EP1520908A1 - Composition pour lave-vaisselle avec des propriétés de rinçage améliorées - Google Patents

Composition pour lave-vaisselle avec des propriétés de rinçage améliorées Download PDF

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Publication number
EP1520908A1
EP1520908A1 EP03022032A EP03022032A EP1520908A1 EP 1520908 A1 EP1520908 A1 EP 1520908A1 EP 03022032 A EP03022032 A EP 03022032A EP 03022032 A EP03022032 A EP 03022032A EP 1520908 A1 EP1520908 A1 EP 1520908A1
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EP
European Patent Office
Prior art keywords
weight
parts
detergent composition
surfactants
protease
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.)
Withdrawn
Application number
EP03022032A
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German (de)
English (en)
Inventor
Elke Dr. Philippsen-Neu
Rene Mol
Robbert De Boer
Jürgen Krichel
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.)
Dalli Werke GmbH and Co KG
Original Assignee
Dalli Werke GmbH and Co KG
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Publication date
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=34306793&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1520908(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Dalli Werke GmbH and Co KG filed Critical Dalli Werke GmbH and Co KG
Priority to EP03022032A priority Critical patent/EP1520908A1/fr
Priority to PL04023137T priority patent/PL1524313T3/pl
Priority to ES04023137T priority patent/ES2283920T3/es
Priority to DE502004003197T priority patent/DE502004003197D1/de
Priority to DK04023137T priority patent/DK1524313T3/da
Priority to EP04023137.5A priority patent/EP1524313B2/fr
Priority to AT04023137T priority patent/ATE356862T1/de
Publication of EP1520908A1 publication Critical patent/EP1520908A1/fr
Withdrawn legal-status Critical Current

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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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/08—Polycarboxylic acids containing no nitrogen or sulfur
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions

Definitions

  • the invention is directed to a detergent composition for Dishwashers, their ingredients to an improved Rinse result.
  • less “filming” is added simultaneously reduced “spotting” achieved.
  • Machine dishwashing generally consists of a pre-wash cycle, one or more intermediate rinses, a rinse cycle and a Drying cycle. This applies in principle to the machine rinsing both in Households, as well as in the commercial sector.
  • the aim of machine rinsing is to obtain an optimal result without mechanical rubbing or wiping as in the case of rinsing is possible by hand.
  • the rinsing result is to form a Films ("filming") or the remaining of spills ("spotting”) prevent on the dishes.
  • a common procedure for obtaining the desired rinsing result was So far, the dishwasher with a cleaner composition, a To fill rinse aid and a salt, wherein the Cleaner composition scored the actual washing result, the salt is filled in the ion exchanger in the machine dishwashing detergent and thus reducing the water hardness during the cleaning and Flushing leads; the rinse aid causes the improved running of the Rinse water on the dishes to keep the "spotting" low.
  • the means used for the automatic cleaning of dishes can be liquid, powdery, pasty or tablet-shaped.
  • the application of tablets is because of the ease of handling and dosing Popular.
  • the object of the invention is to provide a cleaning composition for a To provide application in machine dishwashing detergents, especially good results in terms of "filming", ie the making of a film to effect on the washed dishes while at the same time forming To avoid “spotting” on the washed dishes.
  • the detergent composition contains a so-called “carry-over” surfactant that runs throughout the entire Cleaning process up to the last rinse in the Dishwasher is “taken off”.
  • the Detergent composition also a salt functional polymer containing the Precipitation of Ca and Mg ions in the form of salts prevents or Prevents crystal growth of already formed precipitates.
  • the cleanser composition may be in any commercial form be made up, so e.g. liquid, pasty, in powder, granules or However, particle shape (e.g., beads, or so-called "pearls") will preferably used in the form of a pressed molding.
  • the molded body may be monophase or polyphase.
  • a particularly preferred embodiment represents a multi-phase pressed molded body, wherein the individual Phases in the wash liquor can be solved at different times can.
  • Such a molded body can be in single (or in all) phases include a suitable disintegrant.
  • ingredients mentioned dispersant, carry over surfactant and Salt-functional polymers can be used in multiphase tablets in different Phases or in different concentrations in the individual phases be present at different times (in different Concentrations) are released into the rinsing liquor, but can also in all phases of multiphase tablets evenly distributed.
  • Forming the film on the dishes comes u.a. by the fact that from the triglycerides found in the dishwasher Leftovers from the ingredients of the cleaner composition Fatty acids are saponified.
  • Lime soaps as typical organic salts melt above certain temperatures. The melting temperature is determined by the chain length of the fatty acid. Below this Melting temperature, however, they precipitate out as insoluble soaps and set depend on the dishes.
  • To fail in the form of soaps can prevent either the temperature profile of dishwashers such be varied, that the rinse water temperature is the failure limit of Lime soap does not fall below, or it can be as high as possible Complexation of calcium and magnesium ions in the rinsing liquor with Help of a salt or a remedy with a salt function become.
  • spotting is meant the formation of droplet residues, too after drying the dishes, especially on glasses can be seen. These residual drops of dissolved salts leave stains on the dishes and glasses. To prevent this dripping Surfactants are used in conventional dishwashing detergents which are the Reduce surface tension and thus better run off the Allow drops of dishes.
  • Dishwashing composition By the inventive use of dispersants in the Dishwashing composition also reduces spotting. Without The following explanation is believed to be bound by the decreased residue on the dishes that drops of water from the thus smoother surfaces can run better. This effect will additionally reinforced by the use of carry-over surfactants.
  • dispersants for the saponified fatty acids all agents come in Consider that are capable of not water-soluble organic Compounds such as e.g. Lime soaps in an aqueous composition too dispersing, especially at temperatures at which these compounds in the aqueous medium as insoluble compounds.
  • Such dispersants are those skilled in the art, inter alia from the fields the toilet cleaning article, the cutting oils, from the Textile processing and industrial cleaning. Under The term “lime soap dispersant” common dispersants are easy to find on the internet. Examples of such dispersants are Alkyl monopropionates, alkyl dipropionates, cocoamphocarboxyglycinates, Alcohol ethoxycarboxylates, amine oxides, alkyl dimethyl betaines, Terephthalic acid, cocoamido propyl dimethyl betaine, alkylamino diacetate Citronell esters, as well as polymers based on acrylic acid, Maleic acid and alpha olefins.
  • Carry-over surfactants are surfactants that are based on their hydrophilic-hydrophobic balance in the course of the cleaning and Rinsing process in a dishwasher by the individual cleaning and rinses are "delayed".
  • a statement that is not binding for The invention is to be interpreted, is that these surfactants due to your Hydrophilic-hydrophobic properties not the usual Nernst'schen Be subject to distribution (ie not with the wash and the rinse water removed), but also during the cleaning and rinsing process increasingly adsorb to surfaces. This means that these surfactants not only in the first wash or rinse cycle in the rinsing liquor, but also in the last rinse cycles, although there in lesser Concentration. This causes, even in the last rinses the Surface tension of the water is kept low, which is a better drainage of the water droplets allowed by the dishes.
  • Surfactants which fulfill this task are nonionic 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 ], in which R 1 represents a 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 for a value of at least 15 stands.
  • nonionic surfactants which may be used are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 is 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 X is 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 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, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x is 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, 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.
  • nonionic surfactant having a melting point above room temperature ethoxylated nonionic surfactant resulting from the reaction of a Monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, more preferably at least 15 mol, in particular at least 25, 50 or 80 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
  • a particularly preferred room temperature solid nonionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16 -C 20 alcohol), preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and especially at least 25, 50 or 80 moles of ethylene oxide.
  • C 16 -C 20 alcohol straight chain fatty alcohol having 16 to 20 carbon atoms
  • C 18 alcohol preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and especially at least 25, 50 or 80 moles of ethylene oxide.
  • the so-called “narrow range ethoxylates" are particularly preferred.
  • gemini surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which are known as Dimers are present and excellent compared to Monmeren surfactants Have adsorption behavior.
  • the inventive Detergent composition preferably used a polymer.
  • Salt-functional polymers are known from the prior art, in particular known in the field of water treatment.
  • Example of such polymers are products of the type Acusol 587 (Rohm & Haas), which are equally as Prompted calcium phosphate inhibitors, anti-filming and dispersing agents become.
  • Particularly suitable and preferred polymers are acrylates, Acrylate-maleate copolymers and copolymers with sulfonated groups.
  • the detergent tablets may consist of only one Detergent composition (single-phase tablets), or they can consist of several phases, layers or areas, ie e.g. two- or three-phase molded bodies (e.g., "3 in 1"). In this case, individual components of the cleaning agent from each other be separated so that they can be used at different times during the Cleaning process are provided.
  • the spatial form of the moldings can in their dimensions of Ein Titanauersch be adapted to the dishwasher, but can all Design meaningful manageable shapes. These include e.g. also cylindrical embodiments with an oval or circular cross-section and moldings having a plate-like or tabular structure.
  • One preferred shaped body consists of alternately thick long and thin short segments, so that individual segments of such a bar Breaking points represented by the short thin segments be broken off and placed in the dosing chamber or the cutlery basket Machine can be entered. This principle of the bar-shaped Shaped body can also be in other geometric polygon shapes be realized.
  • a tablet produced in this way preferably has a weight of 5 to 120 g, more preferably from 10 to 30 g.
  • Detergent tablets for different purposes, in particular for Dishwashers are basically known.
  • Such formed as a shaped body detergent formulations usually contain builders, bleaches and bleach activators, Surfactants, tableting aids, disintegrants and other common additives and adjuvants.
  • composition of the Cleaning agent otherwise the usual for dishwashing detergents Contain ingredients.
  • ingredients of the Cleaner compositions are merely preferred embodiments represents.
  • a preferred embodiment of the invention is a phosphate-containing dishwashing detergent tablet containing: 10 to 75 parts by weight Polyphosphate (s), 60 to 0 parts by weight other inorganic builders, 20 to 0 parts by weight organic builders, 7 to 20 parts by weight peroxide bleaching agent, 10 to 1 part by weight Bleach activator (s), 0 to 16 parts by weight Surfactant (s), 0 to 8 parts by weight dispersants 0 to 8 parts by weight polymers 2 to 6 parts by weight other, customary auxiliaries and additives.
  • all layers / phases of the cleaning tablet can be a disintegrating agent but is preferred in only one or two (at Presence of multiple layers / phases) layers / phases included. This is preferable to a first layer / phase that acts quickly contains coming ingredients in a short time in the rinse water to dissolve and provide the ingredients while doing a another layer / phase that contains ingredients that become a later Time of the cleaning process to be used, slower solves because it contains no or a "slower" explosive.
  • builders all can be used in the detergent composition customary and known as such builders are used, in particular Polyphosphates, pyrophosphates, metaphosphates or phosphonates, Phyllosilicates, amorphous silicates, amorphous disilicates and zeolites, as well as Fillers such as sodium carbonate, sodium sulfate, magnesium sulfate, Sodium bicarbonate, citrate and citric acid, succinic acid, Tartaric acid and malic acid. Often, as an auxiliary builder Co-builders and dispersants co-used. Such cobuilders or Dispersants may include, but are not limited to, polyacrylic acids or copolymers Polyacrylic acid and its sodium salts.
  • Typical bleaching agents are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, sodium percarbonate, peroxypyrophosphates, citrate perhydrates, and H 2 O 2 -forming peracidic salts, peracids, such as perbenzoates, peroxyphthalates, diperazelaic acid and diperdodecanedioic acids.
  • peracids such as perbenzoates, peroxyphthalates, diperazelaic acid and diperdodecanedioic acids.
  • bleaching agents or bleach systems may also be present in the composition.
  • suitable peroxygen compounds are in particular hydrogen peroxide and under the washing conditions hydrogen peroxide donating inorganic salts to which alkali metal perborates such.
  • Sodium perborate tetrahydrate and sodium perborate monohydrate further include alkali metal carbonate perhydrates such as sodium carbonate perhydrate ("sodium percarbonate”) and persilicates and / or persulfates such as caroate.
  • the bleach system of the detergent formulation may contain inorganic or organic peracids, especially percarboxylic acids, e.g. B.
  • acids which can be used are peracetic acid, perbenzoic acid, linear or branched octane, nonane, decane or dodecane monoperacids, decane and dodecane diperacids, mono- and diperphthalic acids, isophthalic and terephthalic acids, phthalimidopercaproic acid, terephthaloyldiamidopercaproic acid and e-phthalimido peroxohexanoic acid (PAP).
  • peracetic acid perbenzoic acid
  • linear or branched octane nonane
  • decane or dodecane monoperacids
  • decane and dodecane diperacids mono- and diperphthalic acids
  • isophthalic and terephthalic acids phthalimidopercaproic acid
  • terephthaloyldiamidopercaproic acid e-phthalimido peroxohexanoic acid (PAP).
  • percarboxylic acids can be used as free acids or as salts of the acids, preferably alkali or alkaline earth metal salts.
  • solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle.
  • a particularly preferably used peracid is the peracid available under the trade name Eureco® (Ausimont, Italy).
  • Peroxygen compounds are present in amounts of preferably up to 50% by weight, more preferably from 5% to 30% and most preferably from 8% to 25% by weight.
  • bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.
  • the content of bleaching agents in tablets is preferably 5-60% by weight. and especially 7-20% by weight.
  • bleach catalysts are usually quaternized imines or Sulfone imines used, for example, in US-A-5,360,568, US-A-5,360,569 and EP-A-453 003, as well as manganese complexes, as described, for example, in WO-A 94/21777. Further usable metal-containing bleach catalysts are described in EP-A-458 397, EP-A-458,398 and EP-A-549,272. Bleach catalysts are incorporated in the rule in amounts of up to 1 wt .-%, in particular 0.01 to 0.5 wt .-%, based on the detergent formulation used.
  • Suitable bleach activators are the H 2 O 2 organic peracids forming N-acyl and O-acyl compounds, preferably N, N'-tetraacylated diamines, carboxylic anhydrides and esters of polyols such as glucose pentaacetate. Further, acetylated mixtures of sorbitol and mannitol may be used. Particularly suitable as bleach activators are N, N, N ', N'-tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxohexahydro-1,2,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures ( SORMAN).
  • TAED N, N ', N'-tetraacetylethylenediamine
  • DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,2,5-triazine
  • compounds of the substance classes of polyacylated sugar or sugar derivatives with C 1 -C 10 -acyl radicals can be used, preferably with acetyl, propionyl, octanoyl, nonanoyl or benzoyl radicals, in particular acetyl radicals.
  • Suitable sugars or sugar derivatives are mono- or disaccharides and their reduced or oxidized derivatives, preferably glucose, mannose, fructose, sucrose, xylose or lactose.
  • bleach activators of this class of substances are, for example, pentaacetylglucose, xylose tetraacetate, 1-benzoyl-2,3,4,6-tetraacetylglucose and 1-octanoyl-2,3,4,6-tetraacetylglucose.
  • O-Acyloximester such as O-Acyloximester
  • B O-acetylactone oxime, O-benzoylacetone oxime, bis (propylimino) carbonate or Bis (cyclohexylimino) carbonate.
  • acylated oximes and oxime esters are described for example in EP-A-028 432 and EP-A-267 046.
  • N-acyl caprolactams such as for example, N-acetylcaprolactam, N-benzoylcaprolactam, N-octanoylcaprolactam, N-octanoylcaprolactam or carbonylbiscaprolactam.
  • bleach activators are 2-alkyl or 2-aryl- (4H) -3,1-benzoxain-4-ones, as described for example in EP-B-332 294 and the EP-B-502 013 are described.
  • 2-phenyl- (4H) -3,1-benzoxain-4-one and 2-methyl (4H) -3,1-benzoxain-4-one are described.
  • bleach activators from the classes of N- or O-acyl compounds for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular Tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, Hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic acid anhydrides, in particular phthalic anhydride, Carboxylic acid esters, in particular sodium nonanoyloxybenzenesulfonate, Sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives, such as Pentaacetylglucose be used.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine
  • acylated glycolurils in particular Tetraacetylg
  • a preferred bleach activator is a quaternized one Glycine nitrile from the group N-methylmorpholinium acetonitrile methyl sulfate, sulfate and hydrogen sulfate.
  • bleach system can also all the bleaching agents mentioned in DE 199 59 589 A1 and be included in activators.
  • the bleach systems which are mentioned in the European patent application EP 02 028 958.3 be used.
  • the different components of the Detergent composition in different phases / layers / Regions of the shaped body are included.
  • an ingredient that was previously used in the Cleaning process is to be provided in a phase / layer / Is located in the area in which a disintegrant is included.
  • Surfactants also include one or more surfactant (s) from the group of nonionic, anionic, cationic and / or amphoteric surfactants contain.
  • the automatic dishwashing detergent tablets according to the invention comprise nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 -alcohols with 3 EO or 4 EO, C 9 -C 11 -alcohol with 7 EO, C 13 -C 15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 -alcohol with 3 EO and C 12 -C 18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • detergent tablets according to the invention which contain a nonionic surfactant which has a melting point above Room temperature.
  • preferred Detergent tablets characterized in that they as Ingredient c) Nonionic surfactant (s) with a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C.
  • Suitable nonionic surfactants the melting or softening points in have mentioned temperature range, for example low foaming nonionic surfactants which are solid at room temperature or can be highly viscous. Become at room temperature highly viscous nonionic surfactants used, it is preferred that this has a viscosity above 20 Pas, preferably 35 Pas and in particular above 40 Pas. Also Nonionic surfactants which have waxy consistency at room temperature are prefers.
  • nonionic surfactants which are solid at room temperature from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as Polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
  • structurally complicated surfactants such as Polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
  • PO / EO / PO polyoxypropylene
  • nonionic surfactants are also characterized by good Foam control off.
  • the PO units make up to 25% by weight, particularly preferably 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant.
  • nonionic surfactants are ethoxylated monohydroxyalkanols or Alkylphenols, which additionally polyoxyethylene-polyoxypropylene Have block copolymer units.
  • the alcohol or alkylphenol part 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 the total molecular weight of such nonionic surfactants.
  • nonionic surfactants with melting points above room temperature contain 40 to 70% of a Polyoxypropylene / polyoxyethylene block polymer blends containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 Mole of ethylene oxide and 44 moles of propylene oxide and 25 wt .-% of a Block copolymers of polyoxyethylene and polyoxypropylene, initiated with Trimethylolpropane and containing 24 moles of ethylene oxide and 99 mol Propylene oxide per mole of trimethylolpropane.
  • Nonionic surfactants which are used with particular preference can be, for example, under the name Poly Tergent® SLF-18 of the Company Olin Chemicals available.
  • Further preferred detergent tablets according to the invention contain nonionic 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 ], in which R 1 represents 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 is values between 0.5 and 1.5 and y is a value of at least 15 ,
  • nonionic surfactants which may be used are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 is 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 X is 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 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, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x is 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, 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.
  • alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol are used as nonionic surfactants in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 -alcohols with 3 EO or 4 EO, C 9 -C 11 -alcohols with 7 EO, C 13 -C 15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 -alcohol with 3 EO and C 12 -C 18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the Alkyl chain, in particular fatty acid methyl ester.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide may be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of ethoxylated fatty alcohols, especially not more than half of them.
  • polyhydroxy fatty acid amides of the formula (I) wherein RCO 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 and [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 chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • 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 oxyaryl radical having 1 to 8 carbon atoms, wherein C 1 -C 4 alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.
  • [Z] is preferably reduced by reductive amination Sugar, for example glucose, fructose, maltose, lactose, Galactose, mannose or xylose.
  • reductive amination Sugar for example glucose, fructose, maltose, lactose, Galactose, mannose or xylose.
  • the N-alkoxy or N-aryloxy-substituted Compounds can then be reacted with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides are converted.
  • gemini surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which are known as Dimers present and compared to monomeric surfactants two hydrophobic Own groups per molecule. These groups are usually by one so-called hydrophilic "spacer" separated from each other. Such surfactants are generally characterized by an unusually low critical Micelle concentration and the ability of the surface tension of the To greatly reduce water out. In exceptional cases, however, under The term gemini surfactants not only dimeric, but also trimeric Surfactants understood.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to the German patent application DE-A-43 21 022 or Dimer alcohol bis and trimeralcyl tris sulfates and ether sulfates according to the German patent application DE-A-195 03 061.
  • End phenomenonver notede dimer or trimeric mixed ethers according to the German patent application DE-A-195 13 391 are characterized by their bi- and multi-functionality out.
  • the end-capped surfactants have Good network properties and are low in foaming, so they themselves especially for use in machine washing or cleaning processes suitable.
  • Gemini polyhydroxy fatty acid amides or Poly-polyhydroxy fatty acid amides as described in international patent applications WO-A-95/19953, WO-A-95/19954 and WO-A-95/19955 become.
  • enzymes come in the detergent tablets according to the invention especially those from the classes of hydrolases such as proteases, Esterases lipases or lipolytic enzymes, glucosidases such Amylases, mannanase or cellulase, glycosyl hydrolases and mixtures of mentioned enzymes in question. All of these hydrolases contribute to the removal stains such as proteinaceous, fatty or starchy stains at. For bleaching and oxidoreductases can be used.
  • hydrolases such as proteases, Esterases lipases or lipolytic enzymes, glucosidases such Amylases, mannanase or cellulase, glycosyl hydrolases and mixtures of mentioned enzymes in question. All of these hydrolases contribute to the removal stains such as proteinaceous, fatty or starchy stains at. For bleaching and oxidoreductases can be used.
  • proteases are from Subtilisin type and in particular proteases derived from Bacillus lentus be used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic acting enzymes or from protease, amylase and lipase or lipolytic acting enzymes or protease, lipase or lipolytic acting Enzymes, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular Interest.
  • lipolytic enzymes are the known cutinases.
  • Peroxidases or oxidases have also been found in some Cases proved to be suitable.
  • suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • the enzymes can be adsorbed to carriers or in coating substances be embedded to protect them against premature decomposition.
  • enzyme mixtures or enzyme granules can for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-% be.
  • preferred Detergent tablets are characterized in that they protease and / or amylase.
  • detergent tablets are preferred in which the enzyme (s) not in a phase together with the Bleach-enhancing drug combination is / are included.
  • the cleaning agents according to the invention can be used to protect the items to be washed or the machine contain corrosion inhibitors, taking particular Silver protection agent in the field of automatic dishwashing have special meaning.
  • Can be used the known substances of the State of the art.
  • especially silver protectants are selected from the group of triazoles, the benzotriazoles, the Bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the Transition metal salts or complexes can be used.
  • Especially Preferred to use are benzotriazole and / or alkylaminotriazole.
  • cleaning agent formulations often contain active chlorine Means that significantly reduce the corrosion of the silver surface can.
  • oxygen and nitrogen-containing organic redox-active compounds such as two and trivalent phenols, e.g. Hydroquinone, pyrocatechol, Hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these connection classes.
  • nitrogen-containing organic redox-active compounds such as two and trivalent phenols, e.g. Hydroquinone, pyrocatechol, Hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these connection classes.
  • zinc compounds can Prevention of corrosion can be used on the items to be washed.
  • detergent tablets contain corrosion inhibitors, they are these are preferably separated from the bleaching agents. Accordingly are Detergent tablets in which at least one phase bleach contains at least one other phase anticorrosive contains, preferably.
  • Preferred anionic surfactants are the salts of alkylsulfosuccinic acid, which also referred to as sulfosuccinates or as sulfosuccinic acid ester and the monoesters and / or diesters of sulfosuccinic acid with Alcohols, preferably fatty alcohols and in particular ethoxylated Represent fatty alcohols.
  • Preferred sulfosuccinates contain C8 to C18 Fatty alcohol residues or mixtures of these.
  • Especially preferred Sulfosuccinates contain a fatty alcohol residue which is different from derived ethoxylated fatty acids, which in itself is nonionic Surfactants (see description below).
  • Preferred anionic surfactant mixtures contain combinations of Alk (en) ylsulfates, in particular mixtures of saturated and unsaturated fatty alk (en) ylsulfates, and alkylbenzenesulfonates, sulfated fatty acid glycerol esters and / or ⁇ -sulfofatty acid esters.
  • mixtures are preferred which are anionic Surfactants Alk (en) ylsulfates and alkylbenzenesulfonates, alk (en) ylsulfates and ⁇ -sulfofatty acid methyl ester and / or sulfated fatty acid glycerol esters contain.
  • anionic surfactants are in particular soaps, preferably in amounts of 0.1 to 5 wt.% Into consideration. Suitable examples are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. Particularly preferred are those soap mixtures which are composed of 50 to 100% by weight of saturated C 12 -C 24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
  • the anionic surfactants and soaps may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, Di- or triethanolamine present.
  • the anionic Surfactants in the form of their sodium or potassium salts, in particular in the form their sodium salts.
  • alkaline in water inorganic salts In particular, bicarbonates, carbonates or mixtures thereof.
  • alkali carbonate and especially sodium carbonate used.
  • the alkali metal silicates are in amorphous or crystalline form with a Na 2 O to SiO 2 ratio of 1: 1 to call 1: 2,8.
  • cogranules of Carbonates and silicates which are known as NABION (Rhodia) in the market Are available.
  • Examples of other common additives and auxiliaries are Magnesium silicates, aluminum aluminates, benzotriazole, glycerin, Magnesium stearate, polyalkylene glycols, hexametaphosphate and phosphonates.
  • Substances which have an anti-corrosive effect on Have glass are Substances which have an anti-corrosive effect on Have glass.
  • glass corrosion protection all known means for Corrosion protection can be used.
  • metal oxides such as. Oxides of zinc, aluminum, tin, magnesium, calcium, strontium, Silicon, titanium, zirconium, manganese and lanthanum, or insoluble inorganic zinc compounds, as described in EP 0 383 482 are, or also zinc or magnesium salts of organic compounds, such as they are described in DE 101 40 535.
  • the dishwasher detergents according to the invention can in tablet form dyes and fragrances are added to the to improve the aesthetic impression of the resulting products and the Consumers in addition to the performance of a visual and sensory "typical and as “perfume oils” or “unmistakable” product.
  • Fragrances can be individual fragrance compounds, eg. B. the synthetic products of the ester type, ethers, aldehydes, ketones, Alcohols and hydrocarbons are used. fragrance compounds the type of ester are z.
  • the ethers include Benzyl ethyl ether, to the aldehydes z. B.
  • perfume oils can also be natural Fragrance mixtures contain as accessible from plant sources are, for. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, Lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, Vetiver oil, olibanum oil, galbanum oil and labdanum oil, and orange blossom oil, Neroliol, orange peel oil and sandalwood oil.
  • the fragrances can be directly into the shaped bodies according to the invention incorporated, but it can also be beneficial, the fragrances to apply on carrier.
  • carrier materials have become
  • cyclodextrins have proven useful, with the cyclodextrin-perfume complexes additionally be coated with other excipients can.
  • an incorporation of the fragrances as ingredient d) in the Detergent components according to the invention is possible and leads to a scent impression when opening the machine.
  • the agents according to the invention may be colored (or parts thereof) with suitable dyes.
  • Preferred dyes whose selection the expert no difficulty prepares, possess a high storage stability and insensitivity compared with the other ingredients of the product and against light as well no pronounced substantivity to those with the means too treated substrates such as glass, ceramic or plastic utensils do not stain them.
  • the coloring of individual phases for optical differentiation is preferred.
  • the tablets mentioned in the examples are mono-, double- and Triple-phase tablets can be used.
  • the individual components can be distributed in different areas / phases of the moldings.
  • compositions of dishwashing tablets according to the invention (all amounts in parts by weight).
  • formulation 1 2 3 4 Component: Na tripolyphosphate 35,00 45,00 18,00 60,00 Na carbonate 25,00 20.00 10.00 - Na-bicarbonate - - 10.00 - silicate 4.00 10.00 5.00 - citrate - 5.00 10.00 - Na-percarbonate or Na-perborate 15.00 8.00 20.00 20.00 TAED 4.00 5.00 2.00 2.00 2.00 Lime soap dispersant 5 0.2 - 2 Carry over surfactant 2.00 1.00 5.00 2.00 Nonionic surfactant - - - 2 phosphonate 1.00 0.50 2.00 - Sulphonated polycarboxylate 1 8th 2 4 Acrylate-maleate copolymer 1.00 - 5.00 3.00 enzymes 2.00 1.00 3.00 2.00 Polyethylene glycol 1,500 - 10,000 2.00 3.00 1.00 2.00 Perfume 0.50 0.05 2.00 1.00 explosives 3.50 - 7.00 -

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EP03022032A 2003-10-01 2003-10-01 Composition pour lave-vaisselle avec des propriétés de rinçage améliorées Withdrawn EP1520908A1 (fr)

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EP03022032A EP1520908A1 (fr) 2003-10-01 2003-10-01 Composition pour lave-vaisselle avec des propriétés de rinçage améliorées
PL04023137T PL1524313T3 (pl) 2003-10-01 2004-09-29 Kompozycja do mechanicznego zmywania naczyń o ulepszonych właściwościach zmywania
ES04023137T ES2283920T3 (es) 2003-10-01 2004-09-29 Composicion detergente para lavavajillas con propiedades de lavado mejoradas.
DE502004003197T DE502004003197D1 (de) 2003-10-01 2004-09-29 Maschinengeschirrreiniger mit verbesserten Spüleigenschaften
DK04023137T DK1524313T3 (da) 2003-10-01 2004-09-29 Maskinopvaskemiddel med forbedrede skylleegenskaber
EP04023137.5A EP1524313B2 (fr) 2003-10-01 2004-09-29 Composition pour lave-vaisselle avec des propriétés de rincage ameliorées
AT04023137T ATE356862T1 (de) 2003-10-01 2004-09-29 Maschinengeschirrreiniger mit verbesserten spüleigenschaften

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EP2196531A1 (fr) 2008-12-05 2010-06-16 Dalli-Werke GmbH & Co. KG Pastille de détergent revêtue d'un polymère
EP3075832A1 (fr) 2015-03-30 2016-10-05 Dalli-Werke GmbH & Co. KG Composés d'acide aminé de manganèse dans des compositions de nettoyage

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GB0514004D0 (en) * 2005-07-08 2005-08-17 Reckitt Benckiser Nv Article and method
EP1897933A1 (fr) * 2006-09-05 2008-03-12 Cognis IP Management GmbH Utilisation des alcools gras alkoxylés à long chaîne comme additif au détergent pour le nettoyage de surfaces dures
DE102007019458A1 (de) * 2007-04-25 2008-10-30 Basf Se Phosphatfreies Maschinengeschirrspülmittel mit ausgezeichneter Klarspülleistung
DE102007019457A1 (de) 2007-04-25 2008-10-30 Basf Se Maschinengeschirrspülmittel mit ausgezeichneter Klarspülleistung
DE102007042859A1 (de) † 2007-09-10 2009-03-12 Henkel Ag & Co. Kgaa Reinigungsverfahren
DE102008060471A1 (de) 2008-12-05 2010-06-10 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
PL2392639T3 (pl) 2010-06-04 2018-07-31 Dalli-Werke Gmbh & Co. Kg Mieszanina środka powierzchniowo czynnego zawierająca stały związek dla polepszania działania ułatwiającego płukanie detergentów do automatycznych zmywarek do naczyń
ES2648240T3 (es) 2010-06-04 2017-12-29 Dalli-Werke Gmbh & Co. Kg Composición en partículas de baja higroscopicidad que comprende uno o más compuestos quelantes de aminopolicarboxilato
BR112016020336B1 (pt) 2014-03-07 2022-12-13 Ecolab Usa Inc Composições de enxágue e detergente alcalino e método para limpeza e enxágue de artigo
DK2966161T3 (en) 2014-07-08 2019-02-25 Dalli Werke Gmbh & Co Kg ENZYME BLENDIC CATALYST CATEGRANULATE SUITABLE FOR DETERGENT COMPOSITIONS
EP3053997B2 (fr) 2015-02-05 2021-01-13 Dalli-Werke GmbH & Co. KG Composition de nettoyage comprenant un catalyseur de blanchiment et de la carboxyméthylcellulose
US11021681B2 (en) 2015-05-07 2021-06-01 Novozymes A/S Manganese bleach catalyst granules for use in dishwash detergents
EP3190168B1 (fr) 2016-01-06 2019-04-10 Dalli-Werke GmbH & Co. KG. Catalyseur de blanchiment enrobé
HUE065566T2 (hu) * 2019-06-19 2024-06-28 Dalli Werke Gmbh & Co Kg Gyerekzárral ellátott csomagolás
EP3754003A1 (fr) 2019-06-21 2020-12-23 Dalli-Werke GmbH & Co. KG Emballage unitaire pour détergent dotée d'un poignée

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EP2196531A1 (fr) 2008-12-05 2010-06-16 Dalli-Werke GmbH & Co. KG Pastille de détergent revêtue d'un polymère
EP3075832A1 (fr) 2015-03-30 2016-10-05 Dalli-Werke GmbH & Co. KG Composés d'acide aminé de manganèse dans des compositions de nettoyage

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EP1524313A1 (fr) 2005-04-20
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EP1524313B2 (fr) 2021-12-15
PL1524313T3 (pl) 2007-08-31
ATE356862T1 (de) 2007-04-15
EP1524313B1 (fr) 2007-03-14

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