JPH0219160B2 - - Google Patents

Description

[Detailed description of the invention]

As is well known, food container cleaners used at home, in the food and beverage industry and in factories often contain large amounts of condensed phosphates, especially tripolyphosphates, which are extremely effective for their good cleaning action. The phosphate content of this composition has been criticized in public opinion in connection with environmental protection issues. It is often argued that phosphates reaching rivers and oceans via water promote eutrophication of the water, ie an increase in algae growth and oxygen consumption.
Efforts are therefore being made to remove or significantly reduce the proportion of phosphates from washing and cleaning processes or from the compositions used therein. According to Japanese Patent Publication No. 57-61798, (1) Synthetic surfactant (2) Basically the general formula: (Kat ₂ /nO)x・Al ₂ O ₃ (SiO ₂ )y [In the formula, Kat is calcium n-valent cations that can be exchanged with, x is a number from 0.7 to 1.5, and y is
represents a number from 1.3 to 4], has bound water, and has interference fringes in the X-ray diffraction diagram measured using the Cu-K line. Substantially any of the following d-
Value (Å): − 14.4 12.4 − − 8.8 8.6 − 7.0 − − 4.4(+) 4.1(+) − − 3.8(+) 3.68(+) − 3.38(+) − 3.26(+) − 2.96(+) − - 2.88 (+) - 2.79 (+) 2.73 (+) - - 2.66 (+) 2.60 (+) - Phosphate substitute, water-insoluble, crystallized synthetic active substances and ( 3) Textile detergents containing water-soluble substances capable of complexing and/or precipitating calcium have been proposed. The present invention is a further development of Japanese Patent Publication No. 57-61798, and relates to a cleaning agent for mechanically cleaning food containers, which comprises alkali carbonate and/or alkali hydroxide and/or It contains an alkali metal silicate, an active chlorine-containing substance and a water-insoluble aluminosilicate which may together contain an inorganic phosphorous-containing complexing agent for calcium, the water-insoluble aluminosilicate being finely distributed and anhydrous active substance. per 1g
Formula: 0.7~
It is characterized by being a compound of _1.1Na2O・_Al2O3・_1.3 ~ _2.4SiO2 . Aluminosilicates are used to partially or completely replace phosphates, especially tripolyphosphates, present in conventional food container cleaning agents. Preference is given to using aluminosilicates, at least 80% by weight of which consist of particles with a particle size of 10 to 0.01 .mu.m, preferably 8 to 0.1 .mu.m. Advantageously, the aluminosilicate does not contain primary or secondary particles larger than 40μ. Aluminosilicates of this particle size are referred to herein as "microcrystalline." The production conditions of the aluminosilicate already contribute to the formation of small particle sizes, in which the aluminate solution and the silicate solution mixed with each other (which can be simultaneously introduced into the reaction vessel) are exposed to strong shearing forces. expose to To prepare the crystallized aluminosilicates which are advantageously used according to the invention, the formation of large and possibly penetrating crystals is avoided by slowly stirring the crystallizing material. Nevertheless, since undesired agglomeration of microcrystalline particles may occur during drying, it is recommended to remove these secondary particles in a suitable manner, for example by air sieving. Aluminosilicate which precipitates in a coarse state can also be used after being pulverized to a desired particle size. For example, mills and/or wind sieves or combinations thereof are suitable for this purpose. The latter is, for example, Ullmann's “Enzyklopaedie der technischen Chemie”.
[Volume 1, pages 632-634 (1951)]. Food containers in the sense of the present invention include household,
Used in the food and beverage industry and factories for storage, food preparation and serving, and should be cleaned after use.
Refers to all tableware made of ceramic, glass, plastic, wood, and metal. The cleaning agent according to the invention can also be used in large cooking facilities, in the dairy industry, in the drinking water industry, for example in the brewing industry, in addition to the household and restaurant or lodging industry.
It can also be used in operations producing or processing lemonade, mineral waters and fruit juices, in particular for mechanical cleaning and cleaning of bottle containers. However, the method is also suitable for cleaning equipment contaminated with residues other than food and drink, such as laboratory equipment. The aluminosilicate is preferably used in a concentration of 0.5 to 3 g/g. In particular, it is used in combination with an alkaline-reacting substance, and the alkaline-reacting substance is used in such an amount that the pH value of the treatment bath is within the range of 8 to 13. Such alkaline-reacting substances are preferably alkali metal silicates and alkali metal carbonates and, if high pH values are required, caustic alkalis. According to the invention, the action of the detergents can be improved by the addition of small amounts of surfactants, especially nonionic surfactants. In addition, the addition of substances with oxidizing action, in particular active chlorine compounds, and optionally peroxy compounds, has also proven advantageous. The composition of the cleaning agent according to the invention is generally within the following formulation: optionally an alkali metal carbonate and/or hydroxide and/or an inorganic phosphorus-containing complexing agent, which is preferably an alkali metal silicate (which may be present in an amount corresponding to the maximum P content)
10-60% by weight Aluminosilicate (as active substance) 10-65% by weight Other common ingredients in food container washer cleaners 0-40% by weight Other common ingredients in food container cleaners include: The following substances belong and are usually present in the amounts stated below: Active chlorine- or oxygen-containing substances 0-10% by weight Surface-active agents, especially non-ionic surfactants 0-10% by weight Sodium sulfate and/or ) Water 0-20% by weight The cleaning action of aluminosilicate can be improved by a water-soluble carboxylic acid polymer or a water-soluble salt thereof, which has the ability to form a complex with calcium.
In this case, the aluminosilicates can be partially replaced by the additives mentioned above. Complexing agents of the type of water-soluble polycarboxylic acids (advantageously used in the form of water-soluble salts) used according to the invention in combination with the aluminosilicates as defined above are for example sugars, starches and celluloses. carboxymethyl ether. Furthermore, acrylic acid, hydroxyacrylic acid, maleic acid, itaconic acid,
Polymerization products of mesaconic acid, aconitic acid, methylene maleic acid, citraconic acid, etc., mutually or ethylenically unsaturated compounds of the carboxylic acids, such as ethylene, propylene, isobutylene, vinyl alcohol, vinyl methyl ether, furan, acrone, Copolymerization products with vinyl acetate, acrylamide, acrylonitrile, methacrylic acid, crotonic acid, etc., such as maleic anhydride and ethylene or propylene or furan 1:
1-Copolymerization products belong. Finally, there belongs a group of polyhydroxypolycarboxylic acid or polyaldehydepolycarboxylic acid compounds mainly composed of acrylic acid units and acrolein units or acrylic acid units and vinyl alcohol units,
These are obtained by copolymerization of acrylic acid and acrolein or by polymerization of acrolein followed by Canitzaro reaction optionally in the presence of formaldehyde. These carboxylic acid polymers are preferably used as homo- or copolymerization products of unsaturated mono- or dicarboxylic acids containing up to 6 C atoms in the molecule according to their structure, or as homo- or copolymerization products of unsaturated mono- or dicarboxylic acids containing up to 6 C atoms in their molecules. - unsaturated hydrocarbons, alcohols, containing up to 6 atoms;
These can be understood as copolymerization products with ethers, aldehydes, esters, amides or nitriles (even if they cannot be obtained by polymerization of mixtures of the corresponding starting materials). The combination of aluminosilicate and carboxylic acid polymer or salt thereof used according to the invention is preferably used in a concentration of 0.5 to 3 g/g. In this case, the ratio of aluminosilicate to carboxylic acid polymer is 10:1 ~
1:10, advantageously in the range from 4:1 to 1:4. Other aluminosilicates having a cation exchange function used in the present invention, their properties, and their production are described in the above-mentioned Japanese Patent Publication No. 57-61798. In particular, the content of organic and/or inorganically bound phosphorus in the treatment bath is at most 0.6 g/, in particular at most 0.3 g/;
And in detergents this applies with regard to the possibility of reducing it by up to 6%, preferably up to 3%. EXAMPLES The following examples describe detailed embodiments of compositions according to the invention. Prescriptions according to the state of the art are designated by the letter "V" (Vergleich comparison), and those according to the invention by the letter "a", "b", "c" or "d". The aluminosilicate used had the following composition: 0.9Na ₂ O・Al ₂ O ₃・2.04SiO ₂・4.3H ₂ O (=
H ₂ O2 1.6%) Completely crystalline Calcium binding capacity: AS (anhydrous active substance) CaO 150mg per 1g: 1.5Na ₂ O・Al ₂ O ₃・2SiO ₂・3H ₂ O (=H ₂ O14.4
%) Amorphous by X-rays Calcium binding capacity: 140mg of CaO per 1g of AS: Na ₂ O・Al ₂ O ₃・2SiO ₂・H ₂ O (=H ₂ O6%) Amorphous by X-rays Calcium-binding capacity: 150mg of CaO per 1g of AS XII :0.9Na ₂ O・Al ₂ O ₃・2SiO ₂・3H ₂ O (=H ₂ O11
%) Fully crystalline Calcium binding capacity: 160 mg CaO/g AS The amounts stated for the aluminosilicate in the formulation refer to the anhydrous active substance, determined by dehydration at 800° C. for 1 hour. The water contained in the aluminosilicate is specifically mentioned together with the water optionally further contained in the composition. "DCIC" stands for the sodium or potassium salt of dichloroisocyanuric acid. What is “liquid water glass”? Composition: Na ₂ O・3.35SiO ₂
A 35% solution of sodium silicate. “Nonionik” is an ethylene oxide addition product of polypropylene glycol ether with a molecular weight of 1900, obtained under the commercial name “Pluronic L61”, with a proportion of polypropylene glycol ether of 90% by weight and a proportion of polyethylene glycol ether of 10% by weight. Weight%. Example 1 Glass dishes soiled with adhering or burnt residues of ground meat, milk and starch pudding in a commercial household dishwasher (a) Glass dishes, dried adhering starch - or mashed oats soiled by boiling (a) b) Ceramic dishes, (c) cups stained with hard fat such as lipstick or dried tea scum were cleaned using the following composition. The hardness of the tap water used was lowered to 3°dH by a base exchanger installed in the washer.
The detergent concentration was 3g/.

It has been shown that most soils can be removed with the phosphorus-free or low-containing compositions according to the invention at least as well as with the phosphorus-containing comparison products according to the state of the art. It has been shown that for stubborn and even lightly burnt soils the cleaner according to the invention is even superior to the comparative products. When the above experiment was repeated using unsoftened tap water (16° dH), the same results as when using soft water were obtained. Of course, it was recommended to increase the detergent concentration to 5g/. Example 2 A composition of the following composition is suitable for use in porcelain with delicate decoration:

[Table] Example 3 To prepare a specific granulated cleaning agent for use in domestic washing machines, with the following formulation, nonionic is dissolved in water, water glass is added, and this solution is mixed with other powdered detergents. The mixture of ingredients in a state of motion, which is preferably formed on a granulating device, for example a granulating dish, is sprayed onto the mixture. The desired granules are then obtained after coagulating the water as crystallization water.

Table: The product is used analogously to the product according to Example 1 or 2. Exactly similar results are obtained. Example 4 The following composition is suitable for use in cleaning equipment in large kitchens, hotels, etc.

[Table] Reliably clean utensils can be obtained when dispensing 2 to 4 g/dose. Example 5 The detergent of this example is suitable for the same applications as example 4. Due to its strong alkalinity, it is particularly suitable for use in large commercial installations with a very short action time of the washing liquid, for example only 10 to 20 seconds.

TABLE The compositions according to Examples 5, 10, 15 and 20 are suitable as laboratory cleaners or for cleaning wine, beer, lemonade or mineral water bottles. When cleaning such bottles, it is desirable to increase the sodium hydroxide content of the composition. The following Examples 6-10 contain water-soluble salts of carboxylic acid polymers in addition to the aluminosilicate. The following substances are useful as complex-forming polycarboxylic acids, preferably in the form of their sodium salts. Polyacrylic acid Poly-α-hydroxyacrylic acid Polymaleic acid Polyitaconic acid Itacone/aconitic acid copolymerization product Itacone/acrylic acid copolymerization product Ethylene/maleic acid copolymerization product Vinyl methyl ether/maleic acid copolymerization product Product isobutylene/maleic acid - copolymerization product polyoxycarboxylic acid (=POC) 1 (from acrolein and formaldehyde) = 120, COOH:OH = 1.87 POC2 (from acrolein and formaldehyde)
P=120, COOH:OH=4.0 POC3 (from acrolein)=50, COOH:OH
=8.6 POC4 (from acrolein and acrylic acid) =
10, COOH:OH=3.6 POC5 (from acrolein, acrylic acid and formaldehyde) = 320, COOH:OH=4.6 POC6 (from acrolein, acrylic acid and formaldehyde) = 600, COOH:OH=5.4 POC7 (from acrolein and formaldehyde)
P=5, COOH:OH=1.5 POC8 (from acrolein and acrylic acid)=60,
COOH:OH=2.3 POC9 (from acrolein, acrylic acid, maleic acid) = 65, COOH:OH=4.9 POC10 (from acrolein, maleic acid, formaldehyde) = 90, COOH:OH=1.0 POC11 (acrolein, acrylic acid, formaldehyde) ) = 120, COOH:OH = 2.3 POC12 (from acrolein) = 18, COOH:
OH=8.3 Example 6 The experimental results described in Example 1 were obtained under the same experimental conditions (3
g/, 3° dH) using the following composition.

[Table] When the experiment described here was repeated using unsoftened tap water (16°dH), the same results as when using soft water were obtained. Example 7 A composition of the following composition is suitable for use in porcelain with delicate decoration.

[Table] Example 8 To prepare a special granulated cleaning agent for use in household washing machines, with the following formulation, nonionic is dissolved in water, water glass is added, and this solution is mixed with other powdered The mixture of ingredients (preferably produced on a granulating device, for example a granulating dish) is sprayed in a state of motion. After the water has condensed as water of crystallization, the desired granules are obtained.

Table: This product is used analogously to the products according to Examples 1 or 2 or 6 or 7. Exactly similar results are obtained. Example 9 The following composition is suitable for use in cleaning machines in large kitchens, hotels, etc.

[Table] A dosage of 2 to 4 g/min gives perfectly clean utensils. Example 10 The detergent of this example is suitable for the same intended use as that of example 4. Due to its strong alkalinity, it is particularly suitable for use in large commercial installations with a very short washing action time, for example only 10 to 20 seconds.

Table The following Examples 11 to 15 describe compositions according to the invention in which a portion of the aluminosilicate is replaced by a water-insoluble ion exchanger (also in this case additionally a water-soluble ion exchanger of the carboxylic acid polymer). salt can be used).
As an ion exchanger, CaO135 per gram of active substance
A material based on reticulating polystyrene sulfonic acid (commercial name: "LEWATIT ^R S100") with a calcium binding capacity of 1.0 mg and a particle size of 0.3 to 0.8 mm was used. Example 11 The experimental results described in Example 1 were obtained under the same experimental conditions (3
g/; 3° dH) using the following composition.

[Table] When the experiment described here was repeated using unsoftened tap water (16° dH), the same results were obtained as when using softened water. Example 12 The following composition is suitable for use in porcelain with delicate decoration.

[Table] Example 13 To prepare a specific granulated cleaning agent of the following formulation for use in domestic washing machines, Norionik is dissolved in water, water glass is added and this solution is mixed with other powdered , onto the mixture of ingredients in motion, which is preferably produced on a granulation device, for example a granulation dish. The desired granules are obtained after the water has condensed as water of crystallization.

TABLE This product is used analogously to the products according to Examples 1 or 2 or 11 or 12 with exactly the same results. Example 14 The following composition is suitable for use in washing machines in large kitchens, hotels, etc.

[Table] A dosage of 2 to 4 g/min gives perfectly clean utensils. Example 15 The detergent of this example is suitable for the same intended use as that of examples 4 or 14. Due to its strong alkalinity, it is particularly suitable for use in large commercial installations with a very short washing action time, for example only 10 to 20 seconds.

Table: Comparison of the action of the product according to the invention with a corresponding product containing tonipolyphosphate but without aluminosilicate shows the advantageous action of the product according to the invention: Usual in practice stains are dissolved by the compositions according to the invention at least as well as by the comparative products. For very stubborn soils, the products according to the invention often show superiority over the known ones. Deposition of water-insoluble aluminosilicate in the washing tank of a large washer was not observed, at least when the washing solution was moved continuously and the aluminosilicate was rotated. To ensure that irreversible deposition of aluminosilicates is avoided when left standing for long periods of time,
Incorporating a suitable device for swirling the aluminosilicate in the washing bath or at the bottom of the washing bath so that the particles that may settle as the case may slide to the deepest point.
Therefore, it is recommended that the suction pipe of the washing liquid pump be used to feed the washing liquid back into the circulation. Microcrystalline aluminosilicates have proven particularly advantageous in this respect. This is true for Examples 1-5.
This was demonstrated by replacing the aluminosilicate used in , with a microcrystalline product. The microcrystalline product is the following aluminosilicate. _n : 0.9Na ₂ O・Al ₂ O ₃・2.04SiO ₂・4.3H ₂ O (=
_H2O21.6 %) Completely crystalline Calcium binding capacity: per gram of active substance
CaO170mg XII _n :0.9Na ₂ O・Al ₂ O ₃・2SiO ₂・3H ₂ O (=H ₂ O1
%) Completely crystalline Calcium binding capacity: 175mg of CaO per 1g of AS _n : 0.28Na ₂ O・0.62K ₂ O・Al ₂ O ₃・
2.04SiO ₂・4.3H ₂ O (=H ₂ O20.5%) Completely crystalline Calcium binding capacity: 150 mg of CaO per 1g of AS _n : 0.9Na ₂ O・Al ₂ O ₃・2SiO ₂・4.4H ₂ O (=
Fully crystalline ( _H2O22.2 %) Calcium binding capacity: 172 mg CaO/g AS The particle size distribution of the microcrystalline product (hence indicated by the appended letter "m"), determined by sedimentation analysis, is as follows: It was within the range. >40μ = 0% Particle size of maximum distribution = 1-3μ <10μ = 100% <8μ = 99% The following example describes a product containing microcrystalline aluminosilicate. Example 16 The experimental results described in Example 1 were obtained under the same experimental conditions (3
g/; 3° dH) using the following composition.

[Table] Example 17 The following composition is suitable for use in porcelain with delicate decoration.

[Table] Example 18 To produce a specific granulated cleaning agent for use in household cleaning machines having the following formulation, nonionic is dissolved in water, water glass is added and this solution is mixed with other of the components in a pulverulent, moving state, which is advantageously produced on a granulating device, for example a granulating plate. The desired granules are obtained after the water has condensed as water of crystallization.

Table: This product is used analogously to the products according to Examples 1 and 2 or 16 and 17. Exactly similar results are obtained. Example 19 The following composition is suitable for use in cleaning equipment in large kitchens, hotels, etc.

[Table] A dosage of 2 to 4 g/min gives perfectly clean utensils. Example 20 The detergent of this example is suitable for the same intended use as that of example 4. Due to its strong alkalinity, it is particularly suitable for use in large commercial installations with very short wash action times, for example only 10 to 20 seconds.

【table】

Claims (1)

[Claims] 1 Foods containing alkali metal silicates, active chlorine-containing substances and water-insoluble aluminosilicates, which may together contain alkali carbonates and/or alkali hydroxides and/or inorganic phosphorus-containing complexing agents for calcium. In cleaning agents for mechanically cleaning containers, water-insoluble aluminosilicates are finely distributed, have a calcium binding capacity of 100-200 mg of CaO per gram of anhydrous active substance, contain bound water, and are crystalline. The formula: 0.7~ _1.1Na2O was synthesized.
A cleaning agent for mechanically cleaning food containers, characterized in that it is _a compound _{of Al2O3.1.3-2.4SiO2} .