EP1341896B1 - Alkaline, hydrous paste - Google Patents

Alkaline, hydrous paste Download PDF

Info

Publication number
EP1341896B1
EP1341896B1 EP01999628A EP01999628A EP1341896B1 EP 1341896 B1 EP1341896 B1 EP 1341896B1 EP 01999628 A EP01999628 A EP 01999628A EP 01999628 A EP01999628 A EP 01999628A EP 1341896 B1 EP1341896 B1 EP 1341896B1
Authority
EP
European Patent Office
Prior art keywords
agent
alkyl
agent according
viscosity
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP01999628A
Other languages
German (de)
French (fr)
Other versions
EP1341896A1 (en
Inventor
Khalil Shamayeli
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ecolab Inc
Original Assignee
Ecolab Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ecolab Inc filed Critical Ecolab Inc
Publication of EP1341896A1 publication Critical patent/EP1341896A1/en
Application granted granted Critical
Publication of EP1341896B1 publication Critical patent/EP1341896B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/044—Hydroxides or bases
    • 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
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D2111/40—

Definitions

  • the present invention relates to pasty thixotropic detergents or cleaning agents, the essential proportions of alkalinity, non-ionic surfactants and contain water as well as washing processes using such agents become.
  • the invention also relates to washing processes in which the wastewater or part of the wash liquor is processed using membrane technology becomes.
  • Pasty detergents are known from European patent EP 295 525 B1 known from a liquid in the temperature range below 10 ° C. Phase formed from nonionic surfactant and one dispersed therein solid phase of certain grain size, which consists of washing alkalis, sequestering agents and optionally anionic surfactants are formed. requirement is that surfactants or mixtures thereof are used, the Pour point (solidification point) must be below 5 ° C in order to solidify avoid the paste at low transport and storage temperatures.
  • This Detergent paste is intended for commercial laundries and is like this flowable that they have a suction line using a conventional feed pump can be promoted. However, it has been found that such pastes the homogeneity of their Can guarantee ingredients and often during storage Tend to segregate. The separation does not only concern the separation of the solid ones of the liquid components, but also the phase separation of the liquid Ingredients.
  • Another paste-like detergent which is used as a nonionic surfactant 40 up to 70 wt .-% liquid at room temperature ethoxylated fatty alcohol with 10 to 20 carbon atoms and an average degree of ethoxylation of 1 to 8 as well 20 to 50 wt .-% liquid at room temperature ethoxylated and propoxylated Fatty alcohol with 10 to 20 carbon atoms and a medium one Degree of ethoxylation from 2 to 8 and an average degree of propoxylation from 1 to 6 and 1 to 10 wt .-% soap contains, is in the international patent application WO 95/09229.
  • This pasty detergent or cleaning agent is so pseudoplastic that it is at room temperature under the influence of Gravity is not flowable, but a significantly lower viscosity when sheared and is then flowable under the influence of gravity.
  • the Dosage of this pasty detergent or cleaning agent is preferably carried out in that the agent for lowering the viscosity of the shear is subjected and the then flowable agent dosed by means of feed pumps can be.
  • a pasty detergent for use in commercial laundries which contains nonionic surfactant, organic and / or inorganic builders, alkalizing agents and optionally bleaching agents, enzyme, graying-inhibiting polymer and / or other conventional ingredients and characterized in that it contains 5% by weight to 30% by weight of an ethoxylated alcohol of the general formula R 1 - (OC 2 H 4 ) m -OH (I), in which R 1 is an alkyl or alkenyl radical with 9 means up to 15 carbon atoms and the average degree of ethoxylation m can assume values from 1 to 8, 1% by weight to 20% by weight of an ethoxylated alcohol of the general formula R 2 - (OC 2 H 4 ) n -OH (II ), in which R 2 is an alkyl or alkenyl radical having 12 to 22 carbon atoms and the average degree of ethoxylation n can assume values from 3 to 14 with the proviso that
  • R 3 is an alkyl or alkenyl radical with 6 to 22 C- Atoms, in particular 8 to 22 carbon atoms and R 4 is hydrogen or an alkyl radical with 1 to 6 carbon atoms, and contains up to 15% by weight of organic builders of the polymeric polycarboxylate type, polymerized products of unsaturated polymeric polycarboxylates there Mono- and / or dicarboxylic acids are understood that have no other functionalities apart from carboxyl groups.
  • the agent according to the invention is preferably not an alkali metal certificate added.
  • cleaning Mitel known which according to the statements in column 3 from line 65 weak foaming surfactants, especially non-ionic surfactants, in an amount of up to 10% by weight, preferably 1 to 5% by weight and particularly preferably 2 to 4% by weight may contain.
  • a higher surfactant content which is generally up to 20% by weight, preferably 0.1 to 15, particularly preferably 1 to 10% by weight and extremely preferably 2 to 4% by weight, based on the total mean.
  • nonionic, cationic and amphoteric surfactants especially anionic Surfactants from the group of alkylbenzenesulfonates, fatty alcohol sulfates, Fatty alcohol ether sulfates and others known anionic surfactants.
  • the subject of the present invention is in essentially thixotropic agents, which in a preferred embodiment in In the case of membrane treatment of wastewater or part of the wash liquor have very good membrane compatibility from the washing process.
  • agents according to the invention contain in a preferred embodiment as an alkalinity carrier sodium hydroxide and / or soda.
  • the agents according to the invention preferably additionally contain up to 10% by weight, preferably 0.5% by weight to 8% by weight, of anionic surfactant, in particular C 8 -C 18 alkyl sulfates, C 8 -C 18 alkyl ether sulfates, C 8 - C 18 alkane sulfonates, C 8 -C 18 ⁇ -olefin sulfonates, sulfonated C 8 -C 18 fatty acids, C 8 -C 18 alkyl benzene sulfonates, sulfonic succinic acid mono- and di-C 1 -C 12 alkyl esters, C 8 -C 18- alkyl polyglycol ether carboxylates, C 8 -C 18 -N-acyl taurides, C 8 -C 18 -N-sarcosinates, C 8 -C 18 -alkyl isethionates and mixtures of the foregoing.
  • anionic surfactant
  • the agents according to the invention additionally at least an alkyl polyglucoside with 8 to 14 carbon atoms in the alkyl group and 1 to 5 Glucose units, particularly preferably in a proportion of 0.1 to 5% by weight, based on the total mean.
  • Agents additionally a complexing agent selected from polyphosphonic acids, in particular 1-hydroxy-ethane-1,1-diphosphonic acid, diethylenetriaminepentamethylenephosphonic acid, Ethylene diamine tetramethylene phosphonic acid, N- (2-hydroxyethyl) -, N, N-bis-methylenephosphonic acid and their salts, and / or polycarboxylic acids in particular copolymers of acrylic and maleic acid and their salts or NTA or organic acids, preferably citric acid and its salts, before, in particular with a proportion of 1 to 20 wt .-%, based on the total funds.
  • a complexing agent selected from polyphosphonic acids, in particular 1-hydroxy-ethane-1,1-diphosphonic acid, diethylenetriaminepentamethylenephosphonic acid, Ethylene diamine tetramethylene phosphonic acid, N- (2-hydroxyethyl) -, N, N-bis-methylenephosphonic acid and their salts, and /
  • the agents according to the invention additionally contain 0.5 to 10% by weight of branched or unbranched C 8-22 fatty alcohol.
  • C 8-14 fatty alcohols are particularly preferred, especially those with a branched alkyl group.
  • the agents according to the invention additionally contain a phosphate, preferably tripolyphosphate, particularly preferably in a concentration of 5 up to 50 wt .-%, based on the total agent.
  • a phosphate preferably tripolyphosphate
  • the agent according to the invention can be known, in such Alkaline washing compositions contain additives commonly used, such as co-builders, optical brighteners, dyes and fragrances, small amounts of Neutral salts such as sulfates and chlorides in the form of their sodium or potassium salts, provided that these do not impair the positive properties.
  • More suitable Product additives can include enzymes, bleaches from the per-compound class, which are usually used together with activators, active chlorine compounds as well as colors and fragrances.
  • the oxidizing Have an effect it is recommended to be compatible with appropriate Check reverse osmosis membranes, provided that they play a role in the overall process play.
  • Another object of the present invention is a machine washing process with process-controlled dosing of detergent and water, in which an inventive washing or cleaning agent by means of a process-controlled device for dosing the agent into the tub a washing machine is supplied, it being preferred that the Process waste water and / or part of the wash liquor via a membrane filtration system is processed, and particularly preferably membrane filtration at least one reverse osmosis step is carried out.
  • the wastewater stream to be treated was passed through a self-cleaning 75 ⁇ prefilter.
  • the reverse osmosis membrane used had an area of 40 square meters and a capacity of 15 l per m 2 .h.
  • the material of the reverse osmosis membrane used was organic (polypropylene).
  • the temperature during the reverse osmosis was about 40 ° C.
  • the reverse osmosis was carried out in such a way that about 80% of the wastewater stream to be treated was obtained as a reusable permeate and about 20% of the wastewater stream to be treated as a concentrate to be discarded with a high salt content and high organic load.
  • the duration of the test phases with the four products to be examined was 5 days with 8 hours of operation per day.
  • the reverse osmosis membrane was thoroughly cleaned before each product change.
  • the output power X A expressed in the form of the flow rate [l / h]
  • the reverse osmosis membrane was flushed with water every day during the test period after the end of operation.
  • the final output X E was determined in the form of the flow rate [l / h].
  • the ratio of X E to X A was used to characterize the products tested in the test phases.
  • the ratio of X E / X A can be used as an indication of whether the reverse osmosis membrane needs to be cleaned within shorter or longer intervals under otherwise identical conditions.
  • a standard cleaning was carried out after the end of each test phase, in accordance with the recommendations of the manufacturers of cleaning products for reverse osmosis membranes.
  • the "final performance after cleaning" X ER was determined in the form of the flow rate [l / h].
  • the ratio X ER / X A was then calculated as the characteristic variable.
  • the ratio X ER / X A can be taken as an indication of the extent to which the reverse osmosis membrane can be regenerated with a certain product concept after a certain term. Depending on how good or bad the regenerability of the reverse osmosis membrane is, sooner or later the costly purchase of new reverse osmosis membranes must be carried out.
  • the thixotropy properties of a paste according to the invention were also confirmed in the experiment.
  • the formulation of the example paste 3 was examined at 20 ° C and constantly changing shear rates. Table 3 shows the viscosity that results after different times and shear rates.

Abstract

Hydrous, paste-like, thixotropic detergent or cleaning agent containing, based on the whole agent, a) an alkalinity support, selected from alkali hydroxide and/or alkali carbonate, in a quantity of 5 to 40 wt. %, preferably 8 to 30 wt. %, b) at least 5 wt. %, preferably 15 to 40 wt. % water, and c) more than 3 wt. %, preferably 5.5 to 30 wt. %, particularly preferably 6 to 15 wt. % non-ionic surfactants, wherein, at 25° C., the agent has a viscosity of 50,000 mPas to 250,000 mPas, measured using a Brookfield rotational viscometer (spindle no. 7) at 5 revolutions per minute and, under otherwise identical conditions, at 50 revolutions per minute has a viscosity of 12,000 mPas to 80,000 mPas.

Description

Die vorliegende Erfindung betrifft pastenförmige thixotrope Wasch- oder Reinigungsmittel, die wesentliche Anteile an Alkalitätsträgem, nichtionischen Tensiden und Wasser enthalten sowie Waschverfahren, bei denen derartige Mittel eingesetzt werden. Außerdem betrifft die Erfindung derartige Waschverfahren, bei denen das Abwasser oder ein Teil der Waschflotte über Membrantechnologie aufbereitet wird.The present invention relates to pasty thixotropic detergents or cleaning agents, the essential proportions of alkalinity, non-ionic surfactants and contain water as well as washing processes using such agents become. The invention also relates to washing processes in which the wastewater or part of the wash liquor is processed using membrane technology becomes.

Aus der europäischen Patentschrift EP 295 525 B1 sind pastenförmige Waschmittel bekannt, die aus einer im Temperaturbereich unterhalb 10 °C flüssigen Phase, die aus nichtionischem Tensid gebildet wird, und einer darin dispergierten festen Phase bestimmter Korngröße, die aus Waschalkalien, Sequestrierungsmitteln und gegebenenfalls Aniontensiden gebildet wird, bestehen. Voraussetzung ist, daß Tenside beziehungsweise deren Gemische verwendet werden, deren Stockpunkt (Erstarrungspunkt) unterhalb 5 °C liegen muß, um eine Verfestigung der Paste bei niedrigen Transport- und Lagertemperaturen zu vermeiden. Diese Waschmittelpaste ist für gewerbliche Wäschereien bestimmt und ist derart fließfähig, daß sie über eine Absaugleitung mittels einer üblichen Förderpumpe gefördert werden kann. Es wurde allerdings festgestellt, daß derartige Pasten während ihrer Herstellung nicht immer befriedigend die Homogenität ihrer Inhaltsstoffe gewährleisten können und auch während der Lagerung häufig zum Entmischen neigen. Das Entmischen betrifft nicht nur die Separation der festen von den flüssigen Bestandteilen, sondem auch die Phasentrennung der flüssigen Inhaltsstoffe.Pasty detergents are known from European patent EP 295 525 B1 known from a liquid in the temperature range below 10 ° C. Phase formed from nonionic surfactant and one dispersed therein solid phase of certain grain size, which consists of washing alkalis, sequestering agents and optionally anionic surfactants are formed. requirement is that surfactants or mixtures thereof are used, the Pour point (solidification point) must be below 5 ° C in order to solidify avoid the paste at low transport and storage temperatures. This Detergent paste is intended for commercial laundries and is like this flowable that they have a suction line using a conventional feed pump can be promoted. However, it has been found that such pastes the homogeneity of their Can guarantee ingredients and often during storage Tend to segregate. The separation does not only concern the separation of the solid ones of the liquid components, but also the phase separation of the liquid Ingredients.

Ein weiteres pastenförmiges Waschmittel, welches als nichtionisches Tensid 40 bis 70 Gew.-% bei Raumtemperatur flüssigen ethoxylierten Fettalkohol mit 10 bis 20 Kohlenstoffatomen und einem mittleren Ethoxylierungsgrad von 1 bis 8 sowie 20 bis 50 Gew.-% bei Raumtemperatur flüssigen ethoxylierten und propoxylierten Fettalkohol mit 10 bis 20 Kohlenstoffatomen und einem mittleren Ethoxylierungsgrad von 2 bis 8 und einem mittleren Propoxylierungsgrad von 1 bis 6 sowie 1 bis 10 Gew.-% Seife enthält, wird in der internationalen Patentanmeldung WO 95/09229 beschrieben. Dieses pastenförmige Wasch- oder Reinigungsmittel ist so strukturviskos, daß es bei Raumtemperatur unter Einwirkung der Schwerkraft nicht fließfähig ist, bei Scherung aber eine deutlich niedrigere Viskosität aufweist und dann unter Einwirkung der Schwerkraft fließfähig ist. Die Dosierung dieses pastenförmigen Wasch- oder Reinigungsmittels erfolgt vorzugsweise dadurch, daß das Mittel zur Erniedrigung der Viskosität der Scherung unterworfen wird und das dann fließfähige Mittel mittels Förderpumpen dosiert werden kann.Another paste-like detergent, which is used as a nonionic surfactant 40 up to 70 wt .-% liquid at room temperature ethoxylated fatty alcohol with 10 to 20 carbon atoms and an average degree of ethoxylation of 1 to 8 as well 20 to 50 wt .-% liquid at room temperature ethoxylated and propoxylated Fatty alcohol with 10 to 20 carbon atoms and a medium one Degree of ethoxylation from 2 to 8 and an average degree of propoxylation from 1 to 6 and 1 to 10 wt .-% soap contains, is in the international patent application WO 95/09229. This pasty detergent or cleaning agent is so pseudoplastic that it is at room temperature under the influence of Gravity is not flowable, but a significantly lower viscosity when sheared and is then flowable under the influence of gravity. The Dosage of this pasty detergent or cleaning agent is preferably carried out in that the agent for lowering the viscosity of the shear is subjected and the then flowable agent dosed by means of feed pumps can be.

Aus der internationalen Patentanmeldung WO 98/10049 ist ein pastenförmiges Waschmittel für den Einsatz in der gewerblichen Wäscherei bekannt, das nichtionisches Tensid, organischen und/oder anorganischen Builder, Alkalisierungsmittel, sowie gegebenenfalls Bleichmittel, Enzym, vergrauungsinhibierendes Polymer und/oder sonstige übliche Inhaltsstoffe enthält und dadurch gekennzeichnet ist, daß es 5 Gew.-% bis 30 Gew.-% eines ethoxylierten Alkohols der allgemeinen Formel R1-(OC2H4)m-OH (I), in der R1 einen Alkyl- oder Alkenylrest mit 9 bis 15 C-Atomen bedeutet und der mittlere Ethoxylierungsgrad m Werte von 1 bis 8 annehmen kann, 1 Gew.-% bis 20 Gew.-% eines ethoxylierten Alkohols der allgemeinen Formel R2-(OC2H4)n-OH (II), in der R2 einen Alkyl- oder Alkenylrest mit 12 bis 22 C-Atomen bedeutet und der mittlere Ethoxylierungsgrad n Werte von 3 bis 14 annehmen kann mit der Maßgabe, daß n mindestens um 1,0 größer ist als m, 20 Gew.-% bis 80 Gew.-% Alkalisierungsmittel, insbesondere Alkalimetasilikat, 1 Gew.-% bis 20 Gew.-% mittel- bis langkettigen Alkohol beziehungsweise Alkylether der allgemeinen Formel R3-O-R4 (III), in der R3 einen Alkyl- oder Alkenylrest mit 6 bis 22 C-Atomen, insbesondere 8 bis 22 C-Atomen und R4 Wasserstoff oder einen Alkylrest mit 1 bis 6 C-Atomen bedeutet, und bis zu 15 Gew.-% organischen Builder vom Typ der polymeren Polycarboxylate enthält, wobei dort unter polymeren Polycarboxylaten Polymerisationsprodukte von ungesättigten Mono- und/oder Dicarbonsäuren verstanden werden, die außer Carboxylgruppen keine weiteren Funktionalitäten aufweisen. From the international patent application WO 98/10049 a pasty detergent for use in commercial laundries is known which contains nonionic surfactant, organic and / or inorganic builders, alkalizing agents and optionally bleaching agents, enzyme, graying-inhibiting polymer and / or other conventional ingredients and characterized in that it contains 5% by weight to 30% by weight of an ethoxylated alcohol of the general formula R 1 - (OC 2 H 4 ) m -OH (I), in which R 1 is an alkyl or alkenyl radical with 9 means up to 15 carbon atoms and the average degree of ethoxylation m can assume values from 1 to 8, 1% by weight to 20% by weight of an ethoxylated alcohol of the general formula R 2 - (OC 2 H 4 ) n -OH (II ), in which R 2 is an alkyl or alkenyl radical having 12 to 22 carbon atoms and the average degree of ethoxylation n can assume values from 3 to 14 with the proviso that n is at least 1.0 greater than m, 20 wt. -% to 80 wt .-% Alkalisierungsmi ttel, in particular alkali metal silicate, 1 wt .-% to 20 wt .-% medium to long chain alcohol or alkyl ether of the general formula R 3 -OR 4 (III), in which R 3 is an alkyl or alkenyl radical with 6 to 22 C- Atoms, in particular 8 to 22 carbon atoms and R 4 is hydrogen or an alkyl radical with 1 to 6 carbon atoms, and contains up to 15% by weight of organic builders of the polymeric polycarboxylate type, polymerized products of unsaturated polymeric polycarboxylates there Mono- and / or dicarboxylic acids are understood that have no other functionalities apart from carboxyl groups.

Die aus den oben genannten Dokumenten bekannten Mittel weisen eine hohe Reinigungsleistung auf und sind zum gewerblichen Waschen von verschmutzter Wäsche sehr gut geeignet.The means known from the documents mentioned above are high Cleaning performance and are for commercial washing of dirty Laundry very well suited.

Dabei werden in allen Fällen bestimmte Anforderungen an die nichtionischen Tenside hinsichtlich deren Erstarrungspunkt bzw. deren Zusammensetzung gestellt. Für den Fall, daß das nach Durchführung des Waschvorgangs anfallende Abwasser und/oder ein Teil der Waschflotte über Membranfiltration aufbereitet wird, führen viele nichtionische Tenside zu nicht unerheblichen Problemen. Je nach Auswahl der nichtionischen Tenside kann dies sogar zum Verblocken der Membranen führen. Besonders kritisch ist dieser Punkt bei Membranfiltrationsverfahren zu erachten, in deren Ablauf wenigstens ein Umkehrosmose-Schnitt vorkommt. Mit dem Problem des Verblockens von Membranen bei der Filtration von Abwässern aus Waschverfahren setzt sich auch die DE 197 26 287 auseinander. Gegenstand dieses Dokuments ist ein Verfahren zum Waschen von Wäsche, insbesondere von Berufsbekleidung, worin die Wäsche in einer üblichen Waschmaschine für gewerbliche Wäschereien mit einer Produktkombination aus mindestens zwei Komponenten

  • (A) eine Waschalkalikomponente, enthaltend
  • (A1) anionisches Tensid und wasserlösliches Silikat
    und/oder
  • (A2) Alkalihydroxid
    sowie
  • (A3) Komplexbildner, und
  • (B) eine Tensidkomponente, enthaltend vorzugsweise nichtionisches Tensid, gewaschen und das Abwasser über eine Membranfiltrationsanlage aufbereitet wird.
    • In all cases, certain requirements are placed on the nonionic surfactants with regard to their solidification point or their composition. In the event that the wastewater and / or part of the wash liquor obtained after carrying out the washing process is treated by membrane filtration, many nonionic surfactants lead to not inconsiderable problems. Depending on the selection of non-ionic surfactants, this can even lead to blocking of the membranes. This point is particularly critical in membrane filtration processes, in the course of which at least one reverse osmosis cut occurs. DE 197 26 287 also deals with the problem of blocking membranes in the filtration of waste water from washing processes. The subject of this document is a method for washing laundry, in particular workwear, wherein the laundry in a conventional washing machine for commercial laundries with a product combination of at least two components
  • (A) containing a washing alkali component
  • (A1) anionic surfactant and water-soluble silicate
    and or
  • (A2) alkali hydroxide
    such as
  • (A3) complexing agents, and
  • (B) a surfactant component, preferably containing nonionic surfactant, is washed and the waste water is processed via a membrane filtration system.

    • Ein weiterer Gegenstand des vorgenannten Dokuments ist eine Produktkombination zum Einsatz in gewerblichen Wäschereien aus mindestens zwei Komponenten

  • (A) eine Waschalkalikomponente, enthaltend
  • (A1) anionisches Tensid und wasserlösliches Silikat
    und/oder
  • (A2) Alkalihydroxid
    sowie
  • (A3) Komplexbildner, und
  • (B) eine Tensidkomponente, enthaltend vorzugsweise nichtionisches Tensid.
    • Another object of the aforementioned document is a product combination for use in commercial laundries from at least two components
  • (A) containing a washing alkali component
  • (A1) anionic surfactant and water-soluble silicate
    and or
  • (A2) alkali hydroxide
    such as
  • (A3) complexing agents, and
  • (B) a surfactant component, preferably containing nonionic surfactant.

    • Überraschenderweise wurde bei derartiger Verfahrensweise festgestellt, daß durch den Einsatz der genannten Produktkombination und Verfahrensweise die Durchflußrate durch die Membranen bei der Abwasseraufbereitung nicht nur nicht verschlechtert wird, sondern in vielen Fällen sogar erhöht werden kann, d.h. die Produktkombination anscheinend eine Reinigungswirkung auf die Membranen hat.Surprisingly, it was found with such a procedure that through the use of the product combination and procedure mentioned Flow rate through the membranes in wastewater treatment not only not deteriorates, but in many cases can even be increased, i.e. the Product combination apparently has a cleaning effect on the membranes.

    Dies war zudem unabhängig vom Membranmaterial, so daß insbesondere an den gängigen Membranen auf Basis von Polypropylen, Keramik und Kohlenstoff mit großem Vorteil gearbeitet werden konnte.This was also independent of the membrane material, so that the common membranes based on polypropylene, ceramic and carbon with great advantage could be worked.

    Aufgrund der Vorteile von thixotropen pastenförmigen Mitteln und um das Produktportfolio der Pasten für die Reinigung zu komplettieren bestand der Bedarf, thixotrope, nichtionische Tenside enthaltende Pasten zur Verfügung zu stellen, die sich aufgrund ihrer Zusammensetzung bei der späteren Aufbereitung des Abwassers über Umkehrosmose unkritisch verhalten. Dieser Bedarf bestand um so mehr, als die Aufbereitung von belastetem Abwasser und/oder einem Teil der Waschflotte aus entsprechenden Waschverfahren über Membranfiltrationsanlagen, insbesondere über Umkehrosmose in den letzten Jahren an Bedeutung gewonnen hat. In vielen Fällen ließ sich sogar realisieren, das aufbereitete Wasser erneut in den Prozeß zurückzuführen.Because of the advantages of thixotropic pasty agents and around the product portfolio to complete the pastes for cleaning there was a need to provide pastes containing thixotropic, nonionic surfactants, the due to their composition during the later treatment of the wastewater behave uncritically about reverse osmosis. This was all the more necessary more than the treatment of contaminated wastewater and / or part of the Washing liquor from corresponding washing processes via membrane filtration systems, Reverse osmosis in particular has become increasingly important in recent years Has. In many cases, the treated water could even be realized returned to the process.

    Gegenstand der vorliegenden Erfindung ist ein wasserhaltiges, pastenförmiges, thixotropes Wasch- oder Reinigungsmittel enthaltend, bezogen auf das gesamte Mittel,

  • a) einen Alkalitätsträger ausgewählt aus Alkalihydroxid und/oder Alkalicarbonat in einer Menge von 5 bis 40 Gew.-%, vorzugsweise 8 bis 30 Gew.-%,
  • b) mindestens 5 Gew.-%, vorzugsweise 15 bis 40 Gew.-% Wasser, und
  • c) mehr als 3 Gew.-%, vorzugsweise 5,5 bis 30 Gew.-%, besonders bevorzugt 6 bis 15 Gew.-% nichtionische Tenside, wobei unter den nichtionischen Tensiden wenigstens eine Verbindung der allgemeinen Formel (I) zu verstehen ist, R1-(OC2H4)n-OH in der R1 einen verzweigten oder unverzweigten Alkyl- oder Alkenylrest mit 10 bis 20 C-Atomen bedeutet vorzugsweise ein verzweigter Alkylrest mit 10-16 C-Atomen und der mittlere Ethoxylierungsgrad n Werte von 5 bis 20, vorzugsweise von 7 bis 12, insbesondere von 7 bis 10 aufweist
    • wobei das Mittel bei 25 °C eine Viskosität von 50 000 mPas bis 250 000 mPas, gemessen mit einem Brookfield-Rotationsviskosimeter (Spindel Nr. 7) bei 5 Umdrehungen pro Minute und bei ansonsten gleichen Bedingungen bei 50 Umdrehungen pro Minute eine Viskosität von 12 000 mPas bis 80 000 mPas aufweist und gewünschtenfalls die Viskosität durch Veränderung des Anteils an Wasser und/oder flüssigen Komponenten und/oder sonstigen Viskositätshilfsstoffen einstellbar ist.The present invention relates to a water-containing, pasty, thixotropic detergent or cleaning agent containing, based on the total agent,
  • a) an alkalinity carrier selected from alkali hydroxide and / or alkali carbonate in an amount of 5 to 40% by weight, preferably 8 to 30% by weight,
  • b) at least 5% by weight, preferably 15 to 40% by weight of water, and
  • c) more than 3% by weight, preferably 5.5 to 30% by weight, particularly preferably 6 to 15% by weight, of nonionic surfactants, the nonionic surfactants being understood to mean at least one compound of the general formula (I) . R 1 - (OC 2 H 4 ) n -OH in which R 1 is a branched or unbranched alkyl or alkenyl radical having 10 to 20 carbon atoms, preferably means a branched alkyl radical having 10-16 carbon atoms and the average degree of ethoxylation n is from 5 to 20, preferably from 7 to 12, in particular from 7 to 10
    • the average at 25 ° C a viscosity of 50,000 mPas to 250,000 mPas, measured with a Brookfield rotary viscometer (spindle No. 7) at 5 revolutions per minute and under otherwise identical conditions at 50 revolutions per minute a viscosity of 12,000 mPas up to 80,000 mPas and, if desired, the viscosity can be adjusted by changing the proportion of water and / or liquid components and / or other viscosity aids.

    Vorzugsweise wird dem erfindungsgemäßen Mittel rezepturgemäß kein Alkalimetallsifikat zugesetzt.According to the formulation, the agent according to the invention is preferably not an alkali metal certificate added.

    Aus der DE 198 28 578 sind cremeförmige, hochalkalische, wäßrige. Reinigungsmitel bekannt, die gemäß den Ausführungen in Spalte 3 ab Zeile 65 schwach schäumende Tenside, vor allem nichtionische Tenside, in einer Menge von bis zu 10 Gew.-%, bevorzugt 1 bis 5 Gew.-% und besonders bevorzugt 2 bis 4 Gew.-% enthalten kann. Für den Fall, daß die gemäß der genannten Schrift hergestellten Mittel zum maschinellen Waschen von Wäsche eingesetzt werden, empfiehlt sich ein höherer Tensidgehalt, der in der Regel bis 20 Gew.%, bevorzugt 0,1 bis 15, besonders bevorzugt 1 bis 10 Gew.-% und äußerst bevorzugt 2 bis 4 Gew.-%, bezogen auf das gesamte Mittel, betragen kann. Man verwendet dann neben nichtionischen, kationischen und amphoteren Tensiden besonders anionische Tenside aus der Gruppe der Alkylbenzolsulfonate, der Fettalkoholsulfate, der Fettalkoholethersulfate u.a. bekannter anionischer Tenside.From DE 198 28 578 are creamy, highly alkaline, aqueous. cleaning Mitel known, which according to the statements in column 3 from line 65 weak foaming surfactants, especially non-ionic surfactants, in an amount of up to 10% by weight, preferably 1 to 5% by weight and particularly preferably 2 to 4% by weight may contain. In the event that the manufactured according to the above-mentioned document Means for machine washing laundry are recommended a higher surfactant content, which is generally up to 20% by weight, preferably 0.1 to 15, particularly preferably 1 to 10% by weight and extremely preferably 2 to 4% by weight, based on the total mean. You then use alongside nonionic, cationic and amphoteric surfactants especially anionic Surfactants from the group of alkylbenzenesulfonates, fatty alcohol sulfates, Fatty alcohol ether sulfates and others known anionic surfactants.

    Demgegenüber handelt es sich beim Gegenstand der vorliegenden Erfindung im wesentlichen um thixotrope Mittel, die in einer bevorzugten Ausführungsform im Falle der Membranaufbereitung des Abwassers oder eines Teils der Waschflotte aus dem Waschprozeß sehr gute Membranverträglichkeit aufweisen.In contrast, the subject of the present invention is in essentially thixotropic agents, which in a preferred embodiment in In the case of membrane treatment of wastewater or part of the wash liquor have very good membrane compatibility from the washing process.

    Weiterhin enthalten die erfindungsgemäßen Mittel in bevorzugter Ausführungsform als Alkalitätsträger Natriumhydroxid und/oder Soda.Furthermore, the agents according to the invention contain in a preferred embodiment as an alkalinity carrier sodium hydroxide and / or soda.

    Vorzugsweise enthalten die erfindungsgemäßen Mittel zusätzlich bis zu 10 Gew.-%, vorzugsweise 0,5 Gew.-% bis 8 Gew.-% Aniontensid, insbesondere C8-C18-Alkylsulfate, C8-C18-Alkylethersulfate, C8-C18-Alkansulfonate, C8-C18-α-Olefinsulfonate, sulfonierte C8-C18-Fettsäuren, C8-C18-Alkylbenzolsulfonate, Sulfonbemsteinsäuremomo- und -di-C1-C12-Alkylester, C8-C18-Alkylpolyglykolethercarboxylate, C8-C18-N-Acyltauride, C8-C18-N-Sarkosinate, C8-C18-Alkylisethionate sowie Gemische der voranstehenden.The agents according to the invention preferably additionally contain up to 10% by weight, preferably 0.5% by weight to 8% by weight, of anionic surfactant, in particular C 8 -C 18 alkyl sulfates, C 8 -C 18 alkyl ether sulfates, C 8 - C 18 alkane sulfonates, C 8 -C 18 α-olefin sulfonates, sulfonated C 8 -C 18 fatty acids, C 8 -C 18 alkyl benzene sulfonates, sulfonic succinic acid mono- and di-C 1 -C 12 alkyl esters, C 8 -C 18- alkyl polyglycol ether carboxylates, C 8 -C 18 -N-acyl taurides, C 8 -C 18 -N-sarcosinates, C 8 -C 18 -alkyl isethionates and mixtures of the foregoing.

    Es ist ebenfalls bevorzugt, daß die erfindungsgemäßen Mittel zusätzlich wenigstens ein Alkylpolyglukosid mit 8 bis 14 C-Atomen in der Alkylgruppe und 1 bis 5 Glukoseeinheiten, besonders bevorzugt mit einem Anteil von 0,1 bis 5 % Gew.-%, bezogen auf das gesamte Mittel, enthalten.It is also preferred that the agents according to the invention additionally at least an alkyl polyglucoside with 8 to 14 carbon atoms in the alkyl group and 1 to 5 Glucose units, particularly preferably in a proportion of 0.1 to 5% by weight, based on the total mean.

    Insbesondere durch Zugabe von Alkylpolyglukosid wird erreicht, daß man zu Mitteln mit den erfindungsgemäßen Eigenschaften gelangt.In particular by adding alkyl polyglucoside it is achieved that agents with the properties of the invention.

    In einer anderen bevorzugten Ausführungsform liegt in den erfindungsgemäßen Mitteln zusätzlich ein Komplexbildner ausgewählt aus Polyphosphonsäuren, insbesondere 1-Hydroxy-ethan-1,1-diphosphonsäure, Diethylentriaminpentamethylenphosphonsäure, Ethylen-diamintetramethylenphosphonsäure, N-(2-Hydroxyethyl)-,N,N-bis-methylenphosphonsäure und deren Salzen, und/oder Polycarbonsäuren insbesondere Copolymeren aus Acryl- und Maleinsäure sowie deren Salzen oder NTA oder organische Säuren, vorzugsweise Zitronensäure sowie deren Salze, vor, insbesondere mit einem Anteil von 1 bis 20 Gew.-%, bezogen auf das gesamte Mittel.In another preferred embodiment lies in the invention Agents additionally a complexing agent selected from polyphosphonic acids, in particular 1-hydroxy-ethane-1,1-diphosphonic acid, diethylenetriaminepentamethylenephosphonic acid, Ethylene diamine tetramethylene phosphonic acid, N- (2-hydroxyethyl) -, N, N-bis-methylenephosphonic acid and their salts, and / or polycarboxylic acids in particular copolymers of acrylic and maleic acid and their salts or NTA or organic acids, preferably citric acid and its salts, before, in particular with a proportion of 1 to 20 wt .-%, based on the total funds.

    Weiterhin ist bevorzugt, daß die erfindungsgemäßen Mittel, bezogen auf das gesamte Mittel, zusätzlich 0,5 bis 10 Gew.-% verzweigten oder unverzweigten C8-22-Fettalkohol enthält. Ganz besonders bevorzugt sind C8-14-Fettalkohole, insbesondere mit verzweigter Alkylgruppe.It is further preferred that the agents according to the invention, based on the total agent, additionally contain 0.5 to 10% by weight of branched or unbranched C 8-22 fatty alcohol. C 8-14 fatty alcohols are particularly preferred, especially those with a branched alkyl group.

    Bevorzugt ist auch, daß die erfindungsgemäßen Mittel zusätzlich ein Phosphat, vorzugsweise Tripolyphosphat, besonders bevorzugt in einer Konzentration von 5 bis 50 Gew.-%, bezogen auf das gesamte Mittel, enthalten. Außer den genannten Inhaltsstoffen kann das erfindungsgemäße Mittel bekannte, in derartigen Waschalkalizusammensetzungen üblicherweise eingesetzte Zusatztstoffe enthalten, wie Co-Builder, optische Aufheller, Farb- und Duftstoffe, geringe Mengen an Neutralsalzen wie Sulfate und Chloride in Form ihrer Natrium- oder Kaliumsalze, sofern diese die positiven Eigenschaften nicht beeinträchtigen. Weitere geeignete Produktzusätze können Enzyme, Bleichmittel aus der Klasse der Perverbindungen, die üblicherweise zusammen mit Aktivatoren eingesetzt werden, Aktivchlorverbindungen sowie Farb- und Duftstoffe sein. Im Falle von Zusätzen, die oxidierende Wirkung haben, empfiehlt es sich, die Verträglichkeit mit entsprechenden Umkehrosmosemembranen zu überprüfen, sofern diese eine Rolle im Gesamtverfahren spielen.It is also preferred that the agents according to the invention additionally contain a phosphate, preferably tripolyphosphate, particularly preferably in a concentration of 5 up to 50 wt .-%, based on the total agent. Except for the above Ingredients the agent according to the invention can be known, in such Alkaline washing compositions contain additives commonly used, such as co-builders, optical brighteners, dyes and fragrances, small amounts of Neutral salts such as sulfates and chlorides in the form of their sodium or potassium salts, provided that these do not impair the positive properties. More suitable Product additives can include enzymes, bleaches from the per-compound class, which are usually used together with activators, active chlorine compounds as well as colors and fragrances. In the case of additives, the oxidizing Have an effect, it is recommended to be compatible with appropriate Check reverse osmosis membranes, provided that they play a role in the overall process play.

    Ein weiterer Gegenstand der vorliegenden Erfindung ist ein maschinelles Waschverfahren mit prozeßgesteuerter Dosierung von Waschmittel- und Wassermenge, bei dem ein erfindungsgemäßes Wasch- oder Reinigungsmittel mittels einer prozeßgesteuerten Vorrichtung zum Dosieren des Mittels in den Laugenbehälter einer Waschmaschine zugeführt wird, wobei es bevorzugt ist, daß das bei dem Verfahren anfallende Abwasser und/oder ein Teil der Waschflotte über eine Membranfiltrationsanlage aufbereitet wird, und besonders bevorzugt der Membranfiltration wenigstens ein Umkehrosmose-Schritt durchlaufen wird. Another object of the present invention is a machine washing process with process-controlled dosing of detergent and water, in which an inventive washing or cleaning agent by means of a process-controlled device for dosing the agent into the tub a washing machine is supplied, it being preferred that the Process waste water and / or part of the wash liquor via a membrane filtration system is processed, and particularly preferably membrane filtration at least one reverse osmosis step is carried out.

    BeispieleExamples

    Zur Stützung der vorliegenden Erfindung wurde einerseits der Einfluß von pastenförmigen, thixotropen Wasch- oder Reinigungsmitteln auf die Leistung von Umkehrosmosemembranen untersucht. Andererseits wurden Messungen zur Überprüfung der Thixotropie-Eigenschaften einer erfindungsgemäßen Paste vorgenommen.To support the present invention, the influence of pasty, thixotropic detergents or cleaning agents on the performance of Reverse osmosis membranes examined. On the other hand, measurements for The thixotropy properties of a paste according to the invention were checked.

    Die im Rahmen der Beispiele verwendeten Formulierungen sind in Tabelle 1 enthalten.

    Figure 00090001
    The formulations used in the examples are contained in Table 1.
    Figure 00090001

    Zur Beurteilung des Einflusses auf die Umkehrosmosemembran wurden verschiedene Vorkehrungen getroffen. Der zu behandelnde Abwasserstrom wurde aus dem Abwasserstrom einer kontinuierlich arbeitenden Textilwaschmaschine einer Versuchswäscherei abgezweigt. Das Waschverfahren in der Versuchswäscherei unterschied sich in den verschiedenen Versuchsphasen nur durch Einsatz der unterschiedlichen Produkte: Beispielpasten 1 bis 3 und Vergleichspaste. Jedes der genannten Produkte wurde im jeweiligen Waschverfahren in 2 %iger Konzentration eingesetzt.Various were used to assess the influence on the reverse osmosis membrane Precautions taken. The wastewater stream to be treated was out the wastewater flow of a continuously operating textile washing machine Test laundry branched off. The washing process in the pilot laundry differed in the different test phases only by using the different products: sample pastes 1 to 3 and comparison paste. each of the products mentioned was in the respective washing process in a 2% concentration used.

    Der zu behandelnde Abwasserstrom wurde über einen selbst reinigenden 75 µ-Vorfilter geleitet. Die verwendete Umkehrosmose-Membran hatte eine Fläche von 40 qm und ein Leistungsvermögen von 15 l pro m2.h. Das Material der verwendeten Umkehrosmosemembran war auf organischer Basis (Polypropylen). Die Temperatur während der Umkehrosmose lag bei etwa 40 °C. Die Umkehrosmose wurde so geführt, daß etwa 80 % des zu behandelnden Abwasserstroms als wiederverwendbares Permeat und etwa 20 % des zu behandelnden Abwasserstroms als zu verwerfendes Konzentrat mit hohem Salzgehalt und hoher organischer Fracht anfielen.The wastewater stream to be treated was passed through a self-cleaning 75 µ prefilter. The reverse osmosis membrane used had an area of 40 square meters and a capacity of 15 l per m 2 .h. The material of the reverse osmosis membrane used was organic (polypropylene). The temperature during the reverse osmosis was about 40 ° C. The reverse osmosis was carried out in such a way that about 80% of the wastewater stream to be treated was obtained as a reusable permeate and about 20% of the wastewater stream to be treated as a concentrate to be discarded with a high salt content and high organic load.

    Die Dauer der Versuchsphasen mit den vier zu untersuchenden Produkten belief sich auf je 5 Tage bei 8 Stunden Betriebszeit pro Tag. Vor jedem Produktwechsel wurde eine gründliche Reinigung der Umkehrosmosemembran durchgeführt. Durch diese Maßnahme wurde erreicht, daß die Ausgangsleistung XA, ausgedrückt in Form der Durchflußmenge [l/h], bei allen Versuchen etwa gleich war. Die Umkehrosmosemembran wurde innerhalb des Versuchszeitraums täglich nach Betriebsende mit Wasser durchspült.The duration of the test phases with the four products to be examined was 5 days with 8 hours of operation per day. The reverse osmosis membrane was thoroughly cleaned before each product change. As a result of this measure, the output power X A , expressed in the form of the flow rate [l / h], was approximately the same in all tests. The reverse osmosis membrane was flushed with water every day during the test period after the end of operation.

    Nach Beendigung der jeweiligen Versuchsphase wurde die Endleistung XE in Form der Durchflußmenge [l/h] bestimmt. Das Verhältnis von XE zu XA wurde zur Charakterisierung der in den Versuchsphasen jeweils getesteten Produkte herangezogen. Das Verhältnis von XE / XA kann als Hinweis dafür genommen werden, ob unter ansonsten gleichen Bedingungen innerhalb kürzerer oder längerer Intervalle eine Reinigung der Umkehrosmosmembran nötig wird.After the end of the respective test phase, the final output X E was determined in the form of the flow rate [l / h]. The ratio of X E to X A was used to characterize the products tested in the test phases. The ratio of X E / X A can be used as an indication of whether the reverse osmosis membrane needs to be cleaned within shorter or longer intervals under otherwise identical conditions.

    Zur weitergehenden Charakterisierung wurde nach Beendigung jeder Versuchsphase eine Standardreinigung, gemäß den Empfehlungen der Hersteller von Reinigungsprodukten für Umkehrosmosemembranen, durchgeführt. Nach Abschluß der Reinigung wurde die "Endleistung nach Reinigung" XER in Form der Durchflußmenge [l/h] bestimmt. Als charakteristische Größe wurde sodann das Verhältnis XER / XA errechnet. Das Verhältnis XER / XA kann als Hinweis dafür genommen werden, inwiefern die Umkehrosmosemembran nach einer bestimmten Laufzeit mit einem bestimmten Produktkonzept regenerierbar ist. Je nachdem wie gut oder schlecht die Regenerierbarkeit der Umkehrosmosemembran ist, muß früher oder später die kostenintensive Anschaffung neuer Umkehrosmosemembranen vorgenommen werden. Die bei Einsatz der 3 Beispielpasten sowie der Vergleichspaste erhaltenen Verhältnisse XE / XA und XER / XA
    sind aus Tabelle 2 zu entnehmen. Diese Werte bestätigen, daß die erfindungsgemäßen Pasten hinsichtlich der Verwendung in Verfahren, bei denen das Abwasser über Umkehrosmosemembranen filtriert wird, Vorteile haben.

    Figure 00110001
    For further characterization, a standard cleaning was carried out after the end of each test phase, in accordance with the recommendations of the manufacturers of cleaning products for reverse osmosis membranes. After the cleaning was completed, the "final performance after cleaning" X ER was determined in the form of the flow rate [l / h]. The ratio X ER / X A was then calculated as the characteristic variable. The ratio X ER / X A can be taken as an indication of the extent to which the reverse osmosis membrane can be regenerated with a certain product concept after a certain term. Depending on how good or bad the regenerability of the reverse osmosis membrane is, sooner or later the costly purchase of new reverse osmosis membranes must be carried out. The ratios X E / X A and X ER / X A obtained when using the 3 sample pastes and the comparison paste
    are shown in Table 2. These values confirm that the pastes according to the invention have advantages when used in processes in which the waste water is filtered through reverse osmosis membranes.
    Figure 00110001

    Neben der Auswirkung auf den Umkehrosmose-Vorgang wurde auch die Thixotropie-Eigenschaften einer erfindungsgemäßen Paste im Versuch bestätigt. Hierfür wurde die Formulierung der Beispielpaste 3 bei 20°C und sich laufend verändemden Scherraten untersucht. In Tabelle 3 ist die Viskosität, die sich nach unterschiedlichen Zeiten und Scherraten ergibt, eingetragen.

    Figure 00120001
    In addition to the effect on the reverse osmosis process, the thixotropy properties of a paste according to the invention were also confirmed in the experiment. For this purpose, the formulation of the example paste 3 was examined at 20 ° C and constantly changing shear rates. Table 3 shows the viscosity that results after different times and shear rates.
    Figure 00120001

    Aus der Tabelle wird deutlich, daß die Pasten gemäß vorliegender Erfindung thixotrope Eigenschaften aufweisen. Bei längerer Relaxationszeit bzw. Ruhestellung der Paste nähert sich die Viskosität dem Ausgangspunkt wieder an. Untersuchung der Viskositäten der Beispielpasten 1 bis 3 mit einem Brookfield-Rotationsviskosimeter (Spindel Nr. 7) bei unterschiedlicher Drehzahl Beispiele Viskosität [mPas] 5 Umdrehungen pro Min. 50 Umdrehungen pro Min. 1 185.000 68.000 2 150.000 55.000 3 145.000 42.000 It is clear from the table that the pastes according to the present invention have thixotropic properties. With a longer relaxation time or rest position of the paste, the viscosity approaches the starting point again. Examination of the viscosities of the example pastes 1 to 3 with a Brookfield rotary viscometer (spindle No. 7) at different speeds Examples Viscosity [mPas] 5 revolutions per min. 50 revolutions per min. 1 185000 68,000 2 150000 55,000 3 145000 42,000

    Claims (12)

    1. A hydrous, paste-like, thixotropic detergent or cleaning agent containing, based on the overall agent,
      a) an alkalinity vehicle, selected from alkali hydroxide and/or alkali carbonate, in a quantity of from 5 to 40 wt.-%, preferably from 8 to 30 wt.-%,
      b) at least 5 wt.-%, preferably 15 to 40 wt.-% of water, and
      c) more than 3 wt.-%, preferably 5.5 to 30 wt.-%, more preferably 6 to 15 wt.-% of non-ionic surfactants, said non-ionic surfactants being understood to represent at least one compound of general formula (I), R1-(OC2H4)n-OH
      wherein R1 represents a branched or unbranched alkyl or alkenyl residue having from 10 to 20 C atoms and the average degree of ethoxylation n has values of from 5 to 20,
      wherein, at 25°C, the agent has a viscosity of from 50,000 mPa·s to 250,000 mPa·s, measured using a Brookfield rotational viscometer (spindle No. 7) at 5 revolutions per minute and, under otherwise identical conditions, at 50 revolutions per minute has a viscosity of from 12,000 mPa·s to 80,000 mPa·s and, if desired, the viscosity can be adjusted by varying the proportion of water and/or liquid components and/or other viscosity auxiliaries.
    2. The agent according to claim 1, characterized in that, in accordance with the formulation, no alkali metal silicate is included.
    3. The agent according to any of claims 1 or 2, characterized in that the non-ionic surfactant according to formula (I) has an average degree of ethoxylation n of from 7 to 12, in particular from 7 to 10.
    4. The agent according to one or more of claims 1 to 3, characterized in that sodium hydroxide and/or soda are/is present as alkalinity vehicle.
    5. The agent according to one or more of claims 1 to 4, characterized in that the agent additionally includes up to 10 wt.-%, preferably from 0.5 to 8 wt.-% of an anionic surfactant, in particular C8-C18 alkyl sulfates, C8-C18 alkyl ether sulfates, C8-C18 alkanesulfonates, C8-C18 α-olefinsulfonates, sulfonated C8-C18 fatty acids, C8-C18 alkylbenzenesulfonates, sulfosuccinic mono- and di(C1-C12 alkyl) esters, C8-C18 alkylpolyglycol ether carboxylates, C8-C18 N-acyltaurides, C8-C18 N-sarcosinates, C8-C18 alkyl isethionates, as well as mixtures of the above.
    6. The agent according to one or more of claims 1 to 5, characterized in that the agent additionally includes at least one alkylpolyglucoside having 8 to 14 C atoms in the alkyl group and 1 to 5 glucose units.
    7. The agent according to one or more of claims 1 to 6, characterized in that the agent additionally includes a complexing agent selected from polyphosphonic acids, in particular 1-hydroxyethane-1,1-diphosphonic acid, diethylenetriaminepentamethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, N-(2-hydroxyethyl)-N,N-bismethylenephosphonic acid and their salts, and/or polycarboxylic acids, in particular copolymers of acrylic acid and maleic acid and salts thereof.
    8. The agent according to one or more of claims 1 to 7, characterized in that the agent additionally includes, based on the overall agent, from 0.5 to 10 wt.-% of a branched or unbranched C8-22 fatty alcohol.
    9. The agent according to one or more of claims 1 to 8, characterized in that the agent additionally includes a phosphate, preferably tripolyphosphate.
    10. A mechanical washing process with process-controlled metering of the quantities of detergent and water, wherein a hydrous, paste-like, thixotropic detergent or cleaning agent according to any of claims 1 to 9 is fed into the liquor compartment of a washing machine by means of a process-controlled device for metering the agent.
    11. The mechanical washing process according to claim 10, characterized in that the waste water accumulating during the process is treated by means of a membrane filtration unit.
    12. The process according to claim 11, characterized in that at least one reverse osmosis step is undergone during the membrane filtration.
    EP01999628A 2000-12-09 2001-11-29 Alkaline, hydrous paste Expired - Lifetime EP1341896B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    DE10061416 2000-12-09
    DE10061416A DE10061416A1 (en) 2000-12-09 2000-12-09 Alkaline, water-containing paste
    PCT/EP2001/013961 WO2002046351A1 (en) 2000-12-09 2001-11-29 Alkaline, hydrous paste

    Publications (2)

    Publication Number Publication Date
    EP1341896A1 EP1341896A1 (en) 2003-09-10
    EP1341896B1 true EP1341896B1 (en) 2004-06-16

    Family

    ID=7666511

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP01999628A Expired - Lifetime EP1341896B1 (en) 2000-12-09 2001-11-29 Alkaline, hydrous paste

    Country Status (5)

    Country Link
    US (1) US7056876B2 (en)
    EP (1) EP1341896B1 (en)
    AT (1) ATE269397T1 (en)
    DE (2) DE10061416A1 (en)
    WO (1) WO2002046351A1 (en)

    Cited By (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP3156475B1 (en) 2015-10-16 2018-06-06 Hans Georg Hagleitner Liquid cleaning concentrate

    Families Citing this family (7)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP1558721B1 (en) 2002-11-06 2007-05-16 Unilever N.V. Gel laundry detergent composition
    WO2005118760A1 (en) * 2004-05-28 2005-12-15 Ecolab Inc. Membrane friendly pasty soap composition
    EP2183346B1 (en) * 2007-08-28 2012-05-23 Ecolab INC. Paste-like detergent formulation comprising branched alkoxylated fatty alcohols as non-ionic surfactants
    US8455426B1 (en) 2012-05-04 2013-06-04 AGAIA International, Inc. Cleaning compositions
    MX369146B (en) * 2012-07-13 2019-10-30 Basf Se Use of alkoxylated non-ionic surfactants as additive in aqueous membrane cleaning compositions.
    BR112015016071A2 (en) * 2013-01-03 2017-07-11 Basf Se homogeneous detergent composition and detergent package
    US11434454B2 (en) 2017-12-22 2022-09-06 Church & Dwight Co., Inc. Laundry detergent composition

    Family Cites Families (11)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    GB8619064D0 (en) * 1986-08-05 1986-09-17 Unilever Plc Detergent compositions
    DE3719906A1 (en) 1987-06-15 1988-12-29 Henkel Kgaa MACHINE WASHING PROCESS
    US5691292A (en) * 1992-04-13 1997-11-25 The Procter & Gamble Company Thixotropic liquid automatic dishwashing composition with enzyme
    DE4332849A1 (en) * 1993-09-27 1995-03-30 Henkel Kgaa Pasty detergent
    AU711225B2 (en) * 1995-02-28 1999-10-07 Kay Chemical Company Concentrated liquid gel warewash detergent
    DE19636035A1 (en) * 1996-09-05 1998-03-12 Henkel Ecolab Gmbh & Co Ohg Paste-like detergent and cleaning agent
    DE19726287A1 (en) * 1997-06-20 1998-12-24 Henkel Ecolab Gmbh & Co Ohg Process for washing laundry, in particular workwear
    US6194371B1 (en) 1998-05-01 2001-02-27 Ecolab Inc. Stable alkaline emulsion cleaners
    DE19828578C2 (en) * 1998-06-26 2000-04-20 Henkel Ecolab Gmbh & Co Ohg Process for the production of cream-shaped alkaline aqueous cleaning agents
    DE19857687A1 (en) * 1998-12-15 2000-06-21 Henkel Ecolab Gmbh & Co Ohg Pasty detergent
    US6565613B1 (en) * 1999-04-29 2003-05-20 Genencor International, Inc. Cellulase detergent matrix

    Cited By (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP3156475B1 (en) 2015-10-16 2018-06-06 Hans Georg Hagleitner Liquid cleaning concentrate

    Also Published As

    Publication number Publication date
    ATE269397T1 (en) 2004-07-15
    US20050227899A1 (en) 2005-10-13
    EP1341896A1 (en) 2003-09-10
    US7056876B2 (en) 2006-06-06
    DE50102640D1 (en) 2004-07-22
    DE10061416A1 (en) 2002-06-20
    WO2002046351A1 (en) 2002-06-13

    Similar Documents

    Publication Publication Date Title
    EP0721498B1 (en) Pasty washing agent
    EP0272574A2 (en) Mixtures of liquid non-ionic surfactants
    EP0900266B1 (en) Method of producing compact cleaning agents for industrial dish washing machines
    EP1141212B1 (en) Pasty washing agent
    WO1992006166A1 (en) Bleaching-agent preparation
    EP1341896B1 (en) Alkaline, hydrous paste
    EP2711413B2 (en) Washing agent and method for metering a washing agent
    EP0720644B1 (en) Detergent mixtures and washing or cleaning agents with improved solvent properties
    DE19507532C2 (en) Pasty detergent
    EP0541523A1 (en) Paste-like, phosphate-free detergent with reduced frothing tendency.
    EP0916717B1 (en) Hard surface cleaning agent
    CH616704A5 (en) Detergent and cleaner composition.
    DE19548843A1 (en) Process for washing laundry
    DE2219620C2 (en) Liquid heavy duty detergent
    EP1036157B1 (en) Dish washing detergent with a specific viscosity profile
    EP0990020B1 (en) Method for washing clothes, in particular working clothes
    DE10032589A1 (en) Thickened aqueous liquid bleach, washing or prewash composition based on hydrogen peroxide has a defined pH to improve its viscosity stability and reduce oxidative decolorization of dyed textiles
    EP0848746B1 (en) Aqueous cleaning agent
    DE19822391A1 (en) High viscosity, aqueous, liquid, hydrogen peroxide-containing bleaching or pre-spotting agent
    EP1084224B1 (en) Aqueous bleaching agent with viscose structure
    DE10032588A1 (en) Increasing viscosity stability of thickened aqueous liquid bleach or prewash compositions based on hydrogen peroxide comprises increasing the pH
    EP0460035B1 (en) Water-softening agent in granular to powder form
    EP2128236B1 (en) Light duty detergent
    DE2230453A1 (en) BASIC MATERIAL APPROACH FOR DETERGENTS AND DETERGENTS
    DE10212169A1 (en) Detergent additive with a high content of non-ionic surfactants and quick dissolving power

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    17P Request for examination filed

    Effective date: 20030528

    AK Designated contracting states

    Kind code of ref document: A1

    Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

    17Q First examination report despatched

    Effective date: 20031009

    GRAP Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOSNIGR1

    RAP1 Party data changed (applicant data changed or rights of an application transferred)

    Owner name: ECOLAB INC.

    GRAS Grant fee paid

    Free format text: ORIGINAL CODE: EPIDOSNIGR3

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: IE

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20040616

    Ref country code: CY

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20040616

    Ref country code: FI

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20040616

    Ref country code: TR

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20040616

    Ref country code: NL

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20040616

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: FG4D

    Free format text: NOT ENGLISH

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: EP

    REF Corresponds to:

    Ref document number: 50102640

    Country of ref document: DE

    Date of ref document: 20040722

    Kind code of ref document: P

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FG4D

    Free format text: GERMAN

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: GR

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20040916

    Ref country code: DK

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20040916

    Ref country code: SE

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20040916

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: ES

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20040927

    GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

    Effective date: 20040902

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: LU

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20041129

    Ref country code: AT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20041129

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: MC

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20041130

    Ref country code: BE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20041130

    NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FD4D

    ET Fr: translation filed
    PLBE No opposition filed within time limit

    Free format text: ORIGINAL CODE: 0009261

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

    BERE Be: lapsed

    Owner name: ECOLAB INC.

    Effective date: 20041130

    26N No opposition filed

    Effective date: 20050317

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: GB

    Payment date: 20051004

    Year of fee payment: 5

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: LI

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20051130

    Ref country code: CH

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20051130

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: PL

    GBPC Gb: european patent ceased through non-payment of renewal fee

    Effective date: 20061129

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20061129

    BERE Be: lapsed

    Owner name: *ECOLAB INC.

    Effective date: 20041130

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: PT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20041116

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: DE

    Payment date: 20131127

    Year of fee payment: 13

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R082

    Ref document number: 50102640

    Country of ref document: DE

    Representative=s name: GODEMEYER BLUM LENZE PARTNERSCHAFT, PATENTANWA, DE

    Ref country code: DE

    Ref legal event code: R082

    Ref document number: 50102640

    Country of ref document: DE

    Representative=s name: GODEMEYER BLUM LENZE PATENTANWAELTE, PARTNERSC, DE

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R119

    Ref document number: 50102640

    Country of ref document: DE

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: PLFP

    Year of fee payment: 15

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: DE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20150602

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: PLFP

    Year of fee payment: 16

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: PLFP

    Year of fee payment: 17

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: PLFP

    Year of fee payment: 18

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: IT

    Payment date: 20201013

    Year of fee payment: 20

    Ref country code: FR

    Payment date: 20201013

    Year of fee payment: 20