EP3050948A1 - Nouvelle utilisation d'un agent complexant - Google Patents

Nouvelle utilisation d'un agent complexant Download PDF

Info

Publication number
EP3050948A1
EP3050948A1 EP15153520.0A EP15153520A EP3050948A1 EP 3050948 A1 EP3050948 A1 EP 3050948A1 EP 15153520 A EP15153520 A EP 15153520A EP 3050948 A1 EP3050948 A1 EP 3050948A1
Authority
EP
European Patent Office
Prior art keywords
use according
detergent composition
grams
acid
complexing 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.)
Granted
Application number
EP15153520.0A
Other languages
German (de)
English (en)
Other versions
EP3050948B1 (fr
Inventor
Glenn Steven Ward
Melissa Cuthbertson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=52432753&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP3050948(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
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
Application granted granted Critical
Publication of EP3050948B1 publication Critical patent/EP3050948B1/fr
Priority to JP2019204197A priority patent/JP2020037703A/ja
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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, preferably methyl glycine diacetic acid, in an automatic dishwashing detergent composition. It has been unexpectedly found that the complexing agent, preferably methyl glycine diacetic acid, improves the removal of baked-on burnt-on soils from dishware.
  • the composition comprises about 3 grams to about 6 grams, more preferably from about 3.5 grams to about 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 is preferably selected from the group consisting of methyl-glycine-diacetic acid (MGDA), its salts and derivatives thereof, glutamic-N,N- diacetic acid (GLDA), its salts and derivatives thereof, iminodisuccinic acid (IDS), its salts and derivatives thereof, carboxy methyl inulin, its salts and derivatives thereof and mixtures thereof.
  • MGDA methyl-glycine-diacetic acid
  • GLDA glutamic-N,N- diacetic acid
  • IDS iminodisuccinic acid
  • Especially preferred complexing agent for use herein is selected from the group consisting of MGDA and salts thereof, especially preferred for use herein is the three sodium salt of MGDA.
  • the composition comprises a high level of protease, from about 0.1 to about 50 mg of active protease, more preferably from about 0.1 to about 40 mg of active protease. It seems that the combination of the level of the complexing agent of the composition of the invention, in particular 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
  • a Ag/AgCl electrode for example an Orion sure flow Electrode model 9172BN
  • 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 reserve alkalinity is calculated in the following fashion:
  • 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.
  • a method of removing baked-on burnt-on soils, preferable proteinaceous based soils, from dishware in automatic dishwasher comprising the following steps:
  • composition of the invention described herein apply mutatis mutandis to the use and method aspects of the invention.
  • 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, 022-, 02-, 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).
  • R10 is a linear or branched, aliphatic hydrocarbon radical having from 4 to 18 carbon atoms
  • R2 is a linear or branched aliphatic hydrocarbon radical having from 2 to 26 carbon atoms
  • x is an integer having an average value of from 0.5 to 1.5, more preferably about 1
  • y is an integer having a value of at least 15, more preferably at least 20.
  • 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:
  • Suitable commercially available 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®,
  • 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, ß-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.
  • composition 1 and Composition 2 Two dual-compartment automatic dishwashing pouches were made comprising the ingredients detailed herein below (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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP15153520.0A 2015-02-02 2015-02-02 Nouvelle utilisation d'un agent complexant Active EP3050948B1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
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

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP15153520.0A EP3050948B1 (fr) 2015-02-02 2015-02-02 Nouvelle utilisation d'un agent complexant

Publications (2)

Publication Number Publication Date
EP3050948A1 true EP3050948A1 (fr) 2016-08-03
EP3050948B1 EP3050948B1 (fr) 2018-09-19

Family

ID=52432753

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15153520.0A Active EP3050948B1 (fr) 2015-02-02 2015-02-02 Nouvelle utilisation d'un agent complexant

Country Status (3)

Country Link
EP (1) EP3050948B1 (fr)
JP (2) JP2018505280A (fr)
WO (1) WO2016126580A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108499367A (zh) * 2018-02-11 2018-09-07 湖南华菱节能环保科技有限公司 一种陶瓷膜清洗剂及其制备方法
EP3418366A1 (fr) * 2017-06-19 2018-12-26 The Procter & Gamble Company Composition de nettoyage pour lave-vaisselle automatique
EP3418365A1 (fr) * 2017-06-19 2018-12-26 The Procter & Gamble Company Composition de nettoyage pour lave-vaisselle automatique
EP3418364A1 (fr) * 2017-06-19 2018-12-26 The Procter & Gamble Company Composition de nettoyage pour lave-vaisselle automatique
US10472594B2 (en) 2017-04-11 2019-11-12 Itaconix Corporation Sulfonated copolymers for detergent composition
WO2020106917A1 (fr) * 2018-11-21 2020-05-28 Henkel IP & Holding GmbH Dosettes de détergent renfermant des formulations anti-jaunissement et anti-efflorescence

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3828255B1 (fr) * 2019-11-29 2023-11-22 Henkel AG & Co. KGaA Produit détergent à chambres multiples à contraste élevé entre les chambres
EP4012011A1 (fr) * 2020-12-14 2022-06-15 Henkel AG & Co. KGaA Détergeant, en particulier pour un robot de cuisine
EP4286500A1 (fr) * 2022-06-01 2023-12-06 The Procter & Gamble Company Utilisation de xylanase dans un processus de lavage de vaisselle

Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4246612A (en) 1979-02-28 1981-01-20 Barr & Stroud Limited Optical raster scanning system
US4810410A (en) 1986-12-13 1989-03-07 Interox Chemicals Limited Bleach activation
EP0458397A2 (fr) 1990-05-21 1991-11-27 Unilever N.V. Activation du blanchiment
US5114611A (en) 1989-04-13 1992-05-19 Lever Brothers Company, Divison Of Conopco, Inc. Bleach activation
US5227084A (en) 1991-04-17 1993-07-13 Lever Brothers Company, Division Of Conopco, Inc. Concentrated detergent powder compositions
WO1994022800A1 (fr) 1993-04-05 1994-10-13 Olin Corporation Tensioactifs biodegradables peu moussants pour lave-vaisselle
WO1996023873A1 (fr) 1995-02-03 1996-08-08 Novo Nordisk A/S Alleles d'amylase-alpha
WO1997000324A1 (fr) 1995-06-14 1997-01-03 Kao Corporation Gene codant une alpha-amylase liquefiante alcaline
US5856164A (en) 1994-03-29 1999-01-05 Novo Nordisk A/S Alkaline bacillus amylase
WO1999006521A1 (fr) 1997-08-02 1999-02-11 The Procter & Gamble Company Pastille detergente
WO1999023211A1 (fr) 1997-10-30 1999-05-14 Novo Nordisk A/S Mutants d'alpha-amylase
US6093562A (en) 1996-02-05 2000-07-25 Novo Nordisk A/S Amylase variants
EP1022334A2 (fr) 1998-12-21 2000-07-26 Kao Corporation Nouvelles amylases
WO2000060060A2 (fr) 1999-03-31 2000-10-12 Novozymes A/S Polypeptides presentant une activite alcaline alpha-amylase et acides nucleiques les codant
WO2006002643A2 (fr) 2004-07-05 2006-01-12 Novozymes A/S Variants d'alpha-amylases presentant des proprietes modifiees
US7153818B2 (en) 2000-07-28 2006-12-26 Henkel Kgaa Amylolytic enzyme extracted from bacillus sp. A 7-7 (DSM 12368) and washing and cleaning agents containing this novel amylolytic enzyme
WO2007052004A1 (fr) * 2005-11-07 2007-05-10 Reckitt Benckiser N.V. Cartouche de distribution
WO2007141527A1 (fr) * 2006-06-07 2007-12-13 Reckitt Benckiser N. V. Composition détergente
WO2008010925A2 (fr) 2006-07-18 2008-01-24 Danisco Us, Inc., Genencor Division Variantes de protéases actives sur une large plage de températures
EP2166092A1 (fr) * 2008-09-18 2010-03-24 The Procter and Gamble Company Composition de détergent
WO2011130076A1 (fr) * 2010-04-15 2011-10-20 The Procter & Gamble Company Composition détergente pour le lavage de la vaisselle en machine
WO2015086410A1 (fr) * 2013-12-10 2015-06-18 Henkel Ag & Co. Kgaa Amplificateur du pouvoir nettoyant de lessives pour lave-vaisselle

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2311542A (en) 1996-03-29 1997-10-01 Procter & Gamble Percarbonate bleach composition
WO2002092751A2 (fr) * 2001-05-14 2002-11-21 The Procter & Gamble Company Produit de nettoyage
EP1721962B1 (fr) 2005-05-11 2008-08-13 Unilever N.V. Compositions detergentes pour lave vaisselle et procédé pour nettoyer la vaiselle
DE102005041349A1 (de) * 2005-08-31 2007-03-01 Basf Ag Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophil modifizierte Polycarboxylate
KR20090048455A (ko) * 2006-08-10 2009-05-13 바스프 에스이 식기 세척기용 세정 제제
GB0915572D0 (en) 2009-09-07 2009-10-07 Reckitt Benckiser Nv Detergent composition
KR20120129946A (ko) * 2010-02-09 2012-11-28 바스프 에스이 세제 조성물
JP5952825B2 (ja) * 2010-11-23 2016-07-13 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 洗剤及び清浄剤へのスケール防止添加剤として使用するカルボン酸基、スルホン酸基及びポリアルキレンオキシド基を含有するコポリマー
US8987183B2 (en) 2011-01-13 2015-03-24 Basf Se Use of optionally oxidized thioethers of polyalkylene oxides in washing and cleaning compositions
RU2015102082A (ru) 2012-07-27 2016-09-20 Као Корпорейшн Детергентная композиция для посуды
DE102012215107A1 (de) * 2012-08-24 2014-02-27 Basf Se Festes Geschirrspülmittel mit verbesserter Proteaseleistung
JP6027877B2 (ja) * 2012-12-12 2016-11-16 花王株式会社 自動食器洗浄機用洗浄剤組成物
EP2746381A1 (fr) 2012-12-21 2014-06-25 The Procter & Gamble Company Kit de nettoyage
JP2016530348A (ja) * 2013-07-04 2016-09-29 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 食器の洗浄方法

Patent Citations (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4246612A (en) 1979-02-28 1981-01-20 Barr & Stroud Limited Optical raster scanning system
US4810410A (en) 1986-12-13 1989-03-07 Interox Chemicals Limited Bleach activation
US5114611A (en) 1989-04-13 1992-05-19 Lever Brothers Company, Divison Of Conopco, Inc. Bleach activation
EP0458397A2 (fr) 1990-05-21 1991-11-27 Unilever N.V. Activation du blanchiment
EP0458398A2 (fr) 1990-05-21 1991-11-27 Unilever N.V. Activation du blanchiment
US5227084A (en) 1991-04-17 1993-07-13 Lever Brothers Company, Division Of Conopco, Inc. Concentrated detergent powder compositions
WO1994022800A1 (fr) 1993-04-05 1994-10-13 Olin Corporation Tensioactifs biodegradables peu moussants pour lave-vaisselle
US5856164A (en) 1994-03-29 1999-01-05 Novo Nordisk A/S Alkaline bacillus amylase
WO1996023873A1 (fr) 1995-02-03 1996-08-08 Novo Nordisk A/S Alleles d'amylase-alpha
WO1997000324A1 (fr) 1995-06-14 1997-01-03 Kao Corporation Gene codant une alpha-amylase liquefiante alcaline
US6093562A (en) 1996-02-05 2000-07-25 Novo Nordisk A/S Amylase variants
WO1999006521A1 (fr) 1997-08-02 1999-02-11 The Procter & Gamble Company Pastille detergente
WO1999023211A1 (fr) 1997-10-30 1999-05-14 Novo Nordisk A/S Mutants d'alpha-amylase
EP1022334A2 (fr) 1998-12-21 2000-07-26 Kao Corporation Nouvelles amylases
WO2000060060A2 (fr) 1999-03-31 2000-10-12 Novozymes A/S Polypeptides presentant une activite alcaline alpha-amylase et acides nucleiques les codant
US7153818B2 (en) 2000-07-28 2006-12-26 Henkel Kgaa Amylolytic enzyme extracted from bacillus sp. A 7-7 (DSM 12368) and washing and cleaning agents containing this novel amylolytic enzyme
WO2006002643A2 (fr) 2004-07-05 2006-01-12 Novozymes A/S Variants d'alpha-amylases presentant des proprietes modifiees
WO2007052004A1 (fr) * 2005-11-07 2007-05-10 Reckitt Benckiser N.V. Cartouche de distribution
WO2007141527A1 (fr) * 2006-06-07 2007-12-13 Reckitt Benckiser N. V. Composition détergente
WO2008010925A2 (fr) 2006-07-18 2008-01-24 Danisco Us, Inc., Genencor Division Variantes de protéases actives sur une large plage de températures
EP2166092A1 (fr) * 2008-09-18 2010-03-24 The Procter and Gamble Company Composition de détergent
WO2011130076A1 (fr) * 2010-04-15 2011-10-20 The Procter & Gamble Company Composition détergente pour le lavage de la vaisselle en machine
WO2015086410A1 (fr) * 2013-12-10 2015-06-18 Henkel Ag & Co. Kgaa Amplificateur du pouvoir nettoyant de lessives pour lave-vaisselle

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10472594B2 (en) 2017-04-11 2019-11-12 Itaconix Corporation Sulfonated copolymers for detergent composition
EP3418366A1 (fr) * 2017-06-19 2018-12-26 The Procter & Gamble Company Composition de nettoyage pour lave-vaisselle automatique
EP3418365A1 (fr) * 2017-06-19 2018-12-26 The Procter & Gamble Company Composition de nettoyage pour lave-vaisselle automatique
EP3418364A1 (fr) * 2017-06-19 2018-12-26 The Procter & Gamble Company Composition de nettoyage pour lave-vaisselle automatique
WO2018236810A1 (fr) * 2017-06-19 2018-12-27 The Procter & Gamble Company Composition de nettoyage pour lave-vaisselle automatique
WO2018236841A1 (fr) * 2017-06-19 2018-12-27 The Procter & Gamble Company Composition de nettoyage pour lave-vaisselle automatique
CN108499367A (zh) * 2018-02-11 2018-09-07 湖南华菱节能环保科技有限公司 一种陶瓷膜清洗剂及其制备方法
WO2020106917A1 (fr) * 2018-11-21 2020-05-28 Henkel IP & Holding GmbH Dosettes de détergent renfermant des formulations anti-jaunissement et anti-efflorescence

Also Published As

Publication number Publication date
EP3050948B1 (fr) 2018-09-19
JP2018505280A (ja) 2018-02-22
WO2016126580A1 (fr) 2016-08-11
JP2020037703A (ja) 2020-03-12

Similar Documents

Publication Publication Date Title
EP3050948B1 (fr) Nouvelle utilisation d'un agent complexant
EP3050953B1 (fr) Composition de détergent
US10633615B2 (en) Automatic dishwashing cleaning composition
EP3026103B1 (fr) Poche de nettoyage
WO2018118745A1 (fr) Composition pour lave-vaisselle automatique
EP3050950B1 (fr) Nouvelle utilisation de polymères sulfonés
US20180105770A1 (en) Detergent composition
US20190048290A1 (en) Automatic dishwashing composition
EP3530723B1 (fr) Composition pour lave-vaisselle automatique
WO2016126567A1 (fr) Nouvelle utilisation des polymères sulfonés
WO2018236810A1 (fr) Composition de nettoyage pour lave-vaisselle automatique
EP4108150B1 (fr) Procédé de traitement de la vaisselle dans un lave-vaisselle domestique automatique
EP3456808A1 (fr) Composition de nettoyage pour lave-vaisselle automatique
US20200224125A1 (en) Automatic dishwashing cleaning composition

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20170202

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20180404

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1043274

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181015

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602015016419

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20180919

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181220

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181219

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180919

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180919

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180919

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181219

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180919

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180919

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180919

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180919

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1043274

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180919

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190119

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180919

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180919

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180919

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180919

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180919

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180919

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180919

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180919

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180919

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190119

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180919

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602015016419

Country of ref document: DE

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: HENKEL AG & CO. KGAA

Effective date: 20190618

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180919

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180919

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180919

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190202

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20190228

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190228

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190228

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180919

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190202

PLCK Communication despatched that opposition was rejected

Free format text: ORIGINAL CODE: EPIDOSNREJ1

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180919

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20150202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180919

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230429

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

REG Reference to a national code

Ref country code: DE

Ref legal event code: R100

Ref document number: 602015016419

Country of ref document: DE

PLBN Opposition rejected

Free format text: ORIGINAL CODE: 0009273

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: OPPOSITION REJECTED

27O Opposition rejected

Effective date: 20230628

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20231229

Year of fee payment: 10

Ref country code: GB

Payment date: 20240108

Year of fee payment: 10