EP3625319B1 - Beschichtete granulate, deren verwendung und wasch- und reinigungsmittel enthaltend diese - Google Patents

Beschichtete granulate, deren verwendung und wasch- und reinigungsmittel enthaltend diese Download PDF

Info

Publication number
EP3625319B1
EP3625319B1 EP18719438.6A EP18719438A EP3625319B1 EP 3625319 B1 EP3625319 B1 EP 3625319B1 EP 18719438 A EP18719438 A EP 18719438A EP 3625319 B1 EP3625319 B1 EP 3625319B1
Authority
EP
European Patent Office
Prior art keywords
weight
granules
manganese
contain
acid
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
Application number
EP18719438.6A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP3625319A1 (de
Inventor
Paula Barreleiro
Roman MORSCHH USER
Bo Kuhse
Rolf Ludwig
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Catexel Production GmbH
Original Assignee
Weylchem Wiesbaden GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Weylchem Wiesbaden GmbH filed Critical Weylchem Wiesbaden GmbH
Priority to PL18719438T priority Critical patent/PL3625319T3/pl
Publication of EP3625319A1 publication Critical patent/EP3625319A1/de
Application granted granted Critical
Publication of EP3625319B1 publication Critical patent/EP3625319B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D3/168—Organometallic compounds or orgometallic complexes
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3753—Polyvinylalcohol; Ethers or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/391—Oxygen-containing 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • 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
    • C11D3/3951—Bleaching agents combined with specific additives
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to granules and their use in detergents and cleaning agents, in particular in agents for cleaning dishes.
  • Persalts such as perborates and percarbonates are used in dishwashing detergents for cleaning in order to obtain spotless dishes.
  • the dishwashing detergents generally also contain bleach activators and / or bleach catalysts.
  • Bleach catalysts and / or bleach activators are used in dishwashing detergents, preferably in the form of prefabricated granules, in order to increase their storage stability. In addition to the active substances, these granulates usually also contain binders. Bleach granules are for example in the EP 2966161 A1 , US 2011/245136 A1 , US 2007/072787 A1 , EP 0 985 728 A1 , WO 2007/012451 A1 , WO 2010/115581 A1 , WO 2010/115582 A1 , WO 2014/198368 A1 , and WO 2014/198369 A1 described.
  • the amount of coating is generally 1 to 30% by weight, typically 5 to 30% by weight.
  • Fatty acids, alcohol ethoxylates and film-forming polymers, including polyvinyl alcohol, are proposed as materials for the formation of coatings.
  • DE 2263939 describes tablets containing bleach activators which are coated with up to 5% by weight of film-forming water-soluble polymers, up to 15% by weight of a water-soluble or swellable starch or carboxymethyl starch and up to 1.5% by weight of Mg or Ca salts of saturated Contain C 16 -C 20 fatty acids. Bleach catalysts are not included in these tablets.
  • the present invention was therefore based on the object of providing bleach-activating granules which, compared with granules known from the prior art, are distinguished by increased storage stability and increased bleach activation.
  • the present invention relates to granules which contain one or more bleach catalysts from the group of the manganese salts or the manganese complexes and contain at least one binder from the group of acidic organic compounds, the granules being coated with 0.1 to 3% by weight, based on the total amount of the granules, with a coating containing polyvinyl alcohol, the coating being at least 80% by weight % of polyvinyl alcohol or mixtures thereof, based on the total weight of the envelope.
  • the performance of bleaches in detergents and cleaning agents can be significantly increased if the per compound is brought into contact with a combination of bleach catalyst and bleach activator.
  • the bleaching effect of the catalyst is effectively supported by the peroxycarboxylic acid formed from the activator.
  • the peroxycarboxylic acid makes a significant contribution to killing germs on the items to be cleaned, improves the odor of the washing liquor and prevents the formation of a biofilm in the washing machine or dishwasher.
  • the combination of bleach catalysts and bleach activators is therefore useful to increase the bleaching effect and to ensure hygiene when using bleaches in detergents and cleaning agents.
  • bleach activators and bleach catalysts as separate particles or granules also has disadvantages that can have a negative effect on the bleaching effect.
  • the reactions of the per compound or the hydrogen peroxide released therefrom with the bleach activator and the bleach catalyst take place in parallel. If the bleach catalyst granulate dissolves faster than the bleach activator granulate, then the per compound is already consumed before it can react with the bleach activator. The same applies to the reverse case.
  • Granules containing bleach activators and bleach catalysts are also advantageous in order to ensure the homogeneous distribution of both components in the detergent and cleaning agent and to save space in the formulation. Furthermore, the production costs are cheaper, since only one granulate has to be produced instead of two different granulates.
  • Preferred granules according to the invention therefore contain bleach activators and bleach catalysts from the group of the manganese salts or the manganese complexes.
  • the granules according to the invention contain at least one binder from the group of the acidic organic compounds.
  • the amount of bleach activator (s) in the granules according to the invention is usually 1 to 90% by weight, based on the total amount of granules. Preferred amounts of bleach activator (s) range from 50 to 85% by weight.
  • the amount of bleach catalyst (s) in the granules according to the invention is usually from 0.01 to 30% by weight, based on the total amount of granules. Preferred amounts of bleach catalyst (s) range from 0.1 to 20% by weight.
  • the amount of binder (s) in the granules according to the invention is usually 1 to 30% by weight, based on the total amount of granules. Preferred amounts of binder (s) range from 1 to 20% by weight.
  • the amount of other additives in the granules according to the invention is usually 0 to 25% by weight, preferably 0.1 to 25% by weight, based on the total amount of granules. Particularly preferred amounts are in the range from 2 to 20% by weight.
  • the granules according to the invention can contain compounds known per se from the prior art as bleach activators. These are preferably polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated trlazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU ), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyloxi- or n-lauroyloxibenzenesulfonate (NOBS or LOBS), acylated phenolcarboxylic acids, especially nonanoyloxi- or decanoyloxibenzoic acid (NOBA), in particular phthalic anhydride
  • acylacetals and acyllactams can also be preferred can be used.
  • nitrile derivatives such as n-methyl morpholinium acetonitrile methyl sulfate (MMA) or cyanomorpholine (MOR) can be used as bleach activators. Combinations of bleach activators can also be used.
  • Particularly preferred bleach activators are TAED and DOBA.
  • the granules according to the invention from the prior art contain bleach-enhancing transition metal salts or complexes of manganese which are known per se as bleach catalysts.
  • manganese salts in the oxidation states +2 or +3 are particularly preferred, for example manganese halides, the chlorides being preferred, or the manganese salts of organic acids, such as manganese acetates, manganese acetylacetonates, manganese oxalates or manganese nitrates.
  • Bleach catalysts which are also preferably used are complexes of manganese in the II, III, IV or IV oxidation state, which preferably contain one or more macrocyclic ligand (s) with the N, NR, PR, O and / or S donor functions. Preference is given to using bleach catalysts with ligands which have nitrogen donor functions.
  • Bleach catalysts preferably used as transition metal complexes in the granules according to the invention are complexes which, as macromolecular ligands, are 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN), 1 , 5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1, 4,7-trimethyl-1,4,7-triazacyclononane (MeMeTACN) and / or 2-methyl-1 , 4,7-triazacyclononane (Me / TACN) or bridged ligands such as 1,2-bis- (4,7-dimethyl-1,4,7-triazacyclonono-1-yl) ethane (Me4-DTNE) or derivatives of cyclam or cyclens such as 1,8-dimethylcyclam, 1,7-dimethylcyclen, 1,8-diethylcycl
  • Bleach catalysts are used in the granules according to the invention preferably used manganese complexes as they come from EP 1 445 305 , EP 1 520 910 or EP 1 557 457 are known.
  • Preferred ligands are 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 -TACN), 1,4,7-triazacyclononane (TACN) or bridged ligands such as 1,2-bis- (4,7- Dimethyl-1,4,7-triazacyclonono-1-yl) ethane (Me4-DTNE), as e.g. B. in EP 0 458 397 , EP 0 458 398 , EP 0 549 272 , WO 96/06154 , WO 96/06157 or WO 2006/125517 are described.
  • bleach catalysts are, for example, the polynuclear complexes [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (TACN) 2] (PF 6 ) 2 , [Mn IV 2 ( ⁇ -O) 3 (Me 3 -TACN ) 21 (PF 6 ) 2 , [Mn IV 2 ( ⁇ -O) 3 (Me 3 -TACN) 2] (SO 4 ), [Mn IV 2 (MO) 3 (Me 3 -TACN) 2 ] (OAc) 2 , [Mn IV 2 (MO) 3 (Me 3 -TACN) 2] (Cl) 2 , [Mn IV Mn III 2 ( ⁇ -O) 2 (OAc) (Me 4 -DTE)] (Cl) 2 , [Mn IV Mn III 2 ( ⁇ -O) 2 (OAc) (Me 4 -DTE)] (PF 6 ) 2 or the mononuclear complexes [Mn IV (Me 3 -TACN) 2
  • manganese complexes are, for example, [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAC) 2 (TACN) 2] (PF 6 ) 2 , [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] ( PF 6 ) 2 , [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (SO 4 ), [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (OAc) 2 , [ Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (Cl) 2 , [Mn IV 2 ( ⁇ -O) 3 (Me4-DTE)] (PF 6 ) 2 , [Mn IV 2 ( ⁇ - O) 3 (Me4DTE)] (Cl) 2 , [Mn IV 2 ( ⁇ -O) 3 (Me4-DTE)] (SO) 4 ), [Mn IV 2 ( ⁇ -O) 3 (Me4-D) 3
  • the granules according to the invention contain a binder as a further ingredient in order to improve the cohesion of the granules.
  • Substances selected from fatty acids, alcohol ethoxylates and organic polymers can preferably be used as binders. Mixtures of different binders or different binders of the same type can also be used.
  • organic polymers are understood to mean synthetic and natural polymers, as well as modified polymers of natural origin.
  • the binders can be neutral or acidic organic polymers or else low molecular weight organic compounds. It is preferred to use acidic organic compounds, that is to say acidic low molecular weight organic compounds or acidic polymeric organic compounds. These can be used either in the form of the free acid or in partially neutralized form. In the context of the present invention, the term “organic acid” therefore includes both the organic acids in free form and in partially neutralized form.
  • Alkali metal ions in particular Na ions, are preferred as counterions.
  • Suitable binders include organic fatty acids with 8 to 22 carbon atoms, such as lauric acid, myristic acid, stearic acid or mixtures thereof. Farther organic polymers are preferred.
  • the organic polymers can be anionic, cationic or amphoteric in nature. Natural organic polymers and modified organic polymers of natural origin can be used as well as synthetic organic polymers.
  • the group of organic polymers used with particular preference as binders include polyvinyl alcohols including their acetalized derivatives, polyvinylpyrrolidones and polyalkylene glycols, in particular polyethylene glycols.
  • Polyvinyl alcohols which can preferably be used as binders, are described in more detail below in the description of the polyvinyl alcohols which form the coating.
  • the anionic polymers used with particular preference as binders are, in particular, homo- or copolymeric polycarboxylates.
  • polyacrylic acid or polymethacrylic acid in particular those with a relative molecular weight of 500 to 70,000 g / mol, are preferably used.
  • polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their solubility, the short-chain polyacrylates, which have molar masses from 2,000 to 10,000 g / mol and preferably from 3,000 to 5,000 g / mol, are again preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven particularly suitable.
  • Their relative molecular weight, based on free acids, is preferably 2,000 to 70,000 g / mol, particularly preferably 20,000 to 50,000 g / mol and particularly preferably 30,000 to 40,000 g / mol.
  • the polymers can also have structural units derived from allylsulfonic acids. such as allyloxybenzenesulfonic acid and methallylsulfonic acid.
  • Biological are also particularly preferred Degradable polymers from more than two different monomer units, for example those, the structural units from salts of acrylic acid and maleic acid and from vinyl alcohol or vinyl alcohol derivatives and sugar derivatives or the structural units from salts of acrylic acid and 2-alkylallylsulfonic acid and from sugar derivatives contain.
  • copolymers are those which have structural units derived from acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • anionic polymers used with preference as binders are polymers containing sulfonic acid groups, in particular copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and, if appropriate, further ionic or nonionic monomers.
  • binders are C 8 -C 22 alcohol ethoxylates which are solid at room temperature, preferably C 8 -C 22 alcohol ethoxylates with an average of 10 to 100 ethylene oxide units in the molecule, such as Genapol® T 500 from Clariant or carboxymethyl celluloses.
  • the low molecular weight organic acids likewise preferably used as binders can likewise be used either in the form of the free acid or in partially neutralized form.
  • Low molecular weight organic acids used with preference are citric acid, ascorbic acid, oxalic acid and adipic acid. Succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, fatty acids and mixtures of these.
  • Low molecular weight organic acids which are particularly preferably used are oxalic acid, ascorbic acid, citric acid and fatty acids.
  • the granulate according to the invention has a small amount of coating made of polyvinyl alcohol, which ensures storage stability even in tablet formulations.
  • the proportion of the protective or coating layer in the total granulate is 0.1 to 3% by weight, and in particular 1 to 3% by weight.
  • Typical polyvinyl alcohols used according to the invention to form the envelope or as a binder have a number average molecular weight in the range from 10,000 to 200,000 (measured at 20 ° C. using the gel permeation chromatography (GPC) method) (corresponding to the viscosity of a 4% aqueous solution 20 ° C from approx. 2 to 70 mPa * s; measured with the falling ball viscometer according to Höppler, DIN 53015).
  • GPC gel permeation chromatography
  • Polyvinyl alcohol is generally made by saponifying polyvinyl acetate.
  • Particularly suitable polyvinyl alcohol has a degree of hydrolysis of 70 to 100 mol% and its aqueous solution has a Höppler viscosity at 20 ° C. of 2 to 70 mPa * s.
  • polyvinyl alcohols can have been modified hydrophobically or hydrophilically in any way.
  • hydrophobically modified polyvinyl alcohols which contain water-insoluble monomer units in their main chain are ethylene-containing polyvinyl alcohols of the Exceval® type from Kuraray.
  • polyvinyl alcohols can be equipped with any radicals that can be either hydrophobic or hydrophilic, such as polyvinyl alcohols of the Mowiflex® type from Kuraray.
  • the modified radicals can be arranged in blocks or randomly.
  • Polyvinyl alcohols and acetalized polyvinyl alcohols used with preference have molecular weights in the range from 10,000 to 200,000 g / mol, preferably from 11,000 to 90,000 g / mol, particularly preferably from 12,000 to 80,000 g / mol and particularly preferably from 13,000 to 70,000 g / mol.
  • Polyethylene glycols used with preference have molar masses in the range from 200 to 5,000,000 g / mol, corresponding to degrees of polymerization from 5 to> 100,000.
  • the casing consists to a by far predominant proportion of polyvinyl alcohol or mixtures thereof, that is to say at least 80% by weight of polyvinyl alcohol or mixtures thereof, based on the total weight of the casing.
  • Colorants can optionally also be added to the granules according to the invention.
  • Dyes can be in the granulate core and / or in the casing. Dyes are preferably added to the granulate before it has been provided with a coating.
  • the invention relates to granules containing, in addition to the components described above, further additives.
  • the granules according to the invention can thus have bleach catalysts and / or bleach activators, optionally binders and further additives.
  • siccatives such as calcium sulfate
  • the granules according to the invention can be produced by processes known per se and have already been described in detail in the patent documents mentioned above. In principle, different granulation processes are possible.
  • build-up granulation takes place in mixing apparatus.
  • the components are processed in conventional, batch-wise or continuously working mixing devices, which are usually with rotating mixing elements are equipped.
  • mixing all mixing variants that ensure sufficient mixing of the components are conceivable.
  • all components are mixed at the same time.
  • multi-stage mixing processes are also conceivable in which the individual components are introduced into the overall mixture in various combinations, either individually or together with other additives.
  • the sequence of slow and high-speed mixers can be reversed as required.
  • the residence times in the mixer granulation are preferably 0.5 s to 20 min, particularly preferably 2 s to 10 min.
  • the granulating liquid can be pumped into the mixing apparatus via simple guide tubes.
  • nozzle systems single-fluid or multi-fluid nozzles are also conceivable.
  • the granulation stage is followed by a drying (for solvents) or cooling step (for melts) in order to prevent the granules from sticking together.
  • the coarse grain and fine grain fraction is then separated off by sieving.
  • the coarse grain fraction is comminuted by grinding and, like the fine grain fraction, fed to a new granulation process.
  • the coating is preferably applied in a fluidized bed apparatus, for example in a fluidized bed mixer, provided with a coating.
  • one or more plasticizers are added to the pulverulent constituents (bleach activator and / or bleach catalyst and, if appropriate, further auxiliaries). These can be entered as a liquid or as a melt, with melt-like substances being preferred.
  • the liquid plasticizer is intensively mixed with the powdery active substance and, if necessary, the other additives, so that a plastically deformable mass is created.
  • the mixing step can take place in the above-mentioned mixing apparatus, but kneaders or special types of extruders are also conceivable.
  • the granulating mass is then fed through the nozzle bores of a press die using tools pressed so that cylindrically shaped extrudates are produced.
  • the particle diameter is typically between 0.2 and 2 mm, preferably between 0.5 and 0.8 mm, and the particle length in the range from 0.5 to 3.5 mm. ideally between 0.9 and 2.5 mm.
  • the length or size of the granules can be adjusted, for example, by fixed scraper blades, rotating cutting blades, cutting wires or blades. To round off the cut edges, the granulate can then be rounded again in a rounder.
  • a final solidification step is required in which the solvent is removed or the melt solidifies and then the coating is applied.
  • This step is usually carried out in a fluidized bed apparatus which, depending on the requirements, is operated as a dryer or cooler.
  • the coarse grain and fine grain fraction is then separated off by sieving.
  • the coarse grain fraction is comminuted by grinding and, like the fine grain fraction, fed to a new granulation process.
  • the granulate produced is then provided with a coating in a fluidized bed apparatus, for example in a fluidized bed mixer.
  • the powdered active substances are optionally mixed with other, preferably solid, additives and this mixture is compacted, then ground and then optionally sieved into individual particle size fractions.
  • liquid additives can also be added to the mixture to a certain extent (for example up to 10% by weight).
  • compacting aids are water glass, polyethylene glycols, nonionic surfactants, anionic surfactants, polycarboxylate copolymers, modified and / or unmodified celluloses, bentonites, hectorites, saponites and / or other detergent ingredients.
  • the compaction is preferably carried out on so-called roller compactors (for example from Hosokawa-Bepex, Köppern).
  • roller compactors for example from Hosokawa-Bepex, Köppern.
  • the flakes have to be comminuted in a mill to the desired particle size.
  • gentle types are preferably used as the type of mill.
  • the comminuted particles are then provided with a coating in a fluidized bed apparatus, for example in a fluidized bed mixer.
  • the fine-grain fraction and, if necessary, the coarse-grain fraction are separated from the granulate produced in this way.
  • the coarse grain fraction is fed back into the mill, the fine grain fraction is fed back into the compaction process.
  • common screening machines such as B. tumbler or vibrating screens are used.
  • the granules according to the invention are primarily characterized by their chemical composition. Nevertheless, it has been shown that the action of these granulates can also be advantageously influenced by influencing physical parameters, such as, for example, the particle size, the fine fraction and the content of bleach catalyst and / or bleach activator.
  • preferred granules according to the invention have an average particle size between 0.1 and 1.6 mm, preferably between 0.2 and 1.2 mm and particularly preferably between 0.3 and 1.0 mm, each measured by sieve analysis.
  • Preferred granules according to the invention are further characterized in that their water content is less than 5% by weight (measured according to Karl Fischer), based on the total amount of the granules.
  • Particularly preferred granules according to the invention have a water content of less than 3% by weight, particularly preferably 0 to 2% by weight, based on the total amount of the granules.
  • the granules according to the invention are suitable for use in all detergents or cleaning agents, their use in agents for cleaning dishes, in particular for machine cleaning of dishes, having proven particularly advantageous.
  • the present invention therefore furthermore relates to the use of the granules according to the invention for the production of detergents and cleaning agents and, preferably, of agents for cleaning dishes.
  • the present invention also relates to detergents and cleaning agents, preferably agents for cleaning dishes, containing a granulate according to the invention.
  • Preferred washing and cleaning agents according to the invention in particular the agents for cleaning dishes, contain the granules according to the invention in amounts between 0.1 and 10% by weight, preferably in amounts between 0.2 and 8% by weight and particularly preferably in Amounts between 0.5 and 6% by weight.
  • the detergents and cleaning agents according to the invention in particular the agents for cleaning dishes, which can be in the form of granules, powder or tablet-like solids, but also in liquid or paste form, can, in addition to the granules according to the invention, in principle contain all known ingredients that are usual in such agents contain.
  • the detergents and cleaning agents according to the invention in particular the agents for cleaning dishes, can in particular contain builder substances, peroxygen compounds, enzymes, alkali carriers, surface-active surfactants, pH regulators, organic solvents and other auxiliaries such as glass corrosion inhibitors, silver corrosion inhibitors and foam regulators.
  • the cogranulates according to the invention are suitable for use in both phosphate-containing and phosphate-free formulations.
  • Such an agent is in particular lower alkaline, i. H. its 1% by weight solution has a pH in the range from 8 to 11.5 and preferably from 9 to 11.
  • Water-soluble builder components in the detergents and cleaning agents according to the invention are in principle all builders typically used in such agents.
  • alkali metal phosphates which can be in the form of their alkaline, neutral or acidic sodium or potassium salts, in particular trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • Their amounts can be in the range from 15 to about 65% by weight, preferably from 20 to 60% by weight, based on the total agent.
  • water-soluble builder components are, for example, organic polymers of native or synthetic origin of the polycarboxylate type, which act as co-builders in hard water regions in particular.
  • polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymer acids are suitable.
  • Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
  • the polymers of native origin which can be used as co-builders include, for example, oxidized ones Starch and polyamino acids such as polyglutamic acid or polyaspartic acid.
  • water-soluble builder components are naturally occurring hydroxycarboxylic acids such as, for example, mono-, dihydroxysuccinic acid, alpha-hydroxypropionic acid and gluconic acid.
  • the preferred organic water-soluble builder components include the salts of citric acid, in particular sodium citrate.
  • Anhydrous trisodium citrate and preferably trisodium citrate dihydrate come into consideration as sodium citrate.
  • Trisodium citrate dihydrate can be used as a finely or coarsely crystalline powder.
  • the acids corresponding to the co-builder salts mentioned can also be present.
  • Particularly preferred builder components in phosphate-free formulations are methyl glycine diacetate (MDGA, e.g. Trilon® M, BASF), L-glutamic acid, N, N, (biscarboxymethyl) tert-sodium salt (GLDA, Dissolvine® DL, Akzo Nobel), sodium -Polyaspartates (Baypure®, Lanxess) or salts of iminodisuccinic acid (Baypure®, Lanxess).
  • Preferred peroxygen compounds used in the detergents and cleaning agents according to the invention are perborates and percarbonates, in particular the corresponding sodium salts of these compounds.
  • the enzymes optionally contained in detergents and cleaning agents according to the invention, in particular the agents for cleaning dishes, include proteases, amylases, pullulanases, cutinases and / or lipases, for example proteases such as BLAP TM, Optimase TM, Opticlean TM, Maxacal TM, Maxapem TM, Durazym TM, Purafect TM OxP, Esperase TM and / or Savinase TM, amylases such as Termamyl TM, Amylase-LT TM, Maxamyl TM, Duramyl TM and / or lipases such as Lipolase TM, Lipornax TM, Lumafast TM and / or Lipozym TM .
  • proteases such as BLAP TM, Optimase TM, Opticlean TM, Maxacal TM, Maxapem TM, Durazym TM, Purafect TM OxP, Espe
  • the enzymes used can be adsorbed on carrier substances and / or embedded in coating substances in order to protect them against premature inactivation. They are contained in the detergents and cleaning agents according to the invention, in particular the agents for cleaning dishes, preferably in amounts of up to 10% by weight and particularly preferably in amounts of 0.05 to 5% by weight, with particular preference being given to oxidative degradation stabilized enzymes are used.
  • the washing and cleaning agents according to the invention in particular the agents for cleaning dishes, preferably contain the usual alkali carriers such as alkali metal silicates, alkali metal carbonates and / or alkali metal hydrogen carbonates.
  • Alkali silicates can be used in amounts of up to 40% by weight, in particular from 3 to 30% by weight, based on the total weight of the detergent and cleaning agent.
  • the alkali carrier system preferably used in the detergents and cleaning agents according to the invention, in particular in the agents for cleaning dishes, is a mixture of carbonate and hydrogen carbonate, preferably sodium carbonate and hydrogen carbonate, which is present in an amount of up to 50% by weight and preferably of 5 to 40 wt.% Can be included.
  • the detergents and cleaning agents according to the invention in particular the agents for cleaning dishes, contain from 20 to 60% by weight of water-soluble organic builders, in particular alkali citrate, from 3 to 20% by weight of alkali metal carbonate and from 3 to 40% by weight .-% contain alkali disilicate.
  • Surfactants in particular anionic surfactants, zwitterionic surfactants and preferably low-foaming nonionic surfactants, which facilitate better removal of greasy soiling, as wetting agents and optionally during production, can optionally also be added to the detergents and cleaning agents according to the invention, especially the agents for cleaning dishes these agents serve as granulating agents.
  • Their amount can be up to 20% by weight, preferably up to 10% by weight, and is particularly preferably in the range from 0.5 to 5% by weight, based in each case on the total weight of the detergent and cleaning agent.
  • Extremely low-foam compounds are usually used, especially in agents for machine cleaning of dishes. These include preferably C 12 -C 18 -alkyl polyethylene glycol polypropylene glycol ethers with up to 8 mol of ethylene oxide and propylene oxide units in each molecule.
  • low-foam nonionic surfactants can also be used, such as, for example C 12 -C 18 alkyl polyethylene glycol polybutylene glycol ethers each with up to 8 mol ethylene oxide and butylene oxide units in the molecule, end-capped alkyl polyalkylene glycol mixed ethers and the foaming but ecologically attractive C 8 -C 14 alkyl polyglucosides with a degree of polymerization of about 1 to 4 and / or C 12 -C 14 alkyl polyethylene glycols with 3 to 8 ethylene oxide units in the molecule.
  • C 12 -C 18 alkyl polyethylene glycol polybutylene glycol ethers each with up to 8 mol ethylene oxide and butylene oxide units in the molecule end-capped alkyl polyalkylene glycol mixed ethers and the foaming but ecologically attractive C 8 -C 14 alkyl polyglucosides with a degree of polymerization of about 1 to 4 and / or C 12 -C 14 alkyl
  • Surfactants from the glucamides family such as, for example, alkyl-N-methyl-glucamides, in which the alkyl moiety is preferably derived from a fatty alcohol with a carbon chain length of C 6 -C 14 , are also suitable. It is sometimes advantageous if the surfactants described are used as mixtures, for example the combination of alkyl polyglycosides with fatty alcohol ethoxylates or glucamide with alkyl polyglycosides. The presence of amine oxides, betaines and ethoxylated alkylamines is also possible.
  • the detergents and cleaning agents according to the invention in particular the agents for cleaning dishes, acids that are compatible with the system and the environment, in particular citric acid, acetic acid, tartaric acid, malic acid , Lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali hydroxides.
  • Such pH regulators are contained in the detergents and cleaning agents according to the invention, in particular the agents for cleaning dishes, preferably not more than 10% by weight and particularly preferably from 0.5 to 6% by weight, based in each case on the Total weight of the agent.
  • the organic solvents that can be used in the detergents and cleaning agents according to the invention, especially the agents for cleaning dishes, especially when they are in liquid or pasty form include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert .-Butanol, diols having 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and the ethers which can be derived from the classes of compounds mentioned.
  • Such water-miscible solvents are in the detergents and cleaning agents according to the invention, in particular in the agents for cleaning dishes, preferably present in an amount not exceeding 20% by weight and more preferably from 1 to 15% by weight.
  • Crystalline layered silicates and / or zinc salts are particularly advantageous here.
  • the crystalline layered silicates are sold, for example, by WeylChem Wiesbaden GmbH under the trade name Na-SKS, z. B.
  • Na-SKS-1 Na 2 Si 22 O 45 ⁇ H 2 O, kenyaite
  • Na-SKS-2 Na 2 Si 14 O 29 ⁇ H 2 O, magadiite
  • Na-SKS-3 Na 2 Si 8 O 17 ⁇ H 2 O
  • Na-SKS-4 Na 2 Si 4 O 9 ⁇ xH 2 O, macatite
  • Na-SKS-5 alpha-Na 2 Si 2 O 6
  • Na-SKS-7 beta-Na 2 Si 2 O 6 , natrosilite
  • Na-SKS-9 NaHSi 2 O 5 ⁇ H 2 O
  • Na-SKS-10 NaHSi 2 O 5 ⁇ 3H 2 O, Kanemite
  • Na-SKS-11 t-Na 2 Si 2 O 5
  • Na-SKS-13 NaHSi 2 O 5
  • An overview of crystalline sheet silicates can be found e.g. B. in the in " Seifen- ⁇ le-Fette-Wachse, 116 year, No. 20/1990 ", on pages 805-808 published article.
  • the detergents and cleaning agents according to the invention in particular the agents for cleaning dishes, have an amount of the crystalline layered silicate of 0.1 to 20% by weight, particularly preferably 0.2 to 15% by weight and particularly preferably 0.4 to 10% by weight, based in each case on the total weight of the agent.
  • detergents and cleaning agents according to the invention contain at least one zinc or bismuth salt, preferably selected from the group of organic zinc salts, particularly preferably selected from the group of soluble organic zinc salts, particularly preferably selected from the group of soluble zinc salts of monomeric or polymeric organic acids and extremely preferably selected from the group of zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc oxalate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate.
  • bismuth salts such as. B. bismuth acetates are used.
  • washing and cleaning agents according to the invention in particular agents for cleaning dishes, in which the amount of zinc salt based on the total weight of this agent is 0.1 to 10% by weight, preferably 0.2 to 7% by weight and particularly preferably 0.4 to 4% by weight, regardless of which zinc salts are used, in particular regardless of whether organic or inorganic zinc salts, soluble or insoluble zinc salts or mixtures thereof are used.
  • silver corrosion inhibitors can be used in the detergents and cleaning agents according to the invention, in particular in the agents for cleaning dishes.
  • Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, titanium, zirconium, hafnium, cobalt or cerium salts and / or complexes in which the named Metals are in one of the oxidation states II, III, IV, V or VI, depending on the metal.
  • the detergents and cleaning agents according to the invention in particular the agents for cleaning dishes, for example in the presence of anionic surfactants, foam too much during use, up to 6% by weight, preferably about 0.5 to 4% by weight, can be added to them .-% of a foam-suppressing compound, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations, hydrophobized silica, the bis-fatty acid amides, and other other known commercially available defoamers.
  • a foam-suppressing compound preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations, hydrophobized silica, the bis-fatty acid amides, and other other known commercially available defoamers.
  • the detergents and cleaning agents according to the invention in particular the agents for cleaning dishes, can be used as further ingredients, for example sequestering agents, electrolytes, additional peroxygen activators, dyes or fragrances, such as, for example, from the prior art for such agents.
  • B. perfume oils contain.
  • Detergents and cleaning agents according to the invention in the form of aqueous solutions or solutions containing other customary solvents, in particular corresponding agents for cleaning dishes, are particularly advantageously produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.
  • the detergents and cleaning agents according to the invention are preferably in the form of powdery, granular or tablet-shaped preparations that can be prepared in a manner known per se, for example by mixing, granulating, roller compacting and / or by spray drying of thermally stressable components and Mixing of the more sensitive components, to which in particular enzymes, bleaching agents and the bleaching catalyst are to be included, can be produced.
  • the preferred procedure is to mix all of the ingredients together in a mixer and to apply the mixture using conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the area from 200 ⁇ 10 5 Pa to 1500 ⁇ 10 5 Pa.
  • a tablet produced in this way preferably has a weight of 15 to 40 g, in particular 20 to 30 g, with a diameter of 35 up to 40 mm.
  • the production of detergents and cleaning agents according to the invention in the form of non-dusting, storage-stable, free-flowing powders and / or granules with high bulk densities in the range from 800 to 1,000 g / l, in particular corresponding agents according to the invention for cleaning dishes, can be carried out in that in a first process stage, the builder components are mixed with at least a portion of liquid mixture components, increasing the bulk density of this premix, and subsequently - if desired after intermediate drying - the other constituents of the agent, including the granulate according to the invention, are combined with the premix obtained in this way.
  • Agents according to the invention for the machine cleaning of dishes can be used both in domestic dishwashers and in commercial dishwashers. The addition is done by hand or by means of suitable metering devices.
  • the use concentrations in the cleaning liquor are generally about 1 to 8 g / l, preferably 2 to 5 g / l.
  • a machine wash program is expediently supplemented and ended by a few intermediate wash cycles with clear water and a rinse cycle with a common rinse aid. After drying, when the agents according to the invention are used, completely clean and hygienically perfect crockery is obtained.
  • Example 1 and comparative examples V1 and V2
  • bleach activator granules were coated on a fluidized bed spray granulation system of the Glatt AG400 type by spraying on an aqueous solution of polyvinyl alcohol.
  • Peractive® FDO-X bleach activator granules were used (commercial product from WeylChem Wiesbaden GmbH). These contained a bleach catalyst (MnTACN) and a bleach activator (TAED) as well as the acidic polymer Sokalan® CP 45 (polyacrylate, sodium salt, commercial product from BASF SE).
  • As polyvinyl alcohol that was Product Poval® 6-88 (commercial product from Kuraray) was used. The amount of polyvinyl alcohol was chosen so that the portion of the coating in the finished product was 3%.
  • Example 2 The procedure was as in Example 1, with the change that the amount of polyvinyl alcohol was chosen so that the portion of the coating in the finished product was 6%.
  • the granules coated according to the invention had a significantly improved performance compared to the uncoated granules or to the granules which contained a larger amount of coating.
  • bleach activator granules were coated on a fluidized bed spray granulation system of the Glatt AG400 type by spraying on an aqueous solution of polyvinyl alcohol.
  • Bleach activator granules without a bleach catalyst were used.
  • the granules contained bleach activator (TAED) and the acidic polymer Sokalan® CP 45 (polyacrylate, sodium salt, commercial product from BASF SE).
  • the product Poval® 6-88 commercial product from Kuraray was used as the polyvinyl alcohol.
  • the amount of polyvinyl alcohol was chosen so that the portion of the coating in the finished product was 3%.
  • the following table shows an overview of the test results after 4 weeks of storage at 40 ° C: The following table shows an overview of the test results after 4 weeks of storage granules V3 V4 V5 Pale - [%] performance 31 32 32
  • bleach catalyst granules were coated by spraying an aqueous solution of polyvinyl alcohol on a fluidized bed spray granulation system of the Glatt AG400 type.
  • Bleach catalyst granules without a bleach activator were used.
  • the granules contained bleach catalyst (MnTACN) as well as sodium sulfate, citric acid and rice starch.
  • the product Poval® 6-88 (commercial product from Kuraray) was used as the polyvinyl alcohol.
  • the amount of Polyvinyl alcohol was chosen so that the amount of coating in the finished product was 3%.
  • Example 2 The procedure was as in Example 2, with the change that the amount of polyvinyl alcohol was chosen so that the portion of the coating in the finished product was 6%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
EP18719438.6A 2017-05-17 2018-04-05 Beschichtete granulate, deren verwendung und wasch- und reinigungsmittel enthaltend diese Active EP3625319B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL18719438T PL3625319T3 (pl) 2017-05-17 2018-04-05 Powlekane granulki, ich zastosowanie oraz zawierające je środki do mycia i czyszczenia

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102017004742.1A DE102017004742A1 (de) 2017-05-17 2017-05-17 Beschichtete Granulate, deren Verwendung und Wasch- und Reinigungsmittel enthaltend diese
PCT/EP2018/000162 WO2018210442A1 (de) 2017-05-17 2018-04-05 Beschichtete granulate, deren verwendung und wasch- und reinigungsmittel enthaltend diese

Publications (2)

Publication Number Publication Date
EP3625319A1 EP3625319A1 (de) 2020-03-25
EP3625319B1 true EP3625319B1 (de) 2021-04-21

Family

ID=62044644

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18719438.6A Active EP3625319B1 (de) 2017-05-17 2018-04-05 Beschichtete granulate, deren verwendung und wasch- und reinigungsmittel enthaltend diese

Country Status (12)

Country Link
US (1) US11268048B2 (es)
EP (1) EP3625319B1 (es)
KR (1) KR102442229B1 (es)
CN (1) CN110678536A (es)
AU (1) AU2018268704B2 (es)
CA (1) CA3060091A1 (es)
DE (1) DE102017004742A1 (es)
DK (1) DK3625319T3 (es)
ES (1) ES2876166T3 (es)
HU (1) HUE055719T2 (es)
PL (1) PL3625319T3 (es)
WO (1) WO2018210442A1 (es)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102019005969A1 (de) 2019-08-24 2021-02-25 WeylChem Performance Products GmbH Hydroxycarbonsäureester, Verfahren zu deren Herstellung und deren Verwendung
EP3967742A1 (en) 2020-09-15 2022-03-16 WeylChem Performance Products GmbH Compositions comprising bleaching catalyst, manufacturing process thereof, and bleaching and cleaning agent comprising same
EP4008765A1 (en) 2020-12-07 2022-06-08 WeylChem Performance Products GmbH Compositions comprising protonated triazacyclic compounds and bleaching agent and cleaning agent comprising same
EP4296343A1 (en) 2022-06-24 2023-12-27 WeylChem Performance Products GmbH Compositions comprising protonated triazacyclic compounds and manganese(ii) acetate, manufacturing thereof, and bleaching and cleaning agent comprising same
CN115176810A (zh) * 2022-07-11 2022-10-14 山东神州蓝环保科技有限公司 一种单过硫酸氢钾基础组合消毒剂及其制备方法

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2263939C2 (de) 1972-07-03 1983-01-13 Henkel KGaA, 4000 Düsseldorf Zur Verwendung in perhydrathaltigen Textilwaschmitteln geeignete Bleichaktivator-Tablette
ES2100925T3 (es) 1990-05-21 1997-07-01 Unilever Nv Activacion de blanqueador.
ATE143417T1 (de) 1990-05-25 1996-10-15 Duphar Int Res Verfahren zur abtrennung organischer substanzen
US5194416A (en) 1991-11-26 1993-03-16 Lever Brothers Company, Division Of Conopco, Inc. Manganese catalyst for activating hydrogen peroxide bleaching
GB9127060D0 (en) 1991-12-20 1992-02-19 Unilever Plc Bleach activation
WO1996006157A1 (en) 1994-08-19 1996-02-29 Unilever N.V. Detergent bleach composition
WO1996006154A1 (en) 1994-08-19 1996-02-29 Unilever N.V. Detergent bleach composition
ZA981883B (en) * 1997-03-07 1998-09-01 Univ Kansas Catalysts and methods for catalytic oxidation
DE19841184A1 (de) 1998-09-09 2000-03-16 Clariant Gmbh Bleichaktivatorgranulate
DE19916187A1 (de) * 1999-04-10 2000-10-12 Henkel Kgaa Granulares, Bleichaktivatoren enthaltendes Bleichhilfsmittel
DE10304131A1 (de) 2003-02-03 2004-08-05 Clariant Gmbh Verwendung von Übergangsmetallkomplexen als Bleichkatalysatoren
KR101099450B1 (ko) * 2003-05-21 2011-12-28 시바 홀딩 인코포레이티드 표백 촉매를 포함하는 안정한 미립자 조성물
DE10345273A1 (de) 2003-09-30 2005-04-21 Clariant Gmbh Verwendung von Übergangsmetallkomplexen mit Lactamliganden als Bleichkatalysatoren
DE102004003710A1 (de) 2004-01-24 2005-08-11 Clariant Gmbh Verwendung von Übergangsmetallkomplexen als Bleichkatalysatoren in Wasch- und Reinigungsmitteln
AU2006251406B9 (en) 2005-05-27 2009-09-24 Unilever Plc Process of bleaching
DE102005035916A1 (de) 2005-07-28 2007-02-01 Clariant Produkte (Deutschland) Gmbh Verfahren zur Herstellung von Bleichkatalysator-Granulaten
DE102008045207A1 (de) * 2008-08-30 2010-03-04 Clariant International Limited Bleichkatalysatormischungen bestehend aus Mangansalzen und Oxalsäure oder deren Salze
DE102009017722A1 (de) 2009-04-11 2010-10-14 Clariant International Limited Bleichmittelgranulate mit Aktivcoating
DE102009017724A1 (de) * 2009-04-11 2010-10-14 Clariant International Limited Bleichmittelgranulate
EP2555742B2 (en) 2010-04-06 2018-12-05 The Procter and Gamble Company Encapsulates
US20120028874A1 (en) * 2010-07-20 2012-02-02 Susana Fernandez Prieto Particles
DE102013010549A1 (de) 2013-06-15 2014-12-18 Clariant International Ltd. Bleichmittel-Co-Granulate
DE102013010150A1 (de) 2013-06-15 2014-12-18 Clariant International Ltd. Bleichkatalysatorgranulate
WO2014202954A1 (en) * 2013-06-20 2014-12-24 Chemsenti Limited Bleach and oxidation catalyst
EP2966161B1 (en) * 2014-07-08 2018-10-31 Dalli-Werke GmbH & Co. KG Enzyme-bleach catalyst cogranulate suitable for detergent compositions
US10920177B2 (en) 2017-03-16 2021-02-16 Encapsys, Llc Benefit agent containing delivery particle composition

Also Published As

Publication number Publication date
CN110678536A (zh) 2020-01-10
PL3625319T3 (pl) 2021-09-27
ES2876166T3 (es) 2021-11-12
HUE055719T2 (hu) 2021-12-28
WO2018210442A1 (de) 2018-11-22
KR102442229B1 (ko) 2022-09-13
DE102017004742A1 (de) 2018-11-22
DK3625319T3 (da) 2021-07-12
AU2018268704B2 (en) 2023-05-18
CA3060091A1 (en) 2018-11-22
AU2018268704A1 (en) 2019-10-24
US20200172838A1 (en) 2020-06-04
KR20200007828A (ko) 2020-01-22
EP3625319A1 (de) 2020-03-25
US11268048B2 (en) 2022-03-08

Similar Documents

Publication Publication Date Title
EP2417240B1 (de) Bleichmittelgranulate mit aktivcoating
EP2417238B1 (de) Bleichmittelgranulate
EP3625319B1 (de) Beschichtete granulate, deren verwendung und wasch- und reinigungsmittel enthaltend diese
EP1791939B1 (de) Bleichaktivator-mischungen
EP3008158B1 (de) Bleichmittel-co-granulate, verfahren zu deren herstellung und deren verwendung
EP2329000B1 (de) Verwendung von mangan-oxalaten als bleichkatalysatoren
EP3008157B1 (de) Bleichkatalysatorgranulate, deren verwendung und wasch- und reinigungsmittel enthaltend diese
EP2329001B1 (de) Bleichkatalysatormischungen bestehend aus mangansalzen und oxalsäure oder deren salze
EP3874949A1 (de) Co-granulate, wasch- und reinigungsmittel und deren verwendung
EP3345989A1 (de) Granulate, deren verwendung und wasch- und reinigungsmittel enthaltend diese
EP1934324B1 (de) Granuläre bleichaktivator-mischungen
DE19908051A1 (de) Verfahren zur Herstellung compoundierter Acetonitril-Derivate
EP1794272B1 (de) Bleichmittel-mischungen
DE202023001670U1 (de) Co-Granulate, Wasch- und Reinigungsmittel enthaltend diese und deren Verwendung
DE102004043359A1 (de) Blechaktivator-Granulate
WO2007079858A1 (de) Reinigungsmittel mit bleichkatalytisch aktiven komplexen

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

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

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20191217

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

RIN1 Information on inventor provided before grant (corrected)

Inventor name: MORSCHH USER, ROMAN

Inventor name: BARRELEIRO, PAULA

Inventor name: LUDWIG, ROLF

Inventor name: KUHSE, BO

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 502018004916

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C11D0003160000

Ipc: C11D0003200000

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

RIC1 Information provided on ipc code assigned before grant

Ipc: C11D 3/37 20060101ALI20201207BHEP

Ipc: C11D 3/39 20060101ALI20201207BHEP

Ipc: C11D 17/00 20060101ALI20201207BHEP

Ipc: C11D 11/00 20060101ALI20201207BHEP

Ipc: C11D 3/16 20060101ALI20201207BHEP

Ipc: C11D 3/20 20060101AFI20201207BHEP

Ipc: C11D 7/26 20060101ALI20201207BHEP

Ipc: C11D 3/395 20060101ALI20201207BHEP

INTG Intention to grant announced

Effective date: 20210113

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

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502018004916

Country of ref document: DE

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1384662

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210515

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

Effective date: 20210706

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

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: 20210721

Ref country code: FI

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

Effective date: 20210421

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: 20210421

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: 20210421

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2876166

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20211112

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: 20210821

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: 20210722

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: 20210421

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: 20210421

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: 20210823

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: 20210721

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: 20210421

REG Reference to a national code

Ref country code: HU

Ref legal event code: AG4A

Ref document number: E055719

Country of ref document: HU

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502018004916

Country of ref document: DE

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

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: 20210421

Ref country code: CZ

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

Effective date: 20210421

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: 20210421

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: 20210421

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: 20210421

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20220124

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: 20210821

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: 20210421

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

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: 20210421

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

Ref country code: IE

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

Effective date: 20220405

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

Ref country code: IT

Payment date: 20230426

Year of fee payment: 6

Ref country code: FR

Payment date: 20230424

Year of fee payment: 6

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

Ref country code: HU

Payment date: 20230421

Year of fee payment: 6

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

Ref country code: BE

Payment date: 20230419

Year of fee payment: 6

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

Ref country code: MK

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

Effective date: 20210421

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: 20210421

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

Ref country code: LU

Payment date: 20240418

Year of fee payment: 7

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

Ref country code: NL

Payment date: 20240418

Year of fee payment: 7

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

Ref country code: TR

Payment date: 20240329

Year of fee payment: 7

Ref country code: PL

Payment date: 20240329

Year of fee payment: 7

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

Ref country code: GB

Payment date: 20240419

Year of fee payment: 7

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

Ref country code: DE

Payment date: 20240418

Year of fee payment: 7

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

Ref country code: DK

Payment date: 20240423

Year of fee payment: 7

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

Ref country code: CH

Payment date: 20240501

Year of fee payment: 7

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

Ref country code: ES

Payment date: 20240524

Year of fee payment: 7

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

Ref country code: AT

Payment date: 20240419

Year of fee payment: 7