EP0025551B1 - Use of (meth)acrylic acid and maleic acid copolymers as incrustation inhibitors in detergents - Google Patents

Use of (meth)acrylic acid and maleic acid copolymers as incrustation inhibitors in detergents Download PDF

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EP0025551B1
EP0025551B1 EP80105230A EP80105230A EP0025551B1 EP 0025551 B1 EP0025551 B1 EP 0025551B1 EP 80105230 A EP80105230 A EP 80105230A EP 80105230 A EP80105230 A EP 80105230A EP 0025551 B1 EP0025551 B1 EP 0025551B1
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detergents
copolymers
meth
maleic acid
acrylic acid
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French (fr)
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EP0025551A1 (en
EP0025551B2 (en
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Wolfgang Dr. Trieselt
Johannes Dr. Perner
Albert Dr. Hettche
Walter Denzinger
Gregor Dr. Ley
Heinrich Dr. Hartmann
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—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

  • phosphate substitutes must be used.
  • nitrilotriacetic acid, polycarboxylic acids, such as gluconic acid, citric acid, and then polymeric acids, such as poly (meth) acrylic acid, maleic acid / vinyl ether copolymers, and more recently also polymaleic acids have become known.
  • polycarboxylic acids such as gluconic acid, citric acid
  • polymeric acids such as poly (meth) acrylic acid, maleic acid / vinyl ether copolymers, and more recently also polymaleic acids
  • the phosphates are not only excellent builders with complexing power, they also act as secondary detergents, i.e. they also prevent inorganic, insoluble salts from being deposited on the fabric.
  • This deposit is called incrustation, and it has been shown that none of the phosphate substitutes used hitherto are capable of replacing phosphates on an equivalent basis with regard to the overall effect as a builder and the inhibition ability against incrustation. Additives had to be used to deal with the problem of incrustation.
  • the aim of the present invention was to find substances which, in the smallest possible amounts, added in phosphate-free or low-detergent detergents largely prevent incrustation.
  • copolymers containing 40 to 90% by weight of (meth) acrylic acid and 60 to 10% by weight of maleic acid as monomer units.
  • Their alkali, preferably sodium and ammonium salts are also suitable.
  • the copolymers Compared to pure polyacrylic acid and pure polymaleic acid, the copolymers have an abruptly improved inhibition capacity against incrustations in textile washing processes with phosphate-free and low-phosphate detergents.
  • the copolymers are obtained in a manner known per se by copolymerization of maleic anhydride with (meth) acrylic acid in the proportions given (calculated as maleic acid) and subsequent saponification. Amounts are preferably chosen such that 45 to 85% by weight of (meth) acrylic acid and 55 to 15% by weight of maleic acid are present in the copolymer.
  • the polymerization is carried out by free radical initiation in solution, suspension or as precipitation polymerization.
  • the polymerization temperatures are about 50 to 200, preferably 100 to 150 ° C.
  • Suitable initiators are the customary radical-forming compounds, such as dialkyl peroxides, alkyl hydroperoxides, peresters, diacyl peroxides and azo compounds, such as azoisobutyronitrile.
  • the copolymers obtained in the unsaponified state preferably have K values of 10 to 40, which are determined according to Fikentscher, Cellulosechemie 13, page 58 in methyl ethyl ketone at 25 ° C.
  • copolymers are added to detergents, based on dry substance, in amounts of 0.5 to 10, preferably 2 to 6,% by weight.
  • the copolymers are in the form of the corresponding alkali salts; they can also be used directly as the alkali, preferably sodium or ammonium salt.
  • the three test detergents therefore have a greatly reduced phosphate content compared to conventional detergents (approx. 45 to 55 96 phosphate).
  • the detergent solution contains 5 g / l of detergent A.
  • the detergent solution contained 5 g / l, 8 g / l and 11 g / l test detergent B.
  • the detergent solution contained 5 g / l detergent C.
  • the detergent solution contains 8 g / l test detergent B.

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

Abstract

1. Use of copolymers which, based on the weight of the polymers, contain 40 to 90% of acrylic or methacrylic acid and 60 to 10% of maleic acid as copolymerized units, or of their alkali metal or ammonium salts as incrustation inhibitors in detergents.

Description

In modernen Waschmittelformulierungen muß bekanntlich wegen der Gefahr der Eutrophierung der Gewässer der Gehalt an Phosphaten zumindest stark herabgesetzt werden. Um die Waschwirkung aber auf dem gleichen Stand wie bisher halten zu können, müssen Phosphatersatzstoffe eingesetzt werden. Von diesen sind vor allem Nitrilotriessigsäure, Polycarbonsäuren, wie Gluconsäure, Citronensäure, sodann polymere Säuren, wie Poly(meth)acrylsäure, MaleinsäureNinyläther-Copolymerisate und neuerdings auch Polymaleinsäuren bekannt geworden. Neueste Entwicklungen stellt der Einsatz von anorganischen wasserunlöslichen Aufbaustoffen dar. Es handelt sich um die in der DE-A2412837 beschriebenen Alumosilikate vom Typ Zeolith A.In modern detergent formulations, it is known that the phosphate content must be at least greatly reduced because of the risk of eutrophication of the waters. In order to keep the washing effect at the same level as before, phosphate substitutes must be used. Of these, nitrilotriacetic acid, polycarboxylic acids, such as gluconic acid, citric acid, and then polymeric acids, such as poly (meth) acrylic acid, maleic acid / vinyl ether copolymers, and more recently also polymaleic acids, have become known. The latest developments are the use of inorganic water-insoluble building materials. These are the aluminosilicates of the zeolite A type described in DE-A2412837.

Eine Zusammenfassung über Möglichkeiten des Phosphatersatzes findet sich in Angew. Chemie 87, Seiten 115 bis 142 (1975).A summary of the possibilities of phosphate replacement can be found in Angew. Chemie 87, pages 115 to 142 (1975).

Nun sind aber die Phosphate nicht nur hervorragende Builder mit Komplexierungsvermögen, sondern sie wirken auch als Sekundärwaschmittel, d.h. sie verhindern auch die Ablagerung von anorganischen, unlöslichen Salzen auf dem Gewebe. Diese Ablagerung wird Inkrustation genannt, und es hat sich gezeigt, daß keiner der bisher verwendeten Phosphatersatzstoffe hinsichtlich der Gesamtwirkung als Builder und des Inhibierungsvermögens gegenüber der Inkrustation in der Lage ist, Phosphate gleichwertig zu ersetzen. Man mußte daher Zusatzstoffe einsetzen, um des Problems der Inkrustierung Herr zu werden.However, the phosphates are not only excellent builders with complexing power, they also act as secondary detergents, i.e. they also prevent inorganic, insoluble salts from being deposited on the fabric. This deposit is called incrustation, and it has been shown that none of the phosphate substitutes used hitherto are capable of replacing phosphates on an equivalent basis with regard to the overall effect as a builder and the inhibition ability against incrustation. Additives had to be used to deal with the problem of incrustation.

Aus der DE-C 697 945 und DE-C 540 101 sind Polyacrylsäuren und Copolymerisate der Maleinsäure mit anderen copolymerisierbaren Monomeren (verseifte Maleinsäureanhydrid-Copolymerisate) als Zusätze in Waschmitteln bekannt, und es heißt in der dortgenannten Publikation, daß sich Textilien, die mit derartigen Waschmitteln gewaschen seien, durch einen weichen Griff auszeichneten. Es hat sich gezeigt, daß diese Griffverbesserung zwar auf eine verminderte Inkrustation zurückzuführen ist, jedoch wiesen diese Gewebe einen immer noch zu hohen Aschegehalt auf, d.h. die Inkrustation war noch zu stark.From DE-C 697 945 and DE-C 540 101, polyacrylic acids and copolymers of maleic acid with other copolymerizable monomers (saponified maleic anhydride copolymers) are known as additives in detergents, and it is mentioned in the publication cited there that textiles containing such Detergents are washed, characterized by a soft handle. It has been shown that this improvement in grip can be attributed to reduced incrustation, but these fabrics still had an ash content that was still too high, i.e. the incrustation was still too strong.

Neuerdings wurden auch reine Homopolymerisate der Maleinsäure mit niedrigem Molgewicht für diesen Zweck getetet, und es wurden auch, wie die DE-A 28 40 169 lehrt, gewisse Fortschritte erzielt, aber auch diese reichten indes noch nicht aus.Pure homopolymers of maleic acid with a low molecular weight have recently also been tested for this purpose and, as taught in DE-A 28 40 169, certain progress has also been made, but these have still not been sufficient.

Das Ziel der vorliegenden Erfindung bestand darin, Stoffe aufzufinden, die in phosphatfreien oder - armen Waschmitteln, in möglichst geringen Mengen zugesetzt, die Inkrustation weitestgehend verhindern.The aim of the present invention was to find substances which, in the smallest possible amounts, added in phosphate-free or low-detergent detergents largely prevent incrustation.

Dieses Ziel wurde überraschenderweise mit Copolymerisaten erreicht, die 40 bis 90Gew.% (Meth)acrylsäure und 60 bis 10 Gew.% Maleinsäure als Monomerbausteine enthalten. Geeignet sind auch deren Alkali-, vorzugsweise Natrium- und Ammoniumsalze.This goal was surprisingly achieved with copolymers containing 40 to 90% by weight of (meth) acrylic acid and 60 to 10% by weight of maleic acid as monomer units. Their alkali, preferably sodium and ammonium salts are also suitable.

Die Copolymerisate zeigen gegenüber reiner Polyacrylsäure und gegenüber reiner Polymaleinsäure ein sprunghaft verbessertes Inhibierungsvermögen gegenüber Inkrustationen bei Textilwaschprozessen mit phosphatfreien und phosphatarmen Waschmitteln.Compared to pure polyacrylic acid and pure polymaleic acid, the copolymers have an abruptly improved inhibition capacity against incrustations in textile washing processes with phosphate-free and low-phosphate detergents.

Dieser Befund ist außerordentlich überraschend, da kaum anzunehmen war, daß Copolymerisate derart sprunghafte Änderungen ihrer Eigenschaften zeigen, nachdem die reinen Homopolymerisate ihrer Monomerbausteine wesentlich schlechtere Wirkungen zeigen.This finding is extremely surprising, since it was hardly to be assumed that copolymers exhibit such abrupt changes in their properties after the pure homopolymers of their monomer units have significantly worse effects.

Die Copolymerisate erhält man in an sich bekannter Weise durch Copolymerisation von Maleinsäureanhydrid mit (Meth)acrylsäure in den angegebenen Mengenverhältnissen (berechnet als Maleinsäure) und anschließende Verseifung. Bevorzugt wählt man solche Mengen, daß im Copolymerisat 45 bis 85 Gew.% (Meth)acrylsäure und 55 bis 15 Gew.% Maleinsäure anwesend sind.The copolymers are obtained in a manner known per se by copolymerization of maleic anhydride with (meth) acrylic acid in the proportions given (calculated as maleic acid) and subsequent saponification. Amounts are preferably chosen such that 45 to 85% by weight of (meth) acrylic acid and 55 to 15% by weight of maleic acid are present in the copolymer.

Die Polymerisation wird durch radikalische Initiierung in Lösung, Suspension oder als Fällungspolymerisation durchgeführt.The polymerization is carried out by free radical initiation in solution, suspension or as precipitation polymerization.

Die Polymerisationstemperaturen liegen bei etwa 50 bis 200, vorzugsweise 100 bis 150 °C. Als Initiatoren kommen die üblichen radikalbildenden Verbindungen wie Dialkylperoxide, Alkylhydroperoxide, Perester, Diacylperoxide und Azoverbindungen, wie Azoisobutyronitril in Betracht.The polymerization temperatures are about 50 to 200, preferably 100 to 150 ° C. Suitable initiators are the customary radical-forming compounds, such as dialkyl peroxides, alkyl hydroperoxides, peresters, diacyl peroxides and azo compounds, such as azoisobutyronitrile.

Die erhaltenen Copolymerisate in unverseiftem Zustand weisen bevorzugt K-Werte von 10 bis 40 auf, die gemäß Fikentscher, Cellulosechemie 13, Seite 58 in Methyläthylketon bei 25 °C bestimmt werden.The copolymers obtained in the unsaponified state preferably have K values of 10 to 40, which are determined according to Fikentscher, Cellulosechemie 13, page 58 in methyl ethyl ketone at 25 ° C.

Die Copolymerisate werden Waschmitteln - bezogen auf Trockensubstanz - in Mengen von 0,5 bis 10, vorzugsweise 2 bis 6 Gew.% zugesetzt.The copolymers are added to detergents, based on dry substance, in amounts of 0.5 to 10, preferably 2 to 6,% by weight.

Da die Waschmittel alkalisch reagieren, liegen die Copolymerisate in Form der entsprechend Alkalisalze vor; sie können auch direkt als Alkali-, vorzugsweise Natriumsalz oder Ammoniums eingesetzt werden.Since the detergents react alkaline, the copolymers are in the form of the corresponding alkali salts; they can also be used directly as the alkali, preferably sodium or ammonium salt.

Die nun folgenden Beispiele erläutern die Erfindung.The following examples illustrate the invention.

Allgemeine Versuchsbedingungen :General test conditions:

Figure imgb0001
Figure imgb0001
Figure imgb0002
Figure imgb0002

Testwaschmittel A :Test detergent A:

Figure imgb0003
Figure imgb0003

Testwaschmittel B :Test detergent B:

Figure imgb0004
Figure imgb0004

Testwaschmittel C :Test detergent C:

Figure imgb0005
Figure imgb0005

Die drei Testwaschmittel weisen somit einen gegenüber konventionellen Waschmitteln (ca. 45 bis 55 96 Phosphat), stark verminderten Phosphatgehalt auf.The three test detergents therefore have a greatly reduced phosphate content compared to conventional detergents (approx. 45 to 55 96 phosphate).

Beispiel 1example 1

Die Waschmittellösung enthält 5 g/l Waschmittel A.

Figure imgb0006
The detergent solution contains 5 g / l of detergent A.
Figure imgb0006

Beispiel 1 (Fortsetzung)Example 1 (continued)

Figure imgb0007
Figure imgb0007

Beispiel 2Example 2

Die Waschmittel-Lösung enthielt 5 g/l, 8 g/I und 11 g/l Testwaschmittel BThe detergent solution contained 5 g / l, 8 g / l and 11 g / l test detergent B.

Figure imgb0008
Figure imgb0008

Beispiel 3Example 3

Die Waschmittellösung enthielt 5 g/I Waschmittel C.

Figure imgb0009
The detergent solution contained 5 g / l detergent C.
Figure imgb0009

Beispiel 4Example 4

Die Waschmittellösung enthält 8 g/l Testwaschmittel B.

Figure imgb0010
The detergent solution contains 8 g / l test detergent B.
Figure imgb0010

Claims (1)

  1. Use of copolymers which, based on the weight of the polymers, contain 40 to 90 % of acrylic or methacrylic acid and 60 to 10% of maleic acid as copolymerized units, or of their alkali metal or ammonium salts as incrustation inhibitors in detergents.
EP80105230A 1979-09-13 1980-09-03 Use of (meth)acrylic acid and maleic acid copolymers as incrustation inhibitors in detergents Expired - Lifetime EP0025551B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80105230T ATE1589T1 (en) 1979-09-13 1980-09-03 USE OF (METH)ACRYLIC-MALEIC ACID ECOPOLYMERISATS AS INCRUSTATION INHIBITORS IN DETERGENTS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2936984 1979-09-13
DE19792936984 DE2936984A1 (en) 1979-09-13 1979-09-13 USE OF (METH) ACRYLIC ACID-MALEIC ACID COPOLYMERISATES AS INCREDIBLE INHIBITORS IN DETERGENTS

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EP0025551A1 EP0025551A1 (en) 1981-03-25
EP0025551B1 true EP0025551B1 (en) 1982-09-22
EP0025551B2 EP0025551B2 (en) 1993-01-07

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Publication number Priority date Publication date Assignee Title
DE3444960A1 (en) * 1984-12-10 1986-06-12 Henkel KGaA, 4000 Düsseldorf GRAINY ADSORPTION
WO1990001533A1 (en) 1988-08-01 1990-02-22 Henkel Kommanditgesellschaft Auf Aktien Process for dosing washing agents in paste form
WO1990005175A1 (en) 1988-11-10 1990-05-17 Henkel Kommanditgesellschaft Auf Aktien Process for producing high-density zeolite-containing granules
LT3047B (en) 1992-07-02 1994-10-25 Stockhausen Chem Fab Gmbh Graft copolymers of unsaturated monomers and sugar, a process for the production and the use thereof

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EP0054325B1 (en) * 1980-12-17 1984-04-11 Unilever N.V. Detergent composition with reduced soil-redeposition effect
JPS57168906A (en) * 1981-04-13 1982-10-18 Kao Corp Maleic acid/(meth)acrylic acid copolymer
DE3277630D1 (en) * 1981-05-30 1987-12-17 Procter & Gamble Detergent composition containing performance additive and copolymeric compatibilizing agent therefor
US5175361A (en) * 1981-09-28 1992-12-29 Basf Aktiengesellschaft Preparation of copolymers of monoethylenically unsaturated monocarboxylic acids 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)
DE3233777A1 (en) * 1982-09-11 1984-03-15 Basf Ag, 6700 Ludwigshafen METHOD FOR PRODUCING COPOLYMERS FROM MONOETHYLENICALLY UNSATURATED MONO- AND DICARBONIC ACIDS (ANHYDRIDES)
ATE20476T1 (en) * 1983-04-08 1986-07-15 Procter & Gamble GRANULATED DETERGENT COMPOSITIONS CONTAINING A MIXED POLYMER ADDITIVE SYSTEM.
DE3329400A1 (en) * 1983-08-13 1985-02-28 Henkel KGaA, 4000 Düsseldorf GRAY PREVENTIVE ADDITIVE FOR PHOSPHATE-FREE AND LOW-PHOSPHASE DETERGENTS
DE3340164A1 (en) * 1983-11-07 1985-05-23 S.A. Camp, Fábrica de Jabones, Granollers, Barcelona Detergents
DE3426368A1 (en) * 1984-07-18 1986-01-23 Basf Ag, 6700 Ludwigshafen COPOLYMERISATE FOR DETERGENT AND CLEANING AGENT
JPS61264099A (en) * 1985-05-17 1986-11-21 花王株式会社 Detergent for dyeing machinery
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DE4003172A1 (en) * 1990-02-03 1991-08-08 Basf Ag PFROPOPOPOLYMERISATES OF MONOSACCHARIDES, OLIGOSACCHARIDES, POLYSACCHARIDES AND MODIFIED POLYSACCHARIDES, PROCESS FOR THEIR PREPARATION AND THEIR USE
US5273675A (en) * 1990-02-16 1993-12-28 Rohm And Haas Company Phosphate-free liquid cleaning compositions containing polymer
FR2663940B1 (en) * 1990-07-02 1994-04-08 Rhone Poulenc Chimie GRAFT POLYSACCHARIDES, THEIR PREPARATION PROCESS AND THEIR APPLICATION AS SEQUESTRATION AGENTS.
DE4112075A1 (en) * 1991-04-12 1992-10-15 Henkel Kgaa METHOD FOR PRODUCING STABLE, BIFUNCTIONAL, PHOSPATE AND METASILICATE-FREE LOW-ALKALINE DETERGENT TABLETS FOR THE MACHINE DISHWASHER
DE4211699A1 (en) * 1992-04-08 1993-10-14 Henkel Kgaa Method for increasing the bulk density of spray-dried detergents
DE4239076A1 (en) * 1992-11-20 1994-05-26 Basf Ag Mixtures of polymers of monoethylenically unsaturated dicarboxylic acids and polymers of ethylenically unsaturated monocarboxylic acids and / or polyaminocarboxylic acids and their use
US5866012A (en) * 1993-01-26 1999-02-02 National Starch And Chemical Investment Holding Corporation Multifunctional maleate polymers
DE69433465T2 (en) * 1993-01-26 2004-10-21 Nat Starch Chem Invest Water treatment process for preventing scale formation
AUPM610894A0 (en) * 1994-06-03 1994-06-30 Procter & Gamble Company, The Detergent composition containing polycarboxylate agents
JP6001649B2 (en) 2011-05-20 2016-10-05 ダウ グローバル テクノロジーズ エルエルシー How to promote dirt removal from fabric

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3444960A1 (en) * 1984-12-10 1986-06-12 Henkel KGaA, 4000 Düsseldorf GRAINY ADSORPTION
WO1990001533A1 (en) 1988-08-01 1990-02-22 Henkel Kommanditgesellschaft Auf Aktien Process for dosing washing agents in paste form
WO1990005175A1 (en) 1988-11-10 1990-05-17 Henkel Kommanditgesellschaft Auf Aktien Process for producing high-density zeolite-containing granules
LT3047B (en) 1992-07-02 1994-10-25 Stockhausen Chem Fab Gmbh Graft copolymers of unsaturated monomers and sugar, a process for the production and the use thereof

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DE2936984A1 (en) 1981-04-02
ATE1589T1 (en) 1982-10-15
EP0025551A1 (en) 1981-03-25
DE3060877D1 (en) 1982-11-04
EP0025551B2 (en) 1993-01-07

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