EP1516040B1 - Use of copolymers containing sulfonic acid groups, as an additive in detergents and cleansers - Google Patents

Use of copolymers containing sulfonic acid groups, as an additive in detergents and cleansers Download PDF

Info

Publication number
EP1516040B1
EP1516040B1 EP03740180A EP03740180A EP1516040B1 EP 1516040 B1 EP1516040 B1 EP 1516040B1 EP 03740180 A EP03740180 A EP 03740180A EP 03740180 A EP03740180 A EP 03740180A EP 1516040 B1 EP1516040 B1 EP 1516040B1
Authority
EP
European Patent Office
Prior art keywords
copolymers
acid
mol
sulfonic acid
monoethylenically unsaturated
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
EP03740180A
Other languages
German (de)
French (fr)
Other versions
EP1516040A1 (en
Inventor
Pia Baum
Kathrin Michl
Franz Weingart
Stephan Nied
Gregor Brodt
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
Publication of EP1516040A1 publication Critical patent/EP1516040A1/en
Application granted granted Critical
Publication of EP1516040B1 publication Critical patent/EP1516040B1/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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate

Definitions

  • the invention relates to detergents and cleaners which contain these copolymers as a deposit-inhibiting additive.
  • the so-called "2in1" dishwashing detergents introduced on the market contain, in addition to the cleaner for removing stains on the items to be washed, integral rinse surfactants which ensure a flat flow of water on the items to be washed during the rinse and drying cycle and thus prevent limescale and water stains. Refilling a rinse aid is no longer necessary when using these products.
  • Modern machine dishwashing detergents "3in1" cleaners, are intended to combine the three functions of cleaning, rinsing and water softening in a single detergent formulation, making it unnecessary for the consumer to replenish salt with water hardnesses of 1 to 3.
  • sodium tripolyphosphate is usually added to these cleaners. This in turn, however, results in calcium and magnesium phosphate deposits on the items to be washed.
  • the EP-A-877 002 relates to the use of copolymers of monoethylenically unsaturated acids, unsaturated sulfonic acids and optionally monoethylenically unsaturated dicarboxylic acids and monoethylenically unsaturated comonomers as inhibitors of (poly) phosphate coatings in automatic dishwashing detergents.
  • Nonionic monomers of the formula II are not mentioned.
  • water-soluble copolymers containing sulfonate groups, carboxylate groups and polyalkylene oxide group-containing structural units and having an average molecular weight M w of> 50,000 to 3,000,000 can be used as agents against especially silicate-based scale in water cycles, eg, cooling systems.
  • the sulfonate group-containing structural unit of the individually disclosed copolymers is based on sodium 2-methyl-1,3-butadiene-1-sulfonate.
  • graft copolymers of monoethylenically unsaturated carboxylic acids, monoethylenically unsaturated monomers containing sulfonic acid groups and optionally water-soluble monomers containing alkylene oxide units and other free-radically polymerizable monomers are used on polyhydroxy compounds for inhibiting water hardness in detergents and cleaners.
  • Graft copolymers of acrylic acid, sodium methallylsulfonate and methoxypolyethylene glycol methacrylate on polyvinyl alcohol, triglycerol and starch dextrin are described in detail.
  • the invention was based on the object to remedy the above problems and to provide an additive that can be used advantageously especially in multi-function cleaners and in particular shows a deposit-inhibiting effect.
  • washing and cleaning agents were found which contain the sulfonic acid-containing copolymers as a deposit-inhibiting additive.
  • copolymers comprising sulfonic acid groups comprise as copolymerized component (a) monoethylenically unsaturated carboxylic acids, their esters and / or water-soluble salts, the carboxylic acids themselves or their salts being preferred as component (a).
  • Suitable components (a) are, for example, ⁇ , ⁇ -unsaturated monocarboxylic acids which preferably have 3 to 6 carbon atoms, such as acrylic acid, methacrylic acid, 2-ethylpropenoic acid, crotonic acid and vinylacetic acid.
  • unsaturated dicarboxylic acids preferably having 4 to 6 carbon atoms, such as itaconic acid and maleic acid.
  • Suitable esters are in particular the reaction products of these acids with C 1 -C 6 -alcohols, especially methanol, ethanol and butanol, wherein the dicarboxylic acids may be present as mono- or diesters. Examples which may be mentioned are: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, monomethyl maleate and dimethyl maleate.
  • the salts are preferably alkali metal salts, e.g. Sodium or potassium salts, or ammonium salts, with the sodium salts being preferred.
  • Preferred carboxylic acids (a) are acrylic acid, methacrylic acid and maleic acid.
  • acrylic acid and methacrylic acid which may advantageously also be present together in the copolymers.
  • the proportion of the carboxylic acids (a) in the copolymers to be used according to the invention is 30 to 95 mol%, preferably 50 to 90 mol% and particularly preferably 60 to 90 mol%.
  • acrylic acid and methacrylic acid are present in the copolymers, their molar ratio is preferably from 15: 1 to 0.05: 1, in particular from 10: 1 to 1: 1, especially from 5: 1 to 1: 1.
  • the monomers I are: vinylsulfonic acid, 2-sulfoethyl (meth) acrylic acid, 2-sulfopropyl (meth) acrylic acid, 3-sulfopropyl (meth) acrylic acid and 4-sulfobutyl (meth) acrylic acid and salts thereof, in particular the sodium salts, vinylsulfonic acid, 2-sulfoethylmethacrylic acid and 2-sulfopropylmethacrylic acid and their sodium salts being preferred, and 2-sulfoethylmethacrylic acid and its sodium salt being particularly preferred.
  • the proportion of the sulfonic acid group-containing monomers (b) in the copolymers to be used according to the invention is 3 to 35 mol%, preferably 5 to 25 mol% and in particular 5 to 20 mol%.
  • the monomers II include: methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypoly ( propylene glycol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate, ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, wherein methoxypolyethylene glycol (meth) acrylate and methoxypolypropylene glycol (meth) acrylate are preferred and methoxypolyethylene glycol methacrylate is particularly preferred.
  • the polyalkylene glycols contain 3 to 50, in particular 10 to 30 alkylene oxide units.
  • the proportion of nonionic monomers (c) in the copolymers to be used according to the invention is 2 to 35 mol%, preferably 5 to 25 mol% and especially 5 to 20 mol%.
  • the copolymers to be used according to the invention generally have an average molecular weight M w of from 3,000 to 40,000, preferably from 10,000 to 30,000 and more preferably from 15,000 to 25,000.
  • the K value of the copolymers is usually from 15 to 35, in particular from 20 to 32, especially from 27 to 30 (measured in 1 wt .-% aqueous solution at 25 ° C, according to H. Fikentscher, cellulose chemistry, Vol. 13, pp. 58-64 and 71-74 (1932)).
  • copolymers to be used according to the invention can be prepared by free-radical polymerization of the monomers. It can be worked by all known radical polymerization. In addition to the bulk polymerization, the methods of solution polymerization and emulsion polymerization should be mentioned in particular, with the solution polymerization being preferred.
  • the polymerization is preferably carried out in water as a solvent.
  • alcoholic solvents in particular C 1 -C 4 -alcohols, such as methanol, ethanol and isopropanol, or mixtures of these solvents with water.
  • Suitable polymerization initiators are both thermally and photochemically (photoinitiators) decomposing and thereby radical-forming compounds.
  • thermally activatable polymerization initiators are initiators having a decomposition temperature in the range from 20 to 180 ° C, in particular from 50 to 90 ° C. prefers.
  • suitable thermal initiators are inorganic peroxo compounds, such as peroxodisulfates (ammonium and preferably sodium peroxodisulfate), peroxosulfates, percarbonates and hydrogen peroxide; organic peroxy compounds, such as diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis (o-toloyl) peroxide, succinyl peroxide, tert-butyl peracetate, tert-butyl permalate, tert-butyl perisobutyrate, tert.
  • inorganic peroxo compounds such as pe
  • initiators can be used in combination with reducing compounds as starter / regulator systems.
  • reducing compounds include phosphorus-containing compounds such as phosphorous acid, hypophosphites and phosphinates, sulfur-containing compounds such as sodium hydrogen sulfite, sodium sulfite and sodium formaldehyde sulfoxilate, and hydrazine.
  • photoinitiators examples include benzophenone, acetophenone, benzoin ethers, Benzyldialkylketone and derivatives thereof.
  • thermal initiators are used, with inorganic peroxo compounds, in particular sodium peroxodisulfate (sodium persulfate), being preferred.
  • the peroxo compounds are particularly advantageously used in combination with sulfur-containing reducing agents, in particular sodium hydrogen sulfite, as the redox initiator system.
  • sulfur-containing reducing agents in particular sodium hydrogen sulfite, as the redox initiator system.
  • phosphorus-containing starter / regulator systems may also be used, e.g. Hypophosphites / phosphinates.
  • the amounts of photoinitiator or starter / regulator system are to be matched to the substances used in each case. If, for example, the preferred system peroxodisulfate / hydrogen sulfite is used, usually 2 to 6% by weight, preferably 3 to 5% by weight, of peroxodisulfate and generally 5 to 30% by weight, preferably 5 to 10% by weight. %, Hydrogen sulfite, in each case based on the monomers (a), (b) and (c) used.
  • polymerization regulators can also be used. Suitable compounds are those known in the art, for example sulfur compounds, such as mercaptoethanol, 2-ethylhexyl thioglycolate, Thioglycolic acid and dodecylmercaptan.
  • sulfur compounds such as mercaptoethanol, 2-ethylhexyl thioglycolate, Thioglycolic acid and dodecylmercaptan.
  • their amount used is usually 0.1 to 15 wt .-%, preferably 0.1 to 5 wt .-% and particularly preferably 0.1 to 2.5 wt .-%, based on the monomers (a), (b) and (c).
  • the polymerization temperature is usually at 30 to 200 ° C, preferably at 50 to 150 ° C and particularly preferably at 80 to 120 ° C.
  • the polymerization may be carried out under atmospheric pressure, but is preferably carried out in the closed system under the evolving autogenous pressure.
  • the monomers (a), (b) and (c) can be used as such, but reaction mixtures which are used in the preparation of e.g. the monomers (b) or (c) incurred.
  • reaction mixtures which are used in the preparation of e.g. the monomers (b) or (c) incurred for example, instead of 2-sulfoethyl methacrylate, the monomer mixture obtained in the esterification of 2-hydroxyethanesulfonic acid with an excess of methacrylic acid can be used.
  • methoxypolyethylene glycol methacrylate the monomer mixture obtained in the etherification of methoxypolyethylene glycol with an excess of methacrylic acid can be used.
  • methoxypolyethylene glycol methacrylate the monomer mixture obtained in the etherification of methoxypolyethylene glycol with an excess of methacrylic acid can be used.
  • methoxypolyethylene glycol methacrylate the monomer mixture obtained in the etherification of methoxypolyethylene glyco
  • the aqueous solutions obtained in the preparation of the sulfonic acid group-containing copolymers to be used according to the invention can be neutralized or partially neutralized by adding base, in particular sodium hydroxide solution, i. adjusted to a pH in the range of about 4-8, preferably 4.5-7.5.
  • the sulfonic acid-containing copolymers used in the invention are outstandingly suitable as an additive to detergents and cleaners.
  • the dishwashing detergents can be used in automatic dishwashing detergents. They are characterized mainly by their deposit-inhibiting effect against both inorganic and organic coatings. In particular, there are deposits caused by the remaining components of the cleaner formulation such as linings of calcium and magnesium phosphate, calcium and magnesium silicate and calcium and magnesium phosphonate, and coatings derived from the constituents of the rinse liquor, such as fat, protein and starch deposits called.
  • the copolymers used according to the invention thereby also increase the detergency of the dishwashing detergent. In addition, they already facilitate the drainage of the water from the dishes at low concentrations, so that the proportion of rinse aid surfactants in the dishwashing detergent can be reduced.
  • copolymers containing sulfonic acid When using the copolymers containing sulfonic acid accordingly particularly clear glasses and high-gloss metal cutlery are obtained, especially when the dishwasher is operated without Regeneriersalz for water softening.
  • the copolymers containing sulfonic acid groups can therefore be used advantageously not only in 2-in-1 cleaners but also in 3-in-1 cleaners.
  • the copolymers used according to the invention can be used directly in the form of the aqueous solutions obtained in the preparation as well as in dried, e.g. by spray drying, fluidized spray drying, drum drying or freeze-drying obtained form are used. Accordingly, the washing and cleaning agents according to the invention may be in solid or liquid form, e.g. as powders, granules, extrudates, tablets, liquids or gels.
  • M w methoxypolyethylene glycol methacrylate
  • Example 2 In the reactor of Example 1, a mixture of 145.9 g of distilled water and 4.44 g of phosphorous acid was heated to 100 ° C internal temperature with nitrogen and stirring. Then, a mixture of 139.8 g of acrylic acid, 100.5 g of 2-acrylamido-2-methylpropanesulfonic acid and 402 g of distilled water was added continuously in 5 hours. In parallel, a mixture of 12.0 g of sodium peroxodisulfate and 108.2 g of distilled water and in 5 h 45.1 g of a 11.3 wt .-% strength sodium bisulfite solution was added continuously in 5.25 h. After stirring for one hour at 100 ° C, the reaction mixture was cooled to room temperature and adjusted by the addition of 50 wt .-% sodium hydroxide solution to a pH of 7.2.
  • Dishwasher Miele G 686 SC rinses: 2 rinses 55 ° C normal (without pre-rinse) ware: Knife (WMF table knife Berlin, Monoblock) and barrel-shaped glass beaker (Matador, Ruhr Kri-stall) Dishwashing liquid: 21 g copolymer: 4.2 g Rinse temperature: 65 ° C Water hardness: 25 ° dH
  • the washware was evaluated 18 hours after cleaning by visual inspection in a black painted light box with halogen spot and pinhole using a grading scale from 10 (very good) to 1 (very bad).
  • the highest grade of 10 corresponds to covering and drip-free surfaces, from grades ⁇ 5, coverings and drops are already visible under normal room lighting, so are perceived as disturbing.
  • test results obtained are summarized in the following table.

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)
  • Macromonomer-Based Addition Polymer (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

Sulfonic acid group copolymer composition comprises (a) 30-95 mole% of at least one monoethylenically unsaturated carboxylic acid, (b) 3-35 mole% of at least one sulfonic acid group containing monomers, and (c) 1-35 mole% of nonionic monomer obtained by statistical or block polymerization. Sulfonic acid group copolymer composition comprises: (1) 30-95 mole% of at least one monoethylenically unsaturated carboxylic acid; (2) 3-35 mole% of at least one sulfonic acid group containing monomer of formula (I); and (3) 1-35 mole% of nonionic monomer of formula (II). R = H or Me; R1 = branched 1-4C alkyl; X = chemical bond or -COO-R1; and M = H, alkali metal, or ammonium. R2 = H or Me; R3 = chemical bond or optionally branched 1-6C alkylene; R4 = optionally branched 2-4C alkylene; R5 = optionally branched 1-6C alkyl, 5-8C cycloalkyl, or aryl; n = 3-50. The polymer is obtained by statistical or block polymerization.

Description

Die vorliegende Erfindung betrifft die Verwendung von sulfonsäuregruppenhaltigen Copolymeren, die

  1. (a) 30 bis 95 mol-% mindestens einer monoethylenisch ungesättigten Carbonsäure, eines monoethylenisch ungesättigten Carbonsäureesters oder eines wasserlöslichen Salzes einer monoethylenisch ungesättigten Carbonsäure,
  2. (b) 3 bis 35 mol-% mindestens eines sulfonsäuregruppenhaltigen Monomers der Formel I
    Figure imgb0001
     in der die Variablen folgende Bedeutung haben:
    R
    Wasserstoff oder Methyl;
    X
    eine chemische Bindung oder -COO-R1-;
    R1
    unverzweigtes oder verzweigtes C1-C4-Alkylen;
    M
    Wasserstoff, Alkalimetall oder Ammonium,
    und
  3. (c) 2 bis 35 mol-% mindestens eines nichtionischen Monomers der Formel II
    Figure imgb0002
     in der die Variablen folgende Bedeutung haben:
    R2
    Wasserstoff oder Methyl;
    R3
    eine chemische Bindung oder unverzweigtes oder verzweigtes C1-C6-Alkylen;
    R4
    gleiche oder verschiedene unverzweigte oder verzweigte C2-C4-Alkylenreste;
    R5
    unverzweigtes oder verzweigtes C1-C6-Alkyl;
    n
    3 bis 50,
    statistisch oder blockweise einpolymerisiert enthalten, als Zusatz zu Wasch- und Reinigungsmitteln.
The present invention relates to the use of sulfonic acid group-containing copolymers which
  1. (a) 30 to 95 mol% of at least one monoethylenically unsaturated carboxylic acid, a monoethylenically unsaturated carboxylic acid ester or a water-soluble salt of a monoethylenically unsaturated carboxylic acid,
  2. (B) 3 to 35 mol% of at least one sulfonic acid group-containing monomer of the formula I.
    Figure imgb0001
     in which the variables have the following meaning:
    R
    Hydrogen or methyl;
    X
    a chemical bond or -COO-R 1 -;
    R 1
    unbranched or branched C 1 -C 4 -alkylene;
    M
    Hydrogen, alkali metal or ammonium,
    and
  3. (c) 2 to 35 mol% of at least one nonionic monomer of formula II
    Figure imgb0002
     in which the variables have the following meaning:
    R 2
    Hydrogen or methyl;
    R 3
    a chemical bond or straight or branched C 1 -C 6 alkylene;
    R 4
    identical or different unbranched or branched C 2 -C 4 -alkylene radicals;
    R 5
    unbranched or branched C 1 -C 6 -alkyl;
    n
    3 to 50,
    in copolymerized form, randomly or in blocks, as an additive to detergents and cleaners.

Außerdem betrifft die Erfindung Wasch- und Reinigungsmittel, welche diese Copolymere als belagsinhibierenden Zusatz enthalten.In addition, the invention relates to detergents and cleaners which contain these copolymers as a deposit-inhibiting additive.

Bei der maschinellen Geschirrspülreinigung soll das Spülgut in rückstandsfrei gereinigtem Zustand mit makellos glänzender Oberfläche anfallen, wofür üblicherweise ein Reiniger, ein Klarspüler und Regeneriersalz zur Wasserenthärtung eingesetzt werden müssen.In the automatic dishwashing, the items to be washed in residue-free cleaned state with flawless glossy surface incurred, for which usually a cleaner, a rinse aid and Regeneriersalz must be used for water softening.

Die im Markt eingeführten sogenannten "2in1"-Geschirreiniger enthalten neben dem Reiniger zur Entfernung der Anschmutzungen auf dem Spülgut integrierte Klarspültenside, die während des Klarspül- und Trocknungsgang für einen flächigen Wasserablauf auf dem Spülgut sorgen und so Kalk- und Wasserflecken verhindern. Das Nachfüllen eines Klarspülers ist bei Verwendung dieser Produkte bereits nicht mehr erforderlich.The so-called "2in1" dishwashing detergents introduced on the market contain, in addition to the cleaner for removing stains on the items to be washed, integral rinse surfactants which ensure a flat flow of water on the items to be washed during the rinse and drying cycle and thus prevent limescale and water stains. Refilling a rinse aid is no longer necessary when using these products.

Moderne maschinelle Geschirreiniger, "3in1"-Reiniger, sollen die drei Funktionen des Reinigens, des Klarspülens und der Wasserenthärtung in einer einzigen Reinigerformulierung vereinen, so daß für den Verbraucher auch das Nachfüllen von Salz bei Wasserhärten von 1 bis 3 überflüssig wird. Zur Bindung der härtebildenden Calcium- und Magnesiumionen wird diesen Reinigern üblicherweise Natriumtripolyphosphat zugesetzt. Hieraus resultieren aber wiederum Calcium- und Magnesiumphosphatbeläge auf dem Spülgut.Modern machine dishwashing detergents, "3in1" cleaners, are intended to combine the three functions of cleaning, rinsing and water softening in a single detergent formulation, making it unnecessary for the consumer to replenish salt with water hardnesses of 1 to 3. To bind the hardness-forming calcium and magnesium ions, sodium tripolyphosphate is usually added to these cleaners. This in turn, however, results in calcium and magnesium phosphate deposits on the items to be washed.

In der WO-A-02/04583 werden maschinelle Geschirrspülmittel beschrieben, die Copolymere aus ungesättigten Carbonsäuren, sulfonsäuregruppenhaltigen Monomeren und gegebenenfalls, vorzugsweise jedoch keinen, weiteren nichtionischen Monomeren auf Basis ethylenisch ungesättigter Verbindungen als Belagsinhibitoren enthalten. Weitere Angaben zu den nichtionischen Monomeren werden nicht gemacht.In the WO-A-02/04583 are described automatic dishwashing detergents containing copolymers of unsaturated carboxylic acids, sulfonic acid monomers and optionally, but preferably no, further nonionic monomers based on ethylenically unsaturated compounds as scale inhibitors. Further information on the nonionic monomers is not provided.

Die EP-A-877 002 betrifft die Verwendung von Copolymeren aus monoethylenisch ungesättigten Säuren, ungesättigten Sulfonsäuren und gegebenenfalls monoethylenisch ungesättigten Dicarbonsäuren und monoethylenisch ungesättigten Comonomeren als Inhibitor für (Poly)Phosphatbeläge in maschinellen Geschirrspülmitteln. Im einzelnen offenbart werden Copolymere aus Acrylsäure und 2-Acryl-amido-2-propansulfonsäure bzw. Natriummethallylsulfonat sowie Terpolymere, die zusätzlich tert.-Butylacrylamid einpolymerisiert enthalten. Nichtionische Monomere der Formel II werden nicht genannt.The EP-A-877 002 relates to the use of copolymers of monoethylenically unsaturated acids, unsaturated sulfonic acids and optionally monoethylenically unsaturated dicarboxylic acids and monoethylenically unsaturated comonomers as inhibitors of (poly) phosphate coatings in automatic dishwashing detergents. Specifically disclosed are copolymers of acrylic acid and 2-acrylamido-2-propanesulfonic acid or Natriummethallylsulfonat and terpolymers, which additionally polymerized tert-butylacrylamide contain. Nonionic monomers of the formula II are not mentioned.

Nach der JP-A-2000/7734 können wasserlösliche Copolymere, die Sulfonatgruppen, Carboxylatgruppen und Polyalkylenoxidgruppen enthaltende Struktureinheiten und ein mittleres Molekulargewicht Mw von > 50 000 bis 3 000 000 aufweisen, als Mittel gegen insbesondere auf Silikaten basierenden Kesselstein in Wasserkreisläufen, z.B. Kühlsystemen, verwendet werden. Die sulfonatgruppenhaltige Struktureinheit der im einzelnen offenbarten Copolymere basiert auf Natrium-2-methyl-1,3-butadien-1-sulfonat.After JP-A-2000/7734 For example, water-soluble copolymers containing sulfonate groups, carboxylate groups and polyalkylene oxide group-containing structural units and having an average molecular weight M w of> 50,000 to 3,000,000 can be used as agents against especially silicate-based scale in water cycles, eg, cooling systems. The sulfonate group-containing structural unit of the individually disclosed copolymers is based on sodium 2-methyl-1,3-butadiene-1-sulfonate.

In der DE-A-43 43 993 werden Pfropfcopolymerisate von monoethylenisch ungesättigten Carbonsäuren, monoethylenisch ungesättigten sulfonsäuregruppenhaltigen Monomeren und gegebenenfalls wasserlöslichen Alkylenoxideinheiten enthaltenden Monomeren und weiteren radikalisch polymerisierbaren Monomeren auf Polyhydroxyverbindungen zur Inhibierung der Wasserhärte in Wasch- und Reinigungsmitteln eingesetzt. Im einzelnen beschrieben werden Pfropfcopolymerisate von Acrylsäure, Natriummethallylsulfonat und Methoxypolyethylenglykolmethacrylat auf Polyvinylalkohol, Triglycerin und Stärkedextrin.In the DE-A-43 43 993 graft copolymers of monoethylenically unsaturated carboxylic acids, monoethylenically unsaturated monomers containing sulfonic acid groups and optionally water-soluble monomers containing alkylene oxide units and other free-radically polymerizable monomers are used on polyhydroxy compounds for inhibiting water hardness in detergents and cleaners. Graft copolymers of acrylic acid, sodium methallylsulfonate and methoxypolyethylene glycol methacrylate on polyvinyl alcohol, triglycerol and starch dextrin are described in detail.

Schließlich ist aus der EP-A-278 983 die Verwendung von Copolymeren von Polyalkylenglykolmono(meth)acrylaten, Sulfoalkyl(meth)acrylaten und (Meth)Acrylsäure als wasserlösliches Dispergiermittel für kohlenstoffhaltige Feststoffe bekannt.Finally, out of the EP-A-278 983 the use of copolymers of polyalkylene glycol mono (meth) acrylates, sulfoalkyl (meth) acrylates and (meth) acrylic acid as a water-soluble dispersant for carbonaceous solids.

Der Erfindung lag die Aufgabe zugrunde, den oben geschilderten Problemen abzuhelfen und ein Additiv bereitzustellen, das vorteilhaft vor allem auch in Multifunktionsreinigern eingesetzt werden kann und dabei insbesondere eine belagsinhibierende Wirkung zeigt.The invention was based on the object to remedy the above problems and to provide an additive that can be used advantageously especially in multi-function cleaners and in particular shows a deposit-inhibiting effect.

Demgemäß wurde die Verwendung von sulfonsäuregruppenhaltigen Copolymeren, die

  1. (a) 30 bis 95 mol-% mindestens einer monoethylenisch ungesättigten Carbonsäure, eines monoethylenisch ungesättigten Carbonsäureesters oder eines wasserlöslichen Salzes einer monoethylenisch ungesättigten Carbonsäure,
  2. (b) 3 bis 35 mol-% mindestens eines sulfonsäuregruppenhaltigen Monomers der Formel I
    Figure imgb0003
     in der die Variablen folgende Bedeutung haben:
    R
    Wasserstoff oder Methyl;
    X
    eine chemische Bindung oder -COO-R1-;
    R1
    unverzweigtes oder verzweigtes C1-C4-Alkylen;
    M
    Wasserstoff, Alkalimetall oder Ammonium,
    und
  3. (c) 2 bis 35 mol-% mindestens eines nichtionischen Monomers der Formel II
    Figure imgb0004
     in der die Variablen folgende Bedeutung haben:
    R2
    Wasserstoff oder Methyl;
    R3
    eine chemische Bindung oder unverzweigtes oder verzweigtes C1-C6-Alkylen;
    R4
    gleiche oder verschiedene unverzweigte oder verzweigte C2-C4-Alkylenreste;
    R5
    unverzweigtes oder verzweigtes C1-C6-Alkyl,
    n
    3 bis 50,
    statistisch oder blockweise einpolymerisiert enthalten, als Zusatz zu Wasch- und Reinigungsmitteln gefunden.
Accordingly, the use of sulfonic acid-containing copolymers, the
  1. (a) 30 to 95 mol% of at least one monoethylenically unsaturated carboxylic acid, a monoethylenically unsaturated carboxylic acid ester or a water-soluble salt of a monoethylenically unsaturated carboxylic acid,
  2. (B) 3 to 35 mol% of at least one sulfonic acid group-containing monomer of the formula I.
    Figure imgb0003
     in which the variables have the following meaning:
    R
    Hydrogen or methyl;
    X
    a chemical bond or -COO-R 1 -;
    R 1
    unbranched or branched C 1 -C 4 -alkylene;
    M
    Hydrogen, alkali metal or ammonium,
    and
  3. (c) 2 to 35 mol% of at least one nonionic monomer of formula II
    Figure imgb0004
     in which the variables have the following meaning:
    R 2
    Hydrogen or methyl;
    R 3
    a chemical bond or straight or branched C 1 -C 6 alkylene;
    R 4
    identical or different unbranched or branched C 2 -C 4 -alkylene radicals;
    R 5
    unbranched or branched C 1 -C 6 -alkyl,
    n
    3 to 50,
    contained in random or block polymerized, found as an additive to detergents and cleaners.

Weiterhin wurden Wasch- und Reinigungsmittel gefunden, welche die sulfonsäuregruppenhaltigen Copolymere als belagsinhibierenden Zusatz enthalten.Furthermore, washing and cleaning agents were found which contain the sulfonic acid-containing copolymers as a deposit-inhibiting additive.

Die sulfonsäuregruppenhaltigen Copolymere enthalten als einpolymerisierte Komponente (a) monoethylenisch ungesättigte Carbonsäuren, deren Ester und/oder wasserlösliche Salze, wobei die Carbonsäuren selbst oder ihre Salze als Komponente (a) bevorzugt sind.The copolymers comprising sulfonic acid groups comprise as copolymerized component (a) monoethylenically unsaturated carboxylic acids, their esters and / or water-soluble salts, the carboxylic acids themselves or their salts being preferred as component (a).

Geeignete Komponenten (a) sind beispielsweise α,β-ungesättigte Monocarbonsäuren, die vorzugsweise 3 bis 6 Kohlenstoffatome aufweisen, wie Acrylsäure, Methacrylsäure, 2-Ethylpropensäure, Crotonsäure und Vinylessigsäure.Suitable components (a) are, for example, α, β-unsaturated monocarboxylic acids which preferably have 3 to 6 carbon atoms, such as acrylic acid, methacrylic acid, 2-ethylpropenoic acid, crotonic acid and vinylacetic acid.

Weiterhin geeignet sind z.B. ungesättigte Dicarbonsäuren, die vorzugsweise 4 bis 6 Kohlenstoffatome aufweisen, wie Itaconsäure und Maleinsäure.Further suitable are e.g. unsaturated dicarboxylic acids preferably having 4 to 6 carbon atoms, such as itaconic acid and maleic acid.

Als Ester eignen sich insbesondere die Umsetzungsprodukte dieser Säuren mit C1-C6-Alkoholen, vor allem Methanol, Ethanol und Butanol, wobei die Dicarbonsäuren als Mono- oder als Diester vorliegen können. Beispielhaft seien genannt: Methylacrylat, Methylmethacrylat, Ethylacrylat, Ethylmethacrylat, Butylacrylat, Butylmethacrylat, Monomethylmaleinat und Dimethylmaleinat.Suitable esters are in particular the reaction products of these acids with C 1 -C 6 -alcohols, especially methanol, ethanol and butanol, wherein the dicarboxylic acids may be present as mono- or diesters. Examples which may be mentioned are: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, monomethyl maleate and dimethyl maleate.

Bei den Salzen handelt es sich vorzugsweise um Alkalimetallsalze, z.B. Natrium- oder Kaliumsalze, oder Ammoniumsalze, wobei die Natriumsalze bevorzugt sind.The salts are preferably alkali metal salts, e.g. Sodium or potassium salts, or ammonium salts, with the sodium salts being preferred.

Bevorzugte Carbonsäuren (a) sind Acrylsäure, Methacrylsäure und Maleinsäure.Preferred carboxylic acids (a) are acrylic acid, methacrylic acid and maleic acid.

Besonders bevorzugt sind Acrylsäure und Methacrylsäure, die vorteilhaft auch zusammen in den Copolymeren enthalten sein können.Particular preference is given to acrylic acid and methacrylic acid, which may advantageously also be present together in the copolymers.

Der Anteil der Carbonsäuren (a) an den erfindungsgemäß zu verwendenden Copolymeren beträgt 30 bis 95 mol-%, bevorzugt 50 bis 90 mol-% und besonders bevorzugt 60 bis 90 mol-%.The proportion of the carboxylic acids (a) in the copolymers to be used according to the invention is 30 to 95 mol%, preferably 50 to 90 mol% and particularly preferably 60 to 90 mol%.

Sind Acrylsäure und Methacrylsäure in den Copolymeren enthalten, so beträgt deren Molverhältnis vorzugsweise 15 : 1 bis 0,05 : 1, insbesondere 10 : 1 bis 1 : 1, vor allem 5 : 1 bis 1 : 1.If acrylic acid and methacrylic acid are present in the copolymers, their molar ratio is preferably from 15: 1 to 0.05: 1, in particular from 10: 1 to 1: 1, especially from 5: 1 to 1: 1.

Als einpolymerisierte Komponente (b) enthalten die Copolymere sulfonsäuregruppenhaltige Monomere der Formel I

Figure imgb0005
in der die Variablen folgende Bedeutung haben:

R
Wasserstoff oder bevorzugt Methyl;
X
eine chemische Bindung oder bevorzugt -COO-R1;
R1
unverzweigtes oder verzweigtes C1-C4-Alkylen, bevorzugt C2-C3-Alkylen;
M
Wasserstoff, Ammonium oder bevorzugt ein Alkalimetall.
As copolymerized component (b), the copolymers contain sulfonic acid group-containing monomers of the formula I.
Figure imgb0005
 in which the variables have the following meaning:
R
Hydrogen or preferably methyl;
X
a chemical bond or preferably -COO-R 1 ;
R 1
unbranched or branched C 1 -C 4 -alkylene, preferably C 2 -C 3 -alkylene;
M
Hydrogen, ammonium or preferably an alkali metal.

Als besonders geeignete Beispiele für die Monomere I sind zu nennen: Vinylsulfonsäure, 2-Sulfoethyl(meth)acrylsäure, 2-Sulfopropyl(meth)acrylsäure, 3-Sulfopropyl(meth)acrylsäure und 4-Sulfobutyl(meth)acrylsäure und deren Salze, insbesondere die Natriumsalze, wobei Vinylsulfonsäure, 2-Sulfoethylmethacrylsäure und 2-Sulfopropylmethacrylsäure und deren Natriumsalze bevorzugt und 2-Sulfoethylmethacrylsäure und deren Natriumsalz besonders bevorzugt sind.Particularly suitable examples of the monomers I are: vinylsulfonic acid, 2-sulfoethyl (meth) acrylic acid, 2-sulfopropyl (meth) acrylic acid, 3-sulfopropyl (meth) acrylic acid and 4-sulfobutyl (meth) acrylic acid and salts thereof, in particular the sodium salts, vinylsulfonic acid, 2-sulfoethylmethacrylic acid and 2-sulfopropylmethacrylic acid and their sodium salts being preferred, and 2-sulfoethylmethacrylic acid and its sodium salt being particularly preferred.

Der Anteil der sulfonsäuregruppenhaltigen Monomere (b) an den erfindungsgemäß zu verwendenden Copolymeren beträgt 3 bis 35 mol-%, vorzugsweise 5 bis 25 mol-% und insbesondere 5 bis 20 mol-%.The proportion of the sulfonic acid group-containing monomers (b) in the copolymers to be used according to the invention is 3 to 35 mol%, preferably 5 to 25 mol% and in particular 5 to 20 mol%.

Die Copolymere enthalten weiterhin als Komponente (c) nichtionische Monomere der Formel II

Figure imgb0006
in der die Variablen folgende Bedeutung haben:

R2
Wasserstoff oder bevorzugt Methyl;
R3
unverzweigtes oder verzweigtes C1-C6-Alkylen oder bevorzugt eine chemische Bindung;
R4
gleiche oder verschiedene unverzweigte oder verzweigte C2-C4-Alkylenreste, vor allem C2-C3-Alkylenreste, insbesondere Ethylen;
R5
unverzweigtes oder verzweigtes C1-C6-Alkyl, insbesondere C1-C2-Alkyl;
n
3 bis 50, bevorzugt 5 bis 40, besonders bevorzugt 10 bis 30.
The copolymers furthermore contain nonionic monomers of the formula II as component (c)
Figure imgb0006
 in which the variables have the following meaning:
R 2
Hydrogen or preferably methyl;
R 3
unbranched or branched C 1 -C 6 -alkylene or preferably a chemical bond;
R 4
identical or different unbranched or branched C 2 -C 4 -alkylene radicals, especially C 2 -C 3 -alkylene radicals, in particular ethylene;
R 5
unbranched or branched C 1 -C 6 -alkyl, in particular C 1 -C 2 -alkyl;
n
3 to 50, preferably 5 to 40, particularly preferably 10 to 30.

Als besonders geeignete Beispiele für die Monomere II einen genannt: Methoxypolyethylenglykol(meth)acrylat, Methoxypolypropylenglykol(meth)acrylat, Methoxypolybutylenglykol(meth)acrylat, Methoxypoly(propylenoxid-co-ethylenoxid)(meth)acrylat, Ethoxypolyethylenglykol(meth)acrylat, Ethoxypoly(propylenglykol(meth) acrylat, Ethoxypolybutylenglykol(meth)acrylat, Ethoxypoly(propylenoxid-co-ethylenoxid)(meth)acrylat,
wobei Methoxypolyethylenglykol(meth)acrylat und Methoxypolypropylenglykol(meth)acrylat bevorzugt sind und Methoxypolyethylenglykolmethacrylat besonders bevorzugt ist.Particularly suitable examples of the monomers II include: methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypoly ( propylene glycol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate, ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate,
wherein methoxypolyethylene glycol (meth) acrylate and methoxypolypropylene glycol (meth) acrylate are preferred and methoxypolyethylene glycol methacrylate is particularly preferred.

Die Polyalkylenglykole enthalten dabei 3 bis 50, insbesondere 10 bis 30 Alkylenoxideinheiten.The polyalkylene glycols contain 3 to 50, in particular 10 to 30 alkylene oxide units.

Der Anteil der nichtionischen Monomere (c) an den erfindungsgemäß zu verwendenden Copolymeren beträgt 2 bis 35 mol-%, vorzugsweise 5 bis 25 mol-% und vor allem 5 bis 20 mol-%.The proportion of nonionic monomers (c) in the copolymers to be used according to the invention is 2 to 35 mol%, preferably 5 to 25 mol% and especially 5 to 20 mol%.

Die erfindungsgemäß zu verwendenden Copolymere haben in der Regel ein mittleres Molekulargewicht Mw von 3 000 bis 40 000, bevorzugt von 10 000 bis 30 000 und besonders bevorzugt von 15 000 bis 25 000.The copolymers to be used according to the invention generally have an average molecular weight M w of from 3,000 to 40,000, preferably from 10,000 to 30,000 and more preferably from 15,000 to 25,000.

Der K-Wert der Copolymere liegt üblicherweise bei 15 bis 35, insbesondere bei 20 bis 32, vor allem bei 27 bis 30 (gemessen in 1 gew.-%iger wäßriger Lösung bei 25°C, nach H. Fikentscher, Cellulose-Chemie, Bd. 13, S. 58-64 und 71-74 (1932)).The K value of the copolymers is usually from 15 to 35, in particular from 20 to 32, especially from 27 to 30 (measured in 1 wt .-% aqueous solution at 25 ° C, according to H. Fikentscher, cellulose chemistry, Vol. 13, pp. 58-64 and 71-74 (1932)).

Die erfindungsgemäß zu verwendenden Copolymere können durch radikalische Polymerisation der Monomere hergestellt werden. Dabei kann nach allen bekannten radikalischen Polymerisationsverfahren gearbeitet werden. Neben der Polymerisation in Substanz sind insbesondere die Verfahren der Lösungspolymerisation und der Emulsionspolymerisation zu nennen, wobei die Lösungspolymerisation bevorzugt ist.The copolymers to be used according to the invention can be prepared by free-radical polymerization of the monomers. It can be worked by all known radical polymerization. In addition to the bulk polymerization, the methods of solution polymerization and emulsion polymerization should be mentioned in particular, with the solution polymerization being preferred.

Die Polymerisation wird vorzugsweise in Wasser als Lösungsmittel durchgeführt. Sie kann jedoch auch in alkoholischen Lösungsmitteln, insbesondere C1-C4-Alkoholen, wie Methanol, Ethanol und Isopropanol, oder Mischungen dieser Lösungsmittel mit Wasser vorgenommen werden.The polymerization is preferably carried out in water as a solvent. However, it can also be carried out in alcoholic solvents, in particular C 1 -C 4 -alcohols, such as methanol, ethanol and isopropanol, or mixtures of these solvents with water.

Als Polymerisationsinitiatoren eignen sich sowohl thermisch als auch photochemisch (Photoinitiatoren) zerfallende und dabei Radikale bildende Verbindungen.Suitable polymerization initiators are both thermally and photochemically (photoinitiators) decomposing and thereby radical-forming compounds.

Unter den thermisch aktivierbaren Polymerisationsinitiatoren sind Initiatoren mit einer Zerfallstemperatur im Bereich von 20 bis 180°C, insbesondere von 50 bis 90°C. bevorzugt. Beispiele für geeignete thermische Initiatoren sind anorganische Peroxoverbindungen, wie Peroxodisulfate (Ammonium- und vorzugsweise Natriumperoxodisulfat), Peroxosulfate, Percarbonate und Wasserstoffperoxid; organische Peroxoverbindungen, wie Diacetylperoxid, Di-tert.-butylperoxid, Diamylperoxid, Dioctanoylperoxid, Didecanoylperoxid, Dilauroylperoxid, Dibenzoylperoxid, Bis(o-toloyl)peroxid, Succinylperoxid, tert.-Butylperacetat, tert.-Butylpermaleinat, tert.-Butylperisobutyrat, tert.-Butylperpivalat, tert.-Butylperoctoat, tert.-Butylperneodecanoat, tert.-Butylperbenzoat, tert.-Butylperoxid, tert.-Butylhydroperoxid, Cumolhydroperoxid, tert.-Butylperoxi-2-ethylhexanoat und Diisopropylperoxidicarbamat; Azoverbindungen, wie 2,2'-Azobisisobutyronitril, 2,2'-Azobis(2-methylbutyronitril) und Azobis(2-amidopropan)dihydrochlorid.Among the thermally activatable polymerization initiators are initiators having a decomposition temperature in the range from 20 to 180 ° C, in particular from 50 to 90 ° C. prefers. Examples of suitable thermal initiators are inorganic peroxo compounds, such as peroxodisulfates (ammonium and preferably sodium peroxodisulfate), peroxosulfates, percarbonates and hydrogen peroxide; organic peroxy compounds, such as diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis (o-toloyl) peroxide, succinyl peroxide, tert-butyl peracetate, tert-butyl permalate, tert-butyl perisobutyrate, tert. Butyl perpivalate, tert-butyl peroctoate, tert-butyl perodecanoate, tert-butyl perbenzoate, tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxy-2-ethylhexanoate and diisopropyl peroxydicarbamate; Azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile) and azobis (2-amidopropane) dihydrochloride.

Diese Initiatoren können in Kombination mit reduzierenden Verbindungen als Starter/Regler-Systeme zum Einsatz kommen. Als Beispiele für derartige reduzierende Verbindungen seien phosphorhaltige Verbindungen, wie phosphorige Säure, Hypophosphite und Phosphinate, schwefelhaltige Verbindungen, wie Natriumhydrogensulfit, Natriumsulfit und Natriumformaldehydsulfoxilat, sowie Hydrazin genannt.These initiators can be used in combination with reducing compounds as starter / regulator systems. Examples of such reducing compounds include phosphorus-containing compounds such as phosphorous acid, hypophosphites and phosphinates, sulfur-containing compounds such as sodium hydrogen sulfite, sodium sulfite and sodium formaldehyde sulfoxilate, and hydrazine.

Beispiele für geeignete Photoinitiatoren sind Benzophenon, Acetophenon, Benzoinether, Benzyldialkylketone und deren Derivate.Examples of suitable photoinitiators are benzophenone, acetophenone, benzoin ethers, Benzyldialkylketone and derivatives thereof.

Vorzugsweise werden thermische Initiatoren eingesetzt, wobei anorganische Peroxoverbindungen, insbesondere Natriumperoxodisulfat (Natriumpersulfat), bevorzugt sind. Besonders vorteilhaft kommen die Peroxoverbindungen in Kombination mit schwefelhaltigen Reduktionsmitteln, insbesondere Natriumhydrogensulfit, als Redoxinitiatorsystem zum Einsatz. Bei Verwendung dieses Starter/Regler-Systems werden Copolymere erhalten, die als Endgruppen -SO3-Na+ und/oder -SO4- Na+ enthalten und sich durch besondere Reinigungskraft und belagsinhibierende Wirkung auszeichnen.Preferably, thermal initiators are used, with inorganic peroxo compounds, in particular sodium peroxodisulfate (sodium persulfate), being preferred. The peroxo compounds are particularly advantageously used in combination with sulfur-containing reducing agents, in particular sodium hydrogen sulfite, as the redox initiator system. When using this starter / regulator system copolymers are obtained which contain as end groups -SO 3 -Na + and / or -SO 4 - Na + and are characterized by particular cleaning power and deposit-inhibiting effect.

Alternativ können auch phosphorhaltige Starter/Regler-Systeme verwendet werden, z.B. Hypophosphite/Phosphinate.Alternatively, phosphorus-containing starter / regulator systems may also be used, e.g. Hypophosphites / phosphinates.

Die Mengen Photoinitiator bzw. Starter/Regler-System sind auf die jeweils verwendeten Substanzen abzustimmen. Wird beispielsweise das bevorzugte System Peroxodisulfat/Hydrogensulfit verwendet, so werden üblicherweise 2 bis 6 Gew.-%, vorzugsweise 3 bis 5 Gew.-%, Peroxodisulfat und in der Regel 5 bis 30 Gew.-%, vorzugsweise 5 bis 10 Gew.-%, Hydrogensulfit, jeweils bezogen auf die Monomere (a), (b) und (c), eingesetzt.The amounts of photoinitiator or starter / regulator system are to be matched to the substances used in each case. If, for example, the preferred system peroxodisulfate / hydrogen sulfite is used, usually 2 to 6% by weight, preferably 3 to 5% by weight, of peroxodisulfate and generally 5 to 30% by weight, preferably 5 to 10% by weight. %, Hydrogen sulfite, in each case based on the monomers (a), (b) and (c) used.

Gewünschtenfalls können auch Polymerisationsregler zum Einsatz kommen. Geeignet sind die dem Fachmann bekannten Verbindungen, z.B. Schwefelverbindungen, wie Mercaptoethanol, 2-Ethylhexylthioglykolat, Thioglykolsäure und Dodecylmercaptan. Wenn Polymerisationsregler verwendet werden, beträgt ihre Einsatzmenge in der Regel 0,1 bis 15 Gew.-%, bevorzugt 0,1 bis 5 Gew.-% und besonders bevorzugt 0,1 bis 2,5 Gew.-%, bezogen auf die Monomere (a), (b) und (c).If desired, polymerization regulators can also be used. Suitable compounds are those known in the art, for example sulfur compounds, such as mercaptoethanol, 2-ethylhexyl thioglycolate, Thioglycolic acid and dodecylmercaptan. When polymerization regulators are used, their amount used is usually 0.1 to 15 wt .-%, preferably 0.1 to 5 wt .-% and particularly preferably 0.1 to 2.5 wt .-%, based on the monomers (a), (b) and (c).

Die Polymerisationstemperatur liegt in der Regel bei 30 bis 200°C, bevorzugt bei 50 bis 150°C und besonders bevorzugt bei 80 bis 120°C.The polymerization temperature is usually at 30 to 200 ° C, preferably at 50 to 150 ° C and particularly preferably at 80 to 120 ° C.

Die Polymerisation kann unter atmosphärischem Druck durchgeführt werden, vorzugsweise wird sie jedoch in geschlossenem System unter dem sich entwickelnden Eigendruck vorgenommen.The polymerization may be carried out under atmospheric pressure, but is preferably carried out in the closed system under the evolving autogenous pressure.

Bei der Herstellung der erfindungsgemäß zu verwendenden Copolymere können die Monomere (a), (b) und (c) als solche eingesetzt werden, es können jedoch auch Reaktionsmischungen zum Einsatz kommen, die bei der Herstellung z.B. der Monomere (b) oder (c) anfallen. So kann beispielsweise anstelle von 2-Sulfoethylmethacrylat das bei der Veresterung von 2-Hydroxyethansulfonsäure mit einem Überschuß Methacrylsäure anfallende Monomergemisch verwendet werden. Außerdem kann anstelle von Methoxypolyethylenglykolmethacrylat das bei der Veretherung von Methoxypolyethylenglykol mit einem Überschuß Methacrylsäure anfallende Monomergemisch zum Einsatz kommen. Ebenso ist es z.B. möglich, 2-Sulfoethylmethacrylat und Methoxypolyethylenglykolmethacrylat durch gleichzeitige oder aufeinanderfolgende Veresterung von 2-Hydroxyethansulfonsäure und Methoxypolyethylenglykol mit einem Überschuß an Methacrylsäure herzustellen und das entstehende Monomergemisch zur Polymerisation einzusetzen.In the preparation of the copolymers to be used according to the invention, the monomers (a), (b) and (c) can be used as such, but reaction mixtures which are used in the preparation of e.g. the monomers (b) or (c) incurred. For example, instead of 2-sulfoethyl methacrylate, the monomer mixture obtained in the esterification of 2-hydroxyethanesulfonic acid with an excess of methacrylic acid can be used. In addition, instead of methoxypolyethylene glycol methacrylate, the monomer mixture obtained in the etherification of methoxypolyethylene glycol with an excess of methacrylic acid can be used. Likewise, it is e.g. possible to produce 2-sulfoethyl methacrylate and methoxypolyethylene glycol methacrylate by simultaneous or sequential esterification of 2-hydroxyethanesulfonic acid and methoxypolyethylene glycol with an excess of methacrylic acid and to use the resulting monomer mixture for the polymerization.

Wenn für die Anwendung gewünscht, können die bei der Herstellung der erfindungsgemäß zu verwendenden sulfonsäuregruppenhaltigen Copolymere anfallenden wäßrigen Lösungen durch Zugabe von Base, insbesondere von Natronlauge, neutralisiert oder teilneutralisiert, d.h. auf einen pH-Wert im Bereich von etwa 4-8, vorzugsweise 4,5 - 7,5 eingestellt, werden.If desired for the application, the aqueous solutions obtained in the preparation of the sulfonic acid group-containing copolymers to be used according to the invention can be neutralized or partially neutralized by adding base, in particular sodium hydroxide solution, i. adjusted to a pH in the range of about 4-8, preferably 4.5-7.5.

Die erfindungsgemäß verwendeten sulfonsäuregruppenhaltigen Copolymere eignen sich hervorragend als Zusatz zu Wasch- und Reinigungsmitteln.The sulfonic acid-containing copolymers used in the invention are outstandingly suitable as an additive to detergents and cleaners.

Besonders vorteilhaft können sie in maschinellen Geschirrspülmitteln eingesetzt werden. Sie zeichnen sich dabei vor allem durch ihre belagsinhibierende Wirkung sowohl gegenüber anorganischen als auch organischen Belägen aus. Insbesondere seien Beläge, die durch die übrigen Bestandteile der Reinigerformulierung hervorgerufen werden, wie Beläge von Calcium- und Magnesiumphosphat, Calcium- und Magnesiumsilikat und Calcium- und Magnesiumphosphonat, und Beläge, die aus den Schmutzbestandteilen der Spülflotte stammen, wie Fett-, Eiweiß- und Stärkebeläge, genannt. Die erfindungsgemäß verwendeten Copolymere erhöhen dadurch auch die Reinigungskraft des Geschirrspülmittels. Zusätzlich begünstigen sie bereits in geringen Konzentrationen das Ablaufen des Wassers vom Spülgut, so daß der Anteil an Klarspültensiden im Geschirrspülmittel reduziert werden kann. Bei Anwendung der sulfonsäuregruppenhaltigen Copolymere werden dementsprechend besonders klare Gläser und hochglänzende Metallbesteckteile erhalten, insbesondere auch dann, wenn der Geschirrspüler ohne Regeneriersalz zur Wasserenthärtung betrieben wird. Die sulfonsäuregruppenhaltigen Copolymere können daher nicht nur in 2in1-Reinigern, sondern auch in 3in1-Reinigern vorteilhaft eingesetzt werden.Particularly advantageous they can be used in automatic dishwashing detergents. They are characterized mainly by their deposit-inhibiting effect against both inorganic and organic coatings. In particular, there are deposits caused by the remaining components of the cleaner formulation such as linings of calcium and magnesium phosphate, calcium and magnesium silicate and calcium and magnesium phosphonate, and coatings derived from the constituents of the rinse liquor, such as fat, protein and starch deposits called. The copolymers used according to the invention thereby also increase the detergency of the dishwashing detergent. In addition, they already facilitate the drainage of the water from the dishes at low concentrations, so that the proportion of rinse aid surfactants in the dishwashing detergent can be reduced. When using the copolymers containing sulfonic acid accordingly particularly clear glasses and high-gloss metal cutlery are obtained, especially when the dishwasher is operated without Regeneriersalz for water softening. The copolymers containing sulfonic acid groups can therefore be used advantageously not only in 2-in-1 cleaners but also in 3-in-1 cleaners.

Die erfindungsgemäß verwendeten Copolymere können direkt in Form der bei der Herstellung anfallenden wäßrigen Lösungen sowie auch in getrockneter, z.B. durch Sprühtrocknung, Fluidized Spray Drying, Walzentrocknung oder Gefriertrocknung erhaltener Form zum Einsatz kommen. Die erfindungsgemäßen Wasch- und Reinigungsmittel können dementsprechend in fester oder in flüssiger Form, z.B. als Pulver, Granulate, Extrudate, Tabletten, Flüssigkeiten oder Gele bereitgestellt werden.The copolymers used according to the invention can be used directly in the form of the aqueous solutions obtained in the preparation as well as in dried, e.g. by spray drying, fluidized spray drying, drum drying or freeze-drying obtained form are used. Accordingly, the washing and cleaning agents according to the invention may be in solid or liquid form, e.g. as powders, granules, extrudates, tablets, liquids or gels.

BeispieleExamples A) Herstellung von sulfonsäuregruppenhaltigen CopolymerenA) Preparation of sulfonic acid group-containing copolymers

Die im folgenden angegebenen K-Werte wurden in 1 gew.-%iger wäßriger Lösung bei 25°C nach H. Fikentscher, Cellulose-Chemie, Bd. 13, S. 58-64 und 71-74 (1932 ) bestimmt.The K values indicated below were in 1 wt .-% aqueous solution at 25 ° C after H. Fikentscher, Cellulose Chemistry, Vol. 13, pp. 58-64 and 71-74 (1932 ) certainly.

Die in den Beispielen verwendeten Abkürzungen haben folgende Bedeutung:

AS:
Acrylsäure
MAS:
Methacrylsäure
MPEGMA:
Methoxypolyethylenglykolmethacrylat
SEMA:
2-Sulfoethylmethacrylsäure-Natriumsalz
AMPS:
2-Acrylamido-2-methylpropansulfonsäure
The abbreviations used in the examples have the following meaning:
AS:
acrylic acid
MAS:
methacrylic acid
MPEGMA:
methoxy polyethylene glycol methacrylate
SEMA:
2-sulfoethylmethacrylic sodium salt
AMPS:
2-acrylamido-2-methylpropane

Beispiel 1example 1

In einem Reaktor mit Stickstoffzuführung, Rückflußkühler und Dosiervorrichtung wurde eine Mischung von 782,7 g destilliertem Wasser und 1,98 g phosphoriger Säure unter Stickstoffzufuhr und Rühren auf 100°C Innentemperatur erhitzt. Dann wurde ein Gemisch aus 144,8 g Acrylsäure, 306,8 g einer 50 gew.-%igen wäßrigen Lösung von Methoxypolyethylenglykolmethacrylat (Mw = 1 086), 241,3 g destilliertem Wasser und 34,5 g 2-Sulfoethylmethacrylsäure-Natriumsalz (90 gew.-%ig) kontinuierlich in 5 h zugegeben. Parallel dazu wurden in 5,25 h ein Gemisch aus 16,5 g Natriumperoxodisulfat und 148,1 g destilliertem Wasser sowie in 5 h 123,5 g einer 40 gew.-%igen wäßrigen Natriumhydrogensulfitlösung kontinuierlich zudosiert. Nach zweistündigem Nachrühren bei 100°C wurde das Reaktionsgemisch auf Raumtemperatur abgekühlt und durch Zugabe von 154,5 g 50 gew.-%iger Natronlauge auf einen pH-Wert von 7,2 eingestellt.In a reactor with nitrogen feed, reflux condenser and metering device, a mixture of 782.7 g of distilled water and 1.98 g of phosphorous acid under nitrogen and Stirring heated to 100 ° C internal temperature. Then, a mixture of 144.8 g of acrylic acid, 306.8 g of a 50 wt .-% aqueous solution of methoxypolyethylene glycol methacrylate (M w = 1 086), 241.3 g of distilled water and 34.5 g of 2-sulfoethylmethacrylic acid sodium salt (90 wt .-%) added continuously in 5 h. At the same time, a mixture of 16.5 g of sodium peroxodisulfate and 148.1 g of distilled water and, in 5 hours, 123.5 g of a 40% strength by weight aqueous sodium hydrogen sulfite solution were added continuously in 5.25 h. After two hours of stirring at 100 ° C, the reaction mixture was cooled to room temperature and adjusted by the addition of 154.5 g of 50 wt .-% sodium hydroxide solution to a pH of 7.2.

Es wurde eine leicht gelbliche, klare Lösung des Copolymers der molaren Zusammensetzung AS : SEMA : MPEGMA = 14 : 1 : 1 mit einem Feststoffgehalt von 22,6 Gew.-% und einem K-Wert von 22,6 erhalten.A slightly yellowish, clear solution of the copolymer of the molar composition AS: SEMA: MPEGMA = 14: 1: 1 having a solids content of 22.6% by weight and a K value of 22.6 was obtained.

Beispiel 2Example 2

In dem Reaktor aus Beispiel 1 wurde eine Mischung von 300,0 g destilliertem Wasser und 1,09 g phosphoriger Säure unter Stickstoffzufuhr und Rühren auf 100°C Innentemperatur erhitzt. Dann wurde ein Gemisch aus 61,2 g Acrylsäure, 167,7 g einer 50 gew.-%igen wäßrigen Lösung von Methoxypolyethylenglykolmethacrylat (Mw = 1 086), 116,7 g destilliertem Wasser und 58,6 g einer Mischung aus 85,5 Gew.-% Methacrylsäure und 14,5 Gew.-% 2-Sulfoethylmethacrylsäure-Natriumsalz kontinuierlich in 5 h zugegeben. Parallel dazu wurden in 5,25 h ein Gemisch aus 5,4 g Natriumperoxodisulfat und 94,6 g destilliertem Wasser sowie in 5 h 27 g einer 40 gew.-%igen wäßrigen Natriumhydrogensulfitlösung kontinuierlich zudosiert. Nach zweistündigem Nachrühren bei 100°C wurde das Reaktionsgemisch auf Raumtemperatur abgekühlt und durch Zugabe von 92 g 50 gew.-%iger Natronlauge auf einen pH-Wert von 7,4 eingestellt.In the reactor of Example 1, a mixture of 300.0 g of distilled water and 1.09 g of phosphorous acid was heated with nitrogen supply and stirring to 100 ° C internal temperature. Then a mixture of 61.2 g of acrylic acid, 167.7 g of a 50% strength by weight aqueous solution of methoxypolyethylene glycol methacrylate (M w = 1086), 116.7 g of distilled water and 58.6 g of a mixture of 85, 5 wt .-% of methacrylic acid and 14.5 wt .-% 2-sulfoethylmethacrylic acid sodium salt added continuously in 5 h. In parallel, a mixture of 5.4 g of sodium peroxodisulfate and 94.6 g of distilled water and in 5 h 27 g of a 40 wt .-% aqueous sodium hydrogen sulfite solution were added continuously in 5.25 h. After two hours of stirring at 100 ° C, the reaction mixture was cooled to room temperature and adjusted by the addition of 92 g of 50 wt .-% sodium hydroxide solution to a pH of 7.4.

Es wurde eine leicht gelbliche, schwach trübe Lösung des Copolymers der molaren Zusammensetzung AS : MAS : SEMA : MPEGMA = 11 : 3 : 1 : 1 mit einem Feststoffgehalt von 24,8 Gew.-% und einem K-Wert von 32,3 erhalten.A slightly yellowish, slightly turbid solution of the copolymer of the molar composition AS: MAS: SEMA: MPEGMA = 11: 3: 1: 1 having a solids content of 24.8% by weight and a K value of 32.3 was obtained ,

Beispiel 3Example 3

In dem Reaktor aus Beispiel 1 wurde eine Mischung von 505,1 g destilliertem Wasser und 1,18 g phosphoriger Säure unter Stickstoffzufuhr und Rühren vorgelegt und ohne weitere Stickstoffzufuhr auf 100°C Innentemperatur erhitzt. Dann wurde ein Gemisch aus 42,9 g Acrylsäure, 88,6 g einer 50 gew.-%igen wäßrigen Lösung von Methoxypolyethylenglykolmethacrylat (Mw = 1 100), 197,9 g destilliertem Wasser, 17,6 g 2-Sulfoethylmethacrylsäure-Natriumsalz und 47,0 g Methacrylsäure kontinuierlich in 5 h zugegeben. Parallel dazu wurden in 5,25 h ein Gemisch aus 5,9 g Natriumperoxodisulfat und 53,0 g destilliertem Wasser sowie in 5 h 39,2 g einer 40 gew.-%igen Natriumhydrogensulfitlösung kontinuierlich zudosiert. Nach zweistündigem Nachrühren bei 100°C wurde das Reaktionsgemisch auf Raumtemperatur abgekühlt und durch Zugabe von 50 gew.-%iger Natronlauge auf einen pH-Wert von 7,2 eingestellt.In the reactor from Example 1, a mixture of 505.1 g of distilled water and 1.18 g of phosphorous acid was introduced under nitrogen and stirring and heated without further addition of nitrogen to 100 ° C internal temperature. Then a mixture was made 42.9 g of acrylic acid, 88.6 g of a 50 wt .-% aqueous solution of Methoxypolyethylenglykolmethacrylat (M w = 1 100), 197.9 g of distilled water, 17.6 g of 2-sulfoethylmethacrylic acid sodium salt and 47.0 g Methacrylic acid continuously added in 5 h. At the same time, 5.25 g of sodium peroxodisulfate and 53.0 g of distilled water were continuously added in 5.25 hours, and 39.2 g of a 40% strength by weight sodium hydrogen sulfite solution were added continuously in the course of 5 hours. After two hours of stirring at 100 ° C, the reaction mixture was cooled to room temperature and adjusted by the addition of 50 wt .-% sodium hydroxide solution to a pH of 7.2.

Es wurde eine leicht gelbliche, klare Lösung des Copolymers der molaren Zusammensetzung AS : MAS : SEMA : MPEGMA = 7,3 : 6,7 : 1 : 1 mit einem Feststoffgehalt von 23,1 Gew.-% und einem K-Wert von 30,1 erhalten.A slightly yellowish, clear solution of the copolymer of the molar composition AS: MAS: SEMA: MPEGMA = 7.3: 6.7: 1: 1 with a solids content of 23.1% by weight and a K value of 30 was obtained , 1 received.

Vergleichsbeispiel VComparative Example V

In dem Reaktor aus Beispiel 1 wurde eine Mischung von 145,9 g destilliertem Wasser und 4,44 g phosphoriger Säure unter Stickstoffzufuhr und Rühren auf 100°C Innentemperatur erhitzt. Dann wurde ein Gemisch aus 139,8 g Acrylsäure, 100,5 g 2-Acrylamido-2-methylpropansulfonsäure und 402 g destilliertem Wasser kontinuierlich in 5 h zugegeben. Parallel dazu wurden in 5,25 h ein Gemisch aus 12,0 g Natriumperoxodisulfat und 108,2 g destilliertem Wasser sowie in 5 h 45,1 g einer 11,3 gew.-%igen Natriumhydrogensulfitlösung kontinuierlich zudosiert. Nach einstündigem Nachrühren bei 100°C wurde das Reaktionsgemisch auf Raumtemperatur abgekühlt und durch Zugabe von 50 gew.-%iger Natronlauge auf einen pH-Wert von 7,2 eingestellt.In the reactor of Example 1, a mixture of 145.9 g of distilled water and 4.44 g of phosphorous acid was heated to 100 ° C internal temperature with nitrogen and stirring. Then, a mixture of 139.8 g of acrylic acid, 100.5 g of 2-acrylamido-2-methylpropanesulfonic acid and 402 g of distilled water was added continuously in 5 hours. In parallel, a mixture of 12.0 g of sodium peroxodisulfate and 108.2 g of distilled water and in 5 h 45.1 g of a 11.3 wt .-% strength sodium bisulfite solution was added continuously in 5.25 h. After stirring for one hour at 100 ° C, the reaction mixture was cooled to room temperature and adjusted by the addition of 50 wt .-% sodium hydroxide solution to a pH of 7.2.

Es wurde eine leicht gelbliche, klare Lösung des Copolymers der molaren Zusammensetzung AS : AMPS = 1 : 4 mit einem Feststoffgehalt von 30,5 Gew.-% und einem K-Wert von 33,0 erhalten.A slightly yellowish, clear solution of the copolymer of the molar composition AS: AMPS = 1: 4 having a solids content of 30.5% by weight and a K value of 33.0 was obtained.

B) Anwendung von sulfonsäuregruppenhaltigen Copolymeren in GeschirrspülmittelnB) Use of sulfonic acid-containing copolymers in dishwashing detergents

Zur Prüfung ihrer belagsinhibierenden Wirkung wurden die erhaltenen sulfonsäuregruppenhaltigen Copolymere zusammen mit einer Geschirrspülmittelformulierung folgender Zusammensetzung eingesetzt: 50 Gew.-% Natriumtripolyphosphat (Na3P3O10 · 6 H2O) 27 Gew.-% Natriumcarbonat 3 Gew.-% Natriumdisilikat (x Na2O · y SiO2; x/y = 2,65; 80%ig) 6Gew.-% Natriumpercarbonat (Na2CO3 · 1,5 H2O2) 2 Gew.-% Tetraacetylendiamin (TAED) 2 Gew.-% schaumarmes nichtionisches Tensid auf der Basis von Fettalkoholalkoxylaten 3 Gew.-% Natriumchlorid 5 Gew.-% Natriumsulfat 2 Gew.-% Polyacrylsäure-Natriumsalz (Mw 8 000) To test their scale-inhibiting effect, the resulting copolymers containing sulfonic acid groups were used together with a dishwashing detergent formulation of the following composition: 50% by weight Sodium tripolyphosphate (Na 3 P 3 O 10 .6H 2 O) 27% by weight sodium 3% by weight Sodium disilicate (x Na 2 O.y SiO 2 ; x / y = 2.65; 80%) 6Gew .-% Sodium percarbonate (Na 2 CO 3 · 1.5H 2 O 2 ) 2% by weight Tetraacetylenediamine (TAED) 2% by weight Low foaming nonionic surfactant based on fatty alcohol 3% by weight sodium chloride 5% by weight sodium sulphate 2% by weight Polyacrylic acid sodium salt (M w 8 000)

Die Prüfung erfolgte bei den folgenden Spülbedingungen ohne Zusatz von Ballastschmutz, wobei weder Klarspüler noch Regeneriersalz eingesetzt wurden:The test was carried out at the following rinsing conditions without the addition of ballast dirt, with neither rinse aid nor regeneration salt were used:

Spülbedingungen:flushing:

Geschirrspüler:Dishwasher: Miele G 686 SCMiele G 686 SC Spülgänge:rinses: 2 Spülgänge 55°C Normal (ohne Vorspülen)2 rinses 55 ° C normal (without pre-rinse) Spülgut:ware: Messer (WMF Tafelmesser Berlin, Monoblock) und Faßformglasbecher (Matador, Ruhr Kri-stall)Knife (WMF table knife Berlin, Monoblock) and barrel-shaped glass beaker (Matador, Ruhr Kri-stall) Geschirrspülmittel:Dishwashing liquid: 21 g21 g Copolymer:copolymer: 4,2 g4.2 g Klarspültemperatur:Rinse temperature: 65°C65 ° C Wasserhärte:Water hardness: 25°dH25 ° dH

Die Bewertung des Spülguts erfolgte 18 h nach der Reinigung durch visuelle Abmusterung in einem schwarz lackierten Leuchtkasten mit Halogenspot und Lochblende unter Verwendung einer Notenskala von 10 (sehr gut) bis 1 (sehr schlecht). Die Höchstnote 10 entspricht dabei belags- und tropfenfreien Oberflächen, ab Noten < 5 sind Beläge und Tropfen schon bei normaler Raumbeleuchtung erkennbar, werden also als störend wahrgenommen.The washware was evaluated 18 hours after cleaning by visual inspection in a black painted light box with halogen spot and pinhole using a grading scale from 10 (very good) to 1 (very bad). The highest grade of 10 corresponds to covering and drip-free surfaces, from grades <5, coverings and drops are already visible under normal room lighting, so are perceived as disturbing.

Die erhaltenen Prüfergebnisse sind in der folgenden Tabelle zusammengestellt. Tabelle Copolymer aus Bsp. Bewertung (Note) Messer Gläser 1 7,7 7,4 2 8,5 8,0 3 9,0 8,0 V 7,5 6,0 - 4,0 4,0 The test results obtained are summarized in the following table. table Copolymer from Ex. Rating (grade) knife glasses 1 7.7 7.4 2 8.5 8.0 3 9.0 8.0 V 7.5 6.0 - 4.0 4.0

Claims (9)

  1. The use of copolymers containing sulfonic acid groups, which comprise
    (a) 30 to 95 mol% of at least one monoethylenically unsaturated carboxylic acid, one monoethylenically unsaturated carboxylic acid ester or one water-soluble salt of a monoethylenically unsaturated carboxylic acid,
    (b) 3 to 35 mol% of at least one monomer of the formula I containing sulfonic acid groups
    Figure imgb0009
     in which the variables have the following meaning:
    R is hydrogen or methyl;
    X is a chemical bond or -COO-R1-;
    R1 is unbranched or branched C1-C4-alkylene;
    M is hydrogen, alkali metal or ammonium,
    and
    (c) 2 to 35 mol% of at least one nonionic monomer of formula II
    Figure imgb0010
    in which the variables have the following meanings:
    R2 is hydrogen or methyl;
    R3 is a chemical bond or unbranched or branched C1-C6-alkylene;
    R4 are identical or different unbranched or branched C2-C4-alkylene radicals;
    R5 is unbranched or branched C1-C6-alkyl;
    n is 3 to 50,
    in random or block copolymerized form, as additive for detergents and cleaners.
  2. The use according to claim 1, wherein the copolymers comprise 50 to 90 mol% of component (a), 5 to 25 mol% of component (b) and 5 to 25 mol% of component (c) in copolymerized form.
  3. The use according to claim 1 or 2, wherein the monoethylenically unsaturated carboxylic acid (a) is acrylic acid, methacrylic acid and/or maleic acid.
  4. The use according to claims 1 to 3, wherein the monoethylenically unsaturated carboxylic acid (a) is acrylic acid or a mixture of acrylic acid and methacrylic acid.
  5. The use according to claims 1 to 4, wherein the copolymers comprise, as component (b), a monomer of the formula I containing sulfonic acid groups, in which R is methyl, X is -COO-C2H4- and M is sodium or hydrogen, in copolymerized form.
  6. The use according to claims 1 to 5, wherein the copolymers comprise, as component (c), a nonionic monomer of the formula II in which R2 is methyl, R3 is a chemical bond, R4 is ethylene, R5 is methyl and n is 10 to 30, in copolymerized form.
  7. The use according to claims 1 to 6, wherein the copolymers comprise -SO3- Na+ and/or -SO4- Na+ as end-groups.
  8. The use according to claims 1 to 7, wherein the copolymers are used as deposit-inhibiting additive in machine dishwashing detergents.
  9. A detergent or cleaner which comprises copolymers according to claims 1 to 7 as deposit-inhibiting additive.
EP03740180A 2002-06-10 2003-06-04 Use of copolymers containing sulfonic acid groups, as an additive in detergents and cleansers Expired - Lifetime EP1516040B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10225794 2002-06-10
DE10225794A DE10225794A1 (en) 2002-06-10 2002-06-10 Composition comprising sulfonic acid group containing copolymers, monoethylenically unsaturated carboxylic acid and nonionic monomer useful as a coating inhibiting additive in dishwashers
PCT/EP2003/005821 WO2003104372A1 (en) 2002-06-10 2003-06-04 Use of copolymers containing sulfonic acid groups, as an additive in detergents and cleansers

Publications (2)

Publication Number Publication Date
EP1516040A1 EP1516040A1 (en) 2005-03-23
EP1516040B1 true EP1516040B1 (en) 2009-08-12

Family

ID=29557740

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03740180A Expired - Lifetime EP1516040B1 (en) 2002-06-10 2003-06-04 Use of copolymers containing sulfonic acid groups, as an additive in detergents and cleansers

Country Status (11)

Country Link
US (2) US20050202994A1 (en)
EP (1) EP1516040B1 (en)
JP (1) JP2005533137A (en)
CN (1) CN1297647C (en)
AT (1) ATE439419T1 (en)
AU (1) AU2003274111A1 (en)
CA (1) CA2488329C (en)
DE (2) DE10225794A1 (en)
ES (1) ES2328683T3 (en)
MX (1) MXPA04011362A (en)
WO (1) WO2003104372A1 (en)

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005028460A1 (en) * 2005-06-17 2006-12-28 Basf Ag Use of copolymers containing alkylene oxide units as an additive to aqueous systems
US7713920B2 (en) * 2005-12-14 2010-05-11 The Procter & Gamble Company Detergent compositions containing azo initiator compounds for improved bleaching performance and stain-removal benefits
JP4140923B2 (en) * 2006-03-31 2008-08-27 花王株式会社 Cleaning composition
BRPI0715378A2 (en) * 2006-08-10 2013-06-18 Basf Se dishwasher cleaning formulation, use of a combination of copolymers and complexing agents, and machine dish cleaning process
JP5307412B2 (en) * 2008-01-29 2013-10-02 三洋化成工業株式会社 Anti-contamination agent for liquid detergent and liquid detergent
DE102008008179A1 (en) * 2008-02-08 2009-08-13 Clariant International Ltd. Process for the preparation of polymers by ion exchange
EP2228426A1 (en) * 2009-03-13 2010-09-15 Rohm and Haas Company Scale-reducing additive for automatic dishwashing systems
DE102009029635A1 (en) * 2009-09-21 2011-03-24 Henkel Ag & Co. Kgaa Machine dishwashing detergent
CA2818703A1 (en) * 2010-11-23 2012-05-31 Basf Se Copolymers comprising carboxylic acid groups, sulfo groups and polyalkylene oxide groups as a scale-inhibiting additive to washing and cleaning products
EP2643370B1 (en) * 2010-11-23 2019-07-03 Basf Se Copolymers containing carboxylic acid groups, sulfonic acid groups, and polyalkylene oxide groups, used as scale-inhibiting additives to detergents and cleaning agents
US9670435B2 (en) 2010-11-23 2017-06-06 Basf Se Copolymers comprising carboxylic acid groups, sulfo groups and polyalkylene oxide groups as a scale-inhibiting additive to washing and cleaning products
CN102617811B (en) * 2012-03-21 2013-06-26 陕西科技大学 Preparation method of amphiprotic vinyl polymer concrete mud-resistant agent
DE102013207778A1 (en) * 2013-04-29 2014-10-30 Cht R. Beitlich Gmbh Comb polymers as detergency booster for detergents and cleaners
US9127235B2 (en) 2013-10-09 2015-09-08 Ecolab Usa Inc. Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control
US9487738B2 (en) 2013-10-09 2016-11-08 Ecolab Usa Inc. Solidification matrix comprising a carboxylic acid terpolymer
US9127236B2 (en) 2013-10-09 2015-09-08 Ecolab Usa Inc. Alkaline detergent composition containing a carboxylic acid terpolymer for hard water scale control
EP2896637A1 (en) 2014-01-21 2015-07-22 Rhodia Operations Copolymer comprising units of type A deriving from carboxylic acid monomers and units of type B deriving from sulfonic acid monomers
DE102015213943A1 (en) * 2015-07-23 2017-01-26 Henkel Ag & Co. Kgaa Washing or cleaning agent comprising at least two phases
CN105647678B (en) * 2016-01-14 2018-05-15 广州立白企业集团有限公司 Lift method and detergent composition of the cleaning compositions to albumen soil removal capabilities
ES2802454T3 (en) 2016-04-08 2021-01-19 Procter & Gamble Dishwasher cleaning composition
JP6721417B2 (en) * 2016-05-31 2020-07-15 株式会社日本触媒 Sulfur-containing polymer composition and method for producing the same
GB201809123D0 (en) * 2018-06-04 2018-07-18 Reckitt Benckiser Finish Bv Composition

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA849394B (en) * 1983-12-21 1985-09-25 Goodrich Co B F Lime soap dispersing compositions and their use
KR910009186B1 (en) * 1986-06-27 1991-11-04 가와사끼쥬우고오교 가부시끼가이샤 Dispersant for carbonaceous solid-water slurry and carbonaceous solid-water slurry composition prepared by blending the dispersant
DE4343993A1 (en) * 1993-12-22 1995-06-29 Stockhausen Chem Fab Gmbh Graft copolymers of unsaturated monomers and polyhydroxy compounds, process for their preparation and their use
JPH10158339A (en) * 1996-12-05 1998-06-16 Nippon Shokubai Co Ltd Polymer containing sulfonic group
JP2000007734A (en) * 1998-06-23 2000-01-11 Jsr Corp Water-soluble copolymer (salt) and scale inhibitor
JP2000024691A (en) * 1998-07-09 2000-01-25 Jsr Corp Water-soluble copolymer (salt) and scale inhibitor
DE10050622A1 (en) * 2000-07-07 2002-05-02 Henkel Kgaa Rinse aid II a

Also Published As

Publication number Publication date
CA2488329A1 (en) 2003-12-18
JP2005533137A (en) 2005-11-04
EP1516040A1 (en) 2005-03-23
WO2003104372A1 (en) 2003-12-18
DE50311809D1 (en) 2009-09-24
MXPA04011362A (en) 2005-02-14
AU2003274111A1 (en) 2003-12-22
CA2488329C (en) 2010-11-23
ATE439419T1 (en) 2009-08-15
US20050202994A1 (en) 2005-09-15
CN1297647C (en) 2007-01-31
ES2328683T3 (en) 2009-11-17
CN1659265A (en) 2005-08-24
US20080281053A1 (en) 2008-11-13
US7645345B2 (en) 2010-01-12
DE10225794A1 (en) 2003-12-18

Similar Documents

Publication Publication Date Title
EP1516040B1 (en) Use of copolymers containing sulfonic acid groups, as an additive in detergents and cleansers
EP0285935B1 (en) Use of graft polymers on the base of polyalkylenoxides as greyness inhibitors by washing and aftertreatment of synthetic fibres containing textile goods
EP0451508B1 (en) Process for preparing homo- and copolymers of monoethyleically unsaturated dicarboxylic acids and their use
EP0471710B1 (en) Copolymerizates formed by polymerization of monomers containing polyalkylene oxide blocks, their preparation and use
EP2643370B1 (en) Copolymers containing carboxylic acid groups, sulfonic acid groups, and polyalkylene oxide groups, used as scale-inhibiting additives to detergents and cleaning agents
EP1682645B1 (en) Use of copolymers, containing alkylene oxide units, as deposit inhibitor additives in rinsing compositions of a dishwasher
EP1687348B1 (en) Copolymers comprising polyalkylene oxide groups and quaternary nitrogen atoms
DE4313909A1 (en) Water-softening formulations
EP1513916B1 (en) Use of copolymers containing alkylene oxide units, as an additive in dishwashing compositions
DE3711299C2 (en) Use of graft polymers based on polyvinylpyrrolidone as graying inhibitors in the washing and aftertreatment of textile fibers containing synthetic fibers
EP1791938B1 (en) Clear rinsing agent containing hydrophobically modified polycarboxylates
EP0637627B1 (en) Detergent formulations
EP1660547B1 (en) Copolymers containing sulfonic acid groups and carboxyl groups
EP0622449B1 (en) Water-softening compositions
DE4316744A1 (en) Rinse aids with biodegradable polymers
EP0625567B1 (en) Detergent for mechanical dish-washing
DE102013207778A1 (en) Comb polymers as detergency booster for detergents and cleaners
DE4316743A1 (en) Rinse aids with biodegradable polymers
DE2616261A1 (en) Acrylic copolymer sequestrants for washing agents - comprise copolymers of (meth)acrylic acid and hydroxyalkyl acrylates

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: 20050110

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

RIN1 Information on inventor provided before grant (corrected)

Inventor name: WEINGART, FRANZ

Inventor name: NIED, STEPHAN

Inventor name: BAUM, PIA

Inventor name: BRODT, GREGOR

Inventor name: MICHL, KATHRIN

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BASF SE

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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 BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

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

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 50311809

Country of ref document: DE

Date of ref document: 20090924

Kind code of ref document: P

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2328683

Country of ref document: ES

Kind code of ref document: T3

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

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: 20090812

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: 20090812

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

Ref country code: SI

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: 20090812

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20091212

Ref country code: BG

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: 20091112

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

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: 20090812

Ref country code: CZ

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: 20090812

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: 20090812

Ref country code: RO

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: 20090812

Ref country code: EE

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: 20090812

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

Ref country code: SK

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: 20090812

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

Effective date: 20100517

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: 20091113

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: 20100630

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

Ref country code: CH

Payment date: 20110630

Year of fee payment: 9

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

Ref country code: AT

Payment date: 20110624

Year of fee payment: 9

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

Ref country code: NL

Payment date: 20120629

Year of fee payment: 10

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

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: 20090812

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

Ref country code: GB

Payment date: 20120629

Year of fee payment: 10

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

Ref country code: HU

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: 20100213

Ref country code: LU

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

Effective date: 20100604

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

Ref country code: IT

Payment date: 20120621

Year of fee payment: 10

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

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: 20090812

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

Ref country code: BE

Payment date: 20120726

Year of fee payment: 10

Ref country code: DE

Payment date: 20120830

Year of fee payment: 10

Ref country code: FR

Payment date: 20120720

Year of fee payment: 10

Ref country code: ES

Payment date: 20120717

Year of fee payment: 10

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 439419

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120604

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: CH

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

Effective date: 20120630

Ref country code: LI

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

Effective date: 20120630

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

Ref country code: AT

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

Effective date: 20120604

BERE Be: lapsed

Owner name: BASF SE

Effective date: 20130630

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20140101

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

Effective date: 20130604

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 50311809

Country of ref document: DE

Effective date: 20140101

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20140228

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

Ref country code: BE

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

Effective date: 20130630

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: 20140101

Ref country code: GB

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

Effective date: 20130604

Ref country code: NL

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

Effective date: 20140101

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

Effective date: 20130604

Ref country code: FR

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

Effective date: 20130701

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20140714

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 NON-PAYMENT OF DUE FEES

Effective date: 20130605