EP0075813B2 - Application d'un agent de nettoyage pâteux dans machines à laver la vaisselle - Google Patents

Application d'un agent de nettoyage pâteux dans machines à laver la vaisselle Download PDF

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Publication number
EP0075813B2
EP0075813B2 EP82108636A EP82108636A EP0075813B2 EP 0075813 B2 EP0075813 B2 EP 0075813B2 EP 82108636 A EP82108636 A EP 82108636A EP 82108636 A EP82108636 A EP 82108636A EP 0075813 B2 EP0075813 B2 EP 0075813B2
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EP
European Patent Office
Prior art keywords
weight
detergent
sodium
potassium
viscosity
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP82108636A
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German (de)
English (en)
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EP0075813A3 (en
EP0075813A2 (fr
EP0075813B1 (fr
Inventor
Theodor Dr. Altenschöpfer
Klaus Dr. Schumann
Peter Dr. Christophliemk
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT82108636T priority Critical patent/ATE25108T1/de
Publication of EP0075813A2 publication Critical patent/EP0075813A2/fr
Publication of EP0075813A3 publication Critical patent/EP0075813A3/de
Publication of EP0075813B1 publication Critical patent/EP0075813B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1266—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid compositions

Definitions

  • the detergents used in dishwashers usually consist of powders or granules or tablets. Accordingly, the input devices in which the detergents are deposited before rinsing in these machines are also designed for test products and usually consist of lockable chambers which open during the main wash cycle and release the contents.
  • a number of disadvantages result from this method of working. B. when entering the cleaner, the housewife must shake the storage pack or measuring cup so that the powder slides into the chamber, and it often happens that more or less large portions of the powder are spilled and / or get on the skin. These spilled parts are mostly lost in the rinsing process because they are pumped out together with the cold prewash solution at the end of the pre-rinse cycle.
  • the object of the invention is to develop a cleaner which can be used in dishwashers and which does not have the disadvantages described and which can be used in conventional dishwashers and can also be used in machines to be developed with a stored cleaner. In these cases, automatic dosing from a detergent supply would then take place.
  • the viscosity of the cleaner is preferably 80 to 150 Pa-s.
  • the thixotropy of the cleaner is not significantly disturbed by the measuring process. Such disturbances do not occur at a rotational speed of the spindle inserted into the sample of 5 rpm.
  • a Brookfield viscometer for example, is suitable, but other measurement methods can also be used for the determination, which allow measurement under comparable conditions.
  • the rheological behavior of the cleaner is such that the gel-like paste is affected mechanical forces, for example by shaking or pressure on a deformable storage bottle or tube or liquefied by means of a metering pump and easily squeezed out of a spray nozzle or can be transferred into the induction chamber.
  • the agent solidifies again into a gel which remains unchanged in the induction chamber when the flap is closed. It can thus be achieved that the product survives one or two pre-rinse cycles as a paste and is therefore only available as intended in the cleaning cycle.
  • the closure flap has opened and the agent comes into contact with the moving detergent solution, the gel instantaneously liquefies and the agent distributes itself in the detergent solution in a short time. It is therefore available from the moment the cleaner is released to its cleaning power, which is why the cleaning effect is more intensive than in the conventional rinsing process.
  • the tripolyphosphate used in the cleaners used according to the invention can be completely or partially replaced by water-insoluble, finely divided, bound water-containing alkali alumosilicates which have a calcium binding capacity of 50 to 200 mg CaO / g active substance (AS) and the formula preferably correspond.
  • AS CaO / g active substance
  • Such connections are known for example under the name SASIL®.
  • the calcium binding capacity of the aluminosilicates is determined in the following way:
  • component (A) is also suitable for commercial dishwashers. Less preferred constituents of component (A) are the carbonates or hydrogen carbonates of sodium or potassium, which are generally only used together with alkali compounds which have a more cleaning action.
  • component (A) has the following composition:
  • Component (B) preferably consists of sodium, potassium or lithium hypochlorite.
  • Other useful active chlorine compounds that can be used are chlorinated trinatium or tripotassium o-phosphate.
  • Organic chlorine carriers such as trichloroisocyanuric acid or alkali metal dichloroisocyanurates or N-chlorinated sulfamides or triazines, are less preferred since they are less stable in storage in the cleaners to be used according to the invention.
  • the amount of active chlorine carrier is preferably such that the cleaners contain 0.1 to 3.0% by weight, in particular 0.5 to 2.0% by weight, of active chlorine.
  • Component (C) consists of a thickener resistant to alkalis and active chlorine, which is able to form a thixotropic gel in water.
  • Swellable layered silicates of the montmorillonite type have proven to be suitable which, in 5% by weight aqueous suspension after complete swelling with a conventional rotary viscometer and a speed of the measuring spindle of 5 revolutions per minute, have a viscosity of at least 30 Pa-s (20 ° C.).
  • Complete swelling means that after the thickeners have been completely distributed in water, which is expediently carried out with the aid of a highly effective stirring device at temperatures of 30-60 ° C., after several days of aging or standing at room temperature, the viscosity, even with further thermal or mechanical treatment no longer increases.
  • Natural or synthetic phyllosilicates have proven particularly suitable for component (C) proven of the hectorite type. Both the processed natural and the synthetic hectorites can still contain certain impurities which do not interfere with the use according to the invention by means. In the processed natural hectorites, these are other layered silicate types or small additions to calcite, with synthetically produced z. B. sodium carbonate or sodium sulfate. The water-soluble by-products of the synthesis do not need to be washed out or not completely, which considerably reduces the production outlay.
  • synthetic hectorite it does not need to be dewatered before the cleaner is manufactured, but can be processed further after centrifuging or filtration as an aqueous slurry or moist filter cake without further pretreatment to give the cleaners to be used according to the invention.
  • Hectorites are generally understood to mean trioctahedral layered magnesium silicates of the general formula where x is a value greater than 0 and less than 6, y is a value from 0 to 4 and n is an integer from 1 to 3 and M is a cation.
  • the water content of an air-dry product is generally 5 to 10% by weight.
  • the layered silicates are used in fine-grained form, i. H.
  • the proportion of the sieve analysis on a sieve with a mesh size of 0.25 mm should be less than 5% by weight, preferably less than 1% by weight.
  • the amount of the layered jiculate to be used depends primarily on its ability to swell. In the case of hectorite, generally 1 to 10% by weight, preferably 2 to 6% by weight (based on hectorite dried at 105 ° C.) are used.
  • Optional non-ionic surfactants with low foaming power are used as optional components, which do not decompose in the presence of active chlorine compounds and possibly alkali metal hydroxides.
  • Suitable addition products are the adduct of 10 to 30% by weight of ethyleneokide with a polypropylene glycol with a molecular weight of 1750, the adduct of 20 mol of ethylene oxide or 9 mol of ethylene oxide and 10 mol of propylene oxide with nonylphenol, the adduct of 5 to 12 mol of ethylene oxide to a fatty alcohol mixture of chain lengths C 12 -C 18 with a share of about 30% in oleyl alcohol and the like.
  • the proportion of the non-ionic surfactants can be up to 5% by weight, preferably 0.1 to 1% by weight.
  • chlorine and alkali-resistant dyes and fragrances can be added to the dishwashing detergents.
  • Optional components of the active ingredients used such as sodium sulfate, sodium chloride or mineral admixtures of the layered silicate, are also possible.
  • Other usable complexing agents are active chlorine-resistant, generally non-pollutant-free complexing agents, e.g. B. polyvalent phosphonic acids such as methylenediphosphonic acid or polyhydric P h ospho- include aminocarboxylic as 1.1 diphosphonopropane-1,2-dicarboxylic acid, 1-phosphonopropane-1.2,3-tricarboxylic acid or 2-phosphonobutane-2.3,4-tricarboxylic acid or their sodium or potassium salts. In addition, useful complexing agents are the active chlorine-resistant polycarboxylic acids and their salts.
  • the cleaning agents to be used according to the invention are advantageously prepared by mixing an aqueous solution or slurry containing the cleaning constituents of components (A), in particular the tripolyphosphate and, if appropriate, the alkali silicate (water glass), or a mixture thereof the thickener with heating to 40 to 65 ° C with a high shear agitator, for example an Ultra-Turrax® device, stirred until the thickening takes place. Then the remaining components of component (A), e.g. . B. metasilicate, water glass and possibly the residues of triphosphate and the optional components, such as nonionic surfactants and dyes, are stirred in. After cooling to room temperature, the active chlorine compound is finally added, for example in the form of a sodium hypochlorite solution (chlorine bleach).
  • a sodium hypochlorite solution chlorine bleach
  • the funds can be filled into the storage containers immediately after they have been produced.
  • the maximum value of the viscosity is generally reached after a standing time of 2 to 10 days.
  • a brief liquefaction occurs through vigorous shaking or pressing, however, the gel state is restored just a few seconds after the mechanical stress has ended, i. H. the cleaner introduced into the storage chamber of the dishwasher solidifies sufficiently quickly that it does not flow out after the closure cap of the storage chamber or the loading door of the dishwasher is closed.
  • the cleaners to be used according to the invention are distinguished by a high cleaning power and in particular by a long shelf life.
  • the active chlorine loss during a 6-month service life at 25 ° C was of the same order of magnitude as that of commercially available detergent granules stored in a dry place.
  • repeated heating of the cleaner to temperatures of around 60 ° C. has not proven to be disadvantageous to the storage stability or the active chlorine content.
  • the detergent paste which was repeatedly warmed up by heat transfer, did not suffer any loss of active chlorine which would have an adverse effect on the wash result within the test period of 5 days (2 rinse cycles per day).
  • Another particular advantage is that the agents can be dosed much more easily and precisely than conventional granular or powdered cleaners, which are often spilled when filling the spatially limited induction compartments due to the mostly necessary shaking of the supply package or the dosing cup.
  • the majority contain foam-active surfactants, bleaches containing active chlorine, clay-like fillers, including hectorite, and a special abrasive component as the main component.
  • the thickener primarily serves to prevent the specific light abrasive from settling.
  • DE-A-28 10 187 discloses alkaline agents and a process for pretreating heavily soiled kitchen appliances which are free of abrasives, about 0.25 to about 20% of a clay as a thickener and about 0.5 to about 9% of one Contain alkali metal silicate with a ratio of SiO 2 : M 2 0 of more than about 1 with M equal to sodium or potassium, which have a hypohalite concentration with an active chlorine content of about 0.5 to 10% and whose viscosity is about 1 to about 10,000 Pa- s and are applied to kitchen appliances with dirt that is difficult to remove. Then everything is covered with an excess of water at a temperature of more than about 38 ° C.
  • the viscosity of the preferably thixotropic agents tends to be considerably higher than with the agents of the present invention, since they should adhere well and long to the soiled surfaces, in order to be able to act there, while the consistency of the cleaners according to the invention is only intended to ensure their meterability. In addition, they should be released quickly in the dishwasher cleaning cycle.
  • the devices pre-cleaned according to DE-A-28 10 187 can subsequently be introduced into dishwashers. Their used coating is supposed to suppress foam, but then no longer has a cleaning effect due to a lack of tripolyphosphates.
  • Hectorite 1 is a commercial product from Lanco. in the case of the commercial product Laponite B @ from Laporte ind. Ltd.
  • the water content of the products was 7-8% by weight, the grain size (sieve analysis) was less than 0.2 mm with an average grain size of approx. 0.006-0.008 mm.
  • the viscosity of a 5% by weight aqueous gel was 75 Pa.s for hectorite 1 and 95 Pa.s for hectorite II.
  • the commercial granular cleaner used for comparison has the following composition:
  • a pasty cleaner containing (in% by weight) was produced by stirring the 50% triphosphate solution heated to 55 ° C. with the addition of the hectorite until it had thickened with an intensive stirrer (Ultra-Turrax®). Then 2% by weight sodium metasilicate was stirred in as a powdery powder. After the disilicate had been added in the form of a 54.5% by weight solution, the paste was cooled and the sodium hypochlorite in the form of a NaCl-containing chlorine bleach (active chlorine content 13%) and the rest of the sodium metasilicate were incorporated.
  • the viscosity measured after a standing time of 10 days under the specified conditions was 125 Pa.s.
  • Example 1 was repeated, except that dry potassium tripolyphosphate was stirred into an aqueous swelling made from filter-moist hectorite 1 with an unchanged amount of water. The further processing was carried out as indicated in Example 1. The viscosity of the paste determined under the specified conditions was 115 Pa.s.
  • Example 3 was repeated using the thickener labeled "Hectorite I".
  • the viscosity of the agent was 103 Pa ⁇ s.
  • the cleaner of the following composition was prepared by mixing the ingredients in the order given at 55 ° with an intensive stirrer.
  • the chlorine bleach was incorporated after the paste cooled.
  • the viscosity determined by definition after 10 days of standing was 98 Pa.s.
  • the chlorine bleach was added after the mixture had been heated to 60 ° C.
  • the viscosity was 120 Pa ⁇ s after standing for 10 days.
  • Example 6 was repeated except that prior to addition of chlorine bleaching liquor in addition 0.3% polymeric polypropylene oxide polyethylene oxide block of a nonionic non-foaming surfactant from the class of releasing was added i.
  • the viscosity of the paste after 118 days of standing was 118 Pa.s.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Claims (7)

1. Utilisation, pour l'alimentation dosée par le dispositif de rinçage dans les lave-vaisselle, d'un agent de nettoyage thixotrope aqueux, pâteux à l'état de repos à la température ordinaire, ayant une teneur de
(A) 3 à 40% en poids de tripolyphosphate de sodium et/ou de potassium,
5 à 30% en poids de silicates de sodium et/ou de potassium, consistant en un mélange de métasilicates et de disilicates ou de verre soluble dans le rapport de mélange de 2 : 1 à 1 : 10, calculé en substances anhydres,
0 à 25% en poids d'alumosilicate de sodium finement divisé fixant les sels de calcium et
0 à 20% en poids de carbonate et/ou d'hydroxyde de sodium et/ou de potassium,
(B) un composé à chlore actif ayant une teneur en chlore actif rapportée à l'agent de nettoyage tout entier de 0,1 à 3,0% en poids et
(C) 1 à 10% en poids d'un silicate lamellaire gonflable ayant une grande capacité de gonflement dans des milieux aqueux, dont la viscosité à 20°C déterminée au moyen d'un viscosimètre rotatif selon Brookfield à 5 tours de rotor par minute et se rapportant à une suspension aqueuse à 5% en poids complètement gonflée, s'élève au moins à 30 Pa.s, la viscosité de l'agent de nettoyage, déterminée à 20°C au moyen d'un viscosimètre rotatif à 5 tours de rotor par minute, s'élevant à 70 à 200 Pa.s.
2. Utilisation d'un agent de nettoyage selon la revendication 1, dont la viscosité s'élève à 80 à 150 Pa.s.
3. Utilisation d'un agent de nettoyage selon les revendications 1 et 2, dans lequel le composant (A) se compose des constituants suivants : 5 à 30% en poids de tripolyphosphate de sodium et/ou de potassium, 5 à 30% en poids de silicate de sodium et/ou de potassium sous forme de mélange de métasilicates et de disilicates ou de verre soluble dans le rapport de mélange de 2 : 1 à 1 : 10, de préférence de 1 : 1 à 1 : 5, calculé en substances anhydres, 0 à 10% en poids d'alumosilicate de sodium, 0 à 5% en poids d'hydroxyde de sodium et/ou de potassium.
4. Utilisation d'un agent de nettoyage selon les revendications 1 à 3, dans lequel le composant (B) consiste en un hypochlorite de métal alcalin.
5. Utilisation d'un agent de nettoyage selon les revendications 1 à 4, dans lequel le composant (B) consiste en de l'hypochlorite de sodium et la teneur en chlore actif de l'agent de nettoyage tout entier s'élève à 0,5 à 2,0% en poids.
6. Utilisation d'un agent de nettoyage selon les revendications 1 à 5, dans lequel le composant (C) consiste en de l'hectorite.
7. Utilisation d'un agent de nettoyage selon les revendications 1 à 6, dans lequel la quantité du composant (C) s'élève à 2 à 6% en poids.
EP82108636A 1981-09-26 1982-09-18 Application d'un agent de nettoyage pâteux dans machines à laver la vaisselle Expired - Lifetime EP0075813B2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82108636T ATE25108T1 (de) 1981-09-26 1982-09-18 Verwendung eines pastoesen reinigers in geschirrspuelmaschinen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19813138425 DE3138425A1 (de) 1981-09-26 1981-09-26 "verwendung eines pastoesen reinigers in geschirrspuelmaschinen"
DE3138425 1981-09-26

Publications (4)

Publication Number Publication Date
EP0075813A2 EP0075813A2 (fr) 1983-04-06
EP0075813A3 EP0075813A3 (en) 1984-03-07
EP0075813B1 EP0075813B1 (fr) 1987-01-21
EP0075813B2 true EP0075813B2 (fr) 1991-12-18

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ID=6142735

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82108636A Expired - Lifetime EP0075813B2 (fr) 1981-09-26 1982-09-18 Application d'un agent de nettoyage pâteux dans machines à laver la vaisselle

Country Status (4)

Country Link
US (1) US4801396A (fr)
EP (1) EP0075813B2 (fr)
AT (1) ATE25108T1 (fr)
DE (2) DE3138425A1 (fr)

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DE102015109017A1 (de) 2015-06-08 2016-12-08 Budich International Gmbh Reinigungsmittel zur Reinigung von gewerblichen Gargeräten
DE102015109019A1 (de) 2015-06-08 2016-12-08 Budich International Gmbh Reinigungsvorrichtung für gewerbliche Gargeräte

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US4248728A (en) * 1979-02-28 1981-02-03 Chemed Corporation Liquid scouring cleanser

Also Published As

Publication number Publication date
EP0075813A3 (en) 1984-03-07
EP0075813A2 (fr) 1983-04-06
EP0075813B1 (fr) 1987-01-21
US4801396A (en) 1989-01-31
DE3138425A1 (de) 1983-04-14
ATE25108T1 (de) 1987-02-15
DE3275205D1 (en) 1987-02-26

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