EP0192153A1 - Additives for washing and cleaning agents - Google Patents

Additives for washing and cleaning agents Download PDF

Info

Publication number
EP0192153A1
EP0192153A1 EP86101659A EP86101659A EP0192153A1 EP 0192153 A1 EP0192153 A1 EP 0192153A1 EP 86101659 A EP86101659 A EP 86101659A EP 86101659 A EP86101659 A EP 86101659A EP 0192153 A1 EP0192153 A1 EP 0192153A1
Authority
EP
European Patent Office
Prior art keywords
weight
meth
additives
granular
acrylic 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.)
Granted
Application number
EP86101659A
Other languages
German (de)
French (fr)
Other versions
EP0192153B1 (en
Inventor
Walter Denzinger
Heinrich Dr. Hartmann
Wolfgang Dr. Trieselt
Albert Dr. Hettche
Rolf Dr. Schneider
Hans-Jürgen Raubenheimer
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to AT86101659T priority Critical patent/ATE35148T1/en
Publication of EP0192153A1 publication Critical patent/EP0192153A1/en
Application granted granted Critical
Publication of EP0192153B1 publication Critical patent/EP0192153B1/en
Expired 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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • the invention relates to powdered and / or granular additives for powdered detergent and cleaning agent preparations.
  • Polymeric polycarboxylic acids and their salts are common additives for detergent and cleaning agent preparations which improve the primary washing action and the incrustation and graying inhibitor action in an outstanding manner.
  • the polymer carboxylic acids or their salts are generally added to the detergent slurries in the form of aqueous solutions and then dried.
  • This additive increases the viscosity of the slurries and, in the worst case, precipitation can occur.
  • the polymer carboxylic acids or their salts in solid form and to subsequently add the solid product obtained as powder or granules to the detergents in powder or granule form.
  • the solid polymer carboxylic acids in particular in the form of the salts, have the disadvantage of high hygroscopicity and low bulk density.
  • the object of this invention is to largely reduce these disadvantages in order to enable better technical processing of polymer carboxylic acids and their salts in powder form, i.e. reduce hygroscopicity and bulk density.
  • the solution to the problem consists in the surprising finding that the disadvantages described can be overcome in the mixture with nitrilotriacetic acid or its sodium salts.
  • this powdered or granular mixture as an additive for powdered or granular detergent and cleaning agent preparations.
  • Powdery is to be understood as meaning a finely divided powder up to a granular or granular mass, both in the case of the additive according to the invention and in the case of detergents and cleaning agents.
  • the powdery additives according to the invention can be characterized by particle sizes with an average diameter of 10 to 500 microns. preferably 50 to 300 microns, with a high proportion in the distribution of sizes from 100 to 300 microns.
  • the granules generally have average grain sizes of 0.2 to 10 mm, preferably 0.3 to 5 mm and particularly preferably 0.5 to 2 mm.
  • the particle sizes depend in particular on the type of drying process, spray drying and fluidized bed drying, in particular in the form of spray granulation, being preferred.
  • the (meth) acrylic acid-maleic acid copolymers indicated contain 45 to 85% (meth) acrylic acid and 55 to 15% halic acid as monomer units, based on the total weight of the copolymer.
  • (Heth) acrylic acid means acrylic acid or methacrylic acid or mixtures of the two acids.
  • the preferred copolymers with hydroxyalkyl (meth) acrylates contain, based on the total weight of the copolymer, 10 to 40% by weight (meth) acrylic acid, 10 to 40% by weight maleic acid and 20 to 50% by weight of at least one hydroxyalkyl ( meth) acrylate with 2 to 6 carbon atoms in the hydroxyalkyl group.
  • the hydroxyalkyl ester groups of the hydroxyalkyl (meth) acrylates are derived, for example, from alkanediols, such as 1,2-ethanediol, 1,3 and 1,2-propanediol, and their technical mixtures, neopentylglycol, 1,5-pentanediol or 1-hexanediol, 6 from.
  • alkanediols such as 1,2-ethanediol, 1,3 and 1,2-propanediol
  • neopentylglycol 1,5-pentanediol or 1-hexanediol
  • Examples include hydroxyethyl methacrylate, hydroxypropyl methacrylate, butanediol monomethacrylate, neopentyl glycol monoacrylate, 1,5-pentanediol monoacrylate and 1,6-hexanediol monoacrylate.
  • the preferred hydroxyalkyl esters are hydroxyethyl acrylate, 1,4-butanediol monoacrylate and the hydroxypropyl acrylates.
  • the particularly preferred hydroxyalkyl esters are the hydroxypropyl acrylates, the isomer mixtures of 2-hydroxy-1-propyl acrylate and 1-hydroxy-2-propyl acrylate which are prepared by reacting acrylic acid with propylene oxide being of particular technical importance.
  • the copolymers are preferably used in the form of the water-soluble alkali metal salts, such as the sodium or potassium salts, in particular the sodium salts.
  • they can also be used in the form of the water-soluble ammonium salts or organic amine salts, such as, in particular, the salts of trialkylamines with alkyl radicals of 1 to 4 carbon atoms or the salts of mono-, di- and trialkanolamines with 1 to 4 carbon atoms in the alkanol radical will.
  • Mixtures of the amine salts mentioned may also be suitable. Examples include: mono-, di- and trihydroxyethylamine. It may be appropriate to use different salts, such as sodium and potassium salts or sodium and alkanolamine salts together.
  • the water-soluble salts are expediently partially to completely neutralized salts.
  • 50 to 100 z of the carboxyl groups are generally neutralized.
  • the (meth) acrylic acid-maleic acid copolymers are known and according to known manufacturing processes, e.g. according to EP-A-75 820 or DE-A 3 233 777, 3 233 778, 3 233 775 and 3 233 776.
  • the copolymers with hydroxyalkyl (meth) acrylates can be obtained, for example, according to German patent application P 34 26 368.
  • the copolymers to be used according to the invention have K values of 8 to 150, preferably 10 to 100, measured in 1% aqueous solution adjusted to pH 7 with sodium hydroxide solution at 25 ° C. according to Fikentscher, cellulose chemistry 13, 58 ff ( 1932).
  • the K value is a suitable characterization for these polymeric polycarboxylic acids.
  • the preferred mixing ratios for the additives according to the invention are 30 to 70 and very particularly preferably 60 to 40% by weight a) and 70 to 30 and very particularly preferably 40 to 60% by weight b).
  • a mixing ratio of about 1: 1 has proven to be particularly suitable in the art.
  • the substances c) which are usually additives which are not surface-active for detergents and cleaning agents and which do not necessarily have to be present in the mixture according to the invention, generally include detergent and cleaning agent additives, such as, for example, sodium sulfate, sodium tripolyphosphate, soluble and insoluble sodium silicates.
  • detergent and cleaning agent additives such as, for example, sodium sulfate, sodium tripolyphosphate, soluble and insoluble sodium silicates.
  • Magnesium sulfate, Soda organic phosphonates, sodium aluminum silicates of the zeolite A type and mixtures of the substances mentioned.
  • the additive according to the invention is advantageously prepared by mixing the aqueous solution of the polymer carboxylic acid or a water-soluble salt with the aqueous solution of nitrilotriacetic acid or one of its sodium salts and, if appropriate, the aqueous solution or suspension of one or more substances c) and then drying it.
  • the individual substances can also be added separately in the solid phase to the aqueous solution.
  • These solutions preferably have a pH of 5 to 10, preferably 7 to 9, and a solids content of 20 to 70%.
  • Drying takes place according to the usual methods in the known drying devices at temperatures of 70 to 200 ° C and preferably at 80 to 180 ° C.
  • Suitable drying processes are, for example, belt drying, drum drying, freeze drying, spray drying or fluidized bed drying. Spray drying is particularly suitable for producing a fine powder, and fluidized bed drying is particularly suitable for producing granules, and spray granulation is particularly suitable in a particular embodiment.
  • the particle sizes can be varied within the framework of the drying process used, since the resulting particle sizes depend less on their composition than on the type of drying process.
  • a spray-dried powder according to the invention having average particle sizes of 50 to 500 ⁇ m is advantageously introduced and the particles are then enlarged in a fluidized bed by spraying on further solution.
  • the additives or mixtures according to the invention for detergents and cleaning agents have the advantage that they are extremely easy to handle, represent little hygroscopic powders or granules with a high bulk density and can be added directly to the powder detergents.
  • nitrilotriacetic acid or its sodium salts used to reduce the hygroscopicity and to increase the bulk density are a sequestering agent known for detergents, which has found its way into numerous detergents and cleaning agents and is therefore not a fiber which causes unnecessary stress.
  • the following examples illustrate the invention. Parts specified are parts by weight.
  • the K values are determined according to H. Fikentscher as stated above.
  • the water absorption of the predried powder is determined from a sample of approx. 2 g in a weighing glass of approx. 5 mm diameter after storage for 24 hours at 68% relative atmospheric humidity and 20 ° C.
  • the grain sizes are determined by dry screening the respective powder using an electromagnetic screening machine (Analyzer 3 from Fritsch).
  • a 45% solution of a copolymer of 70% by weight acrylic acid and 30% by weight maleic acid having a K value of 50 and neutralized with 50% sodium hydroxide is mixed with a 38% solution of nitrilotriacetic acid trisodium salt (NTA) and sprayed with a 2-component nozzle dried at 150 ° C air inlet temperature and at 90 ° C air outlet temperature.
  • NTA nitrilotriacetic acid trisodium salt
  • the grain sizes of the powders are between 50 and 500 ⁇ m. 70% of them in a range from 100 to 200 ⁇ m.
  • a 50% solution of a copolymer of 65% by weight acrylic acid and 35% by weight maleic acid of K value 24 neutralized to 50% with sodium hydroxide is mixed with 38% ZTA NTA solution and dried and tested according to Example 1.
  • the grain sizes of the powder are comparable to Example 1.
  • a 38% solution of a copolymer of 50% by weight acrylic acid and 50% by weight maleic acid having a K value of 42 and neutralized with 65% sodium hydroxide is mixed with a 38% NTA solution and dried and tested as in Example 1.
  • the grain sizes of the powder are comparable to Example 1.
  • the grain sizes of the powder are between 25 to 300 ⁇ m, the main proportion of approx. 80% being 70 to 110 ⁇ m.
  • a 40% solution of a copolymer of 30% by weight methacrylic acid, 45% by weight acrylic acid and 25% by weight maleic acid having a K value of 98 and neutralized with 90% sodium hydroxide is mixed with a 40% solution of a nitrilotriacetic acid disodium salt.
  • Half of the mixture is dried in a spray dryer according to Example 1, placed in a fluidized bed and the rest of the mixture is sprayed on at a gas temperature of approximately 140.degree. This spray granulation leads to granules of approximately 0.5 to 5 mm in diameter.
  • the test results are shown in the table below:
  • a 38 Zige solution of a copolymer of 40% acrylic acid neutralized to 70% with sodium hydroxide 40% by weight of maleic acid and 20% by weight of hydroxypropyl acrylate (technical isomer mixture of approx. 67% by weight of 2-hydroxy-1-propyl acrylate and approx. 33% by weight of 1-hydroxy-2-propyl acrylate) from K -Value 42 is mixed with a 38% NTA solution and dried and tested according to Example 1, but with a single-component nozzle.
  • the grain sizes of the powders are 50 to 500 ⁇ m. approx. 70% of them in the range from 200 to 350 ⁇ m.
  • the grain sizes of the powders are comparable to Example 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Pulverulent and/or granular additives for pulverulent detergents and cleaning agents, consisting of (a) from 80 to 20% by weight of one or more copolymers comprising from 40 to 90% by weight of (meth)acrylic acid and from 60 to 10% by weight of maleic acid and/or one or more copolymers comprising from 10 to 45% by weight of (meth)acrylic acid, from 10 to 45% by weight of maleic acid and from 10 to 60% by weight of one or more hydroxyalkyl (meth)acrylates where hydroxyalkyl is of 2 to 6 carbon atoms, if appropriate in the form of a partially or completely neutralized water-soluble salt, (b) from 20 to 80% by weight of nitrilotriacetic acid or its mono-, di- or trisodium or mono-, di- or tripotassium salt and (c) from 0 to 20% by weight of one or more additives conventionally used for detergent and cleaning agent formulations, the use of these pulverulent and/or granular mixtures as additives for pulverulent and/or granular detergents and cleaning agents, and processes for the preparation of the said additives.

Description

Die Erfindung betrifft pulver- und/oder granulatförmige Zusätze für pulverförmige Wasch- und Reinigungsmittelzubereitungen.The invention relates to powdered and / or granular additives for powdered detergent and cleaning agent preparations.

Polymere Polycarbonsäuren und deren Salze sind gebräuchliche Zusätze für Wasch- und Reinigungsmittelzubereitungen, die die Primärwaschwirkung sowie die Inkrustations- und Vergrauungsinhibitorwirkung in hervorragender Weise verbessern. Bei der Herstellung der Waschmittelformulierungen für den Verbrauch werden die Polymercarbonsäuren oder ihre Salze in der Regel in Form von wißrigen Lösungen den Waschmittelslurries zugesetzt und anschließend wird getrocknet. Nachteilig dabei ist, daß dieser Zusatz die Viskosität der Slurries erhöht und im ungunstigsten Fall Ausfällungen auftreten können.Polymeric polycarboxylic acids and their salts are common additives for detergent and cleaning agent preparations which improve the primary washing action and the incrustation and graying inhibitor action in an outstanding manner. In the production of the detergent formulations for consumption, the polymer carboxylic acids or their salts are generally added to the detergent slurries in the form of aqueous solutions and then dried. The disadvantage here is that this additive increases the viscosity of the slurries and, in the worst case, precipitation can occur.

Es ist daher von Vorteil, die Polymercarbonsäuren oder ihre Salze in fester Form herzustellen und das erhaltene Festprodukt als Pulver oder Granulat den pulver- oder granulatförmig vorliegenden Waschmitteln nachträglich beizumischen. Die festen Polymercarbonsäuren weisen insbesondere in Form der Salze jedoch als Nachteil eine hohe Hygroskopizität und ein niedriges Schüttgewicht auf.It is therefore advantageous to prepare the polymer carboxylic acids or their salts in solid form and to subsequently add the solid product obtained as powder or granules to the detergents in powder or granule form. However, the solid polymer carboxylic acids, in particular in the form of the salts, have the disadvantage of high hygroscopicity and low bulk density.

Aufgabe dieser Erfindung ist es, diese Nachteile weitgehend zu reduzieren, um eine bessere technische Verarbeitung von Polymercarbonsäuren und ihrer Salze in Pulverform zu ermöglichen, d.h. die Hygroskopizität zu verringern und das Schüttgewicht zu erhöhen.The object of this invention is to largely reduce these disadvantages in order to enable better technical processing of polymer carboxylic acids and their salts in powder form, i.e. reduce hygroscopicity and bulk density.

Die Lösung der Aufgabe besteht in der überraschenden Feststellung, daß in der Mischung mit Nitrilotriessigsäure oder ihrer Natriumsalze die geschilderten Nachteile überwunden werden können.The solution to the problem consists in the surprising finding that the disadvantages described can be overcome in the mixture with nitrilotriacetic acid or its sodium salts.

Gegenstand der Erfindung ist ein homogenes Gemisch in Form eines Pulvers oder Granulats als Zusatz für pulver- und/oder granulatförmige Wasch- und Reinigungsmittel, bestehend aus

  • a) 80 bis 20 Gew.-X mindestens eines Copolymerisats bestehend aus 40 bis 90 Gew.-X (Meth)Acrylsäure und 60 bis 10 Gew.-X Maleinsäure und/oder aus 10 bis 45 Gew.-X (Meth)Acrylsäure, 10 bis 45 Gew.-X Maleinsäure und 10 bis 60 Gew.-1 mindestens eines Hydroxyalkyl(meth)-acrylats mit 2 bis 6 C-Atomen in der Hydroxyalkylgruppe, gegebenenfalls in der Form eines wasserlöslichen Salzes,
  • b) 20 bis 80 Gew.-z Nitrilotriessigsäure oder ihres Mono-, Di- oder Trinatrium- oder -kaliumsalzes und
  • c) 0 bis 20 Gew.-X eines oder mehrerer für Wasch- und Reinigungsmittelzubereitungen üblicher Zusatzstoffe.
The invention relates to a homogeneous mixture in the form of a powder or granules as an additive for powder and / or granular detergents and cleaning agents, consisting of
  • a) 80 to 20% by weight of at least one copolymer consisting of 40 to 90% by weight of (meth) acrylic acid and 60 to 10% by weight of maleic acid and / or of 10 to 45% by weight of (meth) acrylic acid, 10 to 45% by weight of maleic acid and 10 to 60% by weight of at least one hydroxyalkyl (meth) acrylate with 2 to 6 carbon atoms in the hydroxyalkyl group, optionally in the form of a water-soluble salt,
  • b) 20 to 80% by weight of nitrilotriacetic acid or its mono-, di- or trisodium or potassium salt and
  • c) 0 to 20% by weight of one or more additives customary for detergent and cleaning agent preparations.

und die Verwendung dieser pulver- oder granulatförmigen Mischung als Zusatz für pulver- oder granulatförmige Wasch- und Reinigungsmittelzubereitungen.and the use of this powdered or granular mixture as an additive for powdered or granular detergent and cleaning agent preparations.

Unter pulverförmig soll ein feinteiliges Pulver bis hin zu einer körnigen oder granulatförmigen Masse verstanden werden, sowohl bei dem erfindungsgemäßen Zusatz als auch bei den Wasch- und Reinigungsmitteln.Powdery is to be understood as meaning a finely divided powder up to a granular or granular mass, both in the case of the additive according to the invention and in the case of detergents and cleaning agents.

Die erfindungsgemäßen pulverförmigen Zusätze lassen sich charakterisieren durch Teilchengrößen mit einem mittleren Durchmesser von 10 bis 500 µm. vorzugsweise 50 bis 300 µm, mit einem hohen Anteil in der Verteilung an Größen von 100 bis 300 µm. Die Granulate weisen in der Regel mittlere Korngrößen von 0,2 bis 10 mm, vorzugsweise von 0,3 bis 5 mm und besonders bevorzugt von 0,5 bis 2 mm auf. Die Teilchengrößen hängen insbesondere von der Art des Trocknungsverfahrens ab, wobei Sprühtrocknung und Wirbelbetttrocknung insbesondere in Form der Sprühgranulierung bevorzugt sind.The powdery additives according to the invention can be characterized by particle sizes with an average diameter of 10 to 500 microns. preferably 50 to 300 microns, with a high proportion in the distribution of sizes from 100 to 300 microns. The granules generally have average grain sizes of 0.2 to 10 mm, preferably 0.3 to 5 mm and particularly preferably 0.5 to 2 mm. The particle sizes depend in particular on the type of drying process, spray drying and fluidized bed drying, in particular in the form of spray granulation, being preferred.

Die angegebenen (Meth)Acrylsäure-Maleinsäure-Copolymerisate enthalten in ihrer bevorzugten Ausführungsform, bezogen auf das Gesamtgewicht des Copolymerisats, 45 bis 85 X (Meth)Acrylsäure und 55 bis 15 X Haleinsäure als Monomereinheiten. Unter (Heth)Acrylsäure ist Acrylsäure oder Methacrylsäure oder Mischungen der beiden Säuren zu verstehen.In their preferred embodiment, the (meth) acrylic acid-maleic acid copolymers indicated contain 45 to 85% (meth) acrylic acid and 55 to 15% halic acid as monomer units, based on the total weight of the copolymer. (Heth) acrylic acid means acrylic acid or methacrylic acid or mixtures of the two acids.

Die bevorzugten Copolymerisate mit Hydroxyalkyl(meth)acrylaten enthalten, bezogen auf das Gesamtgewicht des Copolymerisats, 10 bis 40 Gew.-X (Meth)Acrylsäure, 10 bis 40 Gew.-X Maleinsäure und 20 bis 50 Gew.-X mindestens eines Hydroxyalkyl(meth)acrylats mit 2 bis 6 C-Atomen in der Hydroxyalkylgruppe. Die Hydroxyalkylestergruppen der Hydroxyalkyl(meth)-acrylate leiten sich von beispielsweise von Alkandiolen, wie Ethandiol-1,2, Propandiol-1,3 und -1,2 sowie deren technische Gemische, Neopentylglykol, Pentandiol-1,5 oder Hexandiol-1,6 ab. Im einzelnen seien beispielsweise erwähnt Hydroxyethylmethacrylat, Hydroxypropylmethacrylate, Butandiolmonomethacrylat, Neopentylglykolmonoacrylat, 1,5-Pentandiolmonoacrylat und 1,6-Hexandiolmonoacrylat. Die bevorzugten Hydroxyalkylester sind Hydroxyethylacrylat, 1,4-Butandiolmonoacrylat und die Hydroxypropylacrylate. Die besonders bevorzugten Hydroxyalkylester sind die Hydroxypropylacrylate, wobei von besonderer technischer Bedeutung die Isomerengemische aus 2-Hydroxy-1-propylacrylat und 1-Hydroxy-2-propylacrylat sind, die durch Umsetzung von Acrylsäure mit Propylenoxid hergestellt werden.The preferred copolymers with hydroxyalkyl (meth) acrylates contain, based on the total weight of the copolymer, 10 to 40% by weight (meth) acrylic acid, 10 to 40% by weight maleic acid and 20 to 50% by weight of at least one hydroxyalkyl ( meth) acrylate with 2 to 6 carbon atoms in the hydroxyalkyl group. The hydroxyalkyl ester groups of the hydroxyalkyl (meth) acrylates are derived, for example, from alkanediols, such as 1,2-ethanediol, 1,3 and 1,2-propanediol, and their technical mixtures, neopentylglycol, 1,5-pentanediol or 1-hexanediol, 6 from. Examples include hydroxyethyl methacrylate, hydroxypropyl methacrylate, butanediol monomethacrylate, neopentyl glycol monoacrylate, 1,5-pentanediol monoacrylate and 1,6-hexanediol monoacrylate. The preferred hydroxyalkyl esters are hydroxyethyl acrylate, 1,4-butanediol monoacrylate and the hydroxypropyl acrylates. The particularly preferred hydroxyalkyl esters are the hydroxypropyl acrylates, the isomer mixtures of 2-hydroxy-1-propyl acrylate and 1-hydroxy-2-propyl acrylate which are prepared by reacting acrylic acid with propylene oxide being of particular technical importance.

Mischungen der genannten Copolymerisate aus (Meth)Acrylsäure-Maleinsäure und Copolymerisaten aus (Meth)Acrylsäure, Maleinsäure und Hydroxyalkyl-(meth)acrylaten können mit Vorteil verwendet werden.Mixtures of the copolymers of (meth) acrylic acid-maleic acid mentioned and copolymers of (meth) acrylic acid, maleic acid and hydroxyalkyl (meth) acrylates can be used with advantage.

Vorzugsweise werden die Copolymerisate in Form der wasserlöslichen Alkalimetallsalze, wie der Natrium- oder Kaliumsalze, insbesondere der Natriumsalze, verwendet. Sie können aber auch in Form der wasserlöslichen Ammoniumsalze oder organischer Aminsalze, wie insbesondere der Salze von Trialkylaminen mit Alkylresten von 1 bis 4 C-Atomen oder der Salze von Mono-, Di- und Trialkanolaminen mit 1 bis 4 C-Atomen im Alkanolrest, verwendet werden. Gegebenenfalls sind auch Mischungen der genannten Aminsalze geeignet. Im einzelnen seien beispielsweise genannt: Mono-, Di- und Trihydroxyethylamin. Es kann zweckmäßig sein, verschiedene Salze, wie Natrium- und Kaliumsalze oder Natrium- und Alkanolaminsalze zusammen zu verwenden.The copolymers are preferably used in the form of the water-soluble alkali metal salts, such as the sodium or potassium salts, in particular the sodium salts. However, they can also be used in the form of the water-soluble ammonium salts or organic amine salts, such as, in particular, the salts of trialkylamines with alkyl radicals of 1 to 4 carbon atoms or the salts of mono-, di- and trialkanolamines with 1 to 4 carbon atoms in the alkanol radical will. Mixtures of the amine salts mentioned may also be suitable. Examples include: mono-, di- and trihydroxyethylamine. It may be appropriate to use different salts, such as sodium and potassium salts or sodium and alkanolamine salts together.

Bei den wasserlöslichen Salzen handelt es sich zweckmäßigerweise um teilweise bis vollständig neutralisierte Salze. Für die praktische Verwendung werden in der Regel 50 bis 100 z der Carboxylgruppen neutralisiert.The water-soluble salts are expediently partially to completely neutralized salts. For practical use, 50 to 100 z of the carboxyl groups are generally neutralized.

Die (Meth)Acrylsäure-Maleinsäure-Copolymerisate sind bekannt und nach an sich bekannten Herstellungsverfahren, z.B. gemäß der EP-A-75 820 oder den DE-A 3 233 777, 3 233 778, 3 233 775 und 3 233 776, erhältlich. Die Copolymerisate mit Hydroxyalkyl(meth)acrylaten können beispielsweise nach der deutschen Patentanmeldung P 34 26 368 erhalten werden.The (meth) acrylic acid-maleic acid copolymers are known and according to known manufacturing processes, e.g. according to EP-A-75 820 or DE-A 3 233 777, 3 233 778, 3 233 775 and 3 233 776. The copolymers with hydroxyalkyl (meth) acrylates can be obtained, for example, according to German patent application P 34 26 368.

Die erfindungsgemäß zu verwendenden Copolymerisate weisen K-Werte von 8 bis 150, bevorzugt 10 bis 100, auf, gemessen in mit Natronlauge auf pH-Wert 7 eingestellter 1 gew.Ziger wäßriger Lösung bei 25°C nach Fikentscher, Cellulosechemie 13, 58 ff (1932). Für diese polymeren Polycarbonsäuren ist der K-Wert eine zweckmäßige Charakterisierung.The copolymers to be used according to the invention have K values of 8 to 150, preferably 10 to 100, measured in 1% aqueous solution adjusted to pH 7 with sodium hydroxide solution at 25 ° C. according to Fikentscher, cellulose chemistry 13, 58 ff ( 1932). The K value is a suitable characterization for these polymeric polycarboxylic acids.

Die bevorzugten Mischungsverhältnisse für die erfindungsgemäßen Zusätze sind 30 bis 70 und ganz besonders bevorzugt 60 bis 40 Gew.-X a) und 70 bis 30 und ganz besonders bevorzugt 40 bis 60 Gew.-z b). Dabei hat sich in der Technik ein Mischungsverhältnis von etwa 1 : 1 als besonders geeignet erwiesen.The preferred mixing ratios for the additives according to the invention are 30 to 70 and very particularly preferably 60 to 40% by weight a) and 70 to 30 and very particularly preferably 40 to 60% by weight b). A mixing ratio of about 1: 1 has proven to be particularly suitable in the art.

Unter den Stoffen c), üblicherweise für Wasch- und Reinigungsmittel nicht oberflächenaktive Zusatzstoffe, die in dem erfindungsgemäßen Gemisch nicht unbedingt enthalten zu sein brauchen, sind allgemein Wasch- und Reinigungsmittelzusätze, wie beispielsweise Natriumsulfat, Natriumtripolyphosphat, lösliche und unlösliche Natriumsilikate. Magnesiumsulfat, Soda, organische Phosphonate, Natrium-Aluminiumsilikate vom Typ Zeolith A und Mischungen der genannten Stoffe zu verstehen.The substances c), which are usually additives which are not surface-active for detergents and cleaning agents and which do not necessarily have to be present in the mixture according to the invention, generally include detergent and cleaning agent additives, such as, for example, sodium sulfate, sodium tripolyphosphate, soluble and insoluble sodium silicates. Magnesium sulfate, Soda, organic phosphonates, sodium aluminum silicates of the zeolite A type and mixtures of the substances mentioned.

Der erfindungsgemäße Zusatz wird zweckmäßig hergestellt, indem man die wäßrige Lösung der Polymercarbonsäure oder eines wasserlöslichen Salzes mit der wäBrigen Lösung von Nitrilotriessigsäure oder eines ihrer Natriumsalze und gegebenenfalls der wäßrigen Lösung oder Suspension eines oder mehrerer Stoffe c) mischt und anschließend trocknet. Selbstverständlich können die einzelnen Stoffe auch getrennt in fester Phase der wäßrigen Lösung zugegeben werden. Vorzugsweise weisen diese Lösungen einen pH-Wert von 5 bis 10, vorzugsweise von 7 bis 9, und einen Feststoffgehalt von 20 bis 70 % auf.The additive according to the invention is advantageously prepared by mixing the aqueous solution of the polymer carboxylic acid or a water-soluble salt with the aqueous solution of nitrilotriacetic acid or one of its sodium salts and, if appropriate, the aqueous solution or suspension of one or more substances c) and then drying it. Of course, the individual substances can also be added separately in the solid phase to the aqueous solution. These solutions preferably have a pH of 5 to 10, preferably 7 to 9, and a solids content of 20 to 70%.

Die Trocknung erfolgt nach den üblichen Methoden in den bekannten Trocknuingsvorrichtungen bei Temperaturen von 70 bis 200°C und bevorzugt bei 80 bis 180°C. Geeignete Trocknungsverfahren sind beispielsweise Bandtrocknung, Walzentrocknung, Gefriertrocknung, Sprühtrocknung oder Wirbelbetttrocknung. Zur Herstellung eines feinen Pulvers ist die Sprühtrocknung und zur Herstellung von Granulaten die Wirbelbetttrocknung und in einer besonderen Ausführungsform die Sprühgranulierung besonders geeignet.Drying takes place according to the usual methods in the known drying devices at temperatures of 70 to 200 ° C and preferably at 80 to 180 ° C. Suitable drying processes are, for example, belt drying, drum drying, freeze drying, spray drying or fluidized bed drying. Spray drying is particularly suitable for producing a fine powder, and fluidized bed drying is particularly suitable for producing granules, and spray granulation is particularly suitable in a particular embodiment.

Die Teilchengrößen lassen sich im Rahmen des angewandten Trocknungsverfahrens variieren, da die entstehenden Teilchengrößen weniger von ihrer Zusammensetzung als von der Art des TrocknungsprozeBes abhängen. Bei der Sprühgranulierung wird zweckmäßigerweise ein erfindungsgemäßes sprühgetrocknetes Pulver mit mittleren Teilchengrößen von 50 bis 500 µm vorgelegt und darauf in einem Wirbelbett durch Aufsprühen weiterer Lösung die Teilchen vergrößert.The particle sizes can be varied within the framework of the drying process used, since the resulting particle sizes depend less on their composition than on the type of drying process. In the spray granulation, a spray-dried powder according to the invention having average particle sizes of 50 to 500 μm is advantageously introduced and the particles are then enlarged in a fluidized bed by spraying on further solution.

Die erfindungsgemäßen Zusätze bzw. Mischungen für Wasch- und Reinigungsmittel haben den Vorteil, daß sie sich außerordentlich gut handhaben lassen, wenig hygroskopische Pulver oder Granulate mit hohem Schüttgewicht darstellen und direkt den pulverförmigen Waschmitteln zugesetzt werden können.The additives or mixtures according to the invention for detergents and cleaning agents have the advantage that they are extremely easy to handle, represent little hygroscopic powders or granules with a high bulk density and can be added directly to the powder detergents.

Die zur Verminderung der Hygroskopizität und zur Erhöhung des Schüttgewichts eingesetzte Nitrilotriessigsäure oder ihre Natriumsalze sind ein für Waschmittel bekanntes Sequestriermittel, das in zahlreichen Wasch-und Reinigungsmitteln Eingang gefunden hat und somit keinen Ballaststoff darstellt, der unnötige Belastungen hervorruft.The nitrilotriacetic acid or its sodium salts used to reduce the hygroscopicity and to increase the bulk density are a sequestering agent known for detergents, which has found its way into numerous detergents and cleaning agents and is therefore not a fiber which causes unnecessary stress.

Die nun folgenden Beispiele erläutern die Erfindung. Angegebene Teile sind Gewichtsteile. Die K-Werte werden wie oben angegeben, nach H. Fikentscher bestimmt. Bei der Hygroskopizität wird von einer Probe von ca. 2 g in einem Wägeglas von ca. 5 mm Durchmesser die Wasseraufnahme des vorgetrockneten Pulvers nach 24-stündiger Lagerung bei 68 % relativer Luftfeuchtigkeit und 20°C bestimmt. Die Korngrößen werden durch Trockensiebung des jeweiligen Pulvers mit Hilfe einer elektromagnetischen Siebemaschine (Analysette 3 der Firma Fritsch) bestimmt.The following examples illustrate the invention. Parts specified are parts by weight. The K values are determined according to H. Fikentscher as stated above. In the case of hygroscopicity, the water absorption of the predried powder is determined from a sample of approx. 2 g in a weighing glass of approx. 5 mm diameter after storage for 24 hours at 68% relative atmospheric humidity and 20 ° C. The grain sizes are determined by dry screening the respective powder using an electromagnetic screening machine (Analyzer 3 from Fritsch).

Beispiel 1example 1

Eine 45 Zige Lösung eines zu 50 % mit Natriumhydroxid neutralisierten Copolymerisats aus 70 Gew.-% Acrylsäure und 30 Gew.-% Maleinsäure vom K-Wert 50 wird mit einer 38%igen Lösung von Nitrilotriessigsäuretrinatriumsalz (NTA) gemischt und in einem Sprühtrockner mit einer 2-Stoffdüse bei 150°C Lufteintrittstemperatur und bei 90°C Luftaustrittstemperatur getrocknet. Die Mengenverhältnisse, das Schüttgewicht und die Wasseraufnahme zeigt die nachfolgende Tabelle.

Figure imgb0001
A 45% solution of a copolymer of 70% by weight acrylic acid and 30% by weight maleic acid having a K value of 50 and neutralized with 50% sodium hydroxide is mixed with a 38% solution of nitrilotriacetic acid trisodium salt (NTA) and sprayed with a 2-component nozzle dried at 150 ° C air inlet temperature and at 90 ° C air outlet temperature. The following table shows the proportions, bulk density and water absorption.
Figure imgb0001

Die KorngröBen der Pulver liegen zwischen 50 und 500 µm. 70 % davon in einem Bereich von 100 bis 200 µm.The grain sizes of the powders are between 50 and 500 µm. 70% of them in a range from 100 to 200 µm.

Beispiel 2Example 2

Eine 50 %ige Lösung eines zu 50 Z mit Natriumhydroxid neutralisierten Copolymeren aus 65 Gew.-% Acrylsäure und 35 Gew.-X Maleinsäure vom K-Wert 24 wird mit 38 Ziger NTA-Lösung gemischt und gemäß Beispiel 1 getrocknet und geprüft.

Figure imgb0002
A 50% solution of a copolymer of 65% by weight acrylic acid and 35% by weight maleic acid of K value 24 neutralized to 50% with sodium hydroxide is mixed with 38% ZTA NTA solution and dried and tested according to Example 1.
Figure imgb0002

Die Korngrößen des Pulvers sind vergleichbar mit Beispiel 1.The grain sizes of the powder are comparable to Example 1.

Beispiel 3Example 3

Eine 38 %ige Lösung eines zu 65 % mit Natriumhydroxid neutralisierten Copolymeren aus 50 Gew.-% Acrylsäure und 50 Gew.-% Maleinsäure vom K-Wert 42 wird mit 38 %iger NTA-Lösung gemischt und wie in Beispiel 1 getrocknet und geprüft.

Figure imgb0003
A 38% solution of a copolymer of 50% by weight acrylic acid and 50% by weight maleic acid having a K value of 42 and neutralized with 65% sodium hydroxide is mixed with a 38% NTA solution and dried and tested as in Example 1.
Figure imgb0003

Die Korngrößen des Pulvers sind vergleichbar mit Beispiel 1.The grain sizes of the powder are comparable to Example 1.

Beispiel 4Example 4

100 Teile einer 40 %igen Lösung eines zu 60 % mit Natriumhydroxid neutralisierten Copolymeren aus 70 Gew.-% Acrylsäure und 30 Gew.-% Maleinsäure vom K-Wert 60, 132 Teile einer 38 %igen NTA-Lösung und 20 Teile einer 50 %igen Natriumsulfatlösung werden gemischt und getrocknet, wobei die Mischung in einem Sprühturm bei 150°C Lufteintrittstemperatur und 90°C Luftaustrittstemperatur mit einer Zentrifugalzerstäuberscheibe bei 12000 Upm zerstäubt wurde, und geprüft.100 parts of a 40% solution of a copolymer of 70% by weight acrylic acid and 30% by weight maleic acid with a K value of 60, neutralized with 60% sodium hydroxide, 132 parts of a 38% NTA solution and 20 parts of a 50% Sodium sulfate solution are mixed and dried, the mixture being atomized in a spray tower at 150 ° C. air inlet temperature and 90 ° C. air outlet temperature with a centrifugal atomizer disk at 12000 rpm, and tested.

Schüttgewicht: 0,690 [g/ml]Bulk density: 0.690 [g / ml]

H20-Aufnahme: 7,4 %.H 2 0 uptake: 7.4%.

Die Korngrößen des Pulvers liegen zwischen 25 bis 300 µm, wobei der Hauptanteil von ca. 80 % bei 70 bis 110 µm liegt.The grain sizes of the powder are between 25 to 300 µm, the main proportion of approx. 80% being 70 to 110 µm.

Beispiel 5Example 5

Eine 40 %ige Lösung eines zu 90 % mit Natriumhydroxid neutralisierten Copolymerisates aus 30 Gew.-% Methacrylsäure, 45 Gew.-% Acrylsäure und 25 Gew.-% Maleinsäure vom K-Wert 98 wird mit einer 40 %igen Lösung eines Nitrilotriessigsäuredinatriumsalzes gemischt. Die Hälfte der Mischung wird in einem Sprühtrockner gemäß Beispiel 1 getrocknet, in ein Wirbelbett eingebracht und bei einer Gastemperatur von ca. 140°C der Rest der Mischung aufgesprüht. Diese Sprühgranulierung führt zu einem Granulat von etwa 0,5 bis 5 mm Durchmesser. Die Prüfergebnisse zeigt die nachfolgende Tabelle:

Figure imgb0004
A 40% solution of a copolymer of 30% by weight methacrylic acid, 45% by weight acrylic acid and 25% by weight maleic acid having a K value of 98 and neutralized with 90% sodium hydroxide is mixed with a 40% solution of a nitrilotriacetic acid disodium salt. Half of the mixture is dried in a spray dryer according to Example 1, placed in a fluidized bed and the rest of the mixture is sprayed on at a gas temperature of approximately 140.degree. This spray granulation leads to granules of approximately 0.5 to 5 mm in diameter. The test results are shown in the table below:
Figure imgb0004

Beispiel 6Example 6

Eine 38 Zige Lösung eines zu 70 % mit Natriumhydroxid neutralisierten Copolymerisates aus 40 % Acrylsäure. 40 Gew.-% Maleinsäure und 20 Gew.-% Hydroxypropylacrylat (techn. Isomerengemisch aus ca. 67 Gew.-% 2-Hydroxy-1-propylacrylat und ca. 33 Gew.-% 1-Hydroxy-2-propylacrylat) vom K-Wert 42 wird mit einer 38 %igen NTA-Lösung gemischt und gemäß Beispiel 1, jedoch mit einer Einstoffdüse, getrocknet und geprüft.

Figure imgb0005
Die Korngrößen der Pulver liegen bei 50 bis 500 µm. ca. 70 % davon im Bereich von 200 bis 350 µm.A 38 Zige solution of a copolymer of 40% acrylic acid neutralized to 70% with sodium hydroxide. 40% by weight of maleic acid and 20% by weight of hydroxypropyl acrylate (technical isomer mixture of approx. 67% by weight of 2-hydroxy-1-propyl acrylate and approx. 33% by weight of 1-hydroxy-2-propyl acrylate) from K -Value 42 is mixed with a 38% NTA solution and dried and tested according to Example 1, but with a single-component nozzle.
Figure imgb0005
 The grain sizes of the powders are 50 to 500 µm. approx. 70% of them in the range from 200 to 350 µm.

Beispiele 7 bis 12Examples 7 to 12

100 Teile einer 38 %igen Lösung eines zu 90 % mit Natriumhydroxid neutralisierten Copolymeren gemäß der folgenden Tabelle werden mit 100 Teilen einer 38 %igen NTA-Lösung gemischt und gemäß Beispiel 1 getrocknet und geprüft.100 parts of a 38% solution of a copolymer neutralized to 90% with sodium hydroxide according to the following table are mixed with 100 parts of a 38% NTA solution and dried and tested according to Example 1.

Figure imgb0006
Figure imgb0006

Beispiel 13Example 13

50 Teile einer 38 %igen wäßrigen Lösung eines zu 70 % mit Natriumhydroxid neutralisierten Copolymerisats aus 40 Gew.-X Acrylsäure, 40 Gew.-% Maleinsäure und 20 Gew.-% Hydroxipropylacrylat (techn. Isomerengemisch aus ca. 67 Gew.-% 2-Hydroxi-1-propylacylat und ca. 33 Gew.-% 1-Hydroxi-2-propylacrylat) vom K-Wert 42, 50 Teile einer 38 %igen wäßrigen Lösung eines zu 65 Gew.-% mit Natriumhydroxid neutralisierten Copolymerisates aus 50 Gew.-% Acrylsäure und 50 Gew.-% Maleinsäure vom K-Wert 42 wird mit 100 Teilen einer 38 %igen Lösung eines Nitrilotriessigsäuredinatriumsalzes gemischt, wobei sich ein pH-Wert der Lösung von 7,4 ergibt, und gemäß Beispiel 1 getrocknet und geprüft.50 parts of a 38% aqueous solution of a copolymer of 40% by weight acrylic acid, 40% by weight maleic acid and 20% by weight hydroxypropyl acrylate (technical isomer mixture of approx. 67% by weight 2) neutralized with sodium hydroxide by 70% Hydroxy-1-propylacylate and about 33% by weight of 1-hydroxy-2-propylacrylate) with a K value of 42, 50 parts of a 38% strength aqueous solution of a copolymer of 50% by weight neutralized with sodium hydroxide .-% acrylic acid and 50 wt .-% maleic acid with a K value of 42 is mixed with 100 parts of a 38% solution of a nitrilotriacetic acid disodium salt, resulting in a pH of the solution of 7.4, and dried and tested according to Example 1 .

Schüttgewicht: 0.660 [g/ml]Bulk density: 0.660 [g / ml]

HZO-Aufnahme: 5.1 %H Z O absorption: 5.1%

Vergleich:

  • Trockenprodukt aus beiden Copolymerisatlösungen im gleichen Verhältnis.
Comparison:
  • Dry product from both copolymer solutions in the same ratio.

Schüttgewicht: 0.385 [g/ml] H2O-Aufnahme: 9,9 %.Bulk weight: 0.385 [g / ml] H 2 O uptake: 9.9%.

Die Korngrößen der Pulver sind vergleichbar mit Beispiel 1.The grain sizes of the powders are comparable to Example 1.

Claims (3)

1. Pulver- und/oder granulatförmige Zusätze für pulverförmige Wasch- und Reinigungsmittel bestehend aus a) 80 bis 20 Gew.-% mindestens eines Copolymerisats bestehend aus 40 bis 90 Gew.-Z (Meth)Acrylsäure und 60 bis 10 Gew.-% Maleinsäure und/oder aus 10 bis 45 Gew.-% (Meth)Acrylsäure, 10 bis 45 Gew.-% Maleinsäure und 10 bis 60 Gew.-% mindestens eines Hydroxyalkyl(meth)acrylats mit 2 bis 6 C-Atomen in der Hydroxyalkylgruppe, gegebenenfalls in der Form eines wasserlöslichen Salzes, b) 20 bis 80 Gew.-% Nitrilotriessigsäure oder ihres Mono-, Di- oder Trinatrium- oder -kaliumsalzes und c) 0 bis 20 Gew.-% eines oder mehrerer für Wasch- und Reinigungsmittelzubereitungen üblicher Zusatzstoffe. 1. Powder and / or granular additives for powder detergents and cleaning agents consisting of a) 80 to 20% by weight of at least one copolymer consisting of 40 to 90% by weight of Z (meth) acrylic acid and 60 to 10% by weight of maleic acid and / or of 10 to 45% by weight of (meth) acrylic acid, 10 to 45% by weight of maleic acid and 10 to 60% by weight of at least one hydroxyalkyl (meth) acrylate with 2 to 6 C atoms in the hydroxyalkyl group, optionally in the form of a water-soluble salt, b) 20 to 80 wt .-% nitrilotriacetic acid or its mono-, di- or trisodium or potassium salt and c) 0 to 20% by weight of one or more additives customary for detergent and cleaning agent preparations. 2. Verwendung von pulver- und/oder granulatförmiger Mischungen nach Anspruch 1 als Zusatz zu pulver- und/oder granulatförmigen Wasch- und Reinigungsmitteln.2. Use of powdered and / or granular mixtures according to claim 1 as an additive to powdered and / or granular detergents and cleaning agents. 3. Verfahren zur Herstellung von pulver- und/oder granulatförmigen Zusätzen für pulverförmige Wasch- und Reinigungsmittel nach Anspruch 1, dadurch qekennzeichnet. daB man eine wäßrige Lösung oder Suspension, enthaltend 20- bis 70 Gew.-% einer Mischung nach Anspruch 1 in an sich üblicher Weise bei Temperaturen von 70 bis 200°C trocknet.3. A process for the preparation of powder and / or granular additives for powder detergents and cleaning agents according to claim 1, characterized by. that an aqueous solution or suspension containing 20 to 70% by weight of a mixture according to claim 1 is dried in a conventional manner at temperatures of 70 to 200 ° C.
EP86101659A 1985-02-13 1986-02-10 Additives for washing and cleaning agents Expired EP0192153B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86101659T ATE35148T1 (en) 1985-02-13 1986-02-10 ADDITIVES FOR WASHING AND CLEANING AGENTS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853504896 DE3504896A1 (en) 1985-02-13 1985-02-13 ADDITIVES FOR DETERGENT AND CLEANING AGENTS
DE3504896 1985-02-13

Publications (2)

Publication Number Publication Date
EP0192153A1 true EP0192153A1 (en) 1986-08-27
EP0192153B1 EP0192153B1 (en) 1988-06-15

Family

ID=6262405

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86101659A Expired EP0192153B1 (en) 1985-02-13 1986-02-10 Additives for washing and cleaning agents

Country Status (7)

Country Link
US (1) US4698174A (en)
EP (1) EP0192153B1 (en)
JP (1) JPS61188497A (en)
AT (1) ATE35148T1 (en)
CA (1) CA1248838A (en)
DE (2) DE3504896A1 (en)
ES (1) ES8800716A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0193360A2 (en) * 1985-02-23 1986-09-03 The Procter & Gamble Company Detergent compositions

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1219921B (en) * 1987-04-15 1990-05-24 Sandoz Ag COMPOSITION OF BLEACH-FREE DETERGENTS
US5273675A (en) * 1990-02-16 1993-12-28 Rohm And Haas Company Phosphate-free liquid cleaning compositions containing polymer
DE4024657A1 (en) * 1990-08-03 1992-02-06 Henkel Kgaa METHOD FOR DRYING AND GRANULATING WAESS-RATED PASTE WASH ACTIVE AGGREGATE MIXTURES
US5409629A (en) * 1991-07-19 1995-04-25 Rohm And Haas Company Use of acrylic acid/ethyl acrylate copolymers for enhanced clay soil removal in liquid laundry detergents
US5534183A (en) * 1994-07-14 1996-07-09 Basf Corporation Stable, aqueous concentrated liquid detergent compositions containing hydrophilic copolymers
US5900182A (en) * 1994-10-17 1999-05-04 Matsushita Electric Industrial Co., Ltd. Ion-conductive polymer electrolyte, method for producing the same and capacitors using the same electrolyte
CN1093560C (en) * 1994-12-15 2002-10-30 株式会社日本触媒 Detergent builder, process for producing the same, and detergent composition containing said builder
US6165970A (en) * 1996-03-29 2000-12-26 The Procter & Gamble Company Detergent composition comprising acrylic acid-based polymer and amino tricarboxylic acid-based compound
GB2311536A (en) * 1996-03-29 1997-10-01 Procter & Gamble Dishwashing and laundry detergents
DE19850100A1 (en) * 1998-10-29 2000-05-04 Henkel Kgaa Polymer granules through fluidized bed granulation
DE19937345A1 (en) * 1999-08-11 2001-02-15 Basf Ag Mixed powder or mixed granules based on glycine-N, N-diacetic acid
US6492320B2 (en) * 1999-09-24 2002-12-10 Rohm And Hass Company Multifunctional, granulated pellet aid and process
EP1203809A1 (en) * 2000-11-06 2002-05-08 The Procter & Gamble Company Polymer containing granules and compositions thereof
MXPA03011209A (en) * 2002-12-20 2004-06-30 Rohm & Haas Process for manufacturing polymeric detergent additives.
US20040121934A1 (en) * 2002-12-20 2004-06-24 Dougherty Richard Charles Polymeric detergent additives
DE102005026544A1 (en) * 2005-06-08 2006-12-14 Henkel Kgaa Reinforcement of cleaning performance of detergents by polymer
AU2010305833A1 (en) * 2009-10-12 2012-04-19 Basf Se Method for producing a powder containing one or more complexing agent salts
US9279097B1 (en) 2014-08-14 2016-03-08 Ecolab USA, Inc. Polymers for industrial laundry detergents

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0075820A1 (en) * 1981-09-28 1983-04-06 BASF Aktiengesellschaft Process for the production of copolymerisates from monoethylenically unsaturated mono and dicarboxylic acids
DE3233775A1 (en) * 1982-09-11 1984-03-15 Basf Ag, 6700 Ludwigshafen METHOD FOR PRODUCING COPOLYMERS FROM MONOETHYLENICALLY UNSATURATED MONO- AND DICARBONIC ACIDS (ANHYDRIDES)
DE3426368A1 (en) * 1984-07-18 1986-01-23 Basf Ag, 6700 Ludwigshafen COPOLYMERISATE FOR DETERGENT AND CLEANING AGENT

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3405060A (en) * 1966-06-16 1968-10-08 Monsanto Co Sequestration of metal ions
US3708436A (en) * 1969-12-12 1973-01-02 Nalco Chemical Co Detergent builders
US3684779A (en) * 1971-04-07 1972-08-15 John N Rapko Maleic/acrylic/alkenyl phosphonate terpolymers
US4517023A (en) * 1982-12-29 1985-05-14 Gaf Corporation Rust removal process using removable coatings of maleic acid copolymers
DE3305637A1 (en) * 1983-02-18 1984-08-23 Basf Ag, 6700 Ludwigshafen COPOLYMERISATE, THEIR PRODUCTION AND THEIR USE AS AUXILIARIES IN DETERGENT AND CLEANING AGENTS

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0075820A1 (en) * 1981-09-28 1983-04-06 BASF Aktiengesellschaft Process for the production of copolymerisates from monoethylenically unsaturated mono and dicarboxylic acids
DE3233775A1 (en) * 1982-09-11 1984-03-15 Basf Ag, 6700 Ludwigshafen METHOD FOR PRODUCING COPOLYMERS FROM MONOETHYLENICALLY UNSATURATED MONO- AND DICARBONIC ACIDS (ANHYDRIDES)
DE3426368A1 (en) * 1984-07-18 1986-01-23 Basf Ag, 6700 Ludwigshafen COPOLYMERISATE FOR DETERGENT AND CLEANING AGENT

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0193360A2 (en) * 1985-02-23 1986-09-03 The Procter & Gamble Company Detergent compositions
EP0193360B1 (en) * 1985-02-23 1991-01-02 The Procter & Gamble Company Detergent compositions

Also Published As

Publication number Publication date
JPS61188497A (en) 1986-08-22
ES551899A0 (en) 1987-11-16
DE3504896A1 (en) 1986-08-14
US4698174A (en) 1987-10-06
EP0192153B1 (en) 1988-06-15
CA1248838A (en) 1989-01-17
ATE35148T1 (en) 1988-07-15
DE3660311D1 (en) 1988-07-21
ES8800716A1 (en) 1987-11-16

Similar Documents

Publication Publication Date Title
EP0192153B1 (en) Additives for washing and cleaning agents
DE69032929T2 (en) Granules containing polymer
DE2354791A1 (en) ENZYME GRANULES, THE PROCESS FOR THEIR MANUFACTURING AND THEIR USE IN SOLID DETERGENT COMPOSITIONS
DE2514399A1 (en) PROCESS FOR THE PRODUCTION OF ALUMINUM SILICATES
EP0292766B1 (en) Use of water soluble copolymerisates, wherein monomers having at least two ethylenically unsaturated monomers are taking part in wasting and cleaning agents
DE3131668A1 (en) ZEOLITE POWDER, METHOD FOR PRODUCING THE SAME AND A CLEANING MIXTURE CONTAINING SUCH A POWDER
DE69403207T2 (en) FLUIDIZED BED COATED AMIDOPEROXY ACID CONTAINING FLEACHING COMPOSITION
WO1985001039A1 (en) Stabilized aqueous zeolite suspension
DE3838086A1 (en) METHOD FOR PRODUCING HIGH DENSITY GRANULES CONTAINING ZEOLITE
AT397101B (en) GRANULES BASED ON ALKALIAL ALUMINUM SILICATE AND THEIR USE
DE2523733A1 (en) PROCESS FOR THE PREPARATION OF DETERGENT COMPOSITIONS AND DETERGENT COMPOSITIONS PREPARED BY THE PROCESS
DE2539429C2 (en)
EP0005789B2 (en) Storable and flowable silicate suspensions containing dicarboxylic acids for improving flowability and storability
DE2854484A1 (en) STABLE AQUEOUS ZEOLITE SUSPENSIONS
EP0289788B1 (en) Hydrosoluble copolymers, process for their preparation and their use
DE3410611A1 (en) METHOD FOR PRODUCING SOLID PHOTOACTIVATOR PREPARATIONS
DE2431529A1 (en) PROCESS FOR MANUFACTURING SPRAY-DRIED DETERGENTS CONTAINING NON-IONIC SURFACES
DE3604223A1 (en) Additive for detergents and cleaners
DE2453659A1 (en) METHOD OF AGGLOMERATION OF SODIUM CARBONATE PEROXYDE
DE2822231A1 (en) GRANULATES MADE FROM HYDRATED SODIUM TRIPOLYPHOSPHATE AND WATER-INSOLUBLE ALUMOSILICATION EXCHANGE MATERIAL
DE3715052C2 (en)
DE3120744A1 (en) Non-friable granules based on alkali metal aluminium silicate with good dispersibility in aqueous liquor
EP0928308A1 (en) Spray-dried dispersions, processes for their production and use
AT404355B (en) STABLE AQUEOUS SUSPENSIONS OF WATER-INSOLUBLE SILICATE COMPOUNDS
DE927444C (en) Soil improvers

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

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19860703

17Q First examination report despatched

Effective date: 19870507

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 DE FR GB IT LI NL SE

REF Corresponds to:

Ref document number: 35148

Country of ref document: AT

Date of ref document: 19880715

Kind code of ref document: T

ITF It: translation for a ep patent filed
REF Corresponds to:

Ref document number: 3660311

Country of ref document: DE

Date of ref document: 19880721

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

26N No opposition filed
ITTA It: last paid annual fee
EAL Se: european patent in force in sweden

Ref document number: 86101659.0

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

Ref country code: FR

Payment date: 19960122

Year of fee payment: 11

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

Ref country code: SE

Payment date: 19960123

Year of fee payment: 11

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

Ref country code: AT

Payment date: 19960131

Year of fee payment: 11

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

Ref country code: GB

Payment date: 19960201

Year of fee payment: 11

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

Ref country code: BE

Payment date: 19960212

Year of fee payment: 11

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

Ref country code: GB

Effective date: 19970210

Ref country code: AT

Effective date: 19970210

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

Ref country code: SE

Effective date: 19970211

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

Ref country code: BE

Effective date: 19970228

BERE Be: lapsed

Owner name: BASF A.G.

Effective date: 19970228

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

Effective date: 19970210

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

Ref country code: FR

Effective date: 19971030

EUG Se: european patent has lapsed

Ref document number: 86101659.0

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

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

Ref country code: NL

Payment date: 19980130

Year of fee payment: 13

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

Ref country code: CH

Payment date: 19980204

Year of fee payment: 13

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

Ref country code: DE

Payment date: 19980226

Year of fee payment: 13

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: 19990228

Ref country code: CH

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

Effective date: 19990228

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

Ref country code: NL

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

Effective date: 19990901

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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: 19991201

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

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050210