EP2358855B1 - Tablette de détergent pour lave-vaisselle - Google Patents

Tablette de détergent pour lave-vaisselle Download PDF

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Publication number
EP2358855B1
EP2358855B1 EP09768354.4A EP09768354A EP2358855B1 EP 2358855 B1 EP2358855 B1 EP 2358855B1 EP 09768354 A EP09768354 A EP 09768354A EP 2358855 B1 EP2358855 B1 EP 2358855B1
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EP
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Prior art keywords
weight
polymer
phase
detergent
cleaning
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EP09768354.4A
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German (de)
English (en)
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EP2358855A1 (fr
EP2358855B2 (fr
Inventor
Thomas Holderbaum
Nadine Warkotsch
Johannes Zipfel
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL09768354T priority Critical patent/PL2358855T5/pl
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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.
  • 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.
  • 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.
  • washing or cleaning agent tablets according to the invention contain as 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 may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.
  • amphoteric polymers contain as monomer unit a compound of the general formula in which 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 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.
  • the corresponding monomer units of the formula H 2 C C (CH 3 ) -C (O) -NH- (CH 2 ) x -N + (CH 3 ) 3 X -
  • X - chloride, also referred to as MAPTAC (Methyacrylamidopropyl 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 employable amphoteric polymers are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers
  • 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 consisting 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 / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth ) acrylic acid copolymers and their alkali metal and ammonium salts.
  • the amphoteric polymers In terms of tablet properties such as tablet hardness, friability and post-curing properties, the amphoteric polymers have proved superior to the anionic polymers, therefore the amphoteric polymers are used.
  • 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 according to the claims.
  • 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 detergent tablet according to the invention contains 0.5 to 15 wt.%, Preferably 1.0 to 10 wt.% And in particular 2 to 8 wt. or cleaning-active polymer from the group of amphoteric polymers.
  • 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 .-%.
  • 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 include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • ethoxylated nonionic surfactants consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol Alcohol was used.
  • a particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide.
  • C 16-20 alcohol straight-chain fatty alcohol having 16 to 20 carbon atoms
  • C 18 -alcohol preferably a C 18 -alcohol
  • at least 12 mol preferably at least 15 mol and especially at least 20 mol of ethylene oxide.
  • the so-called “narrow range 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 O- (AO) w - (A'O) x - (A "O) y - (A"'O) z -R 2 in which R 1 and R 2 independently of one another represents a straight-chain or branched, saturated or mono- or polyunsaturated C 2-40 alkyl or alkenyl radical;
  • A, A ', A "and A"' independently 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 ( CH 3 ) -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 having 4 to R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is between 0.5 and 1.5 and y is 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.
  • nonionic surfactants 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 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.
  • 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-
  • 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 ,
  • 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 B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the further developments of the abovementioned amylases which are improved for use in detergents and cleaners. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. 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.
  • 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 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid 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, III, 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 compositions of the invention, 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).
  • Me-TACN 1,4,7-trimethyl-1,4,7-triazacyclononan
  • TACN 1,4,7-triazacyclononane
  • TACD 1,5,9-trimethyl-1,5,9-triazacyclododecane
  • Me-TACD 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane
  • 2-methyl-1,4,7-triazacyclononane
  • 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 1.0 to 15% by weight, preferably 2.0 to 12% by weight, and more preferably 4 to 8% by weight.
  • Detergent or detergent tablet characterized in that the second phase B further contains c) 1.0 to 15 wt .-% citric acid, are preferred according to the invention.
  • Some particularly preferred detergent tablets are listed in Tables F to J below.
  • Nonionic surfactant 0.5 to 10 1.0 to 8.0 2.0 to 6.0 2.0 to 6.0 Misc 0 to 40 2 to 30 0 to 40 2 to 30
  • 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.
  • 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 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).
  • liquid polymer preparation b) contains an amphoteric polymer.
  • the first particulate premix 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 0.5 to 10% by weight, preferably 1.0 to 8.0% by weight and in particular 2.0 to 6.0% by weight. % nonionic surfactant (s) containing nonionic surfactants having a melting point above 30 ° 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 according to the invention based on the claims tablet phases are pressed onto a prefabricated single- or multi-phase 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.
  • 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: V1 [% by weight] V2 [% by weight] E1 [% by weight] premix sodium 39.4 37.6 37.6 citrate 27.3 27.3 27.3 polymer solution amphoteric polymer a) 0.4 0.4 * 0.4 ** water - 1.8 * 1.8 ** admixture Nonionic surfactant b) 3.8 3.8 3.8 silicate 3.6 3.6 3.6 enzymes 14.0 14.0 14.0 Misc ad 100 ad 100 ad 100 a) amphoteric copolymer of a Diallyldimethylammoniumsalzes with acrylic acid b) nonionic surfactant from the group of hydroxy mixed ethers * Polymer and water are applied separately ** Polymer and water are applied in the form of a polymer-water mixture.
  • 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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Claims (13)

  1. Pastille d'agent de nettoyage ou de lavage sans phosphates monophasique ou multiphasique, caractérisé en ce que la phase ou l'une des phases, par rapport à son poids total, contient
    a) 15 à 89,8% en poids de carbonate de sodium et/ou de bicarbonate de sodium
    b) 10 à 84,8% en poids de citrate,
    c) 0,05 à 20% en poids de polymère actif pour le lavage ou le nettoyage,
    est dépourvu d'agent de blanchiment et contient, par rapport au poids total de la phase, moins de 1% en poids d'acide citrique, le polymère c) actif pour le lavage ou le nettoyage comprend un polymère du groupe des polymères amphotères.
  2. Pastille d'agent de nettoyage ou de lavage selon la revendication 1, caractérisée en ce que la phase et l'une des phases contient 20 à 50% en poids, de préférence 25 à 45% en poids et en particulier 30 à 40% en poids de carbonate de sodium et/ou de bicarbonate de sodium.
  3. Pastille d'agent de nettoyage ou de lavage selon l'une des revendications précédentes, caractérisée en ce que la phase ou l'une des phases contient 15 à 55% en poids, de préférence 20 à 50% en poids et en particulier 25 à 40% en poids de citrate.
  4. Pastille d'agent de nettoyage ou de lavage selon l'une des revendications précédentes, caractérisée en ce que la phase ou l'une des phases contient 0,05 à 15% en poids, de préférence 0,1 à 10% en poids, et en particulier 0,2 à 8% en poids de polymère actif pour le nettoyage ou le lavage choisi dans le groupe des polymères amphotères, le montant total de polymère actif pour de nettoyage ou de lavage variant à chaque fois également dans la gamme spécifiée.
  5. Pastille d'agent de nettoyage ou de lavage selon l'une des revendications précédentes, caractérisée en ce que la phase ou l'une des phases contient 0,5 à 10% en poids, de préférence 1,0 à 8,0% en poids, et en particulier 2,0 à 6,0% en poids de tensioactif non ionique.
  6. Pastille d'agent de nettoyage ou de lavage selon l'une des revendications précédentes, caractérisée en ce que la phase ou l'une des phases contient 1,0 à 22% en poids, de préférence 2,0 à 20% en poids et en particulier de 5,0 à 18% en poids de préparation enzymatique.
  7. Pastille d'agent de nettoyage ou de lavage comprenant
    i) une première phase A, comprenant
    a) 15 à 89,8% en poids de carbonate de sodium et/ou de bicarbonate de sodium
    b) 10 à 84,8% en poids de citrate,
    c) 0,05 à 20% en poids de polymère actif pour le nettoyage ou le lavage choisi dans le groupe des polymères amphotères,
    d) moins de 1% en poids d'acide citrique et ne comprenant aucun agent de blanchiment ;
    ii) une seconde phase B, comprenant
    a) 15 à 90% en poids de carbonate de sodium et/ou de bicarbonate de sodium
    b) 10 à 85% en poids d'agent de blanchiment à l'oxygène
    d) et ne comprenant pas d'enzymes.
  8. Pastille d'agent de nettoyage ou de lavage selon la revendication 7, caractérisée en ce que la seconde phase B contient en outre
    c) 1,0 à 30% en poids d'acide citrique.
  9. Procédé de fabrication d'une pastille d'agent de nettoyage ou de lavage sans phosphates, comprenant les étapes consistant à :
    a) produire un premier pré-mélange particulaire contenant
    i) 15 à 90% en poids de carbonate de sodium et/ou de bicarbonate de sodium
    ii) 10 à 85% en poids de citrate
    iii) moins de 1% en poids d'acide citrique et ne contenant aucun agent de blanchiment ;
    b) appliquer une préparation de polymère liquide contenant
    i) 40 à 98% en poids d'eau
    ii) 2 à 60% en poids de polymère actif pour le nettoyage ou le lavage au premier pré-mélange particulaire pour obtenir un second pré-mélange particulaire ;
    d) agglomérer le second pré-mélange particulaire pour former une pastille d'agent de nettoyage ou de lavage,
    caractérisé en ce que la préparation de polymère liquide b) contient un polymère amphotère.
  10. Procédé selon la revendication 9, caractérisé en ce que le rapport en poids du premier pré-mélange particulaire à la préparation de polymère liquide est compris entre 150:1 et 10:1, de préférence entre 120:1 et 14:1 et en particulier entre 100:1 et 17:1.
  11. Procédé selon l'une des revendications précédentes, caractérisé en ce que le pré-mélange particulaire aggloméré à l'étape d) contient 0,5 à 10% en poids, de préférence 1,0 à 8,0% en poids et en particulier 2,0 à 6,0% de tensio-actif(s) non ionique(s).
  12. Procédé selon l'une des revendications précédentes, caractérisé en ce que, dans une autre étape de procédé, des substances actives pour le nettoyage et le lavage sont ajoutées au second pré-mélange particulaire après l'étape b) c) avant l'agglomération.
  13. Procédé de nettoyage de la vaisselle dans un lave-vaisselle à l'aide d'un détergent pour lave-vaisselle selon l'une des revendications 1 à 8.
EP09768354.4A 2008-12-05 2009-12-01 Tablette de détergent pour lave-vaisselle Active EP2358855B2 (fr)

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EP2358855B2 (fr) 2021-10-06
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ES2549479T3 (es) 2015-10-28
ES2549479T5 (es) 2022-02-17
DE102008060469A1 (de) 2010-06-10
WO2010063689A1 (fr) 2010-06-10

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