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, in these machines, the input devices in which the detergents are deposited before rinsing are designed for solid products and usually consist of closable chambers that remain open during of the main wash cycle and release the contents.
• a number of disadvantages result from this method of working. When entering the cleaner, the housewife has to shake the storage pack or the measuring cup so that the powder slides into the chamber, and it often happens that more or less large parts of the powder are spilled and / or get on the skin. These spilled parts are usually lost for the rinsing process, since they are pumped out together with the cold prewash solution at the end of the prewash cycle.
• the object of the invention is to develop a cleaner which can be used in dishwashers, who does not have the disadvantages described and can be used both in conventional dishwashers and can also be used in machines still to be developed with stored detergents. In these cases, automatic dosing from a detergent supply would then take place.
• the viscosity of the cleaner is preferably 70 to 200 Pa.s and in particular 80 to 150 Pa.s.
• the thixotropy of the agent 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 can be liquefied by the action of mechanical forces, for example by shaking or pressure on a deformable storage bottle or tube or by means of a metering pump, and can easily be squeezed out of a spray nozzle or 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 gel instantaneously liquefies and the agent distributes itself in the detergent solution in a short time. It is therefore available to the cleaner from the moment the cleaner is released, which is why the cleaning effect is more intensive than in the conventional rinsing process.
• the agents to be used according to the invention contain a cleaning component (A) which consists of polyphosphates, aluminosilicates, silicates, hydroxides or carbonates of sodium or potassium or mixtures thereof.
• Sodium hydroxide or potassium hydroxide are also suitable, in particular for commercially operated dishwashers. Less preferred constituents of component (A) are also 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 (B) consists of an active chlorine compound, preferably sodium, potassium or lithium hypochlorite. Chlorinated trisodium or tripotassium o-phosphate can be used as a further useful compound.
• 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 the 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 which is resistant to alkalis and active chlorine and which can form a thixotropic gel in water.
• Swellable sheet silicates of the Montrnorillonite 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 thickener has been completely distributed in water, which is expediently carried out with the aid of a highly effective stirrer 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 layered silicates of the hectorite type have proven to be particularly suitable for component (C). Both the processed natural and the synthetic hectorites can still contain certain impurities which do not interfere with the use of the compositions according to the invention. In the case of the processed natural hectorites, these are other layered silicate types or low additions to calcite, in the case of synthetically produced e.g. 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 If synthetic hectorite is used, it does not need to be dewatered before the cleaner is produced, but can, after the majority of the water has been separated off, be further processed by centrifuging or filtration as an aqueous slurry or moist filter cake to form the cleaners to be used according to the invention without further pretreatment.
• 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.
• Layered silicates are used in fine-grained form, i.e. 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 silicate to be used depends primarily on its ability to swell. In the case of hectorite, 1 to 10% by weight, preferably 2 to 6% by weight (based on hectorite dried at 105 ° C.) are generally 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 hydroxides.
• Suitable addition products are the adduct of 10 to 30% by weight of ethylene oxide 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 containing about 30% oleyl alcohol and the like.
• This exemplary list is not a limitation.
• the proportion of the nonionic surfactants can be up to 5% by weight, preferably 0.1 to 1% by weight.
• chlorine and alkali-resistant colors and fragrances can be added to the dish detergents.
• Additional components of the active substances used such as sodium sulfate, sodium chloride or mineral admixtures of the layered silicate, are also suitable as optional components.
• complexing agents which can be used are active chlorine-resistant, generally nitrogen-free complexing agents, e.g. polyvalent phosphonic acids such as methylene diphosphonic acid or polyvalent phosphonocarboxylic acids such as 1,1-di-phosphonopropane-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.
• active chlorine-resistant polycarboxylic acids and their salts are also useful complexing agents.
• the cleaning agents to be used according to the invention are advantageously prepared by combining an aqueous solution or slurry containing the cleaning components of component (A), in particular the tripolyphosphate and optionally the alkali silicate (water glass), or a part thereof with the thickener while heating to 40 to 65 ° C with a high shear agitator, for example an Ultra-Turrax® device, until thickening has taken place stirred.
• a high shear agitator for example an Ultra-Turrax® device
• the remaining constituents of component (A) for example metasilicate, water glass and possibly the residues of triphosphate, as well as the optional constituents, such as nonionic surfactants and dyes, can be stirred in.
• the active chlorine compound is finally added, for example in the form of a sodium hypochlorite solution (chlorine bleach).
• the agents can be filled into the storage containers immediately after their manufacture.
• 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 a few seconds after the mechanical stress has ended, i.e. the cleaner introduced into the storage chamber of the dishwasher solidifies sufficiently quickly that it does not flow out after the closing flap of the storage chamber or the loading door of the dishwasher.
• 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 dry commercial 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).
• the agents can be dosed much more easily and precisely than conventional granular or powdered cleaners, which are often spilled in part when filling into the spatially limited induction chambers because of the mostly necessary shaking of the storage package or the dosing cup.
• 4,051,055 and 4,051,056 and DE-OS 25 39 733 and 27 39 776 describe pasty abrasives which contain anionic, nonionic, zwitterionic or ampholytic, ie, in the majority foam-active surfactants, bleaches containing active chlorine , clay-like fillers, including hectorite, and contain a special abrasive component as the main component.
• the thickener primarily serves to prevent the specific light abrasive from settling.
• the idea of using low-foaming, abrasive-free cleaning agents instead of conventional powdered or granulated products in dishwashers is completely foreign to these publications, especially since the task is also completely different.
• Hectorite I is a commercial product from Lanco
• Hectorite II is 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 I and 95 Pa.s for hectorite II.
• the soiling is selected so that removal with other conventional cleaners which have a high cleaning power is only partially possible in order to still have differentiation options even with these high-performance products.
• the evaluation is carried out according to a point system that ranges from 0 to 10, with 0 points meaning "without a recognizable cleaning effect" and 10 points meaning "complete removal of the test soiling".
• 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 I 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 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 ten days of standing.
• Example 6 was repeated, with an additional 0.3% of a nonionic, non-foaming surfactant from the class of the polypropylene oxide-polyethylene oxide block polymer being added before the chlorine bleach.
• 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)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (4)

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ID=6142735

Family Applications (1)

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Cited By (14)

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• 1981
  • 1981-09-26 DE DE19813138425 patent/DE3138425A1/de not_active Withdrawn
• 1982
  • 1982-09-18 DE DE8282108636T patent/DE3275205D1/de not_active Expired
  • 1982-09-18 AT AT82108636T patent/ATE25108T1/de not_active IP Right Cessation
  • 1982-09-18 EP EP82108636A patent/EP0075813B2/fr not_active Expired - Lifetime
• 1987
  • 1987-07-20 US US07/075,284 patent/US4801396A/en not_active Expired - Fee Related

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