EP3622049B1 - Composition de détergent de lave-vaisselle automatique sans phosphate - Google Patents

Composition de détergent de lave-vaisselle automatique sans phosphate Download PDF

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Publication number
EP3622049B1
EP3622049B1 EP18723012.3A EP18723012A EP3622049B1 EP 3622049 B1 EP3622049 B1 EP 3622049B1 EP 18723012 A EP18723012 A EP 18723012A EP 3622049 B1 EP3622049 B1 EP 3622049B1
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EP
European Patent Office
Prior art keywords
builder
detergent composition
acid
citrate
carbonate
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EP18723012.3A
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German (de)
English (en)
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EP3622049C0 (fr
EP3622049A1 (fr
Inventor
Bart Riekus POSTMUS
Jan Hendrik Verkade
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Unilever Global IP Ltd
Unilever IP Holdings BV
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Unilever Global IP Ltd
Unilever IP Holdings BV
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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
    • C11D1/721—End blocked ethers
    • 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
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/3788—Graft polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds

Definitions

  • the present invention relates to a phosphate-free automatic dishwashing detergent composition containing builder, bleach component, a graft copolymer having a polysaccharide backbone and one or more side chains of one or more synthetic monomeric units, nonionic surfactant and optionally one or more other detergent ingredients.
  • the builder component of the detergent composition is composed of:
  • the automatic dishwashing (ADW) detergent composition of the present invention combines a very good cleaning action with minimal spotting and film-forming.
  • the composition is less damaging for glassware compared with current high performing ADW detergents.
  • ADW detergents constitute a distinct class of detergent compositions. Unlike most other detergents, ADW detergents have to be low-foaming. In addition, a spotless and film-free appearance of glasses and silverware is the expected final result of each automatic dishwashing run.
  • ADW detergents are mixtures of ingredients whose purpose, in combination, is to break down and remove food soils; to inhibit foaming caused by certain food soils; and to remove stains which can be caused by beverages such as coffee and tea or by vegetable soils such as carotenoid soils.
  • Spotting and filming of glassware are the chief criteria by which the performance of a dishwashing formulation is judged.
  • Spotting is an obvious reference to discrete residues on glassware which are formed when water droplets evaporate and leave behind dissolved solids.
  • Filming refers to a more uniform deposition over a large, continuous portion of the glass surface. This film can sometimes be of organic origin (resulting from soil in the wash liquor or organic components in the detergent) but is also often inorganic in nature, due to the formation and deposition of some mineral precipitate.
  • ADW detergents may comprise a variety of detergent ingredients, including alkalinity sources, builders, bleaching systems, anti-scalants, corrosion inhibitors, surfactants, antifoams, sheeting polymers and/or enzymes.
  • Builder materials are used to provide alkalinity and buffering capacity, maintain ionic strength, extract metals from soils and/or remove alkaline earth metal ions from washing solutions.
  • builder materials include phosphates, alkali metal citrates, carbonates and bicarbonates; and the salts of nitrilotriacetic acid (NTA); methylglycine diacetic acid (MGDA); glutaric diacetic acid (GLDA), polycarboxylates such as polymaleates, polyacetates, polyhydroxyacrylates, polyacrylate/polymaleate and polyacrylate/polymethacrylate copolymers, as well as zeolites; layered silicas and mixtures thereof.
  • NTA nitrilotriacetic acid
  • MGDA methylglycine diacetic acid
  • GLDA glutaric diacetic acid
  • polycarboxylates such as polymaleates, polyacetates, polyhydroxyacrylates, polyacrylate/polymaleate and polyacrylate/polymethacrylate copolymers, as well as zeolites; layered silicas and mixtures thereof.
  • Sodium tripolyphosphate is among the best of a variety of builder salts.
  • phosphate contents of detergent compositions have been limited by law and regulations in order to minimize eutrophication of inland waters.
  • US 2011/0240063 describes a phosphate- and bleaching agent-free automatic dishwashing agent containing:
  • hybrid copolymer comprising: a synthetic polymer derived from at least one anionic ethylenically unsaturated monomer and a naturally derived hydroxyl containing chain transfer agent as an end group, wherein the chain transfer agent is present from about 75% by weight to about 99% by weight, based on the total weight of the hybrid copolymer.
  • Examples 24 and 28 describe automatic zero phosphate dishwash formulations containing the copolymer, builder and bleach.
  • WO 2011/014783 describes a scale inhibiting composition for aqueous systems, comprising an anionic hybrid copolymer composition wherein said copolymer comprises:
  • Example 1 describes detergent compositions containing a combination of protease and hybrid polymer.
  • Example 1 describes an automatic dishwashing detergent tablet that is composed of three different phases.
  • the tablet contains builder (sodium citrate.2H 2 O; anhydrous sodium citrate; citric acid; and Na 2 CO 3 ), hybrid polymer, bleach and nonionic surfactant.
  • the inventors have developed a phosphate-free ADW detergent composition that combines a very good cleaning action with minimal spotting, film-forming and glassware corrosion.
  • the phosphate-free ADW detergent composition of the present invention consists of:
  • the phosphate-free ADW detergent composition of the present invention produces very good cleaning results for earthenware, glassware, metal as well as plastic.
  • the inventors have discovered that the combination of builder component that largely consists of hydroxycarboxylate builder and precipitating builder, nonionic surfactant and graft copolymer very effectively minimizes spotting and film-forming. This is quite surprising as the detergent composition contains a substantial amount of precipitating builder which traditionally is believed to give rise to filming problems.
  • the ADW detergent composition offers the further advantage that it is less prone to give rise to glassware corrosion.
  • a first aspect of the present invention relates to a phosphate-free ADW detergent composition consisting of:
  • phosphate-free ADW detergent composition refers to an ADW detergent composition that contains less than 0.1 wt.% phosphate.
  • phosphate refers to monophosphate salts, diphosphate salts, triphosphate salts and combinations thereof.
  • phosphate does not include phosphonates.
  • builder refers to a material that is capable of removing calcium ion from aqueous solution by ion exchange, complexation, sequestration and/or precipitation.
  • builder materials include alkali metal citrates, carbonates and bicarbonates; aminopolycarboxylates, polycarboxylates such as polymaleates, polyacetates, polyhydroxyacrylates, polyacrylate/polymaleate and polyacrylate/polymethacrylate copolymers, as well as zeolites; layered silicas and mixtures thereof.
  • surfactant refers to components within the classification described in " Surfactant Science Series", Vol.82, (1999) Handbook of detergents, part A: Properties, chapter 2 (Surfactants, classification), G. Broze (ed .).
  • bleach component refers to substances that are capable of removing coloured stains by oxidizing or reducing the colour components of the stain.
  • oxidizing bleach components include peroxides, such as hydrogen peroxide, sodium percarbonate and sodium perborate.
  • reducing bleach components include sodium dithionite, sodium borohydride and sodium sulfite.
  • the detergent composition may suitably contain bleach activators and/or bleach catalysts.
  • percarbonate refers to an adduct of alkalimetal carbonate and hydrogen peroxide (a perhydrate), such as sodium percarbonate (2Na 2 CO 3 ⁇ 3H 2 O 2 ).
  • carbonate refers to carbonic acid (H 2 CO 3 ) and salts thereof.
  • carbonate as used herein does not encompass percarbonates.
  • citrate refers to citric acid and salts thereof.
  • tartrate gluconate, “silicate”, etc. are to be construed accordingly.
  • polysaccharide refers to a polymeric carbohydrate molecule composed of a chain of at least 5 monosaccharide units bound together by glycosidic linkages.
  • one or more other detergent ingredients refers to detergent ingredients other than builder; bleach component; graft copolymer having a polysaccharide backbone and one or more side chains of one or more synthetic monomeric units; and nonionic surfactant.
  • one or more other builders refers to builders other than citrate, tartrate, gluconate, carbonate and silicate.
  • the phosphate-free ADW detergent composition of the present invention preferably contains less than 0.05 wt.% phosphate, more preferably less than 0.02 wt.% phosphate and most preferably less than 0.01 wt.% phosphate.
  • the phosphate content of the ADW detergent composition preferably is less 0.3% by weight of the builder.
  • concentration of a salt or an acid refers to the equivalent concentration of the salt or acid in anhydrous form.
  • the ADW detergent composition of the present invention preferably is a particulate composition or a solid article, e.g. a tablet.
  • the combination of the builder, the bleach component, the graft copolymer and the nonionic surfactant typically represents at least 40%, more preferably at least 50% and most preferably at least 60% by weight of the detergent composition.
  • the detergent composition of the present invention preferably contains the graft copolymer and the builder in a weight ratio of at least 1:50, more preferably of 1:40 to 1:8 and most preferably of 1:30 to 1:10.
  • Graft copolymer and the hydroxycarboxylate builder are preferably present in the detergent composition in a weight ratio of graft copolymer to the hydroxycarboxylate builder of at least 1:60, more preferably of at least 1:50 and most preferably of 1:40 to 1:5.
  • Graft copolymer and citrate are preferably present in the detergent composition in a weight ratio of graft copolymer to citrate of at least 1:70, more preferably of at least 1:50 and most preferably of 1:40 to 1:5.
  • the graft copolymer and the nonionic surfactant are typically present in the detergent composition in a weight ratio of 1:4 to 3:1, more preferably of 1:3 to 5:2 and most preferably of 1:2.2 to 2:1.
  • the ADW detergent composition of the present invention consists of, calculated by weight of dry matter:
  • the detergent composition typically contains at least 30 wt.% of builder, more preferably 35-70 wt.% of builder and most preferably 40-65 wt.% of builder.
  • the builder contained in the detergent composition preferably comprises 25-65%, more preferably 30-60 wt.% of the hydroxycarboxylate sequestering builder by weight of the builder.
  • the builder preferably comprises 30-75%, more preferably 40-70 wt.% of precipitating builder by weight of the builder.
  • the detergent composition contains not more than 70% citrate by weight of the builder. More preferably, the detergent composition contains 25-65%, most preferably 30-60% of citrate by weight of the builder. As explained before, these concentrations refer to the equivalent concentration of the citrate in anhydrous form.
  • the citrate is alkali metal citrate, most preferably sodium citrate.
  • citrate and carbonate together constitute at least 60 wt.%, more preferably at least 70 wt.% and most preferably at least 80 wt.% of the builder.
  • citrate and the carbonate together constitute at least 30 wt.%, more preferably 35-75 wt.% and most preferably 40-70 wt.% of the detergent composition.
  • citrate and carbonate are present in the detergent composition in a molar ratio of citrate : carbonate of 0.15 to 0.9, more preferably of 0.2-0.8 and most preferably of 0.25 to 0.6.
  • the detergent composition contains not more than 80% carbonate by weight of the builder. More preferably, the detergent composition contains 30-75%, most preferably 40-70% of carbonate by weight of the builder. As explained before, these concentrations refer to the equivalent concentration of the carbonate in anhydrous form.
  • the carbonate is alkali metal carbonate, most preferably sodium carbonate.
  • the silicate content of the builder component of the detergent composition preferably is 0-20% by weight of the builder. More preferably, the detergent composition contains 1-10% silicate, most preferably 1.5-6% silicate by weight of the builder. As explained before, these concentrations refer to the equivalent concentration of the silicate in anhydrous form.
  • the silicate is an alkali metal silicate, most preferably sodium silicate. Examples of silicates that may be applied include disilicate, metasilicate and crystalline phyllosilicates and mixtures thereof. Most preferably, the silicate is selected from disilicate, metasilicate and combinations thereof.
  • the builder preferably comprises less than 15%, more preferably less than 10% of the one or more other builders, calculated by weight of the builder.
  • the detergent composition contains less than 3 wt.%, more preferably less than 2 wt.% and most preferably less than 1 wt.% of aminopolycarboxylate chelant.
  • aminocarboxylate chelant examples include MGDA (methyl-glycine-diacetic acid), GLDA (glutamic,N,N-diacetic acid), iminodisuccinic acid (IDS), aspartic acid-N-monoacetic acid (ASMA), aspartic acid-N,N-diacetic acid (ASDA), aspartic acid-N- monopropionic acid (ASMP) , iminodisuccinic acid (IDA), N-(2-sulfomethyl) aspartic acid (SMAS), N-(2-sulfoethyl) aspartic acid (SEAS), N-(2-sulfomethyl) glutamic acid (SMGL), N-(2- sulfoethyl) glutamic acid (SEGL), iminodiacetic acid and salts and derivatives thereof.
  • MGDA methyl-glycine-diacetic acid
  • GLDA glutamic,N,N-diacetic acid
  • IDS im
  • the detergent composition of the present invention preferably contains 7-22 wt.%, more preferably 8-20 wt.% and most preferably 9-18 wt.% of bleach component.
  • the bleach component employed in the present detergent composition preferably is an oxidizing bleach component.
  • the oxidizing bleach component may suitably comprise a chlorine-, or bromine-releasing agent or a peroxygen compound.
  • the bleach component is selected from peroxides (including peroxide salts such as sodium percarbonate), organic peracids, salts of organic peracids and combinations thereof. More preferably, the bleach component is a peroxide. Examples of peroxides are acids and corresponding salts of monopersulphate, perborate monohydrate, perborate tetrahydrate, and percarbonate. Most preferably, the bleach component is a percarbonate, notably sodium percarbonate.
  • Organic peracids useful herein include alkyl peroxy acids and aryl peroxyacids such as peroxybenzoic acid and ring substituted peroxybenzoic acids (e.g. peroxy-alpha-naphthoic acid), aliphatic and substituted aliphatic monoperoxy acids (e.g. peroxylauric acid and peroxystearic acid), and phthaloyl amido peroxy caproic acid (PAP).
  • alkyl peroxy acids and aryl peroxyacids such as peroxybenzoic acid and ring substituted peroxybenzoic acids (e.g. peroxy-alpha-naphthoic acid), aliphatic and substituted aliphatic monoperoxy acids (e.g. peroxylauric acid and peroxystearic acid), and phthaloyl amido peroxy caproic acid (PAP).
  • peroxybenzoic acid and ring substituted peroxybenzoic acids e.g. peroxy-alpha-n
  • Typical diperoxy acids useful herein include alkyl diperoxy acids and aryldiperoxy acids, such as 1,12 di-peroxy-dodecanedioic acid (DPDA), 1,9 diperoxyazelaic acid, diperoxybrassylic acid, diperoxysebacic acid and diperoxy-isophthalic acid, and 2 decyldiperoxybutane 1,4 dioic acid.
  • DPDA 1,12 di-peroxy-dodecanedioic acid
  • 1,9 diperoxyazelaic acid diperoxybrassylic acid
  • diperoxysebacic acid and diperoxy-isophthalic acid diperoxy-isophthalic acid
  • 2 decyldiperoxybutane 1,4 dioic acid 2,4 di-diperoxybutane 1,4 dioic acid.
  • the detergent composition may contain one or more bleach activators such as peroxyacid bleach precursors.
  • Peroxyacid bleach precursors are well known in the art. As non-limiting examples can be named N,N,N',N'-tetraacetyl ethylene diamine (TAED), sodium nonanoyloxybenzene sulphonate (SNOBS), sodium benzoyloxybenzene sulphonate (SBOBS) and the cationic peroxyacid precursor (SPCC) as described in US-A-4,751,015 .
  • a bleach catalyst such as a manganese complex, e.g. Mn-Me TACN, as described in EP-A-0458397 , or the sulphonimines of US-A-5,041,232 and US-A-5,047,163 , can be incorporated.
  • This bleach catalyst may suitably be present in the composition in the form of a encapsulate, notably an encapsulate that is separate from the bleach particles (to avoid premature bleach activation).
  • Cobalt or iron catalysts can also be used.
  • the graft copolymer employed in accordance with the present invention has a polysaccharide backbone and one or more side chains of one or more synthetic monomeric units.
  • the graft copolymer contains one or more side chains of two or more, even more preferably of three or more synthetic monomeric units.
  • the graft copolymer employed in the detergent composition typically has a molecular weight of at least 4,000 g/mol, more preferably of at least 8,000 g/mol and most preferably at least 15,000 g/mol.
  • the one or more synthetic monomeric units are preferably selected from olefinically unsaturated carboxylate monomers; sulfonate monomers; phosphonate monomers and combinations thereof. More preferably, the one or more synthetic monomeric units are selected from olefinically unsaturated carboxylate monomers; sulfonate monomers and combinations thereof. Most preferably, the synthetic monomeric units are olefinically unsaturated carboxylate monomers.
  • the olefinically unsaturated carboxyate monomers include, for example, aliphatic, branched or cyclic, mono- or dicarboxylic acids, the alkali or alkaline earth metal or ammonium salts thereof, and the anhydrides thereof.
  • Examples of such olefinically unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloro-acrylic acid, ⁇ -cyano acrylic acid, ⁇ -methyl-acrylic acid (crotonic acid), ⁇ -phenyl acrylic acid, ⁇ -acryloxy propionic acid, sorbic acid, ⁇ -chloro sorbic acid, angelic acid, cinnamic acid, p-chloro cinnamic acid, ⁇ -styryl acrylic acid (1-carboxy-4-phenyl butadiene-1 ,3), itaconic acid, maleic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, tricarboxy ethylene, and 2-acryloxypropionic acid.
  • Moieties such as maleic anhydride or acrylamide that can be derivatized to an acid containing group can also be used.
  • combinations of olefinically unsaturated carboxylic acid monomers may be used.
  • the olefinically unsaturated carboxylic acid monomer is selected from acrylic acid, maleic acid, itaconic acid, or methacrylic acid and combinations thereof.
  • sulfonate monomers examples include 2-acrylamido-2-methylpropane sulfonic acid (AMPS), as well as styrene sulfonic acid, (meth-)acrylic acidsulfoalkyl esters, itaconic acidsulfoalkyl esters, preferably in each case as C 1 -C 6 -alkyl esters, vinyl sulfonic acid and the alkali, alkaline earth and/or ammonium salts thereof.
  • AMPS 2-acrylamido-2-methylpropane sulfonic acid
  • styrene sulfonic acid examples include 2-acrylamido-2-methylpropane sulfonic acid (AMPS), as well as styrene sulfonic acid, (meth-)acrylic acidsulfoalkyl esters, itaconic acidsulfoalkyl esters, preferably in each case as C 1 -C 6 -alkyl esters, vinyl s
  • AMPS 2-acrylamido-2-methylpropane sulfonic acid
  • styrene sulfonic acid acrylic acid-sulfopropyl ester
  • itaconic acid-sulfopropyl ester itaconic acid-sulfopropyl ester
  • vinyl sulfonic acid as well as in each case the ammonium, sodium, potassium and/or calcium salts.
  • the polysaccharide that forms the backbone of the graft copolymer is preferably selected from starch, maltodextrin, cellulose, gums (e.g., gum arabic, guar and xanthan), alginates, pectin and gellan. More preferably, the polysaccharide is selected from starch and maltodextrin.
  • the polysaccharides employed in the graft copolymer can be modified or derivatised by etherification (e.g., via treatment with propylene oxide, ethylene oxide, 2,3-epoxypropyl trimethyl ammonium chloride), esterification (e.g., via reaction with acetic anhydride, octenyl succinic anhydride (“OSA”)), acid hydrolysis, dextrinization, oxidation (e.g. oxidized starch) or enzyme treatment, or various combinations of these treatments.
  • etherification e.g., via treatment with propylene oxide, ethylene oxide, 2,3-epoxypropyl trimethyl ammonium chloride
  • esterification e.g., via reaction with acetic anhydride, octenyl succinic anhydride (“OSA”)
  • OSA octenyl succinic anhydride
  • acid hydrolysis e.g., dextrinization, oxidation (e.g. oxidized
  • the polysaccharide of the copolymer is maltodextrin.
  • Maltodextrins are polymers that can be produced by starch hydrolysis and that have D-glucose units linked primarily by ⁇ -1,4 bonds and a dextrose equivalent of less than about 20.
  • Dextrose equivalent (DE) is a measure of the extent of starch hydrolysis. It is determined by measuring the amount of reducing sugars in a sample relative to dextrose (glucose). The DE of dextrose is 100, representing 100% hydrolysis.
  • the polysaccharide in the backbone of the graft copolymer preferably contains a chain of at least 8, more preferably of at least 10 monosaccharide units bound together by glycosidic linkages
  • the graft copolymer preferably has a high degree of polysaccharide.
  • the polysaccharide represents at least 50 wt.%, more preferably at least 60 wt.%, even more preferably at least 70 wt.% and most preferably at least 80 wt.% of the graft copolymer.
  • graft copolymer that may suitably be employed in accordance with the present invention is Alcoguard ® H 5240, which is commercially available from AkzoNobel ® .
  • nonionic surfactants include the condensation products of hydrophobic alkyl, alkenyl, or alkyl aromatic compounds bearing functional groups having free reactive hydrogen available for condensation with hydrophilic alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, polyethylene oxide or polyethylene glycol to form nonionic surfactants.
  • functional groups include hydroxy, carboxy, mercapto, amino or amido groups.
  • Nonionic surfactants are found in the low- to non-foaming ethoxylated/ propoxylated straight-chain alcohols of the Plurafac TM LF series, supplied by the BASF and the Synperonic TM NCA series supplied by Croda.
  • Other nonionics are the end-capped ethoxylated alcohols available as the SLF 18 series from BASF and the alkylpolyethylene glycol ethers made from a linear, saturated C 6 -C 8 fatty alcohol of the Lutensol TM AT series, supplied by BASF.
  • Other suitable nonionics to apply in the composition of the invention are modified fatty alcohol polyglycolethers available as Dehypon TM GRA or Dehypon TM Wet from BASF/Cognis.
  • Other nonionics are from the Lutensol TM TO series of BASF, which are alkylpolyethylene glycol ethers made from a saturated iso-d3 alcohol.
  • the nonionic surfactant is a polyoxyalkylene condensate, represented by the following formula: C x H 2x+1 -O-[CH 2 CH 2 O] n - CH 2 CH(OH)C y H 2y+1 , wherein 4 ⁇ x ⁇ 22, 8 ⁇ n ⁇ 50, 4 ⁇ y ⁇ 22.
  • the detergent composition contains 1.5-10%, more preferably 2-8% of the nonionic surfactant by weight of the composition.
  • the nonionic surfactant employed in the present detergent composition preferably is a low foam nonionic surfactant.
  • low foam nonionic surfactant refers to a nonionic surfactant that at a concentration of 1 wt.% in distilled water and at a temperature of 50 °C has an initial foam height of less than 50 mm, a foam height of less 5 mm after 1 minute, and a foam height of less than 1 mm after 5 minutes in the ASTM D1173-07 test.
  • the nonionic surfactant used typically has a cloud point of at least 25°C. More preferably the nonionic surfactant has a cloud point of 27-60°C, most preferably a cloud point of 28-50°C.
  • cloud point refers to the temperature at which the nonionic surfactant starts to precipitate from an aqueous solution.
  • the inventors have found that, a detergent composition that is not only chemically but also physically very stable can be produced if the nonionic surfactant employed is solid at all temperatures which are relevant in the logistic chain. Thus, it is preferred that the nonionic surfactant is solid below 45°C.
  • the detergent composition may contain other surfactant besides the nonionic surfactant. If an anionic surfactant is used, the total amount present preferably is less than 5 wt.%, more preferably less than 2 wt.%, even more preferably less than 1 wt.% and most preferably less than 0.5 wt.%..
  • the detergent composition preferably contains at least 0.03 wt.%, more preferably at least 0.05 wt.% and most preferably 0.07-3 wt.% of one or more enzymes.
  • enzymes suitable for use in the cleaning compositions of this invention include lipases, cellulases, peroxidases, proteases (proteolytic enzymes), amylases (amylolytic enzymes) and others which degrade, alter or facilitate the degradation or alteration of biochemical soils and stains encountered in cleansing situations so as to remove more easily the soil or stain from the object being washed to make the soil or stain more removable in a subsequent cleansing step. Both degradation and alteration can improve soil removal.
  • the one or more active enzymes contained in the present composition are selected from protease, amylase, cellulase, peroxidase, mannanase, pectate, lyase and lipase.
  • the active enzyme is selected from protease, amylase and combinations thereof.
  • the composition contains at least 10 mg/kg, more preferably at least 20 mg/kg and most preferably at least 50 mg/kg of active amylase.
  • the composition contains at least 100 mg/kg, more preferably at least 200 mg/kg and most preferably at least 400 mg/kg of active protease.
  • Enzymes may be added in liquid or in encapsulated form.
  • encapsulated enzymes are enzyme granule types D, E and HS by Genencor and granule types T, GT, TXT and Evity TM of Novozymes.
  • the proteolytic enzymes in this invention include metalloproteases and serine proteases, including neutral or alkaline microbial serine protease, such as subtilisins (EC 3.4.21.62).
  • the proteolytic enzymes for use in the present invention can be those derived from bacteria of fungi. Chemically or genetically modified mutants (variants) are included.
  • Preferred proteolytic enzymes are those derived from Bacillus, such as B . lentus, B. gibsonii, B. subtilis, B. licheniformis, B. alkalophilus, B. amyloliquefaciens and Bacillus pumilus, of which B. lentus and B. gibsonii are most preferred.
  • proteolytic enzymes examples include Excellase TM , Properase TM , Purafect TM , Purafect TM Prime, Purafect TM Ox by Genencor; and those sold under the trade names Blaze TM ,Ovozyme TM , Savinase TM , Alcalase TM , Everlase TM , Esperase TM , Relase TM , Polarzyme TM , Liquinase TM and Coronase TM by Novozymes.
  • amylolytic enzymes for use in the present invention can be those derived from bacteria or fungi. Chemically or genetically modified mutants (variants) are included.
  • Preferred amylolytic enzyme is an alpha-amylase derived from a strain of Bacillus, such as B . subtilis, B. licheniformis, B. amyloliquefaciens or B. stearothermophilus.
  • amylolytic enzymes are produced and distributed under the trade name of Stainzyme TM , Stainzyme TM Plus, Termamyl TM , Natalase TM and Duramyl TM by Novozymes; as well as Powerase TM , Purastar TM , Purastar TM Oxam by Genencor.
  • Stainzyme TM , Stainzyme TM Plus and Powerase TM are the preferred amylases.
  • Well known enzyme stabilizers such as polyalcohols/borax, calcium, formate or protease inhibitors like 4-formylphenyl boronic acid may also be present in the composition.
  • the detergent composition may suitably contain up to 70 wt.% of a filler. More preferably, the composition contains not more than 60 wt.% of filler, most preferably 10-50 wt.% of filler.
  • the filler employed is a metal sulfate, e.g. sodium sulfate.
  • Glass corrosion inhibitors can prevent the irreversible corrosion and iridescence of glass surfaces in automatic dishwash detergents.
  • the claimed composition may suitably contain glass corrosion inhibitors.
  • Suitable glass corrosion agents can be selected from the group the group consisting of salts of zinc, bismuth, aluminum, tin, magnesium, calcium, strontium, titanium, zirconium, manganese, lanthanum, mixtures thereof and precursors thereof. Most preferred are salts of bismuth, magnesium or zinc or combinations thereof.
  • Anti-tarnishing agents may prevent or reduce the tarnishing, corrosion or oxidation of metals such as silver, copper, aluminium and stainless steel.
  • Anti-tarnishing agents such as benzotriazole, methyl benzotriazole or bis-benzotriazole and substituted or substituted derivatives thereof and those described in EP 723 577 (Unilever ) may also be included in the composition.
  • Other anti-tarnishing agents that may be included in the detergent composition are mentioned in WO 94/26860 and WO 94/26859 .
  • Suitable redox active agents are for example complexes chosen from the group of cerium, cobalt, hafnium, gallium, manganese, titanium, vanadium, zinc or zirconium, in which the metal are in the oxidation state of II, II, IV V or VI.
  • the detergent composition of the present invention can include one or more water conditioning agents.
  • Phosphonates for instance, can suitably be used in the form of water soluble acid salts, particularly the alkali metal salts, such as sodium or potassium; the ammonium salts; or the alkylol amine salts where the alkylol has 2 to 3 carbon atoms, such as mono-, di-, or triethanolamine salts.
  • Preferred phosphonates include the organic phosphonates.
  • Preferred organic phosphonates include phosphono butane tricarboxylic acid (PBTC) and hydroxy ethylidene diphosphonic acid (HEDP).
  • the composition contains 0-10 wt-% organic phosphonate, more preferably 0.2-5 wt.% organic phosphonate, even more preferably 0.3-2 wt.% organic phosphonate and most preferably 0.4-1.5 wt.5 organic phosphonate.
  • compositions such as perfume, colorant or preservatives.
  • Another aspect of the invention relates to the use of a detergent composition as defined herein before as a detergent in an automatic dishwashing apparatus.
  • the aforementioned ADW detergent compositions were prepared as follows: All solid ingredients (i.e. all ingredients in Table 1 except Alcoguard H5240 and Dehypon WET) were introduced into a powder mixer and mixed thoroughly. While mixing, Dehypon WET was carefully sprayed onto the powder in such a manner that it was evenly spread over the powder bed. The resulting powder was subsequently pressed into monolayer tablets. Combined weight of tablet and Alcoguard H5240 was 18 grams.
  • the tablet and Alcoguard H5240 were introduced separately into the dishwasher.
  • the tablet was inserted in the dispenser prior to starting the machine.
  • Alcoguard H5240 was dosed by putting the correct amount in a cup and adding the cup manually when the dispenser opened.
  • ADW detergent compositions was evaluated using the following test procedure: A representative set of dishes consisting of earthenware, glassware, metal and plastics is washed 30 consecutive times in a Miele 1222GSL dishwasher using the 65 °C program. The detergent is dosed in the dispenser prior to every wash. A cup containing 50 grams of frozen Stiwa soil is dosed manually (e.g. opening the dishwasher and putting the cup upside down in the top rack) when the dispenser opens.
  • the dishwasher After every wash the dishwasher is opened and the dishes are allowed to dry completely and cool down to room temperature. After 30 washes the dishes are evaluated.
  • the aesthetic scores were obtained by placing the dishware at 115 cm of a grey wall (RAL 7030) and 45 to 50 cm of the ceiling of the room.
  • the dishware is illuminated with 4 light sources type Philips master TL-D 36 W / 865 2M, 120 cm long and is evaluated on overall appearance i.e. taking into account spots, film, etc. A scale going from 1 to 10 is used, 10 corresponding to a perfect dish.
  • Table 2 Aesthetic 1 2 3 4 Earthenware 6.00 6.00 6.00 6.00 Glass 6.50 4.50 6.50 6.00 Metal 5.50 5.50 4.50 4.50 Plastic 3.75 3.50 3.50 4.00 Combined 21.75 19.50 20.50 20.50
  • Table 4 Aesthetic 1 2 A Earthenware 4.50 4.00 2.50 Glass 5.67 3.44 2.33 Metal 4.25 2.75 1.75 Plastic 3.50 2.50 1.75 Combined 17.92 12.69 8.33
  • Table 6 Aesthetic 1 2 A B Earthenware 5.00 6.00 5.00 4.00 Glass 5.00 5.33 4.00 4.33 Metal 4.75 5.00 4.25 3.75 Plastic 4.00 4.50 3.75 3.50 Combined 18.75 20.83 17.00 15.58
  • Table 8 Aesthetic 1 A B Earthenware 6.00 6.00 5.00 Glass 6.00 6.00 6.00 Metal 4.50 4.00 4.00 Plastic 4.00 3.75 4.25 Combined 20.50 19.75 19.25
  • the performance of the ADW detergent compositions was evaluated using the same test procedure as in Example 1, except that another set of articles was cleaned in the dishwasher, the evaluation was limited to only spotting and the total number of washes was limited to 10.
  • Table 10 A Plastic cup 4 2 Plastic dinner plate 6 4 Stainless steel dinner plate 7 2 Ceramic dinner plate 7 2 Glass 5 4

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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)
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  • Detergent Compositions (AREA)

Claims (14)

  1. Composition de détergent exempte de phosphate consistant en :
    • 20-80 % en masse d'adjuvant ;
    • 5-25 % en masse de constituant blanchissant ;
    • 1-10 % en masse d'un copolymère greffé ayant une structure de polysaccharide et une ou plusieurs chaînes latérales d'une ou plusieurs unités monomères synthétiques ;
    • 1-15 % en masse de tensioactif non-ionique ; dans laquelle le tensioactif non-ionique est un condensat de polyoxyalkylène, représenté par la formule suivante :
    CxH2x+1-O-[CH2CH2O]n-CH2CH(OH)CyH2y+1, dans laquelle 4≤x≤22, 8≤n≤50, 4≤y≤22 ;
    • 0-60 % en masse d'un ou plusieurs autres ingrédients de détergent ;
    dans laquelle le copolymère greffé et l'adjuvant sont présents dans un rapport de masse de copolymère à adjuvant de 1:50 à 1:4 ; et dans laquelle l'adjuvant contient au moins 20 % de citrate en masse de l'adjuvant et au moins 25 % de carbonate en masse de l'adjuvant, et l'adjuvant est composé de :
    a. au plus 70 % en masse d'un adjuvant séquestrant d'hydroxycarboxylate choisi parmi un citrate, tartrate, gluconate et des combinaisons de ceux-ci ;
    b. au plus 80 % en masse d'adjuvant de précipitation choisi parmi un carbonate, silicate et des combinaisons de ceux-ci ;
    c. 0-25 % en masse d'un ou plusieurs autres adjuvants ;
    dans laquelle les citrate et carbonate constituent ensemble au moins 50 % en masse de l'adjuvant ;
    dans laquelle les citrate et carbonate sont présents dans un rapport molaire de citrate: carbonate de 0,1 à 1,0 ; dans laquelle les termes citrate, tartrate, gluconate, carbonate et silicate englobent à la fois les formes d'acide et de sel ; et dans laquelle la concentration d'un sel ou d'un acide fait référence à la concentration équivalente du sel ou de l'acide dans une forme anhydre.
  2. Composition de détergent selon la revendication 1, dans laquelle la composition contient au moins 30 % en masse d'adjuvant.
  3. Composition de détergent selon la revendication 1 ou 2, dans laquelle les citrate et carbonate sont présents dans la composition de détergent dans un rapport molaire de citrate : carbonate de 0,15 à 0,9.
  4. Composition de détergent selon l'une quelconque des revendications précédentes, dans laquelle la composition comprend au moins 25 % de citrate en masse de l'ajduvant.
  5. Composition de détergent selon l'une quelconque des revendications précédentes, dans laquelle la composition comprend au moins 30 % de carbonate en masse de l'adjuvant.
  6. Composition de détergent selon l'une quelconque des revendications précédentes, dans laquelle l'adjuvant comprend moins de 15 % en masse d'un ou plusieurs autres adjuvants.
  7. Composition de détergent selon l'une quelconque des revendications précédentes, dans laquelle le constituant blanchissant est le percarbonate.
  8. Composition de détergent selon l'une quelconque des revendications précédentes, dans laquelle le copolymère greffé et le tensioactif non-ionique sont présents dans un rapport de masse de 1:4 à 3:1.
  9. Composition de détergent selon l'une quelconque des revendications précédentes, dans laquelle le polysaccharide dans le copolymère greffé est choisi parmi l'amidon, la maltodextrine, la cellulose, des gommes, des alginates, de la pectine et de la gomme gellane.
  10. Composition de détergent selon la revendication 9, dans laquelle le polysaccharide est la maltodextrine.
  11. Composition de détergent selon l'une quelconque des revendications précédentes, dans laquelle les unes ou plusieurs unités monomères synthétiques dans le copolymère greffé sont choisies parmi l'acide acrylique, l'acide maléique, l'acide itaconique, ou l'acide méthacrylique et des combinaisons de ceux-ci.
  12. Composition de détergent selon l'une quelconque des revendications précédentes, dans laquelle la combinaison de l'adjuvant, du constituant blanchissant, du copolymère greffé et du tensioactif non-ionique représente au moins 50 % en masse de la composition de détergent.
  13. Composition de détergent selon l'une quelconque des revendications précédentes, dans laquelle la composition est un produit particulaire ou un article solide.
  14. Utilisation d'une composition de détergent selon l'une quelconque des revendications précédentes comme un détergent dans un appareil de lave-vaisselle automatique.
EP18723012.3A 2017-05-12 2018-05-14 Composition de détergent de lave-vaisselle automatique sans phosphate Active EP3622049B1 (fr)

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US9113892B2 (en) 2013-01-08 2015-08-25 Covidien Lp Surgical clip applier
WO2022243533A1 (fr) 2021-05-20 2022-11-24 Nouryon Chemicals International B.V. Polymères fabriqués présentant une fonctionnalité d'oligosaccharide ou de polysaccharide modifiée ou une distribution rétrécie d'oligosaccharides, procédés pour leur préparation, compositions les contenant et procédés pour leur utilisation
EP4347766A1 (fr) * 2021-06-03 2024-04-10 Unilever IP Holdings B.V. Détergent pour lave-vaisselle

Family Cites Families (13)

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Publication number Priority date Publication date Assignee Title
US4751015A (en) 1987-03-17 1988-06-14 Lever Brothers Company Quaternary ammonium or phosphonium substituted peroxy carbonic acid precursors and their use in detergent bleach compositions
US5041232A (en) 1990-03-16 1991-08-20 Lever Brothers Company, Division Of Conopco, Inc. Sulfonimines as bleach catalysts
US5047163A (en) 1990-03-16 1991-09-10 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with sulfonimines
EP0458398B1 (fr) 1990-05-21 1997-03-26 Unilever N.V. Activation du blanchiment
US5898025A (en) 1992-09-25 1999-04-27 Henkel Kommanditgesellschaft Auf Aktien Mildly alkaline dishwashing detergents
HU218021B (hu) 1993-05-08 2000-05-28 Henkel Kommanditgesellschaft Auf Aktien Ezüst korróziója ellen védő szerek (II) és ezeket tartalmazó gépitisztítószerek
DE59405259D1 (de) 1993-05-08 1998-03-19 Henkel Kgaa Silberkorrosionsschutzmittel i
ES2122336T3 (es) 1993-10-14 1998-12-16 Unilever Nv Composiciones detergentes que contienen agentes contra el deslustrado de la plata.
WO2011017223A1 (fr) 2009-07-31 2011-02-10 Akzo Nobel N.V. Compositions de copolymère hybride pour des applications de soin personnel
US20110028371A1 (en) 2009-07-31 2011-02-03 Akzo Nobel N.V. Hybrid copolymers
US7781387B2 (en) 2008-01-22 2010-08-24 Access Business Group International, Llc. Automatic phosphate-free dishwashing detergent providing improved spotting and filming performance
DE102008063801A1 (de) 2008-12-19 2010-06-24 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
DE102014208509A1 (de) 2014-05-07 2015-11-12 Henkel Ag & Co. Kgaa Reinigungsmittel

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