EP3050948B1 - Nouvelle utilisation d'un agent complexant - Google Patents

Nouvelle utilisation d'un agent complexant Download PDF

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Publication number
EP3050948B1
EP3050948B1 EP15153520.0A EP15153520A EP3050948B1 EP 3050948 B1 EP3050948 B1 EP 3050948B1 EP 15153520 A EP15153520 A EP 15153520A EP 3050948 B1 EP3050948 B1 EP 3050948B1
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Prior art keywords
use according
acid
grams
composition
detergent composition
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German (de)
English (en)
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EP3050948A1 (fr
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Glenn Steven Ward
Melissa Cuthbertson
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Procter and Gamble Co
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Procter and Gamble Co
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Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP15153520.0A priority Critical patent/EP3050948B1/fr
Priority to PCT/US2016/015903 priority patent/WO2016126580A1/fr
Priority to JP2017540727A priority patent/JP2018505280A/ja
Publication of EP3050948A1 publication Critical patent/EP3050948A1/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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D17/045—Multi-compartment
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609—Protease or amylase in solid compositions only
    • 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

Definitions

  • the present invention is in the field of automatic dishwashing.
  • it relates to the use of organic complexing agents, in particular methyl glycine diacetic acid for the removal of baked-on burnt-on soils.
  • the automatic dishwashing detergent formulator is continuously looking for ways to improve the performance of detergents.
  • Baked-on, burnt-on soils are among the most difficult soils to remove.
  • baked-on, burnt-on soils containing proteins, such as egg and cheese more in particular baked-on, burnt-on soils containing eggs are really difficult to remove.
  • the removal of baked-on, burnt-on soils is more difficult when the detergent is phosphate free.
  • the present invention is based on the use of an organic complexing agent, methyl glycine diacetic acid, in an automatic dishwashing detergent composition. It has been unexpectedly found that the complexing agent, methyl glycine diacetic acid, improves the removal of baked-on burnt-on soils from dishware.
  • the composition comprises 3 grams to 6 grams, more preferably from 3.5 grams to 5.5 grams of an organic complexing agent, more preferably of methyl glycine diacetic acid.
  • composition for the use of the invention is sometimes herein referred to as "the composition of the invention”.
  • a “complexing agent” is a compound capable of binding polyvalent ions such as calcium, magnesium, lead, copper, zinc, cadmium, mercury, manganese, iron, aluminium and other cationic polyvalent ions to form a water-soluble complex.
  • the complexing agent has a logarithmic stability constant ([log K]) for Ca 2+ of at least 5, preferably at least 6.
  • the stability constant, log K is measured in a solution of ionic strength of 0.1, at a temperature of 25° C.
  • the complexing agent for use herein is the three sodium salt of MGDA.
  • the composition comprises a high level of protease, from 0.1 to 50 mg of active protease, more preferably from 0.1 to 40 mg of active protease and bleach. It seems that the combination of the level of the complexing agent of the composition of the invention, the tri-sodium salt of MGDA and this level of protease provides optimum removal of baked-on, burnt-on soils, in particular proteinaceous soils, such as eggs and milk based soils.
  • the composition comprises more than 0.8, more preferably more than 1 and especially 1.2 or more grams of sulfonated polymer.
  • the sulfonated polymer comprises 2-acrylamido-2-methylpropane sulfonic acid monomers.
  • “dishware” encompasses tableware and cookware and anything that it is usually washed in an automatic dishwasher.
  • sulfonated polymer is a polymer comprising sulphur in any of its forms.
  • the "sulfonated polymer” of the invention preferably comprises carboxyl groups.
  • composition herein is preferably phosphate free.
  • phosphate-free is herein understood that the composition comprises less than 1%, preferably less than 0.1% by weight of the composition of phosphate.
  • compositions of the invention can leave a coloured film on stainless steel items. This problem is avoided when the composition of the invention is free of citrate, thus preferred for use herein are citrate free compositions.
  • the composition of the invention has a pH equal or greater than 9 to 12, more preferably equal or greater than about 10 to about 11.5 as measured in 1% weight/volume aqueous solution in distilled water at 20°C.
  • the composition of the present invention has a reserve alkalinity of 10 or greater, preferably 12 or greater, most preferably 14 or greater.
  • Reserve alkalinity refers to, the ability of an automatic dishwashing composition to maintain an alkali pH in the presence of acid. This is relative to the ability of an automatic dishwashing composition to have sufficient alkali in reserve to deal with any added acid -coming from the water and/or the soils on the dishware- while maintaining the pH.
  • the reserve alkalinity for a solution is determined in the following manner.
  • a pH meter for example An Orion Model 720A with a Ag/AgCl electrode (for example an Orion sure flow Electrode model 9172BN) is standardized using pH 7 and pH 10 buffers.
  • a 1% solution of the composition to be tested is prepared in distilled water. The weight of the sample is noted. The pH of the 1% solution is measured and the solution is titrated down to pH 9.5 using a solution of 0.2N HCL.
  • the composition of the invention is in unit-dose form.
  • unit-dose form is herein meant that the composition is provided in a form sufficient to provide enough detergent for one wash.
  • Suitable unit dose forms include tablets, sachets, capsules, pouches, etc.
  • Preferred for use herein are compositions in unit-dose form wrapped in water-soluble material, for example polyvinyl alcohol, more preferably a polyvinyl alcohol film having a film of less than 100 ⁇ m tickness.
  • the detergent composition of the invention preferably weighs from about 8 to about 25 grams, more preferably from about 10 to about 20 grams. This weight range fits comfortable in a dishwasher dispenser. Even although this range amount to a low amount of detergent, the detergent has been formulated in a way that provides all the benefits mentioned herein above.
  • the present invention relates to the use of from about 3 to about 6 grams of an organic complexing agent, in an automatic dishwashing composition to provide baked-on, burnt-on removal benefits.
  • the detergent composition of the invention can be presented in unit-dose form and it can be in any physical form including solid, liquid and gel form.
  • the composition of the invention is very well suited to be presented in the form of a multi-compartment pack, more in particular a multi-compartment pack comprising compartments with compositions in different physical forms, for example a compartment comprising a composition in solid form and another compartment comprising a composition in liquid form.
  • the composition is preferably enveloped by a water-soluble film such as polyvinyl alcohol, more preferably the film has a thickness of less than 100 ⁇ m.
  • the composition comprises an organic complexing agent and optionally but preferably a sulfonated polymer, bleach, inorganic builder (preferably carbonate and silicate), enzymes in particular protease enzymes, non-ionic surfactant, etc.
  • composition of the invention preferably has a pH as measured in 1% weight/volume aqueous solution in distilled water at 20°C of from about 9 to about 12, more preferably from about 10 to less than about 11.5 and especially from about 10.5 to about 11.5.
  • composition of the invention preferably has a reserve alkalinity of from about 10 to about 20, more preferably from about 12 to about 18 at a pH of 9.5 as measured in NaOH with 100 grams of product at 20°C.
  • a complexing agent is a material capable of sequestering hardness ions, particularly calcium and/or magnesium.
  • the composition of the invention comprises from about 3 to about 6 grams, more preferably from about 3.5 grams to about 5 grams of a complexing agent.
  • the complexing agent is preferably selected from the group consisting of methyl-glycine-diacetic acid, its salts and derivatives thereof, glutamic-N,N-diacetic acid, its salts and derivatives thereof, iminodisuccinic acid, its salts and derivatives thereof, carboxy methyl inulin, its salts and derivatives thereof and mixtures thereof.
  • Especially preferred complexing agent for use herein is a salt of MGDA, in particular the tri-sodium salt of MGDA.
  • the polymer is used in any suitable amount from about 0.1% to about 30%, preferably from 0.5% to about 20%, more preferably from 1% to 10% by weight of the composition.
  • the composition of the invention comprises at least 0.8 gram, preferably at least 1 gram, more preferably at least 1.2 grams of sulfonated polymer and preferably less than 5 grams of sulfonated polymer. Sulfonated/carboxylated polymers are particularly suitable for the composition of the invention.
  • Suitable sulfonated/carboxylated polymers described herein may have a weight average molecular weight of less than or equal to about 100,000 Da, or less than or equal to about 75,000 Da, or less than or equal to about 50,000 Da, or from about 3,000 Da to about 50,000, preferably from about 5,000 Da to about 45,000 Da.
  • the sulfonated/carboxylated polymers may comprise (a) at least one structural unit derived from at least one carboxylic acid monomer having the general formula (I): wherein R 1 to R 4 are independently hydrogen, methyl, carboxylic acid group or CH 2 COOH and wherein the carboxylic acid groups can be neutralized; (b) optionally, one or more structural units derived from at least one nonionic monomer having the general formula (II): wherein R 5 is hydrogen, C 1 to C 6 alkyl, or C 1 to C 6 hydroxyalkyl, and X is either aromatic (with R 5 being hydrogen or methyl when X is aromatic) or X is of the general formula (III): wherein R 6 is (independently of R 5 ) hydrogen, C 1 to C 6 alkyl, or C 1 to C 6 hydroxyalkyl, and Y is O or N; and at least one structural unit derived from at least one sulfonic acid monomer having the general formula (IV): wherein
  • Preferred carboxylic acid monomers include one or more of the following: acrylic acid, maleic acid, itaconic acid, methacrylic acid, or ethoxylate esters of acrylic acids, acrylic and methacrylic acids being more preferred.
  • Preferred sulfonated monomers include one or more of the following: sodium (meth) allyl sulfonate, vinyl sulfonate, sodium phenyl (meth) allyl ether sulfonate, or 2-acrylamido-methyl propane sulfonic acid.
  • Preferred non-ionic monomers include one or more of the following: methyl (meth) acrylate, ethyl (meth) acrylate, t-butyl (meth) acrylate, methyl (meth) acrylamide, ethyl (meth) acrylamide, t-butyl (meth) acrylamide, styrene, or ⁇ -methyl styrene.
  • the polymer comprises the following levels of monomers: from about 40 to about 90%, preferably from about 60 to about 90% by weight of the polymer of one or more carboxylic acid monomer; from about 5 to about 50%, preferably from about 10 to about 40% by weight of the polymer of one or more sulfonic acid monomer; and optionally from about 1% to about 30%, preferably from about 2 to about 20% by weight of the polymer of one or more non-ionic monomer.
  • An especially preferred polymer comprises about 70% to about 80% by weight of the polymer of at least one carboxylic acid monomer and from about 20% to about 30% by weight of the polymer of at least one sulfonic acid monomer.
  • the carboxylic acid is preferably (meth)acrylic acid.
  • the sulfonic acid monomer is preferably one of the following: 2-acrylamido methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allysulfonic acid, methallysulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzensulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrene sulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethylacrylamid, sulfomethylmethacrylamide, and water soluble salts thereof.
  • Preferred commercial available polymers include: Alcosperse 240, Aquatreat AR 540 and Aquatreat MPS supplied by Alco Chemical; Acumer 3100, Acumer 2000, Acusol 587G and Acusol 588G supplied by Rohm & Haas; Goodrich K-798, K-775 and K-797 supplied by BF Goodrich; and ACP 1042 supplied by ISP technologies Inc. Particularly preferred polymers are Acusol 587G and Acusol 588G supplied by Rohm & Haas.
  • all or some of the carboxylic or sulfonic acid groups can be present in neutralized form, i.e. the acidic hydrogen atom of the carboxylic and/or sulfonic acid group in some or all acid groups can be replaced with metal ions, preferably alkali metal ions and in particular with sodium ions.
  • composition of the invention preferably comprises from 1 to 3, preferably from 1.2 to 2.8 and especially from 1.5 to 2.5 grams of bleach.
  • Inorganic and organic bleaches are suitable for use herein.
  • Inorganic bleaches include perhydrate salts such as perborate, percarbonate, perphosphate, persulfate and persilicate salts.
  • the inorganic perhydrate salts are normally the alkali metal salts.
  • the inorganic perhydrate salt may be included as the crystalline solid without additional protection.
  • the salt can be coated. Suitable coatings include sodium sulphate, sodium carbonate, sodium silicate and mixtures thereof. Said coatings can be applied as a mixture applied to the surface or sequentially in layers.
  • Alkali metal percarbonates particularly sodium percarbonate is the preferred bleach for use herein.
  • the percarbonate is most preferably incorporated into the products in a coated form which provides in-product stability.
  • Potassium peroxymonopersulfate is another inorganic perhydrate salt of utility herein.
  • Typical organic bleaches are organic peroxyacids, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid, and diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid are also suitable herein. Diacyl and Tetraacylperoxides, for instance dibenzoyl peroxide and dilauroyl peroxide, are other organic peroxides that can be used in the context of this invention.
  • organic bleaches include the peroxyacids, particular examples being the alkylperoxy acids and the arylperoxy acids.
  • Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid[phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, dip
  • Bleach activators are typically organic peracid precursors that enhance the bleaching action in the course of cleaning at temperatures of 60° C and below.
  • Bleach activators suitable for use herein include compounds which, under perhydrolysis conditions, give aliphatic peroxoycarboxylic acids having preferably from 1 to 12 carbon atoms, in particular from 2 to 10 carbon atoms, and/or optionally substituted perbenzoic acid. Suitable substances bear O-acyl and/or N-acyl groups of the number of carbon atoms specified and/or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), decanoyloxybenzoic acid (DOBA), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-diacet
  • the composition herein preferably contains a bleach catalyst, preferably a metal containing bleach catalyst. More preferably the metal containing bleach catalyst is a transition metal containing bleach catalyst, especially a manganese or cobalt-containing bleach catalyst.
  • Bleach catalysts preferred for use herein include the manganese triazacyclononane and related complexes ( US-A-4246612 , US-A-5227084 ); Co, Cu, Mn and Fe bispyridylamine and related complexes ( US-A-5114611 ); and pentamine acetate cobalt(III) and related complexes( US-A-4810410 ).
  • a complete description of bleach catalysts suitable for use herein can be found in WO 99/06521 , pages 34, line 26 to page 40, line 16.
  • Manganese bleach catalysts are preferred for use in the composition of the invention.
  • Especially preferred catalyst for use here is a dinuclear manganese-complex having the general formula: wherein Mn is manganese which can individually be in the III or IV oxidation state; each x represents a coordinating or bridging species selected from the group consisting of H2O, O22-, O2-, OH-, HO2-, SH-, S2-, >SO, Cl-, N3-, SCN-, RCOO-, NH2- and NR3, with R being H, alkyl or aryl, (optionally substituted); L is a ligand which is an organic molecule containing a number of nitrogen atoms which coordinates via all or some of its nitrogen atoms to the manganese centres; z denotes the charge of the complex and is an integer which can be positive or negative; Y is a monovalent or multivalent counter-ion, leading to charge neutrality, which is dependent upon the charge z of the complex; and
  • Preferred manganese-complexes are those wherein x is either CH 3 COO - or O 2 or mixtures thereof, most preferably wherein the manganese is in the IV oxidation state and x is O 2- .
  • Preferred ligands are those which coordinate via three nitrogen atoms to one of the manganese centres, preferably being of a macrocyclic nature. Particularly preferred ligands are:
  • the type of counter-ion Y for charge neutrality is not critical for the activity of the complex and can be selected from, for example, any of the following counter-ions: chloride; sulphate; nitrate; methylsulphate; surfactant anions, such as the long-chain alkylsulphates, alkylsulphonates, alkylbenzenesulphonates, tosylate, trifluoromethylsulphonate, perchlorate (ClO 4 - ), BPh 4 - , and PF 6 - ' though some counter-ions are more preferred than others for reasons of product property and safety.
  • the preferred manganese complexes useable in the present invention are:
  • the composition of the invention comprises from 0.001 to 1, more preferably from 0.002 to 0.01 grams of bleach catalyst.
  • the bleach catalyst is a manganese bleach catalyst.
  • the composition of the invention preferably comprises an inorganic builder.
  • Suitable inorganic builders are selected from the group consisting of carbonate, silicate and mixtures thereof. Especially preferred for use herein are sodium carbonate and silicate.
  • the composition of the invention comprises from 1 to 8, more preferably from 2 to 6 and especially from 3 to 5 grams of sodium carbonate and from 0.05 to 2 grams of silicate.
  • Surfactants suitable for use herein include non-ionic surfactants, preferably the compositions are free of any other surfactants.
  • non-ionic surfactants have been used in automatic dishwashing for surface modification purposes in particular for sheeting to avoid filming and spotting and to improve shine. It has been found that non-ionic surfactants can also contribute to prevent redeposition of soils.
  • the composition of the invention comprises a non-ionic surfactant or a non-ionic surfactant system, more preferably the non-ionic surfactant or a non-ionic surfactant system has a phase inversion temperature, as measured at a concentration of 1% in distilled water, between 40 and 70°C, preferably between 45 and 65°C.
  • a non-ionic surfactant system is meant herein a mixture of two or more non-ionic surfactants.
  • Preferred for use herein are non-ionic surfactant systems. They seem to have improved cleaning and finishing properties and better stability in product than single non-ionic surfactants.
  • Phase inversion temperature is the temperature below which a surfactant, or a mixture thereof, partitions preferentially into the water phase as oil-swollen micelles and above which it partitions preferentially into the oil phase as water swollen inverted micelles. Phase inversion temperature can be determined visually by identifying at which temperature cloudiness occurs.
  • phase inversion temperature of a non-ionic surfactant or system can be determined as follows: a solution containing 1% of the corresponding surfactant or mixture by weight of the solution in distilled water is prepared. The solution is stirred gently before phase inversion temperature analysis to ensure that the process occurs in chemical equilibrium. The phase inversion temperature is taken in a thermostable bath by immersing the solutions in 75 mm sealed glass test tube. To ensure the absence of leakage, the test tube is weighed before and after phase inversion temperature measurement. The temperature is gradually increased at a rate of less than 1°C per minute, until the temperature reaches a few degrees below the pre-estimated phase inversion temperature. Phase inversion temperature is determined visually at the first sign of turbidity.
  • Suitable nonionic surfactants include: i) ethoxylated non-ionic surfactants prepared by the reaction of a monohydroxy alkanol or alkyphenol with 6 to 20 carbon atoms with preferably at least 12 moles particularly preferred at least 16 moles, and still more preferred at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol; ii) alcohol alkoxylated surfactants having a from 6 to 20 carbon atoms and at least one ethoxy and propoxy group. Preferred for use herein are mixtures of surfactants i) and ii).
  • the surfactant of formula I at least about 10 carbon atoms in the terminal epoxide unit [CH2CH(OH)R2].
  • Suitable surfactants of formula I are Olin Corporation's POLY-TERGENT® SLF-18B nonionic surfactants, as described, for example, in WO 94/22800, published October 13, 1994 by Olin Corporation.
  • Amine oxides surfactants are useful for use in the composition of the invention. Preferred are C10-C18 alkyl dimethylamine oxide, and C10-18 acylamido alkyl dimethylamine oxide.
  • Surfactants may be present in amounts from 0.1 to 10, more preferably from 0.5 to 5 and especially from 0.8 to 3 grams.
  • Suitable proteases include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisins (EC 3.4.21.62) as well as chemically or genetically modified mutants thereof.
  • Suitable proteases include subtilisins (EC 3.4.21.62), including those derived from Bacillus, such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii.
  • Especially preferred proteases for the detergent of the invention are polypeptides demonstrating at least 90%, preferably at least 95%, more preferably at least 98%, even more preferably at least 99% and especially 100% identity with the wild-type enzyme from Bacillus lentus, comprising mutations in one or more, preferably two or more and more preferably three or more of the following positions, using the BPN' numbering system and amino acid abbreviations as illustrated in WO00/37627 , which is incorporated herein by reference:V68A, N87S, S99D, S99SD, S99A, S101G, S101M, S103A, V104N/I, G118V, G118R, S128L, P129Q, S130A, Y167A, R170S, A194P, V205I and/or M222S.
  • protease is selected from the group comprising the below mutations (BPN' numbering system) versus either the PB92 wild-type (SEQ ID NO:2 in WO 08/010925 ) or the subtilisin 309 wild-type (sequence as per PB92 backbone, except comprising a natural variation of N87S).
  • Suitable commercially available protease enzymes include those sold under the trade names Savinase®, Polarzyme®, Kannase®, Ovozyme®, Everlase® and Esperase® by Novozymes A/S (Denmark), those sold under the tradename Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®, Excellase®, Ultimase® and Purafect OXP® by Genencor International, those sold under the tradename Opticlean® and Optimase® by Solvay Enzymes, those available from Henkel/ Kemira, namely BLAP.
  • Preferred levels of protease in the product of the invention include from about 0.1 to about 50, more preferably from about 1 to about 45 and especially from about 10 to about 40 mg of active protease.
  • Preferred enzyme for use herein includes alpha-amylases, including those of bacterial or fungal origin. Chemically or genetically modified mutants (variants) are included.
  • a preferred alkaline alpha-amylase is derived from a strain of Bacillus, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis, or other Bacillus sp., such as Bacillus sp. NCIB 12289, NCIB 12512, NCIB 12513, DSM 9375 (USP 7,153,818 ) DSM 12368, DSMZ no. 12649, KSM AP1378 ( WO 97/00324 ), KSM K36 or KSM K38 ( EP 1,022,334 ).
  • Preferred amylases include:
  • alpha-amylases include DURAMYL®, LIQUEZYME®, TERMAMYL®, TERMAMYL ULTRA®, NATALASE®, SUPRAMYL®, STAINZYME®, STAINZYME PLUS®, POWERASE®, FUNGAMYL® and BAN® (Novozymes A/S, Bagsvaerd, Denmark), KEMZYM® AT 9000 Biozym Biotech Trading GmbH Wehlistrasse 27b A-1200 Wien Austria, RAPIDASE®, PURASTAR®, ENZYSIZE®, OPTISIZE HT PLUS® and PURASTAR OXAM® (Genencor International Inc., Palo Alto, California) and KAM® (Kao, 14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku Tokyo 103-8210, Japan). Amylases especially preferred for use herein include NATALASE®, STAINZYME®, STAINZYME PLUS®, POWER
  • the product of the invention comprises at least 0.01 mg, preferably from about 0.05 to about 10, more preferably from about 0.1 to about 6, especially from about 0.2 to about 5 mg of active amylase.
  • Additional enzymes suitable for use in the product of the invention can comprise one or more enzymes selected from the group comprising hemicellulases, cellulases, cellobiose dehydrogenases, peroxidases, proteases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, amylases, and mixtures thereof.
  • the protease and/or amylase of the product of the invention are in the form of granulates, the granulates comprise less than 29% of sodium sulfate by weight of the granulate or the sodium sulfate and the active enzyme (protease and/or amylase) are in a weight ratio of less than 4:1.
  • Crystal growth inhibitors are materials that can bind to calcium carbonate crystals and prevent further growth of species such as aragonite and calcite.
  • HEDP (1-hydroxyethylidene 1,1-diphosphonic acid).
  • the composition of the invention comprises from 0.01 to 1, more preferably from 0.05 to 0.8 grams of a crystal growth inhibitor, preferably HEDP.
  • Metal care agents may prevent or reduce the tarnishing, corrosion or oxidation of metals, including aluminium, stainless steel and non-ferrous metals, such as silver and copper.
  • the composition of the invention comprises from 0.001 to 0.01, more preferably from 0.002 to 0.009 grams, preferably the metal care agent is benzo triazole (BTA).
  • composition of the invention comprises from 0.001 to 1, more preferably from 0.002 to 0.5 grams of a glass care agent, preferably the glass care agent is a zinc salt.
  • Two dual-compartment automatic dishwashing pouches were made comprising the ingredients detailed herein below (Comparative composition 1 and composition 2).
  • the pouches were made of polyvinyl alcohol (Monosol 8630 available from Kuraray) with the solid and liquid components in different compartments.
  • composition 1 Composition 2 Solid compartment Sodium carbonate 6.42 6.42 Sodium silicate 2R 0.14 0.14 MGDA 2.84 3.58 Sodium percarbonate 0.94 0.94 Sulfonated polymer 1.07 1.07 Protease 0.035 0.035 Amylase 0.009 0.009 Bleach catalyst 0.001 0.001 Miscellaneous Balance to 13.84 Balance to 13.84 Liquid compartment Lutensol TO7 0.70 0.70 Plurafac SLF-180 1.00 1.00 Miscellaneous Balance to 2.1300 Balance to 2.1300 MGDA Tri-sodium salt of methyl glycine diacetic acid Protease Ultimase ® Supplied by Dupont Amylase Stainzyme Plus ® Supplied by Novozymes Lutensol TO7 Nonionic surfactant supplied by BASF Plurafac SLF-180 Nonionic surfactant supplied by BASF
  • the cleaning power of the compositions was assessed by running a performance test containing baked-on /burnt-on soils. Two different burnt soils were tested: Burnt egg in ceramic containers and burnt Macaroni and Cheese in stainless steel pots.
  • Each dishwashing machine is then loaded with two egg bowls and two mac and cheese pans in the bottom basket and clean ballast dishes.
  • the test was executed using Maytag dishwasher in a normal light cycle setting, without prewash.
  • the inlet water was preheated in a storage tank to 50°C and had a 127 ppm of CaCO 3 as hardness; additional 50g of TMD soil were added from frozen at the start of the wash.
  • the test is repeated three more times for each composition.
  • washed egg ceramic bowls are then stained by pouring 100mL of a talcum powder/safranin O solution (1.275g of talcum powder and 0.225g of Safranin O are dissolved in 3L of water) into the dish, swirling around until any residue is stained.
  • the solution can be reused in the next washed egg bowl.
  • the items are then visually graded by three independent judges using a scale from 1 to 10, where 1 is the most soiled and 10 is the cleanest.

Claims (11)

  1. Utilisation de 3 grammes à 6 grammes du sel trisodique d'acide méthyl-glycine diacétique dans une composition détergente enzymatique de lavage automatique de la vaisselle comprenant de 0,1 à 50 mg de protéase active et un agent de blanchiment pour l'élimination de salissures brûlées passées au four contenant des protéines, de la vaisselle dans un lavage automatique de la vaisselle.
  2. Utilisation selon la revendication 1, dans laquelle la composition est sous forme de dose unitaire.
  3. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle la composition détergente est sans phosphate.
  4. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle la composition détergente comprend un catalyseur de blanchiment.
  5. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle le catalyseur de blanchiment est à base de manganèse.
  6. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle la composition détergente comprend un inhibiteur de la cristallogenèse.
  7. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle la composition détergente comprend un agent tensioactif non ionique.
  8. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle la composition détergente a un pH égal ou supérieur à 9 à 12 tel que mesuré dans une solution aqueuse à 1 % en poids/volume à 20 °C.
  9. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle la composition détergente a une alcalinité de réserve égale ou supérieure à 10 à 20 à un pH de 9,5 telle que mesurée dans NaOH avec 100 grammes de produit à 20 °C.
  10. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle la composition détergente est sous forme de dose unitaire, de préférence sous la forme d'un paquet à compartiments multiples enveloppé par un film d'alcool polyvinylique ayant une épaisseur inférieure à 100 µm.
  11. Utilisation selon la revendication précédente, dans laquelle le poids de la dose unitaire va de 10 à 25 grammes.
EP15153520.0A 2015-02-02 2015-02-02 Nouvelle utilisation d'un agent complexant Active EP3050948B1 (fr)

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EP15153520.0A EP3050948B1 (fr) 2015-02-02 2015-02-02 Nouvelle utilisation d'un agent complexant
PCT/US2016/015903 WO2016126580A1 (fr) 2015-02-02 2016-02-01 Nouvelle utilisation d'un agent complexant
JP2017540727A JP2018505280A (ja) 2015-02-02 2016-02-01 錯化剤の新規な使用
JP2019204197A JP2020037703A (ja) 2015-02-02 2019-11-11 錯化剤の新規な使用

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EP3418366A1 (fr) * 2017-06-19 2018-12-26 The Procter & Gamble Company Composition de nettoyage pour lave-vaisselle automatique
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EP3828255B1 (fr) * 2019-11-29 2023-11-22 Henkel AG & Co. KGaA Produit détergent à chambres multiples à contraste élevé entre les chambres
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