EP1682645B1 - Use of copolymers, containing alkylene oxide units, as deposit inhibitor additives in rinsing compositions of a dishwasher - Google Patents

Use of copolymers, containing alkylene oxide units, as deposit inhibitor additives in rinsing compositions of a dishwasher Download PDF

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Publication number
EP1682645B1
EP1682645B1 EP04790785A EP04790785A EP1682645B1 EP 1682645 B1 EP1682645 B1 EP 1682645B1 EP 04790785 A EP04790785 A EP 04790785A EP 04790785 A EP04790785 A EP 04790785A EP 1682645 B1 EP1682645 B1 EP 1682645B1
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mol
copolymers
component
rinse
branched
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EP1682645A1 (en
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Marcus Guzmann
Heike Becker
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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
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets

Definitions

  • the invention relates to rinse aid for machine dishwashers containing these copolymers as a deposit-inhibiting additive, as well as detergent tablets for machine dishwashers, which contain the copolymers formulated as a deposit-inhibiting additive in the rinse aid core.
  • the items to be washed When machine dishwashing, the items to be washed in residue-free cleaned state with flawless glossy surface incurred.
  • the items to be washed should not only be completely cleaned of leftovers but should also have no whitish spots that arise due to the presence of lime or other inorganic and organic salts in the drying of water droplets.
  • rinse aid has been used for some time.
  • the rinse aid is discharged in the rinse after passing through the usually consisting of a pre-rinse cycle and an intermediate rinsing interrupted main wash cycle cleaning program automatically from a dosing tank in the interior of the dishwasher and ensures that the water flows during rinse and drying cycle area and as completely as possible from the dishes and the ware surfaces at the end of the washing program are residue-free and flawlessly shiny.
  • rinse-aid surfactants are already integrated into the detergent formulation, so that the additional metering of a rinse aid can be omitted.
  • Modern machine "3in1" cleaners combine the three functions of cleaning, rinsing and water softening in a single detergent formulation, so that the replenishment of salt at water hardness of 1 to 3 is unnecessary for the consumed.
  • sodium tripolyphosphate is usually added to this cleaner. This in turn, however, results in calcium and magnesium phosphate deposits on the items to be washed.
  • the object of the invention was to provide polymeric additives which are distinguished by their deposit-inhibiting action when used in the rinse cycle of the automatic dishwashing machine.
  • rinse aids for machine dishwashers were found containing these copolymers as a deposit-inhibiting additive.
  • detergent tablets for machine dishwashers were found which contain these copolymers formulated as a deposit-inhibiting additive in the rinse aid core.
  • copolymers to be used according to the invention are not previously published DE-A-102 25 594 ( WO 03/104373 ) described as an additive to detergents and cleaners.
  • the use in rinse aid for machine dishwashers is not described.
  • copolymers containing alkylene oxide units to be used according to the invention comprise 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 methoxypolypropylene glycol (meth) acrylate being preferred and methoxypolyethylene glycol methacrylate being 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, after 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.
  • inorganic peroxo compounds such as
  • 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 for example 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 known to those skilled in the art, e.g. Sulfur compounds such as mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid and dodecylmercaptan.
  • Sulfur compounds such as mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid and dodecylmercaptan.
  • their amount used is usually 0.1 to 15 wt .-%, preferably 0.1 to 5 wt .-% and particularly preferably 0.1 to 2.5 wt .-%, based on the monomers (a), (b) and (c).
  • the polymerization temperature is usually at 30 to 200 ° C, preferably at 50 to 150 ° C and particularly preferably at 80 to 120 ° C.
  • the polymerization may be carried out under atmospheric pressure, but is preferably carried out in the closed system under the evolving autogenous pressure.
  • the monomers (a), (b) and (c) can be used as such, but 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) 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 by adding base, in particular sodium hydroxide solution or partially neutralized, ie, adjusted to a pH in the range of 4-8, preferably 4.5-7.5.
  • copolymers used according to the invention are distinguished by their outstanding deposit-inhibiting action when used in the rinse cycle of the automatic dishwashing machine.
  • deposits which are caused by the carry-over effect in the rinse cycle abducted components of the cleaner formulation such as deposits of calcium and magnesium phosphate, calcium and magnesium silicate and calcium and magnesium phosphonate, and coatings consisting of the Dirt components of the rinse, such as fat, protein and starch coverings, called.
  • the copolymers to be used according to the invention improve the cleaning result by their coating-inhibiting effect.
  • 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 copolymer according to the invention was used together with a commercially available 3in1 dishwashing formulation in tablet form (Somat), the copolymer being added only in the final rinse cycle in order to simulate a delayed release of further copolymer.
  • Somat commercially available 3in1 dishwashing formulation in tablet form
  • test was in the following rinsing conditions with the addition of IKW Ballastschmutz (S ⁇ FW Journal, 124th year, 14/98, p 1029) in the main wash cycle and in addition made to the copolymer in the rinse cycle. In addition, neither regenerating salt nor rinse aid formulation were used.
  • Dishwasher Miele G 686 SC rinses: 1 rinse 55 ° C normal (without pre-rinse) ware: Knife (WMF table knife Berlin, monobloc); Glasses (Willy Becher, 0.3 l); black KS plates, black dessert plates; EMSA Superline - Box (cover PE blue, PP box transparent) Dishwashing liquid: Somat 3 in 1 Ballast soil: 50 g in the main rinse cycle; 2 g in the rinse cycle copolymer: 210 mg in the rinse cycle Rinse temperature: 65 ° C Water hardness: 21 ° dH
  • Table 1 Copolymer from Ex. Rating (grade) Knives, glasses, ceramic plates Plastic parts spotting Filming spotting 1 2.2 2.6 1.2 - 1.8 2.0 0.8
  • the copolymer was added directly to the rinse aid formulation. The test was carried out under the conditions given below with addition of IKW ballast dirt in main and final rinse cycles.
  • the copolymer was used in the following rinse aid formulation: 20% by weight Low-foaming nonionic surfactant based on fatty alcohol alkoxylates 10% by weight Sodium cumene sulphonate (40% by weight) 5% by weight isopropanol 4% by weight Copolymer (active substance) 61% by weight water
  • Dishwasher Miele G 686 SC rinses: 1 rinse 55 ° C normal (without pre-rinse) ware: Knife (WMF table knife Berlin, monobloc); Glasses (Willy Becher, 0.3 l); black KS plates, black dessert plates; EMSA Superline - Box (cover PE blue, PP box transparent) Dishwashing liquid: 21 g Ballast soil: 50 g in the main rinse cycle; 2 g in the rinse cycle Rinse temperature: 65 ° C Rinse-aid: 1 g Water hardness: 3 ° dH
  • the door was opened and the dishes were left to dry for 60 minutes with the machine door open.
  • the rating of the dishes followed by visual matching in a black painted light box with halogen spot and pinhole using the grading scale from 0 to 4 described above.

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Abstract

Use of copolymers comprising alkylene oxide units and comprising, in randomly or blockwise copolymerized form, (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 the formula I 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 is identical or different unbranched or branched C2-C4-alkylene radicals; R4 is unbranched or branched C1-C6-alkyl; n is 3 to 50, as deposit-inhibiting additives in the rinsing cycle of a dishwasher.

Description

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

  1. (a) 50 bis 93 mol-% Acrylsäure und/oder eines wasserlöslichen Salzes der Acrylsäure,
  2. (b) 5 bis 30 mol-% Methacrylsäure und/oder eines wasserlöslichen Salzes der Methacrylsäure
    und
  3. (c) 2 bis 20 mol-% mindestens eines nichtionischen Monomers der Formel 1
    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 belagsinhibierende Additive im Klarspülgang des maschinellen Geschirrspülers.The present invention relates to the use of copolymers containing alkylene oxide units, which
  1. (a) from 50 to 93 mol% of acrylic acid and / or of a water-soluble salt of acrylic acid,
  2. (B) 5 to 30 mol% of methacrylic acid and / or a water-soluble salt of methacrylic acid
    and
  3. (c) 2 to 20 mol% of at least one nonionic monomer of formula 1
    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 deposit-inhibiting additives in the rinse cycle of the automatic dishwashing machine.

Außerdem betrifft die Erfindung Klarspülmittel für maschinelle Geschirrspüler, welche diese Copolymere als belagsinhibierenden Zusatz enthalten, sowie Reinigertabletten für maschinelle Geschirrspüler, welche die Copolymere als belagsinhibierenden Zusatz in den Klarspülkern einformuliert enthalten.In addition, the invention relates to rinse aid for machine dishwashers containing these copolymers as a deposit-inhibiting additive, as well as detergent tablets for machine dishwashers, which contain the copolymers formulated as a deposit-inhibiting additive in the rinse aid core.

Bei der maschinellen Geschirrspülreinigung soll das Spülgut in rückstandsfrei gereinigtem Zustand mit makellos glänzender Oberfläche anfallen. Das Spülgut soll dabei nicht nur völlig von Speiseresten gereinigt sein sondern soll auch keine weißlichen Flecken aufweisen, die aufgrund der Anwesenheit von Kalk oder anderen anorganischen und organischen Salzen bei der Eintrocknung von Wassertropfen entstehen.When machine dishwashing, the items to be washed in residue-free cleaned state with flawless glossy surface incurred. The items to be washed should not only be completely cleaned of leftovers but should also have no whitish spots that arise due to the presence of lime or other inorganic and organic salts in the drying of water droplets.

Aus diesem Grund setzt man schon seit längerem Klarspüler ein. Der Klarspüler wird dabei im Klarspülgang nach Durchlaufen des üblicherweise aus einem Vorspülgang und einem von Zwischenspülgängen unterbrochenen Hauptspülgang bestehenden Reinigungsprogramms automatisch aus einem Dosiertank in den Innenraum der Geschirrspülmaschine abgegeben und sorgt dafür, daß das Wasser während Klarspül- und Trocknungsgang flächig und möglichst vollständig vom Spülgut abfließt und die Spülgutoberflächen am Ende des Spülprogramms rückstandsfrei und makellos glänzend sind.For this reason, rinse aid has been used for some time. The rinse aid is discharged in the rinse after passing through the usually consisting of a pre-rinse cycle and an intermediate rinsing interrupted main wash cycle cleaning program automatically from a dosing tank in the interior of the dishwasher and ensures that the water flows during rinse and drying cycle area and as completely as possible from the dishes and the ware surfaces at the end of the washing program are residue-free and flawlessly shiny.

Bei den im Markt eingeführten sogenannten "2in1 "-Reinigern sind Klarspültenside bereits in die Reinigerformulierung integriert, so daß das zusätzliche Dosieren eines Klarspülmittels unterbleiben kann.In the so-called "2in1" detergents introduced on the market, rinse-aid surfactants are already integrated into the detergent formulation, so that the additional metering of a rinse aid can be omitted.

Moderne maschinelle "3in1"-Reiniger vereinen die drei Funktionen des Reinigens, des Klarspülens und der Wasserenthärtung in einer einzigen Reinigerformulierung, so daß für den Verbrauchter auch das Nachfüllen von Salz bei Wasserhärten von 1 bis 3 überflüssig wird. Zur Bindung der härtebildenden Calcium- und Magnesiumionen wird diesen Reinigem üblicherweise Natriumtripolyphosphat zugesetzt. Hieraus resultieren aber wiederum Calcium- und Magnesiumphosphatbeläge auf dem Spülgut.Modern machine "3in1" cleaners combine the three functions of cleaning, rinsing and water softening in a single detergent formulation, so that the replenishment of salt at water hardness of 1 to 3 is unnecessary for the consumed. To bond the hardness-forming calcium and magnesium ions, sodium tripolyphosphate is usually added to this cleaner. This in turn, however, results in calcium and magnesium phosphate deposits on the items to be washed.

Der Erfindung lag die Aufgabe zugrunde, polymere Additive bereitzustellen, die sich bei der Anwendung im Klarspülgang des maschinellen Geschirrspülers durch ihre belagsinhibierende Wirkung auszeichnen.The object of the invention was to provide polymeric additives which are distinguished by their deposit-inhibiting action when used in the rinse cycle of the automatic dishwashing machine.

Demgemäß wurde die Verwendung von Alkylenoxideinheiten enthaltenden Copolymeren, die

  1. (a) 50 bis 93 mol% Acrylsäure und/oder eines wasserlöslichen Salzes der Acrylsäure,
  2. (b) 5 bis 30 mol-% Methacrylsäure und/oder eines wasserlöslichen Salzes der Methacrylsäure
    und
    Figure imgb0002
     in der die Variablen folgende Bedeutung haben:
    R1
    Wasserstoff oder Methyl;
    R2
    eine chemische Bindung oder unverzweigtes oder verzweigtes C1-C8-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 belagsinhibierende Additive im Klarspülgang des maschinellen Geschirrspülers gefunden.Accordingly, the use of copolymers containing alkylene oxide units, the
  1. (a) 50 to 93 mol% of acrylic acid and / or of a water-soluble salt of acrylic acid,
  2. (B) 5 to 30 mol% of methacrylic acid and / or a water-soluble salt of methacrylic acid
    and
    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 8 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 a random or blockwise copolymerized form, as deposit-inhibiting additives found in the final rinse cycle of the automatic dishwashing machine.

Außerdem wurden Klarspülmittel für maschinelle Geschirrspüler gefunden, die diese Copolymere als belagsinhibierenden Zusatz enthalten.In addition, rinse aids for machine dishwashers were found containing these copolymers as a deposit-inhibiting additive.

Weiterhin wurden Reinigertabletten für maschinelle Geschirrspüler gefunden, die diese Copolymere als belagsinhibierenden Zusatz in den Klarspülkern einformuliert enthalten.Furthermore, detergent tablets for machine dishwashers were found which contain these copolymers formulated as a deposit-inhibiting additive in the rinse aid core.

Die erfindungsgemäß zu verwendenden Copolymere werden in der nicht vorveröffentlichten DE-A-102 25 594 ( WO 03/104373 ) als Zusatz zu Wasch- und Reinigungsmitteln beschrieben. Der Einsatz in Klarspülmittel für maschinelle Geschirrspüler ist nicht beschrieben.The copolymers to be used according to the invention are not previously published DE-A-102 25 594 ( WO 03/104373 ) described as an additive to detergents and cleaners. The use in rinse aid for machine dishwashers is not described.

Die erfindungsgemäß zu verwendenden 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 to be used according to the invention comprise 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 methoxypolypropylene glycol (meth) acrylate being preferred and methoxypolyethylene glycol methacrylate being 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, after H. Fikentscher, Cellulose Chemistry, Vol. 13, pp. 58-64 and 71-74 (1932 )).

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

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

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

Unter den thermisch aktivierbaren Polymerisationsinitiatoren sind Initiatoren mit einer Zerfallstemperatur im Bereich von 20 bis 180°C, insbesondere von 50 bis 90°C, bevorzugt. Beispiele für geeignete thermische Initiatoren sind anorganische Peroxoverbindungen, wie Peroxodisulfate (Ammonium- und vorzugsweise Natriumperoxodisulfat), Peroxosulfate, Percarbonate und Wasserstoffperoxid; organische Peroxoverbindungen, wie Diacetylperoxid, Di-tert.-butylperoxid, Diamylperoxid, Dioctanoylperoxid, Didecanoylperoxid, Dilauroylperoxid, Dibenzoylperoxid, Bis(o-toloyl)peroxid, Succinylperoxid, tert.-Butylperacetat, tert.-Butylpermaleinat, tert.-Butylperisobutyrat, tert.-Butylperpivalat, tert.-Butylperoctoat, tert.-Butylperneodecanoat, tert.-Butylperbenzoat, tert.-Butylperoxid, tert.-Butylhydroperoxid, Cumolhydroperoxid, tert.-Butylperoxi-2-ethylhexanoat und Diisopropylperoxidicarbamat: Azoverbindungen, wie 2,2'-Azobisisobutyronitril, 2,2'-Azobis(2-methylbutyronitril) und Azobis(2-amidopropan)dihydrochlorid.Among the thermally activatable polymerization initiators, 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 perodecanoate, tert-butyl perbenzoate, tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxy-2-ethylhexanoate and diisopropyl peroxydicarbamate: azo compounds such as 2,2'-azobisisobutyronitrile , 2,2'-azobis (2-methylbutyronitrile) and azobis (2-amidopropane) dihydrochloride.

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

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

Vorzugsweise werden thermische Initiatoren eingesetzt, wobei anorganische Peroxoverbindungen, insbesondere Natriumperoxodisulfat (Natriumpersulfat), bevorzugt sind. Besonders vorteilhaft kommen die Peroxoverbindungen in Kombination mit schwefelhaltigen Reduktionsmitteln, insbesondere Natriumhydrogensulfit, als Redoxinitiatorsystem zum Einsatz. Bei Verwendung dieses Starter/Regler-Systems werden Copolymere erhalten, die als Endgruppen -SO3 - Na+ und/oder -SO4 Na+ enthalten und sich durch besondere 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 -SO4 Na + and are characterized by particular deposit-inhibiting effect.

Alternativ können auch phosphorhaltige Starter/Regler-Systeme verwendet werden, z.B. Hypophosphite/Phosphinate.Alternatively, it is also possible to use phosphorus-containing starter / regulator systems, for example 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 known to those skilled in the art, e.g. Sulfur compounds such as mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid and dodecylmercaptan. When polymerization regulators are used, their amount used is usually 0.1 to 15 wt .-%, preferably 0.1 to 5 wt .-% and particularly preferably 0.1 to 2.5 wt .-%, based on the monomers (a), (b) and (c).

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

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

Bei der Herstellung der erfindungsgemäß zu verwendenden Copolymere können die Monomere (a), (b) und (c) als solche eingesetzt werden, es können jedoch auch Reaktionsmischungen zum Einsatz kommen, die bei der Herstellung 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) 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 by adding base, in particular sodium hydroxide solution or partially neutralized, ie, adjusted to a pH in the range of 4-8, preferably 4.5-7.5.

Die erfindungsgemäß verwendeten Copolymere zeichnen sich durch ihre hervorragende belagsinhibierende Wirkung beim Einsatz im Klarspülgang des maschinellen Geschirrspülers aus.The copolymers used according to the invention are distinguished by their outstanding deposit-inhibiting action when used in the rinse cycle of the automatic dishwashing machine.

Sie wirken dabei sowohl gegenüber anorganischen als auch organischen Belägen inhibierend. Insbesondere seien Beläge, die von den durch den "Carry-Over-Effect" in den Klarspülgang verschleppten Bestandteilen 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 zu verwendenden Copolymere verbessern durch ihre belagsinhibierende Wirkung das Reinigungsergebnis nachhaltig. Zusätzlich begünstigen sie bereits in geringen Konzentrationen das Ablaufen des Wassers vom Spülgut, so daß der Anteil an Klarspültensiden im Geschirrspülmittel reduziert werden kann. Dementsprechend werden besonders klare Gläser und hochglänzende Metallbesteckteile erhalten, insbesondere auch dann, wenn der Geschirrspüler ohne Regeneriersalz zur Wasserenthärtung betrieben wird.They inhibit both inorganic and organic deposits. In particular, deposits which are caused by the carry-over effect in the rinse cycle abducted components of the cleaner formulation, such as deposits of calcium and magnesium phosphate, calcium and magnesium silicate and calcium and magnesium phosphonate, and coatings consisting of the Dirt components of the rinse, such as fat, protein and starch coverings, called. The copolymers to be used according to the invention improve the cleaning result by their coating-inhibiting effect. 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. Accordingly, particularly clear glasses and high-gloss metal cutlery are obtained, especially when the dishwasher is operated without Regeneriersalz for water softening.

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.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.

Die erfindungsgemäßen Copolymere können vorteilhaft insbesondere folgendermaßen zur Anwendung kommen:

  • Gelöst in einer Klarspülmittelformulierung, die in der Geschirrspülmaschine zu Beginn des Klarspülgangs automatisch dosiert wird.
  • Formuliert in den Klarspülkern einer Geschirrspülmitteltablette, aus dem sie gezielt im Klarspülgang freigesetzt werden.
  • Als nach einem der oben beschriebenen Verfahren erhaltener Feststoff, der zusätzlich mit einer unter den Klarspülbedingungen (Temperatur, pH-Wert, Restkonzentration an Reinigungsmittelkomponenten im Klarspülgang) löslichen Beschichtung versehen ist oder in eine unter diesen Bedingungen lösliche Matrix eingebaut ist, zusammen mit dem Reinigungsmittel in die Maschine eingebracht und erst im Klarspülgang freigesetzt wird.
    Als Beschichtungsmaterial eignet sich hierfür z.B. durch unvollständige Hydrolyse von Polyvinylacetat hergestellter Polyvinylalkohol (Hydrolysegrad von in der Regel 88 bis 98%, bevorzugt 89 bis 95%, besonders bevorzugt 91 bis 92%).
    Als Matrixmaterial sind beispielsweise Gelatine, Polyvinylalkohol, Polyvinylpyrrolidon, Polyethylenoxid, Cellulose und deren Derivate, Stärke und deren Derivate und Mischungen dieser Materialien geeignet.
The copolymers according to the invention can advantageously be used in particular as follows:
  • Dissolved in a rinse aid formulation that is automatically dispensed in the dishwasher at the beginning of the rinse cycle.
  • Formulated in the rinse-aid core of a dishwashing detergent tablet, from which they are released in a targeted manner in the rinse cycle.
  • A solid obtained according to one of the processes described above, which is additionally provided with a coating which is soluble under the rinse-off conditions (temperature, pH, residual concentration of detergent components in the final rinse cycle) or is incorporated into a matrix soluble under these conditions, together with the cleaning agent in the machine is introduced and released only in the rinse cycle.
    Suitable coating material for this purpose, for example by incomplete hydrolysis of polyvinyl acetate produced polyvinyl alcohol (degree of hydrolysis of usually 88 to 98%, preferably 89 to 95%, particularly preferably 91 to 92%).
    Gelatine, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, cellulose and their derivatives, starch and derivatives thereof and mixtures of these materials are suitable, for example, as the matrix material.

BeispieleExamples A) HerstellungA) Production 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 = 1100) 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 = 1100) 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).

B) Anwendung bei der maschinellen GeschirreinigungB) Use in machine dishwashing B1) Simulierung einer 3in 1-Geschirrspülformulierung mit zusätzlicher Copolymerfreisetzung im KlarspülgangB1) Simulation of a 3-in-1 dishwashing formulation with additional copolymer release in the final rinse cycle

Zur Prüfung seiner Klarspülwirkung wurde das erfindungsgemäße Copolymer zusammen mit einer handelsüblichen 3in1-Geschirrspülformulierung in Tablettenform (Somat) eingesetzt, wobei das Copolymer erst im Klarspülgang zugesetzt wurde, um eine verzögerte Freisetzung von weiterem Copolymer zu simulieren.To test its rinsing effect, the copolymer according to the invention was used together with a commercially available 3in1 dishwashing formulation in tablet form (Somat), the copolymer being added only in the final rinse cycle in order to simulate a delayed release of further copolymer.

Die Prüfung wurde bei den folgenden Spülbedingungen mit Zusatz von IKW-Ballastschmutz (SÖFW-Journal, 124. Jahrgang, 14/98, S. 1029) im Hauptspülgang und zusätzlich zum Copolymer im Klarspülgang vorgenommen. Zusätzlich wurden weder Regeneratsalz noch Klarspülformulierung eingesetzt.The test was in the following rinsing conditions with the addition of IKW Ballastschmutz (SÖFW Journal, 124th year, 14/98, p 1029) in the main wash cycle and in addition made to the copolymer in the rinse cycle. In addition, neither regenerating salt nor rinse aid formulation were used.

Spülbedingungen:flushing:

Geschirrspüler:Dishwasher: Miele G 686 SCMiele G 686 SC Spülgänge:rinses: 1 Spülgang 55°C Normal (ohne Vorspülen)1 rinse 55 ° C normal (without pre-rinse) Spülgut:ware: Messer (WMF Tafelmesser Berlin, Monoblock); Gläser (Willy Becher, 0.3 I); schwarze KS-Teller, schwarze Dessertteller; EMSA Superline - Box (Deckel PE blau, PP Dose transparent)Knife (WMF table knife Berlin, monobloc); Glasses (Willy Becher, 0.3 l); black KS plates, black dessert plates; EMSA Superline - Box (cover PE blue, PP box transparent) Geschirrspülmittel:Dishwashing liquid: Somat 3 in 1Somat 3 in 1 Ballastschmutz:Ballast soil: 50 g im Hauptspülgang; 2 g im Klarspülgang50 g in the main rinse cycle; 2 g in the rinse cycle Copolymer:copolymer: 210 mg im Klarspülgang210 mg in the rinse cycle Klarspültemperatur:Rinse temperature: 65°C65 ° C Wasserhärte:Water hardness: 21°dH21 ° dH

Nach Ende des Spülgangs wurde die Tür geöffnet und das Geschirr bei geöffneter Maschinentür 60 min trocknen gelassen. Die Bewertung des Spülguts erfolgte im Anschluß durch visuelle Abmusterung in einem schwarz lackierten Leuchtkasten mit Halogenspot und Lochblende unter Verwendung einer Notenskala von 0 (sehr schlecht, sehr starke Bildung von getrockneten Tropfen (Spotting), d.h. mehr als 50% der Oberfläche mit Spots belegt, sehr starke Bildung von flächigen Belägen (Filming)) bis 4 (sehr gut, keine Spots, kein Filming).At the end of the wash cycle, the door was opened and the dishes were left to dry for 60 minutes with the machine door open. The evaluation of the dishes followed by visual matching in a black painted light box with halogen spot and pinhole using a grading scale of 0 (very bad, very strong formation of dried drops (spotting), ie more than 50% of the surface occupied by spots, very strong formation of flat coverings (filming)) to 4 (very good, no spots, no filming).

Die erhaltenen Prüfergebnisse sind in Tabelle 1 zusammengestellt, wobei zum Vergleich die Ergebnisse ohne Zusatz von Copolymer aufgeführt sind. Tabelle 1 Copolymer aus Bsp. Bewertung (Note) Messer, Gläser, Keramikteller Kunststoffteile Spotting Filming Spotting 1 2,2 2,6 1,2 - 1,8 2,0 0,8 The test results obtained are summarized in Table 1, wherein for comparison the results are listed without the addition of copolymer. Table 1 Copolymer from Ex. Rating (grade) Knives, glasses, ceramic plates Plastic parts spotting Filming spotting 1 2.2 2.6 1.2 - 1.8 2.0 0.8

B2) Anwendung in einer KlarspülformulierungB2) Application in a rinse aid formulation

Zur Prüfung der Klarspülwirkung im Klarspüler wurde das Copolymer direkt der Klarspülformulierung zugefügt. Die Prüfung wurde unter den unten angegebenen Bedingungen unter Zugabe von IKW-Ballastschmutz in Haupt- und Klarspülgang durchgeführt.To test the rinse effect in the rinse aid, the copolymer was added directly to the rinse aid formulation. The test was carried out under the conditions given below with addition of IKW ballast dirt in main and final rinse cycles.

Als Reiniger wurde die folgende Formulierung verwendet: 50 Gew.-% Natriumtripolyphosphat (Na3P3O10 6 · H2O) 27 Gew.-% Natriumcarbonat 3 Gew.-% Natriumdisilikat (x Na2O · y SiO2; x/y = 2,65; 80 gew.-%ig) 6 Gew.-% Natriumpercarbonat (Na2CO3 · 1,5 H2O) 2 Gew.-% Tetraacetylethylendiamin (TAED) 2 Gew.-% schaumarmes nichtionisches Tensid auf der Basis von Fettalkoholalkoxylaten 3 Gew.-% Natriumchlorid 5 Gew.-% Natriumsulfat 2 Gew.-% Polyacrylsäure-Natriumsalz (Mw 8 000) The cleaner used was the following formulation: 50% by weight Sodium tripolyphosphate (Na 3 P 3 O 10 6 · H 2 O) 27% by weight sodium 3% by weight Sodium disilicate (Na 2 O x · y SiO 2; x / y = 2.65; 80 wt .-% strength) 6% by weight Sodium percarbonate (Na 2 CO 3 · 1.5H 2 O) 2% by weight Tetraacetylethylenediamine (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)

Das Copolymer wurde in der folgenden Klarspülformulierung eingesetzt: 20 Gew.-% schaumarmes nichtionisches Tensid auf der Basis von Fettalkoholalkoxylaten 10 Gew.-% Natriumcumolsulfonat (40 gew.-%ig) 5 Gew.-% Isopropanol 4 Gew.-% Copolymer (Aktivsubstanz) 61 Gew.-% Wasser The copolymer was used in the following rinse aid formulation: 20% by weight Low-foaming nonionic surfactant based on fatty alcohol alkoxylates 10% by weight Sodium cumene sulphonate (40% by weight) 5% by weight isopropanol 4% by weight Copolymer (active substance) 61% by weight water

Es wurden folgende Spülbedingungen verwendet: Geschirrspüler: Miele G 686 SC Spülgänge: 1 Spülgang 55°C Normal (ohne Vorspülen) Spülgut: Messer (WMF Tafelmesser Berlin, Monoblock); Gläser (Willy Becher, 0.3 I); schwarze KS-Teller, schwarze Dessertteller; EMSA Superline - Box (Deckel PE blau, PP Dose transparent) Geschirrspülmittel: 21 g Ballastschmutz: 50 g im Hauptspülgang; 2 g im Klarspülgang Klarspültemperatur: 65°C Klarspülerdosierung: 1 g Wasserhärte: 3°dH The following rinsing conditions were used: Dishwasher: Miele G 686 SC rinses: 1 rinse 55 ° C normal (without pre-rinse) ware: Knife (WMF table knife Berlin, monobloc); Glasses (Willy Becher, 0.3 l); black KS plates, black dessert plates; EMSA Superline - Box (cover PE blue, PP box transparent) Dishwashing liquid: 21 g Ballast soil: 50 g in the main rinse cycle; 2 g in the rinse cycle Rinse temperature: 65 ° C Rinse-aid: 1 g Water hardness: 3 ° dH

Nach Ende des Spülgangs wurde die Tür geöffnet und das Geschirr bei geöffneter Maschinentür 60 min trocknen gelassen. Die Bewertung des Spülguts erfolgte im Anschluß durch visuelle Abmusterung in einem schwarz lackierten Leuchtkasten mit Halogenspot und Lochblende unter Verwendung der oben beschriebenen Notenskala von 0 bis 4.At the end of the wash cycle, the door was opened and the dishes were left to dry for 60 minutes with the machine door open. The rating of the dishes followed by visual matching in a black painted light box with halogen spot and pinhole using the grading scale from 0 to 4 described above.

Die erhaltenen Prüfergebnisse sind in Tabelle 2 zusammengestellt, wobei zum Vergleich die Ergebnisse ohne Zusatz von Copolymer aufgeführt sind. Tabelle 2 Copolymer aus Bsp. Bewertung (Note) Messer, Gläser, Keramikteller Kunststoffteile Spotting Spotting 1 2,2 1,7 - 2,0 1,4 The test results obtained are summarized in Table 2, for comparison, the results are listed without the addition of copolymer. Table 2 Copolymer from Ex. Rating (grade) Knives, glasses, ceramic plates Plastic parts spotting spotting 1 2.2 1.7 - 2.0 1.4

Claims (7)

  1. The use of copolymers comprising alkylene oxide units and comprising, in randomly or blockwise copolymerized form,
    (a) 50 to 93 mol% of acrylic acid and/or a watersoluble 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 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 is identical or different unbranched or branched C2-C4-alkylene radicals;
    R4 is unbranched or branched C1-C6-alkyl;
    n is 3 to 50,
    as deposit-inhibiting additives in rinse aids for dishwashers.
  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. A rinse aid for dishwashers which comprises copolymers according to claims 1 to 6 as deposit-inhibiting additive.
EP04790785A 2003-10-28 2004-10-23 Use of copolymers, containing alkylene oxide units, as deposit inhibitor additives in rinsing compositions of a dishwasher Not-in-force EP1682645B1 (en)

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DE10350420A DE10350420A1 (en) 2003-10-28 2003-10-28 Use of copolymers containing alkylene oxide units as deposit-inhibiting additives in the rinse cycle of the automatic dishwasher
PCT/EP2004/011994 WO2005042684A1 (en) 2003-10-28 2004-10-23 Use of copolymers, containing alkylene oxide units, as deposit inhibitor additives in the rinsing process of a dishwasher

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