EP0187257B1 - Carpet cleaning agent - Google Patents
Carpet cleaning agent Download PDFInfo
- Publication number
- EP0187257B1 EP0187257B1 EP85115249A EP85115249A EP0187257B1 EP 0187257 B1 EP0187257 B1 EP 0187257B1 EP 85115249 A EP85115249 A EP 85115249A EP 85115249 A EP85115249 A EP 85115249A EP 0187257 B1 EP0187257 B1 EP 0187257B1
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- EP
- European Patent Office
- Prior art keywords
- zeolite
- weight
- cleaning preparation
- granules
- dry cleaning
- 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
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Classifications
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- 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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
- C11D3/2017—Monohydric alcohols branched
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- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0031—Carpet, upholstery, fur or leather cleansers
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- 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
- C11D3/128—Aluminium silicates, e.g. zeolites
Definitions
- the present invention relates to a powdery zeolite-containing agent intended for dry cleaning textiles, in particular carpets.
- adsorbents for example synthetic resin foam powder (AT 296 477), fuller's earth, talc, sawdust (DE 15 19 045) and bleached wood flour (CH 461 685).
- a sodium aluminum silicate known as zeolite has proven to be a particularly effective adsorbent both in shampoo formulations and in powder detergents. Agents on this basis, as described, for example, in German Offenlegungsschrift 25 44 605, are distinguished by a high cleaning ability. Problems arise with this material, however, from the dust nuisance and an unusually strong adhesion of the fine-particle zeolite powder to the textile fibers, which means that the cleaning agent can only be removed incompletely and the treated textiles, in particular dark-colored carpets, have a gray appearance.
- the proposal in European patent application EP 62 536 to add zeolite powder to a likewise insoluble carrier material, in particular cellulose powder has not been able to make any decisive changes to these undesirable side effects. It was therefore still the task to develop dry cleaning agents for textiles with better properties overall.
- the present invention offers a solution to this problem in the form of dry cleaning agents in powder form, which contain surfactants, organic solvents and zeolite, and thereby are characterized in that the zeolite is in the form of a porous granulate which is resistant to the mechanical stresses which are usual in dry cleaning.
- the agents according to the invention lack the abovementioned disadvantages of the agents of the prior art, that is to say they do not develop any annoying dust when used and can be removed almost completely from the textiles, so that graying does not occur.
- the re-soiling of the textiles after cleaning is unusually low.
- the agents are further characterized in that when they are used, normally no drying time is required between the incorporation of the powder into the textile and the removal of the powder.
- the finding of the solution according to the invention is particularly surprising that, despite the agglomeration of the zeolite powder to form larger, stable particles, the high cleaning performance of the agents working with finely divided zeolite is retained.
- the preparation of the compositions comprises two stages, namely the production of the zeolite granules, which in the simplest case consist of zeolite and granulating aids, and the mixing of these granules with the other components of the compositions.
- these constituents can be wholly or partly incorporated into the granules in the first stage, so that only the constituents remaining, in particular the organic solvents, have to be mixed with the porous granules, the liquid constituents in particular being taken up by them .
- the starting material for the production of the granules are the finely divided crystalline zeolites of types A, P, X, Y and hydroxysodalite, which are in dry form or in Form aqueous suspensions, such as those obtained in the manufacture, can be used.
- Sodium ions are said to be predominantly present as exchangeable cations in the zeolites.
- Zeolite A is preferably used, which has a particularly high cleaning power and is technically easily accessible. In air-dried commercial form, it has a water content of approximately 15 to 25 percent by weight, which cannot be further reduced without the use of extreme conditions. Unless otherwise stated, data on parts by weight of zeolite therefore include the water content of the zeolites which cannot be removed by air drying.
- the content of zeolite in the finished cleaning agents is 40 to 90 percent by weight, preferably 55 to 75 percent by weight.
- Zeolite granules are known from the literature in a wide variety of compositions, but are generally not suitable in this form for dry cleaning textiles. So you know from DOS 28 06 799 zeolite granules, which are produced by calcining at temperatures around 800 ° C and used to soften drinking water. Another type of zeolite granules is known for example from DAS 27 14 604, DOS 30 07 320, DOS 30 45 221 and EP-PS 21 267. The granules described there are primarily intended for use in detergents, i.e.
- the zeolite granules suitable for the agents according to the invention can also be obtained by built-up granulation, for example by agglomeration of zeolite powder with the aid of water and a granulating aid in a drum or paddle mixer or on a plate granulator.
- Other components of the cleaning agents such as surfactants or acids, can be incorporated into the granules. If water is used in the granulation or if moist starting materials are used, the granulation process is followed by a drying step, for which also conventional processes, such as drying in a fluidized bed at temperatures up to about 200 ° C., can be used.
- a particularly preferred process for the production of suitable porous zeolite granules is the spray drying process, in which an aqueous slurry of the zeolite, the granulating aid and, if appropriate, further constituents is sprayed into droplets which then dry in an air stream when they fall down.
- this process enables aqueous starting materials to be processed without problems and, on the other hand, combines the formation of the granulate particles and their drying in one process.
- the purpose of the granulation is that significantly larger particles are built up from the originally very finely divided zeolite, which have such mechanical stability that they withstand the brushing and friction stress associated with the application.
- Suitable granules have less than 2% by weight of particles with a size of 0.05 mm and below and less than 5% by weight of particles larger than 2 mm (determined by sieve analysis). The best performance properties are shown by granules, the individual parts of which have a diameter of over 0.2 to 1.6 mm, more than 80 percent by weight, preferably over 90 percent by weight.
- the mechanical stability of the granules can be determined with the aid of a simple test: in a vibrating ball mill made of porcelain, which has a content of 1 liter and is loaded with 5 process balls of 28 mm in diameter, 100 g of the granules are run at 1400 revolutions per minute for 1 minute Treated for a minute, then sieved.
- the proportion of particles with sizes up to 0.2 mm increases by no more than 15 percent by weight, preferably by no more than 5 percent by weight, in particular by no more than 2 percent by weight, based on the total weight of the granules.
- Suitable granulation aids are solid, readily water-soluble organic or inorganic substances which have only a slight tendency to crystallize and are not hygroscopic. Substances which tend to polymerize, such as soluble alkali silicates, or which already have a polymeric structure, such as polymeric carboxylic acids and their salts, and soluble cellulose derivatives are particularly suitable. Water-soluble sodium silicate (water glass) and water- or alkali-soluble homo- and copolymers of acrylic acid or methacrylic acid are preferably used. Soluble sodium silicate in combination with polyacrylic acid or polymethacrylic acid is particularly preferred as the granulation aid.
- the amount of granulating aid based on the total cleaning agent, is 1 to 20, preferably 5 to 20 percent by weight. Based on the Content of anhydrous zeolite, the amount of granulation aid is between 3 and 40 percent by weight, preferably between 10 and 30 percent by weight.
- Suitable surfactants for the agents according to the invention are primarily nonionic and anionic surfactants. Nonionic surfactants are preferably used.
- Suitable anionic surfactants are in particular those of the sulfate and sulfonate type, but other types such as soaps, long-chain N-acyl sarcosinates, salts of fatty acid cyanamides or salts of ether carboxylic acids, as are obtainable from long-chain alkyl or alkylphenyl polyglycol ethers and chloroacetic acid, can also be used .
- the anionic surfactants are usually used in the form of the sodium salts.
- Particularly suitable surfactants of the sulfate type are the sulfuric acid monoesters of long-chain primary alcohols of natural and synthetic origin with 10 to 20 carbon atoms, i.e. of fatty alcohols, such as B. coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, or the C10- C20 - oxo alcohols and those of secondary alcohols of these chain lengths.
- fatty alcohols such as B. coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, or the C10- C20 - oxo alcohols and those of secondary alcohols of these chain lengths.
- sulfuric acid monoesters of the aliphatic primary alcohols, secondary alcohols or alkylphenols ethoxylated with 1 to 6 mol of ethylene oxide come into consideration.
- Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.
- the surfactants of the sulfonate type are primarily the salts of sulfosuccinic acid mono- and diesters with 6 to 22 carbon atoms in the alcohol parts, the alkylbenzenesulfonates with C9 - C15 alkyl groups and Esters of ⁇ -sulfo fatty acids, e.g. B. the ⁇ -sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
- alkanesulfonates which are obtainable from C12-C18 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins
- olefin sulfonates which are mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as they are obtained, for example, from long-chain monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
- Suitable nonionic surfactants for the agents according to the invention are in particular addition products of 1 to 30, preferably 4 to 15 moles of ethylene oxide with 1 mole of a compound having 10 to 20 carbon atoms from the group of alcohols, alkylphenols, carboxylic acids and carboxamides.
- the addition products of ethylene oxide with long-chain primary or secondary alcohols, such as, for example, fatty alcohols or oxo alcohols, and with mono- or dialkylphenols having 6 to 14 carbon atoms in the alkyl groups are particularly important.
- non-ionic surfactants which can be used are the water-soluble adducts of ethylene oxide with 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups with polypropylene glycol, alkylenediamine-poly-propylene glycol and with alkylpolypropylene glycols having 1 to 10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic radical .
- nonionic surfactants of the amine oxide, sulfoxide or alkyl glucoside type can be used, for example N-cocoalkyl-N, N-dimethylamine oxide or the condensation products of long-chain alcohols having 10 to 18 carbon atoms and glucose, and also their ethylene oxide adducts.
- nonionic surfactants are the reaction products of 4 to 15 moles of ethylene oxide (EO) and 1 mole of fatty alcohol with 12 to 18 carbon atoms.
- EO ethylene oxide
- Typical representatives of these surfactants are tallow fatty alcohol + 5 EO, tallow fatty alcohol + 14 ED, oleyl / cetyl alcohol + 10 EO and coconut fatty alcohol + 4 EO.
- the agents according to the invention contain 0.5 to 15 percent by weight, preferably 1 to 5 percent by weight. They are preferably wholly or partly in the first step of the manufacture, i.e. incorporated in the granulation of the zeolite.
- the agents of the invention contain organic solvents as a further component. All solvents customary in the field of textile cleaning can be used, but solvents with boiling points above 80 ° C. from the group consisting of gasolines, alcohols, ethers and esters are preferably used. Examples of such solvents are gasoline (boiling range 140 to 200 ° C), isopropanol, isooctanol, triethylene glycol, butyl diglycol and butyl diglycol acetate. Because of their good fat-dissolving power, gasoline, isopropanol, dipropylene glycol momomethyl ether and mixtures thereof are particularly preferred. The proportion of solvent in the cleaning agent is 5 to 30, preferably 8 to 25 percent by weight. Water is contained in the agents only in such an amount as is retained by the zeolites during the production of the granules.
- Synthetic zeolites often contain large amounts of free alkalis, which can be recognized by the high pH of an aqueous slurry. Since many textile materials and dyes are sensitive to alkalis, acids can be added to neutralize the alkali in the preparation of the agents in order to avoid damage. Solid water-soluble organic or inorganic acids, for example amidosulfonic acid and oxalic acid, are preferred. Acidic alkali phosphates, tartaric acid, citric acid and ethylenediaminetetraacetic acid are particularly preferred because their salts, which form during the neutralization, support the cleaning action of the agents. The amount of acid is determined by the alkali content of the zeolite and the desired degree of neutralization.
- no more than 10% by weight of acid, based on the total composition, is used, preferably an amount which causes the zeolite granules to have a pH between 6.5 and 9 (measured on a 1% slurry in water). having.
- Polymeric carboxylic acids such as polyacrylic acid and polymethacrylic acid are also suitable for neutralization. If such acids are already used as granulation aids, it is normally not necessary to add further acids.
- the cleaning agents according to the invention can also contain further active substances customary in the cleaning treatment of textiles.
- active ingredients are antistatic components, optical brighteners, substances that reduce re-soiling and perfume.
- These components together can contain up to 10 percent by weight, preferably make up up to 5% by weight of the cleaning agents. They are preferably added to the zeolite granules with the solvent in the second step of the production process.
- the cleaning of the textiles and carpets takes place in such a way that the agents of this invention are applied to the surfaces to be cleaned and then rubbed intensively into the textiles, for example with the aid of a sponge or a brush, the dirt on the textiles being with the Particles of the detergent connects.
- training times 0.5 to 2.5 minutes, preferably 0.5 to 1.5 minutes per square meter are chosen.
- the residues are then removed from the textiles together with the dirt mechanically, for example by brushing or vacuuming.
- the agents according to the invention use 20 to 200 grams per square meter, but larger quantities can also be applied in places to remove individual stains.
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- Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft ein pulverförmiges, Zeolith enthaltendes Mittel, das zur Trockenreinigung von Textilien, insbesondere von Teppichen, bestimmt ist.The present invention relates to a powdery zeolite-containing agent intended for dry cleaning textiles, in particular carpets.
Zur Reinigung von Teppichen und anderen textilen Belägen an Ort und Stelle verwendet man neben Shampoos in neuerer Zeit zunehmend pulverförmige Reinigungsmittel, die den Vorteil aufweisen, keine Ränder zu hinterlassen und schneller abzutrocknen. Derartige Reinigungspulver enthalten als wesentliche Bestandteile Tenside und Adsorptionsmittel sowie größere Mengen von Wasser in lose gebundener Form. Von den Tensiden wird angenommen, daß sie zusammen mit dem vorhandenen Wasser für die Ablösung der Schmutzteilchen von den Fasern und für deren Transport zum Adsorptionsmittel sorgen, das dann nach dem Abtrocknen des Wassers zusammen mit dem Schmutz abgebürstet oder abgesaugt wird. Als Adsorptionsmittel sind die verschiedensten Materialen vorgeschlagen worden, beispielsweise Kunstharzschaumpulver (AT 296 477), Fullererde, Talcum, Sägemehl (DE 15 19 045) und gebleichtes Holzmehl (CH 461 685).To clean carpets and other textile coverings on the spot, in addition to shampoos, powdered cleaning agents have recently been used which have the advantage of not leaving any edges and drying faster. Such cleaning powders contain, as essential components, surfactants and adsorbents as well as larger amounts of water in loosely bound form. The surfactants are believed to work together with the existing water to detach the dirt particles from the fibers and to transport them to the adsorbent, which is then brushed or vacuumed off with the dirt after the water has dried. A wide variety of materials have been proposed as adsorbents, for example synthetic resin foam powder (AT 296 477), fuller's earth, talc, sawdust (DE 15 19 045) and bleached wood flour (CH 461 685).
Trotz der im Vergleich zu Shampoos deutlich geringeren Flüssigkeitsmengen, die mit diesen pulverförmigen Mitteln aufgebracht werden, müssen auch bei diesen Mitteln Trockenzeiten bis zu mehreren Stunden eingehalten werden, da sonst die Rückstände nur sehr unvollständig entfernt werden können. Dies wirkt sich vor allem bei der gewerblichen Reinigung nachteilig aus.Despite the significantly smaller amounts of liquid that are applied with these powdery compositions compared to shampoos, drying times of up to several hours must also be observed with these compositions, since otherwise the residues can only be removed very incompletely. This has a disadvantageous effect especially in commercial cleaning.
Als ein besonders wirksames Adsorptionsmittel hat sich sowohl in Shampooformulierungen als auch in pulverförmigen Reinigungsmitteln ein als Zeolith bekanntes Natriumaluminiumsilikat herausgestellt. Mittel auf dieser Basis, wie sie beispielsweise in der deutschen Offenlegungsschrift 25 44 605 beschrieben sind, zeichnen sich durch ein hohes Reinigungsvermögen aus. Probleme ergeben sich mit diesem Material aber aus der Staubbelästigung und einer ungewöhnlich starken Haftung des feinteiligen Zeolithpulvers an den Textilfasern, die zur Folge hat, daß das Reinigungsmittel nur unvollständig entfernt werden kann und die behandelten Textilien, insbesondere dunkel gefärbte Teppiche, ein graues Aussehen bekommen. An diesen unerwünschten Begleiterscheinungen hat auch der Vorschlag in der europäischen Offenlegungsschrift EP 62 536, Zeolithpulver an ein ebenfalls unlösliches Trägermaterial, insbesondere Cellulosepulver anzulagern, nichts entscheidendes ändern können. Es bestand daher nach wie vor die Aufgabe, Trockenreinigungsmittel für Textilien mit insgesamt besseren Eigenschaften zu entwickeln.A sodium aluminum silicate known as zeolite has proven to be a particularly effective adsorbent both in shampoo formulations and in powder detergents. Agents on this basis, as described, for example, in German Offenlegungsschrift 25 44 605, are distinguished by a high cleaning ability. Problems arise with this material, however, from the dust nuisance and an unusually strong adhesion of the fine-particle zeolite powder to the textile fibers, which means that the cleaning agent can only be removed incompletely and the treated textiles, in particular dark-colored carpets, have a gray appearance. The proposal in European patent application EP 62 536 to add zeolite powder to a likewise insoluble carrier material, in particular cellulose powder, has not been able to make any decisive changes to these undesirable side effects. It was therefore still the task to develop dry cleaning agents for textiles with better properties overall.
Die vorliegende Erfingung bietet eine Lösung dieser Aufgabe in Gestalt von Trockenreinigungsmitteln in Pulverform, die Tenside, organische Lösungsmittel und Zeolith enthalten und die dadurch gekennzeichnet sind, daß der Zeolith in Form eines porösen, gegen die bei der Trockenreinigung üblichen mechanischen Belastungen beständigen Granulates vorliegt.The present invention offers a solution to this problem in the form of dry cleaning agents in powder form, which contain surfactants, organic solvents and zeolite, and thereby are characterized in that the zeolite is in the form of a porous granulate which is resistant to the mechanical stresses which are usual in dry cleaning.
Den erfindungsgemäßen Mitteln fehlen die oben genannten Nachteile der Mittel des Standes der Technik, das heißt, sie entwickeln bei der Anwendung keinen lästigen Staub und lassen sich nahezu vollständig von den Textilien entfernen, so daß eine Vergrauung nicht auftritt. Die Wiederanschmutzung der Textilien nach der Reinigung ist ungewöhnlich gering. Die Mittel zeichnen sich weiterhin dadurch aus, daß bei ihrer Anwendung im Normalfall keine Trockenzeit zwischen dem Einarbeiten des Pulvers in das Textil und der Wiederentfernung des Pulvers erforderlich ist. Besonders überraschend an der erfindungsgemäßen Lösung ist der Befund, daß trotz der Agglomeration des zeolithpulvers zu größeren stabilen Teilchen die hohe Reinigungsleistung der mit feinverteiltem Zeolith arbeitenden Mittel erhalten bleibt.The agents according to the invention lack the abovementioned disadvantages of the agents of the prior art, that is to say they do not develop any annoying dust when used and can be removed almost completely from the textiles, so that graying does not occur. The re-soiling of the textiles after cleaning is unusually low. The agents are further characterized in that when they are used, normally no drying time is required between the incorporation of the powder into the textile and the removal of the powder. The finding of the solution according to the invention is particularly surprising that, despite the agglomeration of the zeolite powder to form larger, stable particles, the high cleaning performance of the agents working with finely divided zeolite is retained.
Die Herstellung der Mittel umfaßt zwei Stufen, nämlich die Herstellung des Zeolithgranulates, das im einfachsten Fall aus Zeolith und Granulierhilfsmittel besteht, und die Vermischung dieses Granulates mit den sonstigen Bestandteilen der Mittel. Einige dieser Bestandteile können aber ganz oder teilweise bereits in der ersten Stufe in die Granulate eingearbeitet werden, so daß nur die dann noch verbleibenden Bestandteile, insbesondere die organischen Lösungsmittel, mit den porösen Granulaten vermischt werden müssen, wobei insbesondere die flüssigen Bestandteile von diesen aufgenommen werden.The preparation of the compositions comprises two stages, namely the production of the zeolite granules, which in the simplest case consist of zeolite and granulating aids, and the mixing of these granules with the other components of the compositions. However, some or all of these constituents can be wholly or partly incorporated into the granules in the first stage, so that only the constituents remaining, in particular the organic solvents, have to be mixed with the porous granules, the liquid constituents in particular being taken up by them .
Ausgangsmaterial für die Herstellung der Granulate sind die feinteiligen kristallinen Zeolithe der Typen A, P, X, Y und Hydroxysodalith, die in trockener Form oder in Form wäßriger Suspensionen, wie sie bei der Herstellung anfallen, eingesetzt werden können. Als austauschfähige Kationen sollen in den Zeolithen vorwiegend Natriumionen vorliegen. Bevorzugt wird Zeolith A verwendet, der eine besonders hohe Reinigungskraft besitzt und technisch gut zugänglich ist. Er weist in luftgetrockneter handelsüblicher Form einen Wassergehalt von etwa 15 bis 25 Gewichtsprozent auf, der ohne Anwendung extremer Bedingungen nicht weiter reduziert werden kann. Angaben über Gewichtsanteile Zeolith beziehen daher, wenn nichts anderes angegeben ist, den durch Lufttrocknung nicht entfernbaren Wassergehalt der Zeolithe ein.The starting material for the production of the granules are the finely divided crystalline zeolites of types A, P, X, Y and hydroxysodalite, which are in dry form or in Form aqueous suspensions, such as those obtained in the manufacture, can be used. Sodium ions are said to be predominantly present as exchangeable cations in the zeolites. Zeolite A is preferably used, which has a particularly high cleaning power and is technically easily accessible. In air-dried commercial form, it has a water content of approximately 15 to 25 percent by weight, which cannot be further reduced without the use of extreme conditions. Unless otherwise stated, data on parts by weight of zeolite therefore include the water content of the zeolites which cannot be removed by air drying.
In den fertigen Reinigungsmitteln beträgt der Gehalt an Zeolith 40 bis 90 Gewichtsprozent, vorzugsweise 55 bis 75 Gewichtsprozent.The content of zeolite in the finished cleaning agents is 40 to 90 percent by weight, preferably 55 to 75 percent by weight.
Zeolithgranulate sind aus der Literatur in verschiedensten Zusammensetzungen bekannt, aber in der Regel in dieser Form nicht für die Trockenreinigung von Textilien geeignet. So kennt man aus der DOS 28 06 799 Zeolithgranulate, die durch calcinieren bei Temperaturen um 800°C hergestellt und zur Enthärtung von Trinkwasser verwendet werden. Ein anderer Typ von Zeolithgranulaten ist beispielsweise aus der DAS 27 14 604, der DOS 30 07 320, der DOS 30 45 221 und der EP-PS 21 267 bekannt. Die dort beschriebenen Granulate sind in erster Linie für die Anwendung in Waschmitteln bestimmt, das heißt, ihre Zusammensetzung wurde im Hinblick auf einen schnellen Zerfall der Granulate im Waschwasser optimiert, wobei die Granulierung durchweg als Aufbaugranulierung, d.h. durch Agglomerierung des feinteiligen Zeoliths mit Hilde unterschiedlicher Zusatzstoffe durchgeführt wurde.Zeolite granules are known from the literature in a wide variety of compositions, but are generally not suitable in this form for dry cleaning textiles. So you know from DOS 28 06 799 zeolite granules, which are produced by calcining at temperatures around 800 ° C and used to soften drinking water. Another type of zeolite granules is known for example from DAS 27 14 604, DOS 30 07 320, DOS 30 45 221 and EP-PS 21 267. The granules described there are primarily intended for use in detergents, i.e. their composition has been optimized with a view to rapid disintegration of the granules in the washing water, with the granulation consistently as a build-up granulation, that is to say through agglomeration of the finely divided zeolite with various additives was carried out.
Auch die für die erfindungsgemäßen Mittel geeigneten Zeolithgranulate können durch Aufbaugranulation gewonnen werden, beispielsweise durch Agglomeration von Zeolithpulver mit Hilfe von Wasser und einem Granulierhilfsmittel in einem Trommel- oder Schaufelmischer oder auf einem Tellergranulator. Weitere Bestandteile der Reinigungsmittel, wie Tenside oder Säuren können in die Granulate eingearbeitet werden. Sofern Wasser bei der Granulierung verwendet wird oder von feuchten Ausgangsmaterialien ausgegangen wird, schließt sich an den Granulierungsprozeß ein Trocknungsschritt an, für den ebenfalls übliche Verfahren, wie etwa die Trocknung im Fließbett bei Temperaturen bis etwa 200 °C, verwendet werden können.The zeolite granules suitable for the agents according to the invention can also be obtained by built-up granulation, for example by agglomeration of zeolite powder with the aid of water and a granulating aid in a drum or paddle mixer or on a plate granulator. Other components of the cleaning agents, such as surfactants or acids, can be incorporated into the granules. If water is used in the granulation or if moist starting materials are used, the granulation process is followed by a drying step, for which also conventional processes, such as drying in a fluidized bed at temperatures up to about 200 ° C., can be used.
Ein besonders bevorzugtes Verfahren zur Herstellung von geeigneten porösen Zeolithgranulaten ist das Sprühtrockenverfahren, bei dem eine wäßrige Aufschlämmung des Zeoliths, des Granulierhilfsmittels und gegebenenfalls weiterer Bestandteile zu Tröpfchen versprüht wird, die dann beim Herabfallen in einem Luftstrom trocknen. Dieses Verfahren ermöglicht einerseits, problemlos wäßrige Ausgangsmaterialien zu verarbeiten und kombiniert andererseits die Bildung der Granulatteilchen und deren Trocknung in einem Prozeß.A particularly preferred process for the production of suitable porous zeolite granules is the spray drying process, in which an aqueous slurry of the zeolite, the granulating aid and, if appropriate, further constituents is sprayed into droplets which then dry in an air stream when they fall down. On the one hand, this process enables aqueous starting materials to be processed without problems and, on the other hand, combines the formation of the granulate particles and their drying in one process.
In jedem Falle soll durch die Granulierung erreicht werden, daß aus dem ursprünglich sehr feinteiligen Zeolith deutlich größere Teilchen aufgebaut werden, die eine solche mechanische Stabilität aufweisen, daß sie die mit der Anwendung verbundene Bürst- und Reibbeanspruchung überstehen. Geeignete Granulate weisen weniger als 2 Gewichtsprozent an Teilchen mit einer Größe von 0,05 mm und darunter und weniger als 5 Gewichtsprozent an Teilchen mit einer Größe über 2 mm (bestimmt durch Siebanalyse) auf. Die besten Gebrauchseigenschaften zeigen dabei Granulate, deren Einzelteile zu über 80 Gewichtsprozent, vorzugsweise über 90 Gewichtsprozent, Durchmesser von über 0,2 bis 1,6 mm besitzen. Die mechanische Stabilität der Granulate läßt sich mit Hilfe eines einfachen Tests ermitteln: In einer Kugelschwingmühle aus Porzellan, die einem Inhalt von 1 Liter hat und mit 5 Prozellankugeln von 28 mm Durchmesser beladen ist, werden 100 g des Granulates 1 Minute lang bei 1400 Umdrehungen pro Minute behandelt, dann gesiebt. Bei erfindungsgemäß geeigneten Granulaten steigt unter diesen Testbedingungen der Anteil der Teilchen mit Größen bis 0,2 mm um nicht mehr als 15 Gewichtsprozent, vorzugsweise um nicht mehr als 5 Gewichtsprozent, insbesondere um nicht mehr als 2 Gewichtsprozent, bezogen auf das Gesamtgewicht des Granulates.In any case, the purpose of the granulation is that significantly larger particles are built up from the originally very finely divided zeolite, which have such mechanical stability that they withstand the brushing and friction stress associated with the application. Suitable granules have less than 2% by weight of particles with a size of 0.05 mm and below and less than 5% by weight of particles larger than 2 mm (determined by sieve analysis). The best performance properties are shown by granules, the individual parts of which have a diameter of over 0.2 to 1.6 mm, more than 80 percent by weight, preferably over 90 percent by weight. The mechanical stability of the granules can be determined with the aid of a simple test: in a vibrating ball mill made of porcelain, which has a content of 1 liter and is loaded with 5 process balls of 28 mm in diameter, 100 g of the granules are run at 1400 revolutions per minute for 1 minute Treated for a minute, then sieved. In the case of granules suitable according to the invention, the proportion of particles with sizes up to 0.2 mm increases by no more than 15 percent by weight, preferably by no more than 5 percent by weight, in particular by no more than 2 percent by weight, based on the total weight of the granules.
Als Granulierhilfsmittel kommen feste, gut wasserlösliche organische oder anorganische Substanzen, die nur geringe Neigung zur Kristallisation besitzen und nicht hygroskopische sind, in Betracht. Besonders gut eignen sich solche Substanzen, die zur Polymerisation neigen, wie lösliche Alkalisilikate, oder die bereits polymere Struktur aufweisen, wie polymere Carbonsäuren und deren Salze, sowie lösliche Cellulosederivate. Vorzugsweise werden wasserlösliches Natriumsilikat (Wasserglas) und wasser- oder alkalilösliche Homo- und Copolymerisate von Acrylsäure oder Methacrylsäure verwendet. Ganz besonders wird als Granulierhilfsmittel lösliches Natriumsilikat in Kombination mit Polyacrylsäure oder Polymethacrylsäure bevorzugt. Die Menge an Granulierhilfsmittel beträgt, bezogen auf das gesamte Reinigungsmittel, 1 bis 20, vorzugsweise 5 bis 20 Gewichtsprozent. Bezogen auf den Gehalt an wasserfreiem Zeolith liegt die Menge an Granulierhilfsmittel zwischen 3 und 40 Gewichtsprozent, vorzugsweise zwischen 10 und 30 Gewichtsprozent.Suitable granulation aids are solid, readily water-soluble organic or inorganic substances which have only a slight tendency to crystallize and are not hygroscopic. Substances which tend to polymerize, such as soluble alkali silicates, or which already have a polymeric structure, such as polymeric carboxylic acids and their salts, and soluble cellulose derivatives are particularly suitable. Water-soluble sodium silicate (water glass) and water- or alkali-soluble homo- and copolymers of acrylic acid or methacrylic acid are preferably used. Soluble sodium silicate in combination with polyacrylic acid or polymethacrylic acid is particularly preferred as the granulation aid. The amount of granulating aid, based on the total cleaning agent, is 1 to 20, preferably 5 to 20 percent by weight. Based on the Content of anhydrous zeolite, the amount of granulation aid is between 3 and 40 percent by weight, preferably between 10 and 30 percent by weight.
Als Tenside eignen sich für die erfindungsgemäßen Mittel in erster Linie nichtionische und anionische Tenside. Vorzugsweise werden nichtionische Tenside verwendet.Suitable surfactants for the agents according to the invention are primarily nonionic and anionic surfactants. Nonionic surfactants are preferably used.
Geeignete anionische Tenside sind insbesondere solche vom Sulfat- und Sulfonattyp, doch können auch andere Typen wie Seifen, langkettige N-Acylsarkosinate, Salze von Fettsäurecyanamiden oder Salze von Ethercarbonsäuren, wie sie aus langkettigen Alkyl- oder Alkylphenyl-Polyglykolethern und Chloressigsäure zugänglich sind, eingesetzt werden. Die anionischen Tenside werden üblicherweise in Form der Natriumsalze verwendet.Suitable anionic surfactants are in particular those of the sulfate and sulfonate type, but other types such as soaps, long-chain N-acyl sarcosinates, salts of fatty acid cyanamides or salts of ether carboxylic acids, as are obtainable from long-chain alkyl or alkylphenyl polyglycol ethers and chloroacetic acid, can also be used . The anionic surfactants are usually used in the form of the sodium salts.
Besonders geeignete Tenside vom Sulfattyp sind die Schwefelsäuremonoester von langkettigen primären Alkoholen natürlichen und synthetischen Ursprungs mit 10 bis 20 C-Atomen, d.h. von Fettalkoholen, wie z. B. Kokosfettalkoholen, Talgfettalkoholen, Oleylalkohol, oder den C₁₀- C₂₀ - Oxoalkoholen und solche von sekundären Alkoholen dieser Kettenlängen. Daneben kommen die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten aliphatischen primären Alkohole, sekundären Alkohole oder Alkylphenole in Betracht. Ferner eignen sich sulfatierte Fettsäurealkanolamide und sulfatierte Fettsäuremonoglyceride.Particularly suitable surfactants of the sulfate type are the sulfuric acid monoesters of long-chain primary alcohols of natural and synthetic origin with 10 to 20 carbon atoms, i.e. of fatty alcohols, such as B. coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, or the C₁₀- C₂₀ - oxo alcohols and those of secondary alcohols of these chain lengths. In addition, the sulfuric acid monoesters of the aliphatic primary alcohols, secondary alcohols or alkylphenols ethoxylated with 1 to 6 mol of ethylene oxide come into consideration. Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.
Bei den Tensiden vom Sulfonattyp handelt es sich in erster Linie um die Salze vom Sulfobernsteinsäuremono- und diestern mit 6 bis 22 C-Atomen in den Alkoholteilen, die Alkylbenzolsulfonate mit C₉ - C₁₅ -Alkylgruppen und die Ester von α-Sulfofettsäuren, z. B. die α-sulfonierten Methyl- oder Ethylester der hydrierten Kokos-, Palmkern- oder Talgfettsäuren. Weitere brauchbare Tenside vom Sulfonattyp sind die Alkansulfonate, die aus C₁₂ - C₁₈ -Alkanen durch Sulfochlorierung oder Sulfoxidation und anschließende Hydrolyse bzw. Neutralisation oder durch Bisulfitaddition an Olefine erhältlich sind, sowie die Olefinsulfonate, das sind Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus langkettigen Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigen Schwefeltrioxid und anschließender alkalischer oder saurer Hydrolyse der Sulfonierungsprodukte erhält.The surfactants of the sulfonate type are primarily the salts of sulfosuccinic acid mono- and diesters with 6 to 22 carbon atoms in the alcohol parts, the alkylbenzenesulfonates with C₉ - C₁₅ alkyl groups and Esters of α-sulfo fatty acids, e.g. B. the α-sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids. Other useful surfactants of the sulfonate type are the alkanesulfonates which are obtainable from C₁₂-C₁₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and also the olefin sulfonates, which are mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as they are obtained, for example, from long-chain monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
Als nichtionische Tenside eignen sich für die erfindungsgemäßen Mittel insbesondere Anlagerungsprodukte von 1 bis 30, vorzusgweise 4 bis 15 Mol Ethylenoxid an 1 Mol einer Verbindung mit 10 bis 20 Kohlenstoffatomen aus der Gruppe der Alkohole, Alkylphenole, Carbonsäuren und Carbonsäureamide. Besonders wichtig sind die Anlagerungsprodukte von Ethylenoxid an langkettige primäre oder sekundäre Alkohole, wie zum Beispiel Fettalkohole oder Oxoalkohole, sowie an Mono- oder Dialkylphenole mit 6 bis 14 C-Atomen in den Alkylgruppen.Suitable nonionic surfactants for the agents according to the invention are in particular addition products of 1 to 30, preferably 4 to 15 moles of ethylene oxide with 1 mole of a compound having 10 to 20 carbon atoms from the group of alcohols, alkylphenols, carboxylic acids and carboxamides. The addition products of ethylene oxide with long-chain primary or secondary alcohols, such as, for example, fatty alcohols or oxo alcohols, and with mono- or dialkylphenols having 6 to 14 carbon atoms in the alkyl groups are particularly important.
Ferner sind als nichtionische Tenside die wasserlöslichen, 20 bis 250 Ethylenglykolethergruppen und 10 bis 100 Propylenglykolethergruppen enthaltenden Anlagerungsprodukte von Ethylenoxid an Polypropylenglykol, Alkylendiamin-poly-propylenglykol und an Alkylpolypropylenglykole mit 1 bis 10 Kohlenstoffatomen in der Alkylkette brauchbar, in denen die Polypropylenglykolkette als hydrophober Rest fungiert. Auch nichtionische Tenside vom Typ der Aminoxide, der Sulfoxide oder der Alkylglucoside sind verwendbar, beispielsweise N-Kokosalkyl-N,N-Dimethylaminoxid oder die Kondensationsprodukte aus langkettigen Alkoholen mit 10 bis 18 C-Atomen und Glucose, sowie deren Ethylenoxidaddukte.Furthermore, the non-ionic surfactants which can be used are the water-soluble adducts of ethylene oxide with 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups with polypropylene glycol, alkylenediamine-poly-propylene glycol and with alkylpolypropylene glycols having 1 to 10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic radical . Also nonionic surfactants of the amine oxide, sulfoxide or alkyl glucoside type can be used, for example N-cocoalkyl-N, N-dimethylamine oxide or the condensation products of long-chain alcohols having 10 to 18 carbon atoms and glucose, and also their ethylene oxide adducts.
Besonders bevorzugte nichtionische Tenside stellen die Reaktionsprodukte aus 4 bis 15 Mol Ethylenoxid (EO) und 1 Mol Fettalkohol mit 12 bis 18 C-Atomen dar. Typische Vertreter dieser Tenside sind Talgfettalkohol + 5 EO, Talgfettalkohol + 14 ED, Oleyl-/Cetylalkohol + 10 EO und Kokosfettalkohol + 4 EO.Particularly preferred nonionic surfactants are the reaction products of 4 to 15 moles of ethylene oxide (EO) and 1 mole of fatty alcohol with 12 to 18 carbon atoms. Typical representatives of these surfactants are tallow fatty alcohol + 5 EO, tallow fatty alcohol + 14 ED, oleyl / cetyl alcohol + 10 EO and coconut fatty alcohol + 4 EO.
Die Tenside sind in den erfindungsgemäßen Mitteln zu 0,5 bis 15 Gewichtsprozent, vorzugsweise 1 bis 5 Gewichtsprozent enthalten. Sie werden vorzugsweise ganz oder teilweise im ersten Schritt der Herstellung, d.h. bei der Granulierung des Zeoliths, eingearbeitet.The agents according to the invention contain 0.5 to 15 percent by weight, preferably 1 to 5 percent by weight. They are preferably wholly or partly in the first step of the manufacture, i.e. incorporated in the granulation of the zeolite.
Als weitere Komponente enthalten die Mittel der Erfindung organische Lösungsmittel. Verwendbar sind alle auf dem Gebiet der Textilreinigung üblichen Lösungsmittel, doch werden vorzugsweise Lösungsmittel mit Siedepunkten über 80°C aus der Gruppe Benzine, Alkohole, Ether und Ester eingesetzt. Beispiele für derartige Lösungsmittel sind Benzin (Siedebereich 140 bis 200°C), Isopropanol, Isooctanol, Triethylenglykol, Butyldiglykol und Butyldiglykolacetat, Wegen ihres guten Fettlösungsvermögens werden Benzin, Isopropanol, Dipropylenglykolmomomethylether und deren Mischungen besonders bevorzugt . Der Anteil des Lösungsmittels beträgt im Reinigungsmittel 5 bis 30, vorzugsweise 8 bis 25 Gewichtsprozent. Wasser ist in den Mitteln nur in solcher Menge enthalten, wie sie von den Zeolithen bei der Granulatherstellung festgehalten wird.The agents of the invention contain organic solvents as a further component. All solvents customary in the field of textile cleaning can be used, but solvents with boiling points above 80 ° C. from the group consisting of gasolines, alcohols, ethers and esters are preferably used. Examples of such solvents are gasoline (boiling range 140 to 200 ° C), isopropanol, isooctanol, triethylene glycol, butyl diglycol and butyl diglycol acetate. Because of their good fat-dissolving power, gasoline, isopropanol, dipropylene glycol momomethyl ether and mixtures thereof are particularly preferred. The proportion of solvent in the cleaning agent is 5 to 30, preferably 8 to 25 percent by weight. Water is contained in the agents only in such an amount as is retained by the zeolites during the production of the granules.
Synthetische Zeolithe enthalten von der Herstellung her häufig größere Mengen freier Alkalien, erkennbar am hohen pH-Wert einer wäßrigen Aufschlämmung. Da viele Textilmaterialien und Farbstoffe gegen Alkalien empfindlich sind, können, um Schädigungen zu vermeiden, bei der Herstellung der Mittel Säuren zur Neutralisation des Alkalis zugesetzt werden. Bevorzugt werden feste wasserlösliche organische oder anorganische Säuren, beispielsweise Amidosulfonsäure und Oxalsäure. Besonders bevorzugt werden saure Alkaliphosphate, Weinsäure, Zitronensäure und Ethylendiamintetraessigsäure, weil deren Salze, die sich bei der Neutralisation bilden, die Reinigungswirkung der Mittel unterstützen. Die Säuremenge wird durch den Alkaligehalt des Zeoliths und den gewünschten Neutralisationsgrad bestimmt. Man setzt im allgemeinen nicht mehr als 10 Gewichtsprozent Säure, bezogen auf das gesamte Mittel ein, vorzugsweise eine Menge, die dazu führt, daß das Zeolithgranulat einen pH-Wert zwischen 6,5 und 9 (gemessen an einer 1%igen Aufschlämmung in Wasser) aufweist.Synthetic zeolites often contain large amounts of free alkalis, which can be recognized by the high pH of an aqueous slurry. Since many textile materials and dyes are sensitive to alkalis, acids can be added to neutralize the alkali in the preparation of the agents in order to avoid damage. Solid water-soluble organic or inorganic acids, for example amidosulfonic acid and oxalic acid, are preferred. Acidic alkali phosphates, tartaric acid, citric acid and ethylenediaminetetraacetic acid are particularly preferred because their salts, which form during the neutralization, support the cleaning action of the agents. The amount of acid is determined by the alkali content of the zeolite and the desired degree of neutralization. In general, no more than 10% by weight of acid, based on the total composition, is used, preferably an amount which causes the zeolite granules to have a pH between 6.5 and 9 (measured on a 1% slurry in water). having.
Zur Neutralisation eignen sich auch polymere Carbonsäuren wie Polyacrylsäure und Polymethacrylsäure. Werden solche Säuren bereits als Granulierhilfsmittel verwendet, ist normalerweise der Zusatz weiterer Säuren nicht notwendig.Polymeric carboxylic acids such as polyacrylic acid and polymethacrylic acid are also suitable for neutralization. If such acids are already used as granulation aids, it is normally not necessary to add further acids.
Die erfindungsgemäßen Reinigungsmittel können über die genannten Bestandteile hinaus noch weitere, bei der reinigenden Behandlung von Textilien übliche Wirkstoffe enthalten. Beispiele solcher Wirkstoffe sind antistatisch wirkende Komponenten, optischer Aufheller, die Wiederanschmutzung vermindernde Stoffe und Parfüm. Diese Bestandteile können zusammen bis zu 10 Gewichtsprozent, vorzugsweise bis zu 5 Gewichtsprozent der Reinigungsmittel ausmachen. Sie werden vorzugsweise mit dem Lösungsmittel im zweiten Schritt des Herstellungsverfahrens dem Zeolithgranulat zugesetzt.In addition to the constituents mentioned, the cleaning agents according to the invention can also contain further active substances customary in the cleaning treatment of textiles. Examples of such active ingredients are antistatic components, optical brighteners, substances that reduce re-soiling and perfume. These components together can contain up to 10 percent by weight, preferably make up up to 5% by weight of the cleaning agents. They are preferably added to the zeolite granules with the solvent in the second step of the production process.
Die Reinigung der Textilien und Teppiche geschieht in der Weise, daß die Mittel dieser Erfindung auf die zu reinigenden Flächen aufgetragen und dann intensiv in die Textilien, beispielsweise mit Hilfe eines Schwammes oder einer Bürste eingerieben werden,wobei sich der auf den Textilien befindende Schmutz mit den Partikeln der Reinigungsmittel verbindet. In der Regel wählt man Einarbeitungszeiten von 0,5 bis 2,5 Minuten, vorzugsweise 0,5 bis 1,5 Minuten pro Quadratmeter. Anschließend werden die Rückstände zusammen mit dem Schmutz auf mechanischem Wege, beispielsweise durch Ausbürsten oder Absaugen aus den Textilien entfernt. Für die Flächenreinigung von Textilien werden von den erfindungsgemäßen Mitteln je nach Fülle der Textilien und je nach Verschmutzungsgrad 20 bis 200 Gramm pro Quadratmeter angewandt, doch können zur Entfernung einzelner Flecken stellenweise auch größere Mengen aufgetragen werden. Zur Flächenreinigung von Teppichen sind Aufwandmengen von 50 bis 150 Gramm pro Quadratmeter üblich. Obwohl alle Schritte des Verfahrens manuell durchgeführt werden können, liegt die bevorzugte Ausführung, insbesondere bei Teppichen darin, das Einreiben und gegebenenfalls weitere Schritte mit Hilfe von Maschinen, beispielsweise kombinierten Streu- und Bürstmaschinen, auszuführen. Das Reinigungsverfahren eignet sich deshalb sowohl für den Haushaltsbereich als auch für die gewerbliche Anwendung.The cleaning of the textiles and carpets takes place in such a way that the agents of this invention are applied to the surfaces to be cleaned and then rubbed intensively into the textiles, for example with the aid of a sponge or a brush, the dirt on the textiles being with the Particles of the detergent connects. As a rule, training times of 0.5 to 2.5 minutes, preferably 0.5 to 1.5 minutes per square meter are chosen. The residues are then removed from the textiles together with the dirt mechanically, for example by brushing or vacuuming. For the surface cleaning of textiles, depending on the abundance of the textiles and depending on the degree of soiling, the agents according to the invention use 20 to 200 grams per square meter, but larger quantities can also be applied in places to remove individual stains. For cleaning carpets, application rates of 50 to 150 grams per square meter are common. Although all steps of the method can be carried out manually, the preferred embodiment, in particular for carpets, is to carry out the rubbing in and, if appropriate, further steps with the aid of machines, for example combined spreading and brushing machines. The cleaning process is therefore suitable for both the household sector and for commercial use.
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1. In einem für den Laborgebrauch konstruierten Trommelmischer wurden 1,12 kg Zeolith A (Natriumform, Wassergehalt 18,2 %, bestimmt durch Trocknung bei 800 °C) in Pulverform (Teilchengröße unter 40 µm) und 124 g pulverförmige Polymethacrylsäure (Rohagit S der Firma Röhm) vorgelegt und unter ständiger Umwälzung mit einer Lösung von 38 g Wasserglas (25 %ig in H₂O, SiO₂: Na₂O = 4 : 1) und 14 g eines nichtionischen Tensids aus Talgalkohol und 14 Mol EO in 700 ml Leitungswasser besprüht. Nach dem Ende der Zugabe wurde noch 10 Minuten weiter gemischt, dann das entstandene rieselfähige Granulat ausgetragen. Um überschüssiges anhaftendes Wasser zu vertreiben, wurde das Granulat auf einer Schale im Trockenschrank bei 80°C bis zur Gewichtskonstanz getrocknet. Eine einprozentige Aufschlämmung dieses Granulates in Wasser wies einen pH-Wert von 8,5 auf. Die Siebanalyse des Granulates zeigte, daß 95 % davon im Bereich zwischen 0,3 und 1,2 mm lagen. Im Stabilitätstest stieg der Feinanteil (bis 0,2 mm) von 1,2% auf 4,1 % an.
Zur Herstellung des fertigen Reinigungsmittels wurden 750 g des getrockneten Granulates unter Rühren mit einer Lösung von 20 g eines nichtionischen Tensids aus Talgalkohol und 14 Mol EO in 100 g Isopropanol und 130 g Butyldiglykol getränkt. Das entstandene Reinigungsmittelpulver war gut rieselfähig und frei von Staubanteilen.1. In a drum mixer designed for laboratory use, 1.12 kg of zeolite A (sodium form, water content 18.2%, determined by drying at 800 ° C.) in powder form (particle size below 40 μm) and 124 g of powdery polymethacrylic acid (Rohagit S der Company Röhm) submitted and sprayed with constant circulation with a solution of 38 g water glass (25% in H₂O, SiO₂: Na₂O = 4: 1) and 14 g of a nonionic surfactant made from tallow alcohol and 14 mol EO in 700 ml tap water. After the addition had ended, the mixture was mixed for a further 10 minutes, and the free-flowing granules formed were then discharged. In order to drive off excess adhering water, the granules were dried on a tray in a drying cabinet at 80 ° C. to constant weight. A one percent slurry of this granulate in water had a pH of 8.5. The sieve analysis of the granules showed that 95% of them were in the range between 0.3 and 1.2 mm. In the stability test, the fine fraction (up to 0.2 mm) rose from 1.2% to 4.1%.
To produce the finished cleaning agent, 750 g of the dried granules were soaked with stirring with a solution of 20 g of a nonionic surfactant composed of tallow alcohol and 14 mol EO in 100 g isopropanol and 130 g butyl diglycol. The resulting detergent powder was easy to pour and free of dust. -
2. In einem Lödige-Mischer wurden 8,6 kg Zeolith A und 1 kg gepulverte Polymethacrylsäure der gleichen Qualitäten wie im Beispiel 1, sowie 0,4 kg Polyvinylpyrrolidon (Kollidon Cl der Firma BASF), das als Reinigungsverstärker diente, vorgelegt und unter ständiger Umwälzung mit einer Lösung von 0,3 kg Wasserglas (25 %ig in H₂O, SiO₂ : Na₂O = 4 : 1) und 0,15 kg eines nichtionischen Tensids aus Talgalkohol und 14 Mol Ethylenoxid in 5,7 kg Wasser besprüht. Nach Ende der Zugabe lag ein wasserhaltiges Granulat vor, das durch Aufheizen des Mischers auf 110°C und weiteres Umwälzen innerhalb von 5 Minuten getrocknet wurde. Es zeigte in der Siebanalyse zu 91 % Teilchengrößen zwischen 0,5 und 1,5 mm. Der Anteil unter 0,2 mm lag bei 0,6 % und stieg im Stabilitätstest auf 3,8 % an. In Wasser zeigte das Granulat einen pH-Wert von 8,9 (1 %ig).
Die Weiterverarbeitung des Granulates erfolgte in einem offenen Mischbehälter, in dem es durch Zugabe von 25 Gewichtsprozent an Isopropanol (bezogen auf die fertige Mischung) unter langsamen Rühren in das Endprodukt übergeführt wurde.2. In a Lödige mixer, 8.6 kg of zeolite A and 1 kg of powdered polymethacrylic acid of the same qualities as in Example 1, and 0.4 kg of polyvinylpyrrolidone (Kollidon Cl from BASF), which served as a cleaning enhancer, were introduced and kept under constant Circulation with a solution of 0.3 kg of water glass (25% in H₂O, SiO₂: Na₂O = 4: 1) and 0.15 kg of a nonionic surfactant from tallow alcohol and 14 moles of ethylene oxide sprayed in 5.7 kg of water. At the end of the addition, there was a water-containing granulate which was dried within 5 minutes by heating the mixer to 110 ° C. and further stirring. It showed 91% particle sizes between 0.5 and 1.5 mm in the sieve analysis. The proportion below 0.2 mm was 0.6% and rose to 3.8% in the stability test. In water the granules showed a pH of 8.9 (1%).
The granules were further processed in an open mixing container in which they were converted into the end product by adding 25 percent by weight of isopropanol (based on the finished mixture) with slow stirring. -
3. Eine Mischung aus 270 kg einer 45 %ige wäßrigen Suspension von Zeolith Na-A (Gehalt bezogen auf wasserfreien Zeolith), 46 kg Wasserglas (37/40 Be, 34,5 %ige wäßrige Lösung), 18,8 kg Polymethacrylsäure, 4,0 kg Talgalkohol mit 5 Mol EO und 3,5 kg Talgalkohol mit 14 Mol EO wurde homogenisiert, auf 65 °C aufgeheizt und in das obere Ende eines Sprühturmes eingedüst. Die Trocknung erfogte im Gegenstrom mit Luft einer Eintrittstemperatur zwischen 150°C und 180°C. Auf diesem Wege wurde ein Granulat erhalten, das nach Siebanalyse zu 98,2 % aus Teilchen mit Größen zwischen 0,2 und 1,6 mm bestand, 0,2 % Feinanteile unter 0,05 mm und 0,5 % Anteile über 2 mm Durchmesser aufwies. Im Stabilitätstest stieg der Anteil der Teilchen mit Größen bis 0,2 mm von 9,6 % auf 10,8 % an.
Zur Herstellung des fertigen Reinigungsmittels wurden 170 kg des trockenen Granulates in einem Mischbehälter mit 30 kg Benzin (Isopar G) vermischt. Dabei bildete sich ein weißes , sich trocken anfühlendes gut rieselfähiges Produkt.3. A mixture of 270 kg of a 45% aqueous suspension of zeolite Na-A (content based on anhydrous zeolite), 46 kg of water glass (37/40 Be, 34.5% aqueous solution), 18.8 kg of polymethacrylic acid, 4.0 kg of tallow alcohol with 5 moles of EO and 3.5 kg of tallow alcohol with 14 moles of EO were homogenized, heated to 65 ° C. and injected into the upper end of a spray tower. The drying was carried out in countercurrent with air at an inlet temperature between 150 ° C and 180 ° C. In this way, a granulate was obtained, which after sieve analysis 98.2% consisted of particles with sizes between 0.2 and 1.6 mm, 0.2% fine parts under 0.05 mm and 0.5% parts over 2 mm in diameter. In the stability test, the proportion of particles with sizes up to 0.2 mm rose from 9.6% to 10.8%.
To produce the finished cleaning agent, 170 kg of the dry granules were mixed in a mixing container with 30 kg of gasoline (Isopar G). A white, dry-feeling, free-flowing product formed. - 4. Dieses Reinigungsmittel wurde aus demselben Zeolithgranulat wie das Mittel aus Beispiel 3 hergestellt. Zu je 80 kg des Granulates wurden hier aber 20 kg eines Gemisches aus 50 Gewichtsprozent Benzin (Isopar G, Siedepunkt 165°C) und 50 Gewichtsprozent n-Propanol zugesetzt.4. This cleaning agent was produced from the same zeolite granulate as the agent from Example 3. However, 20 kg of a mixture of 50 percent by weight of gasoline (Isopar G, boiling point 165 ° C.) and 50 percent by weight of n-propanol were added to each 80 kg of the granules.
- 5. Entsprechend DOS 25 44 605, Beispiel 21, wurde ein pulverförmiger Teppichreiniger aus Zeolithpulver, das mit Kokosfettsäurediethanolamid beladen war, durch Vermischen mit Kokosalkoholsulfat und Isopropanol hergestellt. Das Produkt bestand überwiegend aus sehr feinen Pulveranteilen unter 0,05 mm Durchmesser; daneben lagen nach dem Umrühren noch lose Agglomerate mit bis zu 5 mm Größe vor. Im Stabilitätstest zerfiel das Produkt vollständig in Teilchen unter 0,2 mm Durchmesser.5. According to DOS 25 44 605, Example 21, a powdered carpet cleaner from zeolite powder, which was loaded with coconut fatty acid diethanolamide, was prepared by mixing with coconut alcohol sulfate and isopropanol. The product mainly consisted of very fine powder fractions less than 0.05 mm in diameter; in addition, loose agglomerates up to 5 mm in size were still present after stirring. In the stability test, the product disintegrated completely into particles less than 0.2 mm in diameter.
- 6. Entsprechend EP-OS 62 536, Beispiel 1, wurde ein pulverförmiges Teppichreinigungsmittel aus Cellulosefaser, Zeolithpulver, Calciumcarbonat, Propylenglykolmethylether und Wasser hergestellt. Es handelte sich um ein flockiges, leicht klebriges Produkt, in dem harte Granulate völlig fehlten.6. According to EP-OS 62 536, Example 1, a powdered carpet cleaning agent was made from cellulose fiber, zeolite powder, calcium carbonate, propylene glycol methyl ether and water. It was a flaky, slightly sticky product with no hard granules.
-
7. Reinigungswirkung, Staubbelastung und Wiederanschmutzung
Die Gebrauchseigenschaften der Reinigungsmittel wurden an natürlich angeschmutzten beigefarbenen Polyamid-Veloursteppichen untersucht. Zu diesem Zweck wurde ein langer Läufer in mehrere Segmente unterteilt, die mit jeweils einem der Reinigungsmittel 1 bis 6 in Mengen von 70 g pro Quadratmeter gleichmäßig bestreut wurden. Unmittelbar nach Aufgabe der Reinigungsmittel wurden diese mit Hilfe einer im gewerblichen Bereich üblichen, 40 kg schweren Einscheiben-Reinigungsmaschine mit rotierender Bürste ca. 45 sec pro Quadratmeter in den Teppich eingearbeitet. Lediglich bei dem Mittel nach EP 62 536 wurde auch, wie dort angegeben, ein Versuch ohne Einbürsten durchgeführt. Nach der für das Abtrocknen ausreichenden Zeit wurden die Teppichsegmente mit einem Bürstsauger etwa 1 Minute pro Quadratmeter soweit wie möglich von den Reinigungsmitteln und anhaftendem Schmutz befreit. Nach der Begutachtung des Reinigungsergebnisses wurde der Läufer wieder zum Gebrauch freigegeben und nach 3 Wochen die Wiederanschmutzung beurteilt.
Die Bewertung der Gebrauchseigenschaften wurde von 5 Prüfern durchgeführt, die Noten zwischen 1 (ausgezeichnet) und 6 (sehr schlecht) zu vergeben hatten. Die Mittelwerte aus den Einzelnoten sind in Tabelle 1 zusammengefaßt.7. Cleaning effect, dust pollution and re-soiling
The usage properties of the cleaning agents were examined on naturally soiled beige colored polyamide velor carpets. For this purpose, a long runner was divided into several segments, each of which was sprinkled evenly with one of the cleaning agents 1 to 6 in amounts of 70 g per square meter. Immediately after the detergents had been dispensed, they were worked into the carpet using a 40 kg single-pane cleaning machine with a rotating brush, which is customary in the commercial sector, for about 45 seconds per square meter. Only with the agent according to EP 62 536, as stated there, was an experiment carried out without brushing in. After the sufficient time for drying, the carpet segments were cleaned with detergents and adhering dirt for about 1 minute per square meter as far as possible. After the cleaning result had been assessed, the runner was released for use again and the re-soiling was assessed after 3 weeks.
The evaluation of the performance properties was carried out by 5 examiners who had to give grades between 1 (excellent) and 6 (very poor). The mean values from the individual grades are summarized in Table 1. -
8. Vergrauung
Zur Bestimmung dieser Eigenschaft wurden dunkelrote Polyamid-Veloursteppiche, die nicht angeschmutzt waren, wie in Beispiel 7 mit den Reinigungsmitteln behandelt. Anschließend wurde die Vergrauung visuell durch Vergleich mit unbehandelten Teppichstücken ermittelt und mit Hilfe einer Punkteskala (1 = keine Vergrauung, 5 = sehr starke Vergrauung) bewertet. Die Ergebnisse sind in der letzten Spalte von Tabelle 1 wiedergegeben.8. Graying
To determine this property, dark red polyamide velor carpets that were not soiled were treated with the cleaning agents as in Example 7. The graying was then determined visually by comparison with untreated pieces of carpet and evaluated using a point scale (1 = no graying, 5 = very strong graying). The results are shown in the last column of Table 1.
Claims (14)
- A powder-form dry cleaning preparation for textiles, containing surfactants, organic solvents and zeolite, characterized in that the zeolite is present together with granulating aid in the form of porous granules which withstands the mechanical stressing normally encountered in dry cleaning.
- A dry cleaning preparation as claimed in claim 1, characterized in that a zeolite of type A containing sodium ions as exchangeable cations is used.
- A dry cleaning preparation as claimed in claim 1 or 2, characterized in that the zeolite granules are produced by spray-drying of an aqueous mixture of zeolite powder, granulating aid and, optionally, other constituents of the cleaning preparation.
- A dry cleaning preparation as claimed in any of claims 1 to 3, characterized in that more than 80% by weight of the granules consist of particles larger than 0.2 to 1.6 mm in diameter.
- A dry cleaning preparation as claimed in any of claims 1 to 4, characterized in that, before or during production of the granules, the zeolite is adjusted with an acid to a pH value of from 6.5 to 9 (as measured on a 1% suspension of the granules in water).
- A dry cleaning preparation as claimed in any of claims 1 to 5, characterized in that it consists of
40 to 90 % by weight zeolite,
0.5 to 15 % by weight surfactant,
5 to 30 % by weight organic solvent,
1 to 20 % by weight granulating aid,
0 to 10 % by weight solid, water-soluble acid and
0 to 10 % by weight other usual constituents. - A dry cleaning preparation as claimed in any of claims 1 to 6, characterized in that the surfactant present is selected from the group of adducts of from 1 to 30 mol of ethylene oxide with long-chain primary or secondary alcohols containing from 10 to 20 carbon atoms or with alkylphenols containing from 6 to 14 carbon atoms in the alkyl groups and mixtures thereof.
- A dry cleaning preparation as claimed in any of claims 1 to 7, characterized in that the organic solvent has a boiling point above 80°C and is selected from the group comprising gasolines, alcohols, ethers, esters and mixtures thereof.
- A dry cleaning preparation as claimed in any of claims 1 to 8, characterized in that the granulating aid is selected from the group comprising water-soluble alkali silicates, water-soluble polymeric carboxylic acids and salts thereof, water-soluble cellulose derivatives and mixtures thereof.
- A dry cleaning preparation as claimed in any of claims 1 to 9, characterized in that it is produced from zeolite granules by mixing with a solution of surfactant and, optionally, other constituents in an organic solvent and consists of55 to 75 % by weight zeolite Na-A,1 to 5 % by weight adduct of from 4 to 15 mol of EO with C₁₂₋₁₈ fatty alcohols,8 to 25 % by weight organic solvent from the group comprising dipropylene glycol monomethyl ether, gasoline, isopropanol and mixtures thereof,5 to 20 % by weight granulating aid in the form of a combination of water-soluble sodium silicate and polyacrylic acid or polymethacrylic acid and0 to 5 % by weight other usual constituents.
- A process for producing a powder-form dry cleaning preparation for textiles in which zeolite powder is converted by means of a granulating aid into porous granules which withstands the methanical stressing normally encountered in dry cleaning and the granules thus obtained are charged with organic solvent and, optionally, other constituents.
- A process as claimed in claim 11, characterized in that the zeolite granules are produced by spray drying of an aqueous mixture of zeolite powder, granulating aid and, optionally, other constituents of the cleaning preparation.
- A process for cleaning textiles, more especially carpets, in which a dry cleaning preparation of the type claimed in any of claims 1 to 10 is applied to the textile in quantities of from 20 to 200 grams per square metre and is intensively rubbed into the textile for 0.5 to 2.5 minutes per square metre, the soil and cleaning preparation combining with one another, after which the residues are mechanically removed from the textile.
- A process for cleaning carpets as claimed in claim 13, characterized in that the rubbing-in of the cleaning preparation and, optionally, other steps of the process are carried out by means of appliances or machines, 50 to 150 grams per square metre of cleaning preparation are used and the rubbing-in time is 0.5 to 1.5 minutes per square metre.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT85115249T ATE66017T1 (en) | 1984-12-10 | 1985-12-02 | CARPET CLEANING AGENT. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19843444959 DE3444959A1 (en) | 1984-12-10 | 1984-12-10 | CARPET CLEANER |
DE3444959 | 1984-12-10 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0187257A2 EP0187257A2 (en) | 1986-07-16 |
EP0187257A3 EP0187257A3 (en) | 1989-10-18 |
EP0187257B1 true EP0187257B1 (en) | 1991-08-07 |
Family
ID=6252350
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP85115249A Expired - Lifetime EP0187257B1 (en) | 1984-12-10 | 1985-12-02 | Carpet cleaning agent |
Country Status (5)
Country | Link |
---|---|
US (1) | US4648882A (en) |
EP (1) | EP0187257B1 (en) |
JP (1) | JPS61138699A (en) |
AT (1) | ATE66017T1 (en) |
DE (2) | DE3444959A1 (en) |
Families Citing this family (34)
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DE3707409A1 (en) * | 1987-03-07 | 1988-09-15 | Henkel Kgaa | METHOD FOR REMOVING TEXTILES |
US4873000A (en) * | 1988-06-03 | 1989-10-10 | Sterling Drug Inc. | Carpet freshening and deodorizing composition |
US5205958A (en) * | 1989-06-16 | 1993-04-27 | The Clorox Company | Zeolite agglomeration process and product |
US5024782A (en) * | 1989-06-16 | 1991-06-18 | The Clorox Company | Zeolite agglomeration process and product |
GB9113675D0 (en) * | 1991-06-25 | 1991-08-14 | Unilever Plc | Particulate detergent composition or component |
US5259994A (en) * | 1992-08-03 | 1993-11-09 | The Procter & Gamble Company | Particulate laundry detergent compositions with polyvinyl pyrollidone |
DE4243474A1 (en) * | 1992-12-22 | 1994-06-23 | Henkel Ecolab Gmbh & Co Ohg | sweeping flour |
US5286400A (en) * | 1993-03-29 | 1994-02-15 | Eastman Kodak Company | Flowable powder carpet cleaning formulations |
CA2204631C (en) * | 1994-11-10 | 2001-02-06 | Stefano Scialla | Method of cleaning carpets |
US5928384A (en) * | 1994-11-10 | 1999-07-27 | The Procter & Gamble Company | Method of cleaning carpets |
WO1996030474A1 (en) * | 1995-03-27 | 1996-10-03 | The Procter & Gamble Company | Use of amine oxide surfactants for improved stain removal performance |
FR2735154A1 (en) * | 1995-06-09 | 1996-12-13 | Protex Manuf Prod Chimiq | Improving effectiveness of (meth)acrylic] polymers when contacted with alkaline earth metal ions |
US5905065A (en) * | 1995-06-27 | 1999-05-18 | The Procter & Gamble Company | Carpet cleaning compositions and method for cleaning carpets |
GB9600547D0 (en) * | 1996-01-11 | 1996-03-13 | Reckitt & Colman Inc | Improved compositions containing organic compounds |
EP0794244A1 (en) * | 1996-03-04 | 1997-09-10 | The Procter & Gamble Company | Method of cleaning carpets |
US6008175A (en) * | 1996-03-04 | 1999-12-28 | The Proctor & Gamble Company | Method of cleaning carpets comprising an amineoxide or acyl sarcosinate and a source of active oxygen |
GB2345264B (en) * | 1998-12-29 | 2001-01-24 | Rue De Int Ltd | Improvement in security features |
DE19912031A1 (en) * | 1999-03-17 | 2000-09-21 | Basf Ag | Use of crosslinked polyvinylpyrrolidone to increase the rate of disintegration of compact particulate detergents and cleaners |
US6576601B1 (en) * | 1999-07-28 | 2003-06-10 | S. C. Johnson & Son, Inc. | Method of reducing fines in a powdered product and fabric cleaner produced therefrom |
AU1644901A (en) * | 1999-11-30 | 2001-06-12 | Medin Okic | Preparation for concentration reduction of allergenic bacteria and fungi and forconcentration reduction of mite allergens and catty allergens |
GB2357294A (en) * | 1999-12-15 | 2001-06-20 | Unilever Plc | Fabric treatment composition |
EP1174490A3 (en) * | 2000-06-19 | 2003-04-02 | The Procter & Gamble Company | Process of treating a carpet with a composition comprising a zeolite |
ES2264926T3 (en) * | 2000-06-19 | 2007-02-01 | THE PROCTER & GAMBLE COMPANY | PROCEDURE TO TREAT A TISSUE GENERATING HEAT. |
EP1184449A1 (en) * | 2000-09-04 | 2002-03-06 | The Procter & Gamble Company | Carpet cleaning composition comprising an absorbent gelling material |
US20040063796A1 (en) * | 2002-09-30 | 2004-04-01 | Winston Anthony E. | High ionic strength tolerant thickening systems and products formulated therewith |
US7435380B2 (en) * | 2002-09-30 | 2008-10-14 | Church & Dwight Co., Inc. | Pseudo-plastic or thixotropic liquid deodorant product for ostomy pouches |
US7135449B2 (en) * | 2004-02-20 | 2006-11-14 | Milliken & Company | Composition for removal of odors and contaminants from textiles and method |
US7521410B2 (en) * | 2004-03-26 | 2009-04-21 | Arrowstar, Llc | Compositions and methods for imparting odor resistance and articles thereof |
US7585426B2 (en) * | 2004-03-26 | 2009-09-08 | Arrowstar, Llc | Compositions and methods for imparting stain resistance, liquid repellency, and enhanced antimicrobial activity to an article and articles thereof |
US7407922B2 (en) * | 2005-10-13 | 2008-08-05 | S.C. Johnson & Son, Inc. | Deodorizing compositions |
US7261742B2 (en) * | 2005-10-13 | 2007-08-28 | S.C. Johnson & Son, Inc. | Method of deodorizing a textile |
US7939479B2 (en) * | 2008-03-12 | 2011-05-10 | Chandler Barry E | Dry hand cleaner comprising corncob particles |
WO2010028226A2 (en) * | 2008-09-05 | 2010-03-11 | Arrowstar, Llc | Compositions and methods for imparting water and oil repellency to fibers and articles thereof |
US10184095B1 (en) * | 2016-03-04 | 2019-01-22 | Spot Stuff, Inc. | Dry and portable calcined phyllosilicate spot removal product and method |
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CA786292A (en) * | 1965-01-04 | 1968-05-28 | D. Hoxie Orville | Art of cleaning carpets |
CH461685A (en) * | 1965-11-01 | 1968-08-31 | Glamorene Products Corp | Detergent and process for its manufacture |
AT336153B (en) * | 1974-10-08 | 1977-04-25 | Henkel & Cie Gmbh | AQUATIC DETERGENT FOR CLEANING TEXTILE FLAT COVERINGS |
GB1516848A (en) * | 1974-11-13 | 1978-07-05 | Procter & Gamble Ltd | Detergent composition |
US4096081A (en) * | 1976-02-06 | 1978-06-20 | The Procter & Gamble Company | Detergent compositions containing aluminosilicate agglomerates |
US4414130A (en) * | 1976-08-17 | 1983-11-08 | Colgate Palmolive Company | Readily disintegrable agglomerates of insoluble detergent builders and detergent compositions containing them |
DE2714604C3 (en) * | 1977-04-01 | 1985-04-25 | Joh. A. Benckiser Gmbh, 6700 Ludwigshafen | Granulate based on polymer phosphate and ion-exchanging alkali aluminosilicate |
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DE2744773C3 (en) * | 1977-10-05 | 1986-08-21 | Joh. A. Benckiser Gmbh, 6700 Ludwigshafen | Granulate based on polymer phosphate and ion-exchanging alkali aluminosilicate |
DE2806799A1 (en) * | 1978-02-17 | 1979-08-23 | Henkel Kgaa | Aluminosilicate granules contg. binder prodn. - useful for partial softening of drinking water to optimum hardness level |
US4288342A (en) * | 1978-03-03 | 1981-09-08 | J. M. Huber Corporation | Inorganic water-softening bead |
US4244834A (en) * | 1979-06-05 | 1981-01-13 | United States Borax & Chemical Corporation | Carpet cleaning and deodorizing compositions |
EP0021267B1 (en) * | 1979-06-18 | 1982-06-16 | PQ Corporation | Agglomerated zeolite ion exchanger |
US4395347A (en) * | 1979-12-04 | 1983-07-26 | Airwick Industries, Inc. | Powdered carpet cleaner containing ether alcohol solvents |
DE3007320A1 (en) * | 1980-02-27 | 1981-09-10 | Henkel KGaA, 4000 Düsseldorf | MACHINE APPLICABLE CLEANING AGENTS |
DE3045221A1 (en) * | 1980-12-01 | 1982-06-03 | Joh. A. Benckiser Gmbh, 6700 Ludwigshafen | ABRASION-RESISTANT GRANULES BASED ON ALKALIAL ALUMINUM SILICATE WITH A GOOD DISPERSING CAPACITY IN AQUEOUS FOLLOW |
US4493781A (en) * | 1981-04-06 | 1985-01-15 | S. C. Johnson & Son, Inc. | Powdered cleansing composition |
US4379080A (en) * | 1981-04-22 | 1983-04-05 | The Procter & Gamble Company | Granular detergent compositions containing film-forming polymers |
DE3206146A1 (en) * | 1982-02-20 | 1983-09-01 | Vorwerk & Co Interholding Gmbh, 5600 Wuppertal | AEROSOL CLEANER |
US4526583A (en) * | 1983-08-08 | 1985-07-02 | Union Carbide Corporation | Powdered carpet treating compositions |
-
1984
- 1984-12-10 DE DE19843444959 patent/DE3444959A1/en not_active Withdrawn
-
1985
- 1985-12-02 EP EP85115249A patent/EP0187257B1/en not_active Expired - Lifetime
- 1985-12-02 AT AT85115249T patent/ATE66017T1/en not_active IP Right Cessation
- 1985-12-02 DE DE8585115249T patent/DE3583733D1/en not_active Expired - Fee Related
- 1985-12-10 JP JP60278866A patent/JPS61138699A/en active Pending
- 1985-12-10 US US06/807,390 patent/US4648882A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
DE3444959A1 (en) | 1986-06-12 |
ATE66017T1 (en) | 1991-08-15 |
EP0187257A2 (en) | 1986-07-16 |
EP0187257A3 (en) | 1989-10-18 |
US4648882A (en) | 1987-03-10 |
DE3583733D1 (en) | 1991-09-12 |
JPS61138699A (en) | 1986-06-26 |
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