WO2010063689A1 - Tablette de détergent pour lave-vaisselle - Google Patents

Tablette de détergent pour lave-vaisselle Download PDF

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Publication number
WO2010063689A1
WO2010063689A1 PCT/EP2009/066101 EP2009066101W WO2010063689A1 WO 2010063689 A1 WO2010063689 A1 WO 2010063689A1 EP 2009066101 W EP2009066101 W EP 2009066101W WO 2010063689 A1 WO2010063689 A1 WO 2010063689A1
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WO
WIPO (PCT)
Prior art keywords
weight
washing
cleaning
phase
detergent
Prior art date
Application number
PCT/EP2009/066101
Other languages
German (de)
English (en)
Inventor
Thomas Holderbaum
Nadine Warkotsch
Johannes Zipfel
Original Assignee
Henkel Ag & 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.)
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=41664893&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2010063689(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel Ag & Co. Kgaa filed Critical Henkel Ag & Co. Kgaa
Priority to PL09768354T priority Critical patent/PL2358855T5/pl
Priority to ES09768354T priority patent/ES2549479T5/es
Priority to EP09768354.4A priority patent/EP2358855B2/fr
Publication of WO2010063689A1 publication Critical patent/WO2010063689A1/fr

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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
    • 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
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or 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
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3796—Amphoteric polymers or zwitterionic polymers

Definitions

  • the present invention is in the field of detergent tablets and relates to phosphate-free detergent tablets and methods for their preparation.
  • Detergent tablets are widely described in the art and are becoming increasingly popular with consumers because of their ease of use. Tableted detergents and cleaners have a number of advantages over powdered ones: they are easier to dose and to handle and, due to their compact structure, have advantages in storage and transport. Also in the patent literature washing and cleaning agent tablets are thus described comprehensively. A problem which occurs again and again in the application of washing and cleaning-active moldings is the too low disintegration and dissolution rate of the moldings under conditions of use. Since sufficiently stable, i.
  • Form-resistant and fracture-resistant molded body can be produced only by relatively high pressing pressures, there is a strong compaction of the molding constituents and a consequent delayed disintegration of the molding in the aqueous liquor and thus to a slow release of the active substances in the washing or cleaning process ,
  • the process products should be next to one sufficient hardness further characterized by good decay properties and a low tendency to abrasion.
  • a first subject of the present application is therefore a single- or multi-phase, phosphate-free detergent or cleaner tablet, characterized in that the phase or one of the phases, based on their total weight, a) 15 to 89.8 wt .-% sodium carbonate and / or sodium bicarbonate b) 10 to 84.8% by weight of citrate c) 0.05 to 20% by weight of washing- or cleaning-active polymer, is free of bleach and, based on the total weight of the phase, less than 1 % By weight of citric acid.
  • the builder system used in the detergent tablets according to the invention comprises 15 to 89.8% by weight of sodium carbonate and / or sodium bicarbonate and 10 to 84.8% by weight of citrate.
  • a single- or multi-phase, phosphate-free detergent or cleaner tablet characterized in that the phase or one of the phases, based on their total weight, a) 15 to 89.8 wt .-% sodium carbonate b) 10 to 84.8 wt C) contains from 0.05 to 20% by weight of washing- or cleaning-active polymer, is free of bleach and, based on the total weight of the phase, contains less than 1% by weight of citric acid
  • a single- or multi-phase, phosphate-free detergent or cleaner tablet characterized in that the phase or one of the phases, based on their total weight, a) 15 to 89.8 wt .-% sodium bicarbonate b) 10 to 84.8 wt C) contains from 0.05 to 20% by weight of washing- or cleaning-active polymer, is free of bleach and, based on the total weight of the phase, contains less than 1% by weight of citric acid if, in these processes, the total amount of sodium carbonate and sodium bicarbonate used, based on the total weight of the tablet phase, is 15 to 89.8% by weight.
  • Mono- or multiphase laundry detergent or detergent tablets according to the invention contain less than 1% by weight of citric acid in their sodium carbonate, citrate and polymer-based phase.
  • citric acid in their sodium carbonate, citrate and polymer-based phase.
  • it has proven advantageous to lower the citric acid content in this phase to less than 0.5% by weight and preferably less than 0.1% by weight.
  • Particularly preferred tablet phases are free of citric acid.
  • a preferred subject of the present application is therefore a single- or multi-phase, phosphate-free detergent or cleaner tablet, characterized in that the phase or one of the phases, based on their total weight, a) 15 to 89.8 wt .-% sodium carbonate and / or sodium bicarbonate b) 10 to 84.8% by weight of citrate c) 0.05 to 20% by weight of washing or cleaning-active polymer and is free of citric acid and of bleaching agent.
  • washing or cleaning agent tablets according to the invention contain as the washing or cleaning-active polymer c) a polymer from the group of amphoteric polymers.
  • amphoteric polymers further comprise, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units, these groups being, for example, carboxylic acids, sulfonic acids or phosphonic acids.
  • particularly preferred amphoteric polymers contain as monomer unit a compound of the general formula
  • R 1 and R 4 are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms;
  • R 2 and R 3 are independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group;
  • x and y independently represent integers between 1 and 3.
  • X represents a counterion, preferably a counterion selected from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.
  • a counterion selected from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate
  • 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, -CH (OH) -CH 3 , -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.
  • amphoteric polymers which have a cationic monomer unit of the above general formula in which R 1 and R 4 are H, R 2 and R 3 are methyl and x and y are each 1.
  • R 1 and R 4 are H
  • R 2 and R 3 are methyl
  • x and y are each 1.
  • amphoteric polymers contain a monomer unit of the general formula
  • R1 HC CR2-C (O) -NH- (CH 2) -N + R3R4R5
  • R 1 , R 2 , R 3 , R 4 and R 5 independently of one another are 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 H and x is an integer between 1 and 6.
  • amphoteric polymers which have a cationic monomer unit of the above general formula in which R 1 is H and R 2 , R 3 , R 4 and R 5 are methyl and x is 3.
  • R 1 is H and R 2 , R 3 , R 4 and R 5 are methyl and x is 3.
  • H 2 C C (CHS) -C (O) -NH- (CH 2 ) X - N + (C HS) 3
  • MAPTAC Metalacrylamidopropyl trimethylammonium chloride
  • amphoteric polymers which contain diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts as monomer units.
  • 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 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, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.
  • Preferred usable amphoteric polymers are selected 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 containing alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid Copolymers, the alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or nonionic
  • amphoteric polymers are selected from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the Methacroylethylbetain / methacrylate copolymers.
  • amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers, methacrylamidoalkyltrialkylammonium chloride and dimethyl (diallyl) ammonium chloride.
  • amphoteric polymers are selected from the group of the methacrylamidoalkyl trialkyl ammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyl trialkyl ammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyl trialkyl ammonium chloride / dimethyl diallyl ammonium chloride / alkyl (meth) acrylic acid copolymers and their alkali metal and ammonium salts.
  • amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyldiallylammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid -Copolymers and their alkali metal and ammonium salts.
  • a second group of preferred detergent tablets according to the invention is characterized in that the liquid polymer preparation b) contains an anionic polymer.
  • anionic polymers in the context of the present application do not have any positively charged groups or monomer units for negatively charged groups or monomer units.
  • These negative groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.
  • anionic copolymers are used in step b).
  • Preferred copolymers (e) comprise i) at least one acid group-containing monomer a) ii) a second monomer other than a) containing acid groups b) and / or further nonionic monomer (s).
  • the acid group-containing monomer i) has a carboxylic acid group and / or a sulfonic acid group.
  • Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • 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, Methacrylamido-hydroxypropanesulfonic 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, Sulfomethacrylamid, Sulfomethylmethacrylannid and mixtures of said acids or their water-soluble salts
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
  • a first group of preferably used anionic copolymers is characterized in that they contain i) monomers from the group of mono- or polyunsaturated carboxylic acids ii) optionally further nonionic, preferably hydrophobic, monomers (e).
  • a second group of preferably used anionic copolymers is characterized in that they contain i) monomers from the group of mono- or polyunsaturated sulfonic acids ii) optionally further nonionic, preferably hydrophobic, monomers (e).
  • Particularly preferred unsaturated hydrocarbon radicals are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2, 4,4-trimethylpentene-1, 2,4,4-trimethylpentene-2, 2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1, 3,5-dimethylhexene-1, 4,4-dimethylhexane-1, ethylcyclohexyne, 1-octene, alpha-olefins of 10 or more Carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and
  • the amphoteric polymers In terms of tablet properties such as tablet hardness, friability and postcure properties, the amphoteric polymers have proved superior to the anionic polymers and, therefore, the amphoteric polymers are preferred over the anionic polymers.
  • the tablets (phases) according to the invention contain the three constituents 15 to 89.8% by weight of sodium carbonate and / or sodium bicarbonate and 10 to 84.8% by weight of citrate and 0.05 to 20% by weight of washing or cleaning-active polymers ,
  • the amount of these builders can be limited in preferred process variants in favor of other washing and cleaning active substances.
  • the phase or one of the phases of the washing or cleaning agent tablet according to the invention 20 to 50 wt .-%, preferably 25 to 45 wt .-% and in particular 30 to 40 wt .-% sodium carbonate and / or sodium bicarbonate ,
  • the phase or one of the phases of the washing or cleaning agent tablet according to the invention contains 15 to 55 wt .-%, preferably 20 to 50 wt .-% and in particular 25 to 40 wt .-% citrate.
  • the phase or one of the phases of the washing or cleaning agent tablet according to the invention contains 0.5 to 15% by weight, preferably 1 to 0 to 10% by weight and in particular 2 to 8% by weight washing. or cleaning-active polymer.
  • Nonionic surfactants and enzymes are particularly suitable as further washing and cleaning-active ingredients of tablet phases according to the invention.
  • nonionic surfactant to the tablets (phases) of the invention improves their positive physical properties. This is especially true for amounts of surfactant to 5.0 wt .-%, preferably up to 4.0 wt .-%.
  • Preferred single-phase or multi-phase detergent tablets according to the invention are therefore characterized in that the phase or one of the phases contains 0.5 to 10% by weight, preferably 1.0 to 8.0% by weight and in particular 2.0 to 6.0 wt .-% nonionic surfactant.
  • compositions according to the invention may furthermore contain surfactants.
  • the group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants.
  • Low-foaming nonionic surfactants are used as preferred surfactants.
  • washing or cleaning agents in particular automatic dishwashing detergents, contain 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.
  • fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • ethoxylated nonionic surfactant selected from C 6 - 2 o-monohydroxy alkanols or C 6 - 2 o-alkyl phenols or C 6 - 2 o-fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol Ethylene oxide per mole of alcohol were used.
  • a particularly preferred nonionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-2 alcohol), preferably a C 18 alcohol obtained and at least 12 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide.
  • C 16-2 alcohol straight chain fatty alcohol having 16 to 20 carbon atoms
  • C 18 alcohol preferably a C 18 alcohol obtained and at least 12 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide.
  • the so-called “narrow ranks ethoxylates" are particularly preferred.
  • Nonionic surfactants which have a melting point above room temperature.
  • nonionic surfactants from the group of hydroxy mixed ethers have proved to be particularly advantageous with respect to the physical properties of the tablets (phases) according to the invention. These nonionic surfactants will be described below.
  • R 1 -CH (OH) CH 2 ⁇ - (AO) w - (A'O) x - (A "O) y - (A"'O) z -R 2 in which R 1 and R 2 are each independently a straight-chain or branched, saturated or mono- or polyunsaturated C 2-4 o alkyl or alkenyl radical; A, A ', A "and A'” are independent of each other a radical 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, where x, y and / or z can also be 0 are preferred according to the invention.
  • end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2 , in addition to a radical R 1 , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having from 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 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 , in which R 1 is a linear or branched aliphatic hydrocarbon radical with 4 R 2 is 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 having a free hydroxyl group on one of the two terminal alkyl radicals By using the above-described nonionic surfactants having a free hydroxyl group on one of the two terminal alkyl radicals, the formation of deposits in machine dishwashing can be markedly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.
  • R 1 O [CH 2 CH 2 O] x [CH 2 CH (R 3 ) O] y CH 2 CH (OH) R 2 in which R 1 and R 2 independently of one another is 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 preferably is -CH 3
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 P] x [CH 2 J k CH (OH) [CH 2 ] J OR 2 in which 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 for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5 stand.
  • 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, 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> 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.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.
  • nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas
  • Preferred single-phase or multiphase washing or cleaning agent tablets are furthermore characterized in that the phase or one of the phases contains less than 1.0% by weight and in particular no anionic surfactant, since the addition of anionic surfactants with respect to the tablets ( phase) properties, in particular their hardness, friability and post-curing has proved to be disadvantageous.
  • detergents or cleaners enzymes can be used. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly.
  • Detergents or cleaning agents contain enzymes preferably in total amounts of 1 ⁇ 10 -6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferable.
  • these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from ⁇ . amyloliquefaciens, from ⁇ . stearothermophilus, from Aspergillus niger and A. oryzae, as well as improved for use in detergents and cleaners further developments of the aforementioned amylases. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from ⁇ . agaradherens (DSM 9948).
  • lipases or cutinases are also usable according to the invention.
  • these include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L.
  • the cutinases can be used, which have been originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • Washing or cleaning agent tablets (phases) which are preferred according to the invention are characterized in that they contain 1.0 to 22% by weight, preferably 2.0 to 20% by weight and in particular 5.0 to 18% by weight of enzyme preparation.
  • the above-described tablet phase based on carbonate, citrate and polymer according to the invention is part of a two-phase or multi-phase detergent or cleaner tablet.
  • This two- or multi-phase detergent or cleaner tablet also contains washing and cleaning-active ingredients in its further phases, the composition of the further phases not being identical to the composition of the first tablet phase.
  • the second tablet phase B further contains an oxygen bleach besides a carbonate based builder system.
  • a particularly preferred two- or more-phase detergent or cleaner tablet comprises i) a first phase A comprising a) from 15 to 89.8% by weight of sodium carbonate and / or sodium bicarbonate b) from 10 to 84.8% by weight of citrate c) 0.05 to 20% by weight washing or cleaning-active polymer d) no bleach, less than 1% by weight, preferably no citric acid; ii) a second phase B comprising a) from 15 to 90% by weight of sodium carbonate and / or sodium bicarbonate b) from 10 to 85% by weight of oxygen bleaching agent d) no enzymes
  • bleach machine dishwashing detergents contain an oxygen bleaching agent from the group sodium percarbonate, Natriumperborattetrahydrat and Natriumperboratmonohydrat.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Because of its good bleaching performance, sodium percarbonate is particularly preferred.
  • a particularly preferred oxygen bleach is the sodium percarbonate.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • Preference is given to polyacylated alkylenediamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable.
  • the bleach catalysts are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • complexes of manganese in the oxidation state II, IM, IV or IV which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S.
  • ligands are used which have nitrogen donor functions.
  • bleach catalyst (s) in the inventive compositions which as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-triazacyclononane (TACN ), 1, 5,9-trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1, 4,7-triazacyclononane (Me / TACN).
  • macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-triazacyclononane (TACN ), 1, 5,9-trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me / Me-TACN) and or 2-
  • Suitable manganese complexes are, for example, [Mn 1 " 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (TACN) 2 ] (Cl ⁇ 4) 2, [Mn 1 " Mn lv ( ⁇ -O) 2 ( ⁇ -OAc) 1 ( TACN) 2 ] (BPh 4 ) 2, [Mn IV 4 ( ⁇ -O) 6 (TACN) 4 ] (Cl ⁇ 4 ) 4 , [Mn '" 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (Me -TACN) 2] (ClO 4) 2, [Mn "'Mn' v ( ⁇ -O) 1 ( ⁇ -OAc) 2 (Me-
  • Preferred washing or cleaning agent tablets according to the invention furthermore contain citric acid as further constituent of the second phase B described above.
  • the content of citric acid in the second phase is preferably from 1, 0 to 15 wt .-%, preferably 2.0 to 12 wt .-% and in particular 4 to 8 wt .-%.
  • Detergent or detergent tablets characterized in that the second phase B further contains c) 1, 0 to 15 wt .-% citric acid, are preferred according to the invention.
  • a further subject of the present application is a process for the preparation of a phosphate-free washing or cleaning agent tablet, comprising the steps: a) providing a first particulate premix comprising, based on the total weight of the particulate premix i) 15 to 90 wt .-% sodium carbonate and / or sodium bicarbonate ii) 10 to 85 wt .-% citrate iii) no bleach, less than 1 wt b) application of a liquid polymer preparation containing, based on the total weight of the liquid polymer preparation i) from 40 to 98% by weight water ii) from 2 to 60% by weight % washing or cleaning active polymer iii) optionally further washing or cleaning active ingredients on the first particulate premix to obtain a second particulate premix; c) optionally admixing further washing or cleaning-active substances; d) tabletting of the second particulate premix
  • the builder system used in step a) of the process according to the invention comprises 15 to 90% by weight of sodium carbonate and / or sodium bicarbonate and 10 to 85% by weight of citrate.
  • a process for preparing a phosphate-free detergent or detergent tablet comprising the steps of: a) providing a first particulate premix containing, based on the total weight of the particulate premix i) 15 to 90% by weight of sodium carbonate ii) 10 to 85% by weight Iii) no bleach, less than 1% by weight, preferably no citric acid iv) optionally further washing or cleaning active ingredients b) application of a liquid polymer preparation containing, based on the total weight of the liquid polymer preparation i) 40 to 98 Wt% water ii) 2 to 60 wt% wash or cleaning active polymer iii) optionally further detergent or cleaning active ingredients on the first particulate premix to give a second particulate premix; c) optionally admixing further washing or cleaning-active substances; d) tabletting of the second particulate premix
  • a process for preparing a phosphate-free detergent or detergent tablet comprising the steps of: a) providing a first particulate premix containing, based on the total weight of the particulate premix i) 15 to 90 wt .-% sodium bicarbonate ii) 10 to 85 wt.
  • the total amount of the sodium carbonate and sodium bicarbonate used, based on the total weight of the first particulate premix, is 15 to 90% by weight.
  • the first particulate premix provided in step a) contains the two constituents 15 to 90% by weight of sodium carbonate and / or sodium bicarbonate and 10 to 85% by weight of citrate.
  • the amount of these builders can be limited in preferred process variants in favor of other washing and cleaning active substances.
  • the first particulate premix based in each case on its total weight, contains 20 to 50% by weight, preferably 25 to 45% by weight and in particular 30 to 40% by weight of sodium carbonate and / or sodium bicarbonate contains.
  • the first particulate premix based in each case on its total weight, contains 15 to 55% by weight, preferably 20 to 50% by weight and in particular 25 to 40% by weight of citrate.
  • the amount of polymer and water used in process step b) can also be varied.
  • the hardness, the decay and the abrasion properties of the tablets are advantageous in doing so inventive method in which the weight ratio of the first particulate premix to the liquid polymer preparation is between 150: 1 and 10: 1, preferably between 120: 1 and 14: 1 and in particular between 100: 1 and 17: 1.
  • the polymer preparation applied in step b), based in each case on its total weight, contains from 5 to 50, preferably from 8 to 40 and in particular from 10 to 30,% by weight Contains polymer.
  • the water content of the polymer preparation used in step b), in each case based on their total weight is preferably 50 to 95% by weight, preferably 60 to 92% by weight and in particular 70 to 90% by weight of water.
  • the second particulate premix provided for tableting after step b) or after step c) of the process according to the invention preferably has a content of washing or cleaning-active polymer, preferably amphoteric polymer, of between 0.05 and 20% by weight. , preferably between 0.05 to 15 wt .-%, preferably between 0.1 to 10 wt .-% and in particular between 0.2 to 8 wt .-% to.
  • washing or cleaning-active substances can also be processed in the process according to the invention.
  • These further washing- or cleaning-active substances may form part of the particulate premix provided in step a), but may alternatively or in addition also be part of the liquid polymer preparation applied in step b).
  • Process variant A Provision of a first particulate premix comprising, based on the total weight of the particulate premix i) 15 to 85% by weight of sodium carbonate and / or sodium bicarbonate ii) 10 to 80% by weight of citrate iii) no bleach, less than 1% by weight, preferably no citric acid iv) from 5 to 75% by weight of further washing or cleaning-active constituents b) application of a liquid polymer preparation containing, based on the total weight of the liquid polymer preparation i) from 40 to 96% by weight of water ii) from 2 to 58% by weight washing or cleaning-active polymer iii) optionally from 2 to 58% by weight of further washing or cleaning-active constituents on the first particulate premix to give a second particulate premix premix; c) optionally admixing further washing or cleaning-active substances; d) tabletting of the second particulate premix
  • Process variant B a) Provision of a first particulate premix containing, based on the total weight of the particulate premix i) 15 to 85% by weight of sodium carbonate and / or sodium bicarbonate ii) 10 to 80% by weight of citrate iii) no bleach, less than 1% by weight, preferably no citric acid vi) optionally 5 to 75% by weight of further washing or cleaning-active constituents b) application of a liquid polymer preparation containing, based on the total weight of the liquid polymer preparation i) 40 to 96% by weight Water ii) from 2% to 58% by weight of detergent or cleaning active polymer; iii) from 2% to 58% by weight of further detergent or cleaning active ingredients on the first particulate premix to obtain a second particulate premix; c) optionally admixing further washing or cleaning-active substances; d) tabletting of the second particulate premix
  • Process Variant C a) Provision of a first particulate premix containing, based on the total weight of the particulate premix i) 15 to 85% by weight of sodium carbonate and / or sodium bicarbonate ii) 10 to 80% by weight of citrate iii) no bleach, less than 1% by weight, preferably no citric acid iv) optionally 5 to 75% by weight of further washing or cleaning-active constituents b) application of a liquid polymer preparation containing, based on the total weight of the liquid polymer preparation i) 40 to 96% by weight Water ii) 2 to 58% by weight wash or cleaning active polymer iii) optionally 2 to 58% by weight of further washing or cleaning active ingredients on the first particulate premix to give a second particulate premix; c) admixing further washing or cleaning-active substances; d) tabletting of the second particulate premix
  • the chemical nature of the washing and cleaning-active polymer used in process step b) may vary. It is
  • liquid polymer preparation b) contains an amphoteric polymer.
  • a copolymer comprising i) from 0.5 to 30% by weight of diallyldimethylammonium salt ii) from 70 to 99.5% by weight of acrylic acid
  • a copolymer comprising i) 0.5 to 30% by weight of methylacrylamidopropyltrimethylammonium salt ii) 70 to 99.5% by weight of acrylic acid
  • a second group of preferred methods according to the invention is characterized in that the liquid polymer preparation b) contains an anionic polymer.
  • a copolymer comprising i) 0.5 to 90% by weight of acrylic acid ii) 10 to 99.5% by weight of an unsaturated carboxylic acid other than acrylic acid
  • Copolymer comprising i) 0.5 to 90% by weight of acrylic acid ii) 10 to 99.5% by weight of maleic acid
  • Copolymer comprising i) from 0.5 to 20% by weight of 2-acrylamido-2-methyl-1-propanesulfonic acid ii) from 80 to 99.5% by weight of acrylic acid
  • Copolymer comprising i) unsaturated sulfonic acid, unsaturated carboxylic acid iii) nonionic monomer
  • the first particulate premix, as well as the liquid polymer formulation applied in step b) may contain other detergent and cleaning active substances. At the same time or in addition thereto, these further washing and cleaning-active substances can also be added to the second particulate premix before tableting in the optional process step c).
  • the group of these other washing and cleaning-active substances include, for example, the surfactants, the enzymes and the fragrances or dyes.
  • Preferred processes according to the invention are characterized in that the particulate premix tableted in step d) contains from 0.5 to 10% by weight, preferably from 1.0 to 8.0% by weight and in particular from 2.0 to 6.0% by weight.
  • % nonionic surfactant (s) containing nonionic surfactants having a melting point above 30 0 C are particularly preferred.
  • the enzymes are preferably incorporated into the premix before tableting in step c) of the process according to the invention.
  • the above-described methods and method variants according to the invention are preferably part of a multi-stage process for producing two-phase or multiphase washing or cleaning agent tablets.
  • the sodium carbonate, citrate and polymer-based tablet phases according to the invention are pressed onto a prefabricated mono- or multiphase tablet.
  • a preferred process variant of this first group of processes for the preparation of a phosphate-free detergent or cleaner tablet comprises the steps of: a) providing a first particulate premix containing i) from 15 to 90% by weight of sodium carbonate and / or sodium bicarbonate ii) from 10 to 85% by weight of citrate iii) no bleach and less than 1% by weight, preferably none
  • citric acid b) applying a liquid polymer preparation containing i) 40 to 98 wt .-% water ii) 2 to 60 wt .-% washing or cleaning active polymer on the first particulate premix to obtain a second particulate premix and applying this second particulate premix the top of a prefabricated single or multi-phase detergent or cleaner tablet; d) tabletting of the second particulate premix on the top of the prefabricated mono- or multi-phase detergent or detergent tablet to form a two- or multi-phase detergent or detergent tablet.
  • a second preferred process variant of this first group of processes for preparing a phosphate-free detergent or detergent tablet comprises the steps of: a) providing a first particulate premix containing i) 15 to 90% by weight sodium carbonate and / or sodium bicarbonate ii) 10 up to 85% by weight of citrate iii) no bleaching agent and less than 1% by weight, preferably no citric acid; b) applying a liquid polymer preparation containing i) from 40 to 98% by weight of water ii) from 2 to 60% by weight of washing or cleaning-active polymer onto the first particulate premix to obtain a second particulate premix
  • a preferred process variant of this second group of processes for the preparation of a phosphate-free detergent or detergent tablet comprises the steps of: a) providing a first particulate premix containing i) 15 to 90% by weight of sodium carbonate and / or sodium bicarbonate ii) 10 to 85% by weight citrate iii) no bleach and less than 1% by weight, preferably no citric acid; b) applying a liquid polymer preparation containing i) from 40 to 98% by weight of water ii) from 2 to 60% by weight of washing or cleaning-active polymer onto the first particulate premix to obtain a second particulate premix
  • a preferred process variant of this second group of processes for the preparation of a phosphate-free detergent or detergent tablet comprises the steps of: a) providing a first particulate premix containing i) 15 to 90% by weight of sodium carbonate and / or sodium bicarbonate ii) 10 to 85% by weight citrate iii) no bleach and less than 1% by weight, preferably no citric acid; b) applying a liquid polymer preparation containing i) from 40 to 98% by weight of water ii) from 2 to 60% by weight of washing or cleaning-active polymer onto the first particulate premix to obtain a second particulate premix
  • Premix c) admixing further washing or cleaning-active substances d) tabletting of the second particulate premix to form a first washing or cleaning agent tablet; e) applying a further, different from the previous particulate premix particulate premix on top of the first detergent or detergent tablet; f) tableting the further particulate premix to form a two- or multi-phase detergent or cleaner tablet;
  • a further subject of the present application is a washing or cleaning agent tablet produced by means of the method according to the invention.
  • the detergent tablets according to the invention are particularly suitable for use in household dishwashers and textile washing machines.
  • a method for cleaning dishes in a dishwasher, using a detergent tablet according to the invention is a further subject of the present application.
  • a last subject of the present application is a process for textile cleaning in a textile washing machine using a detergent tablet according to the invention.
  • detergent tablets according to the invention were prepared and pressed with a press force of 50 kN into single-phase tablets of 20 g total weight.
  • the second particulate preparation thus obtained was then blended with nonionic surfactant, silicate, enzymes and ingredients.
  • the exact composition of the tablet premix resulting therefrom can be found in the following table: O
  • Misc ad 100 ad 100 ad 100 a) amphoteric copolymer of a diallyldimethylammonium salt with acrylic acid b ) nonionic surfactant from the group of hydroxy mixed ethers
  • the resulting tablet premixes were pressed at a pressing force of 55 N into tablets weighing 21 g.
  • the tablets produced by the process according to the invention by addition of a polymer-water mixture harden significantly more vigorously than the tablets prepared in the comparative experiments with the addition of solid polymer preparations at the same pressure and achieve an overall higher overall hardness.

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Abstract

L'invention porte sur des tablettes de détergent ou de produit nettoyant, en une ou plusieurs phases, sans phosphates, caractérisées en ce que la phase, ou l'une des phases, contient par rapport à son poids total a) 15 à 89,8 % en poids de carbonate de sodium et/ou d'hydrogénocarbonate de sodium, b) 10 à 84,8 % en poids de citrate, c) 0,05 à 20 % en poids d'un polymère détergent ou nettoyant ; ne contient aucun agent de blanchiment ; et, par rapport au poids total de la phase, contient moins de 1 % en poids d'acide citrique, les tablettes étant caractérisées par une grande facilité de fabrication et de bonnes propriétés de post-durcissement.
PCT/EP2009/066101 2008-12-05 2009-12-01 Tablette de détergent pour lave-vaisselle WO2010063689A1 (fr)

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PL09768354T PL2358855T5 (pl) 2008-12-05 2009-12-01 Tabletka środka do maszynowego zmywania naczyń
ES09768354T ES2549479T5 (es) 2008-12-05 2009-12-01 Comprimido de lavavajillas a máquina
EP09768354.4A EP2358855B2 (fr) 2008-12-05 2009-12-01 Tablette de détergent pour lave-vaisselle

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DE102008060469A1 (de) 2010-06-10
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