EP1373451B1 - Copolymeres pour empecher la corrosion du verre - Google Patents

Copolymeres pour empecher la corrosion du verre Download PDF

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EP1373451B1
EP1373451B1 EP02719733A EP02719733A EP1373451B1 EP 1373451 B1 EP1373451 B1 EP 1373451B1 EP 02719733 A EP02719733 A EP 02719733A EP 02719733 A EP02719733 A EP 02719733A EP 1373451 B1 EP1373451 B1 EP 1373451B1
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copolymers
weight
carbon atoms
sodium
acid
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EP1373451A1 (fr
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Axel Kistenmacher
Stephan Nied
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/18—Glass; Plastics

Definitions

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

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Claims (9)

  1. Utilisation de copolymères contenant
    a) 20 à 70 % en poids d'au moins un constituant monomère (A) du groupe des acides mono- et dicarboxyliques en C3-C10 monoéthyléniquement insaturés ou leurs anhydrides, le constituant monomère (A) étant de préférence l'acide maléique, l'anhydride de l'acide maléique et/ou l'acide acrylique,
    b) 30 à 80 % 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)-, -OC(=O)-O- ou -C(=O)-NH,
    n vaut 0 ou 1,
    R4 est un radical soit aromatique, soit aliphatique, linéaire, ramifié ou cyclique, contenant 1 à 6 atomes de carbone,
    R2 et R4 forment éventuellement ensemble une unité alkylène contenant 3 à 6 atomes de carbone, qui est éventuellement substituée avec des groupes alkyle en C1-C3, avec formation d'un cycle,
    le constituant monomère (B) étant de préférence le cyclopentène, l'hexène et/ou le diisobutène technique,
    et
    c) 0 à 25 % en poids d'au moins un constituant monomère (C) supplémentaire, copolymérisable avec les constituants monomères (A) et (B), du groupe constitué des α-oléfines contenant 10 atomes de carbone ou plus, des mélanges oléfiniques d'α-oléfines contenant 10 atomes de carbone ou plus, des polyisobutènes réactifs contenant en moyenne 12 à 100 atomes de carbone, des (méth)acrylates en Cn avec n > 6, des (méth)acrylates d'hydroxy, des esters de vinyle en Cn ou des éthers de vinyle en Cn avec n > 6, 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,
    le constituant monomère (C) étant de préférence le 1-dodécène, le 1-octadécène, une α-oléfine en C22, le polyisobutène 1000 et/ou un mélange oléfinique d'α-oléfines en C20-C24,
    dans des formulations de nettoyage pour empêcher la corrosion du verre pendant le processus de nettoyage dans des lave-vaisselle.
  2. Utilisation selon la revendication 1, caractérisée en ce que les copolymères sont utilisés sous la forme de l'acide libre, d'un de ses sels ou de l'anhydride, notamment sous la forme du sel de sodium ou d'ammonium.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que les copolymères contiennent de l'anhydride de l'acide maléique et du diisobutène technique en tant que constituants monomères et se présentent sous la forme du sel de sodium.
  4. Utilisation selon l'une quelconque des revendications 1 à 3, 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.
  5. Utilisation selon l'une quelconque des revendications 1 à 4, caractérisée en ce que les copolymères sont également mis en réaction avec des alcools ou des amines pour former des liaisons ester ou amide.
  6. Utilisation selon l'une quelconque des revendications 1 à 5, caractérisée en ce que les copolymères sont présents dans une 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 3 % en poids.
  7. Utilisation selon l'une quelconque des revendications 1 à 6, 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.
  8. Utilisation selon la revendication 7, 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.
  9. Utilisation selon la revendication 7 ou 8, caractérisée en ce que les copolymères sont incorporés dans des compartiments déterminés de la formulation de nettoyage, les compartiments étant notamment, dans le cas de formulations de nettoyage sous la forme de tablettes, des couches de tablettes et/ou des corps moulés encastrés dans les tablettes, collés aux tablettes ou enrobant les tablettes.
EP02719733A 2001-02-01 2002-01-25 Copolymeres pour empecher la corrosion du verre Expired - Lifetime EP1373451B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10104469 2001-02-01
DE10104469A DE10104469A1 (de) 2001-02-01 2001-02-01 Copolymere zur Verhinderung von Glaskorrosion
PCT/EP2002/000836 WO2002064719A1 (fr) 2001-02-01 2002-01-25 Copolymeres pour empecher la corrosion du verre

Publications (2)

Publication Number Publication Date
EP1373451A1 EP1373451A1 (fr) 2004-01-02
EP1373451B1 true EP1373451B1 (fr) 2009-12-16

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US (1) US20040058846A1 (fr)
EP (1) EP1373451B1 (fr)
JP (1) JP2004518018A (fr)
KR (1) KR20030074767A (fr)
AT (1) ATE452175T1 (fr)
CA (1) CA2435487C (fr)
DE (2) DE10104469A1 (fr)
WO (1) WO2002064719A1 (fr)

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DE50304955D1 (de) † 2003-06-28 2006-10-19 Dalli Werke Gmbh & Co Kg Alpha Olefin- und Alpha Olefin-Cellulose Granulate als Sprengmittel
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DE102004044411A1 (de) 2004-09-14 2006-03-30 Basf Ag Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophob modifizierte Polycarboxylate
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DE102005049701A1 (de) * 2005-10-14 2007-04-26 Basf Ag Verfahren zur Stabilisierung von Flüssigwaschmittelzusammensetzungen und Flüssigwaschmittelzusammensetzungen
DE102006043914A1 (de) * 2006-09-19 2008-03-27 BSH Bosch und Siemens Hausgeräte GmbH Verfahren zum Betreiben eines wasserführenden Haushaltsgeräts
DE102007006628A1 (de) * 2007-02-06 2008-08-07 Henkel Ag & Co. Kgaa Reinigungsmittel
BRPI0810765B1 (pt) * 2007-05-04 2018-05-29 Ecolab Inc. Composições de limpeza contendo composto de magnésio solúvel em água e métodos de uso das mesmas
US8519075B2 (en) * 2007-11-30 2013-08-27 Joseph P. Laurino Polycarbonate resin, and method of use of, poly (2-octadecyl-butanedioic acid) and the salts and esters thereof
DE102009025411B4 (de) 2009-06-16 2011-05-19 Innovent E.V. Technologieentwicklung Verwendung von Zinkstaubpartikeln oder Partikelstaub, der Zink oder eine Zinkverbindung enthält, als Korrosionsschutzmittel für Glas
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CA2844293A1 (fr) 2011-10-19 2013-04-25 Basf Se Formulations, leur utilisation comme detergents pour vaisselle ou pour la fabrication de detergents pour vaisselle, et leur preparation
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WO2013160132A1 (fr) 2012-04-25 2013-10-31 Basf Se Formulations solides et production et utilisation desdites formulations
BR112014026564A2 (pt) 2012-04-25 2017-06-27 Basf Se formulação, uso de uma formulação, e, processo para a preparação de uma formulação
US8846593B2 (en) 2012-04-25 2014-09-30 Basf Se Dishwashing composition comprising a covalently modified alkyleneimine polymer
CN102660404B (zh) * 2012-05-04 2014-01-22 冠宏股份有限公司 一种低温皂洗剂及其制备方法和用途
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Publication number Publication date
JP2004518018A (ja) 2004-06-17
CA2435487C (fr) 2011-06-07
ATE452175T1 (de) 2010-01-15
WO2002064719A1 (fr) 2002-08-22
KR20030074767A (ko) 2003-09-19
DE10104469A1 (de) 2002-08-08
US20040058846A1 (en) 2004-03-25
DE50214096D1 (de) 2010-01-28
EP1373451A1 (fr) 2004-01-02
CA2435487A1 (fr) 2002-08-22

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