EP2882836B1 - Maschinelles geschirrspülmittel enthaltend hydrophob modifizierte polysaccharide - Google Patents

Maschinelles geschirrspülmittel enthaltend hydrophob modifizierte polysaccharide Download PDF

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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
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EP
European Patent Office
Prior art keywords
acid
weight
agent
hydrophobically modified
automatic dishwashing
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EP13718562.5A
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German (de)
English (en)
French (fr)
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EP2882836A1 (de
Inventor
Nina Mussmann
Thomas Eiting
Konstantin Benda
Thorsten Bastigkeit
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL13718562T priority Critical patent/PL2882836T3/pl
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—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.

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EP13718562.5A 2012-08-07 2013-04-19 Maschinelles geschirrspülmittel enthaltend hydrophob modifizierte polysaccharide Not-in-force EP2882836B1 (de)

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PL13718562T PL2882836T3 (pl) 2012-08-07 2013-04-19 Środek do maszynowego zmywania naczyń zawierający hydrofobowo modyfikowane polisacharydy

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DE102012213949.4A DE102012213949A1 (de) 2012-08-07 2012-08-07 Maschinelles Geschirrspülmittel enthaltend hydrophob modifizierte Polysaccharide
PCT/EP2013/058178 WO2014023444A1 (de) 2012-08-07 2013-04-19 Maschinelles geschirrspülmittel enthaltend hydrophob modifizierte polysaccharide

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GB2309975A (en) * 1996-02-08 1997-08-13 Procter & Gamble Use of cellulose ethers in dishwashing
AU1416299A (en) 1997-12-17 1999-07-05 Hercules Incorporated Hydrophobically modified polysaccharides in household preparations
DE10104470A1 (de) 2001-02-01 2002-08-08 Basf Ag Reinigerformulierungen zur Verhinderung der Verfärbung von Kunststoffgegenständen
CA2463613C (en) * 2001-11-14 2009-04-07 The Procter & Gamble Company Automatic dishwashing composition in unit dose form comprising an anti-scaling polymer
US7265081B2 (en) 2002-05-11 2007-09-04 Reckitt Benckisder N.V. Detergent composition comprising a bleach and an edible oil
WO2004087857A1 (en) * 2003-04-03 2004-10-14 Reg Macquarrie Film-form compositions for delivery of soaps and detergents
CN101119703A (zh) 2004-12-16 2008-02-06 赫尔克里士公司 疏水改性的多糖的个人护理和家用组合物
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

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ES2642015T3 (es) 2017-11-14
DE102012213949A1 (de) 2014-02-13
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