EP2674476B1 - Wasch- und Reinigungsmittel - Google Patents
Wasch- und Reinigungsmittel Download PDFInfo
- Publication number
- EP2674476B1 EP2674476B1 EP13171413.1A EP13171413A EP2674476B1 EP 2674476 B1 EP2674476 B1 EP 2674476B1 EP 13171413 A EP13171413 A EP 13171413A EP 2674476 B1 EP2674476 B1 EP 2674476B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mixtures
- group
- enzyme
- detergent composition
- composition according
- 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.)
- Active
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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/382—Vegetable products, e.g. soya meal, wood flour, sawdust
-
- 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
- C11D3/38672—Granulated or coated enzymes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—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
- C11D3/395—Bleaching agents
Definitions
- This invention relates to detergent compositions comprising more than one enzyme as well as methods of making and using such detergents.
- IPCOM000200739D it is disclosed that uniform enzyme granule distribution can be improved by incorporating two or more enzymes combined in one co-granule. Each enzyme will then be present in more granules securing a more uniform distribution of enzymes in the detergent. This also reduces the physical segregation of different enzymes due to different particle sizes.
- WO94/16064 and WO94/16064 describe enzyme co-granules.
- US3451935 describes powdered enzyme attached to a granular carrier.
- US2008/0206830 describes a low dust enzyme-granule.
- GB2085937A describes an enzyme-containing bleaching composition containing anhydrous salts.
- US5318714 describes particles containing enzyme or optical brightener in a bleach composition stabilized by coating with clay.
- interaction between enzymes in an enzyme cogranule can lead to loss of enzyme activity, in particular when one of the enzymes is protease. This problem is particularly acute in detergent compositions comprising low levels of typical strong builders i.e. zeolite and phosphate builders.
- the present invention relates to a detergent composition
- a detergent composition comprising (a) a multi-enzyme co-granule; (b) less than 10 wt% zeolite (anhydrous basis); and (c) less than 10 wt% phosphate salt (anhydrous basis), wherein said enzyme co-granule comprises at least one protease enzyme and from 10 to 98 wt% moisture sink component selected from the group consisting of (a) hydratable salts, (b) dessicated clays, (c) bio-filler and (d) mixtures thereof and the composition additionally comprises from 20 to 80 wt% detergent moisture sink component selected from the group consisting of (a) hydratable sulphate salts, (b) dessicated clays, (c) bio-filler and (d) mixtures thereof.
- the invention also relates to a method of treating and/or cleaning a surface, preferably a fabric surface comprising the steps of (i) contacting said surface with the detergent composition as claimed and described herein in an aqueous wash liquor, (ii) rinsing and/or drying the surface.
- aqueous wash liquor Preferably the temperature of the aqueous liquor is from 5 - 25°C and preferably the aqueous liquor comprises from 0.1g/l to 3g/l of surfactant.
- detergent composition means consumer and institutional products, including but not limited to cleaning and/or treatment compositions, particularly cleaning compositions for laundry, dishwashing, and hard surface cleaning products, other cleaners, and cleaning systems all for the care and cleaning of inanimate surfaces, as well as fabric conditioner products and other products designed specifically for the care and maintenance of fabrics.
- cleaning and/or treatment composition are generally intended to be used or consumed in the form in which they are sold.
- Such products include laundry and rinse additive and/or care, hard surface cleaning and/or treatment including floor and toilet bowl cleaners.
- the compositions of the invention are laundry or dish-washing detergents, most preferably laundry detergents.
- the compositions of the invention are solid i.e.
- a unit-dose detergent composition such as a tablet or pouch which may be single or multi-compartment. However, they may be liquid, gel or paste-form.
- a pouch the composition of the invention will be present within a water-soluble film.
- the pouch is multi-compartment, the composition of the invention will be present in one or more compartments. Further compositions, not in accordance with the invention may be provided in one or more further compartments of the multi-component pouch. All of such products which are applicable may be in standard, concentrated or even highly concentrated form even to the extent that such products may in certain aspect be non-aqueous.
- the multi-enzyme co-granule comprises at least two enzymes, or at least three or four or more enzymes, preferably selected from the group consisting of first-wash lipases, cleaning cellulases, xyloglucanases, perhydrolases, peroxidases, lipoxygenases, laccases, hemicellulases, proteases, care cellulases, cellobiose dehydrogenases, xylanases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, ligninases, pullulanases, tannases, pentosanases, lichenases glucanases, arabinosidases, hyaluronidase, chondroitinase, amylases, and mixtures thereof, wherein the enzyme co-granul
- the co-granule comprises (a) one or more enzymes selected from the group consisting of first-wash lipases, cleaning cellulases, xyloglucanases, perhydrolases, peroxidases, lipoxygenases, laccases and mixtures thereof.
- Preferred enzymes from group (a) are first wash lipases.
- the co-granule preferably comprises (b) one or more enzymes selected from the group consisting of hemicellulases, proteases, care cellulases, cellobiose dehydrogenases, xylanases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, ligninases, pullulanases, tannases, pentosanases, lichenases glucanases, arabinosidases, hyaluronidase, chondroitinase, amylases, and mixtures thereof.
- the co-granule comprises a protease enzyme.
- the co-granule comprises at least two enzymes, for example including:
- the amount of total active enzyme protein incorporated into the co-granule is typically delivers from 0.2 to 1.0wt% active enzyme in the detergent composition.
- the moisture sink component is present in the co-granule in amounts of from 10 to 98 wt% of the co-granule.
- the moisture sink material is herein understood a material that in its anhydrous form can take water to become hydrated and it can easily give up the hydration water when it is placed in a drier or warmer environment.
- the moisture sink materials for use in the composition of the invention have a difference in density between the anhydrous and hydrated form of at least 0.8 g/cm3, more preferably at least 1 g/cm3 and especially at least 1.2 g/cm3.
- This difference in densities provides a mechanism to break particle:particle crystal bridges that have formed as a result of water condensing as the powder temperature fell below the dew point associated with that powder.
- the hydrated material forming a crystal bridge between particles reverts to the anhydrous (or less hydrated) form.
- the higher crystal density associated with the anhydrous (or less hydrated) form provides a mechanism for breaking these crystal bridges due to the reduction in crystal volume. This allows that a period of low temperature does not negatively and permanently affect the structure of the powder and contributes to good handling properties of the composition.
- the moisture sink component is present in amounts from 30, 50 or even 60 wt% of the co-granule, up to 90 or 95 wt% based on the co-granule.
- suitable moisture sink components are capable of absorbing moisture.
- Moisture sink components are selected from the group consisting of (a) hydratable salts, (b) dessicated clays, (c) bio-filler, and (d) mixtures thereof.
- Useful as hydratable salts are typically sodium, calcium, magnesium salts, preferably sodium salts of carbonate, chloride, citrate and sulphate and mixtures thereof.
- Anhydrous sodium carbonate may be preferred.
- Light sodium carbonate may be preferred.
- suitable clays are talc, calcite, kaolin, dolomite and bentonite.
- Preferred dessicated clays have a moisture content of from 0.1 to 20 wt% free moisture, more preferably from 0.1 to 15 or even 0.1 to 10 or even 5 wt% free moisture;
- Suitable as bio-filler is any water soluble or water insoluble agricultural by-product. Examples of water-insoluble agricultural by-products are described in WO2007/147698 .
- Preferred bio-fillers have a moisture content of from 0.1 to 20 wt% free moisture, more preferably from 0.1 to 15 or even 0.1 to 10 wt% or even 5 wt% free moisture;
- the particle size of the moisture sink component is preferably such that at least 90 wt% of the particles of moisture sink component have a diameter less than 700 or even less than 500 or 300 or 250 microns or even less than 100 microns.
- the weight ratio of moisture sink component to active enzyme protein in the co-granule is preferably from 10: 1 or 20:1 or 50:1 or 10:1 up to 100:1 or 90:1 or 75:1.
- Suitable enzyme co-granules for use herein include those formed according to any of the below technologies:
- Preferred enzyme co-granules for use in the composition of the invention, have a core-shell structure.
- the core comprises a central part, preferably free of enzymes, and a surrounding layer containing enzymes and the shell comprises a plurality of layers, the most outer layer being a protective layer.
- the central part of the core and at least one of the layers of the shell comprise an moisture sink material.
- the central part of the core represents from 1% to 60%, more preferably from 3% to 50% and especially from 5% to 40% by weight of the total particle.
- the layer comprising the moisture sink material represents from 0.5% to 40%, more preferably from 1% to 30% and especially from 3% to 20% by weight of the total particle.
- the most outer layer comprises polyvinyl alcohol, more preferably titanium oxide (for aesthetic reasons) and especially a combination thereof.
- the protective layer represents from 0.05% to 20%, more preferably from 0.1% to 15% and especially from 1% to 3% by weight of the total particle.
- the enzyme granulate can also contain adjunct materials such as antioxidants, dyes, activators, solubilizers, binders, etc. Enzymes according to this embodiment can be made by a fluid bed layering process similar to that described in US 5,324,649 , US 6,602,841 B1 and US2008/0206830A1 .
- Enzymes according to this embodiment can also be made by a combination of processes.
- Such enzyme co-granules are built around a core that can be free of enzymes or contain enzymes (preferably comprising an moisture sink material, more preferably sodium sulphate) that can be made using a variety of processes including use of either a mixer granulator or an extruder.
- the cores are then treated in a fluid bed process wherein the enzyme is sprayed onto the core.
- the core is then coated by a layer, preferably comprising an moisture sink material, and more preferably sodium sulphate and finally is coated with a polymer selected from the group comprising hydroxpropylmethylcellulose and/or polyvinylalcohol and derivatives thereof, optionally also containing additional titanium dioxide, polyethylene glycol and/or kaolin or any mixtures thereof.
- a layer preferably comprising an moisture sink material, and more preferably sodium sulphate
- the granulate comprises from about 30% to about 75%, preferably from about 40 to about 50% by weight of the granulate of an moisture sink material, selected from the group comprising sodium sulphate, sodium citrate and mixtures thereof, preferably sodium sulphate.
- an moisture sink material selected from the group comprising sodium sulphate, sodium citrate and mixtures thereof, preferably sodium sulphate.
- the enzyme co-granules have a weight geometric mean particle size of from about 200 ⁇ m to about 1200 ⁇ m, more preferably from about 300 ⁇ m to about 1000 ⁇ m and especially from about 400 ⁇ m to about 600 ⁇ m.
- compositions of the invention comprise less than 10 wt% zeolite (anhydrous basis), more preferably less than 7 or 5 or even below 3wt% zeolite. Zeolite may even be completely absent from the detergent compositions of the invention.
- compositions of the invention comprise less than 10 wt% phosphate salt (anhydrous basis), more preferably less than 7 or 5 or even below 3wt% phosphate salt. Phosphate salts may even be completely absent from the detergent compositions of the invention.
- compositions of the invention comprise from 20 to 80 wt% detergent moisture sink, preferably from 25, or 30 or 35 or 40 wt% to 75 wt% detergent moisture sink.
- Suitable detergent moisture sink components are capable of absorbing moisture and are selected from the group consisting of (a) hydratable sulphate salts, (b) dessicated clays, (c) bio-filler, and (d) mixtures thereof.
- Useful salts are typically as hydratable sodium, calcium, magnesium salts of sulphate and mixtures thereof. Sodium sulphate is particularly preferred, most preferably in its anhydrous form. Light salts may also be preferred.
- suitable clays are talc, calcite, kaolin, dolomite and bentonite.
- Preferred dessicated clays have a moisture content of from 0.1 to 20 wt% free moisture, more preferably from 0.1 to 15 or even 0.1 to 10 or even 5 wt% free moisture.
- Suitable as bio-filler is any water soluble or water insoluble agricultural by-product. Examples of water-insoluble agricultural by-products are described in WO2007/147698 .
- Preferred bio-fillers have a moisture content of from 0.1 to 20 wt% free moisture, more preferably from 0.1 to 15 or even 0.1 to 10 wt% or even 5 wt% free moisture.
- Sodium sulphate is the most preferred detergent moisture sink component.
- the detergent moisture sink component may be dry-added to other detergent adjunct ingredients or may be incorporated into the detergent composition via a pre-formed particle such as an agglomerate or blown powder (particulate formed from a spray-drying process), or may be incorporated via a mixture of these routes.
- the detergent moisture sink component is incorporated into the detergent composition as a dry-added particulate component comprising at least 80 wt%, or even at least 90 wt% or even at least 95 wt% of the detergent moisture sink and in addition via a blown powder comprising from 15 to 70 wt%, or from 20 to 60 wt% based on the blown powder, of the detergent moisture sink component.
- the moisture sink component is incorporated via an agglomerate particle and/or blown powder particle such particle will comprise at least 10 wt% surfactant, based on the weight of the particle.
- the compostion will comprise dry-added sodium sulphate and blown powder and/or agglomerate, preferably blown powder, comprising sodium sulphate.
- the detergent composition additionally comprises a dye transfer inhibiting agent and/or a fabric hueing agents.
- the detergent compositions of the invention may comprise one or more (detergent) adjunct materials. These may enhance cleaning performance, for treatment of the substrate to be cleaned, or modify the aesthetics of the composition for example as is the case with perfumes, speckles, colorants, dyes or the like.
- the levels of any such adjuncts incorporated in the composition of the invention any fabric and home care product are in addition to any materials previously recited for incorporation. The precise nature of these additional components, and levels of incorporation thereof, will depend on the physical form of the consumer product and the nature of the cleaning operation for which it is to be used.
- Suitable adjunct materials include, but are not limited to, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, hueing dyes, perfumes, perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids, solvents and/or pigments. Examples of suitable adjuncts are described below. In addition to the disclosure below, suitable examples of such other adjuncts and levels of use are found in U.S. Patent Nos.
- the composition may comprise a fabric hueing agent.
- Suitable fabric hueing agents include dyes, dye-clay conjugates, and pigments.
- Suitable dyes include small molecule dyes and polymeric dyes.
- Suitable small molecule dyes include small molecule dyes selected from the group consisting of dyes falling into the Colour Index (C.I.) classifications of Direct Blue, Direct Red, Direct Violet, Acid Blue, Acid Red, Acid Violet, Basic Blue, Basic Violet and Basic Red, or mixtures thereof.
- suitable small molecule dyes include small molecule dyes selected from the group consisting of Colour Index (Society of Dyers and Colourists, Bradford, UK) numbers Direct Violet 9, Direct Violet 35, Direct Violet 48, Direct Violet 51, Direct Violet 66, Direct Violet 99, Direct Blue 1, Direct Blue 71, Direct Blue 80, Direct Blue 279, Acid Red 17, Acid Red 73, Acid Red 88, Acid Red 150, Acid Violet 15, Acid Violet 17, Acid Violet 24, Acid Violet 43, Acid Red 52, Acid Violet 49, Acid Blue 15, Acid Blue 17, Acid Blue 25, Acid Blue 29, Acid Blue 40, Acid Blue 45, Acid Blue 75, Acid Blue 80, Acid Blue 83, Acid Blue 90 and Acid Blue 113, Acid Black 1, Basic Violet 1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet 35, Basic Blue 3, Basic Blue 16, Basic Blue 22, Basic Blue 47, Basic Blue 66, Basic Blue 75, Basic Blue 159 and mixtures thereof.
- Colour Index Society of Dyers and Colourists, Bradford, UK
- suitable small molecule dyes include small molecule dyes selected from the group consisting of Colour Index (Society of Dyers and Colourists, Bradford, UK) numbers Acid Violet 17, Acid Violet 43, Acid Red 52, Acid Red 73, Acid Red 88, Acid Red 150, Acid Blue 25, Acid Blue 29, Acid Blue 45, Acid Blue 113, Acid Black 1, Direct Blue 1, Direct Blue 71, Direct Violet 51 and mixtures thereof.
- suitable small molecule dyes include small molecule dyes selected from the group consisting of Colour Index (Society of Dyers and Colourists, Bradford, UK) numbers Acid Violet 17, Direct Blue 71, Direct Violet 51, Direct Blue 1, Acid Red 88, Acid Red 150, Acid Blue 29, Acid Blue 113 or mixtures thereof.
- Suitable polymeric dyes include polymeric dyes selected from the group consisting of polymers containing conjugated chromogens (dye-polymer conjugates) and polymers with chromogens co-polymerized into the backbone of the polymer and mixtures thereof.
- suitable polymeric dyes include polymeric dyes selected from the group consisting of fabric-substantive colorants sold under the name of Liquitint® (Milliken, Spartanburg, South Carolina, USA), dye-polymer conjugates formed from at least one reactive dye and a polymer selected from the group consisting of polymers comprising a moiety selected from the group consisting of a hydroxyl moiety, a primary amine moiety, a secondary amine moiety, a thiol moiety and mixtures thereof.
- suitable polymeric dyes include polymeric dyes selected from the group consisting of Liquitint® (Milliken, Spartanburg, South Carolina, USA) Violet CT, carboxymethyl cellulose (CMC) conjugated with a reactive blue, reactive violet or reactive red dye such as CMC conjugated with C.I. Reactive Blue 19, sold by Megazyme, Wicklow, Ireland under the product name AZO-CM-CELLULOSE, product code S-ACMC, alkoxylated triphenyl-methane polymeric colourants, alkoxylated thiophene polymeric colourants, and mixtures thereof.
- Liquitint® Moquitint®
- CMC carboxymethyl cellulose
- a reactive blue, reactive violet or reactive red dye such as CMC conjugated with C.I. Reactive Blue 19, sold by Megazyme, Wicklow, Ireland under the product name AZO-CM-CELLULOSE
- product code S-ACMC alkoxylated triphenyl-methane polymeric colourants, alkoxylated
- Suitable dye clay conjugates include dye clay conjugates selected from the group comprising at least one cationic/basic dye and a smectite clay, and mixtures thereof.
- suitable dye clay conjugates include dye clay conjugates selected from the group consisting of one cationic/basic dye selected from the group consisting of C.I. Basic Yellow 1 through 108, C.I. Basic Orange 1 through 69, C.I. Basic Red 1 through 118, C.I. Basic Violet 1 through 51, C.I. Basic Blue 1 through 164, C.I. Basic Green 1 through 14, C.I. Basic Brown 1 through 23, CI Basic Black 1 through 11, and a clay selected from the group consisting of Montmorillonite clay, Hectorite clay, Saponite clay and mixtures thereof.
- suitable dye clay conjugates include dye clay conjugates selected from the group consisting of: Montmorillonite Basic Blue B7 C.I. 42595 conjugate, Montmorillonite Basic Blue B9 C.I. 52015 conjugate, Montmorillonite Basic Violet V3 C.I. 42555 conjugate, Montmorillonite Basic Green G1 C.I. 42040 conjugate, Montmorillonite Basic Red R1 C.I. 45160 conjugate, Montmorillonite C.I. Basic Black 2 conjugate, Hectorite Basic Blue B7 C.I. 42595 conjugate, Hectorite Basic Blue B9 C.I. 52015 conjugate, Hectorite Basic Violet V3 C.I.
- Suitable pigments include pigments selected from the group consisting of flavanthrone, indanthrone, chlorinated indanthrone containing from 1 to 4 chlorine atoms, pyranthrone, dichloropyranthrone, monobromodichloropyranthrone, dibromodichloropyranthrone, tetrabromopyranthrone, perylene-3,4,9,10-tetracarboxylic acid diimide, wherein the imide groups may be unsubstituted or substituted by C1-C3 -alkyl or a phenyl or heterocyclic radical, and wherein the phenyl and heterocyclic radicals may additionally carry substituents which do not confer solubility in water, anthrapyrimidinecarboxylic acid amides, violanthrone, isoviolanthrone, dioxazine pigments, copper phthalocyanine which may contain up to 2 chlorine atoms per molecule, polychloro
- suitable pigments include pigments selected from the group consisting of Ultramarine Blue (C.I. Pigment Blue 29), Ultramarine Violet (C.I. Pigment Violet 15) and mixtures thereof.
- the aforementioned fabric hueing agents can be used in combination (any mixture of fabric hueing agents can be used).
- Suitable fabric hueing agents can be purchased from Aldrich, Milwaukee, Wisconsin, USA; Ciba Specialty Chemicals, Basel, Switzerland; BASF, Ludwigshafen, Germany; Dayglo Color Corporation, Mumbai, India; Organic Dyestuffs Corp., East Buffalo, Rhode Island, USA; Dystar, Frankfurt, Germany; Lanxess, Leverkusen, Germany; Megazyme, Wicklow, Ireland; Clariant, Muttenz, Switzerland; Avecia, Manchester, UK and/or made in accordance with the examples contained herein. Suitable hueing agents are described in more detail in US 7,208,459 B2 .
- Encapsulates The composition may comprise an encapsulate.
- an encapsulate comprising a core, a shell having an inner and outer surface, said shell encapsulating said core.
- said core may comprise a material selected from the group consisting of perfumes; brighteners; dyes; insect repellants; silicones; waxes; flavors; vitamins; fabric softening agents; skin care agents in one aspect, paraffins; enzymes; antibacterial agents; bleaches; sensates; and mixtures thereof; and said shell may comprise a material selected from the group consisting of polyethylenes; polyamides; polystyrenes; polyisoprenes; polycarbonates; polyesters; polyacrylates; aminoplasts, in one aspect said aminoplast may comprise a polyureas, polyurethane, and/or polyureaurethane, in one aspect said polyurea may comprise polyoxymethyleneurea and/or melamine formaldehyde; polyolefins; polysaccharides, in one aspect said polysaccharide may comprise alginate and/or chitosan; gelatin; shellac; epoxy resins; vinyl polymers; water insoluble inorganics; silicone;
- suitable encapsulates may comprise a core material and a shell, said shell at least partially surrounding said core material, is disclosed. At least 75%, 85% or even 90% of said encapsulates may have a fracture strength of from about 0.2 MPa to about 10 MPa, from about 0.4 MPa to about 5MPa, from about 0.6 MPa to about 3.5 MPa, or even from about 0.7 MPa to about 3MPa; and a benefit agent leakage of from 0% to about 30%, from 0% to about 20%, or even from 0% to about 5%.
- At least 75%, 85% or even 90% of said encapsulates may have a particle size of from about 1 microns to about 80 microns, about 5 microns to 60 microns, from about 10 microns to about 50 microns, or even from about 15 microns to about 40 microns. In one aspect, at least 75%, 85% or even 90% of said encapsulates may have a particle wall thickness of from about 30 nm to about 250 nm, from about 80 nm to about 180 nm, or even from about 100 nm to about 160 nm.
- said encapsulates' core material may comprise a material selected from the group consisting of a perfume raw material and/or optionally a material selected from the group consisting of vegetable oil, including neat and/or blended vegetable oils including caster oil, coconut oil, cottonseed oil, grape oil, rapeseed, soybean oil, corn oil, palm oil, linseed oil, safflower oil, olive oil, peanut oil, coconut oil, palm kernel oil, castor oil, lemon oil and mixtures thereof; esters of vegetable oils, esters, including dibutyl adipate, dibutyl phthalate, butyl benzyl adipate, benzyl octyl adipate, tricresyl phosphate, trioctyl phosphate and mixtures thereof; straight or branched chain hydrocarbons, including those straight or branched chain hydrocarbons having a boiling point of greater than about 80°C; partially hydrogenated terphenyls, dialkyl phthalates, alkyl
- said encapsulates' wall material may comprise a suitable resin including the reaction product of an aldehyde and an amine
- suitable aldehydes include, formaldehyde.
- suitable amines include melamine, urea, benzoguanamine, glycoluril, and mixtures thereof.
- Suitable melamines include, methylol melamine, methylated methylol melamine, imino melamine and mixtures thereof.
- Suitable ureas include, dimethylol urea, methylated dimethylol urea, urea-resorcinol, and mixtures thereof.
- suitable formaldehyde scavengers may be employed with the encapsulates, for example, in a capsule slurry and/or added to a consumer product before, during or after the encapsulates are added to such consumer product.
- Suitable capsules that can be made by following the teaching of USPA 2008/0305982 A1 ; and/or USPA 2009/0247449 A1 .
- suitable capsules can be purchased from Appleton Papers Inc. of Appleton, Wisconsin USA.
- the materials for making the aforementioned encapsulates can be obtained from Solutia Inc. (St Louis, Missouri U.S.A.), Cytec Industries (West Paterson, New Jersey U.S.A.), sigma-Aldrich (St. Louis, Missouri U.S.A.), CP Kelco Corp. of San Diego, California, USA; BASF AG of Ludwigshafen, Germany; Rhodia Corp. of Cranbury, New Jersey, USA; Hercules Corp. of Wilmington, Delaware, USA; Agrium Inc.
- the consumer product may comprise one or more polymers. Examples are carboxymethylcellulose, poly(vinyl-pyrrolidone), poly (ethylene glycol), poly(vinyl alcohol), poly(vinylpyridine-N-oxide), poly(vinylimidazole), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid co-polymers.
- the consumer product may comprise amphiphilic alkoxylated grease cleaning polymers which have balanced hydrophilic and hydrophobic properties such that they remove grease particles from fabrics and surfaces.
- amphiphilic alkoxylated grease cleaning polymers of the present invention comprise a core structure and a plurality of alkoxylate groups attached to that core structure. These may comprise alkoxylated polyalkylenimines, preferably having an inner polyethylene oxide block and an outer polypropylene oxide block.
- Carboxylate polymer - The detergent composition of the present invention may also include one or more carboxylate polymers such as a maleate/acrylate random copolymer or polyacrylate homopolymer.
- the carboxylate polymer is a polyacrylate homopolymer having a molecular weight of from 4,000 Da to 9,000 Da, or from 6,000 Da to 9,000 Da.
- Soil release polymer - The detergent composition of the present invention may also include one or more soil release polymers having a structure as defined by one of the following structures (I), (II) or (III):
- Suitable soil release polymers are polyester soil release polymers such as Repel-o-tex polymers, including Repel-o-tex SF, SF-2 and SRP6 supplied by Rhodia.
- Other suitable soil release polymers include Texcare polymers, including Texcare SRA100, SRA300, SRN100, SRN170, SRN240, SRN300 and SRN325 supplied by Clariant.
- Other suitable soil release polymers are Marloquest polymers, such as Marloquest SL supplied by Sasol.
- Cellulosic polymer - The detergent composition of the present invention may also include one or more cellulosic polymers including those selected from alkyl cellulose, alkyl alkoxyalkyl cellulose, carboxyalkyl cellulose, alkyl carboxyalkyl cellulose.
- the cellulosic polymers are selected from the group comprising carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose, and mixures thereof.
- the carboxymethyl cellulose has a degree of carboxymethyl substitution from 0.5 to 0.9 and a molecular weight from 100,000 Da to 300,000 Da.
- the detergent composition may comprise one or more additional enzymes which provide cleaning performance and/or fabric care benefits.
- suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof.
- a typical combination is an enzyme cocktail that may comprise, for example, a protease and lipase in conjunction with amylase.
- the aforementioned additional enzymes may be present at levels from about 0.00001% to about 2%, from about 0.0001% to about 1% or even from about 0.001% to about 0.5% enzyme protein by weight of the consumer product.
- the detailed information given below relates to enzymes suitable for incorporation into the co-granule or the detergent composition more generally other than via the co-granule.
- Suitable proteases include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisins (EC 3.4.21.62).
- Suitable proteases include those of animal, vegetable or microbial origin. In one aspect, such suitable protease may be of microbial origin.
- the suitable proteases include chemically or genetically modified mutants of the aforementioned suitable proteases.
- the suitable protease may be a serine protease, such as an alkaline microbial protease or/and a trypsin-type protease.
- suitable neutral or alkaline proteases include:
- Preferred proteases include those derived from Bacillus gibsonii or Bacillus Lentus.
- Suitable commercially available protease enzymes include those sold under the trade names Alcalase®, Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®, Ovozyme®, Neutrase®, Everlase® and Esperase® by Novozymes A/S (Denmark), those sold under the tradename Maxatase®, Maxacal®, Maxapem®, Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®, Excellase® and Purafect OXP® by Genencor International, those sold under the tradename Opticlean® and Optimase® by Solvay Enzymes, those available from Henkel/ Kemira, namely BLAP (sequence shown in Figure 29 of US 5,352,604 with the folowing mutations S99D + S101 R + S
- Suitable alpha-amylases include 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®, 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).
- suitable amylases include NATALASE®, STAINZYME® and STAINZYME PLUS® and mixtures thereof.
- such enzymes may be selected from the group consisting of: lipases, including "first wash lipases” such as those described in U.S. Patent 6,939,702 B1 and US PA 2009/0217464 .
- the lipase is a first-wash lipase, preferably a variant of the wild-type lipase from Thermomyces lanuginosus comprising T231R and N233R mutations.
- the wild-type sequence is the 269 amino acids (amino acids 23 - 291) of the Swissprot accession number Swiss-Prot O59952 (derived from Thermomyces lanuginosus (Humicola lanuginosa)).
- Preferred lipases would include those sold under the tradenames Lipex® and Lipolex®.
- other preferred enzymes include microbial-derived endoglucanases exhibiting endo-beta-1,4-glucanase activity (E.C. 3.2.1.4), including a bacterial polypeptide endogenous to a member of the genus Bacillus which has a sequence of at least 90%, 94%, 97% and even 99% identity to the amino acid sequence SEQ ID NO:2 in 7,141,403B2) and mixtures thereof.
- Suitable endoglucanases are sold under the tradenames Celluclean® and Whitezyme® (Novozymes A/S, Bagsvaerd, Denmark).
- the detergent composition of the present invention may comprise one or more bleaching agents.
- Suitable bleaching agents other than bleaching catalysts include photobleaches, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, pre-formed peracids and mixtures thereof.
- the detergent composition of the present invention may comprise from about 0.1% to about 50% or even from about 0.1% to about 25% bleaching agent by weight of the subject consumer product.
- suitable bleaching agents include:
- Suitable anionic detersive surfactants include sulphate and sulphonate detersive surfactants.
- Suitable sulphonate detersive surfactants include alkyl benzene sulphonate, in one aspect, C 10-13 alkyl benzene sulphonate.
- Suitable alkyl benzene sulphonate (LAS) may be obtained, by sulphonating commercially available linear alkyl benzene (LAB); suitable LAB includes low 2-phenyl LAB, such as those supplied by Sasol under the tradename Isochem® or those supplied by Petresa under the tradename Petrelab®, other suitable LAB include high 2-phenyl LAB, such as those supplied by Sasol under the tradename Hyblene®.
- a suitable anionic detersive surfactant is alkyl benzene sulphonate that is obtained by DETAL catalyzed process, although other synthesis routes, such as HF, may also be suitable.
- Suitable sulphate detersive surfactants include alkyl sulphate, in one aspect, C 8-18 alkyl sulphate, or predominantly C 12 alkyl sulphate.
- alkyl alkoxylated sulphate in one aspect, alkyl ethoxylated sulphate, in one aspect, a C 8-18 alkyl alkoxylated sulphate, in another aspect, a C 8-18 alkyl ethoxylated sulphate, typically the alkyl alkoxylated sulphate has an average degree of alkoxylation of from 0.5 to 20, or from 0.5 to 10, typically the alkyl alkoxylated sulphate is a C 8-18 alkyl ethoxylated sulphate having an average degree of ethoxylation of from 0.5 to 10, from 0.5 to 7, from 0.5 to 5 or even from 0.5 to 3.
- the alkyl sulphate, alkyl alkoxylated sulphate and alkyl benzene sulphonates may be linear or branched, substituted or un-substituted.
- the detersive surfactant may be a mid-chain branched detersive surfactant, in one aspect, a mid-chain branched anionic detersive surfactant, in one aspect, a mid-chain branched alkyl sulphate and/or a mid-chain branched alkyl benzene sulphonate, for example a mid-chain branched alkyl sulphate.
- the mid-chain branches are C 1-4 alkyl groups, typically methyl and/or ethyl groups.
- Suitable non-ionic detersive surfactants are selected from the group consisting of: C 8 -C 18 alkyl ethoxylates, such as, NEODOL® non-ionic surfactants from Shell; C 6 -C 12 alkyl phenol alkoxylates wherein the alkoxylate units may be ethyleneoxy units, propyleneoxy units or a mixture thereof; C 12 -C 18 alcohol and C 6 -C 12 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as Pluronic® from BASF; C 14 -C 22 mid-chain branched alcohols; C 14 -C 22 mid-chain branched alkyl alkoxylates, typically having an average degree of alkoxylation of from 1 to 30; alkylpolysaccharides, in one aspect, alkylpolyglycosides; polyhydroxy fatty acid amides; ether capped poly(oxyalkylated) alcohol surfactants; and mixtures thereof.
- non-ionic detersive surfactants include alkyl polyglucoside and/or an alkyl alkoxylated alcohol.
- non-ionic detersive surfactants include alkyl alkoxylated alcohols, in one aspect C 8-18 alkyl alkoxylated alcohol, for example a C 8-18 alkyl ethoxylated alcohol, the alkyl alkoxylated alcohol may have an average degree of alkoxylation of from 1 to 50, from 1 to 30, from 1 to 20, or from 1 to 10.
- the alkyl alkoxylated alcohol may be a C 8-18 alkyl ethoxylated alcohol having an average degree of ethoxylation of from 1 to 10, from 1 to 7, more from 1 to 5 or from 3 to 7.
- the alkyl alkoxylated alcohol can be linear or branched, and substituted or un-substituted.
- Suitable cationic detersive surfactants include alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl ternary sulphonium compounds, and mixtures thereof.
- Suitable cationic detersive surfactants are quaternary ammonium compounds having the general formula: (R)(R 1 )(R 2 )(R 3 )N + X - wherein, R is a linear or branched, substituted or unsubstituted C 6-18 alkyl or alkenyl moiety, R 1 and R 2 are independently selected from methyl or ethyl moieties, R 3 is a hydroxyl, hydroxymethyl or a hydroxyethyl moiety, X is an anion which provides charge neutrality, suitable anions include: halides, for example chloride; sulphate; and sulphonate.
- Suitable cationic detersive surfactants are mono-C 6-18 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chlorides. Highly suitable cationic detersive surfactants are mono-C 8-10 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride, mono-C 10-12 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride and mono-Cio alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride.
- Chelating Agents The detergent composition herein may contain a chelating agent. Suitable chelating agents include copper, iron and/or manganese chelating agents and mixtures thereof.
- the subject consumer product may comprise from about 0.005% to about 15% or even from about 3.0% to about 10% chelating agent by weight of the subject consumer product.
- Suitable chelants include DTPA (Diethylene triamine pentaacetic acid), HEDP (Hydroxyethane diphosphonic acid), DTPMP (Diethylene triamine penta(methylene phosphonic acid)), 1,2-Dihydroxybenzene-3,5-disulfonic acid disodium salt hydrate, ethylenediamine, diethylene triamine, ethylenediaminedisuccinic acid (EDDS), N-hydroxyethylethylenediaminetri-acetic acid (HEDTA), triethylenetetraaminehexaacetic acid (TTHA), N-hydroxyethyliminodiacetic acid (HEIDA), dihydroxyethylglycine (DHEG), ethylenediaminetetrapropionic acid (EDTP) and derivatives thereof.
- DTPA Diethylene triamine pentaacetic acid
- the detergent composition of the present invention may also include one or more dye transfer inhibiting agents.
- Suitable polymeric dye transfer inhibiting agents include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.
- the dye transfer inhibiting agents may be present at levels from about 0.0001% to about 10%, from about 0.01% to about 5% or even from about 0.1% to about 3% by weight of the consumer product.
- Brighteners The detergent composition of the present invention can also contain additional components that may tint articles being cleaned, such as fluorescent brighteners.
- composition may comprise C.I. fluorescent brightener 260 in alpha-crystalline form having the following structure:
- the brightener is a cold water soluble brightener, such as the C.I. fluorescent brightener 260 in alpha-crystalline form.
- the brightener is predominantly in alpha-crystalline form, which means that typically at least 50wt%, at least 75wt%, at least 90wt%, at least 99wt%, or even substantially all, of the C.I. fluorescent brightener 260 is in alpha-crystalline form.
- the brightener is typically in micronized particulate form, having a weight average primary particle size of from 3 to 30 micrometers, from 3 micrometers to 20 micrometers, or from 3 to 10 micrometers.
- the composition may comprise C.I. fluorescent brightener 260 in beta-crystalline form, and the weight ratio of: (i) C.I. fluorescent brightener 260 in alpha-crystalline form, to (ii) C.I. fluorescent brightener 260 in beta-crystalline form may be at least 0.1, or at least 0.6.
- BE680847 relates to a process for making C.I fluorescent brightener 260 in alpha-crystalline form.
- Suitable fluorescent brightener levels include lower levels of from about 0.01, from about 0.05, from about 0.1 or even from about 0.2 wt % to upper levels of 0.5 or even 0.75 wt %.
- Silicate salts - The detergent composition of the present invention can also contain silicate salts, such as sodium or potassium silicate.
- the composition may comprise from 0wt% to less than 10wt% silicate salt, to 9wt%, or to 8wt%, or to 7wt%, or to 6wt%, or to 5wt%, or to 4wt%, or to 3wt%, or even to 2wt%, and preferably from above 0wt%, or from 0.5wt%, or even from 1wt% silicate salt.
- a suitable silicate salt is sodium silicate.
- Dispersants - The detergent composition of the present invention can also contain dispersants.
- Suitable water-soluble organic materials include the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
- Enzyme Stabilizers - Enzymes for use in the detergent composition can be stabilized by various techniques.
- the enzymes employed herein can be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished fabric and home care products that provide such ions to the enzymes.
- a reversible protease inhibitor such as a boron compound, or compounds such as calcium formate, sodium formate and 1,2-propane diol can be added to further improve stability.
- Solvents - Suitable solvents include water and other solvents such as lipophilic fluids.
- suitable lipophilic fluids include siloxanes, other silicones, hydrocarbons, glycol ethers, glycerine derivatives such as glycerine ethers, perfluorinated amines, perfluorinated and hydrofluoroether solvents, low-volatility nonfluorinated organic solvents, diol solvents, other environmentally-friendly solvents and mixtures thereof.
- the detergent composition of the present invention are preferably in granular form, optionally the granules being incorporated into a unit dose detergent composition as described above.
- the present invention includes a method of treating and/or cleaning a surface, preferably a fabric surface comprising the steps of (i) contacting said surface with a composition according to any of claims 1 to 11 in an aqueous wash liquor, (ii) rinsing and/or drying the surface, preferably the temperature of the aqueous liquor is from 5 - 25°C and preferably the aqueous liquor comprises from 0.1g/l to 3g/l of surfactant.
- Granular laundry detergent compositions designed for hand washing or top-loading washing machines. 1 (wt%) 2 (wt %) 3 (wt%) 4 (wt %) 5 (wt %) 6 (wt%) 7 (wt %) Linear alkylbenzenesulfonate 18 20 22 20 15 20 20 C 12-14 Dimethylhydroxyethyl ammonium chloride 0.5 0.7 0.2 1 0.6 0.0 0 AE3S 1.0 0.9 1 0.9 0.0 0.5 0.9 AE7 2.0 0.0 0.0 0.0 1 0.0 3 Sodium tripolyphosphate 5 5 0.0 4 9 2 0.0 Zeolite A 0 0.0 1 0.0 1 4 1 1.6R Silicate (SiO 2 :Na 2 O at ratio 1.6:1) 6 7 5 2 3 3 5 Sodium carbonate 26 25 20 25 17 18 19 Polyacrylate MW 4500 1 1 0.6 1 1 1.5 1 Random graft copolymer 1 0.1 0.1 0.2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Carboxymethyl
- Granular laundry detergent compositions designed for front-loading automatic washing machines 8 (wt%) 9 (wt%) 10 (wt%) 11 (wt%) 12 (wt%) 13 (wt%) Linear alkylbenzenesulfonate 8 7.1 7 6.5 7.5 7.5 AE3S 0 4.8 0 5.2 4 4 C12-14 Alkylsulfate 1 0 1 0 0 0 AE7 2.2 0 3.2 0 0 0 C 10-12 Dimethyl hydroxyethylammonium chloride 0.75 0.94 0.98 0.98 0 0 Crystalline layered silicate ( ⁇ -Na 2 Si 2 O 5 ) 4.1 0 4.8 0 0 0 0 Zeolite A 5 0 5 0 2 2 Citric Acid 3 5 3 4 2.5 3 Sodium Carbonate 15 20 14 20 23 20 Silicate 2R (SiO 2 :Na 2 O at ratio 2:1) 0.08 0 0.11 0 0 0 0 Soil release agent 0.75 0.72 0.71 0.72
- compositions is used to launder fabrics at a concentration of 7000 to 10000 ppm in water, 20-90 °C, and a 5:1 water:cloth ratio.
- the typical pH is about 10.
- the fabrics are then dried.
- the fabrics are actively dried using a dryer.
- the fabrics are actively dried using an iron.
- the fabrics are merely allowed to dry on a line wherein they are exposed to air and optionally sunlight.
- Raw materials and notes for the composition examples 1-13 Alkylbenzenesulfonate, linear average aliphatic carbon chain length C 11 -C 12 .
- AE3S is C 12-15 alkyl ethoxy (3) sulfate .
- AE7 is C 12-15 alcohol ethoxylate, with an average degree of ethoxylation of 7.
- AE9 is C 12-13 alcohol ethoxylate, with an average degree of ethoxylation of 9.
- HSAS is a mid-branched primary alkyl sulfate with carbon chain length of about 16-17
- Chelants may be diethylenetetraamine pentaacetic acid (DTPA), sodium hydroxyethane di phosphonate (HEDP) or sodium ethylene diamine-N,N- disuccinic acid (S,S)isomer (EDDS) Savinase®, Natalase®, Stainzyme®, Lipex®, CellucleanTM, Mannaway® and Whitezyme® are all products of Novozymes, Bagsvaerd, Denmark.
- DTPA diethylenetetraamine pentaacetic acid
- HEDP sodium hydroxyethane di phosphonate
- S,S)isomer EDDS
- Fluorescent Brightener 1 is Tinopal® AMS
- Fluorescent Brightener 2 is Tinopal® CBS-X
- Sulphonated zinc phthalocyanine NOBS is sodium nonanoyloxybenzenesulfonate.
- TAED is tetraacetylethylenediamine.
- Soil release agent is Repel-o-tex® PF, supplied by Rhodia, Paris, France
- Acrylic Acid/Maleic Acid Copolymer is m wt 70,000 and acrylate:maleate ratio 70:30.
- HSAS is mid-branched alkyl sulfate as disclosed in US 6,020,303 and US 6,060,443
- Liquitint® Violet CT is supplied by Milliken, Spartanburg, South Carolina, USA
- Random graft copolymer is a polyvinyl acetate grafted polyethylene oxide copolymer having a polyethylene oxide backbone and multiple polyvinyl acetate side chains (m wt about 6000, weight ratio of the polyethylene oxide to polyvinyl acetateabout 40 to 60).
Landscapes
- Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Accessory Of Washing/Drying Machine, Commercial Washing/Drying Machine, Other Washing/Drying Machine (AREA)
- Enzymes And Modification Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Claims (15)
- Waschmittelzusammensetzung, umfassend:(a) ein Multi-Enzym-Cogranulat;(b) weniger als 10 Gew.-% Zeolith (wasserfrei);(c) weniger als 10 Gew.-% Phosphatsalz (wasserfrei), wobei das Enzym-Cogranulat mindestens ein Proteaseenzym und von 10 bis 98 Gew.-% Feuchtesenke-Komponente, ausgewählt aus der Gruppe bestehend aus (a) hydratisierbaren Salzen, (b) Aktivtonen, (c) Biofüllstoff und (d) Mischungen davon, umfasst;(d) und die Zusammensetzung zusätzlich von 20 bis 80 Gew.-% Feuchtesenke-Waschmittelkomponente umfasst, ausgewählt aus der Gruppe bestehend aus (a) hydratisierbaren Sulfatsalzen, (b) Aktivtonen, (c) Biofüllstoff und (d) Mischungen davon.
- Waschmittelzusammensetzung nach Anspruch 1, wobei das Multi-Enzym-Cogranulat (a) ein oder mehrere Enzyme, ausgewählt aus der Gruppe bestehend aus Erstwäsche-Lipasen, Reinigungscellulasen, Xyloglucanasen, Perhydrolasen, Peroxidasen, Lipoxygenasen, Laccasen und Mischungen davon umfasst.
- Waschmittelzusammensetzung nach Anspruch 2, wobei das Multi-Enzym-Cogranulat ein oder mehrere Enzyme umfasst, ausgewählt aus der Gruppe bestehend aus Hemicellulasen, Pflegecellulasen, Cellobiosedehydrogenasen, Xylanasen, Phospholipasen, Esterasen, Cutinasen, Pectinasen, Mannanasen, Pektatlyasen, Keratinasen, Reductasen, Oxidasen, Phenoloxidasen, Ligninasen, Pullulanasen, Tannasen, Pentosanasen, Lichenasen Glucanasen, Arabinosidasen, Hyaluronidase, Chondroitinase, Amylasen und Mischungen davon.
- Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche, wobei das Multi-Enzym-Cogranulat eine Lipase umfasst.
- Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche, wobei das Multi-Enzym-Cogranulat Lipase und Protease in einem Gewichtsverhältnis von mindestens 2:5 bis zu 5:2, vorzugsweise von 2:5 bis 1:1, umfasst.
- Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche, wobei die Feuchtesenke-Waschmittelkomponente ein hydratisierbares Salz, vorzugsweise Natriumsulfat umfasst.
- Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche, umfassend die Feuchtesenke-Waschmittelkomponente in einer Menge von mindestens 25 Gew.-%, oder sogar mindestens 30 Gew.-%.
- Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche, wobei die Komponente und das aktive Enzym insgesamt in dem Multi-Enzym-Cogranulat in einem Gewichtsverhältnis von 4:1 oder 6:1 oder 8:1 oder 10:1 bis zu 100:1 oder 60:1 oder 40:1 vorhanden sind.
- Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche, wobei das Multi-Enzym-Cogranulat einen Überzug umfasst, ausgewählt aus der Gruppe umfassend Titandioxid, Polyvinylalkohol, Hydroxypropylmethycellulose, Methylcellulose, Polycarboxylate, Kaolin, Polyethylenglycole und Mischungen davon.
- Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche, wobei die Feuchtesenke-Komponente ausgewählt ist aus der Gruppe bestehend aus: Natriumcarbonat, vorzugsweise wasserfreiem Natriumcarbonat, Aktivton, vorzugsweise Aktivtonen, umfassend von 0,1 bis 15 Gew.-% freie Feuchtigkeit, mehr bevorzugt von 0,1 bis 10 % freie Feuchtigkeit; Natriumsulfat, vorzugsweise wasserfreiem Natriumsulfat; Natriumchlorid, vorzugsweise wasserfreiem Natriumchlorid; Biofüllstoff, umfassend von 0 oder von 0,1 bis 15 % oder 10 % freie Feuchtigkeit, und Mischungen davon.
- Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche, zusätzlich umfassend einen Farbübertragungshemmer.
- Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche zusätzlich umfassend einen Stofftönungsfarbstoff, wie einen Solvens- oder Dispersionsfarbstoff, oder einen Säure-Farbstoff oder einen Direktfarbstoff oder Mischungen davon und/oder Pigment oder Mischungen davon.
- Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche, umfassend einen oder mehrere der folgenden Hilfsstoffe:a) eine Verkapselung, umfassend einen Duftstoff, wobei die Verkapselung vorzugsweise eine Duftstoff-Mikrokapsel umfasst;b) ein Tensidsystem, vorzugsweise umfassend ein anionisches Tensid und ein nichtionisches Tensid, vorzugsweise in dem Gewichtsverhältnis von 20:1 bis 1:10 oder 1:1;c) ein Silicatsalz, vorzugsweise umfassend ein Material, das aus der Gruppe ausgewählt ist bestehend aus Natriumsilicat, Kaliumsilicat und Mischungen davon;d) ein Carboxylatpolymer, vorzugsweise umfassend ein Material, ausgewählt aus der Gruppe bestehend aus Maleat/Acrylat-Random-Copolymer oder Polyacrylat-Homopolymer und Mischungen davon;e) ein Schmutzlösepolymer, vorzugsweise umfassend ein Material, ausgewählt aus der Gruppe bestehend aus Terephthalat-Copolymeren und Mischungen davon;f) ein cellulosisches Polymer, vorzugsweise umfassend ein Material, ausgewählt aus der Gruppe bestehend aus Alkylcellulose, Alkylalkoxyalkylcellulose, Carboxyalkylcellulose, Alkylcarboxyalkylcellulose und Mischungen davon;g) einen Chelatbildner, vorzugsweise umfassend ein Material, ausgewählt aus der Gruppe bestehend aus DTPA (Diethylentriaminpentaessigsäure), HEDP (Hydroxyethandiphosphonsäure), DTPMP (Diethylentriaminpenta(methylenphos-phonsäure)), Ethylendiamindisuccinsäure (EDDS), 1,2-Dihydroxybenzol-3,5-disulfonsäure-dinatriumsalzhydrat, Derivaten der Chelatbildner; undh) Mischungen davon.
- Zusammensetzung nach einen der vorstehenden Ansprüche, zusätzlich umfassend mindestens 2,5 Gew.-%, vorzugsweise mindestens 5 Gew.-% bis zu 35 Gew.-% Natriumpercarbonat, gegebenenfalls überzogen zum Schutz gegen Feuchtigkeit, gegebenenfalls umfassend einen oder mehrere Bleichpartikel, ausgewählt aus der Gruppe bestehend aus:a) einem Bleichkatalysator, vorzugsweise ein Material umfassend, das aus der Gruppe ausgewählt ist, bestehend aus Iminiumkationen, Iminiumpolyionen; Iminiumzwitterionen; modifizierten Aminen; modifizierten Aminoxiden; N-Sulphonyliminen; N-Phosphonyliminen; N-Acyliminen; Thiadiazoldioxiden; Perfluoriminen; cyclischen Zuckerketonen und Übergangsmetallkatalysatoren oder Liganden zur Bildung davon, oder Mischungen davon;b) einen Bleichaktivator, vorzugsweise umfassend ein Material, ausgewählt aus der Gruppe bestehend aus Dodecanoyloxybenzolsulfonat, Decanoyloxybenzolsulfonat, Decanoyloxybenzoesäure oder Salzen davon, 3,5,5-Trimethylhexanoyloxybenzolsulfonat, Tetraacetylethylendiamin (TAED), Nonanoyloxybenzolsulfonat (NOBS) und Mischungen davon;c) einem Metallkatalysator;d) einem Fotobleichmittel, vorzugsweise Zink und/oder Aluminiumphthalocyanin-Verbindungen, Lebensmittelrot, Erythrosin und/oder Bengalrosa; unde) Mischungen davon.
- Verfahren zur Behandlung und/oder Reinigung einer Oberfläche, vorzugsweise einer Textilstoffoberfläche, umfassend die Schritte (i) Kontaktieren der Oberfläche mit einer Zusammensetzung nach einem der Ansprüche 1 bis 11 in einer wässrigen Waschflotte, (ii) Abspülen und/oder Trocknen der Oberfläche, wobei vorzugsweise die Temperatur der wässrigen Waschflotte von 5 - 25 °C beträgt und die wässrige Waschflotte vorzugsweise von 0,1 g/l bis 3 g/l Tensid umfasst.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL13171413T PL2674476T5 (pl) | 2012-06-11 | 2013-06-11 | Kompozycja detergentowa |
EP13171413.1A EP2674476B2 (de) | 2012-06-11 | 2013-06-11 | Wasch- und Reinigungsmittel |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12171551.0A EP2674475A1 (de) | 2012-06-11 | 2012-06-11 | Wasch- und Reinigungsmittel |
EP13171413.1A EP2674476B2 (de) | 2012-06-11 | 2013-06-11 | Wasch- und Reinigungsmittel |
Publications (3)
Publication Number | Publication Date |
---|---|
EP2674476A1 EP2674476A1 (de) | 2013-12-18 |
EP2674476B1 true EP2674476B1 (de) | 2018-04-18 |
EP2674476B2 EP2674476B2 (de) | 2021-11-10 |
Family
ID=48570026
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP12171551.0A Withdrawn EP2674475A1 (de) | 2012-06-11 | 2012-06-11 | Wasch- und Reinigungsmittel |
EP13171413.1A Active EP2674476B2 (de) | 2012-06-11 | 2013-06-11 | Wasch- und Reinigungsmittel |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP12171551.0A Withdrawn EP2674475A1 (de) | 2012-06-11 | 2012-06-11 | Wasch- und Reinigungsmittel |
Country Status (14)
Country | Link |
---|---|
EP (2) | EP2674475A1 (de) |
JP (1) | JP2015528828A (de) |
CN (2) | CN104364364A (de) |
BR (1) | BR112014030417B1 (de) |
DK (1) | DK2674476T4 (de) |
ES (1) | ES2674940T5 (de) |
HU (1) | HUE038095T2 (de) |
IN (1) | IN2014DN10427A (de) |
MX (1) | MX370587B (de) |
PL (1) | PL2674476T5 (de) |
RU (1) | RU2612142C2 (de) |
TR (1) | TR201809430T4 (de) |
WO (1) | WO2013188331A1 (de) |
ZA (1) | ZA201408580B (de) |
Families Citing this family (160)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014068109A2 (en) * | 2012-11-05 | 2014-05-08 | Novozymes A/S | Enzyme compositions enabling re-use of water in laundry |
US20160244699A1 (en) * | 2013-10-15 | 2016-08-25 | Danisco Us Inc. | Clay Granule |
US9834740B2 (en) * | 2014-01-24 | 2017-12-05 | The Procter & Gamble Company | Photoactivators |
WO2015121134A1 (en) * | 2014-02-11 | 2015-08-20 | Novozymes A/S | Detergent composition, method and use of detergent composition |
MX2016013034A (es) | 2014-04-11 | 2017-02-15 | Novozymes As | Composicion detergente. |
EP3037512B1 (de) * | 2014-12-22 | 2018-02-28 | The Procter and Gamble Company | Verfahren zum Recyclen von Waschmittelbeuteln |
US20180112156A1 (en) | 2015-04-10 | 2018-04-26 | Novozymes A/S | Laundry method, use of polypeptide and detergent composition |
EP3280800A1 (de) | 2015-04-10 | 2018-02-14 | Novozymes A/S | Reinigungsmittelzusammensetzung |
EP3317388B1 (de) | 2015-06-30 | 2019-11-13 | Novozymes A/S | Waschmittelzusammensetzung, verfahren zum waschen und verwendung der zusammensetzung |
US20180171269A1 (en) * | 2015-09-01 | 2018-06-21 | Novozymes A/S | Laundry method |
PL3350303T3 (pl) | 2015-09-17 | 2021-01-25 | Henkel Ag & Co. Kgaa | Kompozycje detergentowe zawierające polipeptydy mające aktywność rozkładania ksantanu |
CN108350443B (zh) | 2015-09-17 | 2022-06-28 | 诺维信公司 | 具有黄原胶降解活性的多肽以及编码它们的多核苷酸 |
CN108350441B (zh) | 2015-10-07 | 2022-09-27 | 诺维信公司 | 多肽 |
EP4324919A3 (de) | 2015-10-14 | 2024-05-29 | Novozymes A/S | Polypeptidvarianten |
GB2544470B (en) * | 2015-11-16 | 2019-06-05 | Reckitt Benckiser Vanish Bv | Laundry composition |
WO2017142743A1 (en) | 2016-02-15 | 2017-08-24 | Novozymes A/S | Microbial culture, composition, use and method |
EP3433347B1 (de) | 2016-03-23 | 2020-05-06 | Novozymes A/S | Verwendung eines polypeptids mit dnase-aktivität zur behandlung von geweben |
JP6959259B2 (ja) | 2016-04-29 | 2021-11-02 | ノボザイムス アクティーゼルスカブ | 洗剤組成物およびその使用 |
EP3249037B1 (de) * | 2016-05-23 | 2020-04-22 | The Procter & Gamble Company | Waschmittelzusammensetzung mit einem verkapselten enzym |
BR112018073283A2 (pt) | 2016-05-24 | 2019-03-19 | Novozymes A/S | composição, grânulo, aditivo de ração para animal, ração para animal, ração para animal peletizada, formulação líquida, método para liberar galactose do material à base de planta, método para melhorar um ou mais parâmetros de desempenho de um animal, uso da composição, do grânulo, do aditivo de ração para animal ou da formulação líquida, polipeptídeo isolado, método para produzir o polipeptídeo, polinucleotídeo, construto de ácido nucleico ou vetor de expressão, e, célula hospedeira |
CN109312321A (zh) | 2016-05-24 | 2019-02-05 | 诺维信公司 | 包含具有半乳聚糖酶活性的多肽和具有β-半乳糖苷酶活性的多肽的组合物 |
AU2017269498A1 (en) | 2016-05-24 | 2018-11-08 | Novozymes A/S | Polypeptides having alpha-galactosidase activity and polynucleotides encoding same |
US11058129B2 (en) | 2016-05-24 | 2021-07-13 | Novozymes A/S | Animal feed additives |
CN107486239A (zh) * | 2016-06-10 | 2017-12-19 | 国立大学法人信州大学 | 动物组织加工物、金属纳米粒子催化剂、它们的制造方法 |
WO2018002261A1 (en) | 2016-07-01 | 2018-01-04 | Novozymes A/S | Detergent compositions |
EP3481949B1 (de) | 2016-07-05 | 2021-06-09 | Novozymes A/S | Pektatlyasevarianten und dafür codierende polynukleotide |
AU2017294066A1 (en) | 2016-07-08 | 2019-01-17 | Novozymes A/S | Polypeptides having xylanase activity and polynucleotides encoding same |
AR108861A1 (es) | 2016-07-08 | 2018-10-03 | Novozymes As | Variantes de xilanasa y polinucleótidos que las codifican |
WO2018007573A1 (en) | 2016-07-08 | 2018-01-11 | Novozymes A/S | Detergent compositions with galactanase |
WO2018011276A1 (en) | 2016-07-13 | 2018-01-18 | The Procter & Gamble Company | Bacillus cibi dnase variants and uses thereof |
CN106191882B (zh) * | 2016-08-17 | 2018-09-21 | 安徽红桥金属制造有限公司 | 一种无磷脱脂剂及其制备方法 |
CN110023474A (zh) | 2016-09-29 | 2019-07-16 | 诺维信公司 | 酶用于洗涤的用途、洗涤方法和器皿洗涤组合物 |
EP3532592A1 (de) | 2016-10-25 | 2019-09-04 | Novozymes A/S | Waschmittelzusammensetzungen |
WO2018083093A1 (en) * | 2016-11-01 | 2018-05-11 | Novozymes A/S | Multi-core granules |
CN110088261B (zh) * | 2016-12-02 | 2022-05-06 | 宝洁公司 | 包含酶的清洁组合物 |
WO2018177938A1 (en) | 2017-03-31 | 2018-10-04 | Novozymes A/S | Polypeptides having dnase activity |
US11149233B2 (en) | 2017-03-31 | 2021-10-19 | Novozymes A/S | Polypeptides having RNase activity |
US11053483B2 (en) | 2017-03-31 | 2021-07-06 | Novozymes A/S | Polypeptides having DNase activity |
WO2018185181A1 (en) | 2017-04-04 | 2018-10-11 | Novozymes A/S | Glycosyl hydrolases |
US20200109354A1 (en) | 2017-04-04 | 2020-04-09 | Novozymes A/S | Polypeptides |
US20200109352A1 (en) | 2017-04-04 | 2020-04-09 | Novozymes A/S | Polypeptide compositions and uses thereof |
WO2018185285A1 (en) | 2017-04-06 | 2018-10-11 | Novozymes A/S | Cleaning compositions and uses thereof |
WO2018184818A1 (en) | 2017-04-06 | 2018-10-11 | Novozymes A/S | Cleaning compositions and uses thereof |
WO2018185267A1 (en) | 2017-04-06 | 2018-10-11 | Novozymes A/S | Cleaning compositions and uses thereof |
MX2019011764A (es) | 2017-04-06 | 2019-11-28 | Novozymes As | Composiciones limpiadoras y usos de las mismas. |
WO2018185269A1 (en) | 2017-04-06 | 2018-10-11 | Novozymes A/S | Cleaning compositions and uses thereof |
WO2018185280A1 (en) | 2017-04-06 | 2018-10-11 | Novozymes A/S | Cleaning compositions and uses thereof |
EP3607037A1 (de) | 2017-04-06 | 2020-02-12 | Novozymes A/S | Reinigungszusammensetzungen und verwendungen davon |
EP3607060B1 (de) | 2017-04-06 | 2021-08-11 | Novozymes A/S | Reinigungsmittelzusammensetzungen und verwendungen davon |
CN107151459A (zh) * | 2017-06-08 | 2017-09-12 | 巢湖市天宇渔具有限公司 | 一种废旧渔网的处理方法 |
US11499144B2 (en) | 2017-06-22 | 2022-11-15 | Novozymes A/S | Xylanase variants and polynucleotides encoding same |
EP3675646A1 (de) | 2017-09-01 | 2020-07-08 | Novozymes A/S | Tierfutterzusätze mit polypeptid mit proteaseaktivität und verwendungen davon |
EP3675647A1 (de) | 2017-09-01 | 2020-07-08 | Novozymes A/S | Tierfutterzusätze mit einem polypeptid mit proteaseaktivität und verwendungen davon |
EP3684899A1 (de) | 2017-09-22 | 2020-07-29 | Novozymes A/S | Neuartige polypeptide |
EP3692148A1 (de) | 2017-10-02 | 2020-08-12 | Novozymes A/S | Polypeptide mit mannanaseaktivität und polynukleotide zur codierung davon |
US11746310B2 (en) | 2017-10-02 | 2023-09-05 | Novozymes A/S | Polypeptides having mannanase activity and polynucleotides encoding same |
WO2019076800A1 (en) | 2017-10-16 | 2019-04-25 | Novozymes A/S | CLEANING COMPOSITIONS AND USES THEREOF |
EP3701001A1 (de) | 2017-10-24 | 2020-09-02 | Novozymes A/S | Zusammensetzungen mit polypeptiden mit mannanase-aktivität |
CN117683748A (zh) | 2017-10-27 | 2024-03-12 | 宝洁公司 | 包含多肽变体的洗涤剂组合物 |
WO2019081721A1 (en) | 2017-10-27 | 2019-05-02 | Novozymes A/S | VARIANTS OF DNASE |
US20200291330A1 (en) | 2017-11-01 | 2020-09-17 | Novozymes A/S | Polypeptides and Compositions Comprising Such Polypeptides |
DE102017125560A1 (de) | 2017-11-01 | 2019-05-02 | Henkel Ag & Co. Kgaa | Reinigungszusammensetzungen, die dispersine iii enthalten |
EP4379029A1 (de) | 2017-11-01 | 2024-06-05 | Novozymes A/S | Polypeptide und zusammensetzungen mit solchen polypeptiden |
DE102017125558A1 (de) | 2017-11-01 | 2019-05-02 | Henkel Ag & Co. Kgaa | Reinigungszusammensetzungen, die dispersine i enthalten |
EP3727024A1 (de) | 2017-12-20 | 2020-10-28 | DSM IP Assets B.V. | Tierfutterzusammensetzungen mit muramidase und deren verwendung |
WO2019121930A1 (en) | 2017-12-20 | 2019-06-27 | Dsm Ip Assets B.V. | Animal feed compositions and uses thereof |
MX2020006518A (es) * | 2017-12-21 | 2020-10-28 | Danisco Us Inc | Gránulos de fusión en caliente, que contienen enzimas, que comprenden un desecante termotolerante. |
CN111868251A (zh) | 2018-01-11 | 2020-10-30 | 诺维信公司 | 动物饲料组合物及其用途 |
WO2019201793A1 (en) | 2018-04-17 | 2019-10-24 | Novozymes A/S | Polypeptides comprising carbohydrate binding activity in detergent compositions and their use in reducing wrinkles in textile or fabric. |
JP6633123B2 (ja) * | 2018-04-24 | 2020-01-22 | 花王株式会社 | 衣料用粉末洗浄剤組成物 |
BR112020021365A2 (pt) | 2018-04-25 | 2021-01-19 | Novozymes A/S | Ração animal, método para melhoria do fator de eficiência de produção europeu, ganho de peso corporal e/ou razão de conversão de ração de um animal monogástrico, uso de pelo menos um probiótico em combinação com um polipeptídeo tendo atividade de muramidase em uma composição de ração, e, composição de ração ou uma composição de pré-mistura, ou um aditivo de ração para animais. |
CN112368363A (zh) | 2018-06-28 | 2021-02-12 | 诺维信公司 | 洗涤剂组合物及其用途 |
EP3814473A1 (de) | 2018-06-29 | 2021-05-05 | Novozymes A/S | Reinigungsmittelzusammensetzungen und verwendungen davon |
US12012573B2 (en) | 2018-07-02 | 2024-06-18 | Novozymes A/S | Cleaning compositions and uses thereof |
WO2020007875A1 (en) | 2018-07-03 | 2020-01-09 | Novozymes A/S | Cleaning compositions and uses thereof |
US20210253981A1 (en) | 2018-07-06 | 2021-08-19 | Novozymes A/S | Cleaning compositions and uses thereof |
WO2020008024A1 (en) | 2018-07-06 | 2020-01-09 | Novozymes A/S | Cleaning compositions and uses thereof |
EP3848443A1 (de) | 2018-08-14 | 2021-07-14 | The Procter & Gamble Company | Stoffbehandlungszusammensetzungen mit pflegemittelkapseln |
EP3611246B1 (de) | 2018-08-14 | 2021-03-10 | The Procter & Gamble Company | Stoffbehandlungszusammensetzungen mit pflegemittelkapseln |
EP3848444A1 (de) * | 2018-08-14 | 2021-07-14 | The Procter & Gamble Company | Flüssige stoffbehandlungszusammensetzungen mit aufheller |
CN112566502A (zh) | 2018-08-31 | 2021-03-26 | 诺维信公司 | 具有蛋白酶活性的多肽以及编码它们的多核苷酸 |
US20220040271A1 (en) | 2018-09-17 | 2022-02-10 | Dsm Ip Assets B.V. | Animal feed compositions and uses thereof |
MX2021003035A (es) | 2018-09-17 | 2021-08-11 | Dsm Ip Assets Bv | Composiciones de alimento animal y usos de las mismas. |
MX2021003040A (es) | 2018-09-17 | 2021-07-15 | Dsm Ip Assets Bv | Composiciones de alimentos animales y usos de las mismas. |
US20220054600A1 (en) | 2018-09-17 | 2022-02-24 | Dsm Ip Assets B.V. | Animal feed compositions and uses thereof |
WO2020070063A2 (en) | 2018-10-01 | 2020-04-09 | Novozymes A/S | Detergent compositions and uses thereof |
WO2020070209A1 (en) | 2018-10-02 | 2020-04-09 | Novozymes A/S | Cleaning composition |
WO2020070014A1 (en) | 2018-10-02 | 2020-04-09 | Novozymes A/S | Cleaning composition comprising anionic surfactant and a polypeptide having rnase activity |
US20230287306A1 (en) | 2018-10-02 | 2023-09-14 | Novozymes A/S | Cleaning Composition |
WO2020070199A1 (en) | 2018-10-03 | 2020-04-09 | Novozymes A/S | Polypeptides having alpha-mannan degrading activity and polynucleotides encoding same |
WO2020070249A1 (en) | 2018-10-03 | 2020-04-09 | Novozymes A/S | Cleaning compositions |
EP3864123A1 (de) | 2018-10-09 | 2021-08-18 | Novozymes A/S | Reinigungszusammensetzungen und verwendungen davon |
WO2020074498A1 (en) | 2018-10-09 | 2020-04-16 | Novozymes A/S | Cleaning compositions and uses thereof |
US20220033739A1 (en) | 2018-10-11 | 2022-02-03 | Novozymes A/S | Cleaning compositions and uses thereof |
EP3647398B1 (de) | 2018-10-31 | 2024-05-15 | Henkel AG & Co. KGaA | Reinigungszusammensetzungen mit dispersinen v |
EP3647397A1 (de) | 2018-10-31 | 2020-05-06 | Henkel AG & Co. KGaA | Reinigungsmittel mit dispersins iv |
EP3898962A2 (de) | 2018-12-21 | 2021-10-27 | Novozymes A/S | Polypeptide mit peptidoglycanabbauender aktivität und polynukleotide zur codierung davon |
EP3702452A1 (de) | 2019-03-01 | 2020-09-02 | Novozymes A/S | Waschmittelzusammensetzungen mit zwei proteasen |
EP3942032A1 (de) | 2019-03-21 | 2022-01-26 | Novozymes A/S | Alpha-amylase-varianten und dafür codierende polynukleotide |
CN113874499A (zh) | 2019-04-10 | 2021-12-31 | 诺维信公司 | 多肽变体 |
CN114364778A (zh) * | 2019-07-12 | 2022-04-15 | 诺维信公司 | 用于洗涤剂的酶性乳剂 |
CN114787329A (zh) | 2019-08-27 | 2022-07-22 | 诺维信公司 | 洗涤剂组合物 |
EP4031661A1 (de) | 2019-09-16 | 2022-07-27 | Novozymes A/S | Polypeptide mit beta-glucanase-aktivität und polynukleotide zur codierung davon |
EP4031644A1 (de) | 2019-09-19 | 2022-07-27 | Novozymes A/S | Reinigungsmittelzusammensetzung |
EP4038170A1 (de) | 2019-10-03 | 2022-08-10 | Novozymes A/S | Polypeptide mit mindestens zwei kohlenhydratbindungsdomänen |
EP3805346A1 (de) * | 2019-10-08 | 2021-04-14 | The Procter & Gamble Company | Verfahren zum waschen von stoffen |
WO2021078839A1 (en) | 2019-10-22 | 2021-04-29 | Novozymes A/S | Animal feed composition |
WO2021097601A1 (en) * | 2019-11-18 | 2021-05-27 | Solvay Sa | Solid bleach particles |
US20220411773A1 (en) | 2019-12-20 | 2022-12-29 | Novozymes A/S | Polypeptides having proteolytic activity and use thereof |
EP4077621A2 (de) | 2019-12-20 | 2022-10-26 | Henkel AG & Co. KGaA | Reinigungszusammensetzungen, die dispersine viii umfassen |
US20230045289A1 (en) | 2019-12-20 | 2023-02-09 | Henkel Ag & Co. Kgaa | Cleaning compositions comprising dispersins ix |
WO2021122118A1 (en) | 2019-12-20 | 2021-06-24 | Henkel Ag & Co. Kgaa | Cleaning compositions comprising dispersins vi |
KR20220121235A (ko) | 2019-12-20 | 2022-08-31 | 헨켈 아게 운트 코. 카게아아 | 디스페르신 및 카르보히드라제를 포함하는 세정 조성물 |
WO2021130167A1 (en) | 2019-12-23 | 2021-07-01 | Novozymes A/S | Enzyme compositions and uses thereof |
EP4093842A1 (de) | 2020-01-23 | 2022-11-30 | Novozymes A/S | Enzymzusammensetzungen und verwendungen davon |
EP4097227A1 (de) | 2020-01-31 | 2022-12-07 | Novozymes A/S | Mannanase-varianten und dafür codierende polynukleotide |
EP4097226A1 (de) | 2020-01-31 | 2022-12-07 | Novozymes A/S | Mannanase-varianten und dafür codierende polynukleotide |
EP4103709A2 (de) | 2020-02-10 | 2022-12-21 | Novozymes A/S | Polypeptide, die alpha-amylase-aktivität aufweisen, und für dieselben codierende polynukleotide |
DE102020001458A1 (de) * | 2020-03-06 | 2021-09-09 | WeylChem Performance Products GmbH | Wasch- und Reinigungsmittel, Verfahren zum Desinfizieren und deren Verwendung |
EP3892708A1 (de) | 2020-04-06 | 2021-10-13 | Henkel AG & Co. KGaA | Reinigungszusammensetzungen mit dispersinvarianten |
EP4139431A1 (de) | 2020-04-21 | 2023-03-01 | Novozymes A/S | Reinigungszusammensetzungen mit polypeptiden mit fructanabbauender aktivität |
EP4152945A1 (de) | 2020-05-18 | 2023-03-29 | DSM IP Assets B.V. | Tierfutterzusammensetzungen |
BR112022023230A2 (pt) | 2020-05-18 | 2022-12-27 | Dsm Ip Assets Bv | Composições de ração animal |
CN115836125A (zh) | 2020-06-24 | 2023-03-21 | 诺维信公司 | 纤维素酶用于从纺织品去除尘螨的用途 |
EP3936593A1 (de) | 2020-07-08 | 2022-01-12 | Henkel AG & Co. KGaA | Reinigungszusammensetzungen und verwendungen davon |
JP2023538740A (ja) | 2020-08-25 | 2023-09-11 | ノボザイムス アクティーゼルスカブ | ファミリー44キシログルカナーゼの変異体 |
CN116507725A (zh) | 2020-10-07 | 2023-07-28 | 诺维信公司 | α-淀粉酶变体 |
WO2022084303A2 (en) | 2020-10-20 | 2022-04-28 | Novozymes A/S | Use of polypeptides having dnase activity |
US20230399588A1 (en) | 2020-10-28 | 2023-12-14 | Novozymes A/S | Use of lipoxygenase |
MX2023004938A (es) | 2020-11-02 | 2023-05-17 | Novozymes As | Variantes de glucoamilasa y polinucleotidos que codifican las mismas. |
WO2022106400A1 (en) | 2020-11-18 | 2022-05-27 | Novozymes A/S | Combination of immunochemically different proteases |
WO2022106404A1 (en) | 2020-11-18 | 2022-05-27 | Novozymes A/S | Combination of proteases |
CN116829709A (zh) | 2021-02-12 | 2023-09-29 | 诺维信公司 | α-淀粉酶变体 |
WO2022189521A1 (en) | 2021-03-12 | 2022-09-15 | Novozymes A/S | Polypeptide variants |
WO2022194673A1 (en) | 2021-03-15 | 2022-09-22 | Novozymes A/S | Dnase variants |
EP4060036A1 (de) | 2021-03-15 | 2022-09-21 | Novozymes A/S | Polypeptidvarianten |
BR112023019583A2 (pt) | 2021-04-01 | 2023-12-05 | Sterilex LLC | Desinfetante/sanitizante em pó sem quaternários |
EP4359518A1 (de) | 2021-06-23 | 2024-05-01 | Novozymes A/S | Alpha-amylase-polypeptide |
WO2023288294A1 (en) | 2021-07-16 | 2023-01-19 | Novozymes A/S | Compositions and methods for improving the rainfastness of proteins on plant surfaces |
WO2023144071A1 (en) | 2022-01-28 | 2023-08-03 | Unilever Ip Holdings B.V. | Laundry composition |
WO2023144110A1 (en) | 2022-01-28 | 2023-08-03 | Unilever Ip Holdings B.V. | Laundry composition |
WO2023165507A1 (en) | 2022-03-02 | 2023-09-07 | Novozymes A/S | Use of xyloglucanase for improvement of sustainability of detergents |
WO2023165950A1 (en) | 2022-03-04 | 2023-09-07 | Novozymes A/S | Dnase variants and compositions |
AU2023231428A1 (en) | 2022-03-08 | 2024-07-11 | Novozymes A/S | Fusion polypeptides with deamidase inhibitor and deamidase domains |
EP4242303A1 (de) | 2022-03-08 | 2023-09-13 | Novozymes A/S | Fusionspolypeptide mit desamidasehemmer und desamidasedomänen |
WO2023194204A1 (en) | 2022-04-08 | 2023-10-12 | Novozymes A/S | Hexosaminidase variants and compositions |
WO2023225459A2 (en) | 2022-05-14 | 2023-11-23 | Novozymes A/S | Compositions and methods for preventing, treating, supressing and/or eliminating phytopathogenic infestations and infections |
WO2023247348A1 (en) | 2022-06-21 | 2023-12-28 | Novozymes A/S | Mannanase variants and polynucleotides encoding same |
WO2023247664A2 (en) | 2022-06-24 | 2023-12-28 | Novozymes A/S | Lipase variants and compositions comprising such lipase variants |
WO2024003143A1 (en) | 2022-06-30 | 2024-01-04 | Novozymes A/S | Mutanases and oral care compositions comprising same |
WO2024012912A1 (en) | 2022-07-15 | 2024-01-18 | Novozymes A/S | Polypeptides having deamidase inhibitor activity |
WO2024121070A1 (en) | 2022-12-05 | 2024-06-13 | Novozymes A/S | Protease variants and polynucleotides encoding same |
WO2024121324A1 (en) | 2022-12-08 | 2024-06-13 | Novozymes A/S | Polypeptide having lysozyme activity and polynucleotides encoding same |
WO2024126483A1 (en) | 2022-12-14 | 2024-06-20 | Novozymes A/S | Improved lipase (gcl1) variants |
WO2024137246A1 (en) | 2022-12-19 | 2024-06-27 | Novozymes A/S | Carbohydrate esterase family 1 (ce1) polypeptides having ferulic acid esterase and/or acetyl xylan esterase activity and polynucleotides encoding same |
WO2024137250A1 (en) | 2022-12-19 | 2024-06-27 | Novozymes A/S | Carbohydrate esterase family 3 (ce3) polypeptides having acetyl xylan esterase activity and polynucleotides encoding same |
WO2024133495A1 (en) | 2022-12-21 | 2024-06-27 | Novozymes A/S | Microbial proteases for cell detachment |
WO2024133497A1 (en) | 2022-12-21 | 2024-06-27 | Novozymes A/S | Recombinant protease for cell detachment |
EP4389865A1 (de) | 2022-12-21 | 2024-06-26 | Novozymes A/S | Rekombinante protease zur zellablösung |
WO2024131880A2 (en) | 2022-12-23 | 2024-06-27 | Novozymes A/S | Detergent composition comprising catalase and amylase |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0070066A1 (de) | 1981-07-13 | 1983-01-19 | THE PROCTER & GAMBLE COMPANY | Wäschebleichmittelprodukt mit geregelter Freigabe des Bleichmittels |
US4404128A (en) | 1981-05-29 | 1983-09-13 | The Procter & Gamble Company | Enzyme detergent composition |
EP0206418A2 (de) | 1985-06-28 | 1986-12-30 | The Procter & Gamble Company | Granulierte Zusammensetzung enthaltend ein trockenes Bleichmittel und ein stabiles Enzym |
WO1990009440A1 (en) | 1989-02-20 | 1990-08-23 | Novo Nordisk A/S | Enzyme containing granulate and method for production thereof |
WO2005083046A1 (en) | 2004-02-23 | 2005-09-09 | The Procter & Gamble Company | A granular laundry detergent composition comprising an anionic detersive surfactant, and low levels of, or no, zeolite builders and phosphate builders |
WO2005083049A2 (en) | 2004-02-23 | 2005-09-09 | The Procter & Gamble Company | A granular laundry detergent composition comprising a ternary detersive surfactant system and low levels of, or no, zeolite builders and phosphate builders |
US20070173429A1 (en) * | 2006-01-23 | 2007-07-26 | The Procter & Gamble Company | Composition comprising a lipase and a bleach catalyst |
US20080206830A1 (en) | 1997-12-20 | 2008-08-28 | Becker Nathaniel T | Granule with hydrated barrier material |
EP2377914A1 (de) | 2010-04-19 | 2011-10-19 | The Procter & Gamble Company | Schwach alkalische, feste Waschmittelzusammensetzung mit Perhydrolase und wenig Builder |
WO2012134969A1 (en) | 2011-03-25 | 2012-10-04 | The Procter & Gamble Company | Spray-dried laundry detergent particles |
Family Cites Families (74)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE680847A (de) | 1963-05-27 | 1966-11-14 | ||
CA888690A (en) * | 1966-04-25 | 1971-12-21 | B. Mccarty Charles | Enzyme-containing detergent compositions |
US4016040A (en) | 1969-12-10 | 1977-04-05 | Colgate-Palmolive Company | Preparation of enzyme-containing beads |
GB1590432A (en) | 1976-07-07 | 1981-06-03 | Novo Industri As | Process for the production of an enzyme granulate and the enzyme granuate thus produced |
JPS5950280B2 (ja) * | 1980-10-24 | 1984-12-07 | 花王株式会社 | 酵素入り漂白剤組成物 |
GR76237B (de) | 1981-08-08 | 1984-08-04 | Procter & Gamble | |
US4760025A (en) | 1984-05-29 | 1988-07-26 | Genencor, Inc. | Modified enzymes and methods for making same |
DK263584D0 (da) | 1984-05-29 | 1984-05-29 | Novo Industri As | Enzymholdige granulater anvendt som detergentadditiver |
US4713245A (en) | 1984-06-04 | 1987-12-15 | Mitsui Toatsu Chemicals, Incorporated | Granule containing physiologically-active substance, method for preparing same and use thereof |
US4767557A (en) * | 1985-06-28 | 1988-08-30 | The Procter & Gamble Company | Dry bleach and stable enzyme granular composition |
DK435687D0 (da) | 1987-08-21 | 1987-08-21 | Novo Industri As | Enzymholdigt granulat og fremgangsmaade til fremstilling deraf |
DK435587D0 (da) | 1987-08-21 | 1987-08-21 | Novo Industri As | Fremgangsmaade til fremstilling af et enzymholdigt granulat |
DE68924654T2 (de) | 1988-01-07 | 1996-04-04 | Novonordisk As | Spezifische Protease. |
US5318714A (en) * | 1988-03-14 | 1994-06-07 | Novo Nordisk A/S | Stabilized particulate composition |
DK78089D0 (da) | 1989-02-20 | 1989-02-20 | Novo Industri As | Detergentholdigt granulat og fremgangsmaade til fremstilling deraf |
WO1991002792A1 (en) | 1989-08-25 | 1991-03-07 | Henkel Research Corporation | Alkaline proteolytic enzyme and method of production |
US5879920A (en) | 1991-10-07 | 1999-03-09 | Genencor International, Inc. | Coated enzyme-containing granule |
US5324649A (en) | 1991-10-07 | 1994-06-28 | Genencor International, Inc. | Enzyme-containing granules coated with hydrolyzed polyvinyl alcohol or copolymer thereof |
KR100294361B1 (ko) | 1992-07-23 | 2001-09-17 | 피아 스타르 | 돌연변이체알파-아밀라제,세정제,접시세척제,및액화제 |
DK5593D0 (da) * | 1993-01-18 | 1993-01-18 | Novo Nordisk As | Granulat |
PL310326A1 (en) | 1993-02-11 | 1995-12-11 | Genencor Int | Novel oxidation-stable mutants of alpha-amylase as well as detergent and starch liquefaction compositions containing them |
DE4315397A1 (de) * | 1993-05-08 | 1994-11-10 | Henkel Kgaa | Reinigungsmittel mit Verhinderung des Anlaufens von Tafelsilber in Geschirrspülmaschinen |
DE69434962T2 (de) | 1993-10-14 | 2008-01-17 | The Procter & Gamble Company, Cincinnati | Proteasehaltige reinigungsmittel |
US5824531A (en) | 1994-03-29 | 1998-10-20 | Novid Nordisk | Alkaline bacilus amylase |
GB9407533D0 (en) * | 1994-04-13 | 1994-06-08 | Procter & Gamble | Detergent compositions |
US5534179A (en) | 1995-02-03 | 1996-07-09 | Procter & Gamble | Detergent compositions comprising multiperacid-forming bleach activators |
AR000862A1 (es) | 1995-02-03 | 1997-08-06 | Novozymes As | Variantes de una ó-amilasa madre, un metodo para producir la misma, una estructura de adn y un vector de expresion, una celula transformada por dichaestructura de adn y vector, un aditivo para detergente, composicion detergente, una composicion para lavado de ropa y una composicion para la eliminacion del |
ES2329528T3 (es) | 1995-02-03 | 2009-11-26 | Novozymes A/S | Metodo para diseñar mutantes alfa-amilasa con propiedades determinadas. |
US6093562A (en) | 1996-02-05 | 2000-07-25 | Novo Nordisk A/S | Amylase variants |
JP3025627B2 (ja) | 1995-06-14 | 2000-03-27 | 花王株式会社 | 液化型アルカリα−アミラーゼ遺伝子 |
US5597936A (en) | 1995-06-16 | 1997-01-28 | The Procter & Gamble Company | Method for manufacturing cobalt catalysts |
AUPN502195A0 (en) * | 1995-08-25 | 1995-09-14 | Procter & Gamble Company, The | Detergent composition with bleach system stabilized by enzymes |
US5576282A (en) | 1995-09-11 | 1996-11-19 | The Procter & Gamble Company | Color-safe bleach boosters, compositions and laundry methods employing same |
BR9708625A (pt) | 1996-04-12 | 1999-08-03 | Novo Nordisk As | Grãnulo contendo enzina processo para a produção do mesmo composição detergente composição para ração animal composição para panificação e utilização de grãnulos |
PH11997056158B1 (en) | 1996-04-16 | 2001-10-15 | Procter & Gamble | Mid-chain branched primary alkyl sulphates as surfactants |
MA24136A1 (fr) | 1996-04-16 | 1997-12-31 | Procter & Gamble | Fabrication d'agents de surface . |
EG21623A (en) | 1996-04-16 | 2001-12-31 | Procter & Gamble | Mid-chain branced surfactants |
US5763385A (en) | 1996-05-14 | 1998-06-09 | Genencor International, Inc. | Modified α-amylases having altered calcium binding properties |
CA2268772C (en) | 1996-10-18 | 2008-12-09 | The Procter & Gamble Company | Detergent compositions comprising an amylolytic enzyme and a cationic surfactant |
CA2282466C (en) | 1997-03-07 | 2005-09-20 | The Procter & Gamble Company | Bleach compositions containing metal bleach catalyst, and bleach activators and/or organic percarboxylic acids |
CN1263759C (zh) | 1997-03-07 | 2006-07-12 | 宝洁公司 | 制备交联桥大环化合物的改进方法 |
US6218351B1 (en) | 1998-03-06 | 2001-04-17 | The Procter & Gamble Compnay | Bleach compositions |
ID22981A (id) | 1997-03-07 | 1999-12-23 | Procter & Gamble | Komposisi pengelantang |
MA25044A1 (fr) | 1997-10-23 | 2000-10-01 | Procter & Gamble | Compositions de lavage contenant des variants de proteases multisubstituees. |
EP2386568B1 (de) | 1997-10-30 | 2014-08-06 | Novozymes A/S | Mutanten der alpha-Amylase |
JP2002513563A (ja) * | 1998-05-01 | 2002-05-14 | ザ、プロクター、エンド、ギャンブル、カンパニー | 修飾トランスフェラーゼを含有した洗濯洗剤および/または布帛ケア組成物 |
DE69913146T2 (de) | 1998-06-30 | 2004-09-16 | Novozymes A/S | Neues, verbessertes, enzymhaltiges Granulat |
US6268329B1 (en) | 1998-06-30 | 2001-07-31 | Nouozymes A/S | Enzyme containing granule |
ES2168835T3 (es) * | 1998-07-17 | 2002-06-16 | Procter & Gamble | Metodo para preparar comprimidos detergentes. |
PH11999002190B1 (en) | 1998-09-01 | 2007-08-06 | Unilever Nv | Composition and method for bleaching a substrate |
CA2348893A1 (en) | 1998-11-30 | 2000-06-08 | The Procter & Gamble Company | Process for preparing cross-bridged tetraaza macrocycles |
US6403355B1 (en) | 1998-12-21 | 2002-06-11 | Kao Corporation | Amylases |
JP4745503B2 (ja) | 1999-03-31 | 2011-08-10 | ノボザイムス アクティーゼルスカブ | アルカリα−アミラーゼ活性を有するポリペプチド及びそれらをコードする核酸 |
EP1171581A1 (de) | 1999-03-31 | 2002-01-16 | Novozymes A/S | Lipase-variante |
AU5805400A (en) * | 1999-07-09 | 2001-01-30 | Novo Nordisk A/S | A process for preparing an enzyme containing granule |
US6933141B1 (en) | 1999-10-01 | 2005-08-23 | Novozymes A/S | Enzyme granulate |
DE50107849D1 (de) | 2000-07-28 | 2005-12-01 | Henkel Kgaa | Neues amylolytisches enzym aus bacillus sp. a 7-7 (dsm 12368) sowie wasch- und reinigungsmittel mit diesem neuen amylolytischen enzym |
DE10162728A1 (de) | 2001-12-20 | 2003-07-10 | Henkel Kgaa | Neue Alkalische Protease aus Bacillus gibsonii (DSM 14393) und Wasch-und Reinigungsmittel enthaltend diese neue Alkalische Protease |
US7425528B2 (en) | 2002-07-01 | 2008-09-16 | Novozymes A/S | Stabilization of granules |
GB0325432D0 (en) | 2003-10-31 | 2003-12-03 | Unilever Plc | Ligand and complex for catalytically bleaching a substrate |
US8535927B1 (en) | 2003-11-19 | 2013-09-17 | Danisco Us Inc. | Micrococcineae serine protease polypeptides and compositions thereof |
US7208459B2 (en) | 2004-06-29 | 2007-04-24 | The Procter & Gamble Company | Laundry detergent compositions with efficient hueing dye |
CA2854912A1 (en) | 2004-07-05 | 2006-01-12 | Novozymes A/S | Alpha-amylase variants with altered properties |
RU2433182C2 (ru) | 2005-10-12 | 2011-11-10 | Джененкор Интернэшнл, Инк. | Применение и получение стабильной при хранении нейтральной металлопротеиназы |
CN101370921B (zh) | 2006-01-23 | 2014-08-13 | 宝洁公司 | 包含脂肪酶和漂白催化剂的组合物 |
DE102006018780A1 (de) * | 2006-04-20 | 2007-10-25 | Henkel Kgaa | Granulat eines sensitiven Wasch- oder Reinigungsmittelinhaltsstoffs |
EP2029715A1 (de) | 2006-06-19 | 2009-03-04 | Unilever PLC | Waschmittel |
WO2008084093A2 (en) * | 2007-01-11 | 2008-07-17 | Novozymes A/S | Particles comprising active compounds |
MX2009012974A (es) | 2007-06-11 | 2010-01-18 | Appleton Paper Inc | Agente benefico que contiene una particula de suministro. |
DE102007038031A1 (de) | 2007-08-10 | 2009-06-04 | Henkel Ag & Co. Kgaa | Mittel enthaltend Proteasen |
EP2240579B1 (de) * | 2008-02-14 | 2017-05-03 | Danisco US Inc. | Kleine enzymhaltige granulate |
AR070498A1 (es) | 2008-02-29 | 2010-04-07 | Procter & Gamble | Composicion detergente que comprende lipasa |
CN101970631B (zh) * | 2008-03-14 | 2012-10-10 | 荷兰联合利华有限公司 | 洗衣处理组合物 |
CN101980772A (zh) | 2008-03-26 | 2011-02-23 | 宝洁公司 | 递送颗粒 |
-
2012
- 2012-06-11 EP EP12171551.0A patent/EP2674475A1/de not_active Withdrawn
-
2013
- 2013-06-11 CN CN201380030796.9A patent/CN104364364A/zh active Pending
- 2013-06-11 PL PL13171413T patent/PL2674476T5/pl unknown
- 2013-06-11 RU RU2014149582A patent/RU2612142C2/ru active
- 2013-06-11 CN CN202010099823.XA patent/CN111205939A/zh active Pending
- 2013-06-11 JP JP2015516278A patent/JP2015528828A/ja active Pending
- 2013-06-11 HU HUE13171413A patent/HUE038095T2/hu unknown
- 2013-06-11 TR TR2018/09430T patent/TR201809430T4/tr unknown
- 2013-06-11 MX MX2014015172A patent/MX370587B/es active IP Right Grant
- 2013-06-11 BR BR112014030417-3A patent/BR112014030417B1/pt active IP Right Grant
- 2013-06-11 IN IN10427DEN2014 patent/IN2014DN10427A/en unknown
- 2013-06-11 WO PCT/US2013/045070 patent/WO2013188331A1/en active Application Filing
- 2013-06-11 EP EP13171413.1A patent/EP2674476B2/de active Active
- 2013-06-11 ES ES13171413T patent/ES2674940T5/es active Active
- 2013-06-11 DK DK13171413.1T patent/DK2674476T4/da active
-
2014
- 2014-11-21 ZA ZA2014/08580A patent/ZA201408580B/en unknown
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4404128A (en) | 1981-05-29 | 1983-09-13 | The Procter & Gamble Company | Enzyme detergent composition |
EP0070066A1 (de) | 1981-07-13 | 1983-01-19 | THE PROCTER & GAMBLE COMPANY | Wäschebleichmittelprodukt mit geregelter Freigabe des Bleichmittels |
EP0206418A2 (de) | 1985-06-28 | 1986-12-30 | The Procter & Gamble Company | Granulierte Zusammensetzung enthaltend ein trockenes Bleichmittel und ein stabiles Enzym |
WO1990009440A1 (en) | 1989-02-20 | 1990-08-23 | Novo Nordisk A/S | Enzyme containing granulate and method for production thereof |
US20080206830A1 (en) | 1997-12-20 | 2008-08-28 | Becker Nathaniel T | Granule with hydrated barrier material |
WO2005083046A1 (en) | 2004-02-23 | 2005-09-09 | The Procter & Gamble Company | A granular laundry detergent composition comprising an anionic detersive surfactant, and low levels of, or no, zeolite builders and phosphate builders |
WO2005083049A2 (en) | 2004-02-23 | 2005-09-09 | The Procter & Gamble Company | A granular laundry detergent composition comprising a ternary detersive surfactant system and low levels of, or no, zeolite builders and phosphate builders |
US20070173429A1 (en) * | 2006-01-23 | 2007-07-26 | The Procter & Gamble Company | Composition comprising a lipase and a bleach catalyst |
EP2377914A1 (de) | 2010-04-19 | 2011-10-19 | The Procter & Gamble Company | Schwach alkalische, feste Waschmittelzusammensetzung mit Perhydrolase und wenig Builder |
WO2012134969A1 (en) | 2011-03-25 | 2012-10-04 | The Procter & Gamble Company | Spray-dried laundry detergent particles |
Also Published As
Publication number | Publication date |
---|---|
MX2014015172A (es) | 2015-02-17 |
DK2674476T4 (da) | 2022-01-03 |
ZA201408580B (en) | 2017-04-26 |
IN2014DN10427A (de) | 2015-08-21 |
EP2674475A1 (de) | 2013-12-18 |
MX370587B (es) | 2019-12-17 |
BR112014030417A8 (pt) | 2021-04-13 |
ES2674940T5 (es) | 2022-03-17 |
EP2674476A1 (de) | 2013-12-18 |
JP2015528828A (ja) | 2015-10-01 |
HUE038095T2 (hu) | 2018-10-29 |
BR112014030417B1 (pt) | 2024-02-27 |
CN111205939A (zh) | 2020-05-29 |
TR201809430T4 (tr) | 2018-07-23 |
CN104364364A (zh) | 2015-02-18 |
ES2674940T3 (es) | 2018-07-05 |
EP2674476B2 (de) | 2021-11-10 |
RU2014149582A (ru) | 2016-07-10 |
RU2612142C2 (ru) | 2017-03-02 |
PL2674476T5 (pl) | 2021-12-27 |
BR112014030417A2 (pt) | 2017-06-27 |
WO2013188331A1 (en) | 2013-12-19 |
DK2674476T3 (en) | 2018-07-16 |
PL2674476T3 (pl) | 2018-09-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2674476B1 (de) | Wasch- und Reinigungsmittel | |
US9752103B2 (en) | Detergent composition | |
EP3088506B1 (de) | Reinigungsmittelzusammensetzung | |
EP2828339B1 (de) | Carboxylatfarbstoffe | |
EP3088505B1 (de) | Verfahren zur behandlung eines stoffes | |
EP2714880B1 (de) | Wäschepflegeverfahren mit farbstoffen | |
EP3339377B1 (de) | Wäschepflegezusammensetzungen enthaltend einen carboxylatfarbstoff | |
US9267098B2 (en) | Laundry care composition comprising carboxylate dye | |
US20120322708A1 (en) | Consumer products | |
EP3047010B1 (de) | Wäschepflegezusammensetzungen mit thiophen-azocarboxylat-farbstoffen | |
US20180134995A1 (en) | Laundry Care Compositions Containing Dyes | |
EP3047009B1 (de) | Wäschepflegezusammensetzungen mit carboxylatfarbstoff | |
EP3047007B1 (de) | Wäschepflegezusammensetzungen mit carboxylatfarbstoff | |
EP3047008B1 (de) | Wäschepflegezusammensetzungen mit carboxylatfarbstoff |
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 |
|
17P | Request for examination filed |
Effective date: 20140618 |
|
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 |
|
17Q | First examination report despatched |
Effective date: 20160928 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
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: 20171115 |
|
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: FR Ref legal event code: PLFP Year of fee payment: 6 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 990474 Country of ref document: AT Kind code of ref document: T Effective date: 20180515 |
|
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: 602013035985 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2674940 Country of ref document: ES Kind code of ref document: T3 Effective date: 20180705 |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 Effective date: 20180711 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20180418 |
|
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: 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: 20180418 |
|
REG | Reference to a national code |
Ref country code: HU Ref legal event code: AG4A Ref document number: E038095 Country of ref document: HU |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20180718 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: 20180418 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: 20180418 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: 20180718 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: 20180418 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20180418 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: 20180418 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: 20180418 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: 20180719 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 990474 Country of ref document: AT Kind code of ref document: T Effective date: 20180418 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20180820 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R026 Ref document number: 602013035985 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 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20180418 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: 20180418 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: 20180418 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: 20180418 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
26 | Opposition filed |
Opponent name: NOVOZYMES A/S Effective date: 20190116 |
|
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: 20180418 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: 20180418 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20180630 |
|
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: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180611 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: 20180418 |
|
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: 20180630 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180630 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180611 |
|
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: 20180630 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: 20180418 |
|
PLBB | Reply of patent proprietor to notice(s) of opposition received |
Free format text: ORIGINAL CODE: EPIDOSNOBS3 |
|
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: 20180611 |
|
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 |
|
APAH | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOSCREFNO |
|
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: 20180418 Ref country code: MK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180418 |
|
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: 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: 20180818 |
|
APBU | Appeal procedure closed |
Free format text: ORIGINAL CODE: EPIDOSNNOA9O |
|
PUAH | Patent maintained in amended form |
Free format text: ORIGINAL CODE: 0009272 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT MAINTAINED AS AMENDED |
|
27A | Patent maintained in amended form |
Effective date: 20211110 |
|
AK | Designated contracting states |
Kind code of ref document: B2 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: DE Ref legal event code: R102 Ref document number: 602013035985 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: T4 Effective date: 20211223 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: DC2A Ref document number: 2674940 Country of ref document: ES Kind code of ref document: T5 Effective date: 20220317 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230429 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20230510 Year of fee payment: 11 Ref country code: DK Payment date: 20230613 Year of fee payment: 11 Ref country code: DE Payment date: 20230502 Year of fee payment: 11 Ref country code: CZ Payment date: 20230517 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: TR Payment date: 20230609 Year of fee payment: 11 Ref country code: PL Payment date: 20230516 Year of fee payment: 11 Ref country code: HU Payment date: 20230515 Year of fee payment: 11 Ref country code: FI Payment date: 20230615 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20230504 Year of fee payment: 11 Ref country code: ES Payment date: 20230707 Year of fee payment: 11 |