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EP3674386B1 - Détergent pour lave-vaisselle à performance de rinçage améliorée - Google Patents

Détergent pour lave-vaisselle à performance de rinçage améliorée Download PDF

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Publication number
EP3674386B1
EP3674386B1 EP19214081.2A EP19214081A EP3674386B1 EP 3674386 B1 EP3674386 B1 EP 3674386B1 EP 19214081 A EP19214081 A EP 19214081A EP 3674386 B1 EP3674386 B1 EP 3674386B1
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EP
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Prior art keywords
carbon atoms
functional group
dishwashing detergent
mol
branched
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German (de)
English (en)
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EP3674386A1 (fr
Inventor
Thomas Doering
Astrid Spitz
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

Definitions

  • the present invention relates to a dishwashing agent that A) at least one nonionic surfactant selected from fatty alcohol alkoxylates and B) at least one polymer that is selected by polymerizing itaconic acid with at least one co-monomer selected from (meth)acrylic acid, salts, esters or anhydrides thereof and 2 -Acrylamido-2-methylpropanesulfonic acid or salts thereof.
  • the present invention further relates to a method for cleaning dishes in a dishwasher, using a dishwashing agent of the present invention, and the use of a dishwashing agent according to the present invention to improve the rinse performance of plastic or stainless steel items when washing dishes automatically.
  • dishwashing detergents are known for dishwashers. These are available for purchase as solid, powder, liquid and gel dishwashing detergents. However, unwanted lime deposits often remain on the items to be washed, especially when the water is hard. These residues are particularly visible on glass and metal surfaces, which is not something consumers want.
  • US 2017/022451 A1 discloses dishwashing detergent comprising a copolymer of itaconic acid and acrylic acid and an alkoxylated nonionic surfactant.
  • the copolymer ensures better rinsing behavior on both glass and plastic surfaces.
  • EP 3 418 366 A1 discloses automatic dishwashing detergents comprising a copolymer of itaconic acid and a sulfomonomer selected from 2-acrylamidomethylpropanoic acid and/or styrene sulfonic acid. Specific example formulations also contain an ethoxylated nonionic surfactant.
  • WO 2017/167786 A1 discloses dishwashing detergent with improved rinse performance comprising 0.5 to 20% by weight of a surfactant mixture of an end-capped polyethoxylated nonionic surfactant and a specific hydroxy mixed ether.
  • DE 10 2007 042860 A1 discloses dishwashing detergent containing 10 to 60% by weight of builder, an alkoxylated fatty alcohol and an anionic copolymer.
  • the copolymer is formed from an unsaturated carboxylic acid and a monomer with a sulfonic acid group.
  • the weight ratio of the copolymer and the alkoxylated fatty alcohol is 3:1.
  • US 2018/223016 A1 discloses polyitaconic acid homo- and copolymers that do not have reactive tri-substituted vinyl monomers. It is further disclosed that such homo- or copolymers can be used as builders in detergents.
  • a dishwashing agent that A) at least one nonionic surfactant selected from specific fatty alcohol alkoxylates, as defined below, and B) at least one polymer that is made by polymerizing itaconic acid with at least a co-monomer selected from (meth)acrylic acid, salts, esters or anhydrides thereof and 2-acrylamido-2-methylpropanesulfonic acid or salts thereof.
  • A) at least one nonionic surfactant selected from specific fatty alcohol alkoxylates, as defined below and B) at least one polymer that is made by polymerizing itaconic acid with at least a co-monomer selected from (meth)acrylic acid, salts, esters or anhydrides thereof and 2-acrylamido-2-methylpropanesulfonic acid or salts thereof.
  • the invention in a second aspect, relates to a method for cleaning dishes in a dishwasher, using a dishwashing agent according to the present invention.
  • the invention in a third aspect, relates to the use of a dishwashing agent according to the present invention to improve the rinse performance of plastic or stainless steel items in automatic dishwashing.
  • At least one refers to 1 or more, for example 2, 3, 4, 5, 6, 7, 8, 9 or more. In connection with components of the compounds described herein, this information does not refer to the absolute amount of molecules, but rather to the type of component. “At least one surfactant” therefore means, for example, that only one type of surfactant or several different types of surfactant can be included, without providing information about the amount of the individual compounds.
  • the expression “essentially free of” means that the respective compound can in principle be included, but is then present in an amount that does not impair the function of the other components.
  • the property “substantially free of” a particular compound is therefore preferably a total weight of less than 0.1% by weight, more preferably less than 0.001% by weight, in particular free of this, based on the total weight of detergents and cleaning agents.
  • molecular weight refers to the weight-average molecular weight in g/mol, unless the number-average molecular weight is explicitly stated.
  • Molecular weights are preferably determined by GPC using polystyrene standards.
  • the dishwashing detergent according to the invention contains at least one nonionic surfactant selected from fatty alcohol alkoxylates.
  • nonionic surfactant is available, for example, from BASF under the trade name Dehypon® DA.
  • the fatty alcohol alkoxylates are particularly preferably selected from the group of hydroxy mixed ethers of the general formula C 4-22 -CH(OH)CH 2 O-(EO) 20-120 -C 2-26 .
  • the composition contains C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ether and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ether.
  • EO fatty alcohol
  • Such compounds are commercially available, for example, from BASF under the trade names Dehypon® E127 and Dehypon® GRA.
  • a mixture of the above-mentioned fatty alcohol alkoxylates may be included.
  • the specified C chain lengths and degrees of ethoxylation or alkoxylation of the aforementioned nonionic surfactants represent statistical average values, which can be a whole or a fractional number for a specific product. Due to the manufacturing process, commercial products of the formulas mentioned usually do not consist of an individual representative, but rather of mixtures, which means that average values and the resulting fractional numbers can result for both the C chain lengths and the degrees of ethoxylation or alkoxylation.
  • the at least one nonionic surfactant A) is present in 0.2 to 10% by weight or 0.5 to 9% by weight or 1 to 5% by weight.
  • the dishwashing detergent of the present invention further contains at least one copolymer obtained by polymerizing itaconic acid with at least one co-monomer selected from (meth)acrylic acid, salts, esters or anhydrides thereof, or 2-acrylamido-2-methylpropanesulfonic acid or salts thereof. This is referred to below simply as “polymer”.
  • the polymer is made by polymerizing itaconic acid, in particular more than 25 mol%, in particular 35 to 60 mol%, itaconic acid monomers with less than 75 mol%, of at least one co-monomer selected from (meth)acrylic acid, salts, esters or Anhydrides thereof or 2-acrylamido-2-methylpropanesulfonic acid or salts thereof, in particular a mixture of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid or salts thereof.
  • itaconic acid in particular more than 25 mol%, in particular 35 to 60 mol%, itaconic acid monomers with less than 75 mol%, of at least one co-monomer selected from (meth)acrylic acid, salts, esters or Anhydrides thereof or 2-acrylamido-2-methylpropanesulfonic acid or salts thereof, in particular a mixture of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid or salts thereof.
  • the polymer has a number-average molecular weight of 100 to 100,000 g/mol, in particular 500 to 50,000 g/mol.
  • the polymer may have a number average molecular weight of 100 to 500 g/mol.
  • acrylic acid is used in 30 to 65 mol%, in particular 40 to 50 mol%.
  • 2-acrylamido-2-methylpropanesulfonic acid is used in 0.1 to 20 mol%, preferably 0.5 to 10 mol%.
  • the copolymer is preferably an alternating, random or block copolymer.
  • the copolymer is a terpolymer.
  • the copolymer is etherified from 0.1 to 60%.
  • the copolymer is essentially free of citraconic acid and/or mesaconic acid monomers.
  • the polymerization is preferably carried out in the presence of a redox system, particularly preferably with a mixture of sodium persulfate, tert-butyl perpivalate or tert-butyl perbenzoate and a mixture of the sodium salt of 2-hydroxy-2-sulfinatoacetic acid and sodium sulfite.
  • the polymers can preferably be polymerized by solution polymerization in an aqueous medium. Only water or a mixture of water and organic solvents such as alcohols, especially isoporopyl, can be used.
  • the at least one nonionic surfactant A) and the at least one polymer B) are present in a ratio of 1:1 to 1:5 or 1:2 to 1:3.
  • the dishwashing detergent can have at least one further surfactant different from A).
  • nonionic surfactants known to those skilled in the art can be used as further nonionic surfactants.
  • Suitable further nonionic surfactants are, for example, alkyl glycosides of the general formula RO(G)x, in which R corresponds to a primary linear or methyl-branched, especially methyl-branched, aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms and G that Symbol that stands for a glucose unit with 5 or 6 carbon 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 of the amine oxide type for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallow alkyl-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 component A), in particular not more than half of it.
  • Suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.
  • the composition further comprises at least one anionic surfactant.
  • Suitable anionic surfactants are fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, olefin sulfonates, alkyl sulfates, alkyl sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignin sulfonates.
  • fatty acid cyanamides sulfosuccinates (sulfosuccinic acid esters), in particular sulfosuccinic acid mono- and di-alkyl esters with 8 to 18 carbon atoms, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ethers). phosphates as well as ⁇ -sulfofatty acid salts, acyl glutamates, monoglyceride disulfates and alkyl ethers of glycerine disulfate.
  • composition may further comprise at least one alkyl sulfate, preferably selected from C8-18 fatty alcohol sulfates, more preferably C12-16 fatty alcohol sulfates, in particular lauryl sulfates or myristyl sulfates, most preferred is sodium lauryl sulfate.
  • alkyl sulfate preferably selected from C8-18 fatty alcohol sulfates, more preferably C12-16 fatty alcohol sulfates, in particular lauryl sulfates or myristyl sulfates, most preferred is sodium lauryl sulfate.
  • the at least one anionic surfactant can preferably be used in an amount of 0.1 to 10% by weight, in particular 0.5 to 3% by weight, based on the total weight of the composition.
  • anionic surfactants are preferably used as sodium salts, but can also be present as other alkali or alkaline earth metal salts, for example potassium or magnesium salts, as well as in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts.
  • the composition contains only nonionic surfactants.
  • the dishwashing detergent according to the invention can also preferably contain at least one enzyme.
  • Enzymes can be present in the dishwashing detergent preferably in amounts of 0.0001 to 10% by weight, preferably from 0.01 to 5% by weight, preferably from 0.1 to 4% by weight, particularly preferably between 0.2 and 4% by weight, based on the total weight of the dishwashing detergent, can be used.
  • the dishwashing detergent according to the invention can also preferably contain at least one complexing agent.
  • Preferred complexing agents are selected from ⁇ -alaninediacetic acid, methylglycinediacetic acid (MGDA), iminodisuccinate (IDS), glutamine-N,N-diacetic acid (GLDA), citrates and gluconates or mixtures thereof, in particular methylglycinediacetic acid (MGDA).
  • MGDA methylglycinediacetic acid
  • IDS iminodisuccinate
  • GLDA glutamine-N,N-diacetic acid
  • citrates and gluconates or mixtures thereof in particular methylglycinediacetic acid (MGDA).
  • the at least one complexing agent is contained in 1.0 to 25.0% by weight, preferably in 5.0 to 20.0% by weight, based on the total weight of the composition.
  • the dishwashing detergent according to the invention can further comprise at least one additive. These can be all additives known to those skilled in the field of dishwashing detergents.
  • the dishwashing detergent can also contain builders.
  • Builders are usually substances that help ensure the cleaning performance of the dishwashing detergent by, among other things, inhibiting the formation of limescale on machine components and thus enabling the energy to be transferred efficiently to the water.
  • the proportion by weight of the builders in the total weight of the dishwashing detergent is preferably 5 to 80% by weight and in particular 10 to 60% by weight.
  • the builders include, in particular, carbonates, phosphates, citrates and silicates.
  • alkali carbonate(s) particularly preferably sodium carbonate
  • phosphate(s) is also preferred.
  • alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of greatest importance in the detergent and cleaning agent industry.
  • Alkali metal phosphate is the general name for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can differentiate between metaphosphoric acid (HPO 3 ) n and orthophosphoric acid H 3 PO 4 alongside higher molecular weight representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent lime deposits on machine parts or lime incrustations on the objects to be cleaned and also contribute to cleaning performance.
  • Particularly preferred phosphates are 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 are also preferably used.
  • phosphates are used as builders in the dishwashing detergent in the context of the present application, this contains phosphate(s), preferably alkali metal phosphate(s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 5 to 70 wt .-%, preferably from 15 to 55% by weight and in particular from 20 to 50% by weight, in each case based on the total weight of the dishwashing detergent. In an alternative embodiment, essentially no phosphates are present.
  • alkali metal phosphate(s) particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate)
  • pentasodium or pentapotassium triphosphate sodium or potassium tripolyphosphate
  • essentially no phosphates are present.
  • Polycarboxylates/polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals and dextrins are also used as preferred builders. This class of substances is also referred to as organic cobuilders and is described below.
  • a polycarboxylic acid is used as a builder, it can be used in the form of the free acid and/or its alkali metal salts, in particular sodium salts, whereby polycarboxylic acid is understood to mean a carboxylic acid that carries more than one acid function.
  • NTA nitrilotriacetic acid
  • the free acids typically also have the properties of an acidifying component and are therefore also used to adjust a lower and milder pH value of dishwashing detergents.
  • the dishwashing detergent can particularly preferably contain citrate as a builder, preferably sodium citrate.
  • the dishwashing detergent can preferably contain 2 to 40% by weight, preferably 5 to 30% by weight and in particular 7 to 15% by weight of citrate, in particular sodium citrate, based on the total weight of the dishwashing detergent.
  • the citrates are preferably used together with carbonates and/or bicarbonates.
  • Preferred dishwashing detergents therefore contain a builder combination of phosphate and carbonate/bicarbonate or of citrate and carbonate/bicarbonate or of phosphate, citrate and carbonate/bicarbonate.
  • a particularly preferred dishwashing agent is characterized in that it contains at least two builders from the group of phosphates, carbonates and citrates, the proportion by weight of these builders, based on the total weight of the dishwashing agent, preferably being 5 to 70% by weight, preferably 7 to 60 % by weight and in particular 10 to 25% by weight.
  • the combination of two or more builders from the group mentioned above has proven to be advantageous for the cleaning and rinsing performance of the dishwashing detergent.
  • Polymeric polycarboxylates are also suitable as builders. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a weight-average molecular weight of 500 to 70,000 g/mol.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a weight-average molecular weight of 2000 to 20,000 g/mol. Because of their superior solubility, the short-chain polyacrylates, which have a weight-average molecular weight of 2000 to 10,000 g/mol, and particularly preferably of 3000 to 5000 g/mol, can be preferred from this group.
  • the composition contains a cationic polymer.
  • Suitable cationic polymers are, for example, cationic cellulose derivatives, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone/vinylimidazole polymers such as. B. Luviquate ® (BASF AG, Ludwigshafen/FRG), condensation products of polyglycols and amines, quaternized collagen polypeptides such as Lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat ® L, Grünau GmbH), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers such as. B.
  • Amidomethicone or Dow Corning, Dow Corning Co./US copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetrimamine (Carta retine® , Sandoz/CH), polyaminopolyamides such as. B. described in the FR A 22 52 840 as well as their cross-linked water-soluble polymers, cationic chitin derivatives such as quaternized chitosan, optionally distributed in microcrystalline form, cationic guar gum such as. B. Jaguar ® CBS, Jaguar ® C-17, Jaguar ® C-16 from Celanese/US, quaternized ammonium salt polymers such as. B.
  • Cationic polyacrylates are particularly suitable, preferably with a weight-average molecular weight of 2000 to 20,000 g/mol; such polymers are available, for example, under the trade name Mirapol Surf S 480 PF from Miranol/US. Cationic polyacrylates are preferably contained in 0.1 to 5% by weight, or 0.25 to 4% by weight or 0.5 to 1% by weight.
  • the content of (homo)polymeric polycarboxylates in the dishwashing detergent is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.
  • the dishwashing detergent can use crystalline layered silicates of the general formula as a builder NaMSi x O 2x+1 ⁇ y H 2 O contain, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferably 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20, stands.
  • Amorphous sodium silicates with a modulus NazO:SiOz of 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 are preferably delayed in dissolution, can also be used and have secondary washing properties.
  • the content of silicates is limited to amounts of 0 to 10% by weight, preferably from 0 to 5% by weight and in particular from 0 to 2% by weight.
  • a particularly preferred dishwashing detergent is free of silicates.
  • the dishwashing detergent can contain alkaline agents, preferably alkali metal hydroxides, in particular sodium hydroxide. These alkaline agents are preferably used in the dishwashing detergent in amounts of 0 to 10% by weight, preferably 0 to 5% by weight, particularly preferably between 0.1 and 5% by weight and in particular between 0.5 and 5% by weight .-%, based on the total weight of the dishwashing detergent, used.
  • An alternatively preferred dishwashing detergent is free of alkali metal hydroxides.
  • the dishwashing detergent contains at least one thickener.
  • This is preferably selected from polyacrylate thickeners, xanthan, gellan, guar, alginate, carrageenan, carboxymethylcellulose, bentonites, welan gum, locust bean gum, agar-agar, tragacanth, gum arabic, pectins, polysaccharides, starch, modified starch, dextrins, gelatins and casein , modified celluloses, hydroxyethyl ether and hydroxypropyl ether, more preferably selected from xanthan, gellan, guar, alginate, carrageenan, carboxymethylcellulose, locust bean gum, agar-agar, tragacanth, gum arabic, pectins, starch, modified starch, dextrins, gelatins and casein, and modified Celluloses, most preferably xanthan gum.
  • the at least one thickener is preferably contained in 0.1 to 10% by weight or 0.25 to 5% by weight or 0.3 to 1% by weight.
  • composition can contain perfume oils and/or fragrances.
  • perfume oils for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
  • mixtures of different fragrances are preferably used, which together produce an appealing scent.
  • perfume oils can also contain natural fragrance mixtures such as those available from plant sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • the composition is essentially phosphate-free.
  • the composition is bleach-free.
  • “in the "Substantially phosphate-free”, as used herein, means that the composition in question is essentially free of phosphates, ie in particular phosphates in amounts of less than 0.1% by weight, preferably less than 0.01% by weight, based on the entire composition contains.
  • "Essentially bleach-free” means, analogously, that the composition in question is essentially free of bleaching agents, ie bleaching agent in particular in amounts of less than 0.1% by weight, preferably less than 0.01% by weight on the overall composition.
  • composition may contain corrosion inhibitors.
  • (Glass) corrosion inhibitors prevent the appearance of clouding, streaks and scratches as well as iridescence on the glass surface of machine-cleaned glasses.
  • Preferred glass corrosion inhibitors come from the group of magnesium and/or zinc salts and/or magnesium and/or zinc complexes.
  • the composition can preferably also contain dyes.
  • Dyes are known to those skilled in the art and all common dyes can be used as long as they do not have a negative interaction with the other components of the composition.
  • compositions can be in solid or liquid form.
  • the pH of the liquid compositions described herein can be adjusted using conventional pH regulators.
  • the pH of the composition is in a range from 9.0 to 13.0, preferably 10.0 to 12, in particular 10 to 11.5. Unless otherwise stated, the pH value is preferably measured at 25° C. in the undiluted composition, usually using a pH electrode. Acids and/or bases/alkalis are preferably used as pH adjusters.
  • Suitable acids are in particular organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid, most preferred is citric acid.
  • organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid, most preferred is citric acid.
  • the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof can also be used.
  • Suitable bases come from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular the alkali metal carbonates, of which sodium carbonate is preferred.
  • the composition is in pre-portioned form and/or in particular in liquid form.
  • Liquid means that the composition is in liquid form and in particular flowable at room temperature, i.e. around 20 ° C, and can therefore be poured out of a container, for example.
  • the term as used herein also includes gels.
  • composition according to the invention can be added to 100% by weight with water and/or at least one organic solvent.
  • the liquid forms based on water and/or at least one organic solvent can be thickened, in the form of gels or pasty forms, i.e. non-solid compositions.
  • the composition described herein is in liquid form, for example gel form, and is not pre-portioned. This allows the composition to be applied to the dirty parts and the composition to act.
  • compositions described herein can preferably be prepackaged into dosage units. These dosing units preferably include the amount of cleaning-active substances necessary for a cleaning cycle.
  • the invention relates to a composition which can be present in a water-insoluble, water-soluble or water-dispersible packaging, for example a film containing a single-use portion.
  • the cleaning agent can be formulated in such a way that single-use portions are each packaged separately.
  • the water-soluble covering is preferably formed from a water-soluble film material which is selected from the group consisting of polymers or polymer mixtures.
  • the wrapping may be formed from one or two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and the additional layers, if present, can be the same or different. Films that can be glued and/or sealed to form packaging such as tubes or pillows after they have been filled with an agent are particularly preferred.
  • the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
  • Water-soluble coatings that contain polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with a sufficiently high water solubility, in particular cold water solubility.
  • Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer, the weight-average molecular weight of which is in the range from 10,000 to 1,000,000 g/mol, preferably from 20,000 to 500,000 g/mol, particularly preferably from 30,000 to 100,000 g/mol and in particular from 40,000 to 80,000 g/mol.
  • Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, as the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers, which are produced from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, in particular 81 to 89 mol% and most preferably 82 to 88 mol%.
  • a polyvinyl alcohol-containing film material suitable for producing the water-soluble coating can additionally contain a polymer selected from the group comprising (meth)acrylic acid-containing (co)polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above Polymers may be added.
  • a preferred additional polymer is polylactic acids.
  • preferred polyvinyl alcohol copolymers include dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
  • polyvinyl alcohol copolymers include an ethylenically unsaturated carboxylic acid, its salt or its ester.
  • such polyvinyl alcohol copolymers particularly preferably contain acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.
  • the film material contains further additives.
  • the film material can, for example, contain plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerin, sorbitol, mannitol or mixtures thereof.
  • Other additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, anti-blocking agents, anti-adhesive agents or mixtures thereof.
  • Suitable water-soluble films for use in the water-soluble wrappings of the water-soluble packaging according to the invention are films sold by MonoSol LLC, for example under the names M8630, C8400 or M8900.
  • Other suitable films include films called Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the VF-HP films from Kuraray.
  • composition and/or the film can preferably contain bitter substances.
  • bitter substances are known to those skilled in the art and all common bitter substances can be used. Denatonium benzoate is particularly preferred.
  • the dishwashing detergent is preferably metered or introduced into the interior of a dishwasher while running through a dishwashing program, before the start of the main wash cycle or during the course of the main wash cycle.
  • the dishwashing detergent can be metered in or introduced into the interior of the dishwasher manually, but the dishwashing detergent is preferably dosed into the interior of the dishwasher using the dosing chamber of the dishwasher.
  • no additional water softener and no additional rinse aid are preferably dosed into the interior of the dishwasher.
  • a preferred embodiment is a mechanical dishwashing process using the preferably liquid dishwashing agent, in particular in the form of a previously mentioned shaped body, in particular for improved final rinsing performance for plastic or stainless steel items to be washed.
  • the dishwashing process is preferably carried out at a liquor temperature below 60 ° C, preferably not above 50 ° C, preferably at 35 to 45 ° C.
  • the dishwashing process takes 5 to 90 minutes, in particular 10 to 75 minutes, particularly preferably 20 to 60 minutes.
  • the dishwashing process takes a maximum of 50, 40 or 30 minutes.
  • the dishwashing detergent according to the invention is characterized by improved rinse performance compared to conventional dishwashing detergents.
  • a further subject of the present application is therefore the use of the dishwashing detergent according to the invention to improve the rinse performance of plastic or stainless steel items in automatic dishwashing.
  • the final rinse tests were carried out in a Miele GSL with the program R50°C/8min/KI65°C 2 at a water hardness of 21°dH in the presence of ballast dirt (fat, egg, starch). 28.5g of test product was used per rinse cycle.
  • compositions according to the invention with compositions which only had one of the two components A) and B) or another nonionic surfactant.
  • the following composition was used as a framework recipe: Framework recipe wt% Xanthan gum 0.4 Sodium citrate 9.5 Trilon M Max 18.5 citric acid 1.2 Cationic acrylate copolymer (Mirapol Surf S 480 PF) 0.67 Protease (% by weight of active enzyme) 0.3 Amylase (% by weight of active enzyme) 0.1 Perfume 0.2 Water Ad 100

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  • 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 (12)

  1. Détergent pour vaisselle, en ce qu'il contient ou est constitué par
    A) au moins un tensioactif non ionique choisi parmi les alcoxylates d'alcool gras ;
    B) au moins un polymère, en ce qu'il est obtenu par polymérisation d'acide itaconique avec au moins un comonomère choisi parmi l'acide (méth)acrylique, ses sels, ses esters ou ses anhydrides, ou l'acide 2-acrylamido-2-méthylpropanesulfonique ou ses sels ;
    C) éventuellement au moins un tensioactif différent de A) ;
    D) éventuellement au moins une enzyme ;
    E) éventuellement au moins un agent complexant ; et
    F) éventuellement au moins un additif,
    caractérisé en ce que l'au moins un alcoxylate d'alcool gras est choisi parmi au moins un composé de formule générale R1O(AlkO)xM(OAlk)yOR2, où
    - R1 et R2 représentent, indépendamment l'un de l'autre, un radical alkyle ramifié ou non ramifié, saturé ou insaturé, éventuellement hydroxylé, comportant 4 à 22 atomes de carbone,
    - Alk représente un radical alkylène ramifié comportant 3 ou 4 atomes de carbone ou un radical alkylène non ramifié comportant 2 à 4 atomes de carbone,
    - x et y représentent, indépendamment l'un de l'autre, des valeurs comprises entre 1 et 70 et
    - M représente un radical alkylène du groupe composé de CH2, CHR3, CR3R4, CH2CHR3 et CHR3CHR4, où R3 et R4 représentent, indépendamment l'un de l'autre, un radical alkyle ou alkylène ramifié ou non ramifié, saturé ou insaturé, cyclique ou acyclique, comportant jusqu'à 18 atomes de carbone.
  2. Détergent pour vaisselle selon la revendication 1, dans lequel l'au moins un alcoxylate d'alcool gras est choisi parmi
    i) au moins un composé de formule générale

            R1O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(CH3)O]zCH2CH(OH)R2,

    dans laquelle
    - R1 représente un radical hydrocarboné aliphatique linéaire ou ramifié comportant 4 à 22 atomes de carbone,
    - R2 représente un radical hydrocarboné linéaire ou ramifié comportant 2 ou 3 à 26 atomes de carbone,
    - x et z des valeurs comprises entre 0 et 40 et
    - y représente une valeur d'au moins 15 ; et/ou
    ii) au moins un composé de formule générale

            R1O[CH2CH(R3)O]x[CH2CHO]y[CH2CH(R4)O]zC(O)R2,

    où
    - R1 représente un radical alkyle ramifié ou non ramifié comportant 8 à 16 atomes de carbone,
    - R3 et R4 représentent, indépendamment l'un de l'autre, l'hydrogène ou un radical alkyle ramifié ou non ramifié comportant 1 à 5 atomes de carbone,
    - R2 représente un radical alkyle non ramifié comportant 5 à 17 atomes de carbone,
    - x et z représentent, indépendamment l'un de l'autre, une valeur allant de 1 à 5 et
    - y représente une valeur allant de 13 à 35 ; ou
    iii) au moins un composé de formule générale

            R1-CH(OH)CH2-O(CH2CH2O)xCH2CHR(OCH2CH2)yO-CH2CH(OH)-R2,

    dans laquelle
    - R1 et R2, indépendamment l'un de l'autre, un radical alkyle ou un radical alkylène comportant 6 à 16 atomes de carbone et
    - R représente un radical alkyle linéaire saturé comportant 2 à 12 atomes de carbone, de préférence 4 à 10 atomes de carbone, et
    - x et y présentent, indépendamment l'un de l'autre, des valeurs allant de 5 à 20 ; et/ou
    iv) au moins un composé de formule générale

            R1O[CH2CH2O]yCH2CH(OH)R2,

    dans laquelle
    - R1 représente un radical hydrocarboné aliphatique linéaire ou ramifié comportant 4 à 22 atomes de carbone,
    - R2 désigne un radical hydrocarboné linéaire ou ramifié comportant 2 ou 3 à 26 atomes de carbone et
    - y représente une valeur comprise entre 15 et 120, de préférence 20 à 100 et en particulier 20 à 80 ; et/ou
    v) au moins un composé choisi dans le groupe des hydroxyéthers mixtes de formule générale C4-22-CH(OH)CH2O-(OE)20-120-C2-26, en particulier les éthers d'alcool gras en C8-12-(OE)22-2-hydroxydécyliques et les éthers d'alcool gras en C4-22-(OE)40-80-2-hydroxyalkyliques ; et/ou
    vi) au moins un composé de formule générale

            R1O[CH2CH(R3)O]x[CH2CHO]y[CH2CH(R4)O]zC(O)R2,

    où
    - R1 représente un radical alkyle ramifié ou non ramifié comportant 10 à 15 atomes de carbone,
    - R3 et R4 représentent, indépendamment l'un de l'autre, l'hydrogène ou un radical alkyle ramifié ou non ramifié comportant 2 ou 3 atomes de carbone,
    - R2 représente un radical alkyle non ramifié comportant 8 à 16 atomes de carbone,
    - x et z représentent, indépendamment l'un de l'autre, une valeur allant de 1 à 5 et
    - y représente une valeur allant de 20 à 30.
  3. Détergent pour vaisselle selon l'une des revendications 1 ou 2, dans lequel
    en ce qu'au moins un tensioactif non ionique A) est présent en 0,2 à 10 % en poids ou 0,5 à 9 % en poids.
  4. Détergent pour vaisselle selon l'une des revendications précédentes, dans lequel l'au moins un polymère B)
    i) est obtenu par polymérisation d'acide itaconique, en particulier de plus de 25 % en moles, en particulier de 35 à 60 % en moles, de monomères d'acide itaconique comportant moins de 75 % en moles, d'au moins un comonomère choisi parmi l'acide (méth)acrylique, ses sels, ses esters ou ses anhydrides ou l'acide 2-acrylamido-2-méthylpropanesulfonique ou ses sels, en particulier les comonomères sont l'acide acrylique et l'acide 2-acrylamido-2-méthylpropanesulfonique ou leurs sels ; et/ou
    ii) présente une masse moléculaire moyenne en nombre de 100 à 100 000 g/mol, en particulier de 500 à 50 000 g/mol ; et/ou
    iii) est basé sur 30 à 65 % en moles, en particulier 40 à 50 % en moles, de monomères d'acide acrylique ; et/ou
    iv) est basé sur 0,1 à 20 % en moles, de préférence 0,5 à 10 % en moles, de monomères d'acide 2-acrylamido-2-méthylpropanesulfonique ; et/ou
    v) est un copolymère alterné, un copolymère statistique ou un copolymère séquencé, de préférence un terpolymère ; et/ou
    vi) est éthérifié de 0,1 à 60 %.
  5. Détergent pour vaisselle selon l'une des revendications précédentes, dans lequel
    en ce qu'au moins un tensioactif non ionique A) et l'au moins un polymère B) sont présents dans un rapport de 1:1 à 1:5 ou de 1:2 à 1:3.
  6. Détergent pour vaisselle selon l'une des revendications précédentes, dans lequel
    en ce qu'au moins un tensioactif différent de A) est un tensioactif anionique.
  7. Détergent pour vaisselle selon l'une des revendications précédentes, dans lequel
    en ce qu'au moins une enzyme comprend une amylase et/ou une protéase.
  8. Détergent pour vaisselle selon l'une des revendications précédentes, dans lequel
    en ce que le détergent pour vaisselle est un détergent liquide, en particulier sous forme de gel.
  9. Détergent pour vaisselle selon l'une des revendications précédentes, dans lequel
    en ce qu'au moins un additif comprend un épaississant, de préférence choisi parmi les épaississants polyacrylates, gomme xanthane, gomme gellane, gomme guar, alginate, carraghénane, carboxyméthylcellulose, bentonites, gomme Welan, farine de caroube, agar-agar, gomme adragante, gomme arabique, pectines, polysaccharides, amidon, amidon modifié, dextrines, gélatines et caséine, celluloses modifiées, hydroxyéthyléther et hydroxypropyléther, plus préférablement choisi parmi la gomme xanthane, gomme gellane, gomme guar, alginate, carraghénane, carboxyméthylcellulose, farine de caroube, agar-agar, gomme adragante, gomme arabique, pectines, amidon, amidon modifié, dextrines, gélatines et caséine, et celluloses modifiées, le plus préférablement est la gomme xanthane.
  10. Procédé permettant le nettoyage de vaisselle dans un lave-vaisselle, à l'aide d'un détergent pour vaisselle selon l'une des revendications 1 à 9.
  11. Procédé selon la revendication 10, caractérisé en ce que le procédé de lavage de la vaisselle est effectué à une température de bain inférieure à 60 °C, de préférence non supérieure à 50 °C.
  12. Utilisation d'un détergent pour vaisselle selon l'une des revendications 1 à 9 pour l'amélioration de la performance de rinçage en cas d'articles en matière plastique ou en acier inoxydable lors du lavage de la vaisselle en machine.
EP19214081.2A 2018-12-28 2019-12-06 Détergent pour lave-vaisselle à performance de rinçage améliorée Active EP3674386B1 (fr)

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EP4269548A1 (fr) 2022-04-27 2023-11-01 Dalli-Werke GmbH & Co. KG Composition détergente avec agents anti-tartre

Citations (5)

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Publication number Priority date Publication date Assignee Title
US20090258810A1 (en) 2008-04-01 2009-10-15 Brian Xiaoqing Song Gel automatic dishwashing detergent composition
WO2012123719A1 (fr) 2011-03-14 2012-09-20 Reckitt Benckiser N.V. Composition de détergent présentant une performance de séchage améliorée
US20150275137A1 (en) 2012-12-17 2015-10-01 Henkel Ag & Co. Kgaa Surfactant combination for improved drying
WO2018035131A1 (fr) 2016-08-16 2018-02-22 Diversey, Inc. Composition pour l'amélioration esthétique de récipients pour aliments et boissons, et procédés associés
US20180291312A1 (en) 2017-04-11 2018-10-11 Itaconix Corporation Sulfonated Copolymers For Detergent Composition

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LU68901A1 (fr) 1973-11-30 1975-08-20
DE102007042860A1 (de) * 2007-09-10 2009-03-12 Henkel Ag & Co. Kgaa Reinigungsmittel
CN110105480A (zh) * 2013-03-15 2019-08-09 路博润先进材料公司 衣康酸聚合物
JP7071039B2 (ja) * 2014-03-14 2022-05-18 ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド イタコン酸ポリマーおよびコポリマー
DE102016205344A1 (de) * 2016-03-31 2017-10-05 Henkel Ag & Co. Kgaa Geschirrspülmittel mit verbesserter Klarspülleistung
CN109477040B (zh) * 2016-06-16 2021-06-22 陶氏环球技术有限责任公司 具有防斑表面活性剂的自动餐具洗涤组合物
EP3418366A1 (fr) * 2017-06-19 2018-12-26 The Procter & Gamble Company Composition de nettoyage pour lave-vaisselle automatique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090258810A1 (en) 2008-04-01 2009-10-15 Brian Xiaoqing Song Gel automatic dishwashing detergent composition
WO2012123719A1 (fr) 2011-03-14 2012-09-20 Reckitt Benckiser N.V. Composition de détergent présentant une performance de séchage améliorée
US20150275137A1 (en) 2012-12-17 2015-10-01 Henkel Ag & Co. Kgaa Surfactant combination for improved drying
WO2018035131A1 (fr) 2016-08-16 2018-02-22 Diversey, Inc. Composition pour l'amélioration esthétique de récipients pour aliments et boissons, et procédés associés
US20180291312A1 (en) 2017-04-11 2018-10-11 Itaconix Corporation Sulfonated Copolymers For Detergent Composition

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ES2973653T3 (es) 2024-06-21
PL3674386T3 (pl) 2024-05-20

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