EP1373451B1 - Copolymers that prevent glass from corroding - Google Patents

Copolymers that prevent glass from corroding Download PDF

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Publication number
EP1373451B1
EP1373451B1 EP02719733A EP02719733A EP1373451B1 EP 1373451 B1 EP1373451 B1 EP 1373451B1 EP 02719733 A EP02719733 A EP 02719733A EP 02719733 A EP02719733 A EP 02719733A EP 1373451 B1 EP1373451 B1 EP 1373451B1
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Prior art keywords
copolymers
weight
carbon atoms
sodium
acid
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German (de)
French (fr)
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EP1373451A1 (en
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Axel Kistenmacher
Stephan Nied
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • 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
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion 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
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/18—Glass; Plastics

Definitions

  • the invention relates to the use of certain specified in the text copolymers in detergent formulations to prevent glass corrosion during the cleaning process in dishwashers.
  • Cleaning glasses or other glassware such as plates or bowls in dishwashers presents problems in two ways.
  • a film and staining on the glass dishwashing material is observed, which is caused in particular by incomplete removal of greasy or oily food residues from the relevant glass objects during the cleaning process in dishwashers.
  • This filming and staining can occur after each rinse at each different locations of the rinsed glass objects. Since this is a reversible process, filming and staining can relatively easily be removed again, for example manually with the aid of a dish cloth, from the affected glass objects.
  • the second undesirable side effect of the cleaning process of glass objects in dishwashers is the glass corrosion, which occurs in particular after repeated rinsing. Glass corrosion, in contrast to film and staining, is an irreversible process. Once affected by the glass corrosion areas of the glass objects can not be restored to their original state.
  • Frequently occurring corrosion phenomena are iridescent discoloration, surface and ring-shaped turbidity and scoring.
  • the occurrence of glass corrosion phenomena depends on a variety of parameters, including glass type, glass processing, detergent composition and cleaning temperature.
  • the macroscopically visible glass corrosion is usually based on an uneven removal of the silicate network.
  • cleaner compositions containing a high level of disilicate also have silicate deposits on the glass surface detected, which also lead to visually recognizable turbidity.
  • the problem of glass corrosion is described in detail in the literature (for example in W. Buchmeier et al., SOFW Journal 122 (1996) p. 398 et seq. ).
  • EP-A 462 829 describes a chlorine-free cleaner composition for use in dishwashers. This composition is useful in preventing the aforementioned filming and staining on glasses.
  • relevant cleaner constituents copolymers consist of the monomer maleic acid or its anhydride or a salt thereof and at least one polymerizable monomer from the group of alkanes, alkenes, dienes, alkynes or aromatics, each having at least 4 carbon atoms, in particular isobutylene , Diisobutylene, styrene, decene or eicosene.
  • WO 99/05 248 describes water-soluble cationic or amphoteric polymers as corrosion inhibitors for use in dishwashers, in particular to prevent the corrosion of decorative glass and decorative ceramics.
  • the monomer units used are olefins which have one or more quaternary nitrogen atoms or one or more amine groups.
  • WO 98/02 515 there is described a detergent composition for use in dishwashers which contains special alkali silicates for preventing the corrosion of glasses, crystal and porcelain.
  • WO 96/36 687 describes a cleaning composition in which, with the omission of silicates, aluminum (III) compounds are used as components which are relevant for the prevention of glass corrosion.
  • the aluminum (III) compounds are characterized by a special time-delayed dissolution behavior.
  • the object of the present invention is thus to provide cleaning agents which ensure effective suppression of the corrosion of glassware even with frequent rinsing in dishwashers.
  • the copolymers can be used in dishwashers both in the household and in the commercial sector for the cleaning of Glasdalegut. This is not possible with many commercially available cleaning agents.
  • EP-A 462 829 Detergent formulations containing copolymers, some of which fall within the above defined range of copolymers of the present invention. However, in EP-A 462 829 disclosed no use of the copolymers described there or cleaner formulations to prevent glass corrosion.
  • the copolymers described above contain from 20 to 70 wt .-% of at least one monomer unit (A) from the group of monoethylenically unsaturated C 3 -C 10 mono- and dicarboxylic acids or their anhydrides.
  • Suitable monomeric units (A) are, for example, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid or crotonic acid.
  • the monomer component (A) used is maleic acid, maleic anhydride and / or acrylic acid.
  • R 1 , R 2 and R 3 independently of one another are H, CH 3 , C 2 H 5 , C 3 H 7
  • Suitable monomer building blocks (B) include the substance groups listed below.
  • C 1 -C 6 (meth) acrylic esters such as, for example, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl (meth) acrylate;
  • C 2 -C 8 olefins such as ethene, propene, butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene , Cycloheptene, methylcyclohexene, 2,4,4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1,2,5-dimethylhexene-1
  • the copolymers contain at least one further monomer building block (C), which constitutes from 0 to 25% by weight, based on the total weight of the copolymer.
  • C further monomer building block
  • Suitable monomeric units (C) which can be copolymerized with the monomeric units (A) and (B) are, for example, the substance groups listed below.
  • ⁇ -olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C 22 - ⁇ -olefin, especially 1-dodecene, 1-octadecene or C 22 - ⁇ -olefin;
  • Olefin mixtures of ⁇ -olefins having 10 to 28 carbon atoms such as C 10 -C 12 ⁇ -olefins ( ⁇ -olefins having 10 and 12 carbon atoms, respectively), C 12 -C 14 ⁇ -olefins, C 14 -C 18 ⁇ Olefins, C 20 -C 24 ⁇ -olefins, C 24 -C 28 ⁇ -olefins, preferably
  • copolymers can be used in the form of the free acid, a salt thereof or the anhydride, but they can also be partially neutralized.
  • the copolymers may be in the form of their sodium, potassium or ammonium salts.
  • the copolymers may be subjected to additional reaction.
  • additional reaction are, for example, ester formations with C 1 -C 20 -alcohols, alkylpolyalkylene glycols such as, for example, methylpolyethylene glycol having a mean degree of ethoxylation of 45 or alkylpolyethyleneglycol-block-polypropylene glycols, for example methylpolyethyleneglycol-block-polypropylene glycol having 40 ethylene oxide units and 5 propylene oxide units.
  • This reaction can also be carried out with C 1 -C 20 amines or Alkylpolyalkylenglykolaminen such as methyl polyethylene glycol amine having a mean degree of ethoxylation of 8 to form amide bonds.
  • the weight-average molecular weight of the copolymers is from 1000 to 200,000, preferably from 2,000 to 50,000, more preferably from 2,000 to 20,000.
  • the copolymers are prepared by methods known to the person skilled in the art.
  • copolymers which comprise as monomer building block (A) maleic acid and / or maleic anhydride and at least one monomer building block (B) from the group consisting of cyclopentene, hexene and technical diisobutene. Particular preference is given to using copolymers which contain technical diisobutene as monomer building block (A), maleic anhydride and as monomer building block (B).
  • the copolymers are present in the form of their alkali metal or ammonium salt, particularly preferably in the form of their sodium or ammonium salt.
  • the copolymers are included at 0.01 to 10 wt%, preferably at 0.05 to 5 wt%, more preferably at 0.1 to 3 wt%, based on the total weight of the detergent formulation.
  • copolymers can be used in the form of their aqueous solutions or dispersions. Furthermore, the copolymers can also be used in solid form, for example as a powder or granules. These are available, for example, by spray drying with possible subsequent compaction or by spray granulation. During drying, other water-soluble substances such.
  • sodium sulfate sodium chloride, sodium acetate, sodium citrate, pentasodium triphosphate, sodium carbonate, sodium bicarbonate or polymers such as polyacrylates, polyacrylic acid, polyvinyl alcohol, Sokalan ® CP 5 (copolymer containing polyacrylic acid and maleic acid as monomeric units), cellulose and cellulose derivatives, sugars and sugar derivatives in the sense of a cogranulate be incorporated.
  • substances which are sparingly soluble in water or insoluble in water may also be incorporated or used as carrier substances, such as zeolites and precipitated silicas.
  • Particularly suitable are (co) granules which contain the copolymers and from 10 to 50% by weight of sodium sulfate, sodium carbonate, sodium bicarbonate and / or polyacrylates.
  • copolymers can be used according to the invention both in liquid, gel, powdery, granular and tablet dishwashing detergents. It is possible to incorporate the copolymers optionally with other formulation ingredients into particular compartments such as microcapsules or gelcapsules. Furthermore, the copolymers may also be incorporated in special compartments within dishwashing detergent tablets, which may optionally exhibit different dissolution behavior than the other tablet compartments. These may be both special tablet layers and certain moldings embedded in the tablet, glued to the tablet or encased in the tablet.
  • the cleaner formulation contains additional components known to the person skilled in the art. Examples are listed below.
  • Typical builders which can be present in the detergent formulation at 10 to 90% by weight, based on the total formulation, are, for example, phosphates, such as alkali metal phosphates and polymeric alkali phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
  • Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen phosphate, pentasodium tripolyphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of from 5 to 1000, in particular from 5 to 50, and the corresponding potassium salts or mixtures of sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts , These phosphates are preferably used in the range of 5 wt .-% to 65 wt .-% based on the total formulation and calculated as anhydrous active substance.
  • the crystalline sheet silicates correspond in particular to the general formula NaMSi x O 2x + 1 * y H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably 1.9 to 4, and y is a number from 0 to 33 stands.
  • M sodium or hydrogen
  • x is a number from 1.9 to 22, preferably 1.9 to 4
  • y is a number from 0 to 33 stands.
  • Known examples of these are in particular ⁇ -Na 2 Si 2 O 5 , ⁇ -Na 2 Si 2 O 5 , ⁇ -Na 2 Si 2 O 5 .
  • these include mixtures of the abovementioned builder substances.
  • alkali carriers may be present.
  • Suitable alkali carriers are ammonium and / or alkali metal hydroxides, ammonium and / or alkali metal carbonates, ammonium and / or alkali metal hydrogencarbonates, ammonium and / or alkali metal sesquicarbonates, ammonium and / or alkali metal silicates, ammonium and / or alkali metal silicates and mixtures of the abovementioned substances.
  • ammonium and / or alkali metal carbonates in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate are used.
  • Preferred combinations of builder and alkali carriers are mixtures of tripolyphosphate and sodium carbonate or tripolyphosphate, sodium carbonate and sodium disilicate.
  • the detergent formulation preferably contains, as further component, weakly or low-foaming nonionic surfactants in proportions of from 0.1 to 20% by weight, preferably from 0.1 to 10% by weight, particularly preferably from 0.25 to 4% by weight.
  • R 2 is -O- (CH 2 -CH 2 -O) p - (CHR 1 -CH 2 -O) m -R 3 (II) in which R 1 and R 3 independently of one another represent C n H 2n + 1 and n is 1 to 4, R 2 is C n H 2n + 1 and n is 3 to 30, m and p are independently 0 to 300.
  • di- and multiblock copolymers may be formed from ethylene oxide and propylene oxide, for example, under the name Pluronic ® (BASF Aktiengesellschaft) or Tetronic ® (BASF Corporation) are commercially available.
  • Pluronic ® BASF Aktiengesellschaft
  • Tetronic ® BASF Corporation
  • reaction products of sorbitan esters with ethylene oxide and / or propylene oxide can be used.
  • amine oxides or alkyl glycosides are also suitable.
  • suitable nonionic surfactants are the EP-A 851 023 as well as the DE-A 198 19 187 ,
  • the formulation may further contain anionic or zwitterionic surfactants, preferably in admixture with nonionic surfactants. Suitable anionic and zwitterionic surfactants are also in EP-A 851 023 such as DE-A 198 19 187 called.
  • Bleaching agents are subdivided into oxygen bleaching agents and chlorine-containing bleaching agents.
  • Use as oxygen bleach find alkali metal perborates and their hydrates and alkali metal percarbonates.
  • Preferred bleaching agents here are sodium perborate in the form of the mono- or tetrahydrate, sodium percarbonate or the hydrates of sodium percarbonate.
  • oxygen bleaching agents are persulfates and hydrogen peroxide.
  • Typical oxygen bleaches are also organic peracids such as perbenzoic acid, peroxy-alpha-naphthoic acid, peroxylauric acid, peroxystearic acid, phthalimidoperoxycaproic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxoisophthalic acid or 2-decyldiperoxybutane-1,4-diacid.
  • organic peracids such as perbenzoic acid, peroxy-alpha-naphthoic acid, peroxylauric acid, peroxystearic acid, phthalimidoperoxycaproic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxoisophthalic acid or 2-decyldiperoxybutane-1,4-diacid.
  • Oxygen bleaching agents are used in amounts of from 0.5 to 30% by weight, preferably from 1 to 20% by weight, particularly preferably from 3 to 15% by weight, based on the total detergent formulation.
  • Chlorine-containing bleaches as well as the combination of chlorine-containing bleach with peroxide-containing bleaches can also be used.
  • Known chlorine-containing bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, dichloramine T, chloramine B, N, N'-dichlorobenzoylurea, p-toluenesulfondichloroamide or trichloroethylamine.
  • Preferred chlorine-containing bleaching agents are sodium hypochlorite, calcium hypochlorite, potassium hypochlorite, magnesium hypochlorite, potassium dichloroisocyanurate or sodium dichloroisocyanurate.
  • Chlorine-containing bleaching agents are used in amounts of from 0.1 to 20% by weight, preferably from 0.1 to 10% by weight, particularly preferably from 0.3 to 8% by weight, based on the total detergent formulation.
  • bleach stabilizers such as phosphonates, borates, metaborates, metasilicates or magnesium salts can be added in small amounts.
  • Bleach activators are compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or substituted perbenzoic acid.
  • Suitable compounds are those which contain one or more N- or O-acyl groups and / or optionally substituted benzoyl groups, for example substances from the class of the anhydrides, esters, imides, acylated imidazoles or oximes.
  • TAED tetraethylethylenediamine
  • TAMD tetraacetylmethylenediamine
  • TAGU tetraacetylglycoluril
  • TAHD tetraacetylhexylenediamine
  • N-acylimides such as N-nonanoylsuccinimide (NOSI)
  • acylated phenolsulfonates such as n-nonanoyl or isononanoyloxybenzenesulfonates (n- or n-nonanoyl) iso-NOBS
  • PAG pentaacetylglucose
  • DADHT 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine
  • ISA isatoic anhydride
  • nitrile quats such as, for example, N-methyl-morpholinium-acetonitrile salts (MMA salts) or trimethylammonium acetonitrile salts (TMAQ salts).
  • MMA salts N-methyl-morpholinium-acetonitrile salts
  • TMAQ salts trimethylammonium acetonitrile salts
  • Bleach activators are preferably suitable from the group consisting of polyacylated alkylenediamines, particularly preferably TAED, N-acylimides, particularly preferably NOSI, acylated phenolsulfonates, more preferably n- or iso-NOBS, MMA and TMAQ.
  • Bleach activators are used in amounts of from 0.1 to 10% by weight, preferably from 1 to 9% by weight, particularly preferably from 1.5 to 8% by weight, based on the total detergent formulation.
  • EP-A 446 982 and EP-A 453 003 be known Sulfonimine and / or bleach-enhancing transition metal salts or transition metal complexes as so-called bleach catalysts contained in the cleaner formulations.
  • transition metal compounds include those of DE-A 195 29 905 known manganese, iron, cobalt, ruthenium or Molydän salen complexes and their DE-A 196 20 267 known N-analogues consisting of DE-A 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, which in DE-A 196 05 688 described manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, which DE-A 196 20 411 known cobalt, iron, copper and ruthenium ammine complexes, which in DE-A 44 16 438 described manganese, copper and cobalt complexes in EP-A 272 030 described cobalt complexes consisting of EP-A 693 550 known manganese complexes that are made EP-A 392 592 known manganese, iron, cobalt and
  • Binuclear manganese complexes containing 1,4,7-trimethyl-1,4,7-triazacyclononane (TMTACN) such as, for example, [(TMTACN) 2 Mn IV Mn IV ( ⁇ -O) 3 ] 2+ (PF 6 - ) 2 are also useful as effective bleach catalysts. These manganese complexes are also described in the aforementioned publications.
  • Suitable bleach catalysts are preferably bleach-enhancing transition metal complexes or salts from the group consisting of the manganese salts and complexes and the cobalt salts and complexes. Particularly suitable are the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate or [(TMTACN) 2 Mn IV Mn IV ( ⁇ -O ) 3 ] 2+ (PF 6 - ) 2 .
  • Bleach catalysts are used in amounts of from 0.0001 to 5% by weight, preferably from 0.0025 to 1% by weight, particularly preferably from 0.01 to 0.25% by weight, based on the total detergent formulation.
  • silver protectants from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used.
  • Particularly preferred too use are benzotriazole and / or alkylaminotriazole.
  • active chlorine-containing agents are often used in cleaner formulations, which can significantly reduce the corrosion of the silver surface.
  • chlorine-free cleaners are preferably oxygen and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds used.
  • organic redox-active compounds such as di- and trihydric phenols, such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds used.
  • Salts and complex inorganic compounds such as salts of the metals Mn, Ti, Zr Hf, V, Co and Ce are often used.
  • transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably from the group of the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl ) Complexes, the chlorides of cobalt or manganese and of manganese sulfate.
  • zinc compounds or bismuth compounds can be used to prevent corrosion on the items to be washed.
  • the detergent can be added between 0 and 5 wt .-% of enzymes based on the total preparation in order to increase the performance of the detergents or to ensure the cleaning performance of the same quality under milder conditions.
  • the most commonly used enzymes include lipases, amylases, cellulases and proteases.
  • esterases, pectinases, lactases and peroxidases can be used.
  • Preferred proteases are, for. B. BLAP ® 140 (Biozym), Optimase ® M-440 and Opticlean ® M-250 (Solvay Enzymes), Maxacal ® CX, Maxapem ®, Esperase ® (Gist Brocades), Savinase ® (Novo) or Purafect OxP (Genencor) , Especially suitable cellulases and lipases are Celluzyme ® and Lipolase ® 0.7T 30T (Novo Nordisk).
  • amylases Duramyl ®, Termamyl ® 60 T and Termamyl ® 90 T Novo
  • Amylase-LT ® Solvay Enzymes
  • Maxamyl ® P5000 Gist Brocades
  • Purafect ® OxAm Genencor
  • Paraffin oils and silicone oils can optionally be used as defoamers and for the protection of plastic and metal surfaces. Defoamers are generally dosed in proportions of 0.001% to 5%. In addition, dyes, perfumes and other perfumes may be added to the cleanser formulation. Detergent formulations in tablet form may also contain polyethylene glycol as a tablet auxiliary.
  • the copolymers can be used in cleaner formulations both for the household and for the commercial sector.
  • Commercial cleaner types usually contain a builder system based on pentasodium triphosphate, and / or sodium citrate and / or complexing agents such as e.g. Nitrilotriacetate.
  • a builder system based on pentasodium triphosphate, and / or sodium citrate and / or complexing agents such as e.g. Nitrilotriacetate.
  • Caustic soda or potassium hydroxide solution is used as alkali carrier.
  • chlorine compounds such as sodium dichloroisocyanurate are frequently used as bleaching agents.
  • the experiment is carried out in a new beaker equipped with a magnetic stir bar, a metal mesh bottom insert, a lid and a contact thermometer.
  • MS-PEG4 / DIB 65:35
  • Mw R1, T2 15000 Details of the polymeric glass corrosion inhibitor in% by weight Abbreviations: MS: maleic acid; DIB: technical Diisobutene; AS: acrylic acid; MS-PEG4: half ester of maleic acid and tetraethylene glycol; Cop: copolymer containing the following monomer building blocks; a : in the form of the Na salt; Mw: weight average molecular weight;

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Abstract

The invention relates to the use of copolymers in cleaner formulations for preventing glass from corroding when cleaned in a dishwasher. The copolymers contain: a) 20 to 70% by weight of at least one monomer component (A) from the group of the monoethylenically unsaturated C3-C10 mono- and dicarboxylic acids or the anhydrides thereof; b) 30 to 80% by weight of at least one monomer component (B) of the general formula (I), wherein R<1>, R<2 >and R<3 >independently represent H, CH3, C2H5, C3H7, COOH or OH, Y represents -C(=O)-, -C(=O)-O-, -O-, -O-C(=O)-, -O-C(=O)-O- or -C(=O)-NH-, n equals 0 or 1, R<4 >is either an aromatic or a linear, branched or cyclic aliphatic group with 1 to 6 carbon atoms, and R<2 >and R<4 >optionally form together an alkyl moiety with 3 to 6 carbon atoms, which can be optionally substituted by C1-C3 alkyl groups, thereby forming a cycle; c) 0 to 25% by weight of at least one further monomer component (C) that can be copolymerized with the monomer components (A) and (B) and that is selected from the group consisting of alpha olefins with 10 or more carbon atoms, polyisobutenes with an average of 12 to 100 carbon atoms, Cn-(meth)acrylates wherein n is greater than 6, hydroxy-(meth)acrylates, Cn vinylesters or Cn vinylethers wherein n is greater than 6, acrylnitriles, acrylamides, vinylformamides, allylalcohols, vinylphosphonates, vinyl-substituted heterocycles and unsaturated organosulfonic acids.

Description

Die Erfindung betrifft die Verwendung von bestimmten, im Text spezifizierten Copolymeren in Reinigerformulierungen zur Verhinderung der Glaskorrosion während des Reinigungsvorganges in Geschirrspülmaschinen.The invention relates to the use of certain specified in the text copolymers in detergent formulations to prevent glass corrosion during the cleaning process in dishwashers.

Das Reinigen von Gläsern oder sonstigem Glasgeschirr wie Tellern oder Schüsseln in Geschirrspülmaschinen bereitet in zweierlei Hinsicht Probleme. Einerseits ist eine Film-und Fleckenbildung auf dem Glasspülgut zu beobachten, die insbesondere durch unvollständiges Entfernen fettiger oder öliger Nahrungsmittelreste von den betreffenden Glasgegenständen während des Reinigungsvorganges in Geschirrspülmaschinen verursacht wird. Diese Film- und Fleckenbildung kann nach jedem Spülvorgang an jeweils unterschiedlichen Stellen der gespülten Glasgegenstände auftreten. Da es sich hierbei um einen reversiblen Prozess handelt, kann die Film- und Fleckenbildung relativ einfach, zum Beispiel manuell unter Zuhilfenahme eines Spültuches, wieder von den betroffenen Glasgegenständen entfernt werden.Cleaning glasses or other glassware such as plates or bowls in dishwashers presents problems in two ways. On the one hand, a film and staining on the glass dishwashing material is observed, which is caused in particular by incomplete removal of greasy or oily food residues from the relevant glass objects during the cleaning process in dishwashers. This filming and staining can occur after each rinse at each different locations of the rinsed glass objects. Since this is a reversible process, filming and staining can relatively easily be removed again, for example manually with the aid of a dish cloth, from the affected glass objects.

Der zweite unerwünschte Nebeneffekt des Reinigungsvorganges von Glasgegenständen in Geschirrspülmaschinen ist die Glaskorrosion, die insbesondere nach mehrmaligem Spülen auftritt. Bei der Glaskorrosion handelt es sich im Gegensatz zur Film- und Fleckenbildung um einen irreversiblen Prozess. Einmal von der Glaskorrosion betroffene Bereiche der Glasgegenstände können nicht mehr in ihren ursprünglichen Zustand versetzt werden.The second undesirable side effect of the cleaning process of glass objects in dishwashers is the glass corrosion, which occurs in particular after repeated rinsing. Glass corrosion, in contrast to film and staining, is an irreversible process. Once affected by the glass corrosion areas of the glass objects can not be restored to their original state.

Häufig auftretende Korrosionsphänomene sind irisierende Verfärbungen, flächen- und ringförmige Trübungen und Riefenbildung. Das Auftreten von Glaskorrosionsphänomenen ist von einer Vielzahl von Parametern abhängig, unter anderem von der Glassorte, der Glasverarbeitung, der Reinigerzusammensetzung und der Reinigungstemperatur. Der makroskopisch sichtbaren Glaskorrosion liegt meist ein ungleichmäßiger Abtrag des Silikatnetzwerkes zugrunde. Allerdings wurden bei Reinigerzusammensetzungen mit einem hohen Anteil an Disilikat auch Silikatablagerungen auf der Glasoberfläche detektiert, die ebenfalls zu visuell erkennbaren Trübungen führen. Die Problematik der Glaskorrosion wird eingehend in der Literatur beschrieben (zum Beispiel in W. Buchmeier et al., SÖFW-Journal 122 (1996) S. 398 ff. ).Frequently occurring corrosion phenomena are iridescent discoloration, surface and ring-shaped turbidity and scoring. The occurrence of glass corrosion phenomena depends on a variety of parameters, including glass type, glass processing, detergent composition and cleaning temperature. The macroscopically visible glass corrosion is usually based on an uneven removal of the silicate network. However, cleaner compositions containing a high level of disilicate also have silicate deposits on the glass surface detected, which also lead to visually recognizable turbidity. The problem of glass corrosion is described in detail in the literature (for example in W. Buchmeier et al., SOFW Journal 122 (1996) p. 398 et seq. ).

EP-A 462 829 beschreibt eine chlorfreie Reinigerzusammensetzung zur Anwendung in Geschirrspülmaschinen. Diese Zusammensetzung eignet sich die sich zur Verhinderung der vorstehend erwähnten Film- und Fleckenbildung auf Gläsern. Als hierfür relevante Reinigerbestandteile werden Copolymere beschrieben, die sich aus dem Monomer Maleinsäure bzw. deren Anhydrid oder einem Salz davon sowie mindestens einem polymerisierbaren Monomeren aus der Gruppe der Alkane, Alkene, Diene, Alkine oder Aromaten, die jeweils mindestens 4 Kohlenstoffatome aufweisen, insbesondere Isobutylen, Diisobutylen, Styrol, Decen oder Eicosen, zusammensetzen. EP-A 462 829 describes a chlorine-free cleaner composition for use in dishwashers. This composition is useful in preventing the aforementioned filming and staining on glasses. As relevant cleaner constituents copolymers are described which consist of the monomer maleic acid or its anhydride or a salt thereof and at least one polymerizable monomer from the group of alkanes, alkenes, dienes, alkynes or aromatics, each having at least 4 carbon atoms, in particular isobutylene , Diisobutylene, styrene, decene or eicosene.

Zur Unterbindung des Glaskorrosionsphänomens werden unterschiedliche Arten von Reinigerkompositionen vorgeschlagen. WO 99/05 248 beschreibt wasserlösliche kationische oder amphotere Polymere als Korrosionsinhibitoren für die Anwendung in Geschirrspülmaschinen, insbesondere um die Korrosion von Dekorglas und Dekorkeramik zu verhindern. Als Monomereinheiten werden Olefine verwendet, die über ein oder mehrere quartäre Stickstoffatome oder eine oder mehrere Amingruppen verfügen.To prevent the glass corrosion phenomenon different types of cleaning compositions are proposed. WO 99/05 248 describes water-soluble cationic or amphoteric polymers as corrosion inhibitors for use in dishwashers, in particular to prevent the corrosion of decorative glass and decorative ceramics. The monomer units used are olefins which have one or more quaternary nitrogen atoms or one or more amine groups.

In WO 98/02 515 wird eine Reinigerkomposition zur Verwendung in Geschirrspülmaschinen beschrieben, die spezielle Alkalisilikate zur Verhinderung der Korrosion von Gläsern, Kristall und Porzellan enthält.In WO 98/02 515 there is described a detergent composition for use in dishwashers which contains special alkali silicates for preventing the corrosion of glasses, crystal and porcelain.

WO 96/36 687 beschreibt eine Reinigerzusammensetzung, bei der unter Verzicht auf Silikate Aluminium (III)-Verbindungen als zur Verhinderung der Glaskorrosion relevante Komponenten eingesetzt werden. Die Aluminium (III)-Verbindungen zeichnen sich durch ein spezielles zeitverzögertes Auflösungsverhalten aus. WO 96/36 687 describes a cleaning composition in which, with the omission of silicates, aluminum (III) compounds are used as components which are relevant for the prevention of glass corrosion. The aluminum (III) compounds are characterized by a special time-delayed dissolution behavior.

Die Praxis zeigt allerdings, dass das Problem der Glaskorrosion während des Reinigungsvorganges in Geschirrspülmaschinen bis jetzt nur unbefriedigend gelöst ist. Die Aufgabe der vorliegenden Erfindung besteht somit darin, Reinigungsmittel zur Verfugung zu stellen, die eine wirkungsvolle Unterbindung der Korrosion von Glasspülgut auch bei häufigem Spülen in Geschirrspülmaschinen gewährleisten.However, practice shows that the problem of glass corrosion during the cleaning process in dishwashers has so far been solved only unsatisfactorily. The object of the present invention is thus to provide cleaning agents which ensure effective suppression of the corrosion of glassware even with frequent rinsing in dishwashers.

Diese Aufgabe wird gelöst durch die Verwendung von Copolymeren enthaltend

  1. a) 20 bis 70 Gew.-% mindestens eines Monomerenbausteines (A) aus der Gruppe der monoethylenisch ungesättigten C3-C10-Mono- und Dicarbonsäuren oder deren Anhydriden,
  2. b) 30 bis 80 Gew.-% mindestens eines Monomerenbausteines (B) der allgemeinen Formel (I),
    Figure imgb0001
     in der R1, R2 und R3 unabhängig voneinander für H, CH3, C2H5, C3H7, COOH oder OH stehen,
    Y für -C(=O)-, -C(=O)-O-, -O-, -O-C(=O)-, -O-C(=O)-O- oder -C(=O)-NH- steht,
    n gleich 0 oder 1 ist,
    R4 entweder ein aromatischer oder ein linearer, verzweigter oder cyclischer aliphatischer Rest mit 1 bis 6 Kohlenstoffatomen ist,
    gegebenenfalls bilden R2 und R4 zusammen eine Alkyleneinheit mit 3 bis 6 Kohlenstoffatomen, die gegebenenfalls mit C1-C3-Alkylgruppen substituiert ist, unter Ausbildung eines Zyklus,
  3. c) 0 bis 25 Gew.-% mindestens eines weiteren mit den Monomerenbausteinen (A) und (B) copolymerisierbaren Monomerenbausteines (C) aus der Gruppe bestehend aus α-Olefinen mit 10 oder mehr Kohlenstoffatomen, Olefinmischungen aus α-Olefinen mit 10 oder mehr Kohlenstoffatomen, Polyisobutenen mit im Mittel 12 bis 100 Kohlenstoffatomen, Cn-(Meth)acrylaten mit n größer als 6, Hydroxy-(Meth)acrylaten, Cn-Vinylestern oder Cn-Vinylethern mit n größer als 6, Acrylnitrilen, Acrylamiden, Vinylformamiden, Allylalkoholen, Vinylphosphonaten, vinylsubstituierten Heterozyklen und ungesättigten Organosulfonsäuren.
  4. d) Die erfindungsgemäße Verwendung dieser Copolymere unterbindet die Glaskorrosion während des Spülvorganges in Geschirrspülmaschinen wirkungsvoll. Auch nach einer Vielzahl von Reinigungszyklen sind auf dem gespülten Glasgut weder irisierende Verfärbungen noch flächen- oder ringförmige Trübungen bzw. Riefenbildung zu beobachten. Der korrosionsverhindernde Effekt wird unabhängig von der Glassorte und der Glasverarbeitung beobachtet.
This object is achieved by the use of copolymers containing
  1. a) from 20 to 70% by weight of at least one monomer building block (A) from the group of the monoethylenically unsaturated C 3 -C 10 -mono- and dicarboxylic acids or their anhydrides,
  2. b) from 30 to 80% by weight of at least one monomer building block (B) of the general formula (I),
    Figure imgb0001
     in which R 1 , R 2 and R 3 independently of one another are H, CH 3 , C 2 H 5 , C 3 H 7 , COOH or OH,
    Y is -C (= O) -, -C (= O) -O-, -O-, -OC (= O) -, -OC (= O) -O- or -C (= O) -NH - stands,
    n is 0 or 1,
    R 4 is either an aromatic or a linear, branched or cyclic aliphatic radical having 1 to 6 carbon atoms,
    optionally R 2 and R 4 together form an alkylene moiety having from 3 to 6 carbon atoms optionally substituted with C 1 -C 3 alkyl groups to form a cycle,
  3. c) 0 to 25 wt .-% of at least one further copolymerizable with the monomer units (A) and (B) monomer units (C) from the group consisting of α-olefins having 10 or more carbon atoms, olefin mixtures of α-olefins with 10 or more Carbon atoms, polyisobutenes having an average of 12 to 100 carbon atoms, C n - (meth) acrylates having n greater than 6, hydroxy (meth) acrylates, C n -vinyl esters or C n -vinyl ethers with n greater than 6, acrylonitriles, acrylamides, vinyl formamides, allyl alcohols, vinyl phosphonates, vinyl-substituted heterocycles and unsaturated organosulfonic acids.
  4. d) The use of these copolymers according to the invention effectively prevents glass corrosion during the rinsing process in dishwashers. Even after a large number of cleaning cycles, neither iridescent discoloration nor surface or annular turbidity or scoring are observed on the rinsed glassware. The corrosion preventing effect is observed regardless of the type of glass and the glass processing.

Die Copolymere können in Geschirrspülmaschinen sowohl im Haushalts- als auch im gewerblichen Bereich zur Reinigung von Glasspülgut verwendet werden. Dies ist mit zahlreichen handelsüblichen Reinigungsmitteln nicht möglich.The copolymers can be used in dishwashers both in the household and in the commercial sector for the cleaning of Glasspülgut. This is not possible with many commercially available cleaning agents.

Zwar sind in EP-A 462 829 Reinigerformulierungen offenbart, die Copolymere enthalten, von denen manche auch in den oben definierten Bereich der Copolymere der vorliegenden Erfindung fallen. Allerdings ist in EP-A 462 829 keine Verwendungsmöglichkeit der dort beschriebenen Copolymere bzw. Reinigerformulierungen zur Verhinderung von Glaskorrosion offenbart.True, are in EP-A 462 829 Detergent formulations containing copolymers, some of which fall within the above defined range of copolymers of the present invention. However, in EP-A 462 829 disclosed no use of the copolymers described there or cleaner formulations to prevent glass corrosion.

Die oben beschriebenen Copolymere enthalten zu 20 bis 70 Gew.-% mindestens einen Monomerenbaustein (A) aus der Gruppe der monoethylenisch ungesättigten C3-C10-Mono-und Dicarbonsäuren oder deren Anhydriden.The copolymers described above contain from 20 to 70 wt .-% of at least one monomer unit (A) from the group of monoethylenically unsaturated C 3 -C 10 mono- and dicarboxylic acids or their anhydrides.

Als Monomerenbaustein (A) eignen sich beispielsweise Acrylsäure, Methacrylsäure, Maleinsäure, Maleinsäureanhydrid, Fumarsäure, Itaconsäure, Citraconsäue, Methylenmalonsäure oder Crotonsäure.Suitable monomeric units (A) are, for example, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid or crotonic acid.

In einer bevorzugten Ausführungsform der vorliegenden Erfindung wird als Monomerenbaustein (A) Maleinsäure, Maleinsäureanhydrid und/oder Acrylsäure verwendet.In a preferred embodiment of the present invention, the monomer component (A) used is maleic acid, maleic anhydride and / or acrylic acid.

Weiterhin enthalten die Copolymere 30 bis 80 Gew.-% mindestens eines Monomerenbausteines (B) der allgemeinen Formel (I),

Figure imgb0002
in der R1, R2 und R3 unabhängig voneinander für H, CH3, C2H5, C3H7, COOH oder OH stehen,
Y für -C(=O)-, -C(=O)-O-, -O-, -O-C(=O)-, -O-C(=O)-O- oder -C(=O)-NH- steht,
n gleich 0 oder 1 ist,
R4 entweder ein aromatischer oder ein linearer, verzweigter oder cyclischer aliphatischer Rest mit 1 bis 6 Kohlenstoffatomen ist,
gegebenenfalls bilden R2 und R4 zusammen eine Alkyleneinheit mit 3 bis 6 Kohlenstoffatomen, die gegebenenfalls mit C1-C3-Alkylgruppen substituiert ist, unter Ausbildung eines Zyklus.Furthermore, the copolymers contain from 30 to 80% by weight of at least one monomer building block (B) of the general formula (I),
Figure imgb0002
 in which R 1 , R 2 and R 3 independently of one another are H, CH 3 , C 2 H 5 , C 3 H 7 , COOH or OH,
Y is -C (= O) -, -C (= O) -O-, -O-, -OC (= O) -, -OC (= O) -O- or -C (= O) -NH - stands,
n is 0 or 1,
R 4 is either an aromatic or a linear, branched or cyclic aliphatic radical having 1 to 6 carbon atoms,
optionally, R 2 and R 4 together form an alkylene moiety of from 3 to 6 carbon atoms optionally substituted with C 1 -C 3 alkyl groups to form a cycle.

Beispiele für geeignete Monomerenbausteine (B) umfassen die nachfolgend aufgeführten Substanzgruppen.
C1-C6-(Meth)Acrylester wie beispielsweise Acrylsäuremethylester, Acrylsäureethylester, Methacrylsäuremethylester, Methacrylsäureethylester, Butyl(meth)acrylat;
C2-C8-Olefine wie beispielsweise Ethen, Propen, Buten, Isobuten, Penten, 3-Methylbuten, 2-Methylbuten, Cyclopenten, Hexen, Hexen-1, 2-Methylpenten-1, 3-Methylpenten-1, Cyclohexen, Methylcyclopenten, Cyclohepten, Methylcyclohexen, 2,4,4-Trimethylpenten-1, 2,4,4-Trimethylpenten-2, 2,3-Dimethylhexen-1, 2,4-Dimethylhexen-1, 2,5-Dimethylhexen-1, 3,5-Dimethylhexen-1, 4,4-Dimethylhexen-1, Ethylcyclohexen, 1-Octen oder technisches Diisobuten, das u.a. 2,4,4-Trimethylpenten-1 und 2,4,4-Trimethylpenten-2 enthält, insbesondere eignen sich Cyclopenten, Hexen oder technisches Diisobuten;
Styrole.Examples of suitable monomer building blocks (B) include the substance groups listed below.
C 1 -C 6 (meth) acrylic esters such as, for example, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl (meth) acrylate;
C 2 -C 8 olefins such as ethene, propene, butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene , Cycloheptene, methylcyclohexene, 2,4,4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1,2,5-dimethylhexene-1,3 , 5-dimethylhexene-1, 4,4-dimethylhexene-1, ethylcyclohexene, 1-octene or technical diisobutene, which contains, inter alia, 2,4,4-trimethylpentene-1 and 2,4,4-trimethylpentene-2, in particular are suitable Cyclopentene, hexene or technical diisobutene;
Styrenes.

Gegebenenfalls enthalten die Copolymere mindestens einen weiteren Monomerenbaustein (C), der 0 bis 25 Gew.-% bezogen auf das Gesamtgewicht des Copolymers ausmacht.Optionally, the copolymers contain at least one further monomer building block (C), which constitutes from 0 to 25% by weight, based on the total weight of the copolymer.

Als mit den Monomerenbausteinen (A) und (B) copolymerisierbarer Monomerenbaustein (C) eignen sich beispielsweise die nachfolgend aufgeführten Substanzgruppen.
α-Olefine mit 10 oder mehr Kohlenstoffatomen wie beispielsweise 1-Decen, 1-Dodecen, 1-Hexadecen, 1-Oktadecen und C22-α-Olefm, insbesondere 1-Dodecen, 1-Oktadecen oder C22-α-Olefin;
Olefinmischungen aus α-Olefinen mit 10 bis 28 Kohlenstoffatomen wie beispielsweise C10-C12-α-Olefine (α-Olefine mit 10 bzw. 12 Kohlenstoffatomen), C12-C14-α-Olefine, C14-C18-α-Olefine, C20-C24-α-Olefine, C24-C28-α-Olefine, vorzugsweise C20-C24-α-Olefine;
Olefinmischungen aus mindestens zwei unterschiedlichen α-Olefinen mit 30 oder mehr Kohlenstoffatomen wie beispielsweise C30+-α-Olefine (Olefinmischung aus C30-α-Olefin und mindestens einem weiteren α-Olefin mit einer geradzahligen Anzahl von Kohlenstoffatomen größer als 30);
insbesondere Polyisobutene mit im Mittel 12 bis 100 Kohlenstoffatomen und einem α-Olefinanteil größer 80 % wie beispielsweise Polyisobuten-1000 (Polyisobuten mit einer mittleren molaren Masse von 1000);
Cn-(Meth)acrylate mit n größer als 6 wie beispielsweise Ethylhexyl(meth)acrylat, Lauryl(meth)acrylat, Stearyl(meth)acrylat;
Hydroxy-(Meth)acrylate wie beispielsweise Hydroxyethyl(meth)acrylat, Hydroxypropyl(meth)acrylat;
Alkylpolyethylenglykol(meth)acrylat;
Cn-Vinylester oder Cn-Vinylether mit n größer als 6 wie beispielsweise Dodecensäurevinylester, Stearinsäurevinylester, Dodecylvinylether, Oktadecylvinylether;
Acrylnitrile, Acrylamide, Vinylformamide, Allylalkohole, Vinylphosphonate;
vinylsubstituierte Heterozyklen wie beispielsweise N-Vinylpyrrolidon oder N-Vinylcaprolactam;
ungesättigte Organosulfonsäuren wie beispielsweise Styrolsulfonsäure, 2-Acrylamido-2-Methylpropansulfonsäure, Vinylsulfonsäure, Methallylsulfonsäure.Suitable monomeric units (C) which can be copolymerized with the monomeric units (A) and (B) are, for example, the substance groups listed below.
α-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C 22 -α-olefin, especially 1-dodecene, 1-octadecene or C 22 -α-olefin;
Olefin mixtures of α-olefins having 10 to 28 carbon atoms such as C 10 -C 12 α-olefins (α-olefins having 10 and 12 carbon atoms, respectively), C 12 -C 14 α-olefins, C 14 -C 18 α Olefins, C 20 -C 24 α-olefins, C 24 -C 28 α-olefins, preferably C 20 -C 24 α-olefins;
Olefin mixtures of at least two different α-olefins having 30 or more carbon atoms such as C 30 + α-olefins (olefin mixture of C 30 -α-olefin and at least one other α-olefin having an even number of carbon atoms greater than 30);
in particular polyisobutenes having an average of 12 to 100 carbon atoms and an α-olefin content of greater than 80%, such as, for example, polyisobutene-1000 (polyisobutene having an average molar mass of 1000);
C n - (meth) acrylates with n greater than 6, such as, for example, ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate;
Hydroxy (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate;
Alkylpolyethylene glycol (meth) acrylate;
C n vinyl esters or C n vinyl ethers with n greater than 6, such as vinyl dodecenoate, vinyl stearate, dodecyl vinyl ether, octadecyl vinyl ether;
Acrylonitriles, acrylamides, vinylformamides, allyl alcohols, vinylphosphonates;
vinyl-substituted heterocycles such as N-vinylpyrrolidone or N-vinylcaprolactam;
unsaturated organosulfonic acids such as styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, methallylsulfonic acid.

Die Copolymere können in Form der freien Säure, eines Salzes davon oder des Anhydrides eingesetzt werden, sie können aber auch teilneutralisiert vorliegen. Insbesondere können die Copolymere in Form ihrer Natrium,- Kalium- oder Ammoniumsalze vorliegen.The copolymers can be used in the form of the free acid, a salt thereof or the anhydride, but they can also be partially neutralized. In particular, the copolymers may be in the form of their sodium, potassium or ammonium salts.

Die Copolymere können einer zusätzlichen Umsetzung unterworfen werden. Dies sind beispielsweise Esterbildungen mit C1-C20-Alkoholen, Alkylpolyalkylenglykolen wie beispielsweise Methylpolyethylenglykol mit einem mittleren Ethoxilierungsgrad von 45 oder Alkylpolyethylenglykol-block-polypropylenglykolen wie z.B. Methylpolyethylenglykol-block-Polypropylenglykol mit 40 Ethylenoxid-Einheiten und 5 Propylenoxid-Einheiten. Diese Umsetzung kann ebenso mit C1-C20-Aminen oder Alkylpolyalkylenglykolaminen wie Methylpolyethylenglykolamin mit einem mittleren Ethoxilierungsgrad von 8 unter Ausbildung von Amidbindungen durchgeführt werden.The copolymers may be subjected to additional reaction. These are, for example, ester formations with C 1 -C 20 -alcohols, alkylpolyalkylene glycols such as, for example, methylpolyethylene glycol having a mean degree of ethoxylation of 45 or alkylpolyethyleneglycol-block-polypropylene glycols, for example methylpolyethyleneglycol-block-polypropylene glycol having 40 ethylene oxide units and 5 propylene oxide units. This reaction can also be carried out with C 1 -C 20 amines or Alkylpolyalkylenglykolaminen such as methyl polyethylene glycol amine having a mean degree of ethoxylation of 8 to form amide bonds.

Das gewichtsmittlere Molekulargewicht der Copolymere beträgt 1000 bis 200 000, bevorzugt 2000 bis 50 000, besonders bevorzugt 2000 bis 20 000. Die Copolymere werden mit dem Fachmann bekannten Verfahren hergestellt.The weight-average molecular weight of the copolymers is from 1000 to 200,000, preferably from 2,000 to 50,000, more preferably from 2,000 to 20,000. The copolymers are prepared by methods known to the person skilled in the art.

In einer bevorzugten Ausführung der vorliegenden Erfindung werden Copolymere verwendet, die als Monomerenbaustein (A) Maleinsäure und / oder Maleinsäureanhydrid und mindestens einen Monomerenbaustein (B) aus der Gruppe bestehend aus Cyclopenten, Hexen und technisches Diisobuten enthalten. Besonders bevorzugt werden Copolymere verwendet, die als Monomerenbaustein (A) Maleinsäureanhydrid und als Monomerenbaustein (B) technisches Diisobuten enthalten.In a preferred embodiment of the present invention, copolymers are used which comprise as monomer building block (A) maleic acid and / or maleic anhydride and at least one monomer building block (B) from the group consisting of cyclopentene, hexene and technical diisobutene. Particular preference is given to using copolymers which contain technical diisobutene as monomer building block (A), maleic anhydride and as monomer building block (B).

In einer weiterhin bevorzugten Ausführungsform der vorliegenden Erfindung liegen die Copolymere in Form ihres Alkali- oder Ammoniumsalzes, besonders bevorzugt in Form ihres Natrium- oder Ammoniumsalzes vor.In a further preferred embodiment of the present invention, the copolymers are present in the form of their alkali metal or ammonium salt, particularly preferably in the form of their sodium or ammonium salt.

In der Reinigerformulierung sind die Copolymere zu 0,01 bis 10 Gew.%, bevorzugt zu 0,05 bis 5 Gew.%, besonders bevorzugt zu 0,1 bis 3 Gew.%, bezogen auf das Gesamtgewicht der Reinigerformulierung enthalten.In the detergent formulation, the copolymers are included at 0.01 to 10 wt%, preferably at 0.05 to 5 wt%, more preferably at 0.1 to 3 wt%, based on the total weight of the detergent formulation.

Die Copolymere können in Form ihrer wässrigen Lösungen oder Dispersionen eingesetzt werden. Weiterhin können die Copolymere auch in fester Form, zum Beispiel als Pulver oder Granulat, verwendet werden. Diese sind beispielsweise durch Sprühtrocknung mit eventuell anschließender Kompaktierung oder durch Sprühgranulierung erhältlich. Bei der Trocknung können weitere wasserlösliche Stoffe wie z. B. Natriumsulfat, Natriumchlorid, Natriumacetat, Natriumcitrat, Pentanatriumtriphosphat, Natriumcarbonat, Natriumhydrogencarbonat oder Polymere wie beispielsweise Polyacrylate, Polyacrylsäure, Polyvinylalkohol, Sokalan® CP 5 (Copolymer enthaltend Polyacrylsäure und Maleinsäure als Monomerenbausteine), Cellulose und Cellulosederivate, Zucker und Zuckerderivate im Sinne eines Cogranulates eingearbeitet werden. Weiterhin können auch schwer wasserlösliche oder wasserunlösliche Stoffe eingearbeitet bzw. als Trägersubstanzen verwendet werden wie Zeolithe und gefällte Kieselsäuren. Insbesonders eignen sich (Co-) Granulate, die die Copolymere und zu 10 bis 50 Gew.-% Natriumsulfat, Natriumcarbonat, Natriumhydrogencarbonat und/oder Polyacrylate enthalten.The copolymers can be used in the form of their aqueous solutions or dispersions. Furthermore, the copolymers can also be used in solid form, for example as a powder or granules. These are available, for example, by spray drying with possible subsequent compaction or by spray granulation. During drying, other water-soluble substances such. As sodium sulfate, sodium chloride, sodium acetate, sodium citrate, pentasodium triphosphate, sodium carbonate, sodium bicarbonate or polymers such as polyacrylates, polyacrylic acid, polyvinyl alcohol, Sokalan ® CP 5 (copolymer containing polyacrylic acid and maleic acid as monomeric units), cellulose and cellulose derivatives, sugars and sugar derivatives in the sense of a cogranulate be incorporated. Furthermore, substances which are sparingly soluble in water or insoluble in water may also be incorporated or used as carrier substances, such as zeolites and precipitated silicas. Particularly suitable are (co) granules which contain the copolymers and from 10 to 50% by weight of sodium sulfate, sodium carbonate, sodium bicarbonate and / or polyacrylates.

Die Copolymere können sowohl in flüssigen, gelförmigen, pulverförmigen, granulären als auch tablettenförmigen Geschirrreinigern erfindungsgemäß eingesetzt werden. Es ist möglich, die Copolymere gegebenenfalls mit anderen Formulierungsbestandteilen in besondere Kompartimente wie Mikrokapseln oder Gelkapseln einzuarbeiten. Des Weiteren können die Copolymere auch in speziellen Kompartimenten innerhalb von Geschirrreiniger-Tabletten eingebaut werden, die gegebenenfalls ein gegenüber den anderen Tablettenkompartimenten unterschiedliches Auflöseverhalten zeigen können. Dies können sowohl spezielle Tablettenschichten sein, als auch bestimmte in die Tablette eingelassene, mit der Tablette verklebte oder von der Tablette umhüllte Formkörper.The copolymers can be used according to the invention both in liquid, gel, powdery, granular and tablet dishwashing detergents. It is possible to incorporate the copolymers optionally with other formulation ingredients into particular compartments such as microcapsules or gelcapsules. Furthermore, the copolymers may also be incorporated in special compartments within dishwashing detergent tablets, which may optionally exhibit different dissolution behavior than the other tablet compartments. These may be both special tablet layers and certain moldings embedded in the tablet, glued to the tablet or encased in the tablet.

Außer den zuvor beschriebenen Copolymeren enthält die Reinigerformulierung weitere dem Fachmann bekannte Zusatzkomponenten. Beispiele hierfür sind nachstehend aufgeführt.In addition to the copolymers described above, the cleaner formulation contains additional components known to the person skilled in the art. Examples are listed below.

BuilderBuilder

Es können wasserlösliche und wasserunlösliche Builder eingesetzt werden, deren Hauptaufgabe im Binden von Calcium und Magnesium besteht. Übliche Builder, die mit 10 bis 90 Gew.-% bezogen auf die gesamte Zubereitung in der Reinigerformulierung zugegen sein können, sind beispielsweise Phosphate wie Alkaliphosphate und polymere Alkaliphosphate, die in Form ihrer alkalischen, neutralen oder sauren Natrium- oder Kaliumsalze vorliegen können.It is possible to use water-soluble and water-insoluble builders whose main task is the binding of calcium and magnesium. Typical builders which can be present in the detergent formulation at 10 to 90% by weight, based on the total formulation, are, for example, phosphates, such as alkali metal phosphates and polymeric alkali phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.

Beispiele hierfür sind Trinatriumphosphat, Tetranatriumdiphosphat, Dinatriumdihydrogenphosphat, Pentanatriumtripolyphosphat, sogenanntes Natriumhexametaphosphat, oligomeres Trinatriumphosphat mit Oligomerisierungsgraden von 5 bis 1000, insbesondere von 5 bis 50, sowie die entsprechenden Kaliumsalze bzw. Gemische aus Natriumhexametaphosphat und den entsprechenden Kaliumsalzen bzw. Gemische aus Natrium- und Kaliumsalzen. Diese Phosphate werden vorzugsweise im Bereich von 5 Gew.-% bis 65 Gew.-% bezogen auf die gesamte Rezeptur und berechnet als wasserfreie Aktivsubstanz eingesetzt.Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen phosphate, pentasodium tripolyphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of from 5 to 1000, in particular from 5 to 50, and the corresponding potassium salts or mixtures of sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts , These phosphates are preferably used in the range of 5 wt .-% to 65 wt .-% based on the total formulation and calculated as anhydrous active substance.

Weiterhin können als Builder verwendet werden:

  • niedermolekulare Carbonsäuren sowie deren Salze wie Alkalicitrate, insbesondere wasserfreies Trinatriumcitrat oder Trinatriumcitratdihydrat, Alkalisuccinate, Alkalimalonate, Fettsäuresulfonate, Oxydisuccinat, Alkyl- oder Alkenyldisuccinate, Gluconsäuren, Oxadiacetate, Carboxymethyloxysuccinate, Tartratmonosuccinat, Tartratdisuccinat, Tartratmonoacetat, Tartratdiacetat, α-Hydroxypropionsäure;
  • oxiderte Stärken, oxidierte Polysaccharide;
  • homo- und copolymere Polycarbonsäuren und deren Salze wie Polyacrylsäure, Polymethacrylsäure, Copolymere aus Maleinsäure und Acrylsäure;
  • Pfropfpolymerisate von monoethylenisch ungesättigten Mono- und/oder Dicarbonsäuren auf Monosaccharide, Oligosaccharide, Polysaccharide oder Polyasparaginsäure;
  • Aminopolycarboxylate und Polyasparaginsäure;
  • Komplexbildner und Phosphonate sowie deren Salze wie Nitrilotriessigsäure, Ethylendiamintetraessigsäure, Diethylentriaminpentaessigsäure, Hydroxyethylethylendiamintriessigsäure, Methylglycindiessigsäure, 2-Phosphono-1,2,4-butantricarbonsäure, Aminotri-(methylenphosphonsäure), 1-Hydroxyethylen(1,1-diphosphonsäure), Ethylendiamin-tetramethylen-phosphonsäure, Hexamethylendiamin-tetramethylen-phosphonsäure oder Diethylentriamin-pentamethylen-phosphonsäure;
  • Silikate wie Natriumdisilikat und Natriummetasilikat;
  • wasserunlösliche Builder wie Zeolithe und kristallinen Schichtsilikate.
Furthermore, it is possible to use as builders:
  • low molecular weight carboxylic acids and their salts, such as alkali citrates, in particular anhydrous trisodium citrate or trisodium citrate dihydrate, alkali metal succinates, alkali metal malates, fatty acid sulfonates, oxydisuccinate, alkyl or alkenyl disuccinates, gluconic acids, oxadiacetates, carboxymethyloxysuccinates, tartrate monosuccinate, tartrate disuccinate, tartrate monoacetate, tartrate diacetate, .alpha.-hydroxypropionic acid;
  • oxidized starches, oxidized polysaccharides;
  • homo- and copolymeric polycarboxylic acids and their salts, such as polyacrylic acid, polymethacrylic acid, copolymers of maleic acid and acrylic acid;
  • Graft polymers of monoethylenically unsaturated mono- and / or dicarboxylic acids on monosaccharides, oligosaccharides, polysaccharides or polyaspartic acid;
  • Aminopolycarboxylates and polyaspartic acid;
  • Complexing agents and phosphonates and their salts, such as nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, methylglycinediacetic acid, 2-phosphono-1,2,4-butanetricarboxylic acid, aminotri- (methylenephosphonic acid), 1-hydroxyethylene (1,1-diphosphonic acid), ethylenediamine tetramethylene phosphonic acid, hexamethylenediamine tetramethylene phosphonic acid or diethylene triamine pentamethylene phosphonic acid;
  • Silicates such as sodium disilicate and sodium metasilicate;
  • water-insoluble builders such as zeolites and crystalline phyllosilicates.

Die kristallinen Schichtsilikate entsprechen insbesondere der allgemeinen Formel NaMSixO2x+1 * y H2O, wobei M Natrium oder Wasserstoff darstellt, x eine Zahl von 1,9 bis 22, vorzugweise 1,9 bis 4, ist und y für eine Zahl von 0 bis 33 steht. Bekannte Beispiele hierfür sind insbesondere α-Na2Si2O5, β-Na2Si2O5, δ-Na2Si2O5. Ebenso zählen hierzu Mischungen der vorgenannten Buildersubstanzen. Bevorzugt werden Trinatriumcitrat und/oder Pentanatriumtripolyphosphat und/oder Natriumcarbonat und/oder Natriumbicarbonat und/oder Gluconate und/oder silikatische Builder aus der Klasse der Disilikate und/oder Metasilikate eingesetzt.The crystalline sheet silicates correspond in particular to the general formula NaMSi x O 2x + 1 * y H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably 1.9 to 4, and y is a number from 0 to 33 stands. Known examples of these are in particular α-Na 2 Si 2 O 5 , β-Na 2 Si 2 O 5 , δ-Na 2 Si 2 O 5 . Likewise, these include mixtures of the abovementioned builder substances. Preference is given to using trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicatic builders from the class of disilicates and / or metasilicates.

Alkaliträgeralkali carriers

Als weitere Bestandteile der Reinigerformulierung können Alkaliträger zugegen sein. Als Alkaliträger gelten Ammonium- und/oder Alkalimetallhydroxide, Ammonium- und/oder Alkalimetallcarbonate, Ammonium- und/oder Alkalimetallhydrogencarbonate, Ammonium- und/oder Alkalimetallsesquicarbonate, Ammonium- und/oder Alkalisilikate, Ammonium- und/oder Alkalimetasilikate und Mischungen der vorgenannten Stoffe, wobei bevorzugt Ammonium- und/oder Alkalicarbonate, insbesondere Natriumcarbonat, Natriumhydrogencarbonat oder Natriumsesquicarbonat eingesetzt werden.As further constituents of the cleaner formulation, alkali carriers may be present. Suitable alkali carriers are ammonium and / or alkali metal hydroxides, ammonium and / or alkali metal carbonates, ammonium and / or alkali metal hydrogencarbonates, ammonium and / or alkali metal sesquicarbonates, ammonium and / or alkali metal silicates, ammonium and / or alkali metal silicates and mixtures of the abovementioned substances. preferably ammonium and / or alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate are used.

Bevorzugte Kombinationen aus Builder und Alkaliträger sind Mischungen aus Tripolyphosphat und Natriumcarbonat bzw. Tripolyphosphat, Natriumcarbonat und Natriumdisilikat.Preferred combinations of builder and alkali carriers are mixtures of tripolyphosphate and sodium carbonate or tripolyphosphate, sodium carbonate and sodium disilicate.

Tensidesurfactants

Die Reinigerformulierung enthält bevorzugt als weitere Komponente schwach oder niedrigschäumende nichtionische Tenside in Anteilen von 0,1 bis 20 Gew.%, bevorzugt 0,1 bis 10 Gew.-%, besonders bevorzugt 0,25 bis 4 Gew.-%.The detergent formulation preferably contains, as further component, weakly or low-foaming nonionic surfactants in proportions of from 0.1 to 20% by weight, preferably from 0.1 to 10% by weight, particularly preferably from 0.25 to 4% by weight.

Dies sind zum Beispiel Tenside aus der Gruppe der Fettalkoholalkoxylate der allgemeinen Formel (II), die kommerziell beispielsweise unter den Produktbezeichnungen Plurafac® (BASF Aktiengesellschaft), insbesondere Plurafac LF 403, oder Dehypon® (Cognis) verfügbar sind.

        R2-O-(CH2-CH2-O)p-(CHR1-CH2-O)m-R3     (II)

in der R1 und R3 unabhängig voneinander für CnH2n+1 stehen und n 1 bis 4 ist,
R2 für CnH2n+1 steht und n 3 bis 30 ist,
m und p unabhängig voneinander 0 bis 300 ist.These are for example surfactants from the group of fatty alcohol alkoxylates of the general formula (II) which are commercially available for example under the product Plurafac ® (BASF Aktiengesellschaft) and in particular Plurafac LF 403 ® or Dehypon (Cognis).

R 2 is -O- (CH 2 -CH 2 -O) p - (CHR 1 -CH 2 -O) m -R 3 (II)

in which R 1 and R 3 independently of one another represent C n H 2n + 1 and n is 1 to 4,
R 2 is C n H 2n + 1 and n is 3 to 30,
m and p are independently 0 to 300.

Weiterhin können Di- und Multiblockcopolymerisate aufgebaut aus Ethylenoxid und Propylenoxid eingesetzt werden, die beispielsweise unter der Bezeichnung Pluronic® (BASF Aktiengesellschaft) oder Tetronic® (BASF Corporation) kommerziell erhältlich sind. Weiterhin können Umsetzungsprodukte aus Sorbitanestern mit Ethylenoxid und/oder Propylenoxid verwendet werden. Ebenfalls eignen sich Aminoxide oder Alkylglycoside. Eine Übersicht geeigneter nichtionischer Tenside gibt die EP-A 851 023 sowie die DE-A 198 19 187 .Further, di- and multiblock copolymers may be formed from ethylene oxide and propylene oxide, for example, under the name Pluronic ® (BASF Aktiengesellschaft) or Tetronic ® (BASF Corporation) are commercially available. Furthermore, reaction products of sorbitan esters with ethylene oxide and / or propylene oxide can be used. Also suitable are amine oxides or alkyl glycosides. An overview of suitable nonionic surfactants are the EP-A 851 023 as well as the DE-A 198 19 187 ,

Die Formulierung kann weiterhin anionische oder zwitterionische Tenside enthalten, bevorzugt in Abmischung mit nichtionischen Tensiden. Geeignete anionische und zwitterionischer Tenside sind ebenfalls in EP-A 851 023 sowie DE-A 198 19 187 genannt.The formulation may further contain anionic or zwitterionic surfactants, preferably in admixture with nonionic surfactants. Suitable anionic and zwitterionic surfactants are also in EP-A 851 023 such as DE-A 198 19 187 called.

Bleichmittelbleach

Bleichmittel unterteilen sich in Sauerstoffbleichmittel und chlorhaltige Bleichmittel. Verwendung als Sauerstoffbleichmittel finden Alkalimetallperborate und deren Hydrate sowie Alkalimetallpercarbonate. Bevorzugte Bleichmittel sind hierbei Natriumperborat in Form des Mono- oder Tetrahydrats, Natriumpercarbonat oder die Hydrate von Natriumpercarbonat.Bleaching agents are subdivided into oxygen bleaching agents and chlorine-containing bleaching agents. Use as oxygen bleach find alkali metal perborates and their hydrates and alkali metal percarbonates. Preferred bleaching agents here are sodium perborate in the form of the mono- or tetrahydrate, sodium percarbonate or the hydrates of sodium percarbonate.

Ebenfalls als Sauerstoffbleichinittel einsetzbar sind Persulfate und Wasserstoffperoxid.Also usable as oxygen bleaching agents are persulfates and hydrogen peroxide.

Typische Sauerstoffbleichmittel sind auch organische Persäuren wie beispielsweise Perbenzoesäure, Peroxy-alpha-Naphthoesäure, Peroxylaurinsäure, Peroxystearinsäure, Phthalimidoperoxycapronsäure, 1,12-Diperoxydodecandisäure, 1,9-Diperoxyazelaic-Säure, Diperoxoisophthalsäure oder 2-Decyldiperoxybutan-1,4-disäure.Typical oxygen bleaches are also organic peracids such as perbenzoic acid, peroxy-alpha-naphthoic acid, peroxylauric acid, peroxystearic acid, phthalimidoperoxycaproic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxoisophthalic acid or 2-decyldiperoxybutane-1,4-diacid.

Außerdem können auch folgende Sauerstoffbleichmittel in der Reinigerformulierung Verwendung finden:

  • Kationische Peroxysäuren, die in den Patentanmeldungen US 5,422,028 , US 5,294,362 sowie US 5,292,447 beschrieben sind;
In addition, the following oxygen bleaches can also be used in the detergent formulation:
  • Cationic peroxyacids disclosed in the patent applications US 5,422,028 . US 5,294,362 such as US 5,292,447 are described;

Sulfonylperoxysäuren, die in der Patentanmeldung US 5,039,447 beschrieben sind.Sulfonyl peroxyacids disclosed in the patent application US 5,039,447 are described.

Sauerstoffbleichmittel werden in Mengen von 0,5 bis 30 Gew.%, bevorzugt von 1 bis 20 Gew.%, besonders bevorzugt von 3 bis 15 Gew.%, bezogen auf die gesamte Reinigerformulierung eingesetzt.Oxygen bleaching agents are used in amounts of from 0.5 to 30% by weight, preferably from 1 to 20% by weight, particularly preferably from 3 to 15% by weight, based on the total detergent formulation.

Chlorhaltige Bleichmittel sowie die Kombination von chlorhaltigen Bleichmittel mit peroxidhaltigen Bleichmitteln können ebenfalls verwendet werden. Bekannte chlorhaltige Bleichmittel sind beispielsweise 1,3-Dichloro-5,5-dimethylhydantoin, N-Chlorosulfamid, Chloramin T, Dichloramin T, Chloramin B, N,N'-Dichlorbenzoylharnstoff, p-Toluolsulfondichloroamid oder Trichlorethylamin. Bevorzugte chlorhaltige Bleichmittel sind Natriumhypochlorit, Calciumhypochlorit, Kaliumhypochlorit, Magnesiumhypochlorit, Kaliumdichloroisocyanurat oder Natriumdichloroisocyanurat.Chlorine-containing bleaches as well as the combination of chlorine-containing bleach with peroxide-containing bleaches can also be used. Known chlorine-containing bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, dichloramine T, chloramine B, N, N'-dichlorobenzoylurea, p-toluenesulfondichloroamide or trichloroethylamine. Preferred chlorine-containing bleaching agents are sodium hypochlorite, calcium hypochlorite, potassium hypochlorite, magnesium hypochlorite, potassium dichloroisocyanurate or sodium dichloroisocyanurate.

Chlorhaltige Bleichmittel werden in Mengen von 0,1 bis 20 Gew.%, bevorzugt von 0,1 bis 10 Gew.%, besonders bevorzugt von 0,3 bis 8 Gew.%, bezogen auf die gesamte Reinigerformulierung eingesetzt.Chlorine-containing bleaching agents are used in amounts of from 0.1 to 20% by weight, preferably from 0.1 to 10% by weight, particularly preferably from 0.3 to 8% by weight, based on the total detergent formulation.

Weiterhin können in geringen Mengen Bleichmittelstabilisatoren wie beispielsweise Phosphonate, Borate, Metaborate, Metasilikate oder Magnesiumsalze zugegeben werden.Furthermore, bleach stabilizers such as phosphonates, borates, metaborates, metasilicates or magnesium salts can be added in small amounts.

BleichaktivatorenBleach activators

Bleichaktivatoren sind Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 Kohlenstoffatomen, insbesondere 2 bis 4 Kohlenstoffatomen, und/oder substituierte Perbenzoesäure ergeben. Geeignet sind Verbindungen, die eine oder mehrere N- bzw. O-Acylgruppen und/oder gegebenenfalls substiuierte Benzoylgruppen enthalten, beispielsweise Substanzen aus der Klasse der Anhydride, Ester, Imide, acylierten Imidazole oder Oxime. Beispiele sind Tetracetylethylendiamin (TAED), Tetraacetylmethylendiamin (TAMD), Tetraacetylglykoluril (TAGU), Tetraacetylhexylendiamin (TAHD), N-Acylimide, wie beispielsweise N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, wie beispielsweise n-Nonanoyl- oder Isononanoyloxybenzolsulfonate (n- bzw. iso-NOBS), Pentaacetylglucose (PAG), 1,5-Diacetyl-2,2-dioxo-hexahydro-1,3,5-triazin (DADHT) oder Isatosäureanhydrid (ISA).Bleach activators are compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or substituted perbenzoic acid. Suitable compounds are those which contain one or more N- or O-acyl groups and / or optionally substituted benzoyl groups, for example substances from the class of the anhydrides, esters, imides, acylated imidazoles or oximes. Examples are tetraethylethylenediamine (TAED), tetraacetylmethylenediamine (TAMD), tetraacetylglycoluril (TAGU), tetraacetylhexylenediamine (TAHD), N-acylimides, such as N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, such as n-nonanoyl or isononanoyloxybenzenesulfonates (n- or n-nonanoyl) iso-NOBS), pentaacetylglucose (PAG), 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine (DADHT) or isatoic anhydride (ISA).

Ebenfalls als Bleichaktivatoren eignen sich Nitrilquats wie beispielsweise N-Methyl-Morpholinium-Acetonitril-Salze (MMA-Salze) oder Trimethylammoniumacetonitril-Salze (TMAQ-Salze).Also suitable as bleach activators are nitrile quats, such as, for example, N-methyl-morpholinium-acetonitrile salts (MMA salts) or trimethylammonium acetonitrile salts (TMAQ salts).

Bevorzugt eignen sich Bleichaktivatoren aus der Gruppe bestehend aus mehrfach acylierten Alkylendiamine, besonders bevorzugt TAED, N-Acylimide, besonders bevorzugt NOSI, acylierte Phenolsulfonate, besonders bevorzugt n- oder iso-NOBS, MMA und TMAQ.Bleach activators are preferably suitable from the group consisting of polyacylated alkylenediamines, particularly preferably TAED, N-acylimides, particularly preferably NOSI, acylated phenolsulfonates, more preferably n- or iso-NOBS, MMA and TMAQ.

Weiterhin können folgende Substanzen als Bleichaktivatoren in der Reinigerformulierung Verwendung finden:

  • Carbonsäureanhydride wie beispielsweise Phthalsäureanhydrid;
  • acylierte mehrwertige Alkohole wie beispielsweise Triacetin, Ethylenglykoldiacetat oder 2,5- Diacetoxy-2,5-dihydrofuran;
  • die aus DE-A 196 16 693 und DE-A 196 16 767 bekannten Enolester sowie acetyliertes Sorbitol und Mannitol bzw. deren in EP-A 525 239 beschriebenen Mischungen;
  • acylierte Zuckerderivate, insbesondere Pentaacetylglukose (PAG), Pentaacetylfructose, Tetraacetylxylose und Octaacetyllactose, sowie acetyliertes, gegebenenfalls N-alkyliertes, Glucamin und Gluconolacton, und/oder N-acylierte Lactame, beispielsweise N-Benzoylcaprolactam, die aus den Schriften WO 94/27 970 , WO 94/28 102 , WO 94/28 103 , WO 95/00 626 , WO 95/14 759 sowie WO 95/17 498 bekannt sind;
  • die in DE-A 196 16 769 aufgeführten hydrophil substituierten Acylacetale sowie die in DE-A 196 16 770 und WO 95/14 075 beschriebenen Acyllactame können ebenso wie die aus DE-A 44 43 177 bekannten Kombinationen konventioneller Bleichaktivatoren eingesetzt werden.
Furthermore, the following substances can be used as bleach activators in the detergent formulation:
  • Carboxylic acid anhydrides such as phthalic anhydride;
  • acylated polyhydric alcohols such as triacetin, ethylene glycol diacetate or 2,5-diacetoxy-2,5-dihydrofuran;
  • from DE-A 196 16 693 and DE-A 196 16 767 known enol esters and acetylated sorbitol and mannitol or their in EP-A 525 239 described mixtures;
  • acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, as well as acetylated, optionally N-alkylated, glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are known from the documents WO 94/27 970 . WO 94/28 102 . WO 94/28 103 . WO 95/00626 . WO 95/14759 such as WO 95/17498 are known;
  • in the DE-A 196 16 769 listed hydrophilic substituted acyl acetals and in DE-A 196 16 770 and WO 95/14075 acyl lactams described as well as those from DE-A 44 43 177 known combinations of conventional bleach activators are used.

Bleichaktivatoren werden in Mengen von 0,1 bis 10 Gew.%, bevorzugt von 1 bis 9 Gew.-%, besonders bevorzugt von 1,5 bis 8 Gew.%, bezogen auf die gesamte Reinigerformulierung eingesetzt.Bleach activators are used in amounts of from 0.1 to 10% by weight, preferably from 1 to 9% by weight, particularly preferably from 1.5 to 8% by weight, based on the total detergent formulation.

Bleichkatalysatorenbleach catalysts

Zusätzlich zu den oben aufgeführten konventionellen Bleichaktivatoren bzw. an deren Stelle können auch die aus EP-A 446 982 und EP-A 453 003 bekannten Sulfonimine und/oder bleichverstärkende Übergangsmetallsalze beziehungsweise Übergangsmetallkomplexe als sogenannte Bleichkatalysatoren in den Reinigerformulierungen enthalten sein.In addition to the conventional bleach activators listed above or in their place can also from EP-A 446 982 and EP-A 453 003 be known Sulfonimine and / or bleach-enhancing transition metal salts or transition metal complexes as so-called bleach catalysts contained in the cleaner formulations.

Zu den in Frage kommenden Übergangsmetallverbindungen gehören beispielsweise die aus DE-A 195 29 905 bekannten Mangan-, Eisen-, Cobalt-, Ruthenium- oder Molydän-Salenkomplexe und deren aus DE-A 196 20 267 bekannte N-Analogverbindungen, die aus DE-A 195 36 082 bekannten Mangan-, Eisen-, Cobalt-, Ruthenium- oder Molybdän-Carbonylkomplexe, die in DE-A 196 05 688 beschriebenen Mangan-, Eisen-, Cobalt, Ruthenium-, Molybdän-, Titan-, Vanadium- und Kupfer-Komplexe mit stickstoffhaltigen Tripod-Liganden, die aus DE-A 196 20 411 bekannten Cobalt-, Eisen-, Kupfer- und Ruthenium-Amminkomplexe, die in DE-A 44 16 438 beschriebenen Mangan-, Kupfer-und Cobalt-Komplexe, die in EP-A 272 030 beschriebenen Cobalt-Komplexe, die aus EP-A 693 550 bekannten Mangan-Komplexe, die aus EP-A 392 592 bekannten Mangan-, Eisen-, Cobalt- und Kupfer-Komplexe und/oder die in EP-A 443 651 , EP-A 458 397 , EP-A 458 398 , EP-A 549 271 , EP-A 549 272 , EP-A 544 490 und EP-A 544 519 beschriebenen Mangan-Komplexe. Kombinationen aus Bleichaktivatoren und Übergangsmetall-Bleichkatalysatoren sind beispielsweise aus DE-A 196 13 103 und WO 95/27 775 bekannt.Examples of suitable transition metal compounds include those of DE-A 195 29 905 known manganese, iron, cobalt, ruthenium or Molydän salen complexes and their DE-A 196 20 267 known N-analogues consisting of DE-A 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, which in DE-A 196 05 688 described manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, which DE-A 196 20 411 known cobalt, iron, copper and ruthenium ammine complexes, which in DE-A 44 16 438 described manganese, copper and cobalt complexes in EP-A 272 030 described cobalt complexes consisting of EP-A 693 550 known manganese complexes that are made EP-A 392 592 known manganese, iron, cobalt and copper complexes and / or in EP-A 443 651 . EP-A 458 397 . EP-A 458 398 . EP-A 549 271 . EP-A 549 272 . EP-A 544 490 and EP-A 544 519 described manganese complexes. Combinations of bleach activators and transition metal bleach catalysts are for example DE-A 196 13 103 and WO 95/27 775 known.

Zweikernigen Mangan-Komplexe, die 1,4,7-Trimethyl-1,4,7-triazacyclononan (TMTACN) enthalten, wie beispielsweise [(TMTACN)2MnIVMnIV(µ-O)3]2+(PF6 -)2 eignen sich ebenfalls als wirkungsvolle Bleichkatalysatoren. Diese Mangan-Komplexe sind in den zuvor genannten Schriften ebenfalls beschrieben.Binuclear manganese complexes containing 1,4,7-trimethyl-1,4,7-triazacyclononane (TMTACN) such as, for example, [(TMTACN) 2 Mn IV Mn IV (μ-O) 3 ] 2+ (PF 6 - ) 2 are also useful as effective bleach catalysts. These manganese complexes are also described in the aforementioned publications.

Als Bleichkatalysatoren eignen sich bevorzugt bleichverstärkende Übergangsmetallkomplexe oder -salze aus der Gruppe bestehend aus den Mangansalzen und -komplexen und den Cobaltsalzen und -komplexen. Besonders bevorzugt eignen sich die Cobalt(amin)-Komplexe, die Cobalt(acetat)-Komplexe, die Cobalt(carbonyl)-Komplexe, die Chloride des Cobalts oder Mangans, Mangansulfat oder [(TMTACN)2MnIVMnIV(µ-O)3]2+(PF6 -)2.Suitable bleach catalysts are preferably bleach-enhancing transition metal complexes or salts from the group consisting of the manganese salts and complexes and the cobalt salts and complexes. Particularly suitable are the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate or [(TMTACN) 2 Mn IV Mn IV (μ-O ) 3 ] 2+ (PF 6 - ) 2 .

Bleichkatalysatoren werden in Mengen von 0,0001 bis 5 Gew.%, bevorzugt von 0,0025 bis 1. Gew.%, besonders bevorzugt von 0,01 bis 0,25 Gew.%, bezogen auf die gesamte Reinigerformulierung eingesetzt.Bleach catalysts are used in amounts of from 0.0001 to 5% by weight, preferably from 0.0025 to 1% by weight, particularly preferably from 0.01 to 0.25% by weight, based on the total detergent formulation.

Korrosionsinhibitorencorrosion inhibitors

Insbesondere können Silberschutzmittel aus der Gruppe der Triazole, der Benzotriazole, der Bisbenzotriazole, der Aminotriazole, der Alkylaminotriazole und der Übergangsmetallsalze oder- komplexe eingesetzt werden. Besonders bevorzugt zu verwenden sind Benzotriazol und/oder Alkylaminotriazol. Darüber hinaus verwendet man in Reinigerformulierungen häufig aktivchlorhaltige Mittel, die das Korrodieren der Silberoberfläche deutlich vermindern können. In chlorfreien Reinigern werden bevorzugt Sauerstoff- und stickstoffhaltige organische redoxaktive Verbindungen wie zwei- und dreiwertige Phenole, z.B. Hydrochinon, Brenzkatechin, Hydroxyhydrochinon, Gallussäure, Phloroglucin, Pyrogallol bzw. Derivate dieser Verbindungsklassen, eingesetzt. Auch salz-und komplexartige anorganische Verbindungen wie Salze der Metalle Mn, Ti, Zr Hf, V, Co und Ce finden häufig Verwendung. Bevorzugt werden hierbei die Übergangsmetallsalze, die ausgewählt sind aus der Gruppe der Mangan und/oder Cobaltsalze und/oder -komplexe, besonders bevorzugt aus der Gruppe der Cobalt(amin)-Komplexe, der Cobalt(acetat)-Komplexe, der Cobalt-(Carbonyl)-Komplexe, der Chloride des Cobalts oder Mangans sowie des Mangansulfats. Ebenfalls können Zinkverbindungen oder Wismutverbindungen zur Verhinderung der Korrosion am Spülgut eingesetzt werden.In particular, silver protectants from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used. Particularly preferred too use are benzotriazole and / or alkylaminotriazole. In addition, active chlorine-containing agents are often used in cleaner formulations, which can significantly reduce the corrosion of the silver surface. In chlorine-free cleaners are preferably oxygen and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds used. Salts and complex inorganic compounds such as salts of the metals Mn, Ti, Zr Hf, V, Co and Ce are often used. Preference is given here to the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably from the group of the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl ) Complexes, the chlorides of cobalt or manganese and of manganese sulfate. Also, zinc compounds or bismuth compounds can be used to prevent corrosion on the items to be washed.

Enzymeenzymes

Dem Reinigungsmittel können zwischen 0 und 5 Gew.-% Enzyme bezogen auf die gesamte Zubereitung zugesetzt werden, um die Leistung der Reinigungsmittel zu steigern oder unter milderen Bedingungen die Reinigungsleistung in gleicher Qualität zu gewährleisten. Zu den am häufigsten verwendeten Enzymen gehören Lipasen, Amylasen, Cellulasen und Proteasen. Weiterhin können beispielsweise auch Esterasen, Pectinasen, Lactasen und Peroxidasen eingesetzt werden.The detergent can be added between 0 and 5 wt .-% of enzymes based on the total preparation in order to increase the performance of the detergents or to ensure the cleaning performance of the same quality under milder conditions. The most commonly used enzymes include lipases, amylases, cellulases and proteases. Furthermore, for example, esterases, pectinases, lactases and peroxidases can be used.

Bevorzugte Proteasen sind z. B. BLAP®140 (Biozym), Optimase® M-440 und Opticlean® M-250 (Solvay Enzymes), Maxacal® CX, Maxapem®, Esperase® (Gist Brocades), Savinase® (Novo) oder Purafect OxP (Genencor). Besonders geeignete Cellulasen und Lipasen sind Celluzym® 0,7T und Lipolase® 30T (Novo Nordisk). Besondere Verwendung als Amylasen finden Duramyl®, Termamyl® 60 T und Termamyl® 90 T (Novo), Amylase-LT® (Solvay Enzymes), Maxamyl® P5000 (Gist Brocades) oder Purafect® OxAm (Genencor).Preferred proteases are, for. B. BLAP ® 140 (Biozym), Optimase ® M-440 and Opticlean ® M-250 (Solvay Enzymes), Maxacal ® CX, Maxapem ®, Esperase ® (Gist Brocades), Savinase ® (Novo) or Purafect OxP (Genencor) , Especially suitable cellulases and lipases are Celluzyme ® and Lipolase ® 0.7T 30T (Novo Nordisk). Particular use as amylases Duramyl ®, Termamyl ® 60 T and Termamyl ® 90 T (Novo), Amylase-LT ® (Solvay Enzymes), Maxamyl ® P5000 (Gist Brocades) or Purafect ® OxAm (Genencor).

Weitere ZusätzeOther additives

Paraffinöle und Silikonöle können optional als Entschäumer und zum Schutz von Kunststoff- und Metalloberflächen eingesetzt werden. Entschäumer werden generell in Anteilen von 0,001% bis 5% dosiert. Außerdem können Farbstoffe, Parfüme und sonstige Duftstoffe der Reinigerformulierung zugesetzt werden. Reinigerformulierungen in Tablettenform können zudem Polyethylenglykol als Tabletierhilfsmittel enthalten.Paraffin oils and silicone oils can optionally be used as defoamers and for the protection of plastic and metal surfaces. Defoamers are generally dosed in proportions of 0.001% to 5%. In addition, dyes, perfumes and other perfumes may be added to the cleanser formulation. Detergent formulations in tablet form may also contain polyethylene glycol as a tablet auxiliary.

Erfindungsgemäß können die Copolymere in Reinigerformulierungen sowohl für den Haushaltsbereich als auch für den gewerblichen Bereich eingesetzt werden. Gewerbliche Reinigertypen enthalten meist ein Buildersystem auf Basis von Pentanatriumtriphosphat, und/oder Natriumcitrat und/oder Komplexbildnern wie z.B. Nitrilotriacetat. Häufig wird im Gegensatz zu Haushaltsreinigern mit Natronlauge oder Kalilauge als Alkaliträger gearbeitet. Weiterhin werden als Bleichmittel häufig Chlorverbindungen wie Natriumdichlorisocyanurat eingesetzt.According to the invention, the copolymers can be used in cleaner formulations both for the household and for the commercial sector. Commercial cleaner types usually contain a builder system based on pentasodium triphosphate, and / or sodium citrate and / or complexing agents such as e.g. Nitrilotriacetate. Frequently, in contrast to household cleaners with caustic soda or potassium hydroxide solution is used as alkali carrier. Furthermore, chlorine compounds such as sodium dichloroisocyanurate are frequently used as bleaching agents.

Reinigerformulierungen (Tabellen 1 - 3):Cleaner formulations (Tables 1 - 3):

  • Anmerkungen zu den Tabellen 1 bis 3:Notes to Tables 1 to 3:
  • *Summe aus Amylase und Protease, die im Verhältnis 1:1 vorliegen.* Sum of amylase and protease present in the ratio 1: 1.
  • Abkürzungen: R: Rahmenformulierung; V: Versuchsformulierung; AS: Acrylsäure; MS: Maleinsäure; VAc: Vinylacetat; SKS 6 : Na-SKS-6® (Warenzeichen von Clariant); Mw: gewichtsmittleres Molekulargewicht bestimmt mittels Gelpermeationschromatografie; Co-pentammin-Cl: Cobalt-pentammin-chlorid-Komplex, Plurafac®: (Warenzeichen der BASF Aktiengesellschaft);Abbreviations: R: frame formulation; V: experimental formulation; AS: acrylic acid; MS: maleic acid; VAc: vinyl acetate; SKS 6: Na-SKS- 6® (trademark of Clariant); Mw: weight average molecular weight as determined by gel permeation chromatography; Co-pentammin-Cl: cobalt pentammin-chloride complex, Plurafac ® (trademark of BASF Aktiengesellschaft);
  • Sämtliche Angaben sind in Gew.-%.All data are in wt .-%.
Tabelle 1Table 1 Inhaltsstoffingredient R 1R 1 V1.1V1.1 V1.2V1.2 V1.3V1.3 V1.4V1.4 Pentanatriumtriphosphatpentasodium 40 - 6540 - 65 4848 4242 4444 6161 Natriumcitratsodium citrate 0-100-10 -- -- 55 -- Polyacrylsäure Mw 8000Polyacrylic acid Mw 8000 0-100-10 11 -- 55 -- Polyacrylsäure Mw 4000Polyacrylic acid Mw 4000 0-100-10 -- 22 -- -- Zeolith AZeolite A 0-50-5 -- -- 22 33 Schichtsilikat SKS-6Phyllosilicate SKS-6 0-100-10 -- -- -- 77 Natriumcarbonatsodium 3 - 403 - 40 2222 3333 33 1212 Natriumhydrogencarbonatsodium 0 - 100-10 22 -- -- -- Natriumdisilikatsodium disilicate 1 - 251 - 25 5,35.3 44 2323 22 Natriummetasilikatmetasilicate 0 - 100-10 -- -- 22 -- Borax (Dinatriumtetraborat)Borax (disodium tetraborate) 0-50-5 22 -- -- -- Natriumperborat-MonohydratSodium perborate monohydrate 0 - 150 - 15 1010 -- 99 -- Natriumpercarbonatsodium 0 - 150 - 15 -- 99 -- 88th TAEDTAED 0 - 40 - 4 22 -- 2,12.1 -- MMAMMA 0 - 30 - 3 -- 1,21.2 -- -- TMAQTMAQ 0 - 30 - 3 -- -- -- 11 Co-pentammin-ClCo-pentammin-Cl 0 - 10 - 1 -- -- -- -- Enzyme*enzymes * 0,5 - 60,5 - 6 11 11 11 11 Plurafac® LF 403Plurafac ® LF 403 0,1 - 100.1-10 1,51.5 11 33 1,31.3 1-Hydroxyethylen(1,1-diphosphonsäure)1-hydroxyethylene (1,1-diphosphonic acid) 0 - 20 - 2 -- 0,30.3 -- 0,50.5 Natriumchloridsodium chloride 0 - 100-10 -- -- -- -- Natriumsulfatsodium sulphate 0 - 100-10 -- -- -- -- Wasserwater 0 - 100-10 -- -- -- -- Benzotriazolbenzotriazole 0 - 20 - 2 -- 0,30.3 0,20.2 -- Polyethylenglykolpolyethylene glycol 0 - 80 - 8 44 55 -- 11 Paraffinparaffin 0 - 50 - 5 -- 11 -- 11 ParfümPerfume 0 - 10 - 1 0,20.2 0,20.2 0,20.2 0,20.2 Farbstoffdye 0 - 40 - 4 11 -- 0,50.5 11 Tabelle 2Table 2 Inhaltsstoffingredient R 2R 2 V2.1V2.1 V2.2V2.2 V2.3V2.3 V2.4V2.4 Pentanatriumtriphosphatpentasodium 15 - 3915 - 39 3939 3030 2222 2828 Natriumcitratsodium citrate 0-450-45 -- -- 4545 -- Polyacrylsäure Mw 8000Polyacrylic acid Mw 8000 0-100-10 44 -- 11 -- Polyacrylsäure Mw 4000Polyacrylic acid Mw 4000 0-100-10 -- 22 -- -- Zeolith AZeolite A 0-50-5 -- -- -- -- Schichtsilikat SKS-6Phyllosilicate SKS-6 0-50-5 -- -- -- -- Natriumcarbonatsodium 3 - 403 - 40 3030 3535 1010 66 Natriumhydrogencarbonatsodium 0 - 100-10 -- -- -- -- Natriumdisilikatsodium disilicate 1 - 501 - 50 22 11 4545 Natriummetasilikatmetasilicate 0 - 100-10 -- -- -- -- Borax (Dinatriumtetraborat)Borax (disodium tetraborate) 0 - 50 - 5 0,50.5 -- 11 -- Natriumdichloroisocyanuratsodium dichloroisocyanurate 0 - 50 - 5 -- -- -- 11 Natriumperborat-MonohydratSodium perborate monohydrate 0 - 150 - 15 -- -- 1010 -- Natriumpercarbonatsodium 0 - 150 - 15 -- 44 -- -- TAEDTAED 0-40-4 -- 11 22 -- MMAMMA 0-30-3 -- -- -- -- TMAQTMAQ 0-30-3 -- -- -- -- Co-pentammin-ClCo-pentammin-Cl 0-10-1 -- -- -- -- Enzyme*enzymes * 0,5 - 60,5 - 6 11 33 11 0,50.5 Plurafac® LF 403Plurafac ® LF 403 0,1 - 100.1-10 11 0,50.5 44 -- 1-Hydroxyethylen(1,1-diphosphonsäure)1-hydroxyethylene (1,1-diphosphonic acid) 0 - 20 - 2 -- -- -- -- Natriumchloridsodium chloride 0 - 100-10 -- 9,59.5 -- -- Natriumsulfatsodium sulphate 0 - 100-10 1010 1010 -- 9,59.5 Wasserwater 0 - 100-10 9,39.3 33 33 1010 Benzotriazolbenzotriazole 0 - 20 - 2 0,20.2 -- -- -- Polyethylenglykolpolyethylene glycol 0 - 80 - 8 -- -- -- -- Paraffinparaffin 0-50-5 -- -- -- -- ParfümPerfume 0 - 10 - 1 -- -- -- -- Farbstoffdye 0 - 40 - 4 -- -- -- -- Tabelle 3:Table 3: Inhaltsstoffingredient R 3R 3 V3.1V3.1 V3.2V3.2 V3.3V3.3 V3.4V3.4 Natriumcitratsodium citrate 10 -5010 -50 1818 3535 4343 5050 Pentanatriumtriphosphatpentasodium 0 - 140 - 14 -- Polyacrylsäure Mw 8000Polyacrylic acid Mw 8000 0-100-10 33 -- 55 55 Polyacrylsäure Mw 4000Polyacrylic acid Mw 4000 0-100-10 -- 33 -- -- Zeolith AZeolite A 0-50-5 -- 55 -- -- Schichtsilikat SKS-6Phyllosilicate SKS-6 0-50-5 -- -- -- -- Natriumcarbonatsodium 3 - 403 - 40 1515 33 33 99 Natriumhydrogencarbonatsodium 0 - 250 - 25 -- -- -- 2525 Natriumdisilikatsodium disilicate 1 - 501 - 50 1010 2222 3232 -- Natriummetasilikatmetasilicate 0 - 100-10 -- -- -- -- Borax (Dinatriumtetraborat)Borax (disodium tetraborate) 0 - 50 - 5 1,51.5 -- -- -- Natriumdichloroisocyanuratsodium dichloroisocyanurate 0 - 50 - 5 -- -- -- -- Natriumperborat-MonohydratSodium perborate monohydrate 0 - 150 - 15 99 -- 1010 77 Natriumpercarbonatsodium 0 - 250 - 25 -- 2525 -- -- TAEDTAED 0 - 40 - 4 1,51.5 -- 22 -- MMAMMA 0-30-3 -- -- -- 11 TMAQTMAQ 0 - 30 - 3 -- -- -- -- Co-pentammin-ClCo-pentammin-Cl 0 - 10 - 1 -- 0,50.5 -- -- Enzyme*enzymes * 0,5 - 60,5 - 6 11 11 11 11 Plurafac® LF 403Plurafac ® LF 403 0,1 - 100.1-10 11 1,51.5 33 22 1-Hydroxyethylen (1,1-diphosphonsäure)1-hydroxyethylene (1,1-diphosphonic acid) 0 - 20 - 2 -- 0,80.8 -- -- Natriumchloridsodium chloride 0 - 100-10 -- -- -- -- Natriumsulfatsodium sulphate 0 - 400 - 40 34,534.5 3,23.2 -- -- Wasserwater 0 - 100-10 55 -- 11 -- Benzotriazolbenzotriazole 0 - 20 - 2 0,20.2 -- -- -- Polyethylenglykolpolyethylene glycol 0 - 80 - 8 -- -- -- -- Paraffinparaffin 0 - 50 - 5 -- -- -- -- ParfümPerfume 0 - 10 - 1 0,30.3 -- -- -- Farbstoffdye 0 - 40 - 4 -- -- -- -- Prüfmethode (Immersions-Test):Test method (immersion test):

Der Versuch wird in einem neuen 51 Becherglas durchgeführt, welches mit einem Magnetrührstäbchen, einem metallischen Gitterbodeneinsatz, einem Deckel und einem Kontaktthermometer ausgestattet ist. Dieses Becherglas wird mit 4, 5 Liter entionisiertem Wasser, 20 g der entsprechenden Reinigerformulierung und einer vorgebebenen Menge von x mg des zu prüfenden polymeren Korrosionsinhibitors beschickt. Die Mischung wird aufgerührt. Danach werden in das Becherglas 2 Champagnergläser (Schott Zwiesel, Form-Nr. 5270/77, Order-Nr. 416964, h = 204 mm) und ein Longdrinkglas (Nachtmann - VIVENDI ; Art. Nr. 50/42) gegeben, so dass die Gläser völlig in die Flüssigkeit eingetaucht sind. Unter Rühren wird auf eine Temperatur von 75°C aufgeheizt und die Gläser während 72 Stunden unter diesen Bedingungen gelagert. Danach werden die Gläser entnommen und in einer Geschirrspülmaschine vom Typ Miele G 661 SC mit einem handelsüblichen phosphathaltigen Reiniger einmal gereinigt. Es schließt sich danach eine visuelle Abmusterung der Gläser an. Hierbei werden Glasriefen (sog. Cordlines) und auftretende Glastrübungen wie folgt bewertet:The experiment is carried out in a new beaker equipped with a magnetic stir bar, a metal mesh bottom insert, a lid and a contact thermometer. This beaker is charged with 4.5 liters of deionized water, 20 grams of the appropriate detergent formulation and a predetermined amount of x mg of the polymeric corrosion inhibitor to be tested. The mixture is stirred. Thereafter, 2 champagne glasses (Schott Zwiesel, Form No. 5270/77, Order No. 416964, h = 204 mm) and a long drink glass (Nachtmann - VIVENDI, Item No. 50/42) are placed in the beaker, so that the glasses are completely immersed in the liquid. While stirring, it is heated to a temperature of 75 ° C. and the glasses are stored for 72 hours under these conditions. Thereafter, the glasses are removed and cleaned in a dishwasher of the type Miele G 661 SC with a commercially available phosphate-containing detergent once. This is followed by a visual matching of the glasses. Glass scores (so-called cordlines) and occurring glass opacities are evaluated as follows:

Bewertung Glasriefen (Cordlines)Rating Glass scoring (Cordlines)

Notegrade ZustandStatus R0R0 Keine RiefenNo scores R1R1 In sehr wenigen Bereichen geringe RiefenIn very few areas small grooves R2R2 In einigen Bereichen einige RiefenIn some areas some scores R3R3 In mehreren Bereichen RiefenIn several areas grooves R4R4 Stark ausgeprägte Riefen in vielen BereichenStrong marks in many areas

Bewertung: GlastrübungRating: Glass opacity

Notegrade ZustandStatus T0T0 Keine TrübungNo haze T1T1 In sehr wenigen Bereichen geringe TrübungIn very few areas low turbidity T2T2 In einigen Bereichen TrübungenIn some areas cloudiness T3T3 In mehreren Bereiche TrübungenIn several areas cloudiness T4T4 Stark ausgeprägte Trübung über das gesamte GlasStrong haze over the entire glass

Ergebnisse:Results:

Erfindungsgemäße BeispieleExamples according to the invention Versuch-Nr.Experiment no. Formulierungformulation Dosierung Polymer [mg]Dosage of polymer [mg] Polymerer GlaskorrosionsinhibitorPolymeric glass corrosion inhibitor ErgebnisResult Beispiel 1example 1 V1.1V1.1 100100 Cop.a MS/DIB (51:49),Cop. A MS / DIB (51:49), R1,T0R1, T0 Mw 12 000Mw 12,000 Beispiel 2Example 2 V1.1V1.1 200200 Cop.a MS/DIB (51:49),Cop. A MS / DIB (51:49), R0, T1R0, T1 Mw 12 000Mw 12,000 Beispiel 3Example 3 V1.1V1.1 400400 Cop.a MS/DIB (51:49),Cop. A MS / DIB (51:49), R1,T0R1, T0 Mw 12 000Mw 12,000 Beispiel 4Example 4 V1.3V1.3 200200 Cop.a MS/Hexen (58:42),Cop. A MS / Witches (58:42), R2, T1R2, T1 Mw 6000Mw 6000 Beispiel 5Example 5 V2.1V2.1 200200 Cop.a MS/Isobuten (68:32),Cop. A MS / Isobutene (68:32), R2, T1R2, T1 Mw 4000Mw 4000 Beispiel 6Example 6 V2.2V2.2 200200 Cop. a MS/Isobuten (68:32), Mw 4000Cop. A MS / isobutene (68:32), Mw 4000 R2, T1R2, T1 Beispiel 7Example 7 V2.4V2.4 400400 Cop.a AS/Butylacrylat (70:30),Cop. A AS / butyl acrylate (70:30), R1, T2R1, T2 Mw 14000Mw 14000 Beispiel 8Example 8 V3.1V3.1 300300 Cop.a MS/Styrol (53:47),Cop. A MS / styrene (53:47), R2, T1R2, T1 Mw 10000Mw 10000 Beispiel 9Example 9 V3.2V3.2 200200 Cop.a MS/Styrol (53:47),Cop. A MS / styrene (53:47), R2, T1R2, T1 Mw 10000Mw 10000 Beispiel 10Example 10 V3.4V3.4 200200 Cop.a MS-PEG4/DIB (65:35), MwCop. A MS-PEG4 / DIB (65:35), Mw R1,T2R1, T2 1500015000 Angaben zum polymeren Glaskorrosionsinhibitor in Gew.-%
Abkürzungen: MS: Maleinsäure; DIB: technisches Diisobuten; AS: Acrylsäure; MS-PEG4: Halbester von Maleinsäure und Tetraethylenglykol; Cop: Copolymer enthaltend nachfolgende Monomerenbausteine; a: in Form des Na-Salzes; Mw: gewichtsmittleres Molekulargewicht;Details of the polymeric glass corrosion inhibitor in% by weight
Abbreviations: MS: maleic acid; DIB: technical Diisobutene; AS: acrylic acid; MS-PEG4: half ester of maleic acid and tetraethylene glycol; Cop: copolymer containing the following monomer building blocks; a : in the form of the Na salt; Mw: weight average molecular weight;

Vergleichsbeispiele:Comparative Examples:

Versuch-Nr.Experiment no. Formulierungformulation Dosierung Polymer [mg]Dosage of polymer [mg] Polymerpolymer ErgebnisResult Beispiel 11Example 11 V1.1V1.1 -- -- R3, T2R3, T2 Beispiel 12Example 12 V1.3V1.3 -- -- R3, T4R3, T4 Beispiel 13Example 13 V2.1V2.1 -- -- R3, T2R3, T2 Beispiel 14Example 14 V2.2V2.2 -- -- R3, T2R3, T2 Beispiel 15Example 15 V2.4V2.4 -- -- R2, T4R2, T4 Beispiel 16Example 16 V3.1V3.1 -- -- R4, T1R4, T1 Beispiel 17Example 17 V3.2V3.2 -- -- R3, T2R3, T2 Beispiel 18Example 18 V3.4V3.4 -- -- R2, T3R2, T3 Beispiel 19Example 19 V2.2V2.2 200200 Polyethylenimin Mw 20000Polyethyleneimine Mw 20000 R-*, T4R- *, T4 Beispiel 20Example 20 V2.2V2.2 300300 Terpolymer a Diallyldimethylammonium-chlorid/Acrylsäure/Hydroxy-propylacrylat (35:50:15) Mw 100 000Terpolymer a Diallyldimethylammonium chloride / acrylic acid / hydroxy-propyl acrylate (35:50:15) Mw 100,000 R-* , T4R- *, T4 Beispiel 21Example 21 V1.1V1.1 400400 Polyvinylpyrrolidon Mw 40000Polyvinylpyrrolidone Mw 40000 R2, T3**R2, T3 ** Beispiel 22Example 22 V3.1V3.1 300300 Cop.a MS/C 18-Olefin (31:69)Cop. A MS / C18 Olefin (31:69) R3 , T2R3, T2 Mw 15000Mw 15,000 Beispiel 23Example 23 V1.3V1.3 400400 Cop.a AS/2-EHA (70:30)Cop. A AS / 2-EHA (70:30) R3 , T3R3, T3 Mw 60000Mw 60000 Beispiel 24Example 24 V3.4V3.4 200200 Cop.a MAS/Stearylacrylat (80:20)Cop. A MAS / stearyl acrylate (80:20) R-* , T4R- *, T4 Mw 20000Mw 20000 * Nicht bestimmbar wegen starker Trübung
** gelblich irisierende Schicht
Abkürzungen: 2-EHA: 2-Ethylhexylacrylat; MAS: Methacrylsäure; Cop: Copolymer enthaltend nachfolgende Monomerenbausteine; a: in Form des Na-Salzes; Mw: gewichtsmittleres Molekulargewicht;
Angaben zum Polymer in Gew.-%
Im Unterschied zu den Vergleichsbeispielen (11-24) wird in allen Beispielen (1-10) bei erfindungsgemäßer Verwendung der Copolymere eine signifikante Reduktion der Glaskorrosion aller untersuchter Glasgegenstände beobachtet.* Not determinable due to heavy turbidity
** yellowish iridescent layer
Abbreviations: 2-EHA: 2-ethylhexyl acrylate; MAS: methacrylic acid; Cop: copolymer containing the following monomer building blocks; a : in the form of the Na salt; Mw: weight average molecular weight;
Details of the polymer in% by weight
In contrast to Comparative Examples (11-24), a significant reduction in the glass corrosion of all examined glass articles is observed in all examples (1-10) when the copolymers according to the invention are used.

Claims (9)

  1. The use of copolymers comprising
    a) from 20 to 70% by weight of at least one monomer unit (A) from the group of monoethylenically unsaturated C3-C10 monocarboxylic and dicarboxylic acids or their anhydrides, the monomer unit (A) preferably being maleic acid, maleic anhydride and/or acrylic acid,
    b) from 30 to 80% by weight of at least one monomer unit (B) of the formula (I)
    Figure imgb0004
     where R1, R2 and R3 independently of one another are H, CH3, C2H5, C3H7, COOH or OH,
    Y is -C (=O) -, -C(=O)-O-, - O -., -O-C(=O)-, -O-C (=O) -O- or -C(=O)-NH-,
    n is 0 or 1,
    R4 is either an aromatic or a linear, branched or cyclic aliphatic radical having from 1 to 6 carbon atoms,
    if desired, R2 and R4 together form an alkylene unit having from 3 to 6 carbon atoms which is unsubstituted or substituted by C1-C3 alkyl groups, and so form a ring,
    the monomer unit (B) preferably being cyclopentene, hexene and/or technical-grade diisobutene,
    and
    c) from 0 to 25% by weight of at least one further monomer unit (C), which is copolymerizable with the monomer units (A) and (B) and is from the group consisting of α-olefins having 10 or more carbon atoms, olefin mixtures of α-olefins having 10 or more carbon atoms, reactive polyisobutenes having on average from 12 to 100 carbon atoms, Cn (meth)acrylates where n > 6, hydroxy (meth)acrylates, Cn vinyl esters or Cn vinyl ethers where n > 6, acrylonitriles, acrylamides, vinylformamides, allyl alcohols, vinylphosphonates, vinyl-substituted heterocycles and unsaturated organic sulfonic acids,
    the monomer unit (C) preferably being 1-dodecene, 1-octadecene, C22 α-olefin, polyisobutene 1000 and/or an olefin mixture of C20-C24 α-olefins,
    in detergent formulations for preventing glass corrosion during the cleaning process in machine dishwashers.
  2. The use according to claim 1, wherein the copolymers are used in the form of the free acid, a salt thereof or the anhydride, especially in the form of the sodium salt or ammonium salt.
  3. The use according to claim 1 or 2, wherein the copolymers comprise maleic anhydride and technical-grade diisobutene as monomer units and are in the form of the sodium salt.
  4. The use according to any of claims 1 to 3, wherein the weight-average molecular weight of the copolymers is from 1000 to 200,000, preferably from 2000 to 50,000, with particular preference from 2000 to 20,000.
  5. The use according to any of claims 1 to 4, wherein the copolymers are additionally reacted with alcohols or amines, with the formation of ester or amide linkages respectively.
  6. The use according to any of claims 1 to 5, wherein the copolymers are present at from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, with particular preference from 0.1 to 3% by weight, in a detergent formulation.
  7. The use according to any of claims 1 to 6, wherein the copolymers are used in the form of aqueous solutions or aqueous dispersions, in solid form as powders or granules, or in the form of microcapsules or gel capsules in the detergent formulation.
  8. The use according to claim 7, wherein the granules comprise the copolymers and from 10 to 50% by weight of sodium sulfate, sodium carbonate, sodium hydrogen carbonate and/or polyacrylates.
  9. The use according to claim 7 or 8, wherein the copolymers are incorporated in certain compartments of the detergent formulation, and in the case of detergent formulations in tablet form the compartments are, in particular, tablet layers and/or shapes let into the tablet, bonded to the tablet or enveloping the tablet.
EP02719733A 2001-02-01 2002-01-25 Copolymers that prevent glass from corroding Expired - Lifetime EP1373451B1 (en)

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DE10104469A DE10104469A1 (en) 2001-02-01 2001-02-01 Copolymers to prevent glass corrosion
DE10104469 2001-02-01
PCT/EP2002/000836 WO2002064719A1 (en) 2001-02-01 2002-01-25 Copolymers that prevent glass from corroding

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JP2016530348A (en) 2013-07-04 2016-09-29 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ How to wash dishes
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