WO2020043844A1 - Produit pour lave-vaisselle automatique - Google Patents

Produit pour lave-vaisselle automatique Download PDF

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Publication number
WO2020043844A1
WO2020043844A1 PCT/EP2019/073126 EP2019073126W WO2020043844A1 WO 2020043844 A1 WO2020043844 A1 WO 2020043844A1 EP 2019073126 W EP2019073126 W EP 2019073126W WO 2020043844 A1 WO2020043844 A1 WO 2020043844A1
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WIPO (PCT)
Prior art keywords
methyl
benzotriazole
product
automatic dishwashing
bleaching agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2019/073126
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English (en)
Inventor
Karlheinz Ulrich Hahn
Gerd-Erich HÜTTMANN
Rainer MÜLLER-LEIFHEIT
Addie MUENTZENBERGER
Torsten Roth
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Reckitt Benckiser Finish BV
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Reckitt Benckiser Finish BV
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Publication of WO2020043844A1 publication Critical patent/WO2020043844A1/fr
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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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • 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
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions

Definitions

  • the present disclosure relates to an improved automatic dishwashing product.
  • the present disclosure relates to the use of a silver/copper corrosion inhibitor in an automatic dishwashing product that is equally effective in inhibiting silver and copper corrosion as existing benzotriazole-based inhibitors while reducing the release of harmful and less biodegradable benzotriazoles into the environment.
  • a diverse array of compositions designed for use in automatic dishwasher machines is well known, and a consistent and ongoing effort has been made by detergent manufacturers to reduce the tarnishing of silver and copper items and surfaces in the dishwasher.
  • This problem becomes apparent when bleach-containing compositions are employed, and especially those which contain oxygen-bleaching species.
  • the level of tarnishing observed can range from slight discolouration to the formation of a dense black coating on the surface of the silverware or copperware, depending on the formulation and the bleaching agent.
  • the dual challenge in formulating a product is therefore the optimization of the cleaning of bleachable soils while minimizing the occurrence of tarnishing of silverware items.
  • BTA (1 H-benzotriazole) and/or TTA (a mixture of 4-methyl- //-/-benzotriazole and 5-methyl- //-/-benzotriazole, typically in a ratio of around 40:60).
  • BTA and TTA are both effective at reducing the tarnishing of silverware components in the presence of bleaching agents.
  • BTA was found to be toxic to aquatic life and, in addition, is a potential endocrine disruptor (Seeland et ai, J. Environ. Sci. Pollut. Res. Int, 2012, 19(5), 1781-1790.
  • the present invention provides an automatic dishwashing product comprising a bleaching agent, 5-methyl- //-/-benzotriazole and optionally 4- methyl- 1H- benzotriazole,
  • the product comprises 4-methyl- //-/-benzotriazole
  • the 5-methyl- / /-/-benzotriazole and the 4-methyl- //-/-benzotriazole are present in a weight ratio of at least 4:1 .
  • the present inventors have surprisingly found that despite the high structural similarity between 5-methyl- //-/-benzotriazole and 4-methyl- //-/-benzotriazole, 5-methyl - 1H- benzotriazole is more active in inhibiting the silver and copper corrosion effect of bleach- containing automatic dishwashing products.
  • 5-methyl - 1H- benzotriazole is more active in inhibiting the silver and copper corrosion effect of bleach- containing automatic dishwashing products.
  • the present invention provides a method of automatic dishwashing, the method comprising supplying a product to an automatic dishwasher and releasing the product into a wash cycle of the automatic dishwasher, the product comprising a bleaching agent, 5-methyl- //-/-benzotriazole and optionally 4-methyl - 1H- benzotri azole,
  • the present invention provides a use of 5-methyl- 1 H- benzotriazole, substantially in the absence of 4-methyl- //-/-benzotriazole, for reducing corrosion of silver and/or copper by a bleaching agent in an automatic dishwashing process.
  • the present invention provides an automatic dishwashing product comprising a bleaching agent.
  • the bleaching agent is preferably selected from the group consisting of an oxygen-releasing bleaching agent, a chlorine-releasing bleaching agent and mixtures of two or more thereof. More preferably, the bleaching agent is or comprises an oxygen- releasing bleaching agent.
  • Oxygen-releasing bleaching agents are known to cause particularly pronounced silver and copper tarnishing, since the release of oxygen can lead to the formation of black silver and copper layers during the cleaning process (especially with low-alkaline formulations providing a pH of less than 1 1 .5 at 1 wt% aqueous solution). Accordingly, the effect of the corrosion inhibitor is most pronounced in products comprising oxygen-releasing bleaching agents.
  • the bleaching agent may comprise the active bleach species itself or a precursor to that species.
  • the bleaching agent is selected from the group consisting of an inorganic peroxide, an organic peracid and mixtures of two or more thereof.
  • inorganic peroxide and organic peracid encompass salts and derivatives thereof.
  • Inorganic peroxides include percarbonates, perborates, persulphates, hydrogen peroxide and derivatives and salts thereof.
  • the sodium and potassium salts of these inorganic peroxides are suitable, especially the sodium salts.
  • the bleaching agent is selected from the group consisting of sodium percarbonate, £- phthalimido-peroxy-hexanoic acid (PAP), peracetic acid, potassium peroxymonosulfate (KMPS), and combinations of two or more thereof.
  • PAP phthalimido-peroxy-hexanoic acid
  • KMPS potassium peroxymonosulfate
  • the bleaching agent is present in an amount of from 1 to 50 wt% by weight of the automatic dishwashing product, more preferably from 2 to 30 wt%, and most preferably from 5 to 25 wt%.
  • the term“by weight of the automatic dishwashing product”, as used herein, means based on the weight of the cleaning composition(s) and does not include any packaging or container such as any PVOH film, pouch or capsule housing the cleaning composition(s). All weight percentages expressed herein are by weight of the automatic dishwashing product unless otherwise specified.
  • the automatic dishwashing product may further comprise one or more bleach activators or bleach catalysts.
  • Any suitable bleach activator may be included, for example TAED, if this is desired for the activation of the bleaching agent.
  • Any suitable bleach catalyst may be used, for example manganese-based bleach catalysts and/or cobalt-based bleach catalysts.
  • Exemplary manganese-based bleach catalysts include manganese acetate, manganese oxalate, or dinuclear manganese complexes such as those described in EP 1741774 A1 , the contents of which are incorporated herein by reference.
  • Exemplary cobalt-based bleach catalysts include cobalt complexes such as those described by the formula [Co(NH ) M]T y , wherein cobalt is in the +3 oxidation state, M is a carboxylate ligand and T is one or more counterions present in the number y, wherein y is an integer, preferably 1 or 2, to obtain a charge-balanced salt.
  • Suitable cobalt complexes include those described in WO 1997/00031 1 A1 and US 5703034 A, the contents of which are incorporated herein by reference.
  • the organic peracids such as perbenzoic acid and peroxycarboxylic acids e.g. phthalimidoperoxyhexanoic acid (PAP) do not require the use of a bleach activator or catalyst as these bleaches are active at relatively low temperatures such as about 30°C.
  • the automatic dishwashing product comprises 5- methyl- 7/-/-benzotriazole.
  • the present inventors have found that this isomer is more effective in inhibiting the silver and copper corrosion effect of bleach-containing automatic dishwashing products than 4-methyl- 7/-/-benzotriazole.
  • the automatic dishwashing product does not comprise 4-methyl- 7/-/-benzotriazole.
  • the 5-methyl- 7/-/-benzotriazole and the 4-methyl- 7/-/-benzotriazole are present in a weight ratio of at least 4:1 , preferably at least 10:1 , more preferably at least 20:1 , still more preferably at least 50:1 . It is to be understood that this defines the weight ratio of the 5-methyl- 7/-/-benzotriazole to the 4- methyl- 7/-/-benzotriazole. It is also to be understood that the term “at least 4:1” encompasses 6:1 and 10:1 but not, for example, 4:6.
  • the present inventors finding that 5-methyl- 7 /-/-benzotriazole is the main active isomer in this context means that the amount of 4-methyl- 7/-/-benzotriazole can be reduced or eliminated without compromising the effect on the inhibition of silver and copper corrosion.
  • the automatic dishwashing products of the present invention are equally effective as prior art products in terms of their bleaching performance and limited corrosive effect on silver and copper, while reducing harm to the aquatic environment.
  • the 5-methyl- 7/-/-benzotriazole is present in an amount of from 0.001 to 1 wt% by weight of the automatic dishwashing product, more preferably from 0.01 to 0.5 wt%.
  • the product comprises 4-methyl- 7/-/-benzotriazole
  • the 4-methyl- 7/-/-benzotriazole is preferably present in an amount of less than 0.05 wt%, more preferably less than 0.02 wt%. More preferably, however, the product is free or essentially free of 4-methyl - 1 H- benzotri azole.
  • the 7/-/-benzotriazole is preferably present in an amount of less than 0.05 wt% by weight of the automatic dishwashing product, more preferably less than 0.02 wt%. More preferably, however, the product is free or substantially free of 7/-/-benzotriazole.
  • the bleaching agent and the 5-methyl- 7/-/-benzotriazole are present in a weight ratio of from 20:1 to 200:1 , more preferably from 50:1 to 150:1 .
  • weight ratio is defined above.
  • the product has a pH of less than 1 1.5 at 1 wt% aqueous solution at 20 °C, more preferably from 7 to 10.5.
  • the product preferably has a pH within these ranges when diluted in water in an amount of 1 wt% based on the weight of the aqueous solution that forms.
  • the term“product” refers to the cleaning composition(s) and does not include any packaging or container such as any PVOH film, pouch or capsule housing the cleaning composition(s).
  • the product is formulated to provide, in use, a cleaning solution having a pH of less than 1 1 .5 at a wash cycle temperature of from 40 to 60 °C, more preferably from 7 to 10.5.
  • the product is preferably a “low-alkaline” formulation.
  • Low-alkaline formulations containing bleaching agents, especially oxygen-releasing bleaching agents are known to be particularly corrosive towards silver and copper. This is because the relatively low pH further shifts the oxidation potentials to favour the formation of black silver and copper layers during the cleaning process. Accordingly, the corrosion inhibitor of the present invention is particularly effective in low-alkaline formulations.
  • the automatic dishwashing product may comprise a source of acidity or a source of alkalinity, to obtain or/and buffer the desired pH on dissolution.
  • the source of acidity may be any suitable acidic compound, for example a polycarboxylic acid.
  • the source of alkalinity may, for example, be a carbonate or bicarbonate (such as the alkali metal or alkaline earth metal salts).
  • the source of alkalinity may suitably be any suitable basic compound for example any salt of a strong base and a weak acid.
  • silicates are amongst the suitable sources of alkalinity.
  • Preferred silicates are sodium silicates such as sodium disilicate, sodium metasilicate and crystalline phyllosilicates.
  • the product is free of silicates.
  • the automatic dishwashing product further comprises:
  • the automatic dishwashing product is preferably an automatic dishwashing detergent product.
  • the automatic dishwashing product may comprise a builder (or co-builder).
  • the builder / co-builder may be either a phosphorous-containing builder or a phosphorous-free builder as desired.
  • phosphate builders are banned.
  • the automatic dishwashing product is phosphate-free.
  • phosphorous-containing builders are to be used, it is preferred that mono-phosphates, di-phosphates, tri-polyphosphates or oligomeric-polyphosphates are used.
  • the alkali metal salts of these compounds are preferred, in particular the sodium salts.
  • An especially preferred builder is sodium tripolyphosphate (STPP).
  • STPP sodium tripolyphosphate
  • Conventional amounts of the phosphorous-containing builders may be used typically in the range of from 15 to 60 wt% by weight of the automatic dishwashing product, such as from 20 to 50 wt% or from 25 to 40 wt%.
  • phosphorous-free builder is included, it preferably comprises an aminocarboxylate or a citrate.
  • the builder is selected from the group consisting of methylglycine diacetic acid (MGDA), N,N-dicarboxymethyl glutamic acid (GLDA), citrate and combinations of two or more thereof.
  • MGDA methylglycine diacetic acid
  • GLDA N,N-dicarboxymethyl glutamic acid
  • citrate and combinations of two or more thereof.
  • MGDA GLDA and citrate encompass the free acids as well as salts, esters and derivatives thereof.
  • the citrate is trisodium citrate.
  • succinate based compounds include succinate based compounds.
  • succinate based compound and “succinic acid based compound” are used interchangeably herein.
  • Conventional amounts of the succinate based compounds may be used, typically in the range of from 5 to 80 wt% by weight of the automatic dishwashing product, such as from 15 to 70 wt% or from 20 to 60 wt%.
  • the compounds may be used individually or as a mixture.
  • suitable builders include; for example, 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), N- methyliminodiacetic acid (MIDA), a- alanine- N,N-diacetic acid (a-ALDA), 3-alanine-N,N-diacetic acid (b-ALDA), serine-N,N-diacetic acid (SEDA), isoserine-N,N-d
  • ASMA aspartic acid-N- monoacetic acid
  • ASDA aspartic
  • R, R 1 independently of one another, denote H or OH
  • R 2 , R 3 , R 4 , R 5 independently of one another, denote a cation, hydrogen, alkali metal ions and ammonium ions, ammonium ions having the general formula R 6 R 7 R 8 R 9 N + and R 6 , R 7 , R 8 , R 9 , independently of one another, denote hydrogen, alkyl radicals having 1 to 12 C atoms or hydroxyl-substituted alkyl radicals having 2 to 3 C atoms.
  • Preferred examples include tetrasodium imminosuccinate.
  • Iminodisuccinic acid (IDS) and (hydroxy)iminodisuccinic acid (HIDS) and alkali metal salts or ammonium salts thereof are especially preferred succinate based builder salts.
  • the phosphorous-free co- builder may also or alternatively comprise non-polymeric organic molecules with carboxylic group(s).
  • Builder compounds which are organic molecules containing carboxylic groups include citric acid, fumaric acid, tartaric acid, maleic acid, lactic acid and salts thereof.
  • the alkali or alkaline earth metal salts of these organic compounds may be used, and especially the sodium salts.
  • An especially preferred phosphorous-free builder is sodium citrate.
  • Such polycarboxylates which comprise two carboxyl groups include, for example, water-soluble salts of, malonic acid, (ethylenedioxy)diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid.
  • Such polycarboxylates which contain three carboxyl groups include, for example, water-soluble citrate.
  • a suitable hydroxycarboxylic acid is, for example, citric acid.
  • Preferred secondary builders include homopolymers and copolymers of polycarboxylic acids and their partially or completely neutralized salts, monomeric polycarboxylic acids and hydroxycarboxylic acids and their salts, phosphates and phosphonates, and mixtures of such substances.
  • Preferred salts of the abovementioned compounds are the ammonium and/or alkali metal salts, i.e. the lithium, sodium, and potassium salts, and particularly preferred salts is the sodium salts.
  • Secondary builders which are organic are preferred.
  • a polymeric polycarboxylic acid is the homopolymer of acrylic acid.
  • Other suitable secondary builders are disclosed in WO 95/01416, to the contents of which express reference is hereby made. Most preferably, the secondary builder is trisodium citrate.
  • the total amount of builder present in the automatic dishwashing product is at least 20 wt% by weight of the automatic dishwashing product, and most preferably at least 25 wt%, preferably in an amount of up to 70 wt%, preferably up 60 wt%, more preferably up to 45 wt%.
  • the actual amount used in the product will depend upon the nature of the builder used. If desired a combination of phosphorous-containing and phosphorous-free builders may be used.
  • the automatic dishwashing product is phosphate- free and comprises (i) an aminocarboxylate selected from the group consisting of MGDA, GLDA and a combination thereof, and (ii) trisodium citrate, wherein the aminocarboxylate and the trisodium citrate are present in an amount of from 10 to 60 wt% by weight of the automatic dishwashing product.
  • Surfactants may also be included in the automatic dishwashing product and any of nonionic, anionic, cationic, amphoteric or zwitterionic surface active agents or suitable mixtures thereof may be used. Many such suitable surfactants are described in Kirk Othmer's Encyclopedia of Chemical Technology, 3rd Ed., Vol. 22, pp. 360-379, "Surfactants and Detersive Systems", incorporated by reference herein. In general, bleach-stable surfactants are preferred according to the present invention.
  • the product comprises no more than 2 wt%, no more than 1 wt%, or no, anionic surfactant.
  • the product comprises no more than 5 wt%, no more than 1 wt %, or no, ionic surfactant of any type. Non-ionic surfactants are especially preferred instead for automatic dishwashing products.
  • a preferred class of non-ionic surfactants is ethoxylated non-ionic surfactants prepared by the reaction of a monohydroxy alkanol or alkylphenol with 6 to 20 carbon atoms.
  • the surfactants have at least 12 moles, particularly preferred at least 16 moles, and still more preferred at least 20 moles, such as at least 25 moles, of ethylene oxide per mole of alcohol or alkylphenol.
  • Particularly preferred non-ionic surfactants are the non-ionics from a linear chain fatty alcohol with 16-20 carbon atoms and at least 12 moles, particularly preferred at least 16 and still more preferred at least 20 moles, of ethylene oxide per mole of alcohol.
  • the non-ionic surfactants additionally may comprise propylene oxide units in the molecule.
  • these PO units constitute up to 25 wt%, preferably up to 20 wt%, and still more preferably up to 15 wt% by weight of the overall molecular weight of the non-ionic surfactant.
  • Surfactants which are ethoxylated mono-hydroxy alkanols or alkylphenols, which additionally comprises polyoxyethylene-polyoxypropylene block copolymer units may be used.
  • the alcohol or alkylphenol portion of such surfactants constitutes more than 30 wt%, preferably more than 50 wt%, more preferably more than 70 wt% by weight of the overall molecular weight of the non-ionic surfactant.
  • non-ionic surfactants includes reverse block copolymers of polyoxyethylene and polyoxypropylene and block copolymers of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane.
  • Nonionic surfactant can be described by the formula: Ri0[CH 2 CH(CH3)0]x[CH2CH20]y[CH 2 CH(0H)R2] where Ri represents a linear or branched chain aliphatic hydrocarbon group with 4-18 carbon atoms or mixtures thereof, R 2 represents a linear or branched chain aliphatic hydrocarbon rest with 2-26 carbon atoms or mixtures thereof, x is a value between 0.5 and 1.5, and y is a value of at least 15.
  • non-ionic surfactants are the end-capped polyoxyalkylated non-ionics of formula:
  • Ri and R 2 represent linear or branched chain, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups with 1-30 carbon atoms
  • R 3 represents a hydrogen atom or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl group
  • x is a value between 1 and 30 and
  • k and j are values between 1 and 12, preferably between 1 and 5.
  • Ri and R 2 are preferably linear or branched chain, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups with 6-22 carbon atoms, where groups with 8 to 18 carbon atoms are particularly preferred.
  • group R 3 H, methyl or ethyl is particularly preferred.
  • Particularly preferred values for x are comprised between 1 and 20, preferably between 6 and 15.
  • each R 3 in the formula can be different.
  • Another group of preferred non-ionic surfactants are mixed alkoxylate fatty alcohol nonionic surfactants
  • the standard non-ionic surfactant structure is based on a fatty alcohol with a carbon C8 to C20 chain, wherein the fatty alcohol has been ethoxylated or propoxylated.
  • the degree of ethoxylation is described by the number of ethylene oxide units (EO), and the degree of propoxylation is described by the number of propylene oxide units (PO).
  • Such surfactants may also comprise butylene oxide units (BO) as a result of butoxylation of the fatty alcohol. Preferably, this will be a mix with PO and EO units.
  • the surfactant chain can be terminated with a butyl (Bu) moiety.
  • the mixed alkoxylate fatty alcohol non-ionic surfactants comprise between 3 to 5 moles of the higher alkoxylate group and between 6 to 10 moles the higher lower group.
  • mixed alkoxylate fatty alcohol nonionic surfactants having 4 or 5 moles of the higher alkoxylate group and 7 or 8 moles of the lower alkoxylate group are especially preferred and good results have been obtained with for surfactants with 4 PO moles and 8 EO moles.
  • the mixed alkoxylate fatty alcohol nonionic surfactant is C12-15 8EO/4PO (commercially available as Genapol EP 2584 ex Clariant, Germany).
  • mixtures of different non-ionic surfactants is suitable in the context of the present invention, for instance mixtures of alkoxylated alcohols and hydroxy group containing alkoxylated alcohols.
  • the non-ionic surfactants are present in the automatic dishwashing product in an amount of from 0.1 to 20 wt% by weight of the automatic dishwashing product, more preferably from 1 to 15 wt%, such as from 2 to 10 wt%.
  • Enzymes are present in the automatic dishwashing product in an amount of from 0.1 to 20 wt% by weight of the automatic dishwashing product, more preferably from 1 to 15 wt%, such as from 2 to 10 wt%.
  • the automatic dishwashing product may include one or more enzymes. It is preferred that the one or more enzymes are selected from proteases, lipases, amylases, cellulases and peroxidases, with proteases and amylases being most preferred. It is most preferred that protease and/or amylase enzymes are included in the products according to the invention as such enzymes are especially effective in dishwashing detergent compositions. Any suitable species of these enzymes may be used as desired. More than one species may be used.
  • ADW automatic dishwashing
  • the automatic dishwashing product of the present invention may comprise any other suitable ingredients known in the art.
  • polymers intended to improve the cleaning performance of the automatic dishwashing product may also be included therein.
  • sulphonated polymers may be used.
  • Suitable sulfonated monomers for incorporation in sulfonated (co)polymers are 2- acrylamido-2-methyl-1 -propanesulphonic acid, 2-methacrylamido-2- methyl-1- propanesulphonic acid, 3-methacrylamido-2-hydroxy-propanesulphonic acid, allysulphonic acid, methallysulphonic acid, 2-hydroxy-3-(2 propenyloxy)propanesulphonic acid, 2-methyl-2-propenen-1-sulphonic acid, styrenesulphonic acid, vinylsulphonic acid, 3-sulphopropyl acrylate, 3- sulphopropylmethacrylate, sulphomethylacrylamide, sulphomethylmethacrylamide and water soluble salts thereof.
  • Suitable sulphonated polymers are also described in US 5308532 and in WO 2005/090541 , which are incorporated herein by reference.
  • a sulfonated polymer When a sulfonated polymer is present, it is preferably present in an amount of at least 0.1 wt% by weight of the automatic dishwashing product, preferably at least 0.5 wt%, more preferably at least 1 wt%, and most preferably at least 3 wt%, up to 40 wt%, preferably up to 25 wt%, more preferably up to 15 wt%, and most preferably up to 10 wt%.
  • the automatic dishwashing product may also comprise one or more foam control agents.
  • foam control agents for this purpose are all those conventionally used in this field, such as, for example, silicones and their derivatives and paraffin oil.
  • the foam control agents are preferably present in amounts of 0.5 wt% or less.
  • the automatic dishwashing product may also comprise minor, conventional, amounts of preservatives, fragrances, and the like.
  • the product may be in the form of a tablet, a powder, granules, a liquid, a gel, a paste, or combinations of two or more thereof.
  • the product may comprise a single composition or a plurality of compositions.
  • the product may comprise a single composition comprising the bleaching agent, the 5-methyl- //-/-benzotriazole and, when present, the 4-methyl - 1H- benzotriazole, the single composition preferably being in the form of a tablet, a powder, granules, a liquid, a gel or a paste.
  • the bleaching agent, the 5-methyl- 1H- benzotriazole and, when present, the 4-methyl- 1H- benzotriazole may each be provided in different compositions.
  • the bleaching agent, the 5-methyl- //-/-benzotriazole and, when present, the 4-methyl- //-/-benzotriazole may be present in the same composition.
  • Other permutations of components are possible.
  • the 5-methyl- //-/-benzotriazole and, when present, the 4-methyl - 1H- benzotriazole may be provided in the same composition, and the bleaching agent provided in a different composition.
  • the 5-methyl- //-/-benzotriazole and the bleaching agent may be provided in the same composition, and the 4-methyl - 1H- benzotriazole, when present, being provided in a different composition.
  • the product is in a unit dose or monodose form.
  • the product comprises one or more compositions in the quantity required for a single wash cycle.
  • monodose and unit dose are used interchangeably throughout this disclosure.
  • the monodose product may comprise a tablet with a gel portion or layer.
  • the bleaching agent, the 5-methyl- //-/-benzotriazole and, when present, the 4-methyl- //-/-benzotriazole may be provided in the tablet and/or the gel portion or layer.
  • compressed tablets form a portion of the automatic dishwashing product, they may be homogeneous or composed of multi-layers. If the tablets are multi-layered then different layers may comprise different parts of the detergent. This may be done to increase stability or increase performance, or both.
  • the automatic dishwashing product is housed within a water soluble film or container, preferably a polyvinylalcohol film or container.
  • the film or container may be a PVOH rigid capsule or film blister.
  • the PVOH capsule or blister may have a single compartment or may be multi-compartment. Multi-compartment blisters or capsules may have different portions of the product in each compartment, or the same composition in each compartment. The distinct regions / compartments may contain any proportion of the total amount of ingredients as desired.
  • the PVOH capsules or film blisters may be filled with tablets, powders, gels, pastes or liquids, or combinations of these, within the scope of the invention. These PVOH capsules or blisters may have a single compartment or may be multi-compartment.
  • Multi-compartment blisters or capsules may have different portions of the product in each compartment, or the same composition in each compartment.
  • Each compartment may contain any proportion of the total amount of ingredients as desired.
  • Each compartment may comprise the 5-methyl- //-/-benzotriazole, and/or the bleaching agent, and/or 4-methyl- //-/-benzotriazole, and/or one or more builders, and/or one or more surfactants, and/or one or more enzymes.
  • the PVOH capsules or film blisters may be filled with tablets, powders, granules, liquids, gels, pastes, or combinations of two or more thereof.
  • the film or container may be an injection moulded PVOH capsule with multiple compartments. Each compartment may comprise a different composition. Optionally, one or more of the compartments may contain a gel or liquid composition. Each compartment may comprise the 5-methyl- //-/-benzotriazole, and/or the bleaching agent, and/or 4-methyl- //-/-benzotriazole, and/or one or more builders, and/or one or more surfactants, and/or one or more enzymes. Each compartment may be filled with a tablet, a powder, granules, a liquid, a gel, a paste, or combinations of two or more thereof.
  • the present invention provides a method of automatic dishwashing, the method comprising supplying a product to an automatic dishwasher and releasing the product or a portion thereof into a wash cycle of the automatic dishwasher, the product comprising an oxygen-releasing bleaching agent, 5-methyl- 1 H- benzotriazole and optionally 4-methyl- //-/-benzotriazole,
  • the product comprises 4-methyl- //-/-benzotriazole
  • the 5-methyl- 1 H- benzotriazole and 4-methyl- //-/-benzotriazole are present in a weight ratio of at least 4:1 .
  • the product is the product of the first aspect.
  • the dishwasher contains silverware and/or copperware.
  • silverware and/or copperware refer to articles formed of or coated with silver and copper respectively. It is to be understood that the terms silver and copper encompass the elements themselves and alloys containing the elements.
  • the corrosion inhibitor of the present invention is effective in inhibiting the corrosion of copper and silver. It is to be understood that the silverware and/or copperware are present in the dishwasher during the wash cycle of the method.
  • the product is formulated to provide, in use, a cleaning solution having a pH of less than 1 1.5 at a wash cycle temperature of from 40 to 60 °C, more preferably from 7 to 10.5. That is, the step of releasing the product into the dishwasher preferably comprises dissolving and/or dispersing the product or a portion thereof in water at a temperature of from 40 to 60 °C to form a cleaning solution having a pH of less than 1 1.5, or from 7 to 10.5, and contacting soiled articles (such as silverware and copperware) with the cleaning solution.
  • the product is preferably a“low- alkaline” formulation, as discussed above.
  • step of releasing the product or a portion thereof into a wash cycle of the automatic dishwasher from 0.1 to 6.5 grams of bleaching agent and/or from 1 to 500 milligrams of 5-methyl- 7 /-/-benzotriazole are preferably released into the wash cycle, more preferably from 1 to 4 grams of bleaching agent and from 10 to 400 milligrams of 5-methyl - 1H- benzotri azole.
  • the present invention provides a use of 5-methyl - 1H- benzotriazole, substantially in the absence of 4-methyl- //-/-benzotriazole for reducing corrosion of silver and/or copper by a bleaching agent in an automatic dishwashing process.
  • substantially in the absence of is meant in a product comprising less than 0.02 wt% 4-methyl- //-/-benzotriazole.
  • the use is essentially in the absence of or in the absence of or in the absence of 4-methyl- 1H- benzotriazole.
  • the bleaching agent is an oxygen-releasing bleaching agent.
  • the use of the third aspect comprises the use of the product of the first aspect, optionally in the process of the second aspect. All percentages used in this disclosure are by weight unless otherwise specified.
  • a base powder formulation (1 ) without any silver/copper corrosion inhibitors was prepared and tested. To 20 g of this formulation were added either 27 mg of a TTA powder (2) or 16 mg of 5-methyl- //-/-benzotriazole powder (3).
  • the TTA powder was a commercially available 60:40 mixture of 5-methyl - 1H- benzotriazole and 4-methyl- //-/-benzotriazole.
  • composition of formulation (1) was as follows:
  • Rinse Aid without rinse aid

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

L'invention concerne un produit pour lave-vaisselle automatique comprenant un agent blanchissant et du 5-méthyl-1H-benzotriazole.
PCT/EP2019/073126 2018-08-31 2019-08-29 Produit pour lave-vaisselle automatique Ceased WO2020043844A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB1814188.7A GB201814188D0 (en) 2018-08-31 2018-08-31 Automatic dishwashing product
GB1814188.7 2018-08-31

Publications (1)

Publication Number Publication Date
WO2020043844A1 true WO2020043844A1 (fr) 2020-03-05

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GB (1) GB201814188D0 (fr)
WO (1) WO2020043844A1 (fr)

Citations (11)

* Cited by examiner, † Cited by third party
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GB1347008A (en) * 1970-11-13 1974-02-13 Ciba Geigy Uk Ltd Detergent compositions
US5308532A (en) 1992-03-10 1994-05-03 Rohm And Haas Company Aminoacryloyl-containing terpolymers
WO1995001416A1 (fr) 1993-07-01 1995-01-12 The Procter & Gamble Company Composition pour lave-vaisselle contenant un agent de blanchiment oxygene, de l'huile de paraffine et un compose benzotriazole pour inhiber le ternissement de l'argent
WO1997000311A1 (fr) 1995-06-16 1997-01-03 The Procter & Gamble Company Compositions d'agents de blanchiment comprenant des catalyseurs au cobalt
US5703034A (en) 1995-10-30 1997-12-30 The Procter & Gamble Company Bleach catalyst particles
US5977053A (en) 1995-07-31 1999-11-02 Bayer Ag Detergents and cleaners containing iminodisuccinates
US6194368B1 (en) * 1995-07-13 2001-02-27 Joh A. Benckiser, Gmbh Dishwasher product in tablet form
US6426229B1 (en) 1995-12-22 2002-07-30 Mitsubishi Rayon Co., Ltd. Chelating agent and detergent comprising the same
WO2005090541A1 (fr) 2004-03-15 2005-09-29 The Procter & Gamble Company Procedes destines a traiter des surfaces au moyen de compositions de traitement de surface contenant des polymeres sulfones/carboxyles
EP1741774A1 (fr) 2005-07-08 2007-01-10 Unilever N.V. Compositions pour lave-vaisselle automatique et leur utilisation
WO2012025740A1 (fr) * 2010-08-27 2012-03-01 Reckitt Benckiser N.V. Composition de détergent comprenant de l'oxalate de manganèse

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1347008A (en) * 1970-11-13 1974-02-13 Ciba Geigy Uk Ltd Detergent compositions
US5308532A (en) 1992-03-10 1994-05-03 Rohm And Haas Company Aminoacryloyl-containing terpolymers
WO1995001416A1 (fr) 1993-07-01 1995-01-12 The Procter & Gamble Company Composition pour lave-vaisselle contenant un agent de blanchiment oxygene, de l'huile de paraffine et un compose benzotriazole pour inhiber le ternissement de l'argent
WO1997000311A1 (fr) 1995-06-16 1997-01-03 The Procter & Gamble Company Compositions d'agents de blanchiment comprenant des catalyseurs au cobalt
US6194368B1 (en) * 1995-07-13 2001-02-27 Joh A. Benckiser, Gmbh Dishwasher product in tablet form
US5977053A (en) 1995-07-31 1999-11-02 Bayer Ag Detergents and cleaners containing iminodisuccinates
US5703034A (en) 1995-10-30 1997-12-30 The Procter & Gamble Company Bleach catalyst particles
US6426229B1 (en) 1995-12-22 2002-07-30 Mitsubishi Rayon Co., Ltd. Chelating agent and detergent comprising the same
WO2005090541A1 (fr) 2004-03-15 2005-09-29 The Procter & Gamble Company Procedes destines a traiter des surfaces au moyen de compositions de traitement de surface contenant des polymeres sulfones/carboxyles
EP1741774A1 (fr) 2005-07-08 2007-01-10 Unilever N.V. Compositions pour lave-vaisselle automatique et leur utilisation
WO2012025740A1 (fr) * 2010-08-27 2012-03-01 Reckitt Benckiser N.V. Composition de détergent comprenant de l'oxalate de manganèse

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BRAUCH, WATER RESEARCH AND MANAGEMENT, vol. 1, no. 1, 2011, pages 17 - 28
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