EP1373450B1 - Cleaner formulations that prevent the discoloration of plastic articles - Google Patents

Cleaner formulations that prevent the discoloration of plastic articles Download PDF

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Publication number
EP1373450B1
EP1373450B1 EP02716702A EP02716702A EP1373450B1 EP 1373450 B1 EP1373450 B1 EP 1373450B1 EP 02716702 A EP02716702 A EP 02716702A EP 02716702 A EP02716702 A EP 02716702A EP 1373450 B1 EP1373450 B1 EP 1373450B1
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EP
European Patent Office
Prior art keywords
weight
cleaning formulations
copolymers
formulations according
sodium
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EP02716702A
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German (de)
French (fr)
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EP1373450A1 (en
Inventor
Axel Kistenmacher
Stephan Nied
Marcus Guzmann
Ralf Wiedemann
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BASF SE
Reckitt Benckiser NV
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BASF SE
Reckitt Benckiser NV
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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
    • C11D3/395—Bleaching agents
    • C11D3/3955—Organic bleaching agents
    • 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
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-compounds
    • 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
    • C11D3/395—Bleaching agents
    • C11D3/3953—Inorganic bleaching agents
    • 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 detergent formulations containing certain copolymers specified in the text for preventing discoloration of plastic articles during the dishwashing process.
  • Detergents for use in dishwashers are offered in numerous variations in their composition and mode of action. Among other things, the customer can choose between universal cleaners or cleaning agents that are particularly suitable for problematic items. Furthermore, a distinction is made between detergents for the household or the commercial sector. Detergents for hand harness form another group of special cleaners. These special cleaner formulations are distinguished by component ratios tailored to the respective items to be washed and, for example, allow an improved cleaning action and / or more gentle washing conditions compared with universal cleaners. When rinsing in particular prepare the film and staining on glasses, the discoloration of plastic objects and the removal of greasy or oily food residues problems.
  • EP-A 462 829 discloses a chlorine-free cleaner composition for use in dishwashing machines which is useful for preventing film and stain on glasses.
  • relevant cleaner components exclusively copolymers are described which are composed of the monomer maleic acid, its anhydride or a salt of maleic acid and at least one polymerizable monomer. This comes 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 98/26 036 describes a cleaner composition especially for hand harness that prevents the adhesion of fats or oils on the surface of the items to be washed.
  • a cleaner component relevant for this purpose polymers having a hydrophilic backbone and hydrophobic side chains are used.
  • the hydrophilic backbone may be negatively charged or neutral, as monomers are, for example, (meth) acrylic acid, crotonic acid, acrolein or vinyl methyl ether, as hydrophobic side chains are used saturated or unsaturated alkyl chains having 5 to 24 carbon atoms.
  • the object of the present invention is thus to provide cleaner formulations which ensure an effective inhibition of the discoloration of plastic objects by the action of colored food constituents during the dishwashing process in dishwashers.
  • the bleach system contains at least one component selected from the group consisting of bleach, bleach activator and bleach catalyst.
  • the use according to the invention of the cleaner formulations described above effectively prevents the discoloration of plastic objects caused by the action of colored food constituents during the dishwashing process in dishwashers.
  • the advantage here is that the cleaner formulations in dishwashers for both the household and the commercial sector can be used for cleaning plastic objects, which is not possible with numerous commercially available cleaning agents.
  • EP-A 462 829 Detergent formulations containing copolymers, some of which fall within the above-defined range of copolymers of detergent formulations according to the invention. However, in contrast to the present invention in the cleaner formulations according to EP-A 462 829 no bleach system is present or the presence of chlorine-containing bleach is explicitly excluded. Nor is it in EP-A 462 829 discloses a use of the copolymers or detergent formulations described therein for preventing the discoloration of plastic articles.
  • the use of the detergent formulations according to the invention prevents the absorption of colored food residues or the dyes contained therein on the plastic objects to be washed by the copolymers contained therein. For this reason, caused by the registered pollution load, often irreversible discoloration of plastic objects due to the cleaning process is not observed.
  • the detergent formulations may contain a bleach system in addition to the copolymers.
  • the bleach system often aids the effect produced by the copolymers the reduction of a color transfer.
  • Detergent formulations containing both copolymers and a bleach system often exhibit an improved cleaning effect over the same cleaner formulations without a bleach system.
  • the effect of reducing color transfer through detergent formulations containing a bleach system but no copolymers is generally worse than that of detergent formulations containing copolymers but no bleach system.
  • a bleaching system contains at least one component selected from the group consisting of bleach, bleach activator, and bleach catalyst. Examples of suitable bleaching agents, bleach activators and bleach catalysts that can be used in the detergent formulations of the present invention are listed below.
  • the copolymers described above contain 10 to 60 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.
  • Examples of suitable monomer building blocks (B) include 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, preferably 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 C 20 -C 24 ⁇ -olefins;
  • Olefin mixtures of at least two different ⁇ -olefins having 30 or more carbon atoms such as C 30 + ⁇ -olefins (olefin mixture of C 30 - ⁇ -olefin and at least one other ⁇ -olefin having an even number of carbon atoms greater than 30);
  • Polyisobutenes having an average of 12 to 100 carbon atoms and an ⁇ -olefin content greater than 80% such as polyisobutene-1000 (polyisobutene with an average molar mass of 1000);
  • the copolymers contain at least one further monomer unit (C), which constitutes 0 to 30 wt .-% based on the total weight of the copolymer.
  • Suitable monomeric units (C) which can be copolymerized with the monomeric units (A) and (B) are, for example, 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, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, alkylpolyethylene glycol (meth) acrylate;
  • C 1 -C 6 vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate;
  • C 2 -C 8 olefins such as ethene, propene, butene, isobutene, pentene, cyclopentene, hexene, cyclohexene, 1-octene or (technical) diisobutene, preferably cyclopentene, hexene or technical diisobutene;
  • Styrenes 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.
  • 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 alkylpolyethylene glycol block polypropylene glycols such as methylpolyethylene glycol block polypropylene glycol having 40 ethylene oxide units and 5 propylene oxide units.
  • This reaction may also be with C 1 -C 20 amines or Alkylpolyalkylenglykolaminen such as methyl polyethylene glycol amine having an average degree of ethoxylation of 8 to form amide bonds are performed.
  • the weight-average molecular weight of the copolymers is from 1,000 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 have as monomer building block (A) maleic acid and / or maleic anhydride and at least one monomer building block (B) from the group consisting of 1-dodecene, C 22 - ⁇ -olefin, C 20 -C 24 ⁇ -olefins and polyisobutene-1000.
  • copolymers which are used as monomer building block (A) maleic anhydride and as monomer building block (B) 1-dodecene, C 22 - ⁇ -olefin, C 20 -C 24 - ⁇ -olefins, a mixture of 1-dodecene with polyisobutene-1000 or a mixture of 1-dodecene with C 20 -C 24 - ⁇ -olefins.
  • 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 contain from 10 to 40% by weight of the monomer building block (A).
  • the copolymers are included at 0.01 to 10 wt%, preferably at 0.05 to 5 wt%, more preferably at 0.1 to 5 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, sugar and sugar derivatives in the sense of a cogranulate are 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, gelatinous, pulverulent, granular and tablet-form detergent formulations. 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.
  • Suitable bleaching agents, bleach activators and bleach catalysts which can be used in the bleach system of the detergent formulations of this invention are listed below.
  • 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 bleaches can also be used in the detergent formulation:
  • 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 0.2 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, are 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 in the cleaner formulations of the invention.
  • 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, which 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, cobal
  • 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 0.0001 to 5 wt .-%, preferably from 0.0025 to 1 wt .-%, particularly preferably from 0.01 to 0.25 wt .-%, based on the total detergent formulation.
  • the detergent formulations can be used for any type of plastic articles.
  • Common household or commercial plastics include, for example, polyethylene, polypropylene, polystyrene, polycarbonate, styrene-acrylonitrile plastics, styrene-butadiene plastics, acrylonitrile-butadiene-styrene plastics, acrylonitrile-styrene-acrylic ester plastics, polyvinyl chloride, polytetrafluoroethylene, Polyoxymethylene, polyphenylene oxide, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyamides, phenol-formaldehyde plastics, urea-formaldehyde plastics, melamine-formaldehyde plastics.
  • a preferred use according to the invention of the cleaner formulations is given for plastic articles of polyethylene (LDPE, LLDPE) and polypropylene.
  • Critical dirt loadings in the sense of unwanted plastic discoloration are all types of colored food residues. Examples include leftovers of tomatoes, tomato ketchup, tomato paste, rosehips, carrots, red pepper, saffron, paprika, paprika or spinach, rosehip tea and fruit and vegetable juices such as orange juice, tomato juice, carrot juice or cherry juice.
  • the carotenoid dyes (partially) contained in these foods, such as ⁇ -carotene, lycopene, zeaxanthin, canthaxanthin, cryptoxanthin, rhodoxanthin, crocetin, capsorubin or ⁇ -citraurin, are considered to be the main causes of plastic discoloration.
  • the use of the detergent formulation according to the invention is to be seen in particular in preventing the discoloration of plastic objects which may be caused by the aforementioned food residues, in particular by the carotenoid-containing food residues.
  • the cleaner formulations according to the invention usually comprise further 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 preparation, are, for example, phosphates, such as alkali metal phosphates and polymeric alkali metal phosphates, which are present in the form of their alkaline, neutral or acidic ammonium, sodium or potassium salts can.
  • 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 in the Range of 5 wt .-% to 65 wt .-% based on the total formulation and calculated as anhydrous active substance used.
  • 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.
  • 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.
  • 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 0.1 to 20 wt .-%, preferably 0.1 to 10 wt .-%, particularly preferably 0.25 to 4 wt .-%.
  • 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.
  • 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 to 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.
  • 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.
  • transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably from the group of the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, and manganese sulfate.
  • zinc compounds or bismuth compounds can be used to prevent corrosion on the items to be washed.
  • the cleaning agent can be added between 0 and 5 wt .-% of enzymes based on the total preparation in order to increase the performance of the cleaning agent or to ensure under mild conditions, the cleaning performance of the same quality.
  • 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 such as patent blue, preservatives such as Kathon CG, perfumes and other perfumes may be added to the cleanser formulation.
  • 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 nitrilotriacetate.
  • a builder system based on pentasodium triphosphate, and / or sodium citrate and / or complexing agents such as nitrilotriacetate.
  • caustic soda or potassium hydroxide solution is used as alkali carrier.
  • chlorine compounds such as sodium dichloroisocyanurate are frequently used as bleaching agents.
  • plastic test specimens were polyethylene (commercial cutting board and freezer lid) and polypropylene (commercial freezer bottom).
  • the term discoloration inhibitor (VI) stands for the copolymer 1 which is used according to the invention for preventing the discoloration of the plastic articles.
  • the copolymer 1 has a weight average molecular weight of 4500, it contains 25.5 wt .-% maleic anhydride as the monomer unit (A) and 74.5 wt .-% C 22 - ⁇ -olefin as monomer unit (B).
  • the copolymer 1 is in the form of the sodium salt.
  • the enzymes used are amylase and protease in the ratio 1: 1 1.
  • Example 2 Example 3
  • Example 4 Example 5
  • Example 7 Example 8
  • Example 10 Example 11
  • Example 12 discoloration inhibitor 0,000 0,500 1,000 1,250 2,500 5,000 disilicate 2,700 2,700 2,700 2,700 2,700 sodium trip
  • Example 13 Examination of the effectiveness of the discoloration inhibitor in gel detergent formulations was carried out in accordance with Example 13 at 14 and was carried out in a General Electric Profile dishwasher, program normal wash / heated dry, with a water hardness of 10 ° dH and water inlet temperature of 60 ° C.
  • the dosing of the detergent formulations was carried out in each case with 45 g for the pre-wash cycle and 60 g for the main rinse over the metering chambers of the dishwasher.
  • 50g of tomato ketchup was added to the dishwasher.
  • plastic test specimens were polyethylene (commercial cutting board and freezer lid) and polypropylene (commercial freezer bottom).
  • Example 14 discoloration inhibitor 0,000 0,800 Softened water 81.650 80.850 Kathon CG 0,100 0,100 polyacrylate 1,200 1,200 potassium 6,000 6,000 sodium tripolyphosphate 10,000 10,000 Plurafac LF 500 0,200 0,200 Perfume 0,100 0,100 enzymes 0,700 0,700 Patent Blue 0,050 0,050 total 100000 100000
  • color locus values a and b were determined at 10 defined points on the respective test specimen surfaces by means of a color locometer from Mahlo, type 4790-KI.
  • the color location of the test surface is determined by averaging the measured values.
  • a discoloration of the Kunststoffprüfskos corresponds to a shift of the color location and can be represented as a vector.
  • the length of the vector is a measure of the discoloration of the surface.
  • detergent formulations containing a discoloration inhibitor can effectively prevent the discoloration of plastic articles, unlike detergent formulations which contain no discoloration inhibitor.
  • the comparison of Example 14 with Examples 4 and 5 or 11 and 12 further shows that detergent formulations containing a bleaching system in addition to the discoloration inhibitor can even better prevent discoloration of plastic articles.
  • an improved discoloration inhibition was found on the plastic articles tested, although a lesser amount of the discoloration inhibitor is used than in Example 14.
  • the sole presence of a bleach system does not give satisfactory results in inhibiting discoloration Plastic objects (Ex 1, 7).
  • % Rem. Rem. (n.sp.) x 100 / Rem. (by Sp.) Averaging over measuring points, test specimens and reproductions
  • 1-Dodecene / PIB / MSA 57/24/19) in the form of the Na salt 91 18 Cop.
  • 1-Dodecene / PIB / MSA 50/34/16) in the form of Na salt 88 19 Cop.
  • MSA maleic anhydride
  • Cop . Copolymer containing the following monomeric units.

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Abstract

The invention relates to cleaning formulations and to the use of the cleaning formulations for preventing the discoloration of plastic articles during washing in machine dishwashers. The cleaning formulations comprise the following components: a) copolymers containing a1) from 10 to 60% by weight of at least one monomer unit (A) from the group of the monoethylenically unsaturated C3-C10 monocarboxylic and dicarboxylic acids or their anhydrides, a2) from 40 to 90% by weight of at least one monomer unit (B) of the formula (I) where R<1>, R<2 >and R<3 >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, and R<4 >is a linear or branched, cyclic or acyclic aliphatic radical having from 7 to 100 carbon atoms, and a3) from 0 to 30% by weight of at least one further monomer unit (C) copolymerizable with the monomer units (A) and (B) and from the group consisting of C1-C6 (meth)acrylic esters, C1-C6 vinyl esters, C2-C8 olefins, styrenes, acrylonitriles, acrylamides, vinylformamides, allyl alcohols, vinylphosphonates, vinyl-substituted heterocycles and unsaturated organosulfonic acids, b) a bleaching system comprising at least one component from the group consisting of bleach, bleach activator and bleaching catalyst.

Description

Die Erfindung betrifft die Verwendung von Reinigerformulierungen, die bestimmte, im Text spezifizierte Copolymere enthalten, zur Verhinderung der Verfärbung von Kunststoffgegenständen während des Reinigungsvorganges in Geschirrspülmaschinen.The invention relates to the use of detergent formulations containing certain copolymers specified in the text for preventing discoloration of plastic articles during the dishwashing process.

Reinigungsmittel zur Verwendung in Geschirrspülmaschinen werden in zahlreichen Variationen hinsichtlich ihrer Zusammensetzung sowie ihrer Wirkungsweise angeboten. Unter anderem kann der Kunde zwischen Universalreinigern oder Reinigungsmitteln wählen, die sich speziell für problematisches Spülgut eignen. Ferner wird auch zwischen Reinigungsmitteln für den Haushalt bzw. den gewerblichen Bereich unterschieden. Reinigungsmittel für Handgeschirr bilden eine weitere Gruppe von Spezialreinigungsmitteln. Diese speziellen Reinigerformulierungen zeichnen sich durch auf das jeweilige Spülgut abgestimmte Komponentenverhältnisse aus und ermöglichen beispielsweise eine verbesserte Reinigungswirkung und / oder schonendere Waschbedingungen gegenüber Universalreinigern. Beim Spülen bereiten insbesondere die Film- und Fleckenbildung auf Gläsern, die Verfärbung von Kunststoffgegenständen sowie das Entfernen von fettigen oder öligen Speiseresten Probleme.Detergents for use in dishwashers are offered in numerous variations in their composition and mode of action. Among other things, the customer can choose between universal cleaners or cleaning agents that are particularly suitable for problematic items. Furthermore, a distinction is made between detergents for the household or the commercial sector. Detergents for hand harness form another group of special cleaners. These special cleaner formulations are distinguished by component ratios tailored to the respective items to be washed and, for example, allow an improved cleaning action and / or more gentle washing conditions compared with universal cleaners. When rinsing in particular prepare the film and staining on glasses, the discoloration of plastic objects and the removal of greasy or oily food residues problems.

EP-A 462 829 offenbart eine chlorfreie Reinigerzusammensetzung zur Anwendung in Geschirrspülmaschinen, die sich zur Verhinderung der Film- und Fleckenbildung auf Gläsern eignet. Als hierfür relevante Reinigerbestandteile werden ausschließlich Copolymere beschrieben, die sich aus dem Monomer Maleinsäure, deren Anhydrid oder einem Salz der Maleinsäure sowie mindestens einem polymerisierbaren Monomeren zusammensetzen. Dieses stammt aus der Gruppe der Alkane, Alkene, Diene, Alkine oder Aromaten, die jeweils mindestens 4 Kohlenstoffatome aufweisen, insbesondere Isobutylen, Diisobutylen, Styrol, Decen oder Eicosen. EP-A 462 829 discloses a chlorine-free cleaner composition for use in dishwashing machines which is useful for preventing film and stain on glasses. As relevant cleaner components exclusively copolymers are described which are composed of the monomer maleic acid, its anhydride or a salt of maleic acid and at least one polymerizable monomer. This comes 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 98/26 036 beschreibt eine Reinigerzusammensetzung speziell für Handgeschirr, die das Anhaften von Fetten oder Ölen auf der Oberfläche des Spülgutes unterbindet. Als hierfür relevanter Reinigerbestandteil werden Polymere mit einem hydrophilen Grundgerüst und hydrophoben Seitenketten eingesetzt. Das hydrophile Grundgerüst kann negativ geladen oder neutral sein, als Monomere eignen sich beispielsweise (Meth)acrylsäure, Crotonsäure, Acrolein oder Vinylmethylether, als hydrophobe Seitenketten werden gesättigte oder ungesättigte Alkylketten mit 5 bis 24 Kohlenstoffatomen verwendet. WO 98/26 036 describes a cleaner composition especially for hand harness that prevents the adhesion of fats or oils on the surface of the items to be washed. As a cleaner component relevant for this purpose, polymers having a hydrophilic backbone and hydrophobic side chains are used. The hydrophilic backbone may be negatively charged or neutral, as monomers are, for example, (meth) acrylic acid, crotonic acid, acrolein or vinyl methyl ether, as hydrophobic side chains are used saturated or unsaturated alkyl chains having 5 to 24 carbon atoms.

Farbige Nahrungsmittelbestandteile erweisen sich insbesondere bei der Reinigung von Kunststoffgegenständen in Geschirrspülmaschinen als sehr problematisch. Die meisten Reinigerformulierungen sind nur unzureichend in der Lage, farbige Nahrungsmittelbestandteile vollständig von der Oberfläche von Kunststoffgegenständen zu entfernen bzw. die Resorption von bereits abgelösten Resten an anderen Stellen der zu reinigenden Kunststoffgegenstände zu unterbinden. US 5,827,808 beschreibt diesbezüglich eine Reinigerzusammensetzung, die zur Verhinderung dieser Verfärbung Zelluloseether enthält. Die Reinigercusammensetzung eignet sich insbesondere zur Anwendung in Geschirrspülmaschinen.Colored food ingredients prove to be very problematic especially in the cleaning of plastic objects in dishwashers. Most detergent formulations are insufficient in their ability to completely remove colored food ingredients from the surface of plastic articles, or to inhibit the absorption of previously detached residues elsewhere in the plastic articles to be cleaned. US 5,827,808 in this regard, describes a cleaning composition containing cellulose ethers to prevent this discoloration. The cleaner composition is particularly suitable for use in dishwashers.

Das Problem der Farbanschmutzung von Plastikgegenständen durch farbige Nahrungsmittelbestandteile in Geschirrspülmaschinen ist bis jetzt nur unbefriedigend gelöst. Die Aufgabe der vorliegenden Erfindung besteht somit darin, Reinigerformulierungen zur Verfügung zu stellen, die eine wirkungsvolle Unterbindung der Verfärbung von Kunststoffgegenständen durch Einwirkung von farbigen Nahrungsmittelbestandteilen während des Spülvorganges in Geschirrspülmaschinen gewährleisten.The problem of color contamination of plastic objects by colored food components in dishwashers has so far been solved unsatisfactorily. The object of the present invention is thus to provide cleaner formulations which ensure an effective inhibition of the discoloration of plastic objects by the action of colored food constituents during the dishwashing process in dishwashers.

Diese Aufgabe wird gelöst durch die Verwendung von Reinigerformulierungen, die Copolymere und gegebenenfalls ein Bleichsystem enthalten.This object is achieved by the use of cleaner formulations containing copolymers and optionally a bleach system.

Die Copolymere enthalten

  1. a) 10 bis 60 Gew.-% mindestens eines Monomerenbausteines (A) aus der Gruppe der monoethylenisch ungesättigten C3-C10-Mono- und Dicarbonsäuren oder deren Anhydriden,
  2. b) 40 bis 90 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 ein linearer oder verzweigter, cyclischer oder acyclischer aliphatischer Rest mit 7 bis 100 Kohlenstoffatomen ist,
  3. c) 0 bis 30 Gew.-% mindestens eines weiteren mit den Monomerenbausteinen (A) und (B) copolymerisierbaren Monomerenbausteines (C) aus der Gruppe bestehend aus C1-C6-(Meth)Acrylestern, C1-C6-Vinylestern, C2-C8-Olefinen, Styrolen, Acrylnitrilen, Acrylamiden, Vinylformamiden, Allylalkoholen, Vinylphosphonaten, vinylsubstituierten Heterozyklen und ungesättigten Organosulfonsäuren.
The copolymers contain
  1. a) from 10 to 60% 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) 40 to 90% 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 a linear or branched, cyclic or acyclic aliphatic radical having 7 to 100 carbon atoms,
  3. c) 0 to 30 wt .-% of at least one further copolymerizable with the monomer units (A) and (B) monomer units (C) from the group consisting of C 1 -C 6 - (meth) acrylic esters, C 1 -C 6 vinyl esters , C 2 -C 8 olefins, styrenes, acrylonitriles, acrylamides, vinyl formamides, allyl alcohols, vinyl phosphonates, vinyl-substituted heterocycles and unsaturated organosulfonic acids.

Das Bleichsystem enthält mindestens eine Komponente aus der Gruppe bestehend aus Bleichmittel, Bleichaktivator und Bleichkatalysator.The bleach system contains at least one component selected from the group consisting of bleach, bleach activator and bleach catalyst.

Durch die erfindungsgemäße Verwendung der vorstehend beschriebenen Reinigerformulierungen wird die durch Einwirkung von farbigen Nahrungsmittelbestandteilen verursachte Verfärbung von Kunststoffgegenständen während des Spülvorganges in Geschirrspülmaschinen wirkungsvoll unterbunden. Von Vorteil ist dabei, das die Reinigerformulierungen in Geschirrspülmaschinen sowohl für den Haushalts- als auch den gewerblichen Bereich zur Reinigung von Kunststoffgegenständen verwendet werden können, was mit zahlreichen handelsüblichen Reinigungsmitteln nicht möglich ist.The use according to the invention of the cleaner formulations described above effectively prevents the discoloration of plastic objects caused by the action of colored food constituents during the dishwashing process in dishwashers. The advantage here is that the cleaner formulations in dishwashers for both the household and the commercial sector can be used for cleaning plastic objects, which is not possible with numerous 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 erfindungsgemäßen Reinigerformulierungen fallen. Allerdings ist im Gegensatz zur vorliegenden Erfindung in den Reinigerformulierungen gemäß EP-A 462 829 kein Bleichsystem vorhanden bzw. ist das Vorhandensein von chlorhaltigem Bleichmittel explizit ausgeschlossen. Ebenso wenig ist in EP-A 462 829 eine Verwendungsmöglichkeit der dort beschriebenen Copolymere bzw. Reinigerformulierungen zur Verhinderung der Verfärbung von Kunststoffgegenständen offenbart.True, are in EP-A 462 829 Detergent formulations containing copolymers, some of which fall within the above-defined range of copolymers of detergent formulations according to the invention. However, in contrast to the present invention in the cleaner formulations according to EP-A 462 829 no bleach system is present or the presence of chlorine-containing bleach is explicitly excluded. Nor is it in EP-A 462 829 discloses a use of the copolymers or detergent formulations described therein for preventing the discoloration of plastic articles.

Herkömmliche Reinigungsmittel lösen farbige Nahrungsmittelreste, die an Teilen des eingebrachten, verschmutzten Spülgutes haften, während des Reinigungsvorganges von den betreffenden Stellen ab. Diese abgelösten Nahrungsmittelreste werden von der Geschirrspülmaschine über das gesamte sich in der betreffenden Geschirrspülmaschine befindliche Spülgut verteilt, wobei die farbigen Speisereste zumindest teilweise auf dem Spülgut, insbesondere auf Kunststoffgegenständen, resorbiert werden.Conventional detergents dissolve colored food residues that adhere to parts of the introduced, dirty items to be cleaned during the cleaning process of the bodies concerned. These detached food residues are distributed by the dishwasher over the entire dishwasher goods located in the dishwasher, the colored food particles are at least partially absorbed on the items to be washed, especially on plastic objects.

Die erfindungsgemäße Verwendung der Reinigerformulierungen unterbindet hingegen durch die darin enthaltenen Copolymeren die Resorption von farbigen Nahrungsmittelresten bzw. der darin enthaltenen Farbstoffe an den zu spülenden Kunststoffgegenständen. Aus diesem Grund ist eine durch die eingetragene Schmutzfracht verursachte, oft irreversible Verfärbung der Kunststoffgegenstände infolge des Reinigungsvorganges nicht zu beobachten.By contrast, the use of the detergent formulations according to the invention prevents the absorption of colored food residues or the dyes contained therein on the plastic objects to be washed by the copolymers contained therein. For this reason, caused by the registered pollution load, often irreversible discoloration of plastic objects due to the cleaning process is not observed.

Die Reinigerformulierungen können zusätzlich zu den Copolymeren ein Bleichsystem enthalten. Das Bleichsystem unterstützt häufig den von den Copolymeren bewirkten Effekt der Verminderung einer Farbübertragung. Reinigerformulierungen, die sowohl Copolymere als auch ein Bleichsystem enthalten, zeigen häufig einen verbesserten Reinigungseffekt gegenüber den gleichen Reinigerformulierungen ohne Bleichsystem. Der Effekt der Verminderung einer Farbübertragung durch Reinigerformulierungen, die ein Bleichsystem, aber keine Copolymere enthalten, ist generell schlechter als diejenige von Reinigerformulierungen, die Copolymere, aber kein Bleichsystem enthalten. Ein Bleichsystem enthält mindestens eine Komponente aus der Gruppe bestehend aus Bleichmittel, Bleichaktivator und Bleichkatalysator. Beispiele für geeignete Bleichmittel, Bleichaktivatoren und Bleichkatalysatoren, die in den erfindungsgemäßen Reinigerformulierungen verwendet werden können, sind weiter unten im Text aufgeführt.The detergent formulations may contain a bleach system in addition to the copolymers. The bleach system often aids the effect produced by the copolymers the reduction of a color transfer. Detergent formulations containing both copolymers and a bleach system often exhibit an improved cleaning effect over the same cleaner formulations without a bleach system. The effect of reducing color transfer through detergent formulations containing a bleach system but no copolymers is generally worse than that of detergent formulations containing copolymers but no bleach system. A bleaching system contains at least one component selected from the group consisting of bleach, bleach activator, and bleach catalyst. Examples of suitable bleaching agents, bleach activators and bleach catalysts that can be used in the detergent formulations of the present invention are listed below.

Die oben beschriebenen Copolymere enthalten zu 10 bis 60 Gew.-% mindestens einen Monomerenbaustein (A) aus der Gruppe der monoethylenisch ungesättigten C3-C10-Mono- und Dicarbonsäuren oder deren Anhydriden.The copolymers described above contain 10 to 60 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 40 bis 90 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 ein linearer oder verzweigter, cyclischer oder acyclischer aliphatischer Rest mit 7 bis 100 Kohlenstoffatomen ist.
Furthermore, the copolymers contain from 40 to 90% 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 a linear or branched, cyclic or acyclic aliphatic radical having 7 to 100 carbon atoms.

Beispiele für geeignete Monomerenbausteine (B) umfassen die nachfolgend aufgeführten Substanzgruppen.Examples of suitable monomer building blocks (B) include the substance groups listed below.

α-Olefine mit 10 oder mehr Kohlenstoffatome wie beispielsweise 1-Decen, 1-Dodecen, 1-Hexadecen, 1-Oktadecen und C22-α-Olefin, vorzugsweise 1-Dodecen, 1-Oktadecen oder C22-α-Olefin;α-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C 22 -α-olefin, preferably 1-dodecene, 1-octadecene or C 22 -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;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;

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);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);

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);Polyisobutenes having an average of 12 to 100 carbon atoms and an α-olefin content greater than 80% such as polyisobutene-1000 (polyisobutene with an average molar mass of 1000);

Ethylhexyl(meth)acrylat, Lauryl(meth)acrylat, Stearyl(meth)acrylat, Dodecensäurevinylester, Stearinsäurevinylester, Dodecylvinylether und Oktadecylvinylether.Ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, vinyl dodecenoate, vinyl stearate, dodecyl vinyl ether and octadecyl vinyl ether.

Gegebenenfalls enthalten die Copolymere mindestens einen weiteren Monomerenbaustein (C), der 0 bis 30 Gew.-% bezogen auf das Gesamtgewicht des Copolymers ausmacht.Optionally, the copolymers contain at least one further monomer unit (C), which constitutes 0 to 30 wt .-% 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.Suitable monomeric units (C) which can be copolymerized with the monomeric units (A) and (B) are, for example, the substance groups listed below.

C1-C6-(Meth)Acrylester wie beispielsweise Acrylsäuremethylester, Acrylsäureethylester, Methacrylsäuremethylester, Methacrylsäureethylester, Butyl(meth)acrylat, Hydroxyethyl(meth)acrylat, Hydroxypropyl(meth)acrylat, Alkylpolyethylenglykol(meth)acrylat;C 1 -C 6 (meth) acrylic esters such as, for example, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, alkylpolyethylene glycol (meth) acrylate;

C1-C6-Vinylester wie beispielsweise Vinylformiat, Vinylacetat, Vinylpropionat;C 1 -C 6 vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate;

C2-C8-Olefine wie beispielsweise Ethen, Propen, Buten, Isobuten, Penten, Cyclopenten, Hexen, Cyclohexen, 1-Octen oder (technisches) Diisobuten, bevorzugt Cyclopenten, Hexen oder technisches Diisobuten;C 2 -C 8 olefins such as ethene, propene, butene, isobutene, pentene, cyclopentene, hexene, cyclohexene, 1-octene or (technical) diisobutene, preferably cyclopentene, hexene or technical diisobutene;

Styrole, Acrylnitrile, Acrylamide, Vinylformamide, Allylalkohole, Vinylphosphonate;Styrenes, acrylonitriles, acrylamides, vinylformamides, allyl alcohols, vinylphosphonates;

vinylsubstituierte Heterozyklen wie beispielsweise N-Vinylpyrrolidon oder N-Vinylcaprolactam;vinyl-substituted heterocycles such as N-vinylpyrrolidone or N-vinylcaprolactam;

ungesättigte Organosulfonsäuren wie beispielsweise Styrolsulfonsäure, 2-Acrylamido-2-Methylpropansulfonsäure, Vinylsulfonsäure, Methallylsulfonsäure.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 z.B. Methylpolyethylenglykol mit einem mittleren Ethoxilierungsgrad von 45 oder Alkylpolyethylenglykol-block-Polypropylenglykolen wie z.B. Methylpolyethylenglykolblock-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 alkylpolyethylene glycol block polypropylene glycols such as methylpolyethylene glycol block polypropylene glycol having 40 ethylene oxide units and 5 propylene oxide units. This reaction may also be with C 1 -C 20 amines or Alkylpolyalkylenglykolaminen such as methyl polyethylene glycol amine having an average degree of ethoxylation of 8 to form amide bonds are performed.

Das gewichtsmittlere Molekulargewicht der Copolymere beträgt 1 000 bis 200 000, bevorzugt 2 000 bis 50 000, besonders bevorzugt 2 000 bis 20 000. Die Copolymere werden mit dem Fachmann bekannten Verfahren hergestellt.The weight-average molecular weight of the copolymers is from 1,000 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 1-Dodecen, C22-α-Olefin, C20-C24-α-Olefinen und Polyisobuten-1000 enthalten. Besonders bevorzugt werden Copolymere verwendet, die als Monomerenbaustein (A) Maleinsäureanhydrid und als Monomerenbaustein (B) 1-Dodecen, C22-α-Olefin, C20-C24-α-Olefine, ein Gemisch aus 1-Dodecen mit Polyisobuten-1000 oder ein Gemisch aus 1-Dodecen mit C20-C24-α-Olefinen enthalten.In a preferred embodiment of the present invention, copolymers are used which have as monomer building block (A) maleic acid and / or maleic anhydride and at least one monomer building block (B) from the group consisting of 1-dodecene, C 22 -α-olefin, C 20 -C 24 α-olefins and polyisobutene-1000. Particular preference is given to copolymers which are used as monomer building block (A) maleic anhydride and as monomer building block (B) 1-dodecene, C 22 -α-olefin, C 20 -C 24 -α-olefins, a mixture of 1-dodecene with polyisobutene-1000 or a mixture of 1-dodecene with C 20 -C 24 -α-olefins.

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 einer weiterhin bevorzugten Ausführungsform der vorliegenden Erfindung enthalten die Copolymere 10 bis 40 Gew.-% des Monomerenbausteins (A).In a further preferred embodiment of the present invention, the copolymers contain from 10 to 40% by weight of the monomer building block (A).

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 5 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 5 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. For example, 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, sugar and sugar derivatives in the sense of a cogranulate are 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 Reinigerformulierungen 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, gelatinous, pulverulent, granular and tablet-form detergent formulations. 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.

Geeignete Bleichmittel, Bleichaktivatoren und Bleichkatalysatoren, die in dem Bleichsystem der erfindungsgemäßen Reinigerformulierungen verwendet werden können, sind nachstehend aufgeführt.Suitable bleaching agents, bleach activators and bleach catalysts which can be used in the bleach system of the detergent formulations of this invention are listed below.

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 Sauerstoffbleichmittel 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:In addition, the following oxygen bleaches can also be used in the detergent formulation:

Kationische Peroxysäuren, die in den Patentanmeldungen US 5,422,028 , US 5,294,362 sowie US 5,292,447 beschrieben sind;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 0,2 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 0.2 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, are 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, those from the scriptures 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 erfindungsgemäßen 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 in the cleaner formulations of the invention.

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, which 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 0.0001 to 5 wt .-%, preferably from 0.0025 to 1 wt .-%, particularly preferably from 0.01 to 0.25 wt .-%, based on the total detergent formulation.

Erfindungsgemäß lassen sich die Reinigerformulierungen für jegliche Art von Kunststoffgegenständen verwenden. Übliche, im Haushalt oder im gewerblichen Bereich vorkommende Kunststoffe sind beispielsweise Polyethylen, Polypropylen, Polystyrol, Polycarbonat, Styrol-Acrylnitril-Kunststoffe, Styrol-Butadien-Kunststoffe, AcrylnitrilButadien-Styrol-Kunststoffe, Acrylnitril-Styrol-Acrylester-Kunststoffe, Polyvinylchlorid, Polytetrafluorethylen, Polyoxymethylen, Polyphenylenoxid, Polymethylmethacrylat, Polyethylenterephthalat, Polybutylenterephthalat, Polyamide, Phenol-Formaldehyd-Kunststoffe, Harnstoff-Formaldehyd-Kunststoffe, Melamin-Formaldehyd-Kunststoffe. Eine bevorzugte erfindungsgemäße Verwendung der Reinigerformulierungen ist für Kunststoffgegenstände aus Polyethylen (LDPE, LLDPE) und Polypropylen gegeben.According to the invention, the detergent formulations can be used for any type of plastic articles. Common household or commercial plastics include, for example, polyethylene, polypropylene, polystyrene, polycarbonate, styrene-acrylonitrile plastics, styrene-butadiene plastics, acrylonitrile-butadiene-styrene plastics, acrylonitrile-styrene-acrylic ester plastics, polyvinyl chloride, polytetrafluoroethylene, Polyoxymethylene, polyphenylene oxide, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyamides, phenol-formaldehyde plastics, urea-formaldehyde plastics, melamine-formaldehyde plastics. A preferred use according to the invention of the cleaner formulations is given for plastic articles of polyethylene (LDPE, LLDPE) and polypropylene.

Kritische Schmutzbeladungen im Sinne unerwünschter Kunststoffverfärbungen sind alle Arten von farbigen Nahrungsmittelresten. Beispielsweise seien Speisereste von Tomaten, Tomatenketchup, Tomatenmark, Hagebutten, Karotten, rotem Pfeffer, Safran, Paprika, Paprikagewürz oder Spinat, Hagebuttentee sowie Frucht- und Gemüsesäften wie Orangensaft, Tomatensaft, Karottensaft oder Kirschsaft erwähnt. Die in diesen Nahrungsmittel (teilweise) enthaltenen carotinoiden Farbstoffe wie β-Carotin, Lycopin, Zeaxanthin, Canthaxanthin, Cryptoxanthin, Rhodoxanthin, Crocetin, Capsorubin oder β-Citraurin sind dabei als die Hauptverursacher der Kunststoffverfärbungen anzusehen.Critical dirt loadings in the sense of unwanted plastic discoloration are all types of colored food residues. Examples include leftovers of tomatoes, tomato ketchup, tomato paste, rosehips, carrots, red pepper, saffron, paprika, paprika or spinach, rosehip tea and fruit and vegetable juices such as orange juice, tomato juice, carrot juice or cherry juice. The carotenoid dyes (partially) contained in these foods, such as β-carotene, lycopene, zeaxanthin, canthaxanthin, cryptoxanthin, rhodoxanthin, crocetin, capsorubin or β-citraurin, are considered to be the main causes of plastic discoloration.

Die erfindungsgemäße Verwendung der Reinigerformulierung ist insbesondere in der Unterbindung der Verfärbung von Kunststoffgegenständen zu sehen, die von den zuvor genannten Nahrungsmittelresten, insbesondere von den carotinoidhaltigen Nahrungsmittelresten, verursacht werden kann.The use of the detergent formulation according to the invention is to be seen in particular in preventing the discoloration of plastic objects which may be caused by the aforementioned food residues, in particular by the carotenoid-containing food residues.

Außer den zuvor beschriebenen Copolymeren bzw. gegebenenfalls dem Bleichsystem enthalten die erfindungsgemäßen Reinigerformulierungen üblicherweise weitere dem Fachmann bekannte Zusatzkomponenten. Beispiele hierfür sind nachstehend aufgeführt.Apart from the copolymers described above or, where appropriate, the bleach system, the cleaner formulations according to the invention usually comprise further 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 Ammonium-, 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 preparation, are, for example, phosphates, such as alkali metal phosphates and polymeric alkali metal phosphates, which are present in the form of their alkaline, neutral or acidic ammonium, sodium or potassium salts can.

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 in the Range of 5 wt .-% to 65 wt .-% based on the total formulation and calculated as anhydrous active substance used.

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 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 0.1 to 20 wt .-%, preferably 0.1 to 10 wt .-%, particularly preferably 0.25 to 4 wt .-%.

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 500, 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 500 ® 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.

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 to 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, more preferably from the group of the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, and 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 Reingungsmittel 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 cleaning agent can be added between 0 and 5 wt .-% of enzymes based on the total preparation in order to increase the performance of the cleaning agent or to ensure under mild conditions, the cleaning performance of the same quality. 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 wie beispielsweise Patentblau, Konservierungsmittel wie beispielsweise Kathon CG, Parfüme und sonstige Duftstoffe der Reinigerformulierung zugesetzt werden.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 such as patent blue, preservatives such as Kathon CG, perfumes and other perfumes may be added to the cleanser formulation.

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 Haushaltsreinigem 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 nitrilotriacetate. Frequently, in contrast to household cleaner 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.

Beispiele 1-14Examples 1-14

Methodenbeschreibung zur Überprüfung der FarbübertragungsinhibierungMethod description for checking the color transfer inhibition

• Pulverförmige Reinigungsmittelrezepturen• Powdered detergent formulations

Die Überprüfung der Wirksamkeit der Verfärbungsinhibitoren in pulverförmigen Reinigerformulierungen wurde in einer Geschirrspülmaschine Typ Bosch SMS 5062, Programm 65°C Stark bei einer Wasserhärte von 9°dH durchgeführt. Dazu wurden Reinigerformulierungen gemäß Beispiel 1 bis 6 und 7 bis 12 miteinander verglichen. Die Dosierung der Reinigerformulierungen erfolgte über die Dosierkammer der Spülmaschine mit jeweils 40g (Beispiele 1-6) bzw. mit jeweils 20g (Beispiele 7-12). Zu Beginn des Hauptspülganges wurden 50g Tomatenketchup in das Spülwasser der Geschirrspülmaschine gegeben.The effectiveness of the discoloration inhibitors in pulverulent detergent formulations was tested in a dishwasher type Bosch SMS 5062, program 65 ° C Strong with a water hardness of 9 ° dH. For this purifier formulations according to Examples 1 to 6 and 7 to 12 were compared. The dosing of the cleaner formulations took place via the dosing chamber of the dishwasher with 40 g each (Examples 1-6) or with 20 g each (Examples 7-12). At the beginning of the main rinse, 50g of tomato ketchup was added to the dishwashing water of the dishwasher.

Als Kunststoffprüfkörper dienten Polyethylen (handelsübliches Schneidbrett und Gefrierdosendeckel) und Polypropylen (handelsübliches Gefrierdosenunterteil).As plastic test specimens were polyethylene (commercial cutting board and freezer lid) and polypropylene (commercial freezer bottom).

Alle Tabellenangaben für die Beispiele 1 bis 14 sind in Gewichtsprozent. Die Bezeichnung Verfärbungsinhibitor (VI) steht für das Copolymer 1, das erfindungsgemäß zur Verhinderung der Verfärbung der Kunststoffgegenstände verwendet wird. Das Copolymer 1 hat ein gewichtsmittleres Molekulargewicht von 4500, es enthält zu 25,5 Gew.-% Maleinsäureanhydrid als Monomerenbaustein (A) sowie zu 74,5 Gew.-% C22-α-Olefin als Monomerenbaustein (B). Das Copolymer 1 liegt in Form des Natriumsalzes vor. Als Enzyme werden Amylase und Protease im Verhältnis 1:1 1 verwendet. Tabelle 1 Reinigerkomponenten Beispiel 1 Beispiel 2 Beispiel 3 Beispiel 4 Beispiel 5 Beispiel 6 Verfärbungsinhibitor 0,000 0,500 1,000 1,250 2,500 5,000 Trinatriumcitrat 25,000 25,000 25,000 25,000 25,000 25,000 Natriumcarbonat 15,800 15,800 15,800 15,800 15,800 15,800 Natriumbicarbonat 52,200 51,700 51,200 50,950 49,700 47,200 Phosphonat 0,200 0,200 0,200 0,200 0,200 0,200 Natriumpercarbonat 4,000 4,000 4,000 4,000 4,000 4,000 TAED 1,400 1,400 1,400 1,400 1,400 1,400 Enzyme 0,400 0,400 0,400 0,400 0,400 0,400 Plurafac LF 500 0,850 0,850 0,850 0,850 0,850 0,850 Benzotriazol 0,150 0,150 0,150 0,150 0,150 0,150 Summe 100,000 100,000 100,000 100,000 100,000 100,000 Tabelle 2 Reinigerkomponenten Beispiel 7 Beispiel 8 Beispiel 9 Beispiel 10 Beispiel 11 Beispiel 12 Verfärbungsinhibitor 0,000 0,500 1,000 1,250 2,500 5,000 Disilikat 2,700 2,700 2,700 2,700 2,700 2,700 Natriumtripolyphosphat 55,000 55,000 55,000 55,000 55,000 55,000 Natriumcarbonat 25,800 25,300 24,800 24,550 23,300 20,800 Natriumbicarbonat 2,200 2,200 2,200 2,200 2,200 2,200 Sokalan CP 5 3,500 3,500 3,500 3,500 3,500 3,500 Natriumpercarbonat 6,000 6,000 6,000 6,000 6,000 6,000 TAED 2,000 2,000 2,000 2,000 2,000 2,000 Enzyme 1,400 1,400 1,400 1,400 1,400 1,400 Plurafac LF 500 1,000 1,000 1,000 1,000 1,000 1,000 Benzotriazol 0,250 0,250 0,250 0,250 0,250 0,250 Parfüm 0,150 0,150 0,150 0,150 0,150 0,150 Summe 100,000 100,000 100,000 100,000 100,000 100,000 All table data for Examples 1 to 14 are in percent by weight. The term discoloration inhibitor (VI) stands for the copolymer 1 which is used according to the invention for preventing the discoloration of the plastic articles. The copolymer 1 has a weight average molecular weight of 4500, it contains 25.5 wt .-% maleic anhydride as the monomer unit (A) and 74.5 wt .-% C 22 -α-olefin as monomer unit (B). The copolymer 1 is in the form of the sodium salt. The enzymes used are amylase and protease in the ratio 1: 1 1. <b><u> Table 1 </ u></b> cleaner components example 1 Example 2 Example 3 Example 4 Example 5 Example 6 discoloration inhibitor 0,000 0,500 1,000 1,250 2,500 5,000 trisodium citrate 25,000 25,000 25,000 25,000 25,000 25,000 sodium 15,800 15,800 15,800 15,800 15,800 15,800 sodium bicarbonate 52,200 51,700 51,200 50.950 49,700 47.200 phosphonate 0,200 0,200 0,200 0,200 0,200 0,200 sodium 4,000 4,000 4,000 4,000 4,000 4,000 TAED 1,400 1,400 1,400 1,400 1,400 1,400 enzymes 0,400 0,400 0,400 0,400 0,400 0,400 Plurafac LF 500 0,850 0,850 0,850 0,850 0,850 0,850 benzotriazole 0,150 0,150 0,150 0,150 0,150 0,150 total 100000 100000 100000 100000 100000 100000 cleaner components Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 discoloration inhibitor 0,000 0,500 1,000 1,250 2,500 5,000 disilicate 2,700 2,700 2,700 2,700 2,700 2,700 sodium tripolyphosphate 55,000 55,000 55,000 55,000 55,000 55,000 sodium 25,800 25,300 24,800 24.550 23,300 20,800 sodium bicarbonate 2,200 2,200 2,200 2,200 2,200 2,200 Sokalan CP 5 3,500 3,500 3,500 3,500 3,500 3,500 sodium 6,000 6,000 6,000 6,000 6,000 6,000 TAED 2,000 2,000 2,000 2,000 2,000 2,000 enzymes 1,400 1,400 1,400 1,400 1,400 1,400 Plurafac LF 500 1,000 1,000 1,000 1,000 1,000 1,000 benzotriazole 0,250 0,250 0,250 0,250 0,250 0,250 Perfume 0,150 0,150 0,150 0,150 0,150 0,150 total 100000 100000 100000 100000 100000 100000

• Gelförmige Reinigerrezepturen• Gel-shaped cleanser formulations

Die Überprüfung der Wirksamkeit des Verfärbungsinhibitors in gelförmigen Reinigerformulierungen erfolgte gemäß Beispiel 13 mit 14 und wurde in einer Geschirrspülmaschine Typ General Electric Profile, Programm normal wash/heated dry, bei einer Wasserhärte von 10°dH und Wassereinlasstemperatur von 60°C durchgeführt. Die Dosierung der Reinigerformulierungen erfolgte jeweils mit 45g für den Vorspülgang und 60g für den Hauptspülgang über die Dosierkammern der Spülmaschine. Vor dem Start des Geschirrspülprogramms wurden 50g Tomatenketchup in die Geschirrspülmaschine gegeben. Als Kunststoffprüfkörper dienten Polyethylen (handelsübliches Schneidbrett und Gefrierdosendeckel) und Polypropylen (handelsübliches Gefrierdosenunterteil). Tabelle 3 Reinigerkomponenten Beispiel 13 Beispiel 14 Verfärbungsinhibitor 0,000 0,800 enthärtetes Wasser 81,650 80,850 Kathon CG 0,100 0,100 Polyacrylat 1,200 1,200 Kaliumtripolyphosphat 6,000 6,000 Natriumtripolyphosphat 10,000 10,000 Plurafac LF 500 0,200 0,200 Parfüm 0,100 0,100 Enzyme 0,700 0,700 Patentblau 0,050 0,050 Summe 100,000 100,000 Examination of the effectiveness of the discoloration inhibitor in gel detergent formulations was carried out in accordance with Example 13 at 14 and was carried out in a General Electric Profile dishwasher, program normal wash / heated dry, with a water hardness of 10 ° dH and water inlet temperature of 60 ° C. The dosing of the detergent formulations was carried out in each case with 45 g for the pre-wash cycle and 60 g for the main rinse over the metering chambers of the dishwasher. Before starting the dishwashing program, 50g of tomato ketchup was added to the dishwasher. As plastic test specimens were polyethylene (commercial cutting board and freezer lid) and polypropylene (commercial freezer bottom). <b><u> Table 3 </ u></b> cleaner components Example 13 Example 14 discoloration inhibitor 0,000 0,800 Softened water 81.650 80.850 Kathon CG 0,100 0,100 polyacrylate 1,200 1,200 potassium 6,000 6,000 sodium tripolyphosphate 10,000 10,000 Plurafac LF 500 0,200 0,200 Perfume 0,100 0,100 enzymes 0,700 0,700 Patent Blue 0,050 0,050 total 100000 100000

Prüfergebnissetest results

Sowohl vor wie auch nach dem Reinigungszyklus wurden mittels eines Farbortmessgerätes der Firma Mahlo, Typ 4790-KI, die Farbortwerte a und b an 10 definierten Punkten der jeweiligen Prüfkörperoberflächen bestimmt. Der Farbort der Prüfoberfläche wird durch Mittelwertbildung aus den gemessenen Werten festgelegt. Eine Verfärbung des Kunststoffprüfkörpers entspricht einer Verschiebung des Farbortes und lässt sich als Vektor darstellen. Die Länge des Vektors ist ein Maß für die Verfärbung der Oberfläche. Die prozentuale Längenverkürzung des Vektors aus den Versuchen unter Einsatz des Verfärbungsinhibitors (VI) gegenüber dem Versuch ohne den Verfärbungsinhibitor ist ein Maß für die Inhibierung der Verfärbung (100% = keine Verfärbung). Tabelle 4 Beispiel Nr. Gesamt menge an VI [g] Inhibierung PE-Schneidbrett [%] Inhibierung PE-Deckel [%] Inhibierung PP-Dosen unterteil [%] Inhibier ungsdurch schnitt [%] 1 0 0 0 0 0 2 0,2 49 28 37 38 3 0,4 53 59 42 51 4 0,5 85 79 79 81 5 1,0 90 93 72 85 6 2,0 92 96 85 91 7 0 0 0 0 0 8 0,1 35 28 58 40 9 0,2 44 32 59 45 10 0,25 79 57 74 70 11 0,5 90 81 75 82 12 1,0 92 89 80 87 13 0 0 0 0 0 14 0,84 81 47 52 60 Both before and after the cleaning cycle, color locus values a and b were determined at 10 defined points on the respective test specimen surfaces by means of a color locometer from Mahlo, type 4790-KI. The color location of the test surface is determined by averaging the measured values. A discoloration of the Kunststoffprüfkörpers corresponds to a shift of the color location and can be represented as a vector. The length of the vector is a measure of the discoloration of the surface. The percentage length reduction of the vector from the experiments using the discoloration inhibitor (VI) over the test without the discoloration inhibitor is a measure of the inhibition of discoloration (100% = no discoloration). <b><u> Table 4 </ u></b> Example no. Total amount of VI [g] Inhibition PE cutting board [%] Inhibition PE cover [%] Inhibition of PP cans lower part [%] Inhibition average [%] 1 0 0 0 0 0 2 0.2 49 28 37 38 3 0.4 53 59 42 51 4 0.5 85 79 79 81 5 1.0 90 93 72 85 6 2.0 92 96 85 91 7 0 0 0 0 0 8th 0.1 35 28 58 40 9 0.2 44 32 59 45 10 0.25 79 57 74 70 11 0.5 90 81 75 82 12 1.0 92 89 80 87 13 0 0 0 0 0 14 0.84 81 47 52 60

Aus Tabelle 4 ist ersichtlich, dass Reinigerformulierungen, die einen Verfärbungsinhibitor enthalten, die Verfärbung von Kunststoffgegenständen wirksam unterbinden können im Gegensatz zu Reinigerformulierungen, die keinen Verfärbungsinhibitor enthalten. Der Vergleich des Beispieles 14 mit den Beispielen 4 und 5 bzw. 11 und 12 zeigt weiterhin auf, dass Reinigerformulierungen, die zusätzlich zu dem Verfärbungsinhibitor ein Bleichsystem enthalten, die Verfärbung von Kunststoffgegenständen noch besser unterbinden können. In den Beispielen 4 bzw. 11 wird eine verbesserte Verfärbungsinhibierung an den untersuchten Kunststoffgegenständen gefunden, obwohl eine geringere Menge des Verfärbungsinhibitor verwendet wird als in Beispiel 14. Das alleinige Vorhandensein eines Bleichsystems (ohne Verfärbungsinhibitor) führt zu keinen befriedigenden Ergebnissen bei der Unterbindung der Verfärbung von Kunststoffgegenständen (Bsp. 1, 7).From Table 4 it can be seen that detergent formulations containing a discoloration inhibitor can effectively prevent the discoloration of plastic articles, unlike detergent formulations which contain no discoloration inhibitor. The comparison of Example 14 with Examples 4 and 5 or 11 and 12 further shows that detergent formulations containing a bleaching system in addition to the discoloration inhibitor can even better prevent discoloration of plastic articles. In Examples 4 and 11, respectively, an improved discoloration inhibition was found on the plastic articles tested, although a lesser amount of the discoloration inhibitor is used than in Example 14. The sole presence of a bleach system (without discoloration inhibitor) does not give satisfactory results in inhibiting discoloration Plastic objects (Ex 1, 7).

Beispiele 15 - 25Examples 15-25 PrüfmethodeTest method

Neue handelsübliche Kunststoffgegenstände aus dem Haushaltsbereich wurden in einer handelsüblichen Geschirrspülmaschine zusammen mit einem definierten, farbstoffhaltigen Testschmutz, der separat in einem 100 ml Becherglas in die Geschirrspülmaschine eingebracht wurde, gewaschen. Als Reinigerformulierung wurde ein handelsüblicher Geschirrreiniger verwendet, dem erfindungsgemäß Verfärbungsinhibitoren zugegeben wurden. Zur Versuchsauswertung wurde eine Remissionsmessung an den Kunststoffgegenständen durchgeführt, jeweils an 4 Stellen vor und nach dem Spülgang (n. Sp. / v. Sp.). Als Versuchsergebnis wurde die Remission (Rem.) nach dem Spülgang angegeben, ausgedrückt in % des Ausgangswertes (100% = keine Verfärbung). Dabei wurden die Mittelwerte über die verschiedenen Messpunkte, die verschiedenen Kunststoffgegenstände und die Reproduktionsversuche (insgesamt 3 Versuche je Beispiel) gebildet. Tabelle 5: Prüfungsparameter Reinigerformulierung (RF) gemäß Tabelle 2, Bsp. 7 Menge an RF 20 g Verfärbungsinhibitor (VI) gemäß Tabelle 6 Menge an VI 2 Gew.-% bezogen auf die Reinigerformulierung (Festsubstanz) Geschirrspülmaschine Miele G 661 SC / G 686 SC Testschmutz 50 g Tomatenketchup Wasserhärte 17 ° dH Temperatur 65 °C Kunststoffgegenstände Schneidbrett aus Polyethylen Gefrierdosendeckel aus Polyethylen Gefrierdosenunterteil aus Polypropylen Remissionsmessgerät ELREPHO 2000 ; d / 8° ; 460 nm Remissionsmessung vor bzw. nach dem Spülgang Messpunkte: Unterteil = 8; Deckel = 4; Brett = 3 Berechnung der Rem. % Rem. = Rem. (n. Sp.) x 100 / Rem. (v. Sp.) Mittelwertbildung über Messpunkte, Prüfkörper und Reproduktionen Tabelle 6: Ergebnisse Beispiel Nr. Verfärbungsinbibitor (VI) Remission [%] 15 Cop. 1-Dodecen / MSA (63/37) 90 16 Cop. 1-Dodecen / PIB / MSA (62/15/23), in Form des Na-Salzes 90 17 Cop. 1-Dodecen / PIB / MSA (57/24/19) in Form des Na-Salzes 91 18 Cop. 1-Dodecen / PIB / MSA (50/34/16) in Form des Na-Salzes 88 19 Cop. 1-Dodecen / PIB / MSA (43/43/14) in Form des Na-Salzes 94 20 Cop. 1-Dodecen / PIB / MSA (35/52/13) in Form des Na-Salzes 92 21 Cop. 1-Dodecen / PIB / MSA (59/6/35) in Form des Na-Salzes 91 22 Cop. C20-C24-α-Olefine / MSA (76/24), in Form des Na-Salzes 95 23 Cop. C20-C24-α-Olefine / MSA (76/24), in Form des NH4-Salzes 94 24 Cop. 1-Dodecen / C20-C24-α-Olefinen / MSA (42/28/30) 92 25 kein VI 56 Angaben zum polymeren Verfärbungsinhibitor in Gew.-% New commercial plastic household items were washed in a commercial dishwashing machine together with a defined, colorant-containing test soil separately placed in a 100 ml beaker in the dishwasher. The cleaner formulation used was a commercially available dishwashing detergent to which discoloration inhibitors according to the invention had been added. For the evaluation of the test, a remission measurement was carried out on the plastic objects, in each case at 4 points before and after the rinse (n.sp., v.sp.). As a test result, the remission (Rem.) Was given after the rinse, expressed in% of the initial value (100% = no discoloration). The average values were calculated using the different measuring points, the different plastic objects and the reproduction experiments (a total of 3 experiments per example). <b><u> Table 5: Exam Parameters </ u></b> Cleaner formulation (RF) according to Table 2, Ex. 7 Amount of RF 20 g Discoloration inhibitor (VI) according to Table 6 Amount of VI 2% by weight, based on the detergent formulation (solid substance) dishwasher Miele G 661 SC / G 686 SC test soil 50 g tomato ketchup water hardness 17 ° dH temperature 65 ° C Plastic articles Cutting board made of polyethylene Freezer lid made of polyethylene Freezer bottom part made of polypropylene Remission meter ELREPHO 2000; d / 8 °; 460 nm Remission measurement before or after the rinse Measuring points: lower part = 8; Cover = 4; Board = 3 Calculation of the Rem. % Rem. = Rem. (n.sp.) x 100 / Rem. (by Sp.) Averaging over measuring points, test specimens and reproductions Example no. Discolouration inhibitor (VI) Remission [%] 15 Cop. 1-Dodecene / MSA (63/37) 90 16 Cop. 1-Dodecene / PIB / MSA (62/15/23), in the form of the Na salt 90 17 Cop. 1-Dodecene / PIB / MSA (57/24/19) in the form of the Na salt 91 18 Cop. 1-Dodecene / PIB / MSA (50/34/16) in the form of Na salt 88 19 Cop. 1-Dodecene / PIB / MSA (43/43/14) in the form of the Na salt 94 20 Cop. 1-Dodecene / PIB / MSA (35/52/13) in the form of Na salt 92 21 Cop. 1-Dodecene / PIB / MSA (59/6/35) in the form of the Na salt 91 22 Cop. C 20 -C 24 α-olefins / MSA (76/24), in the form of the Na salt 95 23 Cop. C 20 -C 24 α-olefins / MSA (76/24), in the form of the NH 4 salt 94 24 Cop. 1-Dodecene / C 20 -C 24 α-olefins / MSA (42/28/30) 92 25 no VI 56 Details of the polymeric discoloration inhibitor in% by weight

Abkürzungen: MSA: Maleinsäureanhydrid, PIB: Polyisobuten (mittlere molare Masse = 1000), Cop.: Copolymer enthaltend nachfolgende Monomerenbausteine.Abbreviations: MSA: maleic anhydride, PIB: polyisobutene (average molar mass = 1000), Cop .: Copolymer containing the following monomeric units.

Im Unterschied zu den Vergleichsbeispielen (1, 7, 13, 25), bei denen kein Verfärbungsinhibitor verwendet wird, beobachtet man in allen Beispielen (2-6, 8-12, 14-24) bei erfindungsgemäßer Verwendung des Verfärbungsinhibitors eine signifikante Reduktion der Verfärbung aller untersuchten Kunststoffoberflächen.In contrast to the comparative examples (1, 7, 13, 25), in which no discoloration inhibitor is used, a significant reduction of the discoloration is observed in all examples (2-6, 8-12, 14-24) when using the discoloration inhibitor according to the invention all examined plastic surfaces.

Claims (17)

  1. The use of cleaning formulations comprising the following components:
    a) copolymers comprising
    a1) from 10 to 60% by weight of at least one monomer unit (A) from the group of the monoethylenically unsaturated C3-C10 monocarboxylic and dicarboxylic acids or their anhydrides,
    a2) from 40 to 90% 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, and
    R4 is a linear or branched, cyclic or acyclic aliphatic radical having from 7 to 100 carbon atoms,
    and
    a3) from 0 to 30% by weight of at least one further monomer unit (C) copolymerizable with the monomer units (A) and (B) and from the group consisting of C1-C6 (meth)acrylic esters, C1-C6 vinyl esters, C2-C8 olefins, styrenes, acrylonitriles, acrylamides, vinylformamides, allyl alcohols, vinylphosphonates, vinyl-substituted heterocycles and unsaturated organosulfonic acids,
    b) a bleaching system comprising at least one component from the group consisting of bleach, bleach activator and bleaching catalyst,
    to prevent the discoloration of plastic articles during washing in machine dishwashers.
  2. The use of cleaning formulations according to claim 1, wherein the monomer unit (A) is maleic acid, maleic anhydride and/or acrylic acid.
  3. The use of cleaning formulations according to claim 1 or 2, wherein the monomer unit (B) is 1-dodecene, 1-octadecene, polyisobutene 1000, C22 α-olefin and/or an olefin mixture of C20-C24 α-olefins.
  4. The use of cleaning formulations according to any of claims 1 to 3, wherein the monomer unit (C) is cyclopentene, hexene and/or technical-grade diisobutene.
  5. The use of cleaning formulations according to any of claims 1 to 4, 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.
  6. The use of cleaning formulations according to any of claims 1 to 5, wherein the copolymers comprise as monomer unit (A) maleic anhydride and as monomer unit (B) 1-dodecene, C22 α-olefin, C20-C24 α-olefins, a mixture of 1-dodecene with polyisobutene 1000 or a mixture of 1-dodecene with C20-C24 α-olefins and are in the form of the sodium salt or ammonium salt.
  7. The use of cleaning formulations according to any of claims 1 to 6, wherein the weight-average molecular weight of the copolymers is from 1 000 to 200 000, preferably from 2 000 to 50 000, with particular preference from 2 000 to 20 000.
  8. The use of cleaning formulations according to any of claims 1 to 7, wherein the copolymers are additionally reacted with alcohols or amines to form ester or amide linkages, respectively.
  9. The use of cleaning formulations according to any of claims 1 to 8, wherein the copolymer content in the cleaning formulation is from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, with particular preference from 0.1 to 5% by weight.
  10. The use of cleaning formulations according to any of claims 1 to 9, wherein the copolymers are used in the cleaning formulation 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.
  11. The use of cleaning formulations according to claim 10, wherein the granules comprise the copolymers and from 10 to 50% by weight of sodium sulfate, sodium carbonate, sodium hydrogen carbonate and/or polyacrylates.
  12. The use of cleaning formulations according to claim 10 or 11, wherein the copolymers are incorporated into certain compartments of said formulation and in the case of 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.
  13. The use of cleaning formulations according to any of claims 1 to 12, wherein the bleach is sodium perborate in the form of the monohydrate or tetrahydrate, sodium percarbonate, the hydrates of sodium percarbonate, sodium hypochlorite, calcium hypochlorite, potassium hypochlorite, magnesium hypochlorite, potassium dichloroisocyanurate and/or sodium dichloroisocyanurate.
  14. The use of cleaning formulations according to any of claims 1 to 13, wherein the bleach activator is TAED, NOSI, n-NOBS, iso-NOBS, MMA and/or TMAQ.
  15. The use of cleaning formulations according to any of claims 1 to 14, wherein the bleaching catalyst is a cobalt amine complex, a cobalt acetato complex, a cobalt carbonyl complex, a chloride of cobalt, a chloride of manganese, manganese sulfate and/or [(TMTACN)2MnIVMnIV(µ-O)3]2+(PF6 -)2.
  16. The use of cleaning formulations according to any of claims 1 to 15, wherein
    a) at least one oxygen bleach at from 0.5 to 30% by weight, preferably from 1 to 20% by weight, with particular preference from 3 to 15% by weight, and/or
    b) at least one chlorine bleach at from 0.1 to 20% by weight, preferably from 0.2 to 10% by weight, with particular preference from 0.3 to 8% by weight, and/or
    c) at least one bleach activator at from 0.1 to 10% by weight, preferably from 1 to 9% by weight, with particular preference from 1.5 to 8% by weight, and/or
    d) at least one bleaching catalyst at from 0.0001 to 5% by weight, preferably from 0.0025 to 1% by weight, with particular preference from 0.01 to 0.25% by weight
    is present in the cleaning formulation.
  17. The use of copolymers of the composition as defined in any of claims 1 to 8 to prevent the discoloration of plastic articles during washing in machine dishwashers.
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CA2436359C (en) 2010-05-18
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ATE431392T1 (en) 2009-05-15
EP1373450A1 (en) 2004-01-02
ES2325682T3 (en) 2009-09-14
KR20030074765A (en) 2003-09-19
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WO2002064720A8 (en) 2002-11-14
DE10104470A1 (en) 2002-08-08

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