EP1513916B1 - Use of copolymers containing alkylene oxide units, as an additive in dishwashing compositions - Google Patents

Use of copolymers containing alkylene oxide units, as an additive in dishwashing compositions Download PDF

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Publication number
EP1513916B1
EP1513916B1 EP03740181A EP03740181A EP1513916B1 EP 1513916 B1 EP1513916 B1 EP 1513916B1 EP 03740181 A EP03740181 A EP 03740181A EP 03740181 A EP03740181 A EP 03740181A EP 1513916 B1 EP1513916 B1 EP 1513916B1
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mol
copolymers
component
oxide units
alkylene
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German (de)
French (fr)
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EP1513916A1 (en
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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
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions

Definitions

  • the invention relates to automatic dishwashing compositions which contain these copolymers as a deposit-inhibiting additive.
  • the so-called "2inl" dishwashing detergents introduced on the market contain, in addition to the cleaner for removing stains on the items to be washed, integrated rinse aid surfactants which during the rinse and drying cycle ensure a flat flow of water on the items to be washed and thus prevent limescale and water stains. Refilling a rinse aid is no longer necessary when using these products.
  • Modern machine dishwashing detergents "3inl" 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.
  • EP-A-324 568 describes water-soluble copolymers for detergents and cleaners which are obtained by polymerization of acrylic acid, methacrylic acid and alkoxypolyethylene glycol methacrylates which have a long-chain alkoxy radical and / or a long-chain polyethylene glycol block in the presence of isopropanol.
  • the alkoxypolyethylene glycol methacrylate content of these copolymers is ⁇ 1 mol%.
  • copolymers based on at least one monomer from the group of maleic acid, acrylic acid and methacrylic acid and an optionally methoxy- or ethoxylated polyethylene glycol (meth) acrylate as further monomer having an average molecular weight M w of 1,000 up to 10 000, are used for the desizing, cleaning, bleaching and dyeing of natural and synthetic bevels.
  • copolymers of acrylic acid and methoxypolyethylene glycol methacrylate are examples of acrylic acid and methoxypolyethylene glycol methacrylate.
  • JP-A-2000/24691 describes copolymers of unsaturated carboxylic acids and monomers containing polyalkylene oxide units with average molecular weights M w of> 50,000 to 3,000,000 as agents against, in particular, silicates-based scale in water circulations, eg cooling systems.
  • M w average molecular weight of> 50,000 to 3,000,000
  • acrylic acid and methoxypolyethylene glycol methacrylate are disclosed.
  • 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.
  • the copolymers containing alkylene oxide units contain as copolymerized components (a) and (b) acrylic acid or methacrylic acid and / or water-soluble salts of these acids, in particular the alkali metal salts, such as potassium and especially sodium salts, and ammonium salts.
  • the proportion of acrylic acid (a) in the copolymers to be used according to the invention is 50 to 93 mol%, preferably 65 to 85 mol% and particularly preferably 65 to 75 mol%.
  • Methacrylic acid (b) is contained in the copolymers to be used according to the invention to 5 to 30 mol%, preferably to 10 to 25 mol% and especially to 15 to 25 mol%.
  • Particularly suitable examples of the monomers II are: methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (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 and Ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, with methoxypolyethylene glycol (meth) acrylate and Methoxypolypropylenglykol (meth) acrylate are preferred and Methoxypolyethylenglykolmethacrylat is particularly preferred.
  • the polyalkylene glycols contain 3 to 50, in particular 5 to 40 and especially 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 20 mol%, preferably 5 to 15 mol% and especially 5 to 10 mol%.
  • the copolymers to be used according to the invention generally have an average molecular weight M w of from 3,000 to 50,000, 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 40, in particular from 20 to 35, 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 preference is given to initiators having a decomposition temperature in the range from 20 to 180.degree. C., in particular from 50 to 90.degree.
  • 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,
  • 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 dodecyl mercaptan.
  • sulfur compounds such as mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid and dodecyl mercaptan.
  • polymerization regulators 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 it is also possible to use reaction mixtures which are obtained in the preparation of the monomers (c).
  • reaction mixtures which are obtained in the preparation of the monomers (c).
  • the monomer mixture obtained in the esterification of polyethylene glycol monomethyl ether with an excess of methacrylic acid can be used instead of methoxypolyethylene glycol methacrylate.
  • the esterification can also be carried out in situ in the polymerization mixture by (1) combining acrylic acid, (2) a mixture of methacrylic acid and polyethylene glycol monomethyl ether and (3) free radical initiator in parallel.
  • a catalyst necessary for the esterification such as methanesulfonic acid or p-toluenesulfonic acid, may additionally be used.
  • copolymers to be used according to the invention may also be obtained by polymer-analogous reaction, e.g. by reacting an acrylic acid / methacrylic acid copolymer with polyalkylene glycol monoalkyl ether.
  • polymer-analogous reaction e.g. by reacting an acrylic acid / methacrylic acid copolymer with polyalkylene glycol monoalkyl ether.
  • preferred is the radical copolymerization of the monomers.
  • the aqueous solutions obtained in the preparation of the carboxylic acid group-containing copolymers to be used according to the invention can be neutralized or partially neutralized by addition of base, in particular of sodium hydroxide solution, i. adjusted to a pH in the range of 4-8, preferably 4.5-7.5.
  • the copolymers used according to the invention are outstandingly suitable as an additive to automatic dishwasher detergents. They are characterized mainly by their deposit-inhibiting effect against both inorganic and organic coatings. In particular, coverings caused by the remaining constituents of the detergent formulation are such as toppings of calcium and magnesium phosphate, calcium and magnesium silicate and calcium and magnesium phosphonate, and linings derived from the soil 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.
  • the automatic dishwashing agents of the invention may accordingly be in solid or liquid form, e.g. as powders, granules, extrudates, tablets, liquids or gels.
  • reaction mixture was cooled to room temperature and adjusted by addition of 85 g of 50 wt .-% sodium hydroxide solution to a pH of 7.2.
  • 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.
  • table Copolymer from Ex. Rating (grade) knife glasses 1 8.0 7.7 2 6.2 7.5 - 4.0 4.0

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  • 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)
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Abstract

The use of copolymers containing alkylene oxide units and (mole%): (a) acrylic acid and/or one of its a water soluble (50-93), (b) methacrylic acid and/or one of its a water soluble salts (5-30), and (c) at least one nonionic monomer (2-20), statistically or block polymerized as washing and cleaning material additives is new. The use of copolymers containing alkylene oxide units and (mole%): (a) acrylic acid and/or one of its water soluble salts (50-93); (b) methacrylic acid and/or one of its a water soluble salts (5-30); and (c) at least one nonionic monomer (2-20) of formula (I). R1 = H or Me, R2 = chemical bond or optionally branched 1-6C alkylene, R3 = optionally branched 2-4C alkylene, R4 = optionally branched 1-6C alkyl, n = 3-50, statistically or block polymerized as washing and cleaning material additives. An Independent claim is also included for a washing and cleaning material containing the copolymer as a coating inhibiting additive.

Description

Die vorliegende Erfindung betrifft die Verwendung von Alkylenoxideinheiten enthaltenden Copolymeren, die

  • (a) 50 bis 93 mol-% Acrylsäure und/oder eines wasserlöslichen Salzes der Acrylsäure,
  • (b) 5 bis 30 mol-% Methacrylsäure und/oder eines wasserlöslichen Salzes der Methacrylsäure
    und
  • (c) 2 bis 20 mol-% mindestens eines nichtionischen Monomers der Formel I
    Figure imgb0001
     in der die Variablen folgende Bedeutung haben:
    R1
    Wasserstoff oder Methyl;
    R2
    eine chemische Bindung oder unverzweigtes oder verzweigtes C1-C6-Alkylen;
    R3
    gleiche oder verschiedene unverzweigte oder verzweigte C2-C4-Alkylenreste;
    R4
    unverzweigtes oder verzweigtes C1-C6-Alkyl;
    n
    3 bis 50,
statistisch oder blockweise einpolymerisiert enthalten, als Zusatz zu maschinellen Geschirrspülmitteln.The present invention relates to the use of copolymers containing alkylene oxide units, which
  • (a) from 50 to 93 mol% of acrylic acid and / or of a water-soluble salt of acrylic acid,
  • (B) 5 to 30 mol% of methacrylic acid and / or a water-soluble salt of methacrylic acid
    and
  • (c) 2 to 20 mol% of at least one nonionic monomer of the formula I.
    Figure imgb0001
     in which the variables have the following meaning:
    R 1
    Hydrogen or methyl;
    R 2
    a chemical bond or straight or branched C 1 -C 6 alkylene;
    R 3
    identical or different unbranched or branched C 2 -C 4 -alkylene radicals;
    R 4
    unbranched or branched C 1 -C 6 -alkyl;
    n
    3 to 50,
in copolymerized form, randomly or in blocks, as an additive to automatic dishwashing detergents.

Außerdem betrifft die Erfindung maschinelle Geschirrspülmittel, welche diese Copolymere als belagsinhibierenden Zusatz enthalten.In addition, the invention relates to automatic dishwashing compositions 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 "2inl"-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 "2inl" dishwashing detergents introduced on the market contain, in addition to the cleaner for removing stains on the items to be washed, integrated rinse aid surfactants which during the rinse and drying cycle ensure a flat flow of water on the items to be washed 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 dishwashing detergents, "3inl" 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 EP-A-324 568 werden wasserlösliche Copolymere für Wasch- und Reinigungsmittel beschrieben, die durch Polymerisation von Acrylsäure, Methacrylsäure und Alkoxypolyethylenglykolmethacrylaten, die einen langkettigen Alkoxyrest und/oder einen langkettigen Polyethylenglykolblock aufweisen, in Gegenwart von Isopropanol erhalten werden. Der Alkoxypolyethylenglykolmethacrylatanteil dieser Copolymere liegt bei < 1 mol-%.EP-A-324 568 describes water-soluble copolymers for detergents and cleaners which are obtained by polymerization of acrylic acid, methacrylic acid and alkoxypolyethylene glycol methacrylates which have a long-chain alkoxy radical and / or a long-chain polyethylene glycol block in the presence of isopropanol. The alkoxypolyethylene glycol methacrylate content of these copolymers is <1 mol%.

Nach der JP-A-1991/185184 können Copolymere auf der Basis mindestens eines Monomers aus der Gruppe Maleinsäure, Acrylsäure und Methacrylsäure und eines gegebenenfalls methoxy- oder ethoxylierten Polyethylenglykol(meth)acrylats als weiterem Monomer, die ein mittleres Molekulargewicht Mw von 1 000 bis 10 000 aufweisen, für das Entschlichten, Reinigen, Bleichen und Färben von natürlichen und synthetischen Fasen eingesetzt werden. Im einzelnen offenbart werden Copolymere von Acrylsäure und Methoxypolyethylenglykolmethacrylat.According to JP-A-1991/185184, copolymers based on at least one monomer from the group of maleic acid, acrylic acid and methacrylic acid and an optionally methoxy- or ethoxylated polyethylene glycol (meth) acrylate as further monomer having an average molecular weight M w of 1,000 up to 10 000, are used for the desizing, cleaning, bleaching and dyeing of natural and synthetic bevels. Specifically disclosed are copolymers of acrylic acid and methoxypolyethylene glycol methacrylate.

In der JP-A-2000/24691 werden Copolymere von ungesättigten Carbonsäuren und Polyalkylenoxideinheiten enthaltenden Monomeren mit mittleren Molekulargewichten Mw von > 50 000 bis 3 000 000 als Mittel gegen insbesondere auf Silikaten basierenden Kesselstein in Wasserkreisläufen, z.B. Kühlsystemen, beschrieben. Im einzelnen offenbart sind wiederum nur Copolymere von Acrylsäure und Methoxypolyethylenglykolmethacrylat.JP-A-2000/24691 describes copolymers of unsaturated carboxylic acids and monomers containing polyalkylene oxide units with average molecular weights M w of> 50,000 to 3,000,000 as agents against, in particular, silicates-based scale in water circulations, eg cooling systems. In detail In turn, only copolymers of acrylic acid and methoxypolyethylene glycol methacrylate are disclosed.

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 Alkylenoxideinheiten enthaltenden Copolymeren, die

  • (a) 50 bis 93 mol-% Acrylsäure und/oder eines wasserlöslichen Salzes der Acrylsäure,
  • (b) 5 bis 30 mol-% Methacrylsäure und/oder eines wasserlöslichen Salzes der Methacrylsäure
    und
  • (c) 2 bis 20 mol-% mindestens eines nichtionischen Monomers der Formel I
    Figure imgb0002
     in der die Variablen folgende Bedeutung haben:
    R1
    Wasserstoff oder Methyl;
    R2
    eine chemische Bindung oder unverzweigtes oder verzweigtes C1-C6-Alkylen;
    R3
    gleiche oder verschiedene unverzweigte oder verzweigte C2-C4-Alkylenreste;
    R4
    unverzweigtes oder verzweigtes C1-C6-Alkyl;
    n
    3 bis 50,
statistisch oder blockweise einpolymerisiert enthalten, als Zusatz zu maschinellen Geschirrspülmitteln gefunden.Accordingly, the use of copolymers containing alkylene oxide units, the
  • (a) from 50 to 93 mol% of acrylic acid and / or of a water-soluble salt of acrylic acid,
  • (B) 5 to 30 mol% of methacrylic acid and / or a water-soluble salt of methacrylic acid
    and
  • (c) 2 to 20 mol% of at least one nonionic monomer of the formula I.
    Figure imgb0002
     in which the variables have the following meaning:
    R 1
    Hydrogen or methyl;
    R 2
    a chemical bond or straight or branched C 1 -C 6 alkylene;
    R 3
    identical or different unbranched or branched C 2 -C 4 -alkylene radicals;
    R 4
    unbranched or branched C 1 -C 6 -alkyl;
    n
    3 to 50,
contained in copolymerized form, randomly or in blocks, as an additive to automatic dishwashing detergents.

Weiterhin wurden maschinelle Geschirrspülmittel gefunden, welche die Alkylenoxideinheiten enthaltenden Copolymere als belagsinhibierenden Zusatz enthalten.Furthermore, automatic dishwashing agents were found which contain the copolymers containing alkylene oxide units as a deposit-inhibiting additive.

Die Alkylenoxideinheiten enthaltenden Copolymere enthalten als einpolymerisierte Komponenten (a) und (b) Acrylsäure bzw. Methacrylsäure und/oder wasserlösliche Salze dieser Säuren, insbesondere die Alkalimetallsalze, wie Kalium- und vor allem Natriumsalze, und Ammoniumsalze.The copolymers containing alkylene oxide units contain as copolymerized components (a) and (b) acrylic acid or methacrylic acid and / or water-soluble salts of these acids, in particular the alkali metal salts, such as potassium and especially sodium salts, and ammonium salts.

Der Anteil Acrylsäure (a) an den erfindungsgemäß zu verwendenden Copolymeren beträgt 50 bis 93 mol-%, bevorzugt 65 bis 85 mol-% und besonders bevorzugt 65 bis 75 mol-%.The proportion of acrylic acid (a) in the copolymers to be used according to the invention is 50 to 93 mol%, preferably 65 to 85 mol% and particularly preferably 65 to 75 mol%.

Methacrylsäure (b) ist in den erfindungsgemäß zu verwendenden Copolymeren zu 5 bis 30 mol-%, vorzugsweise zu 10 bis 25 mol-% und vor allem zu 15 bis 25 mol-% enthalten.Methacrylic acid (b) is contained in the copolymers to be used according to the invention to 5 to 30 mol%, preferably to 10 to 25 mol% and especially to 15 to 25 mol%.

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

Figure imgb0003
in der die Variablen folgende Bedeutung haben:

R1
Wasserstoff oder bevorzugt Methyl;
R2
unverzweigtes oder verzweigtes C1-C6-Alkylen oder bevorzugt eine chemische Bindung;
R3
gleiche oder verschiedene unverzweigte oder verzweigte C2-C4-Alkylenreste, vor allem C2-C3-Alkylenreste, insbesondere Ethylen;
R4
unverzweigtes oder verzweigtes C1-C6-Alkyl, bevorzugt C1-C2-Alkyl;
n
3 bis 50, bevorzugt 5 bis 40, besonders bevorzugt 10 bis 30.
The copolymers contain as component (c) nonionic monomers of the formula I.
Figure imgb0003
 in which the variables have the following meaning:
R 1
Hydrogen or preferably methyl;
R 2
unbranched or branched C 1 -C 6 -alkylene or preferably a chemical bond;
R 3
identical or different unbranched or branched C 2 -C 4 -alkylene radicals, especially C 2 -C 3 -alkylene radicals, in particular ethylene;
R 4
unbranched or branched C 1 -C 6 -alkyl, preferably 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 seien genannt: Methoxypolyethylenglykol(meth)acrylat, Methoxypolypropylenglykol(meth)acrylat, Methoxypolybutylenglykol(meth)acrylat, Methoxypoly(propylenoxid-co-ethylenoxid)(meth)acrylat, Ethoxypolyethylenglykol(meth)acrylat, Ethoxypolypropylenglykol(meth)acrylat, Ethoxypolybutylenglykol(meth)acrylat und 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 are: methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (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 and Ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, with methoxypolyethylene glycol (meth) acrylate and Methoxypolypropylenglykol (meth) acrylate are preferred and Methoxypolyethylenglykolmethacrylat is particularly preferred.

Die Polyalkylenglykole enthalten dabei 3 bis 50, insbesondere 5 bis 40 und vor allem 10 bis 30 Alkylenoxideinheiten.The polyalkylene glycols contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units.

Der Anteil der nichtionischen Monomere (c) an den erfindungsgemäß zu verwendenden Copolymeren beträgt 2 bis 20 mol-%, vorzugsweise 5 bis 15 mol-% und vor allem 5 bis 10 mol-%.The proportion of nonionic monomers (c) in the copolymers to be used according to the invention is 2 to 20 mol%, preferably 5 to 15 mol% and especially 5 to 10 mol%.

Die erfindungsgemäß zu verwendenden Copolymere haben in der Regel ein mittleres Molekulargewicht Mw von 3 000 bis 50 000, 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 50,000, 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 40, insbesondere bei 20 bis 35, 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 40, in particular from 20 to 35, 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 Natriumperoxoxdisulfat), 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, preference is given to initiators having a decomposition temperature in the range from 20 to 180.degree. C., in particular from 50 to 90.degree. 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 perneodecanoate, 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 dodecyl mercaptan. When polymerization regulator 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 der Monomere (c) anfallen. So kann beispielsweise anstelle von Methoxypolyethylenglykolmethacrylat das bei der Veresterung von Polyethylenglykolmonomethylether mit einem Überschuß Methacrylsäure anfallende Monomergemisch verwendet werden. Vorteilhaft kann die Veresterung auch in situ im Polymerisationsgemisch durchgeführt werden, indem (1) Acrylsäure, (2) ein Gemisch von Methacrylsäure und Polyethylenglykolmonomethylether und (3) Radikalstarter parallel zusammengegeben werden. Gegebenenfalls kann dabei ein für die Veresterung notwendiger Katalysator, wie Methansulfonsäure oder p-Toluolsulfonsäure, zusätzlich eingesetzt werden.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 it is also possible to use reaction mixtures which are obtained in the preparation of the monomers (c). For example, instead of methoxypolyethylene glycol methacrylate, the monomer mixture obtained in the esterification of polyethylene glycol monomethyl ether with an excess of methacrylic acid can be used. Advantageously, the esterification can also be carried out in situ in the polymerization mixture by (1) combining acrylic acid, (2) a mixture of methacrylic acid and polyethylene glycol monomethyl ether and (3) free radical initiator in parallel. If appropriate, a catalyst necessary for the esterification, such as methanesulfonic acid or p-toluenesulfonic acid, may additionally be used.

Die erfindungsgemäß zu verwendenden Copolymere können auch durch polymeranaloge Reaktion, z.B. durch Umsetzung eines Acrylsäure/Methacrylsäure-Copolymers mit Polyalkylenglykolmonoalkylether, hergestellt werden. Bevorzugt ist jedoch die radikalische Copolymerisation der Monomere.The copolymers to be used according to the invention may also be obtained by polymer-analogous reaction, e.g. by reacting an acrylic acid / methacrylic acid copolymer with polyalkylene glycol monoalkyl ether. However, preferred is the radical copolymerization of the monomers.

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

Die erfindungsgemäß verwendeten Copolymere eignen sich hervorragend als Zusatz zu maschinellen Geschirrspülmitteln. 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.The copolymers used according to the invention are outstandingly suitable as an additive to automatic dishwasher detergents. They are characterized mainly by their deposit-inhibiting effect against both inorganic and organic coatings. In particular, coverings caused by the remaining constituents of the detergent formulation are such as toppings of calcium and magnesium phosphate, calcium and magnesium silicate and calcium and magnesium phosphonate, and linings derived from the soil 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 maschinellen Geschirrspülmittel 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. The automatic dishwashing agents of the invention may accordingly be in solid or liquid form, e.g. as powders, granules, extrudates, tablets, liquids or gels.

BeispieleExamples A) Herstellung von Alkylenoxideinheiten enthaltenden CopolymerenA) Preparation of copolymers containing alkylene oxide units Beispiel 1example 1

In einem Reaktor mit Stickstoffzuführung, Rückflußkühler und Dosiervorrichtung wurde eine Mischung von 619 g destilliertem Wasser und 2,2 g phosphoriger Säure unter Stickstoffzufuhr und Rühren auf 100°C Innentemperatur erhitzt. Dann wurden parallel (1) ein Gemisch aus 123,3 g Acrylsäure und 368,5 g destilliertem Wasser, (2) eine Mischung von 18,4 g Natriumperoxodisulfat und 164,6 g destilliertem Wasser, (3) eine Mischung aus 72,0 g Wasser, 49,1 g Methacrylsäure und 166,9 g Methoxypolyethylenglykolmethacrylat (Mw = 1 100) und (4) 46 g einer 40 gew.-%igen wäßrigen Natriumhydrogensulfitlösung kontinuierlich in 5 h zugegeben. Nach zweistündigem Nachrühren bei 100°C wurde das Reaktionsgemisch auf Raumtemperatur abgekühlt und durch Zugabe von 190 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 619 g of distilled water and 2.2 g of phosphorous acid was heated to 100 ° C internal temperature with nitrogen and stirring. Then, in parallel were (1) a mixture of 123.3 g of acrylic acid and 368.5 g of distilled water, (2) a mixture of 18.4 g of sodium peroxodisulfate and 164.6 g of distilled water, (3) a mixture of 72.0 g of water, 49.1 g of methacrylic acid and 166.9 g of methoxypolyethylene glycol methacrylate (M w = 1 100) and (4) 46 g of a 40 wt .-% aqueous sodium hydrogen sulfite continuously added in 5 h. After two hours of stirring at 100 ° C, the reaction mixture was cooled to room temperature and adjusted by the addition of 190 g of 50 wt .-% sodium hydroxide solution to a pH of 7.2.

Es wurde eine leicht gelbliche, klare Lösung eines Copolymers mit einem Feststoffgehalt von 25,7 Gew.-% und einem K-Wert von 27,2 (1 gew.-%ige wäßrige Lösung, 25°C) erhalten.There was obtained a slightly yellowish, clear solution of a copolymer having a solids content of 25.7 wt .-% and a K value of 27.2 (1 wt .-% aqueous solution, 25 ° C).

Beispiel 2Example 2

In dem Reaktor aus Beispiel 1 wurde eine Mischung von 221,6 g destilliertem Wasser und 1,1 g phosphoriger Säure unter Stickstoffzufuhr und Rühren auf 100°C Innentemperatur erhitzt. Dann wurden parallel (1) ein Gemisch aus 38,6 g Acrylsäure und 231,0 g destilliertem Wasser, (2) eine Mischung aus 29,6 g Toluol, 27,7 g Methacrylsäure und 116,6 g Methoxypolyethylenglykolmethacrylat (Mw = 1 100) und (3) 68,6 g einer 40 gew.-%igen wäßrigen Natriumhydrogensulfitlösung kontinuierlich in 5 h zugegeben. Parallel dazu wurde in 5,25 h ein Gemisch aus 9,1 g Natriumperoxodisulfat und 82,3 g destilliertem Wasser gegeben. Parallel zu diesen Zuläufen wurde kontinuierlich ein Gemisch von Wasser und Toluol abdestilliert, das Wasser wurde zur Reaktion zurückgeführt (Auskreisen des Toluols).In the reactor of Example 1, a mixture of 221.6 g of distilled water and 1.1 g of phosphorous acid was heated with nitrogen and stirring to 100 ° C internal temperature. Then, in parallel, (1) a mixture of 38.6 g of acrylic acid and 231.0 g of distilled water, (2) a mixture of 29.6 g of toluene, 27.7 g of methacrylic acid and 116.6 g of methoxypolyethylene glycol methacrylate (M w = 1 100) and (3) 68.6 g of a 40 wt .-% aqueous sodium bisulfite solution continuously added in 5 h. In parallel, a mixture of 9.1 g of sodium peroxodisulfate and 82.3 g of distilled water was added in 5.25 hours. In parallel to these feeds, a mixture of water and toluene was distilled off continuously, the water was returned to the reaction (removal of the toluene).

Nach einstündigem Nachrühren bei 100°C wurde das Reaktionsgemisch auf Raumtemperatur abgekühlt und durch Zugabe von 85 g 50 gew.-%iger Natronlauge auf einen pH-Wert von 7,2 eingestellt.After stirring for one hour at 100 ° C, the reaction mixture was cooled to room temperature and adjusted by addition of 85 g of 50 wt .-% sodium hydroxide solution to a pH of 7.2.

Es wurde eine klare Polymerlösung mit einem Feststoffgehalt von 28,8 Gew.-% und einem K-Wert von 28,9 (1 gew.-%ige wäßrige Lösung, 25°C) erhalten.There was obtained a clear polymer solution having a solids content of 28.8 wt .-% and a K value of 28.9 (1 wt .-% aqueous solution, 25 ° C).

B) Anwendung von Alkylenoxideinheiten enthaltenden Copolymeren in GeschirrspülmittelnB) Use of copolymers containing alkylene oxide units in dishwashing detergents

Zur Prüfung ihrer belagsinhibierenden Wirkung wurden die erhaltenen 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) 6 Gew.-% 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 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%) 6% by weight 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 alkoxylates 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: Spülbedingungen: Geschirrspüler: Miele G 686 SC Spülgänge: 2 Spülgänge 55°C Normal (ohne Vorspülen) Spülgut: Messer (WMF Tafelmesser Berlin, Monoblock) und Faßformglasbecher (Matador, Ruhr Kristall) Geschirrspülmittel: 21 g Copolymer: 4,2 g Klarspültemperatur: 65°C Wasserhärte: 25°dH 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: flushing: 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 Kristall) Dishwashing liquid: 21 g copolymer: 4.2 g Rinse 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 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 8,0 7,7 2 6,2 7,5 - 4,0 4,0 The test results obtained are summarized in the following table. table Copolymer from Ex. Rating (grade) knife glasses 1 8.0 7.7 2 6.2 7.5 - 4.0 4.0

Claims (8)

  1. The use of copolymers comprising alkylene oxide units which comprise
    (a) 50 to 93 mol% of acrylic acid and/or a water-soluble salt of acrylic acid,
    (b) 5 to 30 mol% of methacrylic acid and/or a water-soluble salt of methacrylic acid
    and
    (c) 2 to 20 mol% of at least one nonionic monomer of formula I
    Figure imgb0005
     in which the variables have the following meanings:
    R1 is hydrogen or methyl;
    R2 is a chemical bond or unbranched or branched C1-C6-alkylene;
    R3 are identical or different unbranched or branched C2-C4-alkylene radicals;
    R4 is unbranched or branched C1-C6-alkyl;
    n is 3 to 50,
    in random or block copolymerized form, as additive for machine dishwashing detergents.
  2. The use according to claim 1, wherein the copolymers comprise 65 to 85 mol% of component (a), 10 to 25 mol% of component (b) and 5 to 15 mol% of component (c) in copolymerized form.
  3. The use according to claim 1 or 2, wherein the copolymers comprise 65 to 75 mol% of component (a), 15 to 25 mol% of component (b) and 5 to 10 mol% of component (c) in copolymerized form.
  4. The use according to claims 1 to 3, wherein the copolymers comprise, as component (c), a nonionic monomer of the formula I in which R1 is methyl, R2 is a chemical bond, R3 is C2-C3-alkylene, R4 is C1-C2-alkyl and n is 5 to 40, in copolymerized form.
  5. The use according to claims 1 to 4, wherein the copolymers comprise, as component (c), a nonionic monomer of the formula I in which R1 is methyl, R2 is a chemical bond, R3 is ethylene, R4 is methyl and n is 10 to 30, in copolymerized form.
  6. The use according to claims 1 to 5, wherein the copolymers comprise -SO3 - Na+ and/or -SO4 - Na+ as end-groups.
  7. The use according to claims 1 to 6, wherein the copolymers are used as deposit-inhibiting additive in machine dishwashing detergents.
  8. A machine dishwashing detergent which comprises copolymers according to claims 1 to 7 as deposit-inhibiting additive.
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DE10350420A1 (en) * 2003-10-28 2005-06-02 Basf Ag Use of copolymers containing alkylene oxide units as deposit-inhibiting additives in the rinse cycle of the automatic dishwasher
DE102005028460A1 (en) * 2005-06-17 2006-12-28 Basf Ag Use of copolymers containing alkylene oxide units as an additive to aqueous systems
DE102005041347A1 (en) * 2005-08-31 2007-03-01 Basf Ag Phosphate-free cleaning formulation, useful in dishwasher, comprises copolymer, chelating agent, weakly foaming non-ionic surfactant, and other optional additives such as bleaching agent and enzymes
DE102005041349A1 (en) 2005-08-31 2007-03-01 Basf Ag Phosphate-free cleaning formulation, useful for dishwasher, comprises: copolymers from monoethylenic unsaturated monocarboxylic acids; complexing agent; nonionic surfactant, bleaching agent; builder; enzyme; and additives
DE102008028229A1 (en) * 2008-06-16 2009-12-17 Fit Gmbh Composition, useful for preparing detergents or in tablet mixture for preparing detergent-molded body for dishwasher, comprises particles comprising alkali metal salt of citric acid and surfactant on their surface layer
US8685911B2 (en) * 2009-11-30 2014-04-01 The Procter & Gamble Company Rinse aid compositions
JP5668936B2 (en) * 2011-09-06 2015-02-12 三浦工業株式会社 Quantitative method for total nitrogen
JPWO2020027310A1 (en) * 2018-08-03 2021-08-02 株式会社日本触媒 Polycarboxylic acid-based copolymer

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JP2901294B2 (en) * 1989-12-12 1999-06-07 日華化学株式会社 Detergency improver for textile products
JP2000024691A (en) * 1998-07-09 2000-01-25 Jsr Corp Water-soluble copolymer (salt) and scale inhibitor
US6998453B2 (en) * 2001-10-03 2006-02-14 Nippon Shokubai Co., Ltd. (Meth)acrylic acid type polymer and unsaturated polyalkylene glycol type copolymer, and methods for production thereof

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JP2005531653A (en) 2005-10-20
ATE342332T1 (en) 2006-11-15
CA2488032A1 (en) 2003-12-18
MXPA04011456A (en) 2005-02-14
DE50305365D1 (en) 2006-11-23
BR0311490A (en) 2005-03-15
DE10225594A1 (en) 2003-12-18
EP1513916A1 (en) 2005-03-16
CN1273577C (en) 2006-09-06
BR0311490B1 (en) 2013-04-09
US20050245427A1 (en) 2005-11-03
CN1659264A (en) 2005-08-24

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