of diethanolamine + 4 mol of 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 mole of C ₁₂ / C 24 alpha-epoxyalkane + 1 mole of diethanolamine +

2 moles 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 mole of Cj ^ / Cj ^ -alpha-epoxyalkane + 1 mole of monoethanolamine +

2 moles of propylene oxide (= product VIII).

As compounds which split off active oxygen, the known alkali perborates, persulfates and percarbonates serve, which are activated by activators such as tetraacetylethylenediamine, Tetraacetylglycoluril, pentaacetylglucose can be activated, but also compounds such as magnesium monoperphthalate, it is possible to dispense with the addition of an activator.

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Suitable nonionic, low-foaming surfactants are preferably ethylene oxide adducts with higher molecular weight polypropylene glycols with weights from 900 to 4,000, and ethylene oxide or ethylene oxide and propylene oxide _{adducts with C. 2} -Cg alkanols and nonylphenol. The preparation takes place in a known manner by adding the alkylene oxides in question in the presence of mostly alkaline catalysts, optionally under pressure and at elevated temperatures, with up to three times the weight

10 · amount of the starting compounds can be added to alkylene oxides. Examples of suitable addition products are the adduct of 10 percent by weight ethylene oxide to a polyoxypropylene glycol with a molecular weight of 1750, as well as the adduct of 9 moles of ethylene oxide and 10 moles of propylene oxide on nonylphenol, and the like.

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

In addition to the constituents mentioned, the claimed mixtures can contain further components, in particular inorganic ones Contain salts such as sodium sulphate as an extender. Furthermore, acidic or alkaline reacting resp. buffering inorganic or organic compounds to set a beneficial for the enzyme action pK value into account. The organic hydroxycarboxylic acids also used as complexing agents are preferred for this purpose, such as citric acid or vialic acid, as well as phosphoric acid or acidic alkali metal orthophosphates. In general

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The pH values - depending on the type of enzyme - between 4 and 12. Finally, the mixtures can also be enzyme-activating Additives such as ammonium chloride, sodium chloride, dyes, perfumes and the like are added.

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

The cleaning agent combinations claimed are characterized by a high wetting effect and an extraordinary one good low-temperature cleaning properties, especially against stubborn soiling, such as Fat, protein and starch toppings.

The application takes place by adding the powdery, granulated, agglomerated or prilled agents of Hand in the dishwashing liquor or preferably by means of automatic dosing devices. The use concentrations in the refining liquor should be about 2 to 7 g / l, v / o at temperatures of about 40 to 45 ° C be applied.

To check the cleaning result of the invention Detergents were used on plates with potato starch and oatmeal stains as well as with grease stick and beef tallow coatings, Bowls with milk, pudding and 5 minced meat stains and cups of ir.it dried on Cleaned tea residues. The tests were carried out in a household dishwasher (HGSM) of the AEG type "Favorite de Luxe Electronics i" with Düsseldorf city water (16 d) carried out the following program steps exhibited:

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1st pre-wash cold,

2nd cleaning cycle 40 C,

O,

60 minutes total running time

3rd intermediate rinse below 40

4th intermediate rinse below 40 C,
5th rinse cycle 55 ⁰ C,

6th drying cycle.

In the cleaning cycle, 30 g cleaning agent, corresponding to 5 g / l liquor, were used. Was in the rinse cycle no rinse aid added so as not to falsify the cleaning results. At the end of the entire program The cleaning ability of the cleaning agents used was assessed visually in each case * The individual ratings were based on a point system that ranged from 0 to 10, with 0 points "No recognizable cleaning effect" and 10 points meant "complete removal of test soiling".

This resulted in a number of intermediate values, which enabled a differentiated statement. The results represent mean values from 4 parallel assessments of 4 test persons.

The test soils consisted of oatmeal porridge and starch in the form of mashed potatoes, which were applied to plates and scraped off. Thereafter, the dishes were left in the air at room temperature for 6 hours and then placed in the dishwasher. In the case of beef tallow contamination, the procedure was as follows: 0.5 to 0.8 g of beef tallow was heated until it liquefied and approx. 2% titanium dioxide was stirred in. then the still warm mass was spread evenly on a red plastic plate using a brush. First was rinsed with a conventional standard cleaning agent (A), which had the following composition:

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Patent application D 7133

Cleaner A :

40 wt -.% Sodium tripolyphosphate, anhydrous, 45 wt -.% Of sodium metasilicate, anhydrous, 5 parts by weight JS Sodium carbonate anhydrous, balance water

There have been further 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. B. the sodium salt of nitrilotriacetic acid as a partial or full phosphate substitute was included in the investigations. These cleaners had the following compositions:

Cleaner B :

20 wt .- ^ sodium triphosphate, anhydrous, 20 wt .- JS zeolite NaA , (calculated as anhydrous substance), 45 wt .- ^ sodium metasilicate, anhydrous,

5 wt. Sodium carbonate, anhydrous, residual water

Cleaner C :

4o wt .- # zeolite NaA, (calculated as anhydrous substance), 45 wt .-% sodium metasilicate, anhydrous,

5% by weight sodium carbonate, anhydrous, remainder water / water

Cleaner D :

20 wt .- $ sodium triphosphate, anhydrous, wt .- / 5 wt .-% nitrilotriacetic acid, sodium salt, % By weight sodium metasilicate, anhydrous,

5 wt .- # sodium carbonate, anhydrous, residual water

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Cleaner E ;

40 wt .- / S nitrilotriacetic acid, sodium salt, 45% by weight sodium metasilicate, anhydrous, 5% by weight sodium carbonate, anhydrous Rest water

The cleaning results can be found in the following table. It shows that the use of cleaning agents of the conventionally varied formulations given above leads to a considerably reduced cleaning ^{performance when the cleaning temperature is reduced by 25 ° C.}

Patent application ^ 7133

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Table 1

Cleaning attempts with AEG Favorit de Luxe Electronics i (with 6 liters of water in the cleaning cycle)

Dosage 30 g cleaner A-E (approx. 5 g / l)

program cleanser
ABCDE 5 5 5 5.5 5 strength 5 5.5 4.75 5.5 5 Beef tallow 5.25 5 5.5 5.25 5.5 oatmeal 4.75 4th 4th 4th 4.25 3.75 4.5 4th 4.75 4th 3.75 2.5 2.25 2.0 2.25 65 ° C -0.25 -1 -1 -1 .5 -0.75 -1 .25 -1 -0.75 -0.75 -1 -1 .50 -2.5 -2.25 -2.25 -2.25 40 ° C Δ 65 ° C 40 ° C Δ 65 ° C 40 ° C Δ

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* Al.

In the following examples, 4% by weight were correspondingly 1.2 g of the sodium metasilicate of the standard formulation A by 1% by weight, corresponding to 0.3 g, of one

(R) 1 ί 1 mixture of amylase and protease (Maxamyl '

(P)
or Maxatase from Koninklijke Nederlandsche Gist en Spiritus-Fabriek NV, Delft) and 3% by weight, corresponding to 0.9 g, of the products indicated in the present table.

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Table 2

No. program ⁰ C 30th G Recipe A. Grading
Beef tallow
distance to
Cleaner A
Λ (65 ⁰ C) A. Normal 65 ⁰ C 30th G Standard cleaner A. 5.25 - B. Normal 40 Standard cleaner 3.75 - 1.50

Normal 4O ⁰ C 28.8 g standard detergent A

+ 0.3 g enzyme mixture 8.00 +2.75

+ 0.9 g of product I.

Normal 4O ⁰ C 28.8 g standard detergent A

+ 0.3 g enzyme mixture B, 50 + 3.25

+ 0.9 g of product II

Normal 40 ° C 28.8 g standard detergent A

+ 0.3 g enzyme mixture 9.25 +4.00

+ 0.9 g of product IV

Normal 4O ⁰ C 28.8 g standard detergent A

+ 0.3 g enzyme mixture 9.0 + 3.75

+ 0.9 g of product V

Normal 4O ⁰ C 28.8 g standard detergent A

+ 0.3 g enzyme mixture 8.50 +3.25

+ 0.9 g of product III

Normal 40 ° C 28.8 g standard detergent A

+ 0.3 g enzyme mixture 7.50 +2.25

+ 0.9 g of product Vl

Normal 40 C 28.2 g standard cleaner A

+ 0.3 g enzyme mixture 10.00 + 4.75 + 1.5 g product VII

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Table 2 Continuation t ζ u η q

Rating to Reini-beef tallow _he g A _ E

No. Program Recipe removal Λ ZA (65 ⁰ C) normal 4Q ° C 28.8 g standard cleaner A

+ 0.3 g enzyme mixture 10.00 +4.75 + 0.9 g product VIII

Normal 40 C 28.8 g standard detergent B

+ 0.3 g enzyme mixture 7.00 + 2.00 + 0.9 g product I.

Normal 4O ⁰ C 28.8 g standard cleaner C

+ 0.3 g enzyme mixture 7.50 + 2.00 + 0.9 g product I.

Normal 40 ° C 28.8 g standard cleaner D

+ 0.3 g of enzyme mixture 8.00 + 2.75 + 0.9 g of product I.

Normal 4O ⁰ C 28.8 g standard cleaners E

+ 0.3 g enzyme mixture 8.00 +2.50 + 0.9 g product I.

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Table 3

Rating for oat cleaner A

No. program ⁰ C 30th G Recipe A. flakes A. (65 ° - O A. Normal 65 ⁰ C 30th G Standard cleaner A. 5.00 0.75 B. Normal 40 Standard cleaner 4.25 -

Normal 4O ⁰ C 28, ag standard cleaner A

+ 0.3 g enzyme mixture 5.75 +0.75 + 0.9 g product I.

Normal 4O ⁰ C 28.8 g standard detergent A

+ 0.3 g enzyme mixture 5.00 + + 0.9 g product II

Normal 4O ⁰ C 28.8 g standard detergent A

+ 0.3 g enzyme mixture 5.00 + + 0.9 g product IV

Normal 4O ⁰ C 28.8 g standard detergent A

+ 0.3 g enzyme mixture 5.50 +0.50 + 0.9 g product V

Normal 4O ⁰ C 28.8 g standard detergent A

+ 0.3 g enzyme mixture 5.00 + + 0.9 g product III

Normal 4O ⁰ C 28.8 g standard detergent A

+ 0.3 g enzyme mixture 5.00 + 0.9 g product VI

Normal 40 C 28.2 g standard cleaner A

+ 0.3 g enzyme mixture 5.00 + 1.5 g product VII

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Table 3 continued

Rating for Reini-Haferger A _ · Ε

No. Program recipe flake> \ _o

/ ^ (65 C;

Normal 40 ° C 28.8 g standard detergent A

+ 0.3 g enzyme mixture 5.25 +0.25 + 0.9 g product Will

Normal 40 ⁰ C 28.8 g standard cleaner B

+ 0.3 g enzyme mixture 6.50 +1.50 + 0.9 g product I.

Normal 40 ⁰ C 28.8 g standard cleaner C

+ 0.3 g enzyme mixture 6.50 +1.50 + 0.9 g product I.

Normal 40 ⁰ C 28.8 g standard cleaner D.

+ 0.3 g enzyme mixture 6.75 +1.25 + 0.9 g product I.

Normal 40 ⁰ C 28.8 g standard cleaner E.

+ 0.3 g enzyme mixture 6.50 +1.50 + 0.9 g product I.

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Table 4

No. program ⁰ C 30th Recipe A. Grading
strength to
cleanser A.
¹ O A. Normal 65 ⁰ C 30th g standard cleaner A. 5.00 - B. Normal 40 g standard cleaner 3.75 - 1 , 25

Normal 4O ⁰ C 28.8 g standard detergent A

+ 0.3 g enzyme mixture 5.25 +0.25 + 0.9 g product I.

Normal 4O ⁰ C 28.8 g standard detergent A

+ 0.3 g enzyme mixture 5.25 +0.25 + 0.9 g product II

Normal 4O ⁰ C 28.8 g standard detergent A

+ 0.3 g enzyme mixture ⁶ > 5E +1.50 + 0.9 g product IV

Normal 4O ⁰ C 28.8 g standard detergent A

+ 0.3 g enzyme mixture ⁵ » ²⁵ +0.25

Pdkt V

+ 0.3 g enzyme gmis + 0.9 g product V

Normal 4O ⁰ C 28.8 g standard detergent A

+ 0.3 g enzyme mixture ⁵ , 25 +0.25 + 0.9 g product III

Normal 40 C 28.8 g standard detergent A

2. g Stnreinig + 0.3 g enzyme mixture 5.00 + 0.9 g product VI

Normal 40 C 28.2 g standard cleaner A

+ 0.3 g enzyme mixture 5.00 + + 1.5 g product VII

? nrt / * 7R ¹ IIQ Λ OA RI

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Table 4 Continuation

Rating for cleaning

ger A-E

No. program recipe starch _Λ

Normal 4Q ° C 28.8 g standard detergent A

g g

0.3 g enzyme mixture 5.00 + 0

+ 0.9 g of product VIII

Normal 40 C 28.8 g standard detergent

, g g

+ 0.3 g enzyme mixture 7.50 + 2.00 + 0.9 g product I.

Normal 40 ° C 28.8 g standard ^{detergent c}

+ 0.3 g of enzyme mixture 7.50 + 2.75 + 0.9 g of product I.

Normal 40 ° C 28.8 g standard cleaner D

+ 0.3 g enzyme mixture 7.25 +1.75

+ 0.9 g of product I.

Normal 40 ° C 28.8 g standard cleaner E.

+ 0.3 g enzyme mixture 7.25 +2.50

+ 0.3 g of product I.

Claims (2)

Patent application D 7133 -2-2- * · HbNKbL fUaaA ZR-FE / Patents PATENT CLAIMS 1. Dishwashing detergents based on polymeric alkali metal phosphates and / or their substitutes, Alkali silicates, alkali carbonates and optionally compounds which split off active oxygen and weakly foaming nonionic surfactants, characterized in that they contain enzymes and higher molecular weight end- or internal epoxyalkanes which are reacted with mono- or diethanolamine and optionally also alkoxylated were included. 2. Means according to claim 1, characterized in that it consists of a combination of 0 to 50, preferably 10 to 40 weight percent of one polymeric alkali metal phosphates from the group of alkali metal diphosphates and alkali metal phate, 0 to 60, preferably 5 to 50 wt .-% 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 phosphates must be present, 10 to 60, preferably 20 to 50 wt .-% alkali metasilicate, 2 to 40, preferably 5 to 30 wt .-% sodium carbonate,
0 to 20, preferably 5 to 20 wt .-% sodium hydrogen carbonate,
1 to 20, preferably 1 to 15 wt .-% water glass, Patent application D 7133 3428833 HENKELKGaA ZR-FE / patents 0.1 to 5, preferably 0.5 to 3% by weight of one Enzyme or enzyme mixture from the group of hydrolases, preferably air.ylases, Proteases and lipases, 0.1 to 10, preferably 0.5 to 5 wt .-% of higher molecular weight terminal or internal epoxyalkanes, which reacted with 1 mole of mono- or diethanolamine per mole of alkane and optionally also with 1 to 5, preferably 1 to 4, mol of ethylene oxide or propylene oxide were alkoxylated in each case, up to 10, preferably 0.5 to 5% by weight of active oxygen releasing agents Compounds, possibly also activators for these, and 0 to 5, preferably 0.5 to 2% by weight of a low-foaming nonionic surfactant from the group of alkylene oxide adducts with C ₁₂ -C 6 alkanols, nonylphenol or polypropylene glycols with a molecular weight of 900 to 4,000. Sd230M38539 3rd Π 83