EP2882836B1 - Agent de lavage au lave-vaisselle contenant des polysaccharides à modification hydrophobe - Google Patents

Agent de lavage au lave-vaisselle contenant des polysaccharides à modification hydrophobe Download PDF

Info

Publication number
EP2882836B1
EP2882836B1 EP13718562.5A EP13718562A EP2882836B1 EP 2882836 B1 EP2882836 B1 EP 2882836B1 EP 13718562 A EP13718562 A EP 13718562A EP 2882836 B1 EP2882836 B1 EP 2882836B1
Authority
EP
European Patent Office
Prior art keywords
acid
weight
agent
hydrophobically modified
automatic dishwashing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP13718562.5A
Other languages
German (de)
English (en)
Other versions
EP2882836A1 (fr
Inventor
Nina Mussmann
Thomas Eiting
Konstantin Benda
Thorsten Bastigkeit
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL13718562T priority Critical patent/PL2882836T3/pl
Publication of EP2882836A1 publication Critical patent/EP2882836A1/fr
Application granted granted Critical
Publication of EP2882836B1 publication Critical patent/EP2882836B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/228—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with phosphorus- or sulfur-containing groups
    • 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
    • C11D3/0021—Dye-stain or dye-transfer inhibiting 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • 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
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate

Definitions

  • the present invention relates to the use of hydrophobically modified polysaccharides for preventing the discoloration of plastic dishes, a machine dishwashing detergent containing hydrophobically modified polysaccharides for preventing discoloration of plastic dishes, the use of this dishwashing detergent, and a machine dishwashing method using this dishwashing detergent.
  • detergents or cleaners which include hydrophobically modified polysaccharides such as hydroxypropylcelluloses. These cellulose ethers have the advantages of being compatible with salts, possessing good solubility in various solvents, and stable under both acidic and alkaline conditions.
  • the hydrophobically modified polysaccharides are suitable for a number of applications. From the WO 99/31211 shows that they can also be used in machine, especially in solid automatic dishwashing detergents.
  • dry powders containing hydrophobically modified polysaccharides can be prepared without problems. However, the property of reducing discoloration of plastic dishes during machine dishwashing can not be deduced from the references.
  • the object of the present invention was to provide further compounds for use in automatic dishwashing detergents which at least reduce the occurrence of discoloration on plastics in the course of automatic dishwashing as a result of colored food residues.
  • a first subject of the present invention is therefore the use of hydrophobically modified polysaccharides selected from hydroxypropylmethylcellulose (HPMC) and / or hydroxyethylmethylcellulose (HEMC). for reducing the discoloration of plastic dishes in automatic dishwashing processes.
  • the reduction in discoloration is generally to be understood as meaning that the transfer of dyes, resulting from colored food residues, to plastic utensils when they are being cleaned in an automatic dishwashing machine is at least reduced, in the best case even completely suppressed.
  • this also means that a change in the color impression of plastic dishes during its cleaning in an automatic dishwashing machine is at least reduced and in the best case completely suppressed.
  • Another object of the present invention is a machine dishwashing detergent containing sulfonic acid-containing polymers as a softener and further at least one hydrophobically modified polysaccharide selected from HPMC and / or HEMC.
  • Another object of the present invention is the use of a machine dishwashing detergent according to the invention for preventing and / or reducing the staining of plastic and / or for preventing the change in the color impression of plastic dishes during its cleaning in an automatic dishwashing machine
  • a further subject matter of the present invention is a machine dishwashing process in which a machine dishwasher detergent according to the invention is used in particular for the purpose of reducing and / or preventing the discoloration of plastics.
  • plastic materials are in a preferred embodiment of polyethylene or polypropylene.
  • hydrophobically modified cellulose derivatives include hydroxyethylmethylcellulose (HEMC), hydroxypropylmethylcellulose (HPMC), or mixtures thereof, or mixtures of at least one of these hydrophobically modified cellulose derivatives with other cellulose derivatives.
  • HEMC hydroxyethylmethylcellulose
  • HPMC hydroxypropylmethylcellulose
  • hydrophilic nature such as carboxymethyl cellulose or sulfoethyl cellulose.
  • Cellulose derivatives can be obtained, for example, under the names Ethocel®, Methocel®, Walocel® or Cellosize® from The Dow Chemical Company.
  • HPMC Hydroxypropylmethylcellulose
  • HEMC hydroxyethylmethylcellulose
  • hydrophobically modified polysaccharides and in particular the hydrophobically modified cellulose derivatives are usually used in amounts of from 0.1 to 10% by weight, based on the total formulation of the agent used. Below the specified minimum quantity, the effects are generally insufficient, whereas above the stated maximum quantity no further overall performance advantages are found.
  • Preferred amounts of hydrophobically modified cellulose derivatives and especially of HPMC and / or HEMC are 1 to 8% by weight and in particular 2 to 6% by weight.
  • the machine dishwashing detergent according to the invention does not contain sulfonic acid-modified cellulose derivatives in a preferred embodiment, it does contain sulfonic acid-containing polymers in addition to the hydrophobically modified cellulose derivatives, which are usually used as softeners in automatic dishwashing detergents.
  • sulfonic acid-containing polymers are known to those skilled in the literature.
  • Particularly preferred as sulfonic acid-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other ionic or nonionic monomers.
  • Preferred copolymeric sulfopolymers contain not only sulfonic acid-containing monomer (s) but also at least one monomer selected from the group consisting of unsaturated carboxylic acids.
  • Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salt
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
  • the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably in each case from 5 to 95% by weight, particularly preferably Proportion of the sulfonic acid group-containing monomer 50 to 90 wt .-% and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred automatic dishwashing agents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • the copolymers in addition to the carboxyl group-containing monomer and the monomer containing the sulfonic acid group, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer.
  • the use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.
  • nonionic monomers are 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-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, ⁇ -olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C
  • the automatic dishwashing agents according to the invention can be solid or liquid in nature and, in particular, can be in the form of powdery solids, in densified particle form, as homogeneous solutions or suspensions.
  • the automatic dishwashing detergent is present in a pre-portioned form.
  • the automatic dishwashing detergent has a plurality of spatially separate compositions, whereby it is possible to separate incompatible ingredients from one another, or to offer compositions in combination, which are used at different times in the dishwasher. This is particularly advantageous if the automatic dishwashing detergents are present in pre-portioned form.
  • At least one of the compositions is solid and / or at least one of the compositions is liquid, wherein the hydrophobically modified polysaccharides are contained in at least one of the compositions, but can also be present in several compositions.
  • the agents according to the invention preferably comprise at least one further constituent, in particular at least two further constituents selected from the group consisting of builders, surfactants, polymers, bleaches, bleach activators, bleach catalysts, in particular catalysts based on manganese or cobalt, enzymes, corrosion inhibitors and glass corrosion inhibitors, Disintegration aids, fragrances and perfume carriers.
  • an agent according to the invention may, in addition to the active ingredients mentioned, additionally comprise a further, known color transfer inhibitor, then preferably in amounts of from 0.01% by weight to 5% by weight, in particular from 0.1% by weight to 1% by weight. %, contain.
  • a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a copolymer of these can be used.
  • polyvinylpyrrolidones having molecular weights of from 15,000 to 50,000 and also polyvinylpyrrolidones having molecular weights of more than 1,000,000, in particular from 1,500,000 to 4,000,000, N-vinylimidazole / N-vinylpyrrolidone copolymers, polyvinyl oxazolidones, polyamine N-oxide Polymers, polyvinyl alcohols and copolymers based on acrylamidoalkenylsulfonic acids.
  • Polyvinylpyrrolidone preferably has an average molecular weight in the range from 10 000 to 60 000, in particular in the range from 25 000 to 50 000, for use in compositions according to the invention.
  • those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5: 1 to 1: 1 having an average molecular weight in the range of 5,000 to 50,000, especially 10,000 to 20,000 are preferred.
  • porous polyamide particles and / or synthetic sheet silicates and / or glycerol esters it is possible to use porous polyamide particles and / or synthetic sheet silicates and / or glycerol esters.
  • builders can be used.
  • the builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.
  • the crystalline layer-form silicates of the formula NaMSi x O 2x + 1 .yH 2 O are for example sold by Clariant GmbH (Germany) under the trade name Na-SKS.
  • silicates Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 ⁇ x H 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 ⁇ xH 2 O, makatite).
  • Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula NaMSi x O 2x + 1 .yH 2 O, in which x is 2.
  • both ⁇ - and ⁇ -sodium disilicates are Na 2 Si 2 O 5 .yH 2 O and furthermore, in particular, Na-SKS-5 ( ⁇ -Na 2 Si 2 O 5 ), Na-SKS-7 ( ⁇ -Na 2 Si 2 O 5, natrosilite), Na-SKS-9 (NaHSi 2 O 5 ⁇ H 2 O), Na-SKS-10 (NaHSi 2 O5 ⁇ 3H 2 O, kanemite), Na-SKS-11 (t-Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), but especially Na-SKS-6 ( ⁇ -Na 2 Si 2 O 5 ).
  • Machine dishwashing detergents preferably contain a weight fraction of the crystalline layered silicate of the formula NaMSi x O 2x + 1 ⁇ yH 2 O of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular of 0.4 to 10 wt .-%, each based on the total weight of these agents.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.
  • the release delay opposite conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • amorphous is understood to mean that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle , cause.
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • phosphates are the pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate).
  • sodium potassium tripolyphosphates Preferably usable according to the invention are the sodium potassium tripolyphosphates.
  • phosphates are used as washing or cleaning substances in machine dishwashing detergent in the present application
  • preferred agents comprise this phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate ), in amounts of 5 to 80 wt .-%, preferably from 15 to 75 wt .-% and in particular from 20 to 70 wt .-%, each based on the weight of the automatic dishwashing detergent.
  • alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates, and mixtures of the abovementioned substances, it being possible to use the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, for the purposes of this invention.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.
  • the optional alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 % By weight and in particular below 2% by weight, in each case based on the total weight of the automatic dishwashing detergent.
  • Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders and phosphonates. These classes of substances are described below.
  • Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures thereof.
  • NTA nitrilotriacetic acid
  • the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of the automatic dishwashing detergents.
  • here are citric acid, Succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof.
  • automatic dishwashing detergents are preferred according to the invention in that the automatic dishwashing agent contains citric acid or a salt of citric acid and the weight fraction of citric acid or of the salt of citric acid is preferably more than 10% by weight, preferably more than 15% by weight in particular between 20 and 40 wt .-% is.
  • phosphate-free builders are aminocarboxylic acids and / or their salts. Particularly preferred members of this class are methylglycinediacetic acid (MGDA) or its salts, and glutamic diacetic acid (GLDA) or its salts or ethylenediaminediacetic acid or its salts (EDDS).
  • MGDA methylglycinediacetic acid
  • GLDA glutamic diacetic acid
  • EDDS ethylenediaminediacetic acid or its salts
  • the content of these aminocarboxylic acids or their salts may for example be between 0.1 and 15% by weight, preferably between 0.5 and 10% by weight and in particular between 0.5 and 6% by weight.
  • Aminocarboxylic acids and their salts can be used together with the abovementioned builders, in particular also with the phosphate-free builders.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of the automatic dishwashing agents in (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight and in particular from 3 to 10% by weight.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • copolymers are those which have as their monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • compositions of the invention may contain surfactants, wherein the nonionic, the anionic, the cationic and the amphoteric surfactants are counted among the group of surfactants.
  • nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art.
  • Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R corresponds to a primary straight-chain or methyl-branched, especially methyl-branched, 2-position aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which is a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • surfactants are the polyhydroxy fatty acid amides known as PHFA.
  • the automatic dishwashing detergents contain nonionic surfactants from the group of the alkoxylated alcohols.
  • nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used, in which the alcohol radical may be methyl linear or preferably in the 2-position methyl-branched or linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants which have a melting point above room temperature.
  • surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • nonionic surfactants of the general formula in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently stand for integers from 1 to 6.
  • nonionic surfactants having a C 9-15 alkyl radical having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units.
  • These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.
  • R 1 is -CH (OH) CH 2 O- (AO) w - (A "O) x - (A" O) y - (A '"O) z -R 2 , in the R 1 and R 2 independently represent a straight-chain or branched, saturated or mono- or polyunsaturated C 2-40 alkyl or alkenyl radical;
  • A, A ', A "and A'” independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 2 -CH 3 ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0, are particularly preferred according to the invention.
  • Very particularly preferred nonionic surfactants in a preferred embodiment have the general formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (CH 3 ) O] z CH 2 CH ( OH) R 2 in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms, in particular 4 to 20 carbon atoms, or mixtures thereof and x and z are values between 0 and 40 and y is a value of at least 15.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.
  • Anionic surfactants can also be used as a component of automatic dishwashing detergents. These include in particular alkylbenzenesulfonates, (fatty) alkyl sulfates, (fatty) alkyl ether sulfates and alkanesulfonates.
  • the content of the anionic surfactant is usually 0 to 10% by weight.
  • the content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. %. Automatic dishwashing detergents containing no cationic or amphoteric surfactants are particularly preferred.
  • the group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners.
  • the washing or cleaning-active polymers for example the rinse aid polymers and / or polymers which act as softeners.
  • cationic, anionic and amphoteric polymers can be used in machine dishwashing detergents in addition to nonionic polymers.
  • “Cationic polymers” in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be done, for example, in the polymer chain present (alkyl) ammonium groups or other positively charged groups can be realized.
  • Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCl designations Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.
  • amphoteric polymers furthermore have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be e.g. to act carboxylic acids, sulfonic acids or phosphonic acids.
  • Preferred employable amphoteric polymers are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth ) -acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or non
  • Preferably usable zwitterionic polymers are selected from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.
  • Machine dishwashing detergents preferably contain the abovementioned cationic and / or amphoteric polymers in amounts of from 0.01 to 10% by weight, based in each case on the total weight of the automatic dishwashing detergent.
  • the bleaching agents are a substance which can be used with particular preference for washing or cleaning.
  • sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid. It is also possible to use all other inorganic or organic peroxy bleaches known to the person skilled in the art.
  • chlorine or bromine releasing substances can be used.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • automatic dishwashing agents which contain from 1 to 35% by weight, preferably from 2.5 to 30% by weight, particularly preferably from 3.5 to 20% by weight and in particular from 5 to 15% by weight of bleaching agent, preferably sodium percarbonate , contain.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulphonates, in particular n -Nonanoyl or Isononanloxybenzolsulfonat (n- or iso-NOBS) is particularly preferably used.
  • TAED tetraacetylethylenediamine
  • DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • TAGU acylated glycolurils
  • bleach activators can also be used. These bleach activators are preferably used in amounts of up to 10% by weight, in particular from 0.1% by weight to 8% by weight, especially from 2 to 8% by weight and more preferably from 2 to 6% by weight, based in each case on the total weight of bleach activator-containing agents.
  • Enzymes can also be used to increase the washing or cleaning performance of automatic dishwasher detergents. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in automatic dishwasher detergents, which can be used correspondingly preferred.
  • Machine dishwashing detergents preferably contain enzymes in total amounts of 1 ⁇ 10 -6 to 5% by weight, based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which produces hydrogen peroxide in water.
  • a mediator compound for the peroxidase for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine, is preferred in this case, with the above-mentioned conventional polymeric color transfer inhibiting agents can additionally be used.
  • the enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • a plurality of enzymes and / or enzyme preparations preferably protease preparations and amylase preparations, in amounts of from 0.1 to 5 wt .-%, preferably from 0.2 to 4.5 wt .-% and in particular from 0.4 to 4 wt .-%, each based on the total enzyme-containing agent used.
  • Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses.
  • Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts and magnesium and zinc complexes.
  • the content of zinc salt in dishwasher detergents is preferably between 0.1 and 5 wt.%, Preferably between 0.2 and 4 wt.% And in particular between 0.4 and 3 wt the content of zinc in oxidized form (calculated as Zn 2+ ) is between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight and in particular between 0.04 and 0.2% by weight .-%, each based on the total weight of the glass corrosion inhibitor-containing agent.
  • disintegration aids so-called tablet disintegrants
  • tablet disintegrants or disintegrants excipients which ensure the rapid disintegration of tablets in water or other media and for the rapid release of the active ingredients.
  • Desintegration aids may preferably be used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.
  • perfume oils or perfumes within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • the preparation of automatic dishwashing agents according to the invention can take place in different ways.
  • the agents may be in solid or liquid form as well as in a combination of solid and liquid forms. Powder, granules, extrudates, compacts, in particular tablets, are particularly suitable as firm supply forms.
  • the liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels.
  • Inventive agents can be formulated in the form of single-phase or multi-phase products.
  • automatic dishwashing detergents with one, two, three or four phases are preferred.
  • Machine dishwashing detergent characterized in that it is in the form of a prefabricated dosing unit with two or more phases, are particularly preferred.
  • the individual phases of multiphase agents may be the same or different Have aggregate states. Machine dishwashing detergents which have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one solid phase are preferred.
  • Automatic dishwasher detergents according to the invention are preferably prefabricated to form metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 16 and 22 g.
  • the automatic dishwasher detergents according to the invention in particular the prefabricated metering units, have a water-soluble coating, with particular preference.
  • the subject matter of the present application is furthermore a method for cleaning dishes in a dishwashing machine, in which the agent according to the invention is metered into the interior of a dishwasher during the passage of a dishwashing program before the main wash cycle or during the main wash cycle.
  • the metering or the entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered by means of the metering chamber into the interior of the dishwasher.
  • a typical framework formulation for a machine dishwashing detergent preferably used, for example in tablet form comprises the following substances: Na tripolyphosphate 20-50% by weight sodium 10-30% by weight sodium 5-18% by weight bleach 0.5-5% by weight bleach catalyst 0.01-1% by weight sulfopolymer 2.5-15% by weight polycarboxylate 0.1-10% by weight nonionic surfactant 0.5-10% by weight phosphonate 0.5-5% by weight protease 0.1-5% by weight amylase 0.1-5% by weight, the data in% by weight are based on the total agent.
  • the tripolyphosphate it is also possible in particular to use 10-50% by weight of citrate or MGDA or GLDA or EDDS or mixtures of two or three of these substances in the formulation.
  • Example 1 Inhibition of the Staining of Plastic in Automatic Dishwashing (Test Arrangement)
  • composition see Table 1 0.73 g of a soil mixture (composition see Table 1) were combined with 10 g of Lupolen® PE-HD (polyethylene spheres, BASF) in 25 ml of water with a hardness of 21 ° dH. 0.12 g (corresponding to 20 g per 4 liters) of a powdered automatic dishwashing detergent (composition see Table 2) and various amounts of the additive to be investigated were added. The mixture was stirred rapidly for 10 minutes at room temperature and then filtered. From the filtrate, 5 ml was taken, added with 5 ml of toluene, shaken for 1 minute and then centrifuged until a phase separation occurred.
  • Table 3 The values given in Table 3 are the means from a triplicate.
  • Table 1 Composition of the soil mixture in% by weight olive oil 12.8 Vinegar essence 4.2 tomato ketchup 68.0 Paprika spice 3.2 Curry spice 3.2 common salt 8.6 phosphate 40.0 sodium 13.5 phosphonate 2.5 Sulfonic acid group-containing polymer 5.5 polyacrylate 8.5 Nonionic surfactants 6.5 percarbonate 15.5 TAED 2.5 bleach catalyst 1.0 amylase 0.8 protease 2.4 zinc acetate 0.2 leftovers ad 100 0.73 g of dirt 0.72 0.73 g + 10 g Lupolen® PE-HD 0.1 0.73 g + 10 g Lupolen® PE-HD + 0.12 g dishwashing detergent 0.2 0.73 g + 10 g Lupolen® PE-HD + 0.12 g dishwashing detergent + 3.125 mg HPMC 0.30 0.73 g + 10 g Lupolen® PE-HD + 0.12 g dishwashing detergent + 6.25 mg HPMC 0.32 0.73
  • Polyethylene breakfast board (PE board) and polypropylene breakfast board (PP board) were subjected to a machine dishwashing process (AEG Proclean dishwasher, Quick program (55 ° C, 50 minutes, water hardness 21 ° dH) g of the soil composition given in Table 1.
  • AEG Proclean dishwasher, Quick program 55 ° C, 50 minutes, water hardness 21 ° dH
  • 20 g of the powdered automatic dishwashing detergent indicated in Table 2 and the amounts of added additive indicated in Table 4 were dosed before and after rinsing using a colorimeter (Datacolor DC 600 -3) the values L, a and b were measured and the ⁇ E value was then determined from these values: the lower the determined ⁇ E value, the smaller is the soiling of the boards The results are shown in Table 4.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Claims (10)

  1. Utilisation de polysaccharides modifiés de manière hydrophobe pour réduire la décoloration de la vaisselle en matière plastique dans un procédé de lavage de la vaisselle en machine, les polysaccharides modifiés de manière hydrophobe étant choisis parmi l'hydroxypropylméthylcellulose (HPMC) et/ou l'hydroxyéthyleméthylcellulose (HEMC).
  2. Agent de lavage de la vaisselle en machine contenant des polymères, contenant des groupes acide sulfonique, comme adoucissants, caractérisé en ce que l'agent comporte en outre au moins un polysaccharide modifié de manière hydrophobe, l'au moins un polysaccharide modifié de manière hydrophobe est choisi parmi l'hydroxypropylméthylcellulose (HPMC) et/ou l'hydroxyéthylméthylcellulose (HEMC).
  3. Mode de réalisation selon la revendication 2, caractérisé en ce que l'agent comporte de la HPMC et/ou HEMC dans des quantités allant de 0,1 à 10% en poids, en particulier de 1 à 8% en poids et de manière particulièrement préférée de 2 à 6% en poids.
  4. Mode de réalisation selon l'une des revendications 2 ou 3, caractérisé en ce que l'agent se présente sous forme solide.
  5. Mode de réalisation selon l'une des revendications 2 ou 3, caractérisé en ce que l'agent se présente sous forme liquide.
  6. Mode de réalisation selon l'une des revendications 2 ou 3, caractérisé en ce que l'agent se présente sous la forme de pré-portion.
  7. Mode de réalisation selon l'une des revendications précédentes, caractérisé en ce que l'agent comprend une pluralité de compositions séparées spatialement les unes des autres dont au moins une composition est solide et/ou une composition est liquide, les polysaccharides modifiés de manière hydrophobe étant contenus dans au moins une des compositions.
  8. Mode de réalisation selon l'une des revendications précédentes, caractérisé en ce que l'agent d'au moins contient un autre ingrédient, de préférence au moins deux autres ingrédients, choisis dans le groupe constitué par des adjuvants, des tensioactifs, des polymères, des agents de blanchiment, des activateurs de blanchiment, des catalyseurs de blanchiment, des enzymes, des inhibiteurs de corrosion, des inhibiteurs de corrosion du verre, des adjuvants de désintégration, des parfums et des supports de parfum.
  9. Utilisation d'un agent de lavage de vaisselle en machine selon l'une des revendications précédentes, pour empêcher et/ou réduire la décoloration de matière plastique et/ou pour empêcher le changement de l'impression de couleur de vaisselle en matière plastique lors de son nettoyage dans un lave-vaisselle automatique.
  10. Procédé de lavage de vaisselle en machine, dans lequel un agent de lavage de la vaisselle selon l'une des revendications 2 à 8 est utilisé.
EP13718562.5A 2012-08-07 2013-04-19 Agent de lavage au lave-vaisselle contenant des polysaccharides à modification hydrophobe Not-in-force EP2882836B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL13718562T PL2882836T3 (pl) 2012-08-07 2013-04-19 Środek do maszynowego zmywania naczyń zawierający hydrofobowo modyfikowane polisacharydy

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012213949.4A DE102012213949A1 (de) 2012-08-07 2012-08-07 Maschinelles Geschirrspülmittel enthaltend hydrophob modifizierte Polysaccharide
PCT/EP2013/058178 WO2014023444A1 (fr) 2012-08-07 2013-04-19 Agent de lavage au lave-vaisselle contenant des polysaccharides à modification hydrophobe

Publications (2)

Publication Number Publication Date
EP2882836A1 EP2882836A1 (fr) 2015-06-17
EP2882836B1 true EP2882836B1 (fr) 2017-08-23

Family

ID=48184186

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13718562.5A Not-in-force EP2882836B1 (fr) 2012-08-07 2013-04-19 Agent de lavage au lave-vaisselle contenant des polysaccharides à modification hydrophobe

Country Status (6)

Country Link
US (1) US9512386B2 (fr)
EP (1) EP2882836B1 (fr)
DE (1) DE102012213949A1 (fr)
ES (1) ES2642015T3 (fr)
PL (1) PL2882836T3 (fr)
WO (1) WO2014023444A1 (fr)

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2309975A (en) * 1996-02-08 1997-08-13 Procter & Gamble Use of cellulose ethers in dishwashing
CN1202231C (zh) 1997-12-17 2005-05-18 赫尔克里士公司 疏水改性多糖在家用卫生用品中的应用
DE10104470A1 (de) 2001-02-01 2002-08-08 Basf Ag Reinigerformulierungen zur Verhinderung der Verfärbung von Kunststoffgegenständen
MXPA04004523A (es) * 2001-11-14 2004-08-11 Procter & Gamble Composicion para el lavado automatico de platos y utensilios de cocina en forma de dosis unitaria que contiene un polimero antiescamas.
EP1504083B1 (fr) 2002-05-11 2009-10-14 Reckitt Benckiser N.V. Utilisation d'un composé hydrophobe dans un procédé de lavage de la vaisselle en machine
WO2004087857A1 (fr) * 2003-04-03 2004-10-14 Reg Macquarrie Compositions filmogenes pour l'application de savons et de detergents
US20060134047A1 (en) 2004-12-16 2006-06-22 Bakeev Kirill N Personal care and household compositions of hydrophobically-modified polysaccharides
US20070249514A1 (en) * 2006-04-19 2007-10-25 The Procter & Gamble Company Rheology modifying systems and detersive compositions comprising same
DE102009004524A1 (de) 2009-01-09 2010-07-15 Henkel Ag & Co. Kgaa Farbschützendes maschinelles Geschirrspülmittel
DE102009027812A1 (de) * 2009-07-17 2011-01-20 Henkel Ag & Co. Kgaa Flüssiges Wasch- oder Reinigungsmittel mit vergrauungsinhibierendem Polymer
DE102009029635A1 (de) * 2009-09-21 2011-03-24 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
EP2882836A1 (fr) 2015-06-17
US9512386B2 (en) 2016-12-06
DE102012213949A1 (de) 2014-02-13
WO2014023444A1 (fr) 2014-02-13
US20150152356A1 (en) 2015-06-04
PL2882836T3 (pl) 2018-02-28
ES2642015T3 (es) 2017-11-14

Similar Documents

Publication Publication Date Title
EP2376615B1 (fr) Composition détergente pour lave-vaisselle protégeant les couleurs
EP3209762B1 (fr) Détergent pour lave-vaisselle contenant des complexes métalliques
EP2768934A1 (fr) Produits de rinçage et de lavage pour vaisselle
DE102014206082A1 (de) Automatisches Geschirrspülmittel mit verbesserter Bleichleistung
WO2015086474A1 (fr) Lessive lave-vaisselle contenant des agents complexants à base de n
EP2802640B1 (fr) Détergents et produits de nettoyage contenant de l'ester de glycérine
EP2922884B1 (fr) Copolymères en masse amphiphiles et détergents de lave-vaisselle contenant lesdits copolymères
EP3080237A1 (fr) Lessive lave-vaisselle contenant des agents complexants à base de n
DE102012214027A1 (de) Verwendung von anionischen Tensiden
EP2882836B1 (fr) Agent de lavage au lave-vaisselle contenant des polysaccharides à modification hydrophobe
EP3436559A1 (fr) Détergents vaisselle à efficacité de rinçage améliorée
DE102016212248A1 (de) Geschirrspülmittel enthaltend Zuckersäure und Aminocarbonsäure
DE102015206485A1 (de) Geschirrspülmittel enthaltend sticksoffbasierte Komplexbildner und MGDA
EP2733194A1 (fr) Produit de rinçage de vaisselle pour lave-vaisselle contenant des copolymères en bloc de polyalkylène-glycols
DE102012212553A1 (de) Wasch- oder Reinigungsmittel enthaltend Thiosulfat
DE102013226440A1 (de) Maschinelles Geschirrspülmittel enthaltend Emulgatoren
DE102014206148A1 (de) Maschinelles Geschirrspülmittel enthaltend Phosphonopolycarbonsäure
DE102022131906A1 (de) Geschirrspülmaschinenreiniger mit verbesserter Fettentfernung und zusätzlicher Kalkentfernung
WO2012123450A1 (fr) Détergents pour vaisselle
DE102013226432A1 (de) Maschinelles Geschirrspülmittel enthaltend Emulgatoren
WO2013068134A1 (fr) Détergent pour lave-vaisselle contenant des émulsifiants
EP3440176A1 (fr) Détergent pour vaisselle contenant des dérivés d'urée
DE102016212054A1 (de) Reinigungsmittel mit verringerter Glaskorrosion

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20150107

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

RIN1 Information on inventor provided before grant (corrected)

Inventor name: EITING, THOMAS

Inventor name: MUSSMANN, NINA

Inventor name: BASTIGKEIT, THORSTEN

Inventor name: BENDA, KONSTANTIN

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20170419

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 921336

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170915

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502013008140

Country of ref document: DE

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2642015

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20171114

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20170823

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171123

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171223

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171124

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171123

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502013008140

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20180524

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20180418

Year of fee payment: 6

Ref country code: TR

Payment date: 20180418

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20180430

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180419

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180430

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180430

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180419

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20190326

Year of fee payment: 7

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 921336

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180419

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20190418

Year of fee payment: 7

Ref country code: ES

Payment date: 20190521

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20190418

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180419

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20190418

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190419

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20130419

Ref country code: MK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170823

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502013008140

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200430

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201103

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20200419

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200419

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20210903

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200420

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190419

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200419