EP1917342A2 - Agents de lavage - Google Patents

Agents de lavage

Info

Publication number
EP1917342A2
EP1917342A2 EP06777028A EP06777028A EP1917342A2 EP 1917342 A2 EP1917342 A2 EP 1917342A2 EP 06777028 A EP06777028 A EP 06777028A EP 06777028 A EP06777028 A EP 06777028A EP 1917342 A2 EP1917342 A2 EP 1917342A2
Authority
EP
European Patent Office
Prior art keywords
weight
cleaning
acid
liquid detergent
washing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP06777028A
Other languages
German (de)
English (en)
Other versions
EP1917342B8 (fr
EP1917342B1 (fr
Inventor
Pavel Gentschev
Maren Jekel
Arnd Kessler
Ulrich Pegelow
Christian Nitsch
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=37192272&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1917342(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from DE102005041709A external-priority patent/DE102005041709A1/de
Priority claimed from DE102006028750A external-priority patent/DE102006028750A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL06777028T priority Critical patent/PL1917342T3/pl
Publication of EP1917342A2 publication Critical patent/EP1917342A2/fr
Application granted granted Critical
Publication of EP1917342B1 publication Critical patent/EP1917342B1/fr
Publication of EP1917342B8 publication Critical patent/EP1917342B8/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L15/00—Washing or rinsing machines for crockery or tableware
    • A47L15/42—Details
    • A47L15/4214—Water supply, recirculation or discharge arrangements; Devices therefor
    • 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
    • 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
    • C11D17/043—Liquid or thixotropic (gel) compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3218—Alkanolamines or alkanolimines
    • 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
    • C11D2111/40—Specific cleaning or washing processes
    • C11D2111/44—Multi-step processes

Definitions

  • the present application relates to dishwashing compositions. More particularly, this application relates to liquid dishwashing detergents and to their use for cleaning bleachable soils
  • Dishwashing detergents are available to the consumer in a variety of forms.
  • automatic dishwashing agents are particularly important with the spread of household dishwashing machines.
  • These automatic dishwashing agents are typically offered to the consumer in solid form, for example as powders or tablets
  • One of the main objectives of the manufacturer of mechanical cleaning agents is the improvement of
  • the cleaning agents were preferably added new ingredients, such as more effective surfactants, polymers or bleach
  • liquid detergent A has a pH (2O 0 C) between 6 and 9
  • liquid detergent B has a pH (20 ° C) between 9 and 14 and none of the cleaning agents A or B contains more than 2% by weight of a bleaching agent
  • the present application further relates to the use of a combination product according to the invention for cleaning bleachable soilings, preferably for cleaning tea stains, on hard surfaces.
  • This application particularly relates to the use of combination products according to the invention for cleaning bleachable stains, in particular for cleaning tea stains, in automatic dishwashing
  • liquid detergents A and B which are present separately from one another in the combination products according to the invention contain, among other ingredients active in washing or cleaning.
  • Gerüststoffe The zeolites in particular pay the zeolites, silicates, carbonates, organic co-builders and where there are no ecological prejudices against their use Phosphate
  • crystalline layered silicates of the general formula NaMSi x O 2x + I y H 2 O are used, wherein M represents sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1, 9 to 4, with particularly preferred values x is 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
  • the crystalline layered silicates of the formula NaMSi x O 2x + 1 y H 2 O are described, for example, by Clanant GmbH (Germany Examples of these silicates are Na-SKS-1 (Na 2 Si 22 O 45 ⁇ H 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 ⁇ H 2 O), Magadiite), Na-SKS-3 (Na 2 Si 8 O 17 ⁇ H 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 ⁇ H 2 O, makatite)
  • Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula NaMSi x O 2x + IyH 2 O, in which x is 2 In particular, both ⁇ - and ⁇ -Natdisilamate Na 2 Si 2 O 5 y H 2 O.
  • Na-SKS-5 Ot-Na 2 Si 2 O 5
  • Na-SKS-7 ⁇ -Na 2 Si 2 O 5 , Natrosilit
  • Na-SKS-9 NaHSi 2 O 5 H 2 O
  • Na-SKS-10 NaHSi 2 O 5 3H 2 O, kanemite
  • Na-SKS-11 t-Na 2 S ⁇ 2 0 5
  • Na-SKS-13 NaHSi 2 O 5
  • Na-SKS-6 5-Na 2 Si 2 O 5
  • the liquid detergents A and / or B preferably comprise a proportion by weight of the crystalline layered silicate of the formula NaMSi x O 2x + IyH 2 O of from 0.1 to 20% by weight of from 0.2 to 15% by weight and in particular of 0 , 4 to 10% by weight, based in each case on the weight of the particular cleaning agent A or B, are contained
  • amorphous sodium silicates having a modulus Na 2 O SiO 2 of from 1 2 to 1 3,3, preferably from 1 2 to 1 2, 8 and in particular from 1 2 to 1, 2, which are preferably loosely delayed and have secondary wash properties Loseverzog für compared to conventional amorphous Nat ⁇ umsilikaten can be caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying
  • the term "amorphous" understood that the silicates in Rontgenbeugungsexpe ⁇ menten provide no sharp X-rays, as they are typical of crystalline substances, but at most one or more maxima of the scattered X-radiation, which have a width of several degrees of the diffraction angle
  • X-ray silicates whose silicate particles produce blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the order of ten to several hundred nm, with values of up to max Such X-ray amorphous silicates are also preferred, in particular up to 20 nm. They also have a loosening delay compared to the conventional waterglass. Particular preference is given to compacted / compacted amorphous silicates, compounded amorphous silicates and dried X-ray amorphous silicates
  • s preferably Alkahsilikate, more preferably crystalline or amorphous Alkalidisilikate
  • Alkalimetaiiphosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to high molecular weight representatives
  • the phosphates combine several advantages in They act as alkali storage, prevent limescale on machine parts or Kalkinkrustationen in tissues and also contribute to the cleaning performance
  • phosphates are pentasodium t-phosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium phosphate, K 5 P 3 O 10 (potassium t-polyphosphate)
  • the sodium potassium t-polyphosphates are also preferably used according to the invention
  • preferred combination products comprise dicloses (s) phosphate (s), preferably alkali metal metal phosphate (s), particularly preferably pentasodium or pentapotassium phosphate ( Sodium or Kaliumt ⁇ polyphosphat), in amounts of 5 to 60% by weight, preferably from 15 to 45% by weight, in particular from 20 to 40% by weight, based in each case on the weight of the respective cleaning agent A or B, are included
  • organic cobuilders include polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and phosphonates. These classes of substances are described below
  • Useful organic framework 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 to mean those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, Fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, as well as mixtures of these.
  • the free acids also typically have the property of Acid component and thus also serve to set a lower and milder pH of detergents or cleaning agents
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof are mentioned
  • the citric acid or salts of citric acid is particularly preferably used as a framework substance.
  • Combination products characterized in that the combination product contains citric acid or a salt of citric acid and the proportion by weight of citric acid or of the salt of citric acid, based on the total weight of the combination product, is between 0, 2 and 12% by weight, preferably between 0.2 and 8% by weight and in particular between 0.2 and 6% by weight, are preferred according to the invention
  • Methylglycmdiessidsaure MGDA
  • Methylglycmdiessidsaure MGDA
  • the combination product methylglycinediacetic or a salt of Methylglycindiessigsaure containing and the weight fraction of Methylglycindiessigsaure or the salt of Methylglycindiessigsaure, based on the total weight of the combination product, between 0.2 and 12% by weight, preferably between 0.2 and 8% by weight and in particular between 0.2 and 6% by weight, are preferred according to the invention
  • polymeric polycarboxylates are suitable, these are for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70000 g / mol
  • the molecular weights given for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by gel permeation chromatography (GPC) using a UV detector. The measurement was carried out against an external polyacrylic acid standard which gives realistic molecular weight values owing to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data in which polystyrenesulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this specification
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, this group can in turn comprise the short-chain polyacrylates, the molar masses of 2,000 to 10,000 g / mol, and particularly preferably 3,000 to 5,000 g / mol, have, be preferred Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid Ais copolymers of acrylic acid with maleic acid have proven to be particularly effective; 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid contain their relative Molecular weight, based on free acids, is generally from 2000 to 70000 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 detergents or cleaning agents in (co) polymeric polycarboxylates is preferably 0.1 to 10% by weight, preferably 0.2 to 8% by weight, more preferably 0.4 to 6% by weight and in particular between 0, 4 and 4% by weight
  • the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or the salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives as monomers
  • copolymers are those which have as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate
  • polymeric aminodicarboxylic acids their salts or their precursors
  • Substances are particularly preferred polyaspartic acids or their salts
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are prepared from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid
  • organic builder substances are dextrins, for example, oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes Preference is given to hydrolysis products having average molecular weights in the range from 400 to 500,000 g / mol.
  • a polysaccharide having a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a Usable measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 is useful are both Maltodextnne with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range of 2000 to 30,000 g / mol
  • oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function
  • Ethylenediamine-N, N-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • Glycidene disuccinates and glycine trisuccinates are also preferred in this context
  • organic cobuilders are, for example, acid-hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups
  • Enzymes include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof These enzymes are in principle of natural origin, starting from the natural molecules stand for detergents or cleaning agents have improved variants which are preferably used accordingly detergents or cleaning agents preferably contain enzymes in total amounts of from 1 ⁇ 10 6 to 5% by weight, based on active protein.
  • the protein concentration can be determined by known methods, for example determined by the BCA method or the biuret method
  • proteases of the Subt ⁇ l ⁇ s ⁇ n type are preferred examples of these are the subtilisins BPN 'and Carlsberg and their advanced forms, the protease PB92, the subtilisins 147th and 309, the alkaline protease from Baallus lentus, subtilisin DY, and the enzymes thermitase, proteinase K, and the proteases TW3 and TW7, which are attributable to the subtilases, but not the subtilisins in the narrower sense
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, S amyloliquefaciens, B stearothermophilus, Aspergillus niger and A oryzae, and the further developments of the abovementioned amylases which are improved for use in detergents and cleaners Amylase from Bacillus sp A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B agaradherens (DSM 9948)
  • an ⁇ -amylase Va ⁇ ante has proven, either from a homologizable with the ⁇ -amylase AA560 starting ⁇ - Amylase can be obtained via amino acid changes in the following positions 9, 149, 182, 186, 202, 257, 295, 299, 323, 339, 345 and optionally further (in the payment according to the ⁇ -amylase AA560) or from the ⁇ - Amylase AA560 can be obtained via the following amino acid changes
  • the ⁇ -amylase Va ⁇ ante is characterized by additionally one or more amino acid changes in the following positions against a ⁇ -amylase homologizable with the oc-amylase AA560 is 118, 183, 184, 195, 320 and 458 (in the payment according to the ⁇ -amylase AA560), wherein the ⁇ -amylase Va ⁇ ante preferably in particular the following amino acid position assignments 118K, 183- (deletion), 184- (deletion), 195F, 320K and / or 458K (in the payment according to the ⁇ -amylase AA560)
  • ⁇ -amylase derivative which can be derived from ⁇ -amylase AA560 or a derivative thereof, and preferably derived therefrom, is particularly preferred
  • Amylase Va ⁇ ante contain, which compared to the ⁇ -amylase AA560 one of the following
  • M202L / M323T / M309L (62) M202I / M382Y / K383R, (68) M202V / M323T / M309L, (73) M202V / M382Y / K383R (82) M202T / M323T / M430I (84) M202T / V214T / R444Y
  • the above-mentioned preferred ⁇ -amylase variants have, in particular in the Lagerund and dosage by means of automatic dosing systems, which contain sufficient cleaning agents for several cleaning procedures, which is why these detergents are stored in these dosing for a long time, by an above-average storage stability and Cleaning performance excellent
  • the protease variant in addition to the described ⁇ -Amy'ase variant according to the invention contain preferred cleaning agents, in particular detergents for the time-delayed dosing, a protease, preferably a Subtihsin protease, wherein the subtilisin protease is a wild-type protease or a protease Vanante
  • the protease variant is an amino acid alteration to a parent protease homologizable with the Baallus lentus alkaline protease in one or more of the following 3, 4, 36, 42, 43, 47, 56, 61, 69, 87, 96, 99, 101, 102, 104, 114, 118, 120, 130, 139, 141, 142, 154, 157, 188, 193, 199, 205, 211, 224, 229, 236, 237, 242, 243, 250, 253, 255 and 268, in the payment of the alkaline proteas
  • lipases or cutinases in particular because of their T ⁇ glyce ⁇ d-cleaving activities, but also to generate from suitable precursors in situ Persauren
  • lipases or cutinases include, for example, originally from Humicola lanuginosa ⁇ Thermomyces lanugmosus) available, or further developed lipases, especially those with the Furthermore, for example, the cutinases which were originally isolated from Fusanum solam pisi and Humicola insolens can be used.
  • Lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusanum solanu can also be used
  • 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 advantageously be used according to the invention to increase the bleaching effect additionally preferably organic, particularly preferably aromatic, interacting with the enzymes compounds added to enhance the activity of the respective oxidoreductases (enhancer) or to ensure at very different redox potentials between the oxidizing enzymes and the stains electron flow (mediators)
  • the enzymes can be used in any form known in the art. These include, for example, the solid obtained by granulation, extrusion or lyophilization Preparations or, in particular in the case of liquid or gel-form agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example, by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer in superposed layers, additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes Capsules of this kind are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • granules of this type for example by application of polymeric film formers, are low in dust and storage-stable due to the coating
  • a protein and / or enzyme can be protected against damage, for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage, especially during storage.
  • damage for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage, especially during storage.
  • inhibition of proteolysis is particularly preferred
  • Detergents or cleaning agents which contain agents for this purpose may also contain stabilizers. The provision of such agents constitutes a preferred embodiment of the present invention
  • a protein and / or enzyme contained in an agent according to the invention can be protected against damage such as inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage during storage. Microbial recovery of the proteins and / or enzymes inhibits proteolysis particularly preferred, especially when the agents contain proteases.
  • Preferred agents according to the invention contain stabilizers for this purpose
  • a group of stabilizers are reversible protease inhibitors Often benzamidine Hydrochlo ⁇ d, borax, boric acids, boronic acids or their salts or esters are used, including in particular derivatives with aromatic groups, such as ortho, meta or para-substituted Phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or esters of the abovementioned compounds. Also peptide aldehydes, ie oligopeptides with a reduced C-terminus, in particular those of 2 to 50 monomers, are used for this purpose.
  • peptidic reversible protease inhibitors are ovomucoid and Leupeptin Specific, reversible peptide inhibitors for the protease subtilisin as well as fusion proteins from proteases and specific peptide inhibitors are also suitable
  • enzyme stabilizers are amino alcohols such as mono-, di-, T ⁇ ethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of said acids. End notever heree Fettsaureamidalkoxylate are suitable for this purpose Certain used as builders organic acids, as disclosed in WO 97/18287, additionally stabilize a contained enzyme
  • Lower aliphatic alcohols but especially polyols such as Glyce ⁇ n, ethylene glycol, propylene glycol or sorbitol are other frequently used enzyme stabilizers
  • di-glycine phosphate protects against denaturation by physical influences
  • calcium and / or magnesium salts are used, such as calcium acetate or calcium formate
  • Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation inter alia against physical influences or pH fluctuations
  • Polyamino-N-Ox ⁇ d- containing polymers act Also known as enzyme stabilizers and as color transfer inhibitors
  • Other polymeric stabilizers are linear C 8 -C 18 polyoxyalkylenes
  • Alkyl polyglycosides can also stabilize and preferably increase the enzymatic components of the agent according to the invention.
  • Crosslinked compounds containing N preferably fulfill a dual function as soil inhibitors. Release agents and as enzyme stabilizers Hydrophobic, nonionic polymer stabilizes in particular an optionally contained cellulase
  • Reducing agents and antioxidants increase the stability of the enzymes to oxidative decomposition, for example sulfur-containing reducing agents are familiar.
  • Other examples are sodium sulfite and reducing sugars
  • Particular preference is given to using combinatons of stabilizers, for example of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts
  • Peptide-aldehyde stabilizers are favorably enhanced by combination with boric acid and / or boric acid derivatives and polyols, and still further by the additional action of divalent cations, such as calcium ions
  • potassium sulfate K 2 SO 4
  • the proportion by weight of the enzymes in the total weight of the liquid detergent A is between 0.1 and 10% by weight.
  • the proportion by weight of the enzyme in the total weight of the cleaning agent A is between 0.2 and 9% by weight and in particular between 0.5 and 8% by weight
  • liquid detergent B may of course also contain enzymes, it is preferred that the enzyme content of the detergent B be less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.5% by weight and especially less as 0 1% by weight particularly preferred combination products are characterized in that the liquid detergent B contains no enzymes
  • one or more enzymes and / or enzyme preparations preferably solid or liquid protease preparations and / or amylase preparations are used.
  • the liquid detergent A comprises a combination of protease and amylase preparations
  • the combination products according to the invention are characterized by a bleach content of less than 2% by weight.
  • Preferred combination products are characterized in that the bleach content of the detergents A and / or B is in each case less than 1% by weight, more preferably less than 0.5% by weight and in particular less than 0.1% by weight is combination products, characterized in that the bleach content of the cleaning agents A and / or B is in each case less than 1% by weight, preferably less than 0.5% by weight and in particular less than 0 1% by weight.
  • amounts are preferred according to the invention
  • washing or Detergent A and / or B contain no bleach
  • the bleaching agents include, in addition to H 2 O 2, for example, the compounds yielding H 2 O 2 in water, sodium carbonate tetrahydrate and sodium borate monohydrate.
  • Further bleaching agents are, for example, peroxypyrophosphates, citrate perhydrate and peracid salts or peracids which yield H 2 O 2 , such as perbenzoates peroxophthalates, diperazelic acid, phthaloimmoic acid or diperdodecanedioure
  • Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, with particular mention being made of alkyl peroxyacids and aryl peroxyacids.
  • Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkyl peroxybenzoic acids, but also peroxybenzoic acids. ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylic acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid
  • Nonenylamidoperadipinsaure and N-Nonenylam ⁇ dopersucc ⁇ nate and (c) aliphatic and arahphatician Peroxydicarbonsauren, such as 1,12-D ⁇ peroxycarbonsaure, 1, 9-D ⁇ peroxyazela ⁇ nsaure, Diperocysebacinsaure, Diperoxybrassylsaure, the Diperoxyphthalsauren, 2-Decyld ⁇ peroxybutan-1, 4-diacid, N, N-terephthaloyl -d ⁇ (6-am ⁇ nopercapronsaue)
  • the group of bleach continue to pay the chlorine or bromine releasing substances such as heterocyclic N-bromo- and N-Chloram ⁇ de, for example Trichlo ⁇ socyanursaure, T ⁇ bromisocyanursaure, Dibromisocyanursaure and / or Dichlo ⁇ socyanursaure (DICA) and / or their salts with cations such as potassium and sodium hydantoin , such as 1, 3-D ⁇ chlor-5,5-d ⁇ methylhi- danthoin also belong to the group of these bleaching agents
  • heterocyclic N-bromo- and N-Chloram ⁇ de for example Trichlo ⁇ socyanursaure, T ⁇ bromisocyanursaure, Dibromisocyanursaure and / or Dichlo ⁇ socyanursaure (DICA) and / or their salts with cations such as potassium and sodium hydantoin , such as 1, 3-D ⁇ chlor-5,5-d ⁇ methyl
  • a further preferred subject matter of the present application is a combination product with a content of oxygen and chlorine bleaches below 2% by weight, preferably below 1% by weight and in particular below 0.5% by weight, comprising a packaging with two separate receiving chambers, and two separate liquid detergents A and B of the composition A present in these receiving chambers and containing from 15 to 75% by weight of gaseous material (s),
  • the liquid detergent A has a pH (2O 0 C) between 6 and 9, while the liquid detergent B has a pH (20 ° C) between 9 and 14 and the pH (2O 0 C) of the liquid washing or cleaning agent A from the pH (20 0 C) of the liquid detergent or cleaning agent B differs by at least two units, and the use of such a combination products for the purification of bleachable stains, especially of Teeanschmutzieux, ( machine) dishwashers
  • a bleach-free combination product comprising a packaging means with two separate receiving chambers, as well as two separate liquid detergents A and B of the composition located in these receiving chambers
  • the liquid cleaning agent A has a pH (2O 0 C) between 6 and 9, preferably between 6.5 and 8.5 and in particular between 7 and 8, during the liquid detergent B has a pH (2O 0 C) between 9 and 14, preferably between 9.5 and 13 and in particular between 10 and 12, and the pH (2O 0 C) of the liquid washing or cleaning agent A from the pH value (20 0 C) of Wegigen washing or cleaning agent B by at least two units is different, as well as the use of such combination products bleachable for cleaning dirt, especially the use of such a combination product for the purification of bleachable stains, especially tea stains, machining in ( ) Wash the dishes
  • the adjustment of the pH-values of the liquid detergents A and B are particularly preferred for the cleaning performance of the resulting combination product of importance combination products in which the pH-value (20 0 C) ofbigigen cleaning agent A between 6.5 and 8.5 and
  • the pH (20 ° C.) of the liquid detergent B is preferably between 9.5 and 13 and in particular between 10 and 12
  • combination products characterized in that the pH (20 ° C) of the liquid detergent or cleaning agent A from the pH (2O 0 C) of the liquid washing or cleaning Detergent B differs by at least two units
  • liquid detergents B additionally comprise alkali metal bearings.
  • a further subject of the present application is therefore a combination product comprising a packaging means with two separate receiving chambers and two chambers located in these receiving chambers.
  • the LIQUID detergent A has a pH value (2O 0 C) between 6 and 9, during the LIQUID cleaning agent B has a pH value (20 0 C) of between 9 and 14 and none of the cleaning agents A or B contains more than 2% by weight of a bleaching agent
  • alkali suspensions are the hydroxides, preferably alkali metal hydroxides, the carbonates, bicarbonates or sesquicarbonates, preferably alkali metal carbonates or alkali metal bicarbonates or alkali metal sesquicarbonates, preference being given to using the alkali metal hydroxides and alkali metal carbonates, in particular sodium hydroxide, potassium hydroxides, sodium carbonate, sodium bicarbonate or sodium mesic acid carbonate for the purposes of this invention
  • the alkali metal hydroxides are preferably used in cleaning agents A and / or B only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably between 0.1 and 5% by weight. % and in particular between 0.5 and 5% by weight, in each case based on the total weight of the cleaning agent B. Particular preference is given to combination products in which the cleaning agent A, based on its total weight, is less than 0.5% by weight and in particular no hydroxides , in particular alkali metal hydroxides
  • Alkahtragern from the group of carbonates and / or bicarbonates preferably alkali metal carbonates, more preferably Natnumcarbonat, in amounts of 0.1 to 15% by weight, preferably from 0.2 to 10% by weight and in particular from 0 , 5 to 8% by weight, in each case based on the weight of the washing or cleaning agent B
  • alkali metal carbonates more preferably Natnumcarbonat
  • combination products in which the detergent A, based on its total weight, less than 0.5% by weight and in particular no carbonate (s) and bicarbonate (s) and sesquicarbonates
  • a further subject of this application is the use of combination products according to the invention for cleaning dried-on and / or burnt-on stains, preferably on hard surfaces.
  • This application particularly relates to the use of combination products according to the invention for cleaning dried-on and / or stained soils, in particular for cleaning dried-on and / or burnt-on stains automatic dishwashers
  • the group of dried-on or burnt-on soils is subject to dried-on heavy soiling, for example of oatmeal, or burnt-on residues, which, in addition to starches such as noodles or potatoes, also include meat residues
  • organic solvents are derived, for example, from the groups of monoalcohols, diols, triols or polyols, ethers, esters and / or amides.
  • Organic solvents which are water-soluble are particularly preferred, with "water-soluble” solvents being solvents in the meaning of the present application which are completely miscible with water at room temperature, ie without any mixing gap
  • Organic solvents that can be used in the inventive means, preferably from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible in the specified concentration range with water
  • the Solvent selected from ethanol, n- or ⁇ -propanol, butanols, glycol, propane or butanediol, Glycenn, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, Ethylenglykolethylet he h, Ethylenglykolpropylether, Etheylenglykolmono-n-butyl ether,
  • organic solvents from the group of the organic amines and / or the alkanolamines have proven to be particularly effective with regard to the cleaning performance and again with regard to the cleaning performance on bleachable soilings, in particular on tea stains
  • Preferred organic amines are, in particular, the primary and secondary alkylamines, the alkylene amines and mixtures of these organic amines.
  • Monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine and cyclohexylamine pay particular preference to the group of the preferred primary alkylamines
  • Particularly preferred alkanolamines are the primary, secondary and tertiary alkanolamines and mixtures thereof.
  • Particularly preferred primary alkanolamines are monoethanolamine (2-aminoethanol, MEA), monoisopropanolamine, diethylethanolamine (2- (dimethylamino) -ethanol).
  • Particularly preferred secondary alkanolamines are diethanolamine (2.2 '-lm ⁇ nod ⁇ ethanol, DEA, B ⁇ s (2-hydroxyethyl) amin), N-methyl-D ⁇ ethanolam ⁇ n, N-ethyl-D ⁇ ethanolam ⁇ n Dnsopropanolamin and morpholine
  • Particularly preferred tertiary alkanolamines are T ⁇ ethanolamin and T ⁇ isopropanolamin
  • Combination products characterized in that they contain an organic solvent, wherein the organic solvent is an organic amine and / or an alkanolamine, preferably monoethanolamine, wherein the weight ratio of water to organic amine and / or alkanolamine in the washing or cleaning agent A or B more than 1 1, preferably more than 2 1 and in particular more than 5 1 amounts
  • a further subject of this application is the use of organic amines, in particular the aforementioned organic amines and / or alkanolamines and, for cleaning bleachable soils, preferably for cleaning Teeanschmutzieux on hard surfaces
  • organic amines in particular the aforementioned organic amines and / or alkanolamines and, for cleaning bleachable soils, preferably for cleaning Teeanschmutzieux on hard surfaces
  • organic Amines and / or alkanolamines preferably the aforementioned alkanolamines, for the purification of bleachable stains, in particular for the cleaning of tea stains in automatic dishwashing
  • Particularly preferred combination products comprise, based on the total weight of the combination product, between 0.1 and 10% by weight, preferably between 0.5 and 8% by weight and in particular between 1, 5 and 6% by weight of an organic solvent from the group
  • Particularly preferred are combination products whose liquid detergent B, based on the total weight of the detergent B, a weight fraction of an organic solvent from the group of organic amine and alkanolamines between 0.1 and 10 wt -%, preferably between 0, 5 and 8 wt .-% and in particular between 1, 5 and 6 wt%, while the weight fraction of organic solvent selected from the group of organic amines and alkanolamines in the liquid detergent A, based on the total weight of the cleaning agent A, preferably less than 5% by weight, preferably less than 3% by weight, more preferably less than 1% by weight and very particularly preferably amounts to less than 0.1% by weight and, in particular, no organic solvent from the group of the organic amines and the alkanolamines is contained in the cleaning agent A.
  • compositions according to the invention described above may contain, in addition to the ingredients described above, other washing and cleaning substances, preferably washing and cleaning substances from the group of surfactants, polymers, bleach activators, glass corrosion inhibitors, corrosion inhibitors, disintegrants, fragrances and perfume carriers, dyes and preservatives Ingredients are described in more detail below
  • nonionic, anionic, cationic and amphoteric surfactants are included in the group of surfactants
  • Suitable nonionic surfactants are all nonionic surfactants known to the person skilled in the art.
  • Suitable nonionic surfactants are, for example, alkylglycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, especially methyl-branched, aliphatic radical of 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol that represents a Glykoseemheit with 5 or 6 C-atoms, preferably glucose, the degree of oligomerization x, the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10, preferably x is 1 2 to 1, 4
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dimethylhydroxylamine, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols. especially not more than half of them
  • surfactants are polyhydroxy fatty acid amides of the formula
  • R is an aliphatic acyl group having 6 to 22 carbon atoms
  • R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms
  • [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chlo ⁇ d
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms
  • Ci 4 alkyl or phenyl radicals preferred are and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can be prepared by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst be converted into the desired polyhydroxy fatty acid amides
  • Nonionic surfactants are used as preferred surfactants. Particular preference is given to detergents or cleaners, in particular automatic dishwashing detergents, nonionic surfactants from the group of alkoxylated alcohols.
  • Nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 C atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used in which the alcohol radical may 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 in particular
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, eg from coconut, palm, tallow or oleyl alcohol and an average of 2 to 8 moles of EO per mole of alcohol are preferably the preferred ethoxylated alcohols go ren, for example C
  • ethoxylated nonionic surfactants the C ⁇ o monohydroxyalkanols or C 6 20 alkylphenols or C 16 . 20 fatty alcohols and preferably more than 15 mol and in particular more than 20 moles of ethylene oxide more than 12 moles, per mole of alcohol, have been used
  • a particularly preferred nonionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C16-C20 alcohol), preferably a C 18 -alcohol and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide recovered.
  • the so-called “narrow-ranked ethoxylates" are particularly preferred
  • further surfactants are used which contain one or more Taigfettalkohole with 20 to 30 EO in combination with a Silikonentschaumer
  • nonionic surfactants having a melting point above room temperature N ⁇ cht ⁇ on ⁇ sche (s)
  • nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa s, preferably above 35 Pa s and in particular above 40 Pa s Also, nonionic surfactants having waxy consistency at room temperature are preferred
  • Nonionic surfactants from the group of alkoxylated alcohols are also used with particular preference
  • the nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule.
  • such PO monomers make up to 25% by weight, more preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant
  • particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such Nonionic surfactants of Preferred Agents are characterized by containing ethoxylated and propoxylated nonionic surfactants wherein the propylene oxide units in the molecule are up to 25% by weight, preferably up to 20% by weight and more preferably up to 15% by weight of the total molecular weight of the nonionic surfactant turn off
  • surfactants come from the groups of alkoxy-terminated nonionic surfactants, in particular the ethoxy-harsh primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) -Tens ⁇ de) Such (PO / EO / PO) -N ⁇ otens ⁇ de are also characterized by good foam control More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene
  • nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6 24 alkyl or alkenyl radical
  • each group R 2 or R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently of one another are integers from 1 to 6
  • the preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene oxide or alkylene oxide.
  • the radical R 1 in the above formula can vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is usually unbranched, the linear radicals are selected from alcohols of natural origin having 12 to 18 carbon atoms, such as coconut, palm, Taigfett- or oleyl alcohol, are accessible from synthetic sources alcohols For example, the Guerbet alcohols or methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten Irrespective of the type of alcohol used for the preparation of the nonionic surfactants contained in the agents Niotenside are preferred in which R 1 in the above formula for an alkyl group having 6 to 24, preferably 8 to 20, especially It preferably 9 to 15 and especially 9 to 11 carbon atoms In addition to propy
  • R 2 or R 3 are selected independently of one another from -CH 2 CH 2 -CH 3 or CH (CH 3 Y 2 are nonionic surfactants of the above formula are suitable preferably used in which R 2 or R 3 is a radical -CH 3, w and x independently of one another for values of 3 or 4 and y and z are independently values of 1 or 2 stand
  • nonionic surfactants preferred are a C 9 15 alkyl radical having 1 to 4 Ethylenoxidem fraud, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, these surfactants have in wass ⁇ ger solution the required low viscosity and can be used according to the invention with particular preference
  • R 1 is -CH (OH) CH 2 O- (AO) w - (AO) x - (A "O) y - (A" O) z -R 2 in which
  • R 1 and R 2 independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C 2 40 alkyl or alkenyl radical, A, A ', A "and A'" independently of one another from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CHs) -CH 2 - , -CH 2 -CH (CH 2 -CH 3 ), and w, x, y and z are values between 0.5 and 90, wherein x, y and / or z can also be 0 are preferred according to the invention
  • radical R 1 which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having from 1 to 30 carbon atoms, where x is between 1 and 90, preferably between 40 and 80, and especially between 40 and 60
  • surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 ,
  • R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof
  • R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15
  • R 1 and R 2 independently represents a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms
  • R 3 is independently selected from -CH 3, -CH 2 CH 3, -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 , but preferably represents -CH 3
  • nonionic surfactants are the end-capped poly (oxyalkyl ⁇ erten) nonionic surfactants of the formula
  • R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical
  • x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5
  • each R 3 in the above formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] J OR 2 may be different
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • each R 3 in the above formula may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket may be varied.
  • the value 3 for x has been chosen as an example and can be quite large where the variation width increases with increasing x values and includes, for example, a large number (EO) groups combined with a small number (PO) groups or vice versa
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18 Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15
  • the C chain lengths given and ethoxy ether degrees or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which may be an integer or a fractional number for a particular product. Because of the preparation processes, commercial products of the formulas mentioned are usually not made up of an individual but of mixtures Mean values and, consequently, fractional numbers can result for both the C chain lengths and for the ethoxy ether degrees or degrees of alkoxylation
  • nonionic surfactants can be used not only as individual substances but also as surfactant mixtures of two, three, four or more surfactants.
  • Surfactant mixtures are not mixtures of nonionic surfactants which in their entirety fall under one of the abovementioned general formulas rather, such mixtures containing two, three, four or more nonionic surfactants which can be described by different of the aforementioned general formulas
  • washing or cleaning agent A further 0.2 to 10% by weight, preferably 0.4 to 7% by weight and in particular 0.6 to 4% by weight nonionic Containing surfactants are preferred according to the invention
  • cationic active substances for example, cationic compounds of the following formulas can be used
  • each R 1 group is independently selected from C 1 6 alkyl, alkenyl or hydroxyalkyl groups
  • each group R 2 is independently selected from C 8 28 alkyl or alkenyl
  • R 3 R 1 or (CH 2 ) n -TR 2
  • R 4 R 1 or R 2 or (CH 2 ) n -TR 2
  • T -CH 2 -, -O-CO- or -CO-O- and n is an integer of 0 to 5 is
  • the group of polymers in particular pay the detergents or cleaning-active polymers, for example the clear-spooled polymers and / or polymers which are effective as softeners.
  • the detergents or cleaning-active polymers for example the clear-spooled polymers and / or polymers which are effective as softeners.
  • cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers
  • “Cationic polymers” in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain preferred cationic polymers are from the groups of quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiailyiammonium salt and ⁇ eren copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrohydone with quaternized derivatives of dialkylamino acrylates and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers listed under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27
  • amphoteric polymers furthermore have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may, for example, be carboxylic acids, sulfonic acids or phosphonic acids
  • particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula
  • R 1 and R 4 independently of one another are H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms
  • R 2 and R 3 independently of one another are an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl radical is linear or branched is and has between 1 and 6 carbon atoms, which is preferably a methyl group X and Y independently of one another represent integers between 1 and 3.
  • X represents a counterion, preferably a counterion from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzoisulfonate, p-touluenesulfonate (tosylate), cumene sulfonate , Xylene sulfonate, phosphate, citrate, formate, acetate or mixtures thereof
  • Preferred radicals R 1 and R 4 in the above formula are selected from -CH 3, -CH 2 -CH 3, -CH 2 - CH 2 -CH 3, -CH (CH 3) -CH 3, -CH 2 -OH , -CH 2 -CH 2 -OH 1 -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H
  • cationic or amphoteric polymers contain a monomer unit of the general formula
  • R1 HC CR2-C (O) -NH- (CH 2) -N + R3R4R5
  • X " in the R 1 , R 2 , R 3 , R 4 and R 5 are independently of one another a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH) -CH 3 , and - (CH 2 CH 2 -O) n is H and x is an integer between 1 and 6
  • amphoteric polymers have not only cationic groups but also anionic groups or monomer units.
  • anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched , saturated or unsaturated sulfates or the linear or branched, saturated or unsaturated sulfonates
  • Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid , maleic acid, fumaric acid, cinnamic acid and its derivatives, the allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids
  • Preferred usable amphoteric polymers come from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the
  • Alkylacrylamide / methylmethacrylic acid copolymers the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylammoalkylmethacrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / Alkylmethacrylat- copolymers and the copolymers of unsaturated carboxylic acids, cationically de ⁇ vatis investigating unsaturated carboxylic acids and optionally further ionic or nonionic monomers
  • Preferred zwitterionic polymers are from the group of acrylamidoalkyltrialkylammoniumchlo ⁇ d / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammoniumchlo ⁇ d / methacrylic acid copolymers and their alkali metal and ammonium salts and the Methacroylethylbetain / methacrylate copolymers Preference is also given to amphoteric polymers, which in addition to one or more anionic
  • amphoteric polymers are from the group of methacrylamidoalkyl- tr ⁇ alkylammon ⁇ umchlo ⁇ d / D ⁇ methyl (d ⁇ allyl) ammon ⁇ umchlo ⁇ d / acrylic acid copolymers, the Methacryl- am ⁇ doalkyltr ⁇ alkylammon ⁇ umchlor ⁇ d / D ⁇ methyl (d ⁇ allyl) ammon ⁇ umchlor ⁇ d / methacrylic acid copolymers and the Methacrylamidoalkyltrialkylammoniumchlo ⁇ d / DimethyKdiallyOammoniumchlo ⁇ d / alkyl
  • amphoteric polymers from the group of:
  • the polymers are present in prefabricated form.
  • the encapsulation of the polymers by means of water-soluble or water-dispersible substances is suitable here
  • Coating compositions preferably by means of water-soluble or water-dispersible natural or synthetic polymers, the encapsulation of the polymers by means of water-insoluble, fusible coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or
  • Paraffins with a melting point above 30 0 C the cogranulation of the polymers with inert Tragermate ⁇ alien, preferably with
  • Tragermate ⁇ alien from the group of washing or cleaning-active substances, particularly preferably from the group of builders (scaffolds) or cobuilders
  • Preferred combination products contain the abovementioned cationic and / or amphoteric polymers, preferably in amounts of between 0.01 and 8% by weight, based in each case on the total weight of the combination product.
  • combination products in which the weight fraction of the cationic and / or or amphoteric polymers between 0.01 and 6% by weight, preferably between 0.01 and 4% by weight, more preferably between 0.01 and 2% by weight and in particular between 0.01 and 1% by weight, based in each case on the total weight of the combination product
  • polymers effective as a softener are the sulfonic acid group-containing polymers which are used with particular preference
  • Copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionogenic or nonionogenic monomers are particularly preferably usable as sulfonic acid group-containing polymers
  • R 1 to R 3 independently of one another are -H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH 2 , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms
  • Particularly preferred monomers containing sulfonic acid groups 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, Methacrylam ⁇ do-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide,
  • ethylenically unsaturated compounds are suitable as further ionic or nonionogenic monomers.
  • the content of the polymers used in these other ionic or nonionic monomers is less than 20% by weight, based on the polymer.
  • copolymers consist of i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or
  • the copolymers may contain the monomers from the groups I) and n) and, if appropriate, in varying amounts, it being possible to combine all representatives from the group I) with all representatives from the group I) and all representatives from the group I) Preferred polymers have certain structural units which are described below
  • copolymers which are structural units of the formula are preferred.
  • Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed.
  • the sulfonic acid groups may be completely or partially in neutralized form, ie that the acidic hydrogen atom of the Suifonsaureoli may be exchanged in some or all sulfonic acid groups for metal ions, preferably alkali metal and especially against sodium ions.
  • the use of partially or fully neutralized sulfonic acid group-containing copolymers according to the invention prefers
  • the monomer distribution of the copolymers preferably used according to the invention is in the case of copolymers which contain only monomers from groups (I) and (I), preferably in each case from 5 to 95% by weight or preferably from 50 to 90% by weight of monomer from the group ⁇ ) and 10 to 50% by weight of monomer from the group n), in each case based on the polymer
  • terpolymers particular preference is given to those containing from 20 to 85% by weight of monomer from the group I), from 10 to 60% by weight of monomer from the group I) and from 5 to 30% by weight of monomer from the group III)
  • the molecular weight 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 intended use.
  • Preferred detergents or cleaners are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol.sup.- 1 , preferably from 4000 to 25,000 gmof 1 and in particular from 5000 to 15,000 gmol 1 have
  • bleach activators are compounds which ahphatician under Perhydrolysebedmgungen Peroxocarbonsauren preferably having 1 to 10 carbon atoms, Particularly suitable are substances which carry O- and / or N-acyl groups of said carbon atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular polyunsaturated alkylenediamines Tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-dimethyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycol oil, especially Tetraacetylglykolu ⁇ l (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI) acylated Phenolsulfonate particular n-nonanoyl or Isononanoyloxybenzolsulfonat (n- or iso-NOBS), Carbonsaureanhydnde particular Phthalsaureanhyd ⁇ d, acyi Being polyhydric alcohols, in particular T ⁇ acetin, ethylene glycol diacetate and 2, 5-D ⁇ acetoxy-2,5-d ⁇ hydro
  • R 1 is -H-CH 3 , a C 2 24 alkyl or alkenyl radical, a substituted C 2 24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, -OH, - NH 2 , -CN, an alkyl or alkenylaryl radical having a C 1 24 -alkyl group, or a substituted alkyl or alkenylaryl radical having a C 1 24 -alkyl group and at least one further substituent on the aromatic ring
  • R 2 and R 3 are independently are selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , - CH (CH 3 ) -CH 3 -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH -CH 2 -
  • bleach activators are compounds which are aliphatic under perhydrolysis conditions Peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid are used.
  • Substances which are suitable are O- and / or N-acyl groups of the stated carbon atom number and / or, if appropriate Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-dimethyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolyls, in particular tetraacetylglycol chloride (TAGU) , N-Acyl ⁇ m ⁇ de, in particular N-Nonanoylsucc ⁇ n ⁇ m ⁇ d (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or Isononanoyloxybenzolsulfonat (n- or iso-NOBS), Carbonsaureanhyd ⁇ de, especially Phthalsaureanhydnd, acyl
  • bleach activators preference is given to bleach activators from the group of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylmethylenes, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (US Pat. n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA)
  • TAED tetraacetylethylenediamine
  • NOSI N-nonanoylsuccinimide
  • acylated phenolsulfonates in particular n-nonanoyl or isononanoyloxybenzenesulfonate (US Pat. n- or iso-NOBS), n-methyl-morpholinium-acetonit
  • bleach catalysts can also be used. These substances are bleaching-intensifying transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing T ⁇ pod ligands and Co, Fe, Cu and Ru amine complexes can be used as bleach catalysts
  • Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammine) Complexes containing cobalt (acetate) complexes, cobalt (carbonyl) complexes, chlorides of cobalt or manganese, manganese sulfate
  • Glass corrosion inhibitors prevent the occurrence of turbidity, streaks and scratches, but also iridescence of the glass surface of mechanically cleaned glasses.
  • Preferred glass corrosion inhibitors are derived from the group of magnesium and / or zinc salts and / or magnesium and / or zinc complexes
  • the spectrum of erfmdungsgespecialized preferred zinc salts preferably organic acids, more preferably organic carboxylic acids, ranging from salts that are difficult or insoluble in water so a Loshchkeit below 100 mg / l, preferably below 10 mg / l, especially below 0.01 mg / l, to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and especially above 5 g / l (all solvents at 20 ° C water temperature )
  • the first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate; the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate
  • At least one zinc salt of an organic carboxylic acid more preferably a zinc salt from the group Zmkstearat, Zinkoleat, zinc gluconate, zinc acetate, zinc lactate and / or zinc citrate Zink ⁇ cinoleat, Zinkabietat and Zmkoxalat are preferred.
  • soluble inorganic zinc salts in particular the zinc sulfate, zinc nitrate and Zinkchlo ⁇ d
  • Corrosion inhibitors are used to protect the Spulgutes or the machine, wherein in the field of automatic dishwashing, especially silver protectants have a special meaning Can be used, the known substances of the prior art Generally, especially silver protectants selected from the group of T ⁇ azole, the Benzot ⁇ azole, Bisbenzotnazole, the Particularly preferably to be used are Benzot ⁇ azol and / or Alkylaminot ⁇ azol Erfmdungsge naval 3-Am ⁇ no-5-alkyl-1, 2,4-tr ⁇ azole or their physiologically acceptable salts are preferably used, these Substestanzen with particular preference in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2% by weight, particularly preferably 0.01 to 0.04% by weight are used Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, Carbonic acid, sulphurous acid, organic Ca Acids, such as acetic, glycolic, citric, succinic, 5-penty
  • Chlorine-free detergents also contain oxygen- and nitrogen-containing organic redox-active compounds, such as dihydric and trihydric phenols, for example hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, Phloroglucin, pyrogallol or derivatives of these compounds used also salt and complex inorganic compounds, such as salts of metals Mn, Ti, Zr, Hf, V, Co and Ce are often used
  • preference is given to the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate be used to prevent corrosion on Spulgut
  • redox-active substances can be used. These substances are preferably inorganic redox-active substances from the group of the manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium oxides. Salts and / or complexes, wherein the metals are preferably present in one of the oxidation states II, IM, IV, V or VI
  • the metal salts or metal complexes used should be at least partially soluble in water.
  • the counterions suitable for salt formation comprise all conventional mono-, di-, or tri-negatively charged inorganic anions, for example oxide, sulfate, nitrate, fluoride, but also organic anions such as stearate
  • metal salts and / or metal complexes are selected from the group MnSO 4 , Mn (II) -citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [I -Hydroxyethane-1, 1- diphosphonate], V 2 O 5 , V 2 O 4 , VO 2 , TiOSO 4 , K 2 TiF 6 , K 2 ZrF 6 , CoSO 4 , Co (NO 3 ) 2 , Ce (NO 3 ) 3 , and mixtures thereof, such that the metal salts and / or metal complexes are selected from the group MnSO 4 , Mn (II) -citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1- diphosphonate], V 2 O 5 , V 2 O 4 ,
  • the inorganic redox-active substances are preferably coated, ie completely coated with a water-tight material which is readily soluble in the cleaning temperatures, in order to prevent their premature decomposition or oxidation during storage.
  • Preferred coating materials which, by known processes, for example Sandwik melt coating processes from the food industry are applied to paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax beeswax, high-melting alcohols such as hexadecanol, soaps or fatty acids
  • perfume oils or perfumes may be selected from the group consisting of synthetic esters, ethers, aldehydes, ketones, alcohols and hydrocarbons. Preferably, however, mixtures of different fragrances are used which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures such as those available from vegetable sources, such as pine, citrus, jasmine, patchouly, rose or ylang-ylang oil
  • a perfume In order to be perceptible, a perfume must be volatile, in addition to the nature of the functional groups and the structure of the chemical compound and the molecular weight plays an important role So most perfumes have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and more represent an exception Due to the different odor of odoriferous substances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note”, “middle note” or “middle note” Since the perception of odor is based to a large extent on the odor intensity, the top note of a perfume or fragrance is not made up of volatile compounds alone, while the base note consists for the most part of less volatiles, ie Adherent fragrances persists in the composition of perfumes For example, it is easier for volatile fragrances to be bound to specific fixatives, which prevents them from evaporating too quickly. The subsequent classification of the fragrances into "light volatile” or "firmly adher
  • the fragrances can be processed directly, but it may also be advantageous to apply the fragrances on wearers, which provide a slower fragrance release for long-lasting fragrance As such Tragermate ⁇ alien example Cyclodext ⁇ ne have preserved, the Cyclodext ⁇ n- perfume complexes additionally with other excipients can be coated
  • Preferred dyestuffs the choice of which presents no difficulty to a person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light and no pronounced substantivity to those with the dye-containing agents treating substrates such as textiles, glass, ceramics or plastic crockery so as not to stain them
  • the colorants have a high storage stability and insensitivity to light and not too strong affinity for glass, ceramic or plastic dishes
  • colorants have different stabilities to the oxidation
  • water-insoluble colorants are more stable to oxidation than water-soluble colorants.
  • concentration of the colorant in the detergents or cleaners varies.
  • colorant concentrations in the range of a few 10 2 are typically up to 10 3 % by weight selected
  • suitable concentration of the colorant is washing or cleaning on the other hand, typically at some 10 3 to 10 4 % by weight
  • Colorants which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It is advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, e.g. B anionic nitrosoticianbstoffe
  • inventive detergents or cleaning agents may further contain preservatives
  • preservatives from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and Formals, benzamidines, isothiazoles and their derivatives such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinone, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynylbutyl carbamate, iodine, iodophores and peroxides
  • Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol
  • a combination product comprising a packaging means and two separate liquid washing or cleaning agents A and B of the composition contained in said packaging means
  • liquid detergent A has a pH (20 0 C) between 6 and 9
  • liquid detergent B has a pH (20 0 C) between 9 and 14 and none of the detergents A or B contains more than 2% by weight of a bleaching agent
  • such combination products have proven advantageous in which at least one of the detergents A or B has a viscosity of more than 10,000 mPas, preferably more than 50,000 mPas and in particular more than 100,000 mPas combination products, characterized that the viscosity (Brookfield LVT-II at 20 U / mm and 20 0 C, spindle 3) of at least one of the washing or cleaning agents A or B between 200 and 10,000 mPas, preferably between 500 and 7000 mPas and in particular between 1000 and amounts to 4000 mPas, accordance with the invention are preferably the viscosity (Brookfield viscometer LVT-II / m ⁇ n at 20 U and 20 0 C, spindle 3) is particularly preferred detergent or cleaning agent is above 500 mPas, preferably above 1000 mPas and in particular above 2000 mPas
  • these agents are preferably thickeners, in particular thickeners from the group of agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins , Polyoses, guar gum, locust bean gum, starch, dextrins, gelatin, casein, carboxymethylcellulose, gum ethers, polyacrylic and polymethacrylic Compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides, polysilicic acids, clay minerals such as montmorillonites, zeolites and silicic acids, it being particularly advantageous if the detergents or cleaning agents have thickening agents in amounts of between 0.1 and 8% by weight. %, preferably between 0.2 and 6% by weight and more preferably between 0.4 and 4% by weight, based on the total weight of the washing or cleaning
  • Naturally derived polymers which are used as thickening agents in the present invention are as described above, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein
  • Modified natural products come mainly from the group of modified starches and celluloses, examples include carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and core flour ethers mentioned
  • a large group of thickeners which find wide use in a variety of applications, are the fully synthetic polymers such as polyacrylic and polymethacrylic Verbmditch, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes thickeners from these classes of substances are commercially widely available and are, for example the trade names Acusol ® -820
  • the combination products according to the invention also comprise a packaging means.
  • the two cleaning agents A and B are separated from one another, ie they do not form a common phase boundary, but rather are located in separate regions of the packaging means
  • Such a packaging means is suitable for example water-insoluble a two- or Mehrcrobehalter
  • a two- or Mehrcrobehalter typically has a total volume between 100 and 5000 ml, preferably between 200 and 2000 ml
  • the volume of the individual chambers is preferably between 50 and 2000 ml, preferably between 100 and 1000 ml
  • Preferred two- or Mehrcrobehalter have a bottle shape
  • the liquid washing or cleaning agent of the two- or Mehrcrobehalter preferably has at least one spout, which may be configured, for example in the form of a common spout for all contained in the bottle means.
  • such two- or Mehrcrobehalter are preferred in which each of the Containment chambers of the container has its own spout
  • the packaging means is a two- or multi-chamber container, wherein preferably each of the receiving chambers of the packaging means is provided with a spout, are preferred
  • the packaging means is a water-soluble two- or Mehrschbehalter, for example, a water-soluble bag with two or more separate receiving chambers
  • thermoforming bodies can have two, three or more receiving chambers. These receiving chambers can be arranged in the deep-drawn part next to one another and / or one above the other and / or one inside the other
  • Water-soluble polymers such as, for example, cellulose ethers, pectins, polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, alginates, gelatin or starch are particularly suitable as packaging materials for the water-soluble containers
  • the water-soluble bags are preferably thermoformed or molded bodies
  • thermoforming body refers to such containers which are obtained by deep-drawing a first film-like Hullmate ⁇ als
  • Thermoforming is preferably carried out by bringing the Hullmate ⁇ als over one in a die forming the Tiefzielandere receiving trough and forming the Hullmate ⁇ als in this receiving trough by the action of pressure and / or vacuum v / erformt
  • the Hullmate ⁇ ai before doing before or during the forming by the action heat and / or solvent and / or conditioning may be pretreated by ambient relative humidity and / or temperature changes.
  • the pressure may be applied through two parts of a tool which act as positive and negative with respect to each other and deform a film placed between these tools as they are compressed
  • the action of compressed air and / or the weight of the film and / or the weight of an active substance applied to the upper side of the film is also suitable as pressure forces
  • the deep-drawn Hullmate ⁇ alien be after deep drawing preferably by using a vacuum within the receiving wells and achieved in their thermoforming space fixed
  • the vacuum is preferably continuously applied from deep drawing to Befullen until sealing and in particular until the separation of the receiving chambers created with comparable results
  • a discontinuous vacuum for example for deep drawing of the receiving chambers and (before interrupting) before and during filling the receiving chambers, possible
  • the continuous or discontinuous vacuum vary in its strength and, for example, at the beginning of the process (during deep drawing of Foil) take higher values than at the end (when filling or sealing or separating)
  • the Hullmate ⁇ al before or during the forming into the receiving troughs of the matrices can be pretreated by the action of heat
  • the Hullmate ⁇ al preferably a water-soluble or water-dispersible polymer film, thereby for up to 5 seconds, preferably for 0 1 to 4 seconds, particularly preferably for 0.2 to 3 seconds and in particular for 0.4 to 2 seconds to temperatures above 60 0 C, preferably above 80 0 C, more preferably between 100 and 120 0 C and in particular heated to temperatures between 105 and 115 ° C.
  • the cooling is preferably carried out at temperatures below 20 ° C, preferably below 15 ° C, more preferably Tempe Temperatures between 2 and 14 ° C and in particular at temperatures between 4 and 12 ° C.
  • the cooling is carried out continuously from the beginning of the deep-drawing process to the sealing and separation of the receiving chambers for cooling are in particular Kuhlmanntechniken, preferably water, which in special Kuhltechnischen be circulated within the matrix
  • This cooling has the advantage of preventing shrinkage of the deep-drawn containers after deep-drawing, which not only improves the appearance of the process product, but also simultaneously discharges the means filled into the receiving chambers avoiding the edge of the receiving chamber, for example in the sealing areas of the chamber problems in the sealing of the filled chambers are thus avoided
  • the deep-drawing process can be between methods in which the Hullmate ⁇ al horizontally in a forming station and from there in a horizontal manner for filling and / or sealing and / or separating is performed and methods in which the Hullmate ⁇ al on a continuously rotating Mat ⁇ zenformwalze (optionally optionally with The first-mentioned process variant of the flat bed process is to operate both continuously and discontinuously, the process variant using a molding roll is usually continuous All mentioned deep-drawing process are suitable for the production of the preferred means according to the invention.
  • the receiving troughs located in the temples can be arranged "in series" or staggered
  • the water-soluble containers can also be produced by injection molding.
  • molding means that a mass contained in a mass cylinder for more than one injection molding plastically softens under heat and flows under pressure through a nozzle into the cavity of a previously closed tool
  • the injection molding is a very economical modern process for the production of non-cutting shaped objects and is particularly suitable for automated mass production
  • the thermoplastic molding compounds prowder, grains, cubes, pastes etc.
  • the liquefaction up to 180 0 C
  • high pressure up to 140 MPa
  • closed, two-piece that is, from the die (die earlier) and core (formerly Pat ⁇ ze part), preferably wassergek hlte hollow shapes, where they cool and solidify usable are piston and Schneckensp ⁇ tzgußmaschinen
  • Combination products according to the invention characterized in that the packaging means are a water-soluble container with two separate receiving chambers, are preferred
  • the combination product according to the invention is particularly suitable as a machine dishwashing liquid.
  • a further subject of the present application is therefore a machine dishwashing process in which two liquid washing or cleaning agents A and B are metered into the interior of a dishwashing machine. or cleaning agents A and B have the following composition: A - from 10 to 75% by weight of grafting substance (s),
  • liquid detergent A has a pH (2O 0 C) between 6 and 9
  • liquid detergent B has a pH (2O 0 C) between 9 and 14 and none the cleaning agent A or B contains more than 2% by weight of a bleaching agent
  • washing or cleaning agents A or B are formulated in water-soluble containers, they have a viscosity of more than 10,000 mPas, preferably more than 50,000 mPas and in particular more than 100,000 mPas on combination products, characterized by that they are present in a packaging with two separate receiving chambers, wherein the viscosity (Brookfield LVT-II at 20 U / min and 20 ° C, spindle 3) of at least one of detergents or cleaning agents A or B between 5000 and 200,000 mPas , preferably between 10,000 and 150,000 mPas and in particular between 20,000 and 100,000 mPas, are preferred according to the invention
  • the dosage of the two liquid washing or cleaning agents A and B can be done for example in the metering chamber in the door or an additional Dosierbehalter in the interior of the dishwasher or directly on the soiled dishes Alternatively, the two detergents or cleaning agents on one of the inner walls of the dishwasher For example, the inside of the door, be dosed
  • the inventive method for mechanical Cleaning of dishes in a dishwasher characterized in that in the course of a cleaning program, which includes a booster and a cleaning cycle, in this cleaning cycle on two consecutive times ti and t2 two liquid detergents A and B of the composition A - 10 b ⁇ s 75 wt -% Geruststoff (e),
  • the liquid detergent A has a pH (20 ° C) between 6 and 9 and is metered in at time t1
  • the liquid detergent B has a pH value (20 ° C.) between 9 and 14 and is metered in at time t2
  • the bleach content of the cleaning agents A and B is in each case less than 2% by weight.
  • the bleach content of the cleaning agents A and B is less than 0.5% by weight and in particular less than 0.1% by weight
  • Particularly preferred methods according to the invention are those in which the cleaning agents A and B contain no bleaching agents
  • the implementation of this inventive preferred method is carried out in the interior of a commercial dishwasher
  • the cleaning program can be selected and set in a dishwasher usually before carrying out the dishwashing by the consumer
  • the used in this inventive preferred method cleaning program of the dishwasher comprises at least one Vorpulgang and a cleaning cycle
  • cleaning programs which include further cleaning or winding operations for example a rinse cycle, are preferred.
  • the process according to the invention is thus not restricted to those cleaning programs which consist exclusively of a forward cycle and a cleaning cycle
  • the inventive method is particularly preferred part of a cleaning program comprising a forward, a cleaning cycle and a Klarspulgang
  • the cleaning programs of automatic dishwashers can differ in terms of their duration, their water consumption and the temperature of the cleaning liquor
  • the inventive method is preferably used in conjunction with such cleaning programs in which the wash liquor is heated in the course of the cleaning cycle
  • the cleaning cycle in the course of which the detergent A and B are metered into the interior of the dishwasher characterized in that in its course, the temperature of the handsfiotte to values above 30O 0 C, preferably above 40 ° C and especially above 50 ° C increases
  • the temperature of the wash liquor at time t1 is in a preferred embodiment between 12 and 45 ° C, preferably between 15 and 40 0 C and in particular between 20 and 35 ° C, while the temperature of the wash liquor at time t2 preferably between 30 and 65 0 C. , preferably between 35 and 60 0 C and in particular between 40 and 55 ° C amounts
  • the wash liquor may have the same or different temperatures.
  • the temperature of the wash liquor at time t1 is different from the temperature of the wash liquor at time t2, the temperature at time t1 being above or below the temperature at the time
  • Particularly advantageous cleaning results could be achieved in processes according to the invention in which the temperature of the wash liquor was below the temperature of the wash liquor at time t 2 at time t 1. Corresponding processes are therefore preferred
  • the temperature of the wash liquor at time t2 preferably at least 5 0 C, preferably at least 10 ° C and especially between 10 and 40 ° C, but especially between 10 and 20 ° C above the temperature of the wash liquor at time t1
  • the dosing of the two liquid detergents A and B takes place in the course of the cleaning cycle at two successive times t1 and t2, the detergent A being metered in at time t1 and the detergent B at time t2 and the time t1 being earlier than time t2
  • the time t1 is preferably within the first ten minutes after the beginning of the cleaning cycle, preferably within the first eight minutes after the beginning of the cleaning cycle and in particular within the first five minutes after the beginning of the cleaning cycle
  • the time difference between the times t1 and t2 is preferably between 2 and 30 minutes, preferably between 4 and 25 minutes and in particular between 6 and 20 minutes
  • the cleaning agent A has a pH (20 ° C.) between 6 5 and 5 preferably between 7 and 1, while the pH Value (20 ° C.) of the cleaning agent B is between 9.5 and 13, preferably between 10 and 12
  • the detergents A and B are preferably required from a self-sufficient dosing in the interior of the dishwasher as "self-sufficient" is called a dosing, which is not an integral part of the dishwasher used
  • a dosing device preferably has its own storage container for the detergent A and B. and via its own metering device for demanding and metering of the cleaning agents A and B in the interior of the dishwasher.
  • the metering device is further provided with an independent power supply
  • the cleaning agents A and B may each be required by an independent dosing in the interior of the dishwashing machine However, it is preferred to combine the cleaning agents A and B in a common Dosiergerat
  • the liquid cleaning agents A and B in a preferred embodiment in a water-insoluble Two- or Mehrcrovorratsbehalter ago
  • the detergents A and B are preferably spatially separated from each other in this container and are metered from this container in the interior of the dishwasher by the separation of the detergent from each other physical and chemical interactions of the detergent are prevented
  • the volume of the respective chambers of the storage container is preferably sufficient for receiving at least five, preferably at least ten, and particularly preferably at least 20 metering units of a cleaning agent A or B. Since the metering amount of the cleaning agents A and B during a cleaning process is preferably between 5 and 50 ml, preferably amounts to between 10 and 40 ml and in particular between 10 and 30 ml amounts to the preferred volume of the storage chamber for the detergent A or for the detergent B at least 25 ml, preferably at least 50 and especially at least 100 ml Preference Dosiers, each having a chamber for the cleaning agents A and B, wherein the volume of each of these chambers between 50 and 1000 ml, preferably between 100 and 800 ml and in particular between 200 and 600 ml
  • the sedimentation power in the method according to the invention can also be influenced by the metering rate of the metering device in addition to the parameters mentioned above.
  • the metering rate of the metering device is preferably between 1 and 40 ml per minute, preferably between 2 and 30 ml per minute and in particular between 4 and 20 ml per minute
  • the detergents A and B used in the process according to the invention contain, in addition to other ingredients active in washing or cleaning.
  • Gerüstscher The zeolites in particular pay the zeolites, silicates, carbonates, organic co-builders and -where there are no ecological prejudices against their use-also the phosphates Description of these skeletons can be found above in the text
  • the liquid detergents A and / or B preferably comprise a proportion by weight of the crystalline layered silicate of the formula NaMSi x O 2x + IyH 2 O of from 0.1 to 20% by weight of from 0.2 to 15% by weight and in particular of 0 , 4 to 10% by weight, based in each case on the weight of the particular cleaning agent A or B, are contained
  • preferred combination products comprise dicloses (s) phosphate (s), preferably alkali metal metal phosphate (s), particularly preferably pentasodium or pentapotassium phosphate ( Sodium or Kaliumt ⁇ polyphosphat), in amounts of 5 to 60% by weight, preferably from 15 to 45% by weight, in particular from 20 to 40% by weight, based in each case on the weight of the respective cleaning agent A or B, are included
  • Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymers
  • Polycarboxylates aspartic acid, polyacetals, dextrins, other organic cobuilders as well
  • the citric acid or salts of citric acid is particularly preferably used as a framework substance.
  • Combination products characterized in that the at least one of the cleaning agents A or B contains citric acid or a salt of citric acid and the weight proportion of citric acid or of the salt of citric acid, based on the total weight of the cleaning agent, between 0.2 and 12% by weight, preferably between 0.2 and 8% by weight and in particular between 0.2 and 6% by weight, are preferred according to the invention
  • Another particularly preferred framework substance is the methylglycinediacride acid (MGDA) process according to the invention, characterized in that the cleaning agent contains methylglycinediacetic acid or a salt of methylglycinediacetic acid and the weight fraction of methylglycinediacetic acid or the salt of methylglycinediacetic acid is preferably between 0.2 and 12% by weight, preferably between 0.2 and 8% by weight and in particular between 0.2 and 6% by weight, are preferred according to the invention
  • the content of detergents or cleaning agents in (co) polymeric polycarboxylates is preferably 0.1 to 10% by weight, preferably 0.2 to 8% by weight, more preferably 0.4 to 6% by weight and in particular between 0, 4 and 4% by weight
  • composition used as cleaning agent A in the process according to the invention contains enzymes. To avoid repetitions, reference is made at this point to the detailed description above in the text
  • the proportion by weight of the enzymes in the total weight of the liquid detergent A is between 0.1 and 10% by weight.
  • the proportion by weight of the enzyme in the total weight of the cleaning agent A is between 0.2 and 9% by weight and in particular between 0.5 and 8% by weight
  • liquid detergent B may of course also contain enzymes, it is preferred that the enzyme content of the detergent B be less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.5% by weight and especially less when 0.1% by weight is particularly preferred processes according to the invention are characterized in that the liquid cleaning agent B contains no enzymes
  • one or more enzymes and / or enzyme preparations preferably solid or liquid protease preparations and / or amylase preparations are used.
  • the liquid detergent A comprises a combination of protease and amylase preparations
  • solvents which have already been described above are also suitable as solvents in the detergents A and B used in the process according to the invention, the organic amines and / or alkanolamines also described having special significance
  • Another object of this application is the use of organic amines, in particular the aforementioned organic amines and / or alkanolamines in the inventive method, for the purification of bleachable stains, preferably for cleaning Teeanschmutzache on hard surfaces
  • Particularly preferred cleaning agents A and / or B contain, based on the total weight of the respective cleaning agent, between 0.1 and 10% by weight, preferably between 0.5 and 8% by weight and in particular between 1, 5 and 6% by weight of an organic Solvents from the group of organic amines and alkanolamines
  • the liquid detergent B based on the total weight of the cleaning agent B, contains from 0.1 to 10% by weight of an organic solvent from the group of organic amines and alkanolamines 10% by weight, preferably between 0.5 and 8% by weight and in particular between 1, 5 and 6% by weight, while the proportion by weight of organic solvent from the group of organic amines and alkanolamines in the liquid detergent A, based on the total weight of the cleaning agent A, preferably less than 5% by weight, preferably less than 3% by weight, particularly preferably less than 1% by weight and very particularly preferably less than 0.1% by weight, and in particular no organic solvent from the group of organic amines and alkano
  • the bleaching agent content of the liquid detergents A and B is chosen to be low and is preferably less than 2% by weight.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des produits combinés comportant un agent de conditionnement et deux agents de lavage ou de nettoyage (A et B), distincts, situés dans l'agent de conditionnement, l'agent A étant composé de 10 à 75 % en poids d'adjuvants de lavage, de 0,1 à 10 % en poids d'enzymes, et de 24,9 à 89,9 % en poids en poids d'eau, et B étant composé de 10 à 75 % en poids d'adjuvants de lavage, et de 25 à 90 % en poids d'eau. L'invention est caractérisée en ce que l'agent de lavage liquide A présente un pH de 6 à 9 à 20 °C tandis que l'agent de lavage liquide B présente un pH de 9 à 14 à 20 °C, et en ce que ni A ni B ne contient plus de 2 % en poids d'un agent de blanchiment. Les agents de lavage selon l'invention se caractérisent par un meilleur pouvoir lavant par rapport à des agents de lavage de la vaisselle habituels, notamment sur des tâches blanchissables.
EP06777028.9A 2005-09-02 2006-08-23 Agents de lavage Active EP1917342B8 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL06777028T PL1917342T3 (pl) 2005-09-02 2006-08-23 Środki czyszczące

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102005041709A DE102005041709A1 (de) 2005-09-02 2005-09-02 Reinigungsmittel
DE102006028750A DE102006028750A1 (de) 2006-06-20 2006-06-20 Reinigungsverfahren
PCT/EP2006/008271 WO2007025665A2 (fr) 2005-09-02 2006-08-23 Agents de lavage

Publications (3)

Publication Number Publication Date
EP1917342A2 true EP1917342A2 (fr) 2008-05-07
EP1917342B1 EP1917342B1 (fr) 2012-10-24
EP1917342B8 EP1917342B8 (fr) 2013-05-15

Family

ID=37192272

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06777028.9A Active EP1917342B8 (fr) 2005-09-02 2006-08-23 Agents de lavage

Country Status (5)

Country Link
US (2) US20090165821A1 (fr)
EP (1) EP1917342B8 (fr)
ES (1) ES2395044T3 (fr)
PL (1) PL1917342T3 (fr)
WO (1) WO2007025665A2 (fr)

Families Citing this family (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006028750A1 (de) 2006-06-20 2007-12-27 Henkel Kgaa Reinigungsverfahren
DE102005041708A1 (de) 2005-09-02 2007-03-08 Henkel Kgaa Reinigungsmittel
EP2274410A4 (fr) * 2008-04-07 2012-05-09 Ecolab Inc Composition de dégraissage solide ultra-concentrée
DE102009000879A1 (de) * 2009-02-16 2010-08-19 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102009027162A1 (de) * 2009-06-24 2010-12-30 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
DE102009027164A1 (de) * 2009-06-24 2010-12-30 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
EP2611898A1 (fr) * 2010-08-30 2013-07-10 Novozymes A/S Lavage à trempage concentré
RU2013114297A (ru) * 2010-08-30 2014-10-10 Новозимс А/С Стирка с двумя замачиваниями
DE102011079260A1 (de) * 2011-07-15 2013-01-17 Henkel Ag & Co. Kgaa Klarspül- und Reinigungsmittel
KR101882182B1 (ko) * 2011-11-22 2018-07-27 삼성전자주식회사 식기 세척기 및 그 제어 방법
DE102012210993A1 (de) 2012-06-27 2014-01-02 Henkel Ag & Co. Kgaa Verbesserung des Glanzes auf Edelstahl
DE102012210992A1 (de) 2012-06-27 2014-01-02 Henkel Ag & Co. Kgaa Verwendung von Sulfopolymer als Enzymstabilisator
DE102012210991A1 (de) 2012-06-27 2014-01-02 Henkel Ag & Co. Kgaa Kombinationsprodukt
DE102012213748A1 (de) 2012-08-03 2014-02-06 Henkel Ag & Co. Kgaa Kombinationsprodukt
US8888924B2 (en) * 2012-08-24 2014-11-18 Ecolab Usa Inc. Freestanding detergent composition not requiring an automated dispenser
TR201818916T4 (tr) * 2012-09-25 2019-01-21 Dalli Werke Gmbh & Co Kg Yıkama maddesi ve bir yıkama maddesinin dozajı için yöntem.
DE102013202450A1 (de) * 2013-02-14 2014-08-14 Henkel Ag & Co. Kgaa Flüssiges Wasch- oder Reinigungsmittel mit verbesserter Enzymstabilität
DE102013208599A1 (de) * 2013-05-10 2014-11-13 Henkel Ag & Co. Kgaa Kombinationsprodukt mit verbessertem Ausfließverhalten
EA031650B1 (ru) * 2013-06-25 2019-02-28 Юнилевер Н.В. Композиция, содержащая глутаминовую-n,n-диуксусную кислоту (glda), воду и фермент
GB201320176D0 (en) * 2013-11-15 2014-01-01 Reckitt Benckiser Brands Ltd Machine cleaning composition
DE102013225920A1 (de) * 2013-12-13 2015-06-18 Henkel Ag & Co. Kgaa Phosphatfreies flüssiges Geschirrspülmittel
KR101611297B1 (ko) * 2014-07-21 2016-04-11 엘지전자 주식회사 식기세척기의 제어방법
EP3026100B1 (fr) 2014-11-26 2018-07-25 The Procter and Gamble Company Poche de nettoyage
PL3034588T3 (pl) 2014-12-17 2019-09-30 The Procter And Gamble Company Kompozycja detergentu
GB201507289D0 (en) * 2015-04-29 2015-06-10 Reckitt Benckiser Brands Ltd Method of cleaning tableware
DE102015210828A1 (de) * 2015-06-12 2016-12-15 Henkel Ag & Co. Kgaa Phosphatfreies flüssiges Geschirrspülmittel
DE102015226572A1 (de) * 2015-12-22 2017-06-22 BSH Hausgeräte GmbH Wasserführendes Haushaltsgerät und Verfahren zum Betreiben eines wasserführenden Haushaltsgeräts
CN110536956A (zh) 2017-04-27 2019-12-03 埃科莱布美国股份有限公司 固体控释碳酸盐洗涤剂组合物
CA3081788C (fr) 2017-11-14 2022-08-09 Ecolab Usa Inc. Compositions detergentes caustiques a liberation controlee de matieres solides
DE102018220191A1 (de) 2018-11-23 2020-05-28 Henkel Ag & Co. Kgaa Reinigungsmittel mit Klarspüler für automatische Dosiereinheit
EP3656272A1 (fr) 2018-11-23 2020-05-27 Henkel AG & Co. KGaA Procédé pour éliminer les taches pendant un cycle de nettoyage d'un appareil ménager
ES3028186T3 (en) * 2019-05-22 2025-06-18 Procter & Gamble Automatic dishwashing method
CN114222808A (zh) 2019-09-27 2022-03-22 埃科莱布美国股份有限公司 浓缩二合一洗碗机洗涤剂和漂洗助剂
EP4194535A1 (fr) 2021-12-09 2023-06-14 Henkel AG & Co. KGaA Composition de nettoyage à deux phases avec des particules de détergent visiblement distinctes
EP4474466A1 (fr) * 2023-06-07 2024-12-11 The Procter & Gamble Company Procédé de traitement de vaisselle dans un lave-vaisselle domestique automatique

Family Cites Families (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2727463A1 (de) * 1976-06-24 1978-01-05 Procter & Gamble Reinigungsmittel, das insbesondere zur verwendung in geschirrspuelmaschinen geeignet ist
US4243546A (en) * 1979-03-23 1981-01-06 The Drackett Company Stable aqueous compositions containing enzymes
US4243543A (en) * 1979-05-11 1981-01-06 Economics Laboratory, Inc. Stabilized liquid enzyme-containing detergent compositions
US5240633A (en) * 1991-05-31 1993-08-31 Colgate-Palmolive Company Liquid automatic dishwashing composition containing enzymes
US5372740A (en) * 1993-09-03 1994-12-13 Lever Brothers Company, Division Of Conopco, Inc. Homogeneous liquid automatic dishwashing detergent composition based on sodium potassium tripolyphosphate
US5741767A (en) 1995-11-16 1998-04-21 Lever Brothers Company, Division Of Conopco, Inc. Peracid based dishwashing detergent composition
WO1997031087A1 (fr) 1996-02-23 1997-08-28 The Clorox Company Composition pour nettoyage de surfaces et appareil correspondant
CN1359417A (zh) * 1999-06-28 2002-07-17 宝洁公司 含有泡腾体系的水性液体洗涤剂组合物
US20040147423A1 (en) 1999-06-28 2004-07-29 The Procter & Gamble Company Dual-compartment laundry composition containing peroxyacids
US6844305B1 (en) * 1999-08-27 2005-01-18 The Proctor & Gamble Company Aqueous liquid detergent compositions comprising a polymeric stabilization system
DE19957036A1 (de) * 1999-11-26 2001-05-31 Henkel Kgaa Verfahren zur Herstellung teilchenförmiger Wasch- oder Reinigungsmittel
US20020142931A1 (en) * 2000-07-19 2002-10-03 The Procter & Gamble Company Gel form automatic dishwashing compositions, methods of preparation and use thereof
US20020169090A1 (en) * 2000-07-19 2002-11-14 Foley Peter Robert Cleaning composition
US7125828B2 (en) * 2000-11-27 2006-10-24 The Procter & Gamble Company Detergent products, methods and manufacture
PL362604A1 (en) * 2000-11-27 2004-11-02 The Procter & Gamble Company Dishwashing method
GB2374580B (en) * 2001-04-20 2003-07-16 Reckitt Benckiser Water-soluble containers
TWI264465B (en) * 2001-07-10 2006-10-21 Kao Corp Two-agent type liquid bleaching compositions
HUP0401286A3 (en) * 2001-08-17 2009-06-29 Henkel Ag & Co Kgaa Dishwasher detergent with improved protection against glass corrosion
EP1378563B1 (fr) * 2002-07-03 2007-01-03 The Procter & Gamble Company Composition détergente
BR0312782B1 (pt) 2002-07-20 2014-04-22 Reckitt Benckiser Nv Composição para o tratamento de manchas
DE10257387A1 (de) * 2002-12-06 2004-06-24 Henkel Kgaa Mehrkomponenten-Flüssigwaschmittel
US7448556B2 (en) * 2002-08-16 2008-11-11 Henkel Kgaa Dispenser bottle for at least two active fluids
DE10238431A1 (de) 2002-08-16 2004-03-04 Henkel Kgaa Spenderflasche für mindestens zwei Wirkstofffluide
DE10313453A1 (de) 2003-03-25 2004-10-14 Henkel Kgaa Portionierte Wasch- oder Reinigungsmittelzusammensetzung
EP1518922A1 (fr) 2003-09-26 2005-03-30 Unilever N.V. Compositions pour lave-vaisselle automatique
PL1673314T3 (pl) * 2003-10-17 2008-08-29 Reckitt Benckiser Finish Bv Kompozycja rozpuszczalnego w wodzie szkła
DE10358535A1 (de) * 2003-12-13 2005-07-14 Henkel Kgaa Hybridenzyme mit kationischer Bindedomäne
DE102004007860A1 (de) * 2004-02-17 2005-09-15 Henkel Kgaa Spenderflasche für Flüssigwaschmittel, die aus mindestens zwei Teilzusammensetzungen bestehen
DE102006028750A1 (de) * 2006-06-20 2007-12-27 Henkel Kgaa Reinigungsverfahren
DE102005041708A1 (de) * 2005-09-02 2007-03-08 Henkel Kgaa Reinigungsmittel
DE102005041709A1 (de) * 2005-09-02 2007-03-08 Henkel Kgaa Reinigungsmittel
WO2007025666A2 (fr) * 2005-09-02 2007-03-08 Henkel Kommanditgesellschaft Auf Aktien Agents de lavage

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007025665A3 *

Also Published As

Publication number Publication date
US20130146101A1 (en) 2013-06-13
EP1917342B8 (fr) 2013-05-15
ES2395044T3 (es) 2013-02-07
PL1917342T3 (pl) 2013-03-29
WO2007025665A2 (fr) 2007-03-08
EP1917342B1 (fr) 2012-10-24
WO2007025665A3 (fr) 2007-05-03
US8920576B2 (en) 2014-12-30
US20090165821A1 (en) 2009-07-02

Similar Documents

Publication Publication Date Title
EP2029719B1 (fr) Procédé de nettoyage
EP1917342A2 (fr) Agents de lavage
EP1917343A2 (fr) Agents de lavage
DE102005041708A1 (de) Reinigungsmittel
DE102009004524A1 (de) Farbschützendes maschinelles Geschirrspülmittel
DE102007059970A1 (de) Reinigungsmittel
DE102007038031A1 (de) Mittel enthaltend Proteasen
EP2181185A1 (fr) Agents nettoyants
DE102007059968A1 (de) Reinigungsmittel
DE102004005344A1 (de) Maschinelles Geschirrspülmittel ####
DE102005041709A1 (de) Reinigungsmittel
WO2007073801A1 (fr) Détergent pour lave-vaisselle
WO2006128543A1 (fr) Compose tensioactif
DE102005034752A1 (de) Reinigungs- und Pflegemittel mit verbesserter Emulgierfähigkeit
WO2013182510A1 (fr) Détergents pour vaisselle
EP1987119A1 (fr) Agent de lavage ou de nettoyage
EP1727884A1 (fr) Produits de lavage pour lave-vaisselle
WO2008061817A1 (fr) Système de bouchage muni d'un dispositif de positionnement tête en bas
EP3078732A1 (fr) Produit de rinçage pour lave vaisselle comprenant des complexants a base d'azote et mgda
EP2963102A2 (fr) Produit de nettoyage comprenant de l'acide hydroxamique et/ou ses sels
EP1871865B1 (fr) Lessive ou detergent
DE102011005695A1 (de) Geschirrspülmittel
DE102004020033A1 (de) Verbrauchsanzeiger für maschinelle Geschirrspülmittel
DE102006056248A1 (de) Bleichkatalysatorgranulat
DE102011079260A1 (de) Klarspül- und Reinigungsmittel

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20080208

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: HENKEL AG & CO. KGAA

17Q First examination report despatched

Effective date: 20080616

RIC1 Information provided on ipc code assigned before grant

Ipc: C11D 11/00 20060101ALI20120420BHEP

Ipc: C11D 3/386 20060101ALI20120420BHEP

Ipc: C11D 17/04 20060101AFI20120420BHEP

Ipc: C11D 3/43 20060101ALI20120420BHEP

Ipc: C11D 7/32 20060101ALI20120420BHEP

Ipc: C11D 3/30 20060101ALI20120420BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

DAX Request for extension of the european patent (deleted)
GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 580991

Country of ref document: AT

Kind code of ref document: T

Effective date: 20121115

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502006012139

Country of ref document: DE

Effective date: 20121220

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2395044

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20130207

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20121024

RIN2 Information on inventor provided after grant (corrected)

Inventor name: ZIPFEL, JOHANNES

Inventor name: PEGELOW, ULRICH

Inventor name: NITSCH, CHRISTIAN

Inventor name: KESSLER, ARND

Inventor name: GENTSCHEV, PAVEL

Inventor name: JEKEL, MAREN

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: 20121024

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: 20121024

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: 20130224

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: 20121024

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

Ref country code: CY

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

Effective date: 20121024

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: 20130225

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: 20121024

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: 20121024

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: 20130125

RIN2 Information on inventor provided after grant (corrected)

Inventor name: JEKEL, MAREN

Inventor name: NITSCH, CHRISTIAN

Inventor name: PEGELOW, ULRICH

Inventor name: ZIPFEL, JOHANNES

Inventor name: GENTSCHEV, PAVEL

Inventor name: KESSLER, ARND

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: 20121024

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: 20121024

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: 20121024

Ref country code: BG

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

Effective date: 20130124

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: 20121024

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

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

Ref country code: RO

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

Effective date: 20121024

26 Opposition filed

Opponent name: RECKITT BENCKISER (BRANDS) LIMITED

Effective date: 20130724

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

Free format text: ORIGINAL CODE: EPIDOSNOBS2

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 502006012139

Country of ref document: DE

Effective date: 20130724

PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

Free format text: ORIGINAL CODE: EPIDOSCOBS2

BERE Be: lapsed

Owner name: HENKEL A.G. & CO. KGAA

Effective date: 20130831

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Free format text: ORIGINAL CODE: EPIDOSNOBS3

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20130823

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

Ref country code: LI

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

Effective date: 20130831

Ref country code: MC

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

Effective date: 20121024

Ref country code: CH

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

Effective date: 20130831

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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

Ref country code: BE

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

Effective date: 20130831

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

Ref country code: GB

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

Effective date: 20130823

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: 20121024

Ref country code: IE

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

Effective date: 20130823

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

Ref country code: HU

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

Effective date: 20060823

PLCK Communication despatched that opposition was rejected

Free format text: ORIGINAL CODE: EPIDOSNREJ1

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

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

Ref country code: LU

Payment date: 20170821

Year of fee payment: 12

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

Ref country code: AT

Payment date: 20170822

Year of fee payment: 12

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 580991

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180823

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

Ref country code: LU

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

Effective date: 20180823

Ref country code: AT

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

Effective date: 20180823

REG Reference to a national code

Ref country code: DE

Ref legal event code: R100

Ref document number: 502006012139

Country of ref document: DE

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

PLBN Opposition rejected

Free format text: ORIGINAL CODE: 0009273

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

Free format text: STATUS: OPPOSITION REJECTED

27O Opposition rejected

Effective date: 20191009

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

Effective date: 20230530

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

Ref country code: TR

Payment date: 20230821

Year of fee payment: 18

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

Ref country code: ES

Payment date: 20250925

Year of fee payment: 20

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

Ref country code: DE

Payment date: 20250820

Year of fee payment: 20

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

Ref country code: PL

Payment date: 20250818

Year of fee payment: 20

Ref country code: IT

Payment date: 20250825

Year of fee payment: 20

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

Ref country code: FR

Payment date: 20250829

Year of fee payment: 20