DE2062465A1 - Scouring agent - for dish washing machines, contg aminopolycarboxylic acid and alkali silicate - Google Patents

Abstract

Dish cleaning agent, useful as substitute for phosphate cleaners, contains (a) 5-90wt.% aminopolycarboxylic acid or salts, (b) 90-5wt.% soluble alkali silicate (esp. with alkali oxide:SiO2 1:0.5-3.5 ratio (c) 0-5wt.% alkali hydroxide or carbonate, (d) 0-10 wt.% weakly foaming non-ionogenic tenside e.g. alkylene oxide adducts on higher fatty alcohols or 12-18C alkylphenols or on polypropylene glycols of 900-4000 mol.wt., (e) 0-10 wt.% active Cl-yielding cpd. esp. K di-chloroisocyanurate, (f) 0.5wt.% enzyme(s) such as hydrolases, esp. amylases, proteases and lipases, (g) 0-10wt.% complexing agents, e.g. hydroxypolycarboxylic, aminopolyphosphonic and hydroxyalkanephosphonic acids, and their water-soluble salts; composn. pH being 7-12 (8-11 in dilute aq. soln.). Liquid composn. esp. contains 10-50 wt.% (a), 2-20wt.% (b), 2-20 wt.% alkali hydroxide, 30-86 wt.% water. Composns. opt. contain, as (a), EDTA, aminotriacetic acid or their salts, and pref. (b):(a) ratio is 1-0.5 to 18.

Description

Dishwashing detergents The invention relates to dishwashing detergents for the machine winding of dishes with high cleaning power is difficult food residues to be removed as well as favorable corrosion behavior sensitive items to be washed.

For machine washing of dishes are usually alkaline Cleaning agent mixtures used, which are essentially based on polyphosphates, Silicates, alkali carbonates or alkali hydroxides are produced.

Draw phosphate-based cleaners with a weakly alkaline setting with good cleaning properties due to a relatively low corrosion effect against sensitive items to be washed. But they have certain weaknesses in particular critical soiling, such as burnt-on food residues in pots and pans or starchy deposits on the wash ware. Regardless, it will z. Z. also discussed whether phosphate-containing agents are undesirable can contribute to water eutrophication. Although this question is still not entirely clarified, some states are considering measures against cleaning agents containing phosphates.

Strongly alkaline cleaning agents based on alkali carbonates or caustic alkalis, on the other hand, have a relatively strong cleaning power all types of soiling, but with an increased corrosive effect Glass and onglaze decorations must be accepted.

The invention is based on the object of providing a dishwashing detergent develop, which should have the following properties in particular: 1. increased cleaning power in the case of difficult visual uses, such as burnt, protein-containing food residues, 2, less corrosive than the currently used phosphate-containing or alkaline cleaner 3. Absent or greatly reduced phosphate content.

This task is solved by a combination of 5 - 90 wt. an aminopolycarboxylic acid or its salts, 90-5% by weight of a soluble alkali silicate, O - 5% by weight of an alkali hydroxide or alkali carbonate, O - 10% by weight of a weak one foaming nonionic surfactant from the group of alkylene oxide adducts to higher Fatty alcohols or alkylphenols with 12-18 carbon atoms or on polypropylene glycols the molecular weights 900 - 4000, 0 - 10 wt .-% of an active chlorine-releasing compound, 0-5% by weight of an enzyme or enzyme mixture from the group of hydrolases, preferably Amylases, proteases and lipases, 0-10% by weight of a complexing agent from the Group of hydroxypolycarboxylic acids, aminopolyphosphonic acids and hydroxyalkanephosphonic acids, and their water-soluble salts.

The mixtures according to the invention can be used for various purposes and Requirements to be adapted to the practice. A cleaning combination that is special Strong cleaning effect on protein-containing, burnt-in food residues unfolded, has approximately the following composition: 50-80% by weight of an aminopolycarboxylic acid or their salts, 18-48% by weight of a soluble alkali silicate, O-5% by weight of a Alkali hydroxide or alkali carbonate, 1-5% by weight of a low foaming nonionic Surfactants from the group of alkylene oxide adducts with higher fatty alcohols or alkylphenols with 12 - 18 carbon atoms or on polypropylene glycols with a molecular weight of 900 - 4000, 1 - 5% by weight of an active chlorine-releasing compound For an enzyme-containing combination with a particularly good effectiveness against starchy soiling the following composition is given: 60-90% by weight of an aminopolycarboxylic acid or their salts, 5-38% by weight of a soluble alkali silicate, 0-5% by weight of a Alkali hydroxide or alkali carbonate, 1-5% by weight of a low foaming nonionic Surfactants from the group of alkylene oxide adducts with higher fatty alcohols or alkylphenols with 12 - 18 carbon atoms or on polypropylene glycols with a molecular weight of 900 - 4000, 1 - 5% by weight of an enzyme or enzyme mixture from the group of hydrolases, preferably Amylases, proteases and lipases, 0-10% by weight of a complexing agent from the Group of hydroxypolycarboxylic acids, aminopolyphosphonic acids and hydroxyalkanephosphones acids, as well as their water-soluble salts.

While the above basic formulas focus on solid, lumpy or powdered cleaners, liquid or paste-like mixtures, which are particularly easy to dose automatically, for example according to the following Formulation obtained: lo - 50 wt .-% of an aminopolycarboxylic acid or its Salts, 2 - 3o wt .-% of a soluble alkali silicate, 2 - 20 wt .-% of an alkali hydroxide, 30-86% by weight water.

Essential to the invention and for the properties of the cleaning agents claimed The decisive factor is the combination of soluble alkali silicates and aminopolycarboxylic acids or their salts. The ratio of alkali silicate to aminopolycarboxylic acids should 1: 0.5 to 18, with a ratio of for mixtures containing active chlorine 1: 1.2 to 4, for enzymatic mixtures a ratio of 1: 1.5 to 18 is preferred will.

Examples of suitable aminopolycarboxylic acids are aminotriacetic acid, Ethylenediaminotetraacetic acid, diethylenetriaminopentaacetic acid, triethylenetetraaminohexaacetic acid and their higher homologues, also ethylenediamine hydroxyethane triacetic acid, as well as their alkali and amine salts. The first two compounds mentioned are technical readily available and therefore preferred. They are under the short name NTA or EDTA known. The aforementioned aminopolycarboxylic acids are used in the claimed Mixtures as a substitute for the phosphates used in conventional cleaning agents. For reasons of cost savings, however, these can be partially replaced by the customary Alkali phosphates or alkali polyphosphates used in cleaning agents, such as sodium hexameaphosphate or pentasodium triphosphate.

Sodium or potassium metasilicates are used as soluble alkali silicates used in which the ratio of alkali oxide to silicon dioxide is about 1: - 0.5 to 3.5. If alkali hydroxides or alkali carbonates are also used in the mixtures are primarily used for this purpose, sodium hydroxide or potassium hydroxide or the corresponding carbonates into consideration. However, no more than 30 percent by weight should be used the alkali silicates are replaced by caustic alkalis, since the resulting stronger alkaline reaction lead to an increased corrosion effect of the cleaner can.

To improve the use effect of the mixtures, it is useful low-foaming, non-ionic surfactants are also used. As such come preferred {ethylene oxide adducts to higher molecular weight polypropylene glycols with a molecular weight of 900-4000 as well as adducts of ethylene oxide or ethylene oxide and propylene oxide with higher fatty alcohols, such as dodecyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol and their mixtures as well as synthetically, for example, alcohols of the chain lengths produced by oxo synthesis C12 - C18, as well as corresponding alkylene oxide adducts with nonylphenol are possible. the Production takes place in a known manner by addition of the alkylene oxides in question in the presence of alkaline catalysts, optionally under pressure and at elevated levels Temperatures, with up to three times the amount by weight of the starting compounds Alkylene oxides is added. Examples of suitable addition products are the adduct of lo - 30 percent by weight of ethylene oxide with a polypropylene glycol des Molar weight 1750, the adduct of 20 moles of ethylene oxide or of 9 moles of ethylene oxide and lo moles of propylene oxide on nonylphenol, the adduct of 5 - 12 moles of ethylene oxide on a fatty alcohol mixture of chain lengths C12 - C18 with a share of about 3o% to oleyl alcohol and the like.

Impurities that are particularly difficult to remove, such as burnt-in food residues, Lipstick and tea stains expediently require the use of active chlorine-splitting agents Compounds or enzymes in the detergent mixes.

The alkali metal salts are preferred as active chlorine-releasing compounds of isocyanuric acids, e.g. B. potassium dichloroisocyanurate is used. Keep coming also alkali hypochlorites, such as lithium or sodium hypochlorite, and hypochlorites containing complex salts, e.g. B. so-called chlorinated phosphates into consideration.

Suitable enzymes are made from; animal and vegetable materials, obtained in particular from digestive enzymes, yeasts and bacterial strains. they provide mostly a complex mixture of different enzymatic active ingredients . Of particular interest are starch, protein or fat-splitting enzymes, such as Amylases, proteases and lipases.

The enzymes are made from bacterial strains using a wide variety of processes, Mushrooms, yeast or animal organs. Usually it is Mixtures of enzymes that have a combined effect, especially against starch and protein own. The enzyme preparations obtained from Bacillus subtilis are against alkalis relatively stable and are not noticeable at temperatures between 45 and 70 ° C inactivated, making them particularly suitable for use in dishwasher detergents tteln own.

For binding the hardness components of the water, from heavy metal traces and complexing agents can also be used as buffer substances. Examples these are hydroxypolycarboxylic acids such as citric acid and tartaric acid, aminotri (methylenephosphonic acid), Ethylenediaminotetra- (methylenephosphonic acid), l-hydroxyethane-l, l-diphosphonic acid and the higher homologues of the polyphosphonic acids mentioned, etc. Instead of the Free acids their water-soluble salts are also suitable.

In addition to the constituents mentioned, the claimed mixtures other components, especially inorganic salts such as sodium sulfate or sodium chloride, included as diluent. Other possible additives are those that act as buffers Substances, dyes, perfumes and, if necessary, enzyme-activating additives, such as ammonium chloride or the like.

As far as the claimed agents are in powder form, they are packaged in a known manner by grinding and mixing the ingredients. To an intimate To achieve connection of the powder components, it can be useful to use the powder during the mixing process or afterwards with an aqueous solution crystallizing salts, e.g. 8th.

Sodium sulfate, or one of the mentioned nonionic surfactants spray. This treatment also reduces the tendency of the powder to Dusts reduced.

Liquid products are made useful by dissolving the individual components obtained in water and then mixing the solutions. It can be expedient his - especially for bringing the organic components into solution - auxiliary solvents, such as ethanol, propanol or isopropanol to be used with. Adjusting the viscosity, especially with pasty products, can be done by means of water-soluble polymer compounds, such as methyl cellulose, carboxymethyl cellulose or polyacrylates. Liquid or paste-like products are available as tradable concentrates with a content from 14 to 70 percent by weight, preferably 20 to 50 percent by weight, of solids assembled.

The cleaning agent combinations used are characterized by a high cleaning power. They are particularly suitable for burnt protein-containing To remove leftover food, lipstick marks and tea stains. So much for the mix If they contain enzymes, they are able to prevent the formation of starch deposits Dish surfaces to prevent or remove existing deposits. Of particular note is the low corrosive effect of the claimed mixtures, especially in the case of porcelain on-glaze decorations. Finally, due to the greatly reduced or missing phosphate content, the possible Prevents the risk of undesired water eutrophication.

The claimed funds can be used both in household dishwashers as used in commercial dishwashers. The addition is done by hand or by means of suitable metering devices. The liquid ones are particularly suitable Concentrates for use in automatic liquid dispensing devices such as they are already in use in many cases. The application concentrations in of the cleaning liquor are about 0.5 - lo g / l, preferably 2 - 5 g / l, so far it is a solid or powdery mixture.

In the case of liquid mixtures, the application rate is about 6 - lo g / l. The pH values of the cleaning liquors are between pH 7-12, preferably pH 8 - 11.

The wash program is generally done by some on the cleaning cycle the following intermediate rinse cycles with clear water and a rinse cycle with a common one Rinse aid supplemented and finished. After drying, you get a completely clean one and hygienically perfect dishes, example 1 Glass dishes were used to test the cleaning results of the cleaning agent mixtures claimed with burnt-on food residues, milk chocolate pudding and minced meat sauce in a household dishwasher with 3 g of detergent per liter of detergent in the cleaning cycle treated. The soiling is chosen so that it can only be removed with cleaners, which have a particularly high cleaning power is possible. It was made with a Cleaner rinsed with the following composition: 40 ß sodium metasilicate with a ratio from sodium oxide to silicon dioxide like 1 X 1 60% sodium aminotriacetate in the rinse cycle 0.4 g / l of a commercially available acidic rinse aid were dosed. To At the end of the entire wash program, the cleaning ability was assessed in each case the detergent mixtures used. A point system was used for the individual evaluations, that ranges from 0 to lo, where O points with no noticeable cleaning effect "and lo Points mean complete removal of test soiling ". This results a number of intermediate values that enable a differentiated statement. in the The following cleaning result was obtained as an example of the cleaning agent mixture listed above achieved: Removal of burnt milk: lo Removal of burnt chocolate pudding: 9 Removal of burnt minced meat: 8 With a good standard, powdery When used appropriately, phosphate-based cleaners achieved the following cleaning values preserved: Removal of burnt milk: 8 Removal of burnt chocolate pudding: 7 Removal of burnt minced meat: 6 Example 2 It was under the conditions of Example 1 with 3 g / l of the following cleaning mixture rinsed: 40 ffi sodium metasilicate with a sodium oxide to silicon dioxide ratio as 1: 1 1 60% sodium ethylenediaminetetraacetate The cleaning result corresponded Example 1, Example 3 It was as in Example 1 with 3 g / l of the following cleaners Composition rinsed: 4o% sodium metasilicate with a ratio of sodium oxide to silicon dioxide such as 1: 2.75 59% sodium aminotriacetate 1% of an adduct of 30 mole percent of ethylene oxide on a polypropylene glycol of molecular weight 900 It was The following cleaning result is achieved: Removal of burnt milk: lo removal from burnt chocolate pudding: 9 Removal of burnt minced meat: 9 Example 4 It was as in Example 1 with 3 g / l of the following cleaning composition rinsed: 40% sodium metasilicate with a ratio of sodium oxide to silicon dioxide like 1: 1.25 59% sodium ethylene diamine tetraacetate 1% of an adduct of 5 mol Ethylene oxide on an unsaturated fatty alcohol mixture of chain lengths C12 - C18 Das The cleaning result corresponded to example 3.

Example 5 A detergent mixture of the following composition was made used with a concentration of 3 g / l in a household dishwasher: 30% sodium metasilicate with a ratio of sodium oxide to silicon dioxide like 1: 1> 35 lo% soda '57 ffi sodium aminotriacetate 2% potassium dichloroisocyanurate 1% of an adduct of 5 moles of ethylene oxide with an unsaturated fatty alcohol mixture of chain lengths C12 -C18 Cups soiled with tea and lipstick residues and Glasses were rinsed completely clean, taking good care of the decoration.

Example 6 The following detergent mixture was used in one concentration of 3 g / l used in a commercial dishwasher: 30 ffi sodium metasilicate with a ratio of sodium oxide to silicon dioxide such as 1: 0.95 lo ffi caustic soda 57% sodium ethylenediaminetetraacetate 2% potassium dichloroisocyanurate 1% of an adduct of 30 mol percent ethylene oxide to a polypropylene glycol of molecular weight 900 Es was an excellent cleaning result in the practical dishwashing operation of a factory canteen obtain. Difficult and burnt-on food residues were also completely removed.

Example 7 Soils containing protein and starch became special well removed with 3 g / l of a detergent mixture of the following composition: 8.5 % Metasilicate with a sodium oxide to silicon dioxide ratio such as 1: 3.35 85% sodium aminotriacetate 3.5% citric acid 2 ffi an enzyme with amyolytic and proteolytic effectiveness (Termozym 264R, manufacturer: Novo-Industri, Copenhagen) 1 ffi of an adduct of 5 moles of ethylene oxide with an unsaturated fatty alcohol mixture of chain lengths C12-C18 Example 8 A detergent mixture with similar effectiveness against protein and starchy soiling has the following composition: 84% sodium ethylenediaminetetraacetate 5 ß sodium metasilicate with a ratio from sodium oxide to silicon dioxide as 1: 3.35 lo% of an enzyme with proteolytic and amyolytic activity (Thermozym 264 #) 1% of an adduct of 5 moles of ethylene oxide to an unsaturated fatty alcohol mixture with chain lengths Cl2-Cl8.

The purification values of this mixture are in the removal of Strongest at 9 to 10 points.

Example 9 A cleaning test was carried out with lo g / l of a liquid Rinsed detergent of the following composition: 30% sodium aminotriacetate 5% Sodium hydroxide solution 50% 20% sodium metasilicate solution 30% rest water It the following cleaning result was achieved: Removal of burnt milk: lo Removal of burnt chocolate pudding: lo Removal of burnt minced meat: lo The cleaning result can be described as optimal.

Example lo Another liquid cleaner has the following composition: 30% sodium ethylenediamine tetracetate lo% sodium hydroxide solution 50% lo ffi sodium metasilicate with a ratio of sodium oxide to silicon dioxide like 1: rest water The cleaning result was analogous to example 9.

Example 11 Decor test according to DIN 51035 It is particularly important that the dishwashing detergents do not damage the onglaze colors of dishes too much. The aggressiveness of detergents is determined according to German standards DIN 51035 "Determination of the resistance of burned-in onglaze colors and decorations to alkaline cleaning agents ". The test is carried out by treatment with 1% trisodium phosphate solution at boiling temperature and duration for 30 minutes. The one with it The attack achieved on the onglaze colors is approximately 5000 in intensity Equate passes in a dishwasher.

The results of the test carried out with various Pcr 1ttCin according to the invention Decor tests are compiled in the table below. The test clearly shows the gentle effect of the tested mixtures compared to Trinatirumphospha or a commercially available alkaline cleaner (Somat #).

Decor test according to DIN 51.035 Rosenthal test plate Seltmann - test - plate cleanser blue red yellow blue yellow d'grün gray h'grün red gold matt gold shiny Water - - - - - - - - - - - Na3PO4 weaker weaker weaker - Abried Abried - - - stained - Abrasion Abrasion Abrasion DIN test weaker weaker Somat - - - Abrasion - - - stained - Abrasion abrasion mixture in - - - - - - - - - - - - game 1 Mixture weaker In - - - Abrasion - - - - - - - - game 2 - means: no visible attack

Claims (1)

P A T E N T A N S P R Ü C H E 1. Dishwashing detergent for the machine Washing dishes, characterized by a combination of 5 - 90% by weight of one Aminopolycarboxylic acid or its salts, 90 - 5% by weight of a soluble alkali silicate, o - 5% by weight of an alkali hydroxide or alkali carbonate, o - lo Uew. - one weak foaming nonionic surfactant from the group of alkylene oxide adducts to higher Fatty alcohols or alkylphenols with 12-18 carbon atoms or on polypropylene glycols the molecular weights 900-4000, o-lo wt .-% of an active chlorine-releasing compound o -5% by weight of an enzyme or enzyme mixture from the group of hydrolases, preferably Amylases, proteases and lipases, o - 10 wt. Of a complexing agent from the Group of hydroxypolycarboxylic acids, aminopolyphosphonic acids and hydroxylalkanephosphonic acids, and their water-soluble salts 2. Solid or powder detergent according to claim 1, characterized by a combination of 50 - 80 wt. - An aminopolycarboxylic acid or their salts, 18-48% by weight of a soluble alkali silicate o-5% by weight of a Alkali hydroxide or alkali carbonate, 1-5% by weight of a low foaming nonionic Surfactants from the group of alkylene oxide adducts with higher fatty alcohols or alkylphenols with 12 - 18 carbon atoms or on folypropylene glycols with a molecular weight of 900 - 4000 1 - 5% by weight of an active chlorine-releasing compound. 3. Dishwashing detergent according to claim 1 and 2, characterized by a content of potassium dichloroisocyanurate as an active chlorine-releasing compound. 4. Solid or powder dishwashing detergent according to claim 1, characterized by a combination of 60-90% by weight of an aminopolycarboxylic acid or their salts, 5 - D8 wt .-% of a soluble alkali silicate, o - 5 wt .-% of a Alkali hydroxide or alkali carbonate, 1-5% by weight of a low foaming nonionic Surfactants from the group of alkylene oxide adducts with higher fatty alcohols or alkylphenols with 12 - 18 carbon atoms or on polypropylene glycols with a molecular weight of 900 - 4000 1 - 5% by weight of an enzyme or enzyme mixture from the group of hydrolases, preferably Amylases, proteases and lipases, 0 - lo% by weight of a complexing agent from the Group of hydroxypolycarboxylic acids, aminopolyphosphonic acids and hydroxyalkanephosphonic acids, and their water-soluble salts. 5. Dishwashing detergent according to claim 1 and 4, characterized by a content of an enzyme obtained from Bacillus subtilis with amylolytic and proteolytic effect. 6. Liquid dishwashing detergent according to claim 1, characterized by a combination of lo - 50% by weight of an aminopolyearboxylic acid or its salts, 2 - 50% by weight of a soluble alkali metal silicate, 2 - 20% by weight of an alkali metal hydroxide, 3o - 86 wt. Water. 7. Dishwashing detergent according to claim 1-6, characterized by a Content of ethylenediaminotetraacetic acid or aminotriacetic acid or their salts. 8. Dishwashing detergent according to claim 1-6, characterized by a Content of a soluble alkali silicate with a ratio of alkali oxide: silicon dioxide like 1: 0.5 to 3.5. 9. Dishwashing detergent according to claim 1-8, characterized by a Ratio of alkali silicate to aminopolycarboxylic acids or their salts such as 1: 0.5 to 18. lo. Dishwashing detergent according to claims 1-9, characterized by a pH value from 7 to 12, preferably 8 to 11 in dilute aqueous solution.