EP1373450B1 - Formulations de nettoyants pour empecher la decoloration d'articles en matiere plastique - Google Patents

Formulations de nettoyants pour empecher la decoloration d'articles en matiere plastique 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)
English (en)
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EP1373450A1 (fr
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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Claims (17)

  1. Utilisation de formulations de nettoyage comprenant les composants suivants :
    a) des copolymères qui contiennent
    a1) 10 à 60 % en poids d'au moins un constituant monomère (A) du groupe des acides mono- ou dicarboxyliques en C3 à C10 monoéthyléniquement insaturés ou leurs anhydrides,
    a2) 40 à 90 % en poids d'au moins un constituant monomère (B) de formule générale (I),
    Figure imgb0005
    dans laquelle R1, R2 et R3 représentent indépendamment les uns des autres H, CH3, C2H5, C3H7, COOH ou OH,
    Y représente -C(=O)-, -C(=O)-O-, -O-, -O-C(=O)-, -O-C-(=O)-O- ou -C(=O)-NH-,
    n représente 0 ou 1,
    R4 représente un radical aliphatique linéaire ou ramifié, cyclique ou acyclique, qui comporte 7 à 100 atomes de carbone,
    et
    a3) 0 à 30 % en poids d'au moins un constituant monomère (C) supplémentaire, copolymérisable avec les constituants monomères (A) et (B), du groupe constitué des esters (méth)acryliques en C1-C6, des esters vinyliques en C1-C6, des oléfines en C2-C8, des styrènes, des acrylonitriles, des acrylamides, des vinylformamides, des alcools allyliques, des phosphonates de vinyle, des hétérocycles substitués par des groupes vinyles et des acides organosulfoniques insaturés,
    b) un système blanchissant, contenant au moins un composant du groupe constitué d'un agent de blanchiment, d'un activateur de blanchiment et d'un catalyseur de blanchiment,
    pour empêcher la coloration d'articles en plastique pendant le processus de nettoyage dans des machines à laver la vaisselle.
  2. Utilisation de formulations de nettoyage selon la revendication 1, caractérisée en ce que le constituant monomère (A) est l'acide maléique, l'anhydride de l'acide maléique et/ou l'acide acrylique.
  3. Utilisation de formulations de nettoyage selon la revendication 1 ou 2, caractérisée en ce que le constituant monomère (B) est le 1-dodécène, le 1-octadécène, le polyisobutène-1000, une α-oléfine en C22 et/ou un mélange oléfinique d'α-oléfines en C20-C24.
  4. Utilisation de formulations de nettoyage selon l'une quelconque des revendications 1 à 3, caractérisée en ce que le constituant monomère (C) est le cyclopentène, l'hexène et/ou le diisobutène technique.
  5. Utilisation de formulations de nettoyage selon l'une quelconque des revendications 1 à 4, caractérisée en ce que les copolymères sont utilisés sous la forme des acides libres, d'un de leurs sels ou des anhydrides, notamment sous la forme du sel de sodium ou d'ammonium
  6. Utilisation de formulations de nettoyage selon l'une quelconque des revendications 1 à 5, caractérisée en ce que les copolymères contiennent en tant que constituant monomère (A) l'anhydride de l'acide maléique et en tant que constituant monomère (B) le 1-dodécène, une α-oléfine en C22, des α-oléfines en C20-C24, un mélange de 1-dodécène avec du polyisobutène-1000 ou un mélange de 1-dodécène avec des α-oléfines en C20-C24 et se présentent sous la forme du sel de sodium ou d'ammonium.
  7. Utilisation de formulations de nettoyage selon l'une quelconque des revendications 1 à 6, caractérisée en ce que le poids moléculaire moyen en poids des copolymères est de 1 000 à 200 000, de préférence de 2 000 à 50 000, de manière particulièrement préférée de 2 000 à 20 000.
  8. Utilisation de formulations de nettoyage selon l'une quelconque des revendications 1 à 7, caractérisée en ce que les copolymères sont également mis en réaction avec des alcools ou des amines, avec formation de liaisons esters ou amides.
  9. Utilisation de formulations de nettoyage selon l'une quelconque des revendications 1 à 8, caractérisée en ce que les copolymères sont présents dans la formulation de nettoyage à hauteur de 0,01 à 10 % en poids, de préférence à hauteur de 0,05 à 5 % en poids, de manière particulièrement préférée à hauteur de 0,1 à 5 % en poids.
  10. Utilisation de formulations de nettoyage selon l'une quelconque des revendications 1 à 9, caractérisée en ce que les copolymères sont utilisés dans la formulation de nettoyage sous la forme de solutions aqueuses ou de dispersions aqueuses, sous forme solide en tant que poudre ou granulat, ou sous la forme de microgélules ou de gélules.
  11. Utilisation de formulations de nettoyage selon la revendication 10, caractérisée en ce que le granulat contient les copolymères et 10 à 50 % en poids de sulfate de sodium, carbonate de sodium, hydrogénocarbonate de sodium et/ou polyacrylates.
  12. Utilisation de formulations de nettoyage selon la revendication 10 ou 11, caractérisée en ce que les copolymères sont incorporés dans des compartiments déterminés de la formulation de nettoyage, dans le cas d'une formulation de nettoyage sous la forme de tablettes, les compartiments étant notamment des couches de tablettes et/ou des corps moulés encastrés dans les tablettes, collés aux tablettes ou enrobant les tablettes.
  13. Utilisation de formulations de nettoyage selon l'une quelconque des revendications 1 à 12, caractérisée en ce que l'agent de blanchiment est le perborate de sodium sous la forme mono- ou tétrahydrate, le percarbonate de sodium, les hydrates du percarbonate de sodium, l'hypochlorite de sodium, l'hypochlorite de calcium, l'hypochlorite de potassium, l'hypochlorite de magnésium, le dichloroisocyanurate de potassium et/ou le dichloroisocyanurate de sodium.
  14. Utilisation de formulations de nettoyage selon l'une quelconque des revendications 1 à 13, caractérisée en ce que l'activateur de blanchiment est TAED, NOSI, n-NOBS, iso-NOBS, MMA et/ou TMAQ.
  15. Utilisation de formulations de nettoyage selon l'une quelconque des revendications 1 à 14, caractérisée en ce que le catalyseur de blanchiment est un complexe cobalt(amine), un complexe cobalt(acétate), un complexe cobalt(carbonyle), un chlorure de cobalt, un chlorure de manganèse, un sulfate de manganèse et/ou [(TMTACN)2MnIVMnIV(µ-O)3]2+(PF6 -)2.
  16. Utilisation de formulations de nettoyage selon l'une quelconque des revendications 1 à 15, caractérisée en ce que la formulation de nettoyage contient
    a) au moins un agent de blanchiment contenant de l'oxygène à hauteur de 0,5 à 30 % en poids, de préférence à hauteur de 1 à 20 % en poids, de manière particulièrement préférée à hauteur de 3 à 15 % en poids, et/ou
    b) au moins un agent de blanchiment contenant du chlore à hauteur de 0,1 à 20 % en poids, de préférence à hauteur de 0,2 à 10 % en poids, de manière particulièrement préférée à hauteur de 0,3 à 8 % en poids, et/ou
    c) au moins un activateur de blanchiment à hauteur de 0,1 à 10 % en poids, de préférence à hauteur de 1 à 9 % en poids, de manière particulièrement préférée à hauteur de 1,5 à 8 % en poids, et/ou
    d) au moins un catalyseur de blanchiment à hauteur de 0,0001 à 5 % en poids, de préférence à hauteur de 0,0025 à 1 % en poids, de manière particulièrement préférée à hauteur de 0,01 à 0,25 % en poids.
  17. Utilisation de copolymères selon la composition définie dans l'une quelconque des revendications 1 à 8 pour empêcher la coloration d'articles en plastique pendant le processus de nettoyage dans des machines à laver la vaisselle.
EP02716702A 2001-02-01 2002-01-30 Formulations de nettoyants pour empecher la decoloration d'articles en matiere plastique Expired - Lifetime EP1373450B1 (fr)

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DE10104470A DE10104470A1 (de) 2001-02-01 2001-02-01 Reinigerformulierungen zur Verhinderung der Verfärbung von Kunststoffgegenständen
DE10104470 2001-02-01
PCT/EP2002/000962 WO2002064720A1 (fr) 2001-02-01 2002-01-30 Formulations de nettoyants pour empecher la decoloration d'articles en matiere plastique

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ATE431392T1 (de) 2009-05-15
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KR100856765B1 (ko) 2008-09-05
US20040072716A1 (en) 2004-04-15
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