EP1516040A1 - 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

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Publication number
EP1516040A1
EP1516040A1 EP03740180A EP03740180A EP1516040A1 EP 1516040 A1 EP1516040 A1 EP 1516040A1 EP 03740180 A EP03740180 A EP 03740180A EP 03740180 A EP03740180 A EP 03740180A EP 1516040 A1 EP1516040 A1 EP 1516040A1
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EP
European Patent Office
Prior art keywords
copolymers
acid
mol
sulfonic acid
monoethylenically unsaturated
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EP03740180A
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German (de)
French (fr)
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EP1516040B1 (en
Inventor
Pia Baum
Kathrin Michl
Franz Weingart
Stephan Nied
Gregor Brodt
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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
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate

Definitions

  • copolymers containing sulfonic acid groups as additives in detergents and cleaning agents
  • the present invention relates to the use of copolymers containing sulfonic acid groups which
  • R 1 unbranched or branched C ⁇ C alkylene
  • H 2 C C-COO R 3 - R 4 - 0- R5
  • R 2 is hydrogen or methyl
  • R 3 is a chemical bond or unbranched or branched Ci-C ⁇ alkylene;
  • R 4 are identical or different unbranched or branched C -C alkylene radicals;
  • R 5 unbranched or branched Ci-C ⁇ alkyl, Cs-Cs-cycloalkyl or aryl; n 3 to 50,
  • the invention relates to detergents and cleaning agents which contain these copolymers as a deposit-inhibiting additive.
  • the dishes In automatic dishwashing, the dishes should be cleaned in a residue-free state with an immaculately shiny surface, for which a cleaner, rinse aid and regeneration salt usually have to be used to soften the water.
  • the so-called "2inl" dishwashing detergents introduced on the market contain, in addition to the detergent for removing the soiling on the wash ware, integrated rinse aid surfactants, which ensure that water runs off the wash ware 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 dishwashers "3inl" cleaners, are to combine the three functions of cleaning, rinsing and water softening in a single detergent formulation, so that the refill of salt with water hardness levels of 1 to 3 is also superfluous for the consumer.
  • Sodium tripolyphosphate is usually added to these cleaners to bind the hardness-forming calcium and magnesium ions. This in turn results in calcium and magnesium phosphate deposits on the wash ware.
  • WO-A-02/04583 describes automatic dishwashing detergents which contain copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally, but preferably no, other nonionic monomers based on ethylenically unsaturated compounds as scale inhibitors. No further information is given on the nonionic monomers.
  • 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 for (poly) phosphate deposits in automatic dishwashing detergents.
  • Copolymers of acrylic acid and 2-acrylamido-2-propanesulfonic acid or sodium methallylsulfonate and also are disclosed in detail
  • Terpolymers that additionally tert. -Polymerized butyl acrylamide contain.
  • Non-ionic monomers of the formula II are not mentioned.
  • water-soluble copolymers which have structural units containing sulfonate groups, carboxylate groups and polyalkylene oxide groups and an average molecular weight M w of> 50,000 to 3,000,000 can be used as an agent against scale based in particular on silicates in water circuits, for example cooling systems , be used.
  • the structural unit containing sulfonate groups of the copolymers disclosed in detail is based on sodium 2-methyl-1,3-butadiene-1-sulfonate.
  • DE-A-43 43 993 uses graft copolymers of monoethylenically unsaturated carboxylic acids, monoethylenically unsaturated monomers containing sulfonic acid groups and optionally monomers containing water-soluble alkylene oxide units and other free-radically polymerizable monomers on polyhydroxy compounds to inhibit the water hardness in washing and cleaning agents. Graft copolymers of acrylic acid, sodium methallyl sulfonate and methoxypolyethylene glycol methacrylate on polyvinyl alcohol, triglycerol and starch dextrin are described in detail.
  • EP-A-278 983 discloses the use of copolymers of polyalkylene glycol mono (meth) acrylates, sulfoalkyl (meth) acrylates and (meth) acrylic acid as a water-soluble dispersant for carbon-containing solids.
  • the object of the invention was to remedy the problems outlined above and to provide an additive which can also be used advantageously, in particular, in multifunctional cleaners and in particular has a deposit-inhibiting effect.
  • R is hydrogen or methyl
  • X is a chemical bond or -COO-R 1 -;
  • R 1 unbranched or branched C ⁇ C alkylene; M hydrogen, alkali metal or ammonium,
  • R 2 is hydrogen or methyl
  • R 3 is a chemical bond or unbranched or branched Ci-C ⁇ alkylene
  • R 4 same or different unbranched or branched
  • C -C alkylene radicals R 5 unbranched or branched Ci-Cg-alkyl, Cs-Cs-cycloalkyl or aryl; n 3 to 50,
  • copolymerized randomly or in blocks found as an additive to detergents and cleaning agents.
  • detergents and cleaning agents have been found which contain the copolymers containing sulfonic acid groups as a coating-inhibiting additive.
  • the copolymers containing sulfonic acid groups contain, 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 vinyl acetic acid.
  • unsaturated dicarboxylic acids preferably having 4 to 6 carbon atoms, such as itaconic acid and maleic acid.
  • esters are the reaction products of these acids with C 1 -C 6 -alcohols, especially methanol, ethanol and butanol, it being possible for the dicarboxylic acids to be present as mono- or as diesters.
  • examples include: 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 can advantageously also be contained together in the copolymers, are particularly preferred.
  • the proportion of 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 15: 1 to 0.05: 1, in particular 10: 1 to 1: 1, especially 5: 1 to 1: 1.
  • the copolymers contain, as copolymerized component (b), monomers of the formula I containing sulfonic acid groups
  • R is hydrogen or preferably methyl;
  • X is a chemical bond or preferably -COO-R 1 ;
  • R 1 unbranched or branched C ⁇ -C alkylene, preferably C 2 -C 3 alkylene; M is hydrogen, ammonium or preferably an alkali metal.
  • 4-sulfobutyl (meth) acrylic acid and its salts in particular the sodium salts, vinylsulfonic acid, 2-sulfoethyl methacrylic acid and 2-sulfopropyl methacrylic acid and their sodium salts being preferred, and 2-sulfoethyl methacrylic acid and its sodium salt being particularly preferred.
  • the proportion of the monomers (b) containing sulfonic acid groups 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 15 20 mol%.
  • the copolymers also contain, as component (c), nonionic monomers of the formula II
  • H 2 C C-COO R 3 "R 4 - - o- II 0- R5
  • R 2 is hydrogen or preferably methyl
  • R 3 unbranched or branched Ci-Cg-alkylene or preferably a chemical bond; R 4 identical or different unbranched or branched 30 C -C alkylene radicals, especially C -C 3 alkylene radicals, in particular
  • R 5 aryl, especially phenyl or naphthyl, which can in each case be substituted by alkyl, Cs-Cs-cycloalkyl, especially cyclohexyl, or preferably unbranched or branched C 1 -C 6 -alkyl, in particular C 1 -C 6 -alkyl; n 3 to 50, preferably 5 to 40, particularly preferably 10 to 30.
  • 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 of from 3,000 to 40,000, preferably from 10,000 to 30,000 and particularly preferably from 15,000 to 25,000.
  • the K value of the copolymers is usually 15 to 35, in particular 20 to 32, especially 27 to 30 (measured in 1% strength by weight aqueous solution at 25 ° C., according to H. Fikentscher, cellulose se-Chemie, vol. 13, pp. 58-64 and 71-74 (1932)).
  • copolymers to be used according to the invention can be produced by radical polymerization of the monomers. All known radical polymerization processes can be used. In addition to bulk polymerization, the methods of solution polymerization and emulsion polymerization should be mentioned in particular, with 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.
  • thermally activatable polymerization initiators include initiators with a decomposition temperature in the range from 20 to 180 ° C., in particular from 50 to 90 ° C., are preferred.
  • suitable thermal initiators are inorganic peroxo compounds, such as peroxodisulfates (ammonium and preferably sodium peroxodisulfate), peroxosulfates, percarbonates and hydrogen peroxide; organic peroxo 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 peryl butyl butyl peracetate, tert.
  • inorganic peroxo compounds such as peroxodisulfates (ammonium and preferably
  • tert-butyl perpivalate tert. -Butyl-perroctoate, tert. -Butyl perneodecanoate, tert-butyl perbenzoate, tert-butyl peroxide, tert. -Butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxy-2-ethylhexanoate and diisopropyl peroxidicarbamate; Azo compounds, such as 2, 2 '-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile) and azobis (2-amidopropane) dihydrochloride.
  • Azo compounds such as 2, 2 '-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile) and azobis (2-amidopropane) dihydrochloride.
  • initiators can be used in combination with reducing compounds as starter / controller systems.
  • reducing compounds include phosphorus-containing compounds, such as phosphorous acid, hypophosphites and phosphinates, sulfur-containing compounds, such as sodium bisulfite, sodium sulfite and sodium formaldehyde sulfoxilate, and hydrazine.
  • photoinitiators examples include benzophenone, aceto-phenone, benzoin ether, benzyl dialkyl ketones and their derivatives.
  • Thermal initiators are preferably used, with inorganic peroxo compounds, in particular sodium peroxodisulfate (sodium persulfate) being preferred.
  • the peroxo compounds are used particularly advantageously in combination with sulfur-containing reducing agents, in particular sodium bisulfite, as the redox initiator system.
  • sulfur-containing reducing agents in particular sodium bisulfite
  • copolymers are obtained which contain -S0 3 ⁇ Na + and / or -S0 ⁇ Na + as end groups and are notable for particular cleaning power and deposit-inhibiting action.
  • starter / regulator systems containing phosphorus can also be used, e.g. Hypophosphites / phosphinates.
  • the quantities of photoinitiator and starter / regulator system must be matched to the substances used. If, for example, the preferred system peroxodisulfate / hydrogen sulfite is used, 2 to 6% by weight, preferably 3 to 5% by weight, peroxodisulfate and usually 5 to 30% by weight, preferably 5 to 10% by weight, are usually used. %, Hydrogen sulfite, based in each case on the monomers (a), (b) and (c).
  • polymerization regulators can also be used.
  • the compounds known to the person skilled in the art are suitable, for example sulfur compounds, such as mercaptoethanol, 2-ethylhexylthio glycolate, thioglycolic acid and dodecyl mercaptan.
  • sulfur compounds such as mercaptoethanol, 2-ethylhexylthio glycolate, thioglycolic acid and dodecyl mercaptan.
  • the amount used is generally 0.1 to 15% by weight, preferably 0.1 to 5% by weight and particularly preferably 0.1 to 2.5% by weight, based on the monomers (a), (b) and (c).
  • the polymerization temperature is generally 30 to 200 ° C, preferably 50 to 150 ° C and particularly preferably 80 to 120 ° C.
  • the polymerization can be carried out under atmospheric pressure, but is preferably carried out in a closed system under the self-developing pressure.
  • the monomers (a), (b) and (c) can be used as such, but it is also possible to use reaction mixtures which are used in the preparation, e.g. of the monomers (b) or (c).
  • reaction mixtures which are used in the preparation e.g. of the monomers (b) or (c).
  • the monomers (b) or (c) 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. It is also e.g.
  • the aqueous solutions obtained in the preparation of the copolymers containing sulfonic acid groups to be used according to the invention can be neutralized or partially neutralized by adding base, in particular sodium hydroxide solution, i.e. adjusted to a pH in the range of about 4-8, preferably 4.5-7.5.
  • copolymers containing sulfonic acid groups used according to the invention are outstandingly suitable as additives for detergents and cleaning agents.
  • the copolymers used according to the invention thereby also increase the cleaning power of the dishwashing detergent. In addition, they promote the drainage of the water from the wash items even in low concentrations, so that the proportion of rinse aid surfactants in the dishwashing detergent can be reduced.
  • copolymers containing sulfonic acid groups are used, in particular also when the dishwasher is operated without water regeneration salt for water softening.
  • the copolymers containing sulfonic acid groups can therefore be used advantageously not only in 2inl cleaners but also in 3inl cleaners.
  • copolymers used according to the invention can be used directly in the form of the aqueous solutions obtained in the preparation and also in dried, e.g. form obtained by spray drying, fluidized spray drying, roller drying or freeze drying. Accordingly, the detergents and cleaning agents according to the invention can be in solid or liquid form, e.g. be provided as powders, granules, extrudates, tablets, liquids or gels.
  • MPEGMA methoxypolyethylene glycol methacrylate
  • SEMA 2-sulfoethyl methacrylic acid sodium salt
  • Dishwasher Miele G 686 SC rinses: 2 rinses 55 ° C normal (without pre-rinsing) dishes: knives (WMF table knife Berlin, monoblock) and barrel-shaped glass beakers (Matador, Ruhr Kristall)
  • Dishwashing liquid 21 g copolymer: 4.2 g
  • Rinse aid temperature 65 ° C
  • Water hardness 25 ° dH
  • the items to be washed were assessed 18 hours after cleaning by visual inspection in a black-painted light box with a halogen spot and pinhole using a grading scale from 10 (very good) to 1 (very bad).
  • the highest grade 10 corresponds to surfaces free of deposits and drips, from scores ⁇ 5 deposits and drops are already recognizable with normal room lighting, so they are perceived as disturbing.

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  • Chemical & Material Sciences (AREA)
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  • 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)
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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

Verwendung von sulfonsauregruppenhaltigen Copolymeren als Zusatz in Wasch- und ReinigungsmittelnUse of copolymers containing sulfonic acid groups as additives in detergents and cleaning agents
Beschreibungdescription
Die vorliegende Erfindung betrifft die Verwendung von sulfonsauregruppenhaltigen Copolymeren, dieThe present invention relates to the use of copolymers containing sulfonic acid groups which
(a) 30 bis 95 mol-% mindestens einer monoethylenisch ungesättigten Carbonsäure, eines monoethylenisch ungesättigten Carbonsäureesters oder eines wasserlöslichen Salzes einer monoethylenisch ungesättigten Carbonsäure,(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,
(b) 3 bis 35 mol-% mindestens eines sulfonsauregruppenhaltigen Monomers der Formel I(b) 3 to 35 mol% of at least one monomer of the formula I containing sulfonic acid groups
RR
I τ H2C= C—X S03MI τ H 2 C = C-X S0 3 M
in der die Variablen folgende Bedeutung haben:in which the variables have the following meaning:
R Wasserstoff oder Methyl; ' X eine chemische Bindung oder -C00-R1- ;R is hydrogen or methyl; ' X is a chemical bond or -C00-R 1 -;
R1 unverzweigtes oder verzweigtes Cι~C -Alkylen;R 1 unbranched or branched C ~ C alkylene;
M Wasserstoff, Alkalimetall oder Ammonium,M hydrogen, alkali metal or ammonium,
undand
(c) 2 bis 35 mol-% mindestens eines nichtionischen Monomers der Formel II(c) 2 to 35 mol% of at least one nonionic monomer of the formula II
R2R2
I III II
H2C=C—COO R3- R4 — 0- R5H 2 C = C-COO R 3 - R 4 - 0- R5
in der die Variablen folgende Bedeutung haben:in which the variables have the following meaning:
R2 Wasserstoff oder Methyl;R 2 is hydrogen or methyl;
R3 eine chemische Bindung oder unverzweigtes oder verzweigtes Ci-Cδ-Alkylen; R4 gleiche oder verschiedene unverzweigte oder verzweigte C -C -Alkylenreste; R5 unverzweigtes oder verzweigtes Ci-Cδ-Alkyl, Cs-Cs-Cyclo- alkyl oder Aryl ; n 3 bis 50 ,R 3 is a chemical bond or unbranched or branched Ci-C δ alkylene; R 4 are identical or different unbranched or branched C -C alkylene radicals; R 5 unbranched or branched Ci-C δ alkyl, Cs-Cs-cycloalkyl or aryl; n 3 to 50,
statistisch oder blockweise einpolymerisiert enthalten, als Zusatz zu Wasch- und Reinigungsmitteln.copolymerized randomly or in blocks, as an additive to detergents and cleaning agents.
Außerdem betrifft die Erfindung Wasch- und Reinigungsmittel, welche diese Copolymere als belagsinhibierenden Zusatz enthalten.In addition, the invention relates to detergents and cleaning agents 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 automatic dishwashing, the dishes should be cleaned in a residue-free state with an immaculately shiny surface, for which a cleaner, rinse aid and regeneration salt usually have to be used to soften the water.
Die im Markt eingeführten sogenannten "2inl"-Geschirreiniger ent- halten 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 "2inl" dishwashing detergents introduced on the market contain, in addition to the detergent for removing the soiling on the wash ware, integrated rinse aid surfactants, which ensure that water runs off the wash ware 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, "3inl"-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 dishwashers, "3inl" cleaners, are to combine the three functions of cleaning, rinsing and water softening in a single detergent formulation, so that the refill of salt with water hardness levels of 1 to 3 is also superfluous for the consumer. Sodium tripolyphosphate is usually added to these cleaners to bind the hardness-forming calcium and magnesium ions. This in turn results in calcium and magnesium phosphate deposits on the wash ware.
In der WO-A-02/04583 werden maschinelle Geschirrspülmittel beschrieben, die Copolymere aus ungesättigten Carbonsäuren, sulfonsauregruppenhaltigen Monomeren und gegebenenf lls, vorzugsweise jedoch keinen, weiteren nichtionischen Monomeren auf Basis ethylenisch ungesättigter Verbindungen als Belagsinhibitoren enthalten. Weitere Angaben zu den nichtionischen Monomeren werden nicht gemacht.WO-A-02/04583 describes automatic dishwashing detergents which contain copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally, but preferably no, other nonionic monomers based on ethylenically unsaturated compounds as scale inhibitors. No further information is given on the nonionic monomers.
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 sowieEP-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 for (poly) phosphate deposits in automatic dishwashing detergents. Copolymers of acrylic acid and 2-acrylamido-2-propanesulfonic acid or sodium methallylsulfonate and also are disclosed in detail
Terpolymere, die zusätzlich tert . -Butylacrylamid einpolymerisiert enthalten. Nichtionische Monomere der Formel II werden nicht genannt.Terpolymers that additionally tert. -Polymerized butyl acrylamide contain. Non-ionic 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 sulfonatgruppen- haltige Struktureinheit der im einzelnen offenbarten Copolymere basiert auf Natrium-2-methyl-l, 3-butadien-l-sulfonat .According to JP-A-2000/7734, water-soluble copolymers which have structural units containing sulfonate groups, carboxylate groups and polyalkylene oxide groups and an average molecular weight M w of> 50,000 to 3,000,000 can be used as an agent against scale based in particular on silicates in water circuits, for example cooling systems , be used. The structural unit containing sulfonate groups of the copolymers disclosed in detail 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 sulfonsauregruppenhaltigen Monomeren und gegebenenfalls wasserlöslichen Alkylenoxideinheiten enthaltenden Monomeren und weiteren radikalisch polymerisierbaren Monomeren auf Poly- hydroxyverbindungen zur Inhibierung der Wasserhärte in Wasch- und Reinigungsmitteln eingesetzt. Im einzelnen beschrieben werden Pfropfcopolymerisate von Acrylsäure, Natriummethallylsulfonat und Methoxypolyethylenglykolmethacrylat auf Polyvinylalkohol , Tri- glycerin und Stärkedextrin.DE-A-43 43 993 uses graft copolymers of monoethylenically unsaturated carboxylic acids, monoethylenically unsaturated monomers containing sulfonic acid groups and optionally monomers containing water-soluble alkylene oxide units and other free-radically polymerizable monomers on polyhydroxy compounds to inhibit the water hardness in washing and cleaning agents. Graft copolymers of acrylic acid, sodium methallyl sulfonate 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, Sulfoal- kyl (meth) acrylaten und (Meth) Acrylsäure als wasserlösliches Dispergiermittel für kohlenstoffhaltige Feststoffe bekannt.Finally, EP-A-278 983 discloses the use of copolymers of polyalkylene glycol mono (meth) acrylates, sulfoalkyl (meth) acrylates and (meth) acrylic acid as a water-soluble dispersant for carbon-containing 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 object of the invention was to remedy the problems outlined above and to provide an additive which can also be used advantageously, in particular, in multifunctional cleaners and in particular has a deposit-inhibiting effect.
Demgemäß wurde die Verwendung von sulfonsauregruppenhaltigen Copolymeren, dieAccordingly, the use of copolymers containing sulfonic acid groups, the
(a) 30 bis 95 mol-% mindestens einer monoethylenisch ungesättigten Carbonsäure, eines monoethylenisch ungesättigten Carbon- säureesters oder eines wasserlöslichen Salzes einer monoethylenisch ungesättigten Carbonsäure,(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,
(b) 3 bis 35 mol-% mindestens eines sulfonsauregruppenhaltigen Monomers der Formel I R(b) 3 to 35 mol% of at least one monomer of the formula I containing sulfonic acid groups R
I τ I τ
H2C= C— X S03MH 2 C = C - X S0 3 M
in der die Variablen folgende Bedeutung haben:in which the variables have the following meaning:
R Wasserstoff oder Methyl;R is hydrogen or methyl;
X eine chemische Bindung oder -COO-R1-;X is a chemical bond or -COO-R 1 -;
R1 unverzweigtes oder verzweigtes Cι~C -Alkylen; M Wasserstoff, Alkalimetall oder Ammonium,R 1 unbranched or branched C ~ C alkylene; M hydrogen, alkali metal or ammonium,
undand
(c) 2 bis 35 mol-% mindestens eines nichtionischen Monomers der Formel II(c) 2 to 35 mol% of at least one nonionic monomer of the formula II
R2R2
IIII
H2C= C—C00 R3" R4 o- R5H 2 C = C-C00 R 3 "R4 o-R5
in der die Variablen folgende Bedeutung haben:in which the variables have the following meaning:
R2 Wasserstoff oder Methyl;R 2 is hydrogen or methyl;
R3 eine chemische Bindung oder unverzweigtes oder verzweig- tes Ci-Cδ-Alkylen;R 3 is a chemical bond or unbranched or branched Ci-C δ alkylene;
R4 gleiche oder verschiedene unverzweigte oder verzweigteR 4 same or different unbranched or branched
C -C -Alkylenreste; R5 unverzweigtes oder verzweigtes Ci-Cg-Alkyl, Cs-Cs-Cyclo- alkyl oder Aryl ; n 3 bis 50,C -C alkylene radicals; R 5 unbranched or branched Ci-Cg-alkyl, Cs-Cs-cycloalkyl or aryl; n 3 to 50,
statistisch oder blockweise einpolymerisiert enthalten, als Zusatz zu Wasch- und Reinigungsmitteln gefunden.copolymerized randomly or in blocks, found as an additive to detergents and cleaning agents.
Weiterhin wurden Wasch- und Reinigungsmittel gefunden, welche die sulfonsauregruppenhaltigen Copolymere als belagsinhibierenden Zusatz enthalten.Furthermore, detergents and cleaning agents have been found which contain the copolymers containing sulfonic acid groups as a coating-inhibiting additive.
Die sulfonsauregruppenhaltigen Copolymere enthalten als einpoly- merisierte Komponente (a) monoethylenisch ungesättigte Carbonsäuren, deren Ester und/oder wasserlösliche Salze, wobei die Carbonsäuren selbst oder ihre Salze als Komponente (a) bevorzugt sind. Geeignete Komponenten (a) sind beispielsweise α,ß-ungesättigte Monocarbonsäuren, die vorzugsweise 3 bis 6 Kohlenstoffatome aufweisen, wie Acrylsäure, Methacrylsäure, 2-Ethylpropensäure, Crotonsäure und Vinylessigsäure.The copolymers containing sulfonic acid groups contain, 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, 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 vinyl acetic acid.
Weiterhin geeignet sind z.B. ungesättigte Dicarbonsäuren, die vorzugsweise 4 bis 6 Kohlenstoffatome aufweisen, wie Itaconsäure und Maleinsäure.Also 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 Ci-Cδ-Alkoholen, vor allem Methanol, Ethanol und Butanol, wobei die Dicarbonsäuren als Mono- oder als Diester vorliegen können. Beispielhaft seien genannt: Methylacrylat, Methyl- methacrylat, Ethylacrylat, Ethylmethacrylat, Butylacrylat, Butyl- methacrylat, Monomethylmaleinat und Dimethylmaleinat .Particularly suitable as esters are the reaction products of these acids with C 1 -C 6 -alcohols, especially methanol, ethanol and butanol, it being possible for the dicarboxylic acids to be present as mono- or as diesters. Examples include: 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 vor- teilhaft auch zusammen in den Copolymeren enthalten sein können.Acrylic acid and methacrylic acid, which can advantageously also be contained together in the copolymers, are particularly preferred.
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 rrtol-%.The proportion of 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 15: 1 to 0.05: 1, in particular 10: 1 to 1: 1, especially 5: 1 to 1: 1.
Als einpolymerisierte Komponente (b) enthalten die Copolymere sulfonsäuregruppenhaltige Monomere der Formel IThe copolymers contain, as copolymerized component (b), monomers of the formula I containing sulfonic acid groups
R H2C= C—X S03M I RH 2 C = C-X S0 3 M I
in der die Variablen folgende Bedeutung haben:in which the variables have the following meaning:
R Wasserstoff oder bevorzugt Methyl; X eine chemische Bindung oder bevorzugt -COO-R1;R is hydrogen or preferably methyl; X is a chemical bond or preferably -COO-R 1 ;
R1 unverzweigtes oder verzweigtes Cχ-C -Alkylen, bevorzugt C2-C3-Alkylen; M Wasserstoff, Ammonium oder bevorzugt ein Alkalimetall.R 1 unbranched or branched Cχ-C alkylene, preferably C 2 -C 3 alkylene; M is hydrogen, ammonium or preferably an alkali metal.
Als besonders geeignete Beispiele für die Monomere I sind zu nennen: Vinylsulfonsäure, 2-Sulfoethyl (meth) acrylsäure, 2-Sulfo- 5 propyl (meth) acrylsäure, 3-Sulfopropyl (meth) acrylsäure undThe following are particularly suitable examples of the monomers I: vinylsulfonic acid, 2-sulfoethyl (meth) acrylic acid, 2-sulfo-5-propyl (meth) acrylic acid, 3-sulfopropyl (meth) acrylic acid and
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 10 bevorzugt sind.4-sulfobutyl (meth) acrylic acid and its salts, in particular the sodium salts, vinylsulfonic acid, 2-sulfoethyl methacrylic acid and 2-sulfopropyl methacrylic acid and their sodium salts being preferred, and 2-sulfoethyl methacrylic acid and its sodium salt being particularly preferred.
Der Anteil der sulfonsauregruppenhaltigen Monomere (b) an den erfindungsgemäß zu verwendenden Copolymeren beträgt 3 bis 35 mol-%, vorzugsweise 5 bis 25 mol-% und insbesondere 5 bis 15 20 mol-%.The proportion of the monomers (b) containing sulfonic acid groups 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 15 20 mol%.
Die Copolymere enthalten weiterhin als Komponente (c) nichtionische Monomere der Formel IIThe copolymers also contain, as component (c), nonionic monomers of the formula II
20 R2 20 R 2
H2C= C—COO R3" R4 — — o- II 0- R5H 2 C = C-COO R 3 "R 4 - - o- II 0- R5
in der die Variablen folgende Bedeutung haben:in which the variables have the following meaning:
2525
R2 Wasserstoff oder bevorzugt Methyl;R 2 is hydrogen or preferably methyl;
R3 unverzweigtes oder verzweigtes Ci-Cg-Alkylen oder bevorzugt eine chemische Bindung; R4 gleiche oder verschiedene unverzweigte oder verzweigte 30 C -C -Alkylenreste, vor allem C -C3-Alkylenreste, insbesondereR 3 unbranched or branched Ci-Cg-alkylene or preferably a chemical bond; R 4 identical or different unbranched or branched 30 C -C alkylene radicals, especially C -C 3 alkylene radicals, in particular
Ethylen; R5 Aryl, vor allem Phenyl oder Naphthyl, das jeweils durch Alkyl substituiert sein kann, Cs-Cs-Cycloalkyl , vor allem Cyclo- hexyl , oder bevorzugt unverzweigtes oder verzweigtes 35 Cι-C6-Alkyl, insbesondere Cι-C -Alkyl; n 3 bis 50, bevorzugt 5 bis 40, besonders bevorzugt 10 bis 30.ethylene; R 5 aryl, especially phenyl or naphthyl, which can in each case be substituted by alkyl, Cs-Cs-cycloalkyl, especially cyclohexyl, or preferably unbranched or branched C 1 -C 6 -alkyl, in particular C 1 -C 6 -alkyl; n 3 to 50, preferably 5 to 40, particularly preferably 10 to 30.
Als besonders geeignete Beispiele für die Monomere II seien genannt: Methoxypolyethylenglykol (meth) acrylat, Methoxypolypropy-The following may be mentioned as particularly suitable examples of the monomers II: methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene
40 lenglykol (meth) acrylat , Methoxypolybutylenglykol (meth) acrylat , Methoxypoly (propylenoxid-co-ethylenoxid) (meth) acrylat , Ethoxypo- lyethylenglykol (meth) acrylat, Ethoxypolypropylenglykol (meth) acrylat , Ethoxypolybutylenglykol (meth) acrylat , Ethoxypoly (propylenoxid-co-ethylenoxid) (meth) acrylat, Phenoxypolyethylengly-40 lenglycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate, ethoxypoly (propylene co-ethylene oxide) (meth) acrylate, phenoxypolyethylene glycol
45 kol (meth) acrylat, p-Nonylphenoxypolyethylenglykol (meth) acrylat, Naphthoxypolyethylenglykol (meth) acrylat , Phenoxypolypropylengly- kol (meth) acrylat, Naphthoxypolypropylenglykol (meth) acrylat, p-Me- thylphenoxypolyethylenglykol (meth) acrylat und Cyclohexoxypolye- thylenglykol (meth) acrylat, wobei Methoxypolyethylengly- kol (meth) acrylat und Methoxypolypropylenglykol (meth) acrylat bevorzugt sind und Methoxypolyethylenglykolmethacrylat besonders bevorzugt ist.45 kol (meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, naphthoxypolyethylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, naphthoxypolypropylene glycol (meth) acrylate, p-Me- thylphenoxypolyethylene glycol (meth) acrylate and cyclohexoxypolyethylene glycol (meth) acrylate, with methoxypolyethylene glycol (meth) acrylate and methoxypolypropylene glycol (meth) acrylate being preferred and methoxypolyethylene glycol methacrylate being 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 M„ 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 of from 3,000 to 40,000, preferably from 10,000 to 30,000 and particularly preferably from 15,000 to 25,000.
Der K-Wert der Copolymere liegt üblicherweise bei 15 bis 35, ins- besondere bei 20 bis 32, vor allem bei 27 bis 30 (gemessen in 1 gew.-%iger wäßriger Lösung bei 25°C, nach H. Fikentscher, Cellulo- se-Chemie, Bd. 13, S. 58-64 und 71-74 (1932)).The K value of the copolymers is usually 15 to 35, in particular 20 to 32, especially 27 to 30 (measured in 1% strength by weight aqueous solution at 25 ° C., according to H. Fikentscher, cellulose se-Chemie, 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 Lösungspoly- merisation bevorzugt ist.The copolymers to be used according to the invention can be produced by radical polymerization of the monomers. All known radical polymerization processes can be used. In addition to bulk polymerization, the methods of solution polymerization and emulsion polymerization should be mentioned in particular, with solution polymerization being preferred.
Die Polymerisation wird vorzugsweise in Wasser als Lösungsmittel durchgeführt. Sie kann jedoch auch in alkoholischen Lösungsmitteln, insbesondere Cι-C-Alkoholen, wie Methanol, Ethanol und Iso- propanol, 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 Radi- kale bildende Verbindungen.Compounds which decompose thermally and photochemically (photoinitiators) and thereby form radicals are suitable as polymerization initiators.
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 ge- eignete thermische Initiatoren sind anorganische Peroxoverbindun- gen, wie Peroxodisulfate (Ammonium- und vorzugsweise Natriumper- oxodisulfat) , Peroxosulfate, Percarbonate und Wasserstoffperoxid; organische Peroxoverbindungen, wie Diacetylperoxid, Di-tert.-bu- tylperoxid, Diamylperoxid, Dioctanoylperoxid, Didecanoylperoxid, Dilauroylperoxid, Dibenzoylperoxid, Bis (o-toloyl)peroxid, Succinylperoxid, tert .-Butylperacetat, tert .-Butylpermaleinat, tert .-Butylperisobutyrat, tert .-Butylperpivalat, tert . -Butylpe- roctoat, tert . -Butylperneodecanoat, tert .-Butylperbenzoat, tert.- Butylperoxid, tert . -Butylhydroperoxid, Cumolhydroperoxid, tert.- Butylperoxi-2-ethylhexanoat und Diisopropylperoxidicarbamat; Azo- verbindungen, wie 2 , 2 '-Azobisisobutyronitril, 2,2 '-Azo- bis (2-methylbutyronitril) und Azobis (2-amidopropan) dihydro- chlorid.Among the thermally activatable polymerization initiators, initiators with a decomposition temperature in the range from 20 to 180 ° C., in particular from 50 to 90 ° C., are preferred. Examples of suitable thermal initiators are inorganic peroxo compounds, such as peroxodisulfates (ammonium and preferably sodium peroxodisulfate), peroxosulfates, percarbonates and hydrogen peroxide; organic peroxo 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 peryl butyl butyl peracetate, tert. tert-butyl perpivalate, tert. -Butyl-perroctoate, tert. -Butyl perneodecanoate, tert-butyl perbenzoate, tert-butyl peroxide, tert. -Butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxy-2-ethylhexanoate and diisopropyl peroxidicarbamate; 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 phosphor- haltige Verbindungen, wie phosphorige Säure, Hypophosphite und Phosphinate, schwefelhaltige Verbindungen, wie Natriumhydrogensulfit, Natriumsulfit und Natriumformaldehydsulfoxilat, sowie Hy- drazin genannt.These initiators can be used in combination with reducing compounds as starter / controller systems. Examples of such reducing compounds include phosphorus-containing compounds, such as phosphorous acid, hypophosphites and phosphinates, sulfur-containing compounds, such as sodium bisulfite, sodium sulfite and sodium formaldehyde sulfoxilate, and hydrazine.
Beispiele für geeignete Photoinitiatoren sind Benzophenon, Aceto- phenon, Benzoinether, Benzyldialkylketone und deren Derivate.Examples of suitable photoinitiators are benzophenone, aceto-phenone, benzoin ether, benzyl dialkyl ketones and their derivatives.
Vorzugsweise werden thermische Initiatoren eingesetzt, wobei an- organische Peroxoverbindungen, insbesondere Natriumperoxodisulfat (Natriumpersulfat) , bevorzugt sind. Besonders vorteilhaft kommen die Peroxoverbindungen in Kombination mit schwefelhaltigen Reduktionsmitteln, insbesondere Natriumhydrogensulfit, als Redox- initiatorsystem zum Einsatz. Bei Verwendung dieses Starter/Reg- ler-Systems werden Copolymere erhalten, die als Endgruppen -S03 ~ Na+ und/oder -S0~ Na+ enthalten und sich durch besondere Reinigungskraft und belagsinhibierende Wirkung auszeichnen.Thermal initiators are preferably used, with inorganic peroxo compounds, in particular sodium peroxodisulfate (sodium persulfate) being preferred. The peroxo compounds are used particularly advantageously in combination with sulfur-containing reducing agents, in particular sodium bisulfite, as the redox initiator system. When this starter / controller system is used, copolymers are obtained which contain -S0 3 ~ Na + and / or -S0 ~ Na + as end groups and are notable for particular cleaning power and deposit-inhibiting action.
Alternativ können auch phosphorhaltige Starter/Regler-Systeme verwendet werden, z.B. Hypophosphite/Phosphinate .Alternatively, starter / regulator systems containing phosphorus can 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 quantities of photoinitiator and starter / regulator system must be matched to the substances used. If, for example, the preferred system peroxodisulfate / hydrogen sulfite is used, 2 to 6% by weight, preferably 3 to 5% by weight, peroxodisulfate and usually 5 to 30% by weight, preferably 5 to 10% by weight, are usually used. %, Hydrogen sulfite, based in each case on the monomers (a), (b) and (c).
Gewünschtenfalls können auch Polymerisationsregler zum Einsatz kommen. Geeignet sind die dem Fachmann bekannten Verbindungen, z.B. SchwefelVerbindungen, wie Mercaptoethanol , 2-Ethylhexylthio- glykolat, 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. The compounds known to the person skilled in the art are suitable, for example sulfur compounds, such as mercaptoethanol, 2-ethylhexylthio glycolate, thioglycolic acid and dodecyl mercaptan. If polymerization regulators are used, the amount used is generally 0.1 to 15% by weight, preferably 0.1 to 5% by weight and particularly preferably 0.1 to 2.5% by weight, 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 generally 30 to 200 ° C, preferably 50 to 150 ° C and particularly preferably 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 can be carried out under atmospheric pressure, but is preferably carried out in a closed system under the self-developing pressure.
Bei der Herstellung der erfindungsgemäß zu verwendendenIn the manufacture of those to be used according to the invention
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-Sulfoethyl- methacrylat das bei der Veresterung von 2-Hydroxyethansulfonsäure mit einem Überschuß Methacrylsäure anfallende Monomergemiseh verwendet werden. Außerdem kann anstelle von Methoxypolyethylen- glykolmethacrylat das bei der Veretherung von Methoxypolyethylen- glykol mit einem Überschuß Methacrylsäure anfallende Monomer- gemisch zum Einsatz kommen. Ebenso ist es z.B. möglich, 2-Sulfo- ethylmethacrylat und Methoxypolyethylenglykolmethacrylat durch gleichzeitige oder aufeinanderfolgende Veresterung von 2-Hydroxy- ethansulfonsäure und Methoxypolyethylenglykol mit einem Überschuß an Methacrylsäure herzustellen und das entstehende Monomergemiseh zur Polymerisation einzusetzen.Copolymers, the monomers (a), (b) and (c) can be used as such, but it is also possible to use reaction mixtures which are used in the preparation, e.g. of the monomers (b) or (c). 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. It is also e.g. possible to produce 2-sulfoethyl methacrylate and methoxypolyethylene glycol methacrylate by simultaneous or successive 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 sulfonsauregruppenhaltigen 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 copolymers containing sulfonic acid groups to be used according to the invention can be neutralized or partially neutralized by adding base, in particular sodium hydroxide solution, i.e. adjusted to a pH in the range of about 4-8, preferably 4.5-7.5.
Die erfindungsgemäß verwendeten sulfonsauregruppenhaltigen Copolymere eignen sich hervorragend als Zusatz zu Wasch- und Reinigungsmitteln.The copolymers containing sulfonic acid groups used according to the invention are outstandingly suitable as additives for detergents and cleaning agents.
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 hervorge- rufen werden, wie Beläge von Calcium- und Magnesiumphosphat, Calcium- und Magnesiumsilikat und Calcium- und Magnesiumphospho- nat, 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 sulfonsäure- gruppenhaltigen Copolymere werden dementsprechend besonders klare Gläser und hochglänzende Metallbesteckteile erhalten, insbesondere auch dann, wenn der Geschirrspüler ohne Regeneriersalz zur Wasserenthärtung betrieben wird. Die sulfonsauregruppenhaltigen Copolymere können daher nicht nur in 2inl-Reinigern, sondern auch in 3inl-Reinigern vorteilhaft eingesetzt werden.They can be used particularly advantageously in machine dishwashing detergents. They are characterized above all by their deposit-inhibiting effect on both inorganic and organic coverings. In particular, coverings that are caused by the other components of the detergent formulation are called, such as deposits of calcium and magnesium phosphate, calcium and magnesium silicate and calcium and magnesium phosphonate, and deposits that come from the dirt components of the washing liquor, such as fat, protein and starch deposits. The copolymers used according to the invention thereby also increase the cleaning power of the dishwashing detergent. In addition, they promote the drainage of the water from the wash items even in low concentrations, so that the proportion of rinse aid surfactants in the dishwashing detergent can be reduced. Accordingly, particularly clear glasses and high-gloss metal cutlery parts are obtained when the copolymers containing sulfonic acid groups are used, in particular also when the dishwasher is operated without water regeneration salt for water softening. The copolymers containing sulfonic acid groups can therefore be used advantageously not only in 2inl cleaners but also in 3inl 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 and also in dried, e.g. form obtained by spray drying, fluidized spray drying, roller drying or freeze drying. Accordingly, the detergents and cleaning agents according to the invention can be in solid or liquid form, e.g. be provided as powders, granules, extrudates, tablets, liquids or gels.
BeispieleExamples
A) Herstellung von sulfonsauregruppenhaltigen CopolymerenA) Preparation of copolymers containing sulfonic acid groups
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 given below were determined in 1% strength by weight aqueous solution at 25 ° C. according to H. Fikentscher, Cellulose-Chemie, Vol. 13, pp. 58-64 and 71-74 (1932).
Die in den Beispielen verwendeten Abkürzungen haben folgende Be- deutung:The abbreviations used in the examples have the following meaning:
AS : Acry1säureAS: Acrylic acid
MAS: MethacrylsäureMAS: methacrylic acid
MPEGMA : Methoxypolyethylenglykolmethacrylat SEMA: 2-Sulfoethylmethacrylsäure-NatriumsalzMPEGMA: methoxypolyethylene glycol methacrylate SEMA: 2-sulfoethyl methacrylic acid sodium salt
AMPS : 2-Acrylamido-2-methylpropansulfonsäureAMPS: 2-acrylamido-2-methylpropanesulfonic acid
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-Na- triumsalz (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 was fed with 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% by weight aqueous solution of methoxypolyethylene glycol methacrylate (M w = 1 086), 241.3 g of distilled water and 34.5 g of 2-sulfoethyl methacrylic acid Na - Trium salt (90 wt .-%) added continuously in 5 h. In parallel, a mixture of 16.5 g of sodium peroxodisulfate and 148.1 g of distilled water and 5.2 hours of 123.5 g of a 40% strength by weight aqueous sodium bisulfite solution were metered in continuously. After stirring for two hours at 100 ° C., the reaction mixture was cooled to room temperature and adjusted to a pH of 7.2 by adding 154.5 g of 50% strength by weight sodium hydroxide solution.
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 with 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 Methoxypolyethylenglykolmethacry- lat (Mw = 1 086), 116,7 g destilliertem Wasser und 58,6 g einer Mischung aus 85,5 Gew.-% Methacrylsäure und 14,5 Gew.-% 2-Sulfo- ethylmethacrylsäure-Natriumsalz kontinuierlich in 5 h zugegeben. Parallel dazu wurden in 5,25 h ein Gemisch aus 5,4 g Natriumper- oxodisulfat 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 from Example 1, a mixture of 300.0 g of distilled water and 1.09 g of phosphorous acid was heated to 100 ° C. internal temperature with the addition of nitrogen and stirring. 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 = 1 086), 116.7 g of distilled water and 58.6 g of a mixture was then made up of 85.5% by weight of methacrylic acid and 14.5% by weight of 2-sulfoethyl methacrylic acid sodium salt were added continuously in 5 h. At the same time, a mixture of 5.4 g of sodium peroxodisulfate and 94.6 g of distilled water and 5.2 g of 27 g of a 40% strength by weight aqueous sodium bisulfite solution were metered in continuously in 5.25 hours. After stirring for two hours at 100 ° C., the reaction mixture was cooled to room temperature and adjusted to a pH of 7.4 by adding 92 g of 50% strength by weight sodium hydroxide solution.
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 cloudy solution of the copolymer of the molar composition AS: MAS: SEMA: MPEGMA = 11: 3: 1: 1 with 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 de- stilliertem 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 5 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 10 Natronlauge auf einen pH-Wert von 7,2 eingestellt.A mixture of 505.1 g of distilled water and 1.18 g of phosphorous acid was introduced into the reactor from Example 1 with the addition of nitrogen and stirring, and the mixture was heated to an internal temperature of 100 ° C. without any further supply of nitrogen. Then a mixture was made 42.9 g of acrylic acid, 88.6 g of a 50% strength by weight aqueous solution of methoxypolyethylene glycol methacrylate (M w = 1 100), 197.9 g of distilled water, 17.6 g of 2-sulfoethyl methacrylic acid sodium salt and 47.0 g Methacrylic acid added continuously in 5 h. In parallel 5, a mixture of 5.9 g of sodium peroxodisulfate and 53.0 g of distilled water and in 5 h of 39.2 g of a 40% by weight sodium bisulfite solution were metered in continuously in 5.25 hours. After stirring for two hours at 100 ° C., the reaction mixture was cooled to room temperature and adjusted to a pH of 7.2 by adding 50% strength by weight sodium hydroxide solution.
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 15 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 15 30.1 received.
Vergleichsbeispiel VComparative Example V
In dem Reaktor aus Beispiel 1 wurde eine Mischung von 145,9 g de- 20 stilliertem 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-Acryl- amido-2-methylpropansulfonsäure und 402 g destilliertem Wasser kontinuierlich in 5 h zugegeben. Parallel dazu wurden in 5,25 h 25 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 30 einen pH-Wert von 7,2 eingestellt.In the reactor from 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 the addition of 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 over 5 hours. In parallel, a mixture of 12.0 g of sodium peroxodisulfate and 108.2 g of distilled water and 5.2 h of 45.1 g of an 11.3% by weight sodium bisulfite solution were metered in continuously in 5.25 h. After stirring for one hour at 100 ° C., the reaction mixture was cooled to room temperature and the pH was adjusted to 7.2 by adding 50% by weight sodium hydroxide solution.
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. 35A slightly yellowish, clear solution of the copolymer of the molar composition AS: AMPS = 1: 4 with a solids content of 30.5% by weight and a K value of 33.0 was obtained. 35
B) Anwendung von sulfonsauregruppenhaltigen Copolymeren in GeschirrspülmittelnB) Use of copolymers containing sulfonic acid groups in dishwashing detergents
Zur Prüfung ihrer belagsinhibierenden Wirkung wurden die 40 erhaltenen sulfonsauregruppenhaltigen Copolymere zusammen mit einer Geschirrspülmittelformulierung folgender Zusammensetzung eingesetzt :To test their deposit-inhibiting effect, the 40 copolymers obtained which contained sulfonic acid groups were used together with a dishwashing detergent formulation of the following composition:
50 Gew.-% Natriumtripolyphosphat (Na3P3Oιo • 6 H0)50% by weight sodium tripolyphosphate (Na 3 P 3 Oιo • 6 H0)
45 27 Gew.-% Natriumcarbonat45 27% by weight sodium carbonate
3 Gew.-% Natriumdisilikat (x Na20 • y Si02; x/y = 2,65; 80%ig)3% by weight sodium disilicate (x Na 2 0 • y Si0 2 ; x / y = 2.65; 80%)
6 Gew.-% Natriumpercarbonat (NaC03 • 1,5 H20 ) 2 Gew.-% Tetraacetylendiamin (TAED)6% by weight sodium percarbonate (NaC0 3 • 1.5 H 2 0) 2% by weight tetraacetylenediamine (TAED)
2 Gew.-% schaumarmes nichtionisches Tensid auf der Basis von2% by weight low-foaming nonionic surfactant based on
Fettalkoholalkoxylatenfatty alcohol
3 Gew.-% Natriumchlorid 5 Gew.-% Natriumsulfat3% by weight sodium chloride 5% by weight sodium sulfate
2 Gew.-% Polyacrylsäure-Natriumsalz (Mw 8 000)2% by weight of polyacrylic acid sodium salt (M w 8 000)
Die Prüfung erfolgte bei den folgenden Spülbedingungen ohne Zusatz von Ballastschmutz, wobei weder Klarspüler noch Regenerier- salz eingesetzt wurden:The test was carried out under the following rinsing conditions without the addition of ballast soiling, neither rinse aid nor regeneration salt being used:
Spülbedingungen :Rinsing conditions:
Geschirrspüler: Miele G 686 SC Spülgänge : 2 Spülgänge 55°C Normal (ohne Vorspülen) Spülgut : Messer (WMF Tafelmesser Berlin, Monoblock) und Faßformglasbecher (Matador, Ruhr Kristall)Dishwasher: Miele G 686 SC rinses: 2 rinses 55 ° C normal (without pre-rinsing) dishes: knives (WMF table knife Berlin, monoblock) and barrel-shaped glass beakers (Matador, Ruhr Kristall)
Geschirrspülmittel : 21 g Copolymer: 4,2 gDishwashing liquid: 21 g copolymer: 4.2 g
Klarspültemperatur : 65°C Wasserhärte: 25°dHRinse aid temperature: 65 ° C Water hardness: 25 ° 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 items to be washed were assessed 18 hours after cleaning by visual inspection in a black-painted light box with a halogen spot and pinhole using a grading scale from 10 (very good) to 1 (very bad). The highest grade 10 corresponds to surfaces free of deposits and drips, from scores <5 deposits and drops are already recognizable with normal room lighting, so they are perceived as disturbing.
Die erhaltenen Prüfergebnisse sind in der folgenden Tabelle zusammengestellt .The test results obtained are summarized in the following table.
Tabelletable

Claims

Patentansprüche claims
1. Verwendung von sulfonsauregruppenhaltigen Copolymeren, die1. Use of copolymers containing sulfonic acid groups, the
(a) 30 bis 95 mol-% mindestens einer monoethylenisch ungesättigten Carbonsäure, eines monoethylenisch ungesättigten Carbonsäureesters oder eines wasserlöslichen Salzes einer monoethylenisch ungesättigten Carbon- säure,(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,
(b) 3 bis 35 mol-% mindestens eines sulfonsauregruppenhaltigen Monomers der Formel I(b) 3 to 35 mol% of at least one monomer of the formula I containing sulfonic acid groups
R H2C= C—X S03M I RH 2 C = C-X S0 3 M I
in der die Variablen folgende Bedeutung haben:in which the variables have the following meaning:
R Wasserstoff oder Methyl;R is hydrogen or methyl;
X eine chemische Bindung oder -COO-R1-;X is a chemical bond or -COO-R 1 -;
R1 unverzweigtes oder verzweigtes Cι-C -Alkylen;R 1 unbranched or branched -CC alkylene;
M Wasserstoff, Alkalimetall oder Ammonium,M hydrogen, alkali metal or ammonium,
undand
(c) 2 bis 35 mol-% mindestens eines nichtionischen Monomers der Formel II(c) 2 to 35 mol% of at least one nonionic monomer of the formula II
R2 R 2
IIII
H2C= C—C00 R3- R4— 0- R5H 2 C = C-C00 R 3 - R 4 - 0- R5
in der die Variablen folgende Bedeutung haben:in which the variables have the following meaning:
R2 Wasserstoff oder Methyl;R 2 is hydrogen or methyl;
R3 eine chemische Bindung oder unverzweigtes oder verzweigtes Cι-C6-Alkylen; R4 gleiche oder verschiedene unverzweigte oder verzweigte C2-C-Alkylenreste; R5 unverzweigtes oder verzweigtes Ci-Cδ-Alkyl, Cs-Cs-Cyclo- alkyl oder Aryl ; n 3 bis 50, statistisch oder blockweise einpolymerisiert enthalten, als Zusatz zu Wasch- und Reinigungsmitteln.R 3 is a chemical bond or unbranched or branched -CC 6 alkylene; R 4 are identical or different unbranched or branched C 2 -C alkylene radicals; R 5 unbranched or branched Ci-C δ alkyl, Cs-Cs-cycloalkyl or aryl; n 3 to 50, copolymerized randomly or in blocks, as an additive to detergents and cleaning agents.
2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß die Copolymere 50 bis 90 mol-% der Komponente (a) , 5 bis 25 mol-% der Komponente (b) und 5 bis 25 mol-% der Komponente (c) einpolymerisiert enthalten.2. Use according to claim 1, characterized in that the copolymers contain 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. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die monoethylenisch ungesättigte Carbonsäure (a) Acrylsäure, Methacrylsäure und/oder Maleinsäure ist.3. Use according to claim 1 or 2, characterized in that the monoethylenically unsaturated carboxylic acid (a) is acrylic acid, methacrylic acid and / or maleic acid.
4. Verwendung nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß die monoethylenisch ungesättigte Carbonsäure (a) Acrylsäure oder eine Mischung von Acrylsäure und Methacrylsäure ist.4. Use according to claims 1 to 3, characterized in that the monoethylenically unsaturated carboxylic acid (a) is acrylic acid or a mixture of acrylic acid and methacrylic acid.
5. Verwendung nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß die Copolymere als Komponente (b) ein sulfonsäure- gruppenhaltiges Monomer der Formel I, in der R Methyl, X5. Use according to claims 1 to 4, characterized in that the copolymers as component (b) a sulfonic acid group-containing monomer of the formula I in which R is methyl, X
-C00-CH- und M Natrium oder Wasserstoff bedeuten, einpolymerisiert enthalten.-C00-CH- and M mean sodium or hydrogen, contained in copolymerized form.
6. Verwendung nach den Ansprüchen 1 bis 5, dadurch gekennzeich- net, daß die Copolymere als Komponente (c) ein nichtionisches6. Use according to claims 1 to 5, characterized in that the copolymers as component (c) is a nonionic
Monomer der Formel II, in der R2 Methyl, R3 eine chemische Bindung, R4 Ethylen, R5 Methyl und n 10 bis 30 bedeuten, einpolymerisiert enthalten.Monomer of the formula II, in which R 2 is methyl, R 3 is a chemical bond, R 4 is ethylene, R 5 is methyl and n is 10 to 30, copolymerized.
7. Verwendung nach den Ansprüchen 1 bis 6, dadurch gekennzeichnet, daß die Copolymere als Endgruppen -S03 ~ Na+ und/oder -S0~ Na+ enthalten.7. Use according to claims 1 to 6, characterized in that the copolymers contain -S0 3 ~ Na + and / or -S0 ~ Na + as end groups.
8. Verwendung nach den Ansprüchen 1 bis 7, dadurch gekennzeich- net, daß die Copolymere als belagsinhibierender Zusatz in maschinellen Geschirrspülmitteln eingesetzt werden.8. Use according to claims 1 to 7, characterized in that the copolymers are used as a deposit-inhibiting additive in automatic dishwashing detergents.
9. Wasch- und Reinigungsmittel, die Copolymere gemäß den Ansprüchen 1 bis 7 als belagsinhibierenden Zusatz enthalten. 9. washing and cleaning agents which contain copolymers according to claims 1 to 7 as a 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)

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DE10225794A1 (en) 2003-12-18
CN1297647C (en) 2007-01-31
US7645345B2 (en) 2010-01-12
JP2005533137A (en) 2005-11-04
DE50311809D1 (en) 2009-09-24
CA2488329A1 (en) 2003-12-18
US20080281053A1 (en) 2008-11-13
ATE439419T1 (en) 2009-08-15
CN1659265A (en) 2005-08-24
US20050202994A1 (en) 2005-09-15
ES2328683T3 (en) 2009-11-17
MXPA04011362A (en) 2005-02-14
CA2488329C (en) 2010-11-23
EP1516040B1 (en) 2009-08-12
WO2003104372A1 (en) 2003-12-18

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