EP3914686B1 - Formulations de produit de nettoyage pour lavage de vaisselle automatique avec agent de blanchiment - Google Patents

Formulations de produit de nettoyage pour lavage de vaisselle automatique avec agent de blanchiment Download PDF

Info

Publication number
EP3914686B1
EP3914686B1 EP20700896.2A EP20700896A EP3914686B1 EP 3914686 B1 EP3914686 B1 EP 3914686B1 EP 20700896 A EP20700896 A EP 20700896A EP 3914686 B1 EP3914686 B1 EP 3914686B1
Authority
EP
European Patent Office
Prior art keywords
weight
cleaning agent
acid
preparation
detergent
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
EP20700896.2A
Other languages
German (de)
English (en)
Other versions
EP3914686A1 (fr
Inventor
Thomas Doering
Brigitte Kempen
Arnd Kessler
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP3914686A1 publication Critical patent/EP3914686A1/fr
Application granted granted Critical
Publication of EP3914686B1 publication Critical patent/EP3914686B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/045—Multi-compartment
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/046—Insoluble free body dispenser
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/2082—Polycarboxylic 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/38618—Protease or amylase in liquid compositions only
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
    • 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
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • 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
    • 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 invention relates to detergent supply forms for automatic dishwashing, which contain different detergent preparations and a spatially separate bleach preparation.
  • devices for multiple dosing of cleaning agents are desired by the consumer.
  • Devices that are now integrated into the dishwasher can be differentiated from dosing containers on the one hand and devices that are independent of the dishwasher on the other.
  • portions of cleaning agent are automatically or semi-automatically metered into the interior of the cleaning machine in the course of several successive cleaning processes. This eliminates the need for the consumer to dose the detergent before the start of each individual cleaning cycle.
  • Dishwashers in particular, which are loaded with dishes over several days and in which the soiled items to be washed remain uncleaned inside the dishwasher for some time before a washing cycle is carried out, have the problem that unpleasant odors develop, e.g. due to milk becoming sour, etc.
  • the WO2012126536 A1 describes a dosing system for a dishwasher, which contains at least one agent for the essentially continuous, water-induced release of at least one additive substance into the wash water during a wash program of the dishwasher, particularly preferably from the group of bleach catalysts, bleach activators, bleaches, glass corrosion inhibitors, surfactants and/or disinfectant preparations .
  • the cleaning agents contained in these devices for multiple dosing are also exposed to changing temperatures in particular over a longer period of time, these temperatures being the same as the water temperatures used to carry out the cleaning process to a first approximation. These temperatures can be up to 95°C, with machine dishwashing usually only reaching temperatures between 50 and 75°C.
  • a cleaning agent contained in a device intended for multiple dosing is accordingly repeatedly heated in the course of several cleaning processes to temperatures well above the temperatures customary for transport and storage, with temperature-sensitive active substances in particular being affected.
  • hydrolytic enzymes such as proteases and amylases are components of numerous dishwashing detergents.
  • cleaning agents that are only based on compositions containing enzymes only inadequately remove, for example, coffee and tea stains on the objects to be cleaned.
  • Cleaning compositions containing bleach are very good at removing this type of soiling. However, these compositions have weaknesses in removing soiling such as minced meat, egg yolk or spaghetti. A combination of enzymes and bleach-containing cleaning compositions in cleaning agents is therefore desirable in order to remove these soils with different requirements in a single wash cycle of an automatic dishwasher.
  • Possibilities are therefore being sought for using both enzymes and strong oxidizing agents, in particular chlorine-containing oxidizing agents, on the objects to be cleaned in a rinse cycle of an automatic dishwasher without reducing the cleaning performance, in particular that of the enzymes.
  • the object of the present application is accordingly to provide a cleaning agent supply form which also delivers good cleaning performance on bleachable stains and at the same time contains compositions which are stable to changes in temperature.
  • the cleaning agent supply form is characterized in that the cleaning agent preparations are preferably phosphate-free, i.e. they contain less than 1% by weight phosphate, preferably less than 0.5% by weight phosphate, particularly preferably less than 0.1% by weight phosphate and in particular contain no phosphate.
  • the cleaning agent preparation A contains one or more builders as the first essential component.
  • the builders include, in particular, carbonates, organic cobuilders and silicates.
  • Cleaning agent supply forms according to the invention are preferably characterized in that the builder a1) is selected from the group consisting of the carbonates, the hydrogen carbonates, the citrates, the silicates, the polymeric carboxylates and those containing sulfonic acid groups polymers or mixtures thereof.
  • Preferred cleaning-agent presentation forms comprise a cleaning-agent preparation A which, based on its total weight, contains 2% to 50% by weight, preferably 6% to 45% by weight and in particular 10% to 40% by weight of builder.
  • builders a1) from the group of carbonates and/or hydrogen carbonates, preferably alkali metal carbonates, particularly preferably sodium carbonate, in amounts of 2 to 30% by weight, preferably 3 to 20% by weight and in particular 4 up to 15% by weight, based in each case on the weight of cleaning agent preparation A.
  • alkali metal carbonates particularly preferably sodium carbonate
  • Polycarboxylates/polycarboxylic acids polymeric carboxylates, (poly)aspartic acid, polyacetals, dextrins and organic cobuilders can be mentioned in particular as organic cobuilders. These substance classes are described below.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of the free acid and/or their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, provided such use is not objectionable for ecological reasons, and mixtures of these.
  • Polycarboxylic acids are preferably to be understood as meaning non-polymeric polycarboxylates. Such polymeric polycarboxylates have a larger number, preferably 4 or more, carboxylic acid-containing monomers.
  • the free acids typically also have the property of an acidifying component and are therefore also used to adjust a lower and milder pH of cleaning agents.
  • an acidifying component particularly mention should be made here of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these.
  • Particularly preferred cleaning-agent preparations A according to the invention contain citrate as one of their essential builders.
  • Detergent supply forms characterized in that the detergent preparation A, based on its total weight, contain 2 to 40% by weight, preferably 5 to 30% by weight and in particular 7 to 20% by weight of citrate are preferred according to the invention.
  • Citrate or citric acid particularly in combination with phosphonate, particularly 1-hydroxyethane-1,1-diphosphonic acid, and/or the polymers containing sulfonic acid groups have proven to be the most effective builders in terms of cleaning performance, rinsing performance and particularly deposit inhibition.
  • Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular mass of 500 to 70,000 g/mol.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2000 to 20,000 g/mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g/mol, and particularly preferably from 3000 to 5000 g/mol, may in turn be 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 to be particularly suitable.
  • Their relative molecular mass, based on free acids, is generally from 2000 to 70,000 g/mol, preferably from 20,000 to 50,000 g/mol and in particular from 30,000 to 40,000 g/mol.
  • the content of (co)polymeric polycarboxylates in the machine dishwashing detergents is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.
  • Dishwashing detergents according to the invention can use crystalline layered silicates of the general formula NaMSi x O 2x+1 ⁇ y HzO, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred ones, as a builder Values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
  • Amorphous sodium silicates with a NazO:SiOz modulus of 1:2 to 1:3.3, preferably of 1:2 to 1:2.8 and in particular of 1:2 to 1:2.6, which are preferably delayed in dissolution, can also be used and have secondary washing properties.
  • the content of silicates is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight.
  • Particularly preferred automatic dishwashing detergents according to the invention are silicate-free.
  • machine dishwashing detergents according to the invention can contain the abovementioned builders either in the form of individual substances or in the form of substance mixtures of two, three, four or more builders.
  • liquid automatic dishwashing detergents are characterized in that the dishwashing detergent contains at least two builders from the group consisting of carbonates and citrates and polymers containing sulfonic acid groups, the proportion by weight of these builders, based on the total weight of the automatic dishwashing detergent, being preferably 2 to 50% by weight %, preferably 5 to 45% by weight and in particular 10 to 40% by weight.
  • the combination of two or more builders from the above group has for the Cleaning and rinsing performance of automatic dishwashing detergents according to the invention proved to be advantageous.
  • the polymer containing sulfone groups is preferably a sulfone polymer, preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate.
  • the copolymers can have two, three, four or more different monomer units.
  • preferred copolymeric polysulfonates contain at least one monomer from the group of unsaturated carboxylic acids.
  • the unsaturated carboxylic acid(s) used is/are particularly preferably unsaturated carboxylic acids of the formula R 1 (R 2 )C ⁇ C(R 3 )COOH, in which R 1 to R 3 independently represent -H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH2, -OH or -COOH as defined above or for -COOH or -COOR 4 where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • unsaturated dicarboxylic acids can also be used.
  • H 2 C CH-X-SO 3 H
  • the cleaning-agent preparation in particular cleaning-agent preparation A, contains a polymer comprising acrylamidopropanesulfonic acids, methacrylamidomethylpropanesulfonic acids or acrylamidomethylpropanesulfonic acid as the monomer containing sulfonic acid groups.
  • Particularly preferred sulfonic acid group-containing monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- Methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or their
  • some or all of the sulfonic acid groups can be present in neutralized form, ie the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular sodium ions.
  • metal ions preferably alkali metal ions and in particular sodium ions.
  • the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which only contain carboxylic acid group-containing monomers and sulfonic acid group-containing monomers is preferably 5 to 95% by weight in each case, and the proportion of the sulfonic acid group-containing monomer is particularly preferably 50 to 90% by weight. % and the proportion of the carboxylic acid group-containing monomer is 10 to 50% by weight; the monomers are preferably selected from those mentioned above.
  • the molar mass of the sulfo-copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired application.
  • Preferred cleaning agents are characterized in that the copolymers have molar masses from 2000 to 200,000 g.mol -1 , preferably from 4000 to 25,000 g.mol -1 and in particular from 5000 to 15,000 g.mol -1 .
  • the copolymers also comprise at least one nonionic, preferably hydrophobic, monomer in addition to monomer containing carboxyl groups and monomer containing sulfonic acid groups.
  • nonionic, preferably hydrophobic, monomer in addition to monomer containing carboxyl groups and monomer containing sulfonic acid groups.
  • the nonionic monomers used are preferably monomers of the general formula R 1 (R 2 )C ⁇ C(R 3 )—XR 4 , in which R 1 to R 3 independently represent —H, —CH 3 or —C 2 H 5 , X is an optionally present spacer group selected from -CH 2 -, -C(O)O- and -C(O)-NH-, and R 4 is a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.
  • nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 ,4-Trimethylpentene-1, 2,4,4-Trimethylpentene-2,2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4 ,4-dimethylhexane-1, ethylcyclohexyne, 1-octene, ⁇ -olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and
  • the cleaning agent preparation A contains a complexing agent which is different from the builders mentioned above.
  • the proportion by weight of the complexing agent in the total weight of the cleaning agent preparation A is preferably 2 to 60% by weight, preferably 3 to 55% by weight, preferably 4 to 55% by weight and in particular 8 to 50% by weight.
  • a first group of preferred complexing agents are the phosphonates.
  • the complex-forming phosphonates include a number of different compounds such as, for example, diethylenetriaminepenta-(methylenephosphonic acid) (DTPMP).
  • DTPMP diethylenetriaminepenta-(methylenephosphonic acid)
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably used in the form of the neutral sodium salts, e.g. B. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP. HEDP from the class of the phosphonates is preferably used as the builder.
  • the amino alkane phosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may be preferable, particularly if the agents also contain bleach, to use aminoalkane phosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • detergent compositions A which contain 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) as the phosphonate.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepenta(methylenephosphonic acid)
  • the automatic dishwashing detergents according to the invention can contain two or more different phosphonates.
  • the proportion by weight of the phosphonates in the total weight of detergent compositions A according to the invention is preferably 1 to 8% by weight, preferably 1.2 to 6% by weight, preferably 1.3 to 5% by weight; particularly preferably 1.4 to 4.5% by weight and in particular 1.5 to 4% by weight.
  • the complexing agent a2) is selected from the group consisting of hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glutamic aciddiacetic acid, in particular L-glutamic acid- N , N -diacetic acid, iminodisuccinic acid, hydroxyiminodisuccinic acid, methylglycinediacetic acid, aspartic aciddiacetic acid, hydroxyethane-1,1- diphosphonic acid or diethylenetriaminepenta(methylenephosphonic acid) and salts thereof or mixtures thereof, preferably L-glutamic acid- N , N -diacetic acid and/or methylglycinediacetic acid and salts thereof.
  • the designation methylglycinediacetic acid or L-glutamic acid- N , N -diacetic acid includes not only the free acids but also their salt
  • the cleaning agent preparations A according to the invention can contain, in particular, L-glutamic acid- N , N -diacetic acid and/or the corresponding alkali metal salt (GLDA), preferably the tetrasodium salt, and/or methylglycinediacetic acid and/or the corresponding alkali metal salt, preferably the trisodium salt, as particularly preferred complexing agents.
  • GLDA alkali metal salt
  • the trisodium salt of methylglycine diacetic acid (MGDA) or the corresponding sodium salts is very particularly preferably included, with preferred cleaning agent preparations A being characterized in that these, based on the total weight of the cleaning agent preparations A, contain 3.0 to 35% by weight, preferably 4 0 to 30% by weight and in particular 8.0 to 25% by weight of methylglycinediacetic acid.
  • the cleaning agent preparation A contains the complexing agents selected from phosphonates, if permissible for regulatory reasons, and/or MGDA and their respective salts.
  • the builders then include citrate and carbonate and/or bicarbonate.
  • cleaning agent preparation A contains, in each case based on its total weight, MGDA and/or salts thereof in amounts of 5 to 30% by weight, in particular 8 to 25% by weight, for example 10 to 15% by weight %, citrate in amounts of 3 to 20% by weight, in particular 4 to 15% by weight, and carbonate in amounts of 5 to 30% by weight, in particular 7 to 20% by weight.
  • MGDA and/or salts thereof in amounts of 5 to 30% by weight, in particular 8 to 25% by weight, for example 10 to 15% by weight %
  • citrate in amounts of 3 to 20% by weight, in particular 4 to 15% by weight
  • carbonate in amounts of 5 to 30% by weight, in particular 7 to 20% by weight.
  • phosphonate and/or its salt is also preferably present in amounts of 1.2 to 6% by weight, in particular 1.5 to 4% by weight, provided this is permissible for regulatory reasons.
  • preparation A in addition to citrate in amounts of 3 to 20% by weight, in particular 4 to 15% by weight, and carbonate in amounts of 5 to 30% by weight, in particular 7 to 20% by weight, if permitted for regulatory reasons, phosphonate and/or its salt in amounts of 1.2 to 6% by weight, particularly preferably 1.4 to 4.5% by weight, in particular 1.5 to 4% by weight. % contain.
  • preparation A may also be free of MGDA and/or GLDA, i.e.
  • MGDA and/or GLDA contains less than 1% by weight MGDA and/or GLDA, preferably less than 0.5% by weight MGDA and/or GLDA, especially preferably less than 0.1% by weight of MGDA and/or GLDA and in particular no MGDA and/or GLDA.
  • one of the cleaning agent preparations also contains at least one surfactant, in particular selected from anionic, nonionic, zwitterionic and amphoteric surfactants.
  • the surfactants can also be contained in a cleaning-agent preparation that differs from cleaning-agent preparations A and B.
  • Surfactants are in one cleaning agent preparation B according to the invention, if used, preferably in an amount of up to 40% by weight, in particular 2 to 40% by weight or 4 to 40% by weight, particularly preferably in an amount of 5 to 35% by weight, in particular 10 to 30% by weight.
  • Cleaning agent preparation A preferably contains less than 2% by weight of surfactant, preferably less than 1% by weight of surfactant, particularly preferably less than 1% by weight of surfactant, in particular no surfactant, based in each case on the total weight of cleaning agent preparation A.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols preferably having 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, such as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals from alcohols of natural origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are preferred.
  • Preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO, 4 EO or 7 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention. Block copolymers with EO-PO block units or PO-EO block units can be used here, but also EO-PO-EO copolymers or PO-EO-PO copolymers. It is of course also possible to use mixed alkoxylated nonionic surfactants in which EO and PO units are distributed randomly rather than in blocks. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.
  • the content of nonionic surfactants in the cleaning preparation B is 5 to 30% by weight, preferably 7 to 20% by weight and in particular 9 to 15% by weight, based on the total amount of the cleaning preparation B.
  • the cleaning preparation B can also contain anionic surfactants.
  • anionic surfactants for example, those of the sulfonate type and sulfates used.
  • Surfactants of the sulfonate type are preferably C 9-13 -alkylbenzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained, for example, from C 12-18 -monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfofatty acids esters of ⁇ -sulfofatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • the anionic surfactants, including soaps can be in the form of their sodium, potassium or ammonium salts, as well as soluble salts of organic bases such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the content of anionic surfactants in cleaning preparation B is 0.1 to 30% by weight, preferably 2 to 20% by weight, based on the total amount of cleaning preparation B.
  • a preferred pH of cleaning preparations A according to the invention is between 9 and 14, in particular 9 and 12.
  • the pH can be adjusted, if necessary, using appropriate pH adjusters, in particular sodium hydroxide or potassium hydroxide.
  • the cleaning-agent preparations B according to the invention contain at least one cleaning-active enzyme as their first essential component.
  • the proportion by weight of the cleaning-active enzyme preparation in the total weight of the cleaning-agent preparation B is preferably between 5 and 80% by weight, preferably between 5 and 60% by weight, particularly preferably between 10 and 50% by weight and in particular between 10 and 30% by weight. %.
  • the enzyme preparations used in this way each contain from 0.1 to 40% by weight, preferably from 0.2 to 30% by weight and particularly preferably from 0.4 to 20% by weight and in particular from 0.8% up to 10% by weight of active enzyme protein.
  • the enzymes used with particular preference include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are in principle of natural origin; Based on the natural molecules, improved variants are available for use in cleaning agents, which are used with preference accordingly. Cleaning agents preferably contain enzymes in total amounts of 1 ⁇ 10 -6 to 5% by weight, based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the Biuret method.
  • liquid cleaning agent preparations B according to the invention characterized in that they contain at least one cleaning-active enzyme from the group of amylases and/or proteases and/or cellulases and/or Mannanases, in particular from the group of amylases and/or proteases, are preferred.
  • subtilisin type those of the subtilisin type are preferred.
  • subtilisins BPN' and Carlsberg and their further developed forms the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, which can be assigned to the subtilases, but no longer to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • Liquid cleaning agent preparations B preferred according to the invention contain, based on the total weight of the cleaning agent preparation, 5 to 50% by weight, preferably 7 to 40% by weight and in particular 10 to 30% by weight of protease preparations. Particular preference is given to detergent preparations B which, based on their total weight, contain 15 to 25% by weight of protease preparations.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae and the further developments of the aforementioned amylases which have been improved for use in cleaning agents. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • Liquid cleaning agent preparations B preferred according to the invention contain, based on the total weight of the cleaning agent preparation, 0.1 to 30% by weight, preferably 1.0 to 25% by weight and in particular 2.0 to 20% by weight of amylase preparations. Particular preference is given to detergent preparations B which, based on their total weight, contain 4.0 to 16% by weight of amylase preparations.
  • liquid cleaning preparations B contain, based on the total weight of the cleaning agent preparation, 0.1 to 30% by weight, preferably 1.0 to 25% by weight and in particular 2.0 to 20% by weight of cellulase preparations.
  • liquid cleaning preparations B contain, based on the total weight of the cleaning agent preparation, 0.1 to 30% by weight, preferably 1.0 to 25% by weight and in particular 2.0 to 20% by weight of mannanase preparations.
  • Lipases or cutinases can also be used according to the invention, in particular because of their triglyceride-splitting activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally available from Humicola lanuginosa ( Thermomyces lanuginosus ) or further developed, in particular those with the D96L amino acid substitution. Furthermore, for example, the cutinases can be used which were originally isolated from Fusarium solani pisi and Humicola insolens . It is also possible to use lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii .
  • liquid cleaning preparations B contain, based on the total weight of the cleaning agent preparation, 0.1 to 30% by weight, preferably 1.0 to 25% by weight and in particular 2.0 to 20% by weight of lipase preparations.
  • enzymes which are summarized under the term hemicellulases.
  • oxidoreductases for example oxidases, oxygenases, catalases, peroxidases such as halo-, chloro-, bromo-, lignin-, glucose- or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used to increase the bleaching effect.
  • organic, particularly preferably aromatic, compounds that interact with the enzymes are additionally added in order to increase the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons in the case of greatly differing redox potentials between the oxidizing enzymes and the soiling (mediators).
  • Cleaning-active enzymes in particular proteases and amylases, are generally not provided in the form of the pure protein but rather in the form of stabilized preparations that can be stored and transported.
  • These ready-made preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like preparations, solutions of the enzymes, advantageously as concentrated as possible, low in water and/or mixed with stabilizers or other auxiliaries.
  • the enzymes can be encapsulated for both the solid and the liquid dosage form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer, or in the form of capsules, for example those in which the enzymes are enclosed as in a set gel or in such of the core-shell type, in which an enzyme-containing core is coated with a water, air and/or chemical impermeable protective layer.
  • Additional active substances for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can also be applied in superimposed layers.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example due to the application of polymeric film formers, produce little dust and are stable in storage due to the coating.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and amylase preparations preferably used according to the invention contain from 0.1 to 40% by weight, preferably from 0.2 to 30% by weight, particularly preferably from 0.4 to 20% by weight and in particular from 0 8 to 10% by weight of the enzyme protein.
  • Liquid cleaning agent preparations B that are particularly preferred according to the invention therefore contain, based on the total weight of the cleaning agent preparation, 7 to 40% by weight, in particular 10 to 30% by weight, of protease preparations and 2 to 20% by weight, in particular 4.0 to 16 Wt .-% amylase preparations used, each containing 0.4 to 20 wt .-%, in particular from 0.8 to 10 wt .-% active protein.
  • the liquid cleaning agent preparations B comprise amylases and/or proteases and/or cellulases and/or hemicellulases and/or lipases, in particular amylases and/or proteases, preferably in an amount of 0.01 to 5% by weight 0.05 to 2.5% by weight, in particular 0.1 to 1.5% by weight, of active enzyme protein, based on the total weight of detergent preparation B.
  • a plurality of enzymes and/or enzyme preparations preferably liquid protease preparations and/or amylase preparations, and optionally cellulase preparations and/or mannanase preparations are preferably used.
  • a preferred pH of cleaning agent preparations B according to the invention is between 6 and 9.
  • the cleaning agent preparations B of the cleaning agent forms according to the invention preferably contain less than 2.5% by weight of complexing agents. They preferably contain less than 2.5% by weight of complexing agents and/or builders.
  • the lowering of the complexing agent content below these upper limits has proven to be beneficial for the cleaning performance proven beneficial.
  • a further increase in the cleaning performance of cleaning agent forms according to the invention can be achieved by further reducing the content of complexing agent to well below the upper limits.
  • cleaning agent supply forms according to the invention are characterized in that the cleaning agent preparation B contains less than 2.0% by weight of complexing agent, preferably less than 1.0% by weight of complexing agent, particularly preferably less than 0.5% by weight of complexing agent and in particular none Contains complexing agents.
  • the total amount of the complexing agent and/or builders contained in the detergent preparation B is preferably less than 10% by weight, preferably less than 6% by weight, particularly preferably less than 2% by weight and in particular 0% by weight.
  • organic solvents come from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers.
  • the solvents are preferably selected from ethanol, n- or i-propanol, butanol, glycol, propane or butanediol, glycerol, monoethanolamine, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether , diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy trig
  • Preferred solvents are preferably selected from glycerol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol and polyethylene glycols, in particular those polyethylene glycols which have an average molecular weight between 100 and 800, preferably 200 and 600 g/mol.
  • the proportion by weight of these organic solvents in the total weight of the respective cleaning agent preparations according to the invention is preferably 5 to 80% by weight, preferably 10 to 60% by weight and in particular 20 to 50% by weight.
  • a particularly preferred organic solvent that is particularly effective with regard to the stabilization of the cleaning-agent preparation, in particular cleaning-agent preparation B is 1,2-propylene glycol.
  • the proportion by weight of 1,2-propylene glycol in the total weight of the cleaning agent preparations B according to the invention can vary within wide limits, but such preparations have proven to be particularly stable which, based on the total weight of the respective cleaning agent preparation B, 5 to 80% by weight, preferably 10 to 60% by weight and in particular 20 to 50% by weight of 1,2-propylene glycol. Corresponding preparations are therefore preferred according to the invention.
  • a further optional component of the cleaning agent preparations B according to the invention is a boric acid or a boric acid derivative.
  • the boronic acids or their salts or esters are preferably used in particular, including above all derivatives with aromatic groups, such as ortho-, meta- or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid (4-FPBA), or the Salts or esters of the compounds mentioned.
  • the proportion by weight of boric acid or boric acid derivatives in the total weight of cleaning agent preparations B according to the invention is preferably between 0.001 and 10% by weight, more preferably 0.002 and 6% by weight and in particular 0.05 and 3% by weight.
  • a boric acid derivative which is particularly preferred and which is particularly effective in terms of stabilizing the cleaning agent preparation is 4-formylphenylboronic acid.
  • the proportion by weight of 4-formylphenylboronic acid in the total weight of the cleaning agent preparations according to the invention can vary within wide limits, but such preparations have proven to be particularly stable which, based on the total weight of the cleaning agent preparation B, 0.001 to 10% by weight, preferably 0.002 to 6% by weight and in particular 0.05 to 3% by weight. Corresponding preparations are therefore preferred according to the invention.
  • Another optional component of the cleaning agent preparations according to the invention is a Ca or Mg ion source.
  • the proportion by weight of the Ca or Mg ion source in the total weight of cleaning agent preparations B according to the invention is preferably between 0.01 and 10% by weight, more preferably 0.2 and 8% by weight and in particular 0.5 and 5% by weight.
  • the organic calcium salts have proven to be particularly preferred sources of calcium ions, which are particularly effective in terms of stabilizing the cleaning agent preparation B.
  • the proportion by weight of the organic calcium salts in the total weight of the cleaning agent preparations according to the invention can vary within wide limits, but those preparations which, based on the total weight of the cleaning agent preparation, contain 0.01 to 10% by weight, preferably 0.2 to 8% by weight and in particular 0.5 to 5% by weight. Corresponding preparations are therefore preferred according to the invention.
  • cleaning agent preparations B according to the invention can also contain polyols, in particular sorbitol.
  • the liquid cleaning-agent preparations B contain, based on their total weight, preferably 30% by weight and less, preferably 25% by weight and less, in particular 15% by weight and less water. In a further preferred embodiment, the Cleaning agent preparations B contain from 0.5 to 30% by weight, preferably from 1.0 to 25% by weight and in particular from 1.5 to 30% by weight, of water, based on their total weight.
  • the cleaning agent supply form also comprises a liquid cleaning agent preparation C, where the cleaning agent preparation C differs from the cleaning agent preparations A and B.
  • the cleaning agent preparations A and B and the active ingredient composition D are used in a preferred embodiment in combination with at least one further cleaning agent preparation C.
  • this cleaning agent preparation C is liquid (20° C.), preferably phosphate-free, preferably containing surfactants and/or acids, preferably containing surfactants and acids.
  • the group of these nonionic surfactants includes, for example, the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ether and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ether.
  • the proportion by weight of the nonionic surfactant in the total weight of the cleaning agent preparation C is preferably from 1.0 to 20% by weight, preferably from 2.0 to 18% by weight, particularly preferably from 4.0 to 15% by weight and in particular from 6.0 to 12% by weight.
  • At least one cleaning agent preparation in particular at least one cleaning agent preparation further comprising a nonionic surfactant, particularly preferably at least cleaning agent preparation B and/or D contains at least one hydrotrope (hereinafter also referred to as solubility promoter).
  • Preferred hydrotropes are xylene sulfonate, cumene sulfonate, urea and/or N-methylacetamide, particularly preferably cumene sulfonate and/or xylene sulfonate, especially cumene sulfonate. It has been found that the use of hydrotropes, particularly cumene sulfonate, greatly improves phase stability with respect to temperature variations.
  • At least the cleaning agent preparation C in particular the cleaning agent preparations C and B, contains at least one hydrotrope, preferably xylene sulfonate, cumene sulfonate, urea and/or N- methylacetamide, particularly preferably cumene sulfonate and/or xylene sulfonate, in particular cumene sulfonate, preferably in a quantity from 2 to 25% by weight, in particular from 4 to 20% by weight and particularly preferably in an amount from 6 to 15% by weight, for example from 7 to 12% by weight, based on the total weight of the cleaning agent preparation in question.
  • hydrotrope preferably xylene sulfonate, cumene sulfonate, urea and/or N- methylacetamide, particularly preferably cumene sulfonate and/or xylene sulfonate, in particular cumene sulfonate, preferably in a quantity from 2 to 25% by weight, in
  • the weight ratio of the at least one nonionic surfactant to the at least one hydrotrope is preferably xylene sulfonate, cumene sulfonate, urea and/or N- methylacetamide, particularly preferably cumene sulfonate and/or xylene sulfonate, in particular cumene sulfonate. 2:1 to 1:2, especially 1.6:1 to 1:1.
  • the cleaning agent preparations C according to the invention preferably contain at least one acidifying agent c1) when used in a dishwashing process.
  • Acidifiers can be added to the detergent preparations C according to the invention in order to lower the pH of the liquor in the rinse cycle.
  • Both inorganic acids and organic acids are suitable here, provided they are compatible with the other ingredients.
  • the solid mono-, oligo- and polycarboxylic acids can be used in particular. From this group, in turn, preference is given to formic acid, citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid.
  • Organic sulfonic acids such as amidosulfonic acid can also be used.
  • Sokalan® DCS commercially available and used as an acidifying agent in the present invention Sokalan® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight), can likewise preferably be used.
  • Cleaning agent preparations C which, based on the total weight of the cleaning agent preparation C, contain one or more acidifying agents, preferably mono-, oligo- and polycarboxylic acids, particularly preferably formic acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid and in particular formic acid, acetic acid and /or citric acid in amounts of 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.3 to 8.0% by weight are preferred embodiments of the present invention.
  • acidifying agents preferably mono-, oligo- and polycarboxylic acids, particularly preferably formic acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid and in particular formic acid, acetic acid and /or citric acid in amounts of 0.1 to 12% by weight, preferably 0.2 to 10% by weight
  • the use of formic acid is preferred because, in addition to the acid function to improve the rinsing result, it also has a positive influence on the storage stability of cleaning preparation C, which, as explained above, is subject to severe temperature fluctuations due to storage inside the dishwasher. Furthermore, it has a disinfecting effect, so that when formic acid is used in the rinse cycle, the number of bacteria is reduced. This applies both to those bacteria that are in the rinsing liquor of the final rinse cycle and to those that are in the rinsing liquor remaining in the sump of the dishwasher and the interior of the dishwasher during and after the rinsing process. This can also reduce the number of residual germs on the washed dishes.
  • an active ingredient composition D in particular comprising fragrances and/or fragrance scavengers
  • formic acid is used as acidifying agent in preparation C.
  • the formic acid itself has a slightly pungent odor that is unpleasant for sensitive consumers. Due to the separate storage of the active ingredient composition and the release of the at least one active ingredient D, in particular if it is one or more fragrances, in particular those preferred above, and / or one or more fragrance scavengers, in particular e.g. zinc ricinoleate, neither arises during the dishwashing process an unpleasant odor inside the dishwasher even in the time between the cleaning cycles.
  • the cleaning agent preparations A, B and C described above differ in terms of their composition and are therefore not identical.
  • the cleaning-agent preparations A, B and/or C according to the invention preferably contain at least one glass corrosion inhibitor.
  • the preparation(s) A and/or the preparation(s) C particularly preferably contain a corresponding amount of glass corrosion inhibitor(s).
  • These glass corrosion inhibitors are preferably selected from water-soluble zinc salts, preferably zinc chloride, Zinc sulphate and/or zinc acetate, particularly preferably zinc acetate, polyalkyleneimines, in particular polyethyleneimines.
  • the preparations according to the invention contain as a further component at least one zinc salt, in particular inorganic or organic, as a glass corrosion inhibitor.
  • the inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate.
  • the organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group of zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate.
  • zinc acetate is used as the zinc salt.
  • the zinc salt is preferably present in cleaning agent preparations according to the invention in an amount of 0.01% by weight to 5% by weight, particularly preferably in an amount of 0.05% by weight to 3% by weight, in particular in an amount of 0.1% by weight to 2% by weight, based on the total weight of the respective cleaning agent preparation, in particular the respective cleaning agent preparation A or C.
  • Polyethyleneimines such as those available under the name Lupasol® (BASF) are preferably used in an amount of 0 to 5% by weight, in particular 0.01 to 2% by weight, based on the total weight of the preparation in question Glass corrosion inhibitors are used.
  • the bleach preparation E contains at least the alkali metal hypochlorite as an oxidizing agent, in 0.15 to 3.0% by weight and more preferably in 0.2 to 1% by weight, based on the total weight of the bleach preparation.
  • Suitable cleaning agent preparations E contain an oxygen bleach selected from hydrogen peroxide, peroxomonosulphate salts, peroxodisulphate salts and PAP, the proportion by weight of the oxygen bleach in the total weight of the bleach preparation E being preferably between 0.1 and 50% by weight, preferably between 0.2 and 35% by weight. -%, particularly preferably between 0.5 and 20% by weight and in particular between 1.0 and 10% by weight.
  • an oxygen bleach selected from hydrogen peroxide, peroxomonosulphate salts, peroxodisulphate salts and PAP, the proportion by weight of the oxygen bleach in the total weight of the bleach preparation E being preferably between 0.1 and 50% by weight, preferably between 0.2 and 35% by weight. -%, particularly preferably between 0.5 and 20% by weight and in particular between 1.0 and 10% by weight.
  • the oxidizing agent is preferably selected from chlorine dioxide, calcium hypochlorite, potassium hypochlorite, sodium hypochlorite.
  • the bleach preparation comprises sodium hypochlorite as the oxidizing agent.
  • the bleaching agent composition E contains the at least one oxidizing agent, sodium hypochlorite, in amounts of 0.15 to 3.0% by weight, and more preferably 0.2 to 1.0% by weight, based on the total weight of bleach preparation.
  • the bleach preparation E comprises alkali metal hypochlorite, particularly preferably sodium hypochlorite, and also a phosphonate.
  • alkali metal hypochlorite particularly preferably sodium hypochlorite
  • a phosphonate also a phosphonate.
  • the (preferably organic) phosphonates already described above are suitable for this purpose, in particular the complex-forming phosphonates described above.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • PBTC 2-phosphonobutane-1,2,4-tricarboxylic acid
  • the proportion by weight of the phosphonates, preferably HEDP or PBTC, based on the total weight of bleach preparations E according to the invention is preferably 0.01 to 15% by weight, preferably 0.05 to 12% by weight and in particular 1.0 to 10% by weight .
  • At least one of the cleaning agent preparations A and/or B comprises at least one bleach activator from the group of transition metal catalysts.
  • the proportion by weight of the bleach activator in the total weight of the cleaning-agent preparation B is preferably 0.001 to 2.0% by weight, preferably 0.001 to 1.0% by weight and in particular 0.001 to 0.5% by weight.
  • the bleaching composition is preferably aqueous, i.e. it has a water content of 10 to 98% by weight, in particular 15 to 96% by weight, particularly preferably 20 to 95% by weight, based in each case on the total amount of the bleaching composition E.
  • the pH of the bleaching agent composition E is preferably alkaline, i.e. it has a pH at 20°C (undiluted) of pH 8 and higher, preferably pH 9 and higher, in particular pH 10 and higher. This is preferably achieved by the presence of alkalizing agents in the bleach composition E.
  • the hydroxides preferably alkali metal hydroxides, the carbonates, hydrogen carbonates or sesquicarbonates, preferably alkali metal carbonates or alkali metal hydrogen carbonates or alkali metal sesquicarbonates, are particularly suitable as alkalizing agents, with the alkali metal hydroxides and alkali metal carbonates, in particular sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, being more preferred for the purposes of this invention
  • Sodium hydroxide, potassium hydroxide are used.
  • alkali metal carbonates, especially sodium carbonate can also be used as pH adjusters.
  • the cleaning-agent preparations A and/or B and, if appropriate, C are preferably essentially free of bleach, with "essentially free of bleach” meaning that preferably less than 0.1% by weight, in particular less than 0.01% by weight , and most preferably no bleach at all is included in the respective detergent composition. It is particularly preferred if none of the cleaning agent preparations A, B and C contain bleach.
  • composition of some exemplary cleaning agent supply forms according to the invention comprising cleaning agent preparations A, B, C and E, can be found in the following tables.
  • W.-uR preparation A [% by weight] [% by weight] [% by weight] [% by weight] [% by weight] [% by weight] [% by weight] builder 2 to 50 2 to 50 2 to 30 4 to 30 4 to 30 MGDA 2 to 60 8 to 30 10 to 20 12 to 15 0 Phosphonates where permitted by regulation 0 to 10 1 to 8 1.2 to 6 1.5 to 4 1.5 to 4.5 mix to 100 to 100 to 100 to 100 to 100 ingredients W.
  • -uR preparation B Enzyme preparation, preferably protease and/or amylase preparation at least 5 at least 5 at least 5 at least 5 at least 5 complexing agent ⁇ 2.5 ⁇ 2.5 ⁇ 2.5 ⁇ 2.5 0 surfactants 2 to 40 4 to 40 5 to 35 5 to 35 mix to 100 to 100 to 100 to 100 to 100 ingredients
  • the combination of cleaning agents described above is packaged using a packaging means in which the cleaning agent preparations A and B and E, or A, B and C and E are present separately from one another.
  • This separation can be achieved, for example, by receiving chambers that are separate from one another, with each of these receiving chambers containing one of the cleaning agents combined with one another.
  • Examples of such packaging forms are cartridges with three, four or more receiving chambers that are separate from one another, for example three-, four- or multi-chamber bottles.
  • the packaging means in addition to the preparations A, B and E, also contains at least one active ingredient composition, preferably separate from the cleaning agent preparations, in particular from the cleaning agent preparations A and B, which contains at least one fragrance D.
  • the polymeric carrier material of the particles consists at least partly of ethylene/vinyl acetate copolymer.
  • a further preferred subject matter of the present application is therefore a cleaning agent supply form as described above, characterized in that a polymeric carrier material contains at least 10% by weight, preferably at least 30% by weight, particularly preferably at least 70% by weight, of ethylene/vinyl acetate copolymer contains, preferably made entirely of ethylene / vinyl acetate copolymer.
  • Ethylene/vinyl acetate copolymers is the designation for copolymers of ethylene and vinyl acetate. This polymer is basically produced in a process comparable to the production of low-density polyethylene (LDPE). With a As the proportion of vinyl acetate increases, the crystallinity of the polyethylene is interrupted and the melting and softening points and hardness of the resulting products are reduced in this way. The vinyl acetate also makes the copolymer more polar, thereby improving its adhesion to polar substrates.
  • LDPE low-density polyethylene
  • ethylene/vinyl acetate copolymers described above are widely available commercially, for example under the trademark Elvax® (Dupont).
  • Elvax® Duont
  • polyvinyl alcohols that are particularly suitable for the purposes of the present invention are Elvax® 265, Elvax® 240, Elvax® 205 W, Elvax® 200 W and Elvax® 360.
  • Products available under the trademark Evatane® ( Arkema) are also suitable, for example.
  • active substance compositions are particularly preferred in which ethylene/vinyl acetate copolymer is used as the polymeric carrier material and this copolymer contains 5 to 50% by weight of vinyl acetate, preferably 10 to 40% by weight % vinyl acetate and in particular 20 to 30% by weight vinyl acetate, based in each case on the total weight of the copolymer.
  • Suitable carrier materials are the cyclodextrins.
  • inorganic support materials preference is given to using inorganic support materials.
  • detergent supply forms characterized in that at least one of the carrier materials is an inorganic carrier material, preferably a silicate, phosphate or borate.
  • the silicates, phosphates or borates are preferably in the form of a glass, particularly preferably in the form of a water-soluble glass.
  • Particularly preferred glasses are glasses containing zinc and/or bismuth, in particular glasses containing bismuth phosphate and/or zinc phosphate.
  • the carrier material is water-soluble and in its substance already contains the active ingredient directly, in particular the glass corrosion inhibitors zinc and/or bismuth) in the carrier material.
  • the cleaning agent supply forms can contain such zinc- or bismuth-containing glasses, particularly preferably zinc phosphate-containing glass, in addition to a further active substance composition comprising a carrier material, preferably a water-insoluble carrier material and at least one active substance D. These can then be contained in a common chamber or in separate chambers, in particular in one or more chambers which have openings, in particular openings such that the washing liquor and/or the air can flow through them.
  • a glass containing zinc phosphate or bismuth phosphate contain and also contain at least one, preferably two, three, or more active substance compositions which comprise one or more fragrances and/or one or more fragrance scavengers as active substances.
  • thermoplastic carrier materials or carrier materials which deform plastically under the influence of the ambient temperatures occurring during use. Due to the plastic deformation of the carrier materials in the course of one or more applications, a change in the carrier material surface, in particular a change in the size of the carrier material surface, is achieved, which in turn has an advantageous effect on the release profile and the release kinetics of the cleaning active ingredients contained in the active ingredient compositions.
  • Dosing devices characterized in that at least one polymeric carrier material has a melting or softening point of between 40 and 125°C, preferably between 60 and 100°C, particularly preferably a melting point of 70 to 90°C and in particular between 73 and 80°C ( preferred determination method for the melting point according to ISO 11357-3) are preferred according to the invention.
  • the cleaning agent supply forms according to the invention are particularly suitable for multiple dosing of the active ingredients contained in them.
  • it has proven advantageous to use exclusively water-insoluble carrier materials.
  • these water-insoluble carrier materials simplify the production of presentation forms according to the invention. Preferred forms of supply are therefore characterized in that all carrier materials used are water-insoluble.
  • the active substance compositions can assume all states of aggregation and/or three-dimensional shapes that can be realized depending on the chemical and physical properties of the carrier materials.
  • at least one of the active substance compositions is in the form of a gel.
  • At least one of the active substance compositions is present as a solid. Active substance compositions are used with particular preference in the form of individual blocks comprising an entire active substance composition.
  • the active substance compositions can preferably be in particulate form, the active substance compositions in which the carrier material of at least one of the active substance compositions is in particle form, these particles preferably having an average diameter of 0.5 to 20 mm, preferably from 1 to 10 mm and in particular from 3 up to 6 mm are particularly preferred.
  • Active substance compositions which comprise at least one colored active substance composition are particularly preferably used. By coloring at least one of the active substance compositions, an optical differentiation of these compositions can be achieved and the multiple benefits of these different compositions can be illustrated in a simple manner. Furthermore, the dyes are also suitable as an indicator, in particular as a consumption indicator for the colored active substance compositions.
  • Preferred dyes the selection of which does not pose any difficulty for the person skilled in the art, have a high storage stability and are not sensitive to the other ingredients of the agent and to light and have no pronounced substantivity to the substrates to be treated with the dye-containing agents, such as glass, ceramics or plastic tableware, to avoid them to color
  • colorant When choosing the colorant, care must be taken to ensure that the colorant has a long shelf life and is insensitive to light and does not have too great an affinity for glass, ceramics or plastic tableware. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities with respect to oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergent varies. In the case of colorants which are readily water-soluble, colorant concentrations in the range from a few 10 -2 to 10 -3 % by weight are typically chosen. In contrast, in the case of the pigment dyes which are particularly preferred because of their brilliance but are less readily water-soluble, the suitable concentration of the colorant in cleaning agents is typically a few 10 -3 to 10 -4 % by weight.
  • the cleaning agent supply form is characterized in that the at least one active ingredient D is selected from the group of fragrances, preferably linalyl acetate, dihydromyrcenol, citronellonitrile, menthyl acetate, methylphenylbutanol, eucalyptol and mixtures thereof, fragrance scavengers such as zinc ricinoleate, cyclodextrins, 2- menthyl-5-cyclohexylpentanol and 1-cyclohexylethanol, especially zinc ricinoleate; Dyes, glass corrosion inhibitors, antimicrobial agents, germicides or fungicides and mixtures thereof, preferably mixtures of at least one scent scavenger, preferably with one, two, three or more scents and/or at least one dye. Further preferred are mixtures of at least one fragrance, preferably two, three or more fragrances, and at least one dye.
  • fragrances preferably linalyl acetate, dihydromyr
  • Perfume oils or fragrances which can be used in the context of the present invention are individual odorant compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. However, preference is given Mixtures of different fragrances used, which together produce an appealing fragrance. Perfume oils of this type can also contain natural mixtures of fragrances, such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • a fragrance In order to be perceptible, a fragrance must be volatile, with the nature of the functional groups and the structure of the chemical compound also having an important role to play in terms of molar mass. Thus, most fragrances have molar masses of up to about 200 daltons, while molar masses of 300 daltons and above tend to be an exception. Due to the different volatility of odoriferous substances, the odor of a perfume or fragrance composed of several odoriferous substances changes during evaporation, with the odor impressions being divided into “top note” (top note), “middle note” (middle note or body ) and “base note” (end note or dry out).
  • the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note consists for the most part of less volatile, i.e. adherent fragrances.
  • more volatile fragrances can be bound to certain fixatives, for example, which prevents them from evaporating too quickly.
  • fixatives for example, which prevents them from evaporating too quickly.
  • the fragrances can be processed directly, but it can also be advantageous to apply the fragrances to carriers that ensure a long-lasting fragrance through slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can also be coated with other auxiliaries.
  • particularly preferred fragrances are linalyl acetate, dihydromyrcenol, citronellonitrile, menthyl acetate, methylphenylbutanol and/or eucalyptol and mixtures thereof.
  • the known ricenoleates in particular the zinc ricenoleates, for example, can be used as fragrance scavengers (or, as hereinafter also used synonymously, odor neutralizers or scent neutralizers, agents against malodour or bad odours).
  • fragrance scavengers are 2-menthyl-5-cyclohexylpentanol and 1-cyclohexylethanol.
  • Activated carbon and/or cyclodextrins and/or zeolites, preferably acid-modified zeolites, can also be used with particular preference.
  • Zinc ricinoleate alone or in combination with one or more of the fragrances and/or fragrance scavengers mentioned above as preferred is particularly important preferred because it also has a positive effect on inhibiting glass corrosion during the rinsing process.
  • antimicrobial active ingredients can be used as an alternative or in addition to the above-mentioned fragrances and/or fragrance scavengers.
  • fragrances and/or fragrance scavengers can be used as an alternative or in addition to the above-mentioned fragrances and/or fragrance scavengers.
  • bacteriostatics and bactericides fungistatics and fungicides, etc.
  • Important substances from these groups are, for example, benzalkonium chloride, alkyl aryl sulfonates, halogenated phenols and phenolmercury acetate, although these compounds can also be dispensed with entirely.
  • the active ingredients can in principle be present in any desired amounts in the active ingredient preparations.
  • the proportion by weight of the active substance(s) is 1 to 70% by weight, preferably 10 to 60% by weight, particularly preferably 20 to 50% by weight, in particular 30 to 40% by weight, in each case based on the total weight of the active ingredient composition(s).
  • active substance compositions can be present separately from one another or alongside one another in the packaging of the detergent presentation.
  • the different active substance compositions can preferably be present next to one another, ie in direct contact with one another, in the packaging means of the cleaning agent supply form.
  • the viscosity of all cleaning agent preparations A and B or A, B and C is less than 120 mPas (measured at 20° C. with a Brookfield Instrument LVDV II+, spindle 31, 100 rpm).
  • the viscosity of all cleaning agent preparations is particularly preferably from 1 to 100 mPas, in particular 10 to 80 mPas, preferably 20 to 60 mPas (measured at 20° C. using a Brookfield Instrument LVDV II+, spindle 31, 100 rpm).
  • the above-described cartridges of the cleaning agent supply forms are provided with a dosing device that can be detached from the cartridge.
  • a dosing device can be connected to the cartridge, for example, by means of an adhesive, snap-in, snap-in or plug-in connection.
  • the detachable connection between the cartridge and the dosing device allows the cartridges to be exchanged on the dosing device. Such an exchange can be indicated, for example, when the cleaning program is changed or after the cartridge has been completely emptied.
  • the aforementioned cleaning agent dosing systems comprising the cleaning agent supply form according to the invention, a cartridge and a dosing device detachably connected to the cartridge, are present in a common outer packaging, with the filled cartridge and the dosing device particularly preferably being contained separately from one another in the outer packaging.
  • the outer packaging is used for storage, transport and presentation of the cleaning agent supply form according to the invention and protects it from dirt, impact and impact.
  • the outer packaging should be at least partially transparent.
  • the dosing system according to the invention consists of the basic components of a cartridge filled with the cleaning agent according to the invention and a dosing device that can be coupled to the cartridge, which in turn is formed from other assemblies, such as a component carrier, actuator, closure element, sensor, energy source and/or control unit.
  • the dosing system according to the invention is movable. Movable in the context of this application means that the dosing system is not permanently connected to a water-carrying device such as a dishwasher or the like, but can be removed from a dishwasher by the user or positioned in a dishwasher, i.e. can be handled independently
  • the dosing device is not detachably connected to a water-carrying device such as a dishwasher or the like for the user and only the cartridge is movable.
  • the preparations to be dosed can have a pH of between 2 and 14, in particular 2 and 12, depending on the intended use, all components of the dosing system that come into contact with the preparations should have a corresponding acid and/or alkali resistance. Furthermore, these components should be largely chemically inert, for example to nonionic surfactants, enzymes and/or fragrances, by selecting a suitable material.
  • a cartridge is understood to mean a packaging means which is suitable for enclosing or holding together free-flowing or spreadable preparations and which can be coupled to a dosing device in order to dispense the preparation.
  • a cartridge can also comprise a plurality of chambers which can be filled with compositions that differ from one another. It is also conceivable for a plurality of containers to be arranged in a cartridge unit.
  • the cartridge prefferably has at least one outlet opening which is arranged in such a way that the preparation can be released from the container by gravity when the dosing device is in the position of use.
  • no further means of conveyance are required for releasing preparation from the container, as a result of which the structure of the dosing device can be kept simple and the production costs can be kept low.
  • At least one second chamber is provided for accommodating at least one second free-flowing or spreadable preparation, the second chamber having at least one outlet opening which is arranged in such a way that the product is released from the second chamber by gravity when the dosing device is in the position of use is effected.
  • the arrangement of a second chamber is particularly advantageous if preparations are stored in the separate containers that are usually not stable when stored together, such as bleaches and enzymes.
  • At least one of the chambers for releasing active ingredient(s) D is designed in such a way that it has openings through which the washing liquor and/or the air can flow .
  • the cartridge is designed in one piece.
  • the cartridges can be formed cost-effectively in one production step, in particular by means of suitable blow molding processes.
  • the chambers of a cartridge can be separated from one another, for example, by webs or material bridges.
  • the cartridge can also be formed in several pieces by components that are produced by injection molding and then joined together. Furthermore, it is conceivable that the cartridge is formed in several pieces in such a way that at least one chamber, preferably all chambers, can be individually removed from the dosing device or inserted into the dosing device. In this way it is possible, when a preparation from one chamber is used to varying degrees, to exchange an already emptied chamber, while the others, which can still be filled with preparation, remain in the dosing device. In this way, the individual chambers or their preparations can be refilled in a targeted and needs-based manner.
  • the chambers of a cartridge can be fixed to one another by suitable connection methods, so that a container unit is formed.
  • the chambers can be fixed to one another in a detachable or non-detachable manner by means of a suitable positive, non-positive or material connection.
  • the fixation can be done by one or more of the connection types from the group of snap-in connections, Velcro connections, press connections, fusion connections, adhesive connections, welded connections, soldered connections, screw connections, wedge connections, clamp connections or snap connections.
  • the fixation can also be formed by a shrink tube (so-called sleeve), which is pulled over the whole or sections of the cartridge in a heated state and firmly encloses the chambers or the cartridge in the cooled state.
  • the bottom of the chambers can be inclined in a funnel shape towards the discharge opening.
  • the inner wall of a chamber can be designed by selecting a suitable material and/or surface design in such a way that there is little material adhesion of the preparation to the inner Chamber wall is realized. This measure also allows the remaining emptying of a chamber to be further optimized.
  • the chambers of a cartridge can have the same or different filling volumes.
  • the ratio of the container volumes is preferably 5:1, in a configuration with three chambers it is preferably 4:1:1, these configurations being particularly suitable for use in dishwashers.
  • the cartridge preferably has 4, 5 or 6 chambers.
  • the first chamber contains an alkaline cleaning preparation
  • the second chamber contains an enzymatic preparation
  • the third chamber contains a rinse aid, with the volume ratio of the chambers being approximately 4:1:1.
  • the fourth chamber contains the at least one active substance composition, comprising the at least one active substance D and a carrier material, preferably a water-insoluble carrier material.
  • a dosing chamber can be formed in or on one chamber, in the direction of flow of the preparation in front of the outlet opening.
  • the amount of preparation that is to be released into the environment when the preparation is released from the chamber is determined by the dosing chamber. This is particularly advantageous when the closure element of the dosing device, which causes the preparation to be released from a chamber to the environment, can only be put into a release and a closed state without checking the amount released.
  • the dosing chamber then ensures that a predefined amount of preparation is released without immediate feedback of the amount of preparation dispensed.
  • the dosing chambers can be formed in one piece or in several pieces.
  • one or more chambers has, in addition to an outlet opening, a chamber opening that can be closed in a liquid-tight manner.
  • This chamber opening makes it possible, for example, to refill the preparation stored in this chamber.
  • ventilation options can be provided in particular in the head area of the cartridge in order to ensure pressure equalization between the inside of the cartridge chambers and the environment when the filling level of the chambers falls.
  • These ventilation options can be designed, for example, as a valve, in particular a silicone valve, micro-openings in the cartridge wall or the like.
  • the cartridge chambers are not ventilated directly, but via the dosing device or no ventilation, for example when using flexible containers such as bags, this has the advantage that with increased Temperatures in the course of a rinsing cycle of a dishwasher by heating the chamber contents, a pressure is built up, which pushes the preparations to be dosed in the direction of the outlet openings, so that the cartridge can be easily emptied of residues. Furthermore, with such air-free packaging there is no risk of substances in the preparation oxidizing, which makes pouch packaging or bag-in-bottle packaging appear expedient, particularly for preparations which are sensitive to oxidation.
  • the cartridge usually has a filling volume of ⁇ 5000 ml, in particular ⁇ 1000 ml, preferably ⁇ 500 ml, particularly preferably ⁇ 250 ml, very particularly preferably ⁇ 50 ml.
  • the cartridge can assume any shape. It can, for example, be cube-like, spherical or plate-like.
  • the cartridge and the dosing device can in particular be designed with regard to their three-dimensional shape in such a way that they ensure the lowest possible loss of useful volume, in particular in a dishwasher.
  • the dosing device In order to use the dosing device in dishwashers, it is particularly advantageous to shape the device based on dishes to be cleaned in dishwashers. For example, this can be plate-shaped, approximately the dimensions of a plate. This allows the dosing device to be positioned in a space-saving manner, e.g. in the lower basket of the dishwasher. Furthermore, the correct positioning of the dosing unit is immediately intuitive to the user due to the plate-like shape.
  • the cartridge preferably has a height:width:depth ratio of between 5:5:1 and 50:50:1, particularly preferably about 10:10:1.
  • the "slim" design of the dosing device and the cartridge makes it possible in particular to position the device in the lower cutlery basket of a dishwasher in the receptacles provided for plates. This has the advantage that the preparations dispensed from the dosing device get directly into the washing liquor and cannot adhere to other items to be washed.
  • the dosing system is dimensioned such that the dosing system can only be positioned in the receptacles provided for this purpose in the lower basket.
  • the width and the height of the dosing system can be selected in particular between 150 mm and 300 mm, particularly preferably between 175 mm and 250 mm.
  • the dosing unit in the form of a cup with an essentially circular or square base.
  • a further possibility for reducing the influence of heat on a preparation in a chamber of the cartridge is to isolate the chamber by suitable measures, e.g. by using thermal insulation materials such as Styrofoam, which completely or partially enclose the chamber or the cartridge in a suitable manner.
  • the cartridge has an RFID tag that contains at least information about the contents of the cartridge and that can be read by the sensor unit.
  • This information can be used to select a dosing program stored in the control unit. This can ensure that a dosing program that is optimal for a specific preparation is always used. It can also be provided that if an RFID label is not present or if there is an RFID label with an incorrect or faulty identifier, no dosing takes place through the dosing device and instead an optical or acoustic signal is generated that alerts the user to the error present indicates.
  • the cartridges can also have structural elements which interact with corresponding elements of the dispensing device according to the lock and key principle, so that, for example, only cartridges of a specific type can be coupled to the dispensing device. Furthermore, this embodiment makes it possible for information about the cartridge coupled to the dosing device to be transmitted to the control unit, as a result of which the dosing device can be controlled in a way that is tailored to the content of the corresponding container.
  • the cartridge is designed in particular to hold free-flowing cleaning agents.
  • a cartridge particularly preferably has a plurality of chambers for the spatially separated reception of different preparations of a cleaning agent.
  • the cartridge can be designed in such a way that it can be arranged detachably or permanently in or on the dishwasher.
  • control unit The control unit, sensor unit and at least one actuator required for operation are integrated in the dosing device.
  • An energy source is also preferably arranged in the dosing device.
  • the dosing device preferably consists of a splash-proof housing that prevents splashing water, which can occur, for example, when used in a dishwasher, from penetrating into the interior of the dosing device.
  • the dosing device comprises at least one first interface, which interacts with a corresponding interface formed in or on a water-bearing device, in particular a water-bearing household appliance, preferably a dishwasher, in such a way that electrical energy is transmitted from the water-bearing device to the dosing device is realized.
  • a water-bearing device in particular a water-bearing household appliance, preferably a dishwasher
  • the interfaces are formed by plug connectors.
  • the interfaces can be designed in such a way that wireless transmission of electrical energy is effected.
  • a second interface on the dosing device and the water-bearing device such as a dishwasher, for the transmission of electromagnetic signals, which in particular contain operating status, measurement and/or control information of the dosing device and/or the water-bearing device such as a Represent dishwasher trained.
  • An adapter can be used to easily couple the dosing system to a water-bearing household appliance.
  • the adapter is used to mechanically and/or electrically connect the dosing system to the water-bearing household appliance.
  • the adapter is preferably permanently connected to a water-carrying line of the household appliance.
  • the adapter it is also conceivable to provide the adapter for positioning in or on the household appliance, in which the adapter is caught by the water flow and/or spray jet of the household appliance.
  • the adapter makes it possible to run a dosing system for both a self-sufficient and a "build-in" version. It is also possible to design the adapter as a kind of charging station for the dosing system, in which, for example, the energy source of the dosing device is charged or data is exchanged between the dosing device and the adapter.
  • the adapter can be arranged on one of the inner walls of the washing chamber, in particular on the inner side of the dishwasher door.
  • the adapter as such is not positioned in the water-bearing household appliance so that it is not accessible to the user, so that the dosing device is inserted into the adapter, for example during assembly of the household appliance, with the adapter, the dosing device and the household appliance being designed in this way that a cartridge can be coupled to the dosing device by the user.
  • the detergent dosage forms according to the invention are suitable for use in dishwashing, although the use of a detergent dosage form according to the invention or a detergent metering system for dishwashing in an automatic dishwashing process is preferred.
  • the cleaning agents according to the invention are distinguished by particular physical and chemical stability, in particular with regard to temperature fluctuations.
  • the cleaning agents according to the invention are therefore exceptionally suitable for dosing by means of a dosing system located in the interior of a dishwasher.
  • a dosing system which can be immovably integrated into the interior of the dishwasher (machine-integrated dosing device), but of course can also be introduced into the interior as a mobile device (autonomous dosing device), contains many times the amount of cleaning agent required to carry out a machine cleaning process .
  • Movable in the sense of this application means that the dispensing and dosing system is not permanently connected to a device such as a dishwasher or the like, but can be removed from a dishwasher or positioned in a dishwasher.
  • An example of an immovable cartridge is a container that is immovably integrated into the interior, for example into the side wall or the inner paneling of the door of a dishwasher.
  • An example of a movable cartridge is a container that is placed in the interior of the dishwasher by the consumer and remains there throughout the course of a cleaning cycle. Such a cartridge can be integrated into the interior, for example by simply placing it in the cutlery or crockery basket, but the consumer can also remove it from the interior of the dishwasher again.
  • the cleaning agent or the cleaning agent combination is preferably metered from the cartridge into the interior of the dishwasher as described above by means of a dosing device that can be detached from the cartridge.
  • a dosing device can be connected to the cartridge by means of an adhesive, snap-in, snap-in or plug-in connection.
  • cartridges with an inseparably connected dosing device can of course also be used.
  • a detergent delivery form according to the invention as a detergent reservoir for i) a dosing device immovably integrated in the interior of a dishwasher or ii) a movable dosing device provided for positioning in the interior of a dishwasher is preferred.
  • the cleaning agents and cleaning agent combinations according to the invention are preferably used as dishwasher detergents.
  • the invention also relates to an automatic dishwashing process in which the active ingredient composition is located in the cartridge and the washing liquor and/or the air flows through openings.
  • the active ingredient composition is located in the cartridge and the washing liquor and/or the air flows through openings.
  • the cleaning-agent preparation A and the cleaning-agent preparation B and optionally the cleaning-agent preparation C are metered in at different times of the cleaning cycle.
  • the time t2 is at least 1 minute, preferably at least 2 minutes and in particular between 3 and 30 minutes, in particular between 3 and 20 minutes , before or after, preferably before time t1.
  • Dosing t4 preferably takes place at least 1 minute, preferably at least 2 minutes and in particular between 5 and 40 minutes, in particular between 7 and 35 minutes, before or after, preferably after time t2 .
  • the figure 1 shows a detergent dosing system 101, with a dosing device 102 and a cartridge 103.
  • the cartridge has a chamber 104 for storing active ingredient composition.
  • a slide 105 with a handle 107 is optionally provided for selectively closing and opening the chamber. By moving the slider 105, the column 106 is closed or opened. Inside the column 106 is also a membrane - not shown here - attached.
  • a membrane 108 is attached to an outer wall of a chamber 109 for storing preparation, through which a negative pressure in this chamber 109 is prevented when the chamber 109 is emptied.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Claims (16)

  1. Forme d'offre de détergent comprenant
    a) une préparation détergente A liquide à 20° C, contenant a1) un
    adjuvant ;
    a2) Agent complexant
    b) une préparation de nettoyage B, liquide à 20 °C, différente de la préparation de nettoyage A, contenant
    b1) au moins une préparation enzymatique active pour le nettoyage ainsi que b2) éventuellement au moins un agent tensioactif non ionique
    ainsi que
    c) le cas échéant, une préparation détergente C,
    liquide à 20 °C, différente des préparations
    détergentes A et B,
    contenant
    c1) un agent d'acidification, ainsi qu'éventuellement moins de 1 % en poids, de préférence moins de 0,5 % en poids, en particulier moins de 0,1 % en poids de préparation enzymatique, et
    d) un moyen d'emballage dans lequel les préparations de nettoyage A et/ou B ainsi que, le cas échéant, C se présentent séparément les unes des autres, caractérisé en ce qu'il comprend une préparation d'agent de blanchiment E séparée spatialement des autres préparations de nettoyage,
    dans laquelle ledit au moins un agent oxydant est contenu dans la préparation de blanchiment E, l'hypochlorite de métal alcalin, à raison de 0,15 à 3,0 % en poids, et de manière plus préférée à raison de 0,2 à 1,0 % en poids, par rapport au poids total de la préparation de blanchiment.
  2. Forme d'offre de détergent selon la revendication 1, caractérisée en ce que l'hypochlorite de métal alcalin est de l'hypochlorite de sodium.
  3. Forme d'offre de détergent selon l'une quelconque des revendications précédentes, caractérisée en ce que la préparation d'agent de blanchiment E, comprenant de l'hypochlorite de métal alcalin, comprend en outre un phosphonate, de préférence en une quantité de 0,01 à 15,0 % en poids, de préférence de 0,05 à 12,0 % en poids, et
    en particulier de 0,1 à 10,0 % en poids.
  4. Forme d'offre de détergent selon l'une des revendications précédentes, caractérisée en ce que la préparation de détergent A contient, par rapport à son poids total, 2 à 50 % en poids, de préférence 6 à 45 % en poids et en particulier 10 à 40 % en poids d'adjuvant et/ou l'adjuvant a1) est choisi dans le groupe des carbonates, des hydrogénocarbonates, des citrates, des silicates, des carboxylates polymères et des polymères contenant des groupes acide sulfonique.
  5. Forme d'offre de détergent selon l'une des revendications précédentes, caractérisée en ce que l'agent complexant a2) est choisi dans le groupe constitué par l'acide hydroxyéthyléthylènediaminetriacétique, l'acide éthylènediaminetétraacétique, l'acide diéthylènetriaminepentaacétique, l'acide glutamiquediacétique, en particulier l'acide L-glutamique-N,N-diacétique, l'acide iminodisuccinique, acide hydroxyimino-disuccinique, acide méthylglycinediacétique, acide aspartiquediacétique, acide hydroxyéthane-1,1-diphosphonique ou acide diéthylènetriaminepenta-(méthylènephosphonique) ainsi que leurs sels ou leurs mélanges, de préférence l'acide L-glutamique-N,N-diacétique et/ou l'acide méthylglycinediacétique ainsi que leurs sels et/ou la préparation de nettoyage A 2 à 60 % en poids.-%, de préférence de 4 à 55 % en poids et en particulier de 8 à 50 % en poids d'agent complexant.
  6. Forme d'offre de détergent selon l'une des revendications précédentes, caractérisée en ce que la préparation de détergent B contient une enzyme active pour le nettoyage choisie dans le groupe des amylases et/ou des protéases et/ou des cellulases et/ou des hémicellulases et/ou des lipases, en particulier des amylases et/ou des
    Protéases, de préférence en une quantité de 0,01 à 5 % en poids, de préférence de 0,05 à 2,5 % en poids, en particulier de 0,1 à 1,5 % en poids de protéine enzymatique active par rapport au poids total de la préparation de détergent B.
  7. Forme d'offre de détergent selon l'une des revendications précédentes, caractérisée en ce que la préparation de détergent B contient, par rapport à son poids total, 30 % en poids et moins, de préférence 25 % en poids et moins, en particulier 15 % en poids d'eau et moins d'eau et/ou la préparation détergente B contient un solvant organique, de préférence choisi parmi le glycérol, le 1,2-propylèneglycol, le 1,3-propylèneglycol, le dipropylèneglycol ainsi que les polyéthylèneglycols, en particulier le 1,2-propylèneglycol, la proportion en poids du 1,2-propylèneglycol, par rapport au poids total de la préparation détergente, étant de préférence de 5 à 80 % en poids, de préférence de 10 à 60 % en poids et en particulier de 20 à 50 % en poids.
  8. Forme d'offre de détergent selon l'une des revendications précédentes, caractérisée en ce que la préparation de détergent B et/ou C contient des tensioactifs respectivement en une quantité de 5 à 35 % en poids, en particulier de 10 à 30 % en poids, par rapport au poids total de la préparation respective.
  9. Forme d'offre de détergent selon l'une des revendications précédentes, caractérisée en ce que la préparation de détergent C contient l'agent d'acidification c1) choisi parmi l'acide formique, l'acide tartrique, l'acide succinique, l'acide malonique, l'acide adipique, l'acide maléique, l'acide fumarique, l'acide oxalique et/ou l'acide polyacrylique, en particulier l'acide formique, l'acide acétique et/ou l'acide citrique, et/ou la préparation de détergent C contient l'agent d'acidification c1) de préférence en quantités de 0,1 à 12 % en poids.%, de préférence 0,2 à 10 % en poids et en particulier 0,3 à 8,0 % en poids, à chaque fois par rapport au poids total de la préparation de détergent C.
  10. Forme d'offre de détergent selon l'une des revendications précédentes, caractérisée en ce que la préparation de détergent C comprend un la préparation de détergent C contient l'inhibiteur de corrosion du verre c2), qui est de préférence choisi parmi les polyalkylèneimines, en particulier les polyéthylèneimines, et/ou les sels de zinc solubles dans l'eau, de préférence le chlorure de zinc, le sulfate de zinc et/ou l'acétate de zinc, de manière particulièrement préférée l'acétate de zinc, et/ou la préparation de détergent C contient l'inhibiteur de corrosion du verre c2) de préférence dans des quantités de 0,01 % en poids à 5 % en poids, de préférence de 0,05 % à 3 % en poids, en particulier de 0,1 % à 2 % en poids, par rapport au poids total de la préparation de nettoyage.
    C, contient.
  11. Forme d'offre de détergent selon l'une des revendications précédentes, caractérisée en ce que la préparation de détergent C contient un hydrotrope c3), qui est de préférence choisi parmi le xylènesulfonate, le cumènesulfonate, et/ou le N-méthylacétamide, de manière particulièrement préférée le cumènesulfonate et/ou le xylènesulfonate, en particulier le cumènesulfonate, et/ou la préparation de détergent C contient l'hydrotrope c3) en une quantité de 2 à 25 % en poids.%, en particulier de 4 à 20 % en poids et de manière particulièrement préférée en une quantité de 6 à 15, par exemple de 7 à 12 % en poids, par rapport au poids total de la préparation détergente C.
  12. Utilisation d'une forme d'offre de détergent selon l'une des revendications précédentes comme réservoir de détergent pour
    i) un doseur intégré de manière immobile à l'intérieur d'un lave-vaisselle, ou
    ii) un doseur mobile prévu pour être positionné à l'intérieur d'un.
  13. Utilisation d'une forme d'offre de détergent selon l'une des revendications précédentes pour le remplissage
    i) d'un immobile dans le l'intérieur d'un cartouche d'un système de dosage intégrée dans un lave-vaisselle, ou
    ii) une cartouche mobile d'un système de dosage prévue pour être placée à l'intérieur d'un lave-vaisselle
    avec une quantité de cette forme d'offre de détergent suffisante pour effectuer au moins deux fois, de préférence au moins quatre fois et en particulier au moins huit fois, un processus de lavage de la vaisselle en machine.
  14. Système de dosage de détergent, comprenant
    a) une forme d'offre de détergent selon l'une des revendications précédentes, comprenant une quantité de préparation d'agent de blanchiment E, ainsi que de préparations de détergent A et B, et éventuellement C, suffisante pour la mise en oeuvre d'un procédé de lavage de la vaisselle en machine au moins deux fois, de préférence au moins quatre fois et en particulier au moins huit fois ;
    b) un dispositif de dosage relié de manière amovible à la forme d'offre de détergent.
  15. Utilisation d'une forme d'offre de détergent ou d'un système de dosage de détergent selon l'une des revendications précédentes pour le nettoyage de la vaisselle dans un procédé de lavage de la vaisselle en machine.
  16. Procédé de lavage de la vaisselle en machine utilisant une forme de distribution de détergent ou un système de dosage de détergent selon l'une des revendications précédentes, au cours duquel une cartouche se trouvant dans l'espace intérieur du lave-vaisselle est vidée de son contenu.
    - une quantité partielle a de la préparation de détergent A se trouvant dans la cartouche est dosée dans l'espace intérieur du lave-vaisselle, une quantité résiduelle de la préparation de détergent se trouvant dans la cartouche restant dans la cartouche jusqu'à la fin du processus de lavage de la vaisselle, caractérisé en ce que cette quantité résiduelle correspond au moins au double, de préférence au moins au quadruple et en particulier au moins au huitième de la quantité partielle a ; et
    - une quantité partielle b de la préparation détergente B se trouvant dans la cartouche est dosée dans l'espace intérieur du lave-vaisselle, une quantité résiduelle de la préparation détergente se trouvant dans la cartouche restant dans la cartouche jusqu'à la fin du processus de lavage de la vaisselle, caractérisé en ce que cette quantité résiduelle correspond au moins au double, de préférence au moins au quadruple et en particulier au moins à l'octuple de la quantité partielle b ; ainsi que
    - le cas échéant, une quantité partielle c de la préparation de détergent C se trouvant éventuellement dans la cartouche est dosée dans l'espace intérieur du lave-vaisselle, une quantité résiduelle de la préparation de détergent se trouvant dans la cartouche restant dans la cartouche jusqu'à la fin du processus de lavage de la vaisselle, caractérisé en ce que cette quantité résiduelle correspond au moins au double, de préférence au moins au quadruple et en particulier au moins à l'octuple de la quantité partielle c, et
    - une quantité partielle e de la préparation d'agent de blanchiment E se trouvant dans la cartouche est dosée dans l'espace intérieur du lave-vaisselle, une quantité résiduelle de la préparation de détergent se trouvant dans la cartouche restant dans la cartouche jusqu'à la fin du processus de lavage de la vaisselle, caractérisé en ce que cette quantité résiduelle correspond au moins au double, de préférence au moins au quadruple et en particulier au moins à huit fois la quantité partielle e.
EP20700896.2A 2019-01-21 2020-01-15 Formulations de produit de nettoyage pour lavage de vaisselle automatique avec agent de blanchiment Active EP3914686B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102019200701.5A DE102019200701A1 (de) 2019-01-21 2019-01-21 Reinigerformulierungen zum automatischen Geschirrspülen mit Bleichmittel
PCT/EP2020/050893 WO2020152005A1 (fr) 2019-01-21 2020-01-15 Formulations de produit de nettoyage pour lavage de vaisselle automatique avec agent de blanchiment

Publications (2)

Publication Number Publication Date
EP3914686A1 EP3914686A1 (fr) 2021-12-01
EP3914686B1 true EP3914686B1 (fr) 2023-06-14

Family

ID=69172804

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20700896.2A Active EP3914686B1 (fr) 2019-01-21 2020-01-15 Formulations de produit de nettoyage pour lavage de vaisselle automatique avec agent de blanchiment

Country Status (5)

Country Link
EP (1) EP3914686B1 (fr)
DE (1) DE102019200701A1 (fr)
ES (1) ES2952573T3 (fr)
PL (1) PL3914686T3 (fr)
WO (1) WO2020152005A1 (fr)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2386129B (en) 2002-03-06 2004-12-01 Reckitt Benckiser Nv Detergent dosing device
GB2400608A (en) * 2003-03-07 2004-10-20 Reckitt Benckiser Nv Emanator blister for the release of a detergent
DE102005062479A1 (de) 2005-12-27 2007-07-05 BSH Bosch und Siemens Hausgeräte GmbH Dosiervorrichtung für die Zugabe eines Zuschlagmittels in einen Behandlungsraum und Geschirrspülmaschine mit einer Dosiervorrichtung
WO2011051418A1 (fr) * 2009-10-30 2011-05-05 Henkel Ag & Co. Kgaa Procédé de lavage en machine
DE102010028482A1 (de) * 2010-05-03 2011-11-03 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülverfahren
DE102010030021A1 (de) * 2010-06-14 2011-12-15 Henkel Ag & Co. Kgaa Maschinelles Reinigungsverfahren
DE102011005980A1 (de) 2011-03-23 2012-09-27 Henkel Ag & Co. Kgaa Dosiersystem für eine Geschirrspülmaschine

Also Published As

Publication number Publication date
PL3914686T3 (pl) 2023-10-23
ES2952573T3 (es) 2023-11-02
WO2020152005A1 (fr) 2020-07-30
DE102019200701A1 (de) 2020-07-23
EP3914686A1 (fr) 2021-12-01

Similar Documents

Publication Publication Date Title
EP2446013B1 (fr) Détergent pour lave-vaisselle
EP2414498B1 (fr) Détergents
EP2414499B1 (fr) Détergents
EP2494023A1 (fr) Procédé de lavage en machine
WO2011051416A1 (fr) Procédé de lavage en machine
EP3914685A1 (fr) Système de nettoyage à plusieurs composants
WO2011051415A1 (fr) Procédé de lavage en machine
WO2020104445A1 (fr) Système de nettoyage à plusieurs composants
WO2011138165A1 (fr) Procédé de lavage de vaisselle et de linge en machine
EP3656839B1 (fr) Détergent destiné au dosage automatique
WO2011051419A1 (fr) Détergent pour lave-vaisselle
EP3914686B1 (fr) Formulations de produit de nettoyage pour lavage de vaisselle automatique avec agent de blanchiment
WO2011157630A1 (fr) Procédé de lavage en machine
EP3884020A1 (fr) Produit de nettoyage contenant un liquide de rinçage pour une unité de dosage automatique
EP3835397B1 (fr) Produit de nettoyage
EP4004175A1 (fr) Produit de lavage comprenant une protéase permettant un dosage automatique
WO2011051418A1 (fr) Procédé de lavage en machine
DE102018220187A1 (de) Niedrigviskose Reinigerformulierungen zum automatischen Geschirrspülen
DE102018220188A1 (de) Transparente Formulierungen zum automatischen Geschirrspülen
DE102010030151A1 (de) Maschinelles Reinigungsverfahren

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: 20210625

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

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
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: 20221014

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

INTC Intention to grant announced (deleted)
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: 20230322

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: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502020003777

Country of ref document: DE

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

Effective date: 20230531

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1579260

Country of ref document: AT

Kind code of ref document: T

Effective date: 20230715

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20230614

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

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: 20230614

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: 20230914

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2952573

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20231102

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

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: 20230614

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: 20230614

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: 20230614

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: 20230614

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: 20230614

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: 20230915

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

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: 20230614

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

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: 20230614

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: 20231014

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: 20230614

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: 20230614

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: 20230614

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: 20231016

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: 20231014

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: 20230614

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: 20230614

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502020003777

Country of ref document: DE

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

Ref country code: ES

Payment date: 20240228

Year of fee payment: 5

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

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

Ref country code: DK

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

Effective date: 20230614

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

Ref country code: DE

Payment date: 20240119

Year of fee payment: 5

Ref country code: GB

Payment date: 20240123

Year of fee payment: 5

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

Ref country code: SI

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

Effective date: 20230614

26N No opposition filed

Effective date: 20240315