Manufacturing process for washing or cleaning agent tablets

Abstract

Process for producing a washing or cleaning agent tablet or a washing or cleaning agent tablet phase, comprehensively the steps: i) providing a first powdered premix containing, based on its total weight a) 15 to 55 wt% sodium carbonate; b) 8 to 32 wt% sodium percarbonate; c) 8 to 30 wt% methylglycinediacetic acid (MGDA) and its salts; d) 0.2 to 8 wt.% non-ionic surfactant; e) 2 to 18 wt.% washing or cleaning active polymer; f) 0 to 2% by weight of citrate; by mixing its components; ii) optional storage of the powdered premix; iii) feeding the powdered premix to a dosing device of a tablet press; iv) Dosing the powdered premix into the die of the die table of the tablet press; v) pressing the powdered premix in the die with a pressing force of 15 to 50 kN; (vi) ejecting the washing or cleaning agent tablet or the washing or cleaning agent tablet phase from the die; vii) Optionally, packaging of the washing or cleaning tablet or the washing or cleaning tablet phase.

Description

The present application relates to a method for producing laundry or cleaning agent tablets. In particular, the application relates to a multistage production process, during which a specific pulverulent premix is pressed to form a detergent tablet or a detergent tablet phase.The confection and supply forms of washing or cleaning agents are subject to continuously changing requirements. A focus has been on the convenient metering of washing or cleaning agents by the consumer for some time and the simplification of the working steps required for carrying out a washing or cleaning process. A solution offers pre-sized washing or cleaning agents, for example foil bags with one or more receiving chambers for solid or liquid preparations or washing or cleaning agent tablets.The advantages of solid pre-sized washing or cleaning agents consist, inter alia, in the extensive reduction of solvents which are not active in washing or cleaning and, in the case of tablets or castings, the temporally stable three-dimensional shape.Their use is in laundry or cleaning agent tablets in the machine cleaning of textiles or dishes. For this purpose, the laundry or cleaning agent tablets are introduced into the aqueous washing or cleaning liquor, for example, via a metering drawer, a metering chamber or a metering aid. Essential for the active washing or cleaning action of the tablet is its rapid disintegration in the aqueous liquor and the rapid release of the active washing or cleaning ingredients present in the tablet. The aim of a process for producing laundry detergent or cleaning agent tablets is therefore generally to provide a tablet which, on the one hand, has a sufficient hardness so as not to break during its packaging, its transport and handling by the consumer, but, on the other hand, decomposes rapidly in the aqueous laundry detergent or cleaning liquor.European patent application EP 711 828 A2 describes the production of laundry detergent or cleaning agent tablets by tableting binder-containing premix products.The tablet hardness is determined essentially by the force used in pressing the pulverulent premix. As the force increases, the tablet hardness increases, but its tendency to break down decreases. One aim of developing methods for producing laundry or cleaning agent tablets is therefore to provide pulverulent premix powders for tableting, which can be compressed to stable laundry or cleaning agent tablets with a low force effect. These premixtures should be produced by means of cost-effective and low-energy methods; in particular, the tablet premixture after its production should be tabletable without storage or tempering, but in the case of intermediate storage should be storable and, for example, retain its flowability and should not cure during the intermediate storage.Against this background, the object of the application was to provide a process for the efficient production of laundry detergent or cleaning agent tablets which enables tablets with sufficient hardness to be produced in a simple and efficient manner with good disintegration properties at the same time.A method for producing a laundry or cleaning agent tablet or a laundry or cleaning agent tablet phase is suitable for achieving this object, comprising the steps: i) providing a first pulverulent premix comprising, based on its total weight a), 15 to 55% by weight of sodium carbonate; b) 8 to 32% by weight of sodium percarbonate; c) 8 to 30% by weight of methylglycinediacetic acid (MGDA) and its salts; d) 0.2 to 8% by weight of nonionic surfactant; e) 2 to 18% by weight of laundry or cleaning-active polymer; f) 0 to 2% by weight of citrate; by mixing its constituents; ii) optionally storing the pulverulent premix; iii) supplying the pulverulent premix to a metering device of a tablet press; iv) Metering the pulverulent premix into the die of the die table of the tablet press; v) Compressing the pulverulent premix in the die with a compression force of 15 to 50 kN. vi) Expelling the washing or cleaning agent tablet or the washing or cleaning agent tablet phase from the die; vii) Optionally Packaging the washing or cleaning agent tablet or the washing or cleaning agent tablet phase.The method described serves for the production of laundry detergent or cleaning agent tablets, i.e. for example single-phase, two-phase, three-phase or four-phase laundry detergent or cleaning agent tablets, it being possible for one phase, two phases, three phases or all phases of the laundry detergent or cleaning agent tablets to be produced by means of this method. The method also serves, however, for the production of detergent or cleaning agent phases which are subsequently processed further into a detergent or cleaning agent, for example by filling a trough located in the detergent or cleaning agent tablet phases or by combination with a powder, a gel or a liquid.Surprisingly, it has been found that, due to the specific composition of the tablet premix used, storage of the premix, as is required, for example, in comparable formulations based on alternative builders, can be dispensed with. The premix is also free from such storage and transportable and is suitable for processing in a tablet press. In particular, the premix shows a reduced tendency to adhere to container walls and tabletting tools such as punches or dies compared to formulations based on alternative builders. Tabletting processes using this premix are therefore distinguished by a low production waste of defective tablets and shorter maintenance times.Furthermore, the specific tablet premix enables the production of laundry or cleaning agent tablets or laundry or cleaning agent tablet phases with high hardnesses with simultaneously sufficient disintegration times in aqueous liquors even at low pressing forces.A characteristic of the process is the use of a tablet premix with specific proportions of builders.A first obligatory builder is the sodium carbonate, which is contained in the premix, based on its total weight, with a proportion by weight of 15 to 55% by weight. With regard to the technical advantages described above, it has proven advantageous if the first pulverulent premix contains 25 to 55% by weight, preferably 30 to 50% by weight, of sodium carbonate, based on its total weight.The properties of the first pulverulent premix can be further improved by the particle diameters of the builders used. The proportion by weight of the particles of sodium carbonate having a particle diameter of 125 to 2000 μm in the first pulverulent premix is therefore preferably more than 70% by weight, particularly preferably more than 80% by weight and in particular more than 85% by weight. Very particular preference is given to first pulverulent premixtures in which the proportion by weight of the particles of sodium carbonate having a particle diameter of 200 to 1600 μm is more than 85% by weight.In addition to sodium carbonate, the first pulverulent premix comprises from 8 to 32% by weight of sodium percarbonate as second optional constituent. Industrially preferred pulverulent premix contains, based on their total weight, 10 to 30% by weight, in particular 12 to 28% by weight, of sodium percarbonate.As described above for sodium carbonate, the particle diameter of the sodium percarbonate also has an additional influence on the properties relevant for the storage, transport and tabletting of the premix. For this reason, the proportion by weight of the particles of sodium percarbonate having a particle diameter of 125 to 2000 μm in the pulverulent premix is preferably more than 70% by weight, more preferably more than 80% by weight and in particular more than 85% by weight. It is very particularly preferred if the proportion by weight of the particles of sodium percarbonate having a particle diameter of 200 to 1600 μm in the pulverulent premix is more than 85% by weight.A third essential constituent of the first pulverulent premix is methylglycinediacetic acid with a weight fraction of from 8 to 32% by weight. Because of their storage, transport and tabletting properties, preferred premix products contain, based on their total weight, 10 to 32 wt %, particularly preferably 12 to 30 wt %, methyl glycine diacetic acid (MGDA) and salts thereof.The first particulate premix further contains nonionic surfactant, preferably in weight fractions of 0.4 to 7% by weight, in particular 0.8 to 6% by weight.Suitable nonionic surfactants are preferably solid at room temperature. Nonionic surfactants having a melting point above 30° C., in particular in the range from 40 to 60° C., have proven to be particularly suitable. The melting point of the surfactant (in ° C.) is determined by means of differential calorimetry (DSC) according to ISO standard 11357. In this context, the melting point in the context of the invention is considered to be the peak temperature determinable by means of DSC in the second heating run. This is the temperature at which the peak / maximum deflection (on the y-axis) is present in the DSC diagram. If a plurality of peaks-within the scope of 5% of the maximum deflection observed in the second heating run-are present in a surfactant (commercial product), the temperature of the first peak is regarded as the melting point according to the invention.Suitable surfactants are, in particular, linear, saturated fatty acid alcohol ethoxylates having 14 to 18 carbon atoms in the alkyl chain and 10 to 100 ethylene oxide units, which are preferably not end group-capped.Nonionic surfactants of the formula R 1 O[CH 2 CH(CH 3) O] x[ CH 2 CH 2 O] y[ CH 2 CH(CH 3) O] z R2 have proved particularly suitable, in whichR 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms,R 2 denotes a preferably hydroxylated, linear or branched hydrocarbon radical having 2 to 26 carbon atoms,x and z are values from 0 to 40 andy is a value of at least 15.The nonionic surfactant is particularly preferably selected from the group of the compounds of the general formula C 4-22- CH(OH)CH 2 O-(EO) 20-120- C 2-26, in particular from the group of the compounds of the general formula C 8-12 fatty alcohol (EO) 22-2- hydroxydecyl ether or C 4-22 fatty alcohol (EO) 40-80-2- hydroxyalkyl ether.To further improve the storage, transport and tabletting capacity of the premix, it is advantageous to set the weight ratio of sodium carbonate and sodium percarbonate and methyl glycine diacetic acid (MGDA) and their salts to nonionic surfactant in the first pulverulent premix to a range above 6:1, preferably above 12:1 and in particular above 18:1.Preferred first powdery pre-mixtures contain, based on their total weight, less than 1% by weight, preferably less than 0.5% by weight, particularly preferably less than 0.1% by weight and in particular no anionic surfactant.As a fifth essential constituent, the first pulverulent premix comprises 2 to 18% by weight of active washing or cleaning polymer, preference being given to pulverulent premix which, based on their total weight, comprise 5 to 16% by weight, preferably 8 to 15% by weight, of active washing or cleaning polymer.The group of the wash- or cleaning-active polymers includes in particular the polycarboxylates. The active washing- or cleaning-active ingredient is preferably selected from the group of polycarboxylates, preferably from the group of homopolymeric polycarboxylates.Alternatively or in combination with the homopolymeric polycarboxylates, preferred pulverulent premixtures comprise copolymeric polycarboxylates, particularly preferably from the group of the sulfonic acid group-containing copolymeric polycarboxylates and in particular from the group of the hydrophobically modified sulfonic acid group-containing copolymeric polycarboxylates.The copolymers may have two, three, four or more different monomer units. Preferred copolymeric polysulfonates contain, in addition to monomer(s) containing sulfonic acid groups, at least one monomer from the group of unsaturated carboxylic acids.Unsaturated carboxylic acid(s) used with particular preference are unsaturated carboxylic acids of the formula R 1( R 2) C=C(R 3) COOH in which R 1 to R 3 independently of one another, are -H, -CH 3, a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH 2, - OH or -COOH, as defined above, or are -COOH or -COOR 4 where R 4 is a saturated or unsaturated, The hydrocarbon radical is a straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It is of course also possible to use the unsaturated dicarboxylic acids.In the case of the monomers containing sulphonic acid groups, those of the formula R 5( R 6) C=C(R 1)- X-SO 3 H are preferred, in which R 5 to R 7 independently of one another, represents -H, -CH 3, a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH 2, - OH or -COOH or represents -COOH or -COOR 4 where R 4 represents a saturated or unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, unsaturated, A straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optionally present spacer group selected from -(CH 2)n- where n=0 to 4, -COO-(CH 2)k- where k=1 to 6, -C(O)-NH-C(CH 3)2-, - C(O)-NH-C(CH 3)2- CH 2- and -C(O)-NH-CH(CH 3)- CH 2-.Preferred among these monomers are those of the formulae H 2 C=CH-X-SO 3 H, H 2 C=C(CH 3)- X-SO 3 H or HO 3 S-X-(R 6) C=C(R 7)- X-SO 3 H in which R 6 and R7 are selected independently of one another from -H, -CH3, -CH2CH3, -ch_ner66_ch_ner67_ch_ner68_und -CH(CH 3)2 and X represents an optionally present spacer group selected from -(CH 2)n- where n=0 to 4, -COO-(CH 2)k- where k=1 to 6, -C(O)-NH-C(CH 3)2-, - C(O)-NH-C(CH 3)2- CH 2- and -C(O)-NH-CH(CH 3)- CH 2-.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, 3-methacrylamido-2-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, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or water-soluble salts thereof. In the polymers, the sulfonic acid groups can be present wholly or partly in neutralized form, that is to say that the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions. The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.The monomer distribution of the copolymers preferably used according to the invention is preferably in each case 5 to 95% by weight, particularly preferably the proportion of the monomer containing sulfonic acid groups is 50 to 90% by weight and the proportion of the monomer containing carboxylic acid groups is 10 to 50% by weight, in the case of copolymers which contain only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, the monomers here preferably being selected from the abovementioned. The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200 000 g·mol -1, preferably of 4000 to 25 000 g·mol -1 and in particular of 5000 to 15 000 g·mol -1.In a further preferred embodiment, the copolymers comprise, in addition to carboxyl group-containing monomer and sulfonic acid group-containing monomer, also at least one non-ionic, preferably hydrophobic monomer. The use of these hydrophobically modified polymers has in particular been able to improve the final rinse performance of dishwashing detergents according to the invention.Particularly preferably, the pulverulent first premix comprises an anionic copolymer, wherein the anionic copolymer used is a copolymer comprising i) carboxylic acid group-containing monomers ii) sulfonic acid group-containing monomers iii) nonionic monomers, in particular hydrophobic monomers.The nonionic monomers used are preferably monomers of the general formula R 1( R 2) C=C(R 3)- X-R 4 in which R 1 to R 3 independently of one another, denote -H, -CH 3 or -C 2 H 5 X denotes an optionally present spacer group selected from -CH 2-, - C(O)O- and -C(O)-NH-, and R4represents a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, unsaturated, saturated or unsaturated, unsaturated, unsaturated, hydroxyl radical, preferably, aromatic radicals having 6 to 22 carbon atoms.Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4,4-trimethylpentene-1, 2,4,4-trimethylpentene-2,2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4,4-dimethylhexane-1, ethylcyclohexyne, 1-octene, α-olefins having 10 or more carbon atoms, such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C 22- α-olefin, 2-Styrene, α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N-(methyl)acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N-(2-ethylhexyl)acrylamide, octyl acrylate, octyl methacrylate, N-(octyl)acrylamide, lauryl acrylate, lauryl methacrylate, N-(lauryl)acrylamide, stearyl acrylate, stearyl methacrylate, N-(stearyl)acrylamide, behenyl acrylate, Behenyl methacrylate and N-(behenyl)acrylamide or mixtures thereof, in particular acrylic acid, ethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and mixtures thereof.The proportion by weight of the active substance with washing or cleaning activity from the group of the homopolymeric polycarboxylates and the copolymer polyacrylates containing sulphonic acid groups, based on the total weight of the first pulverulent premix, is preferably from 2 to 18% by weight, particularly preferably from 5 to 16% by weight and in particular from 8 to 15% by weight.Preferred first particulate preblends are characterized by low compositional complexity, except for the optional ingredients described above.Preferred first powdery premix contains, based on its total weight, less than 1% by weight, preferably less than 0.5% by weight, particularly preferably less than 0.1% by weight and in particular no citrate. Dispensing with the use of citrate has proven to be particularly advantageous for the storage, transport and tabletting capacity of the premix.Preferred first particulate preblends further preferably contain no phosphate. Preferably, the first particulate premix is further free of phosphonate.As stated at the outset, the laundry detergent or cleaning agent tablets produced in the process described or a laundry detergent or cleaning agent tablet phase are distinguished by good disintegration properties in aqueous liquors at a hardness which is sufficient for storage, transport and use. Owing to these advantageous properties, the laundry or cleaning agent tablets produced in the method described or a laundry or cleaning agent tablet phase do not require the addition of either tableting auxiliaries from the group of polyethylene glycols or disintegration auxiliaries from the group of disintegrants.In preferred process variants, the first pulverulent premix, based on its total weight, therefore comprises less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.1% by weight, and in particular no tableting aid from the group of the polyethylene glycols.Likewise, in preferred process variants, the first pulverulent premix comprises, based on its total weight, less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.1% by weight, and in particular no disintegration aid from the group of disintegrants, in particular cellulose-based disintegrants, and also the spray systems.The addition of enzyme preparations has proven advantageous for the washing and cleaning action. The proportion by weight of the enzyme preparation relative to the total weight of the first pulverulent premix is preferably 0.2 to 4% by weight, more preferably 0.4 to 3% by weight and in particular 0.8 to 2.5% by weight. In particular, the use of encapsulated, mechanically sensitive enzyme preparations is particularly preferred for the method because of the low pressing force used.The composition of some preferably produced laundry or cleaning agent tablets or laundry or cleaning agent tablet phases can be found in the following tables (data in wt. % based on the total weight of the preparation, unless otherwise stated. The sign "-" stands for "free of".)Sodium carbonate15 from 55 to 5525 from 55 to 5525 from 55 to 5530 50 to 50Sodium percarbonate8 from 32 to 3210 from 30 to 3010 from 30 to 3012 from 28 to 28Methyl glycine diacetic acid and its salts8 from 32 to 3225 from 55 to 5525 from 55 to 5525 from 55 to 55nonionic surfactant0,2 up to 80,4 up to 70,8 up to 60,8 up to 6Washing- or Cleaning-Active Polymer2 up to 185 from 16 to 168 from 15 to 158 from 15 to 15Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate0 up to 20 up to 10 from 0,5--MiscAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADSodium carbonate15 from 55 to 5525 from 55 to 5525 from 55 to 5530 50 to 50Sodium percarbonate8 from 32 to 3210 from 30 to 3010 from 30 to 3012 from 28 to 28Methyl glycine diacetic acid and its salts8 from 32 to 3225 from 55 to 5525 from 55 to 5525 from 55 to 55Nonionic Surfactant 1)0,2 up to 80,4 up to 70,8 up to 60,8 up to 6Washing- or Cleaning-Active Polymer2 up to 185 from 16 to 168 from 15 to 158 from 15 to 15Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate0 up to 20 up to 10 from 0,5--MiscAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADSodium carbonate15 from 55 to 5525 from 55 to 5525 from 55 to 5530 50 to 50Sodium percarbonate8 from 32 to 3210 from 30 to 3010 from 30 to 3012 from 28 to 28Methyl glycine diacetic acid and its salts8 from 32 to 3225 from 55 to 5525 from 55 to 5525 from 55 to 55nonionic surfactant0,2 up to 80,4 up to 70,8 up to 60,8 up to 6Washing- or Cleaning-Active Polymer 2)2 up to 185 from 16 to 168 from 15 to 158 from 15 to 15Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate0 up to 20 up to 10 from 0,5--MiscAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADSodium carbonate15 from 55 to 5525 from 55 to 5525 from 55 to 5530 50 to 50Sodium percarbonate8 from 32 to 3210 from 30 to 3010 from 30 to 3012 from 28 to 28Methyl glycine diacetic acid and its salts8 from 32 to 3225 from 55 to 5525 from 55 to 5525 from 55 to 55Nonionic Surfactant 1)0,2 up to 80,4 up to 70,8 up to 60,8 up to 6Washing- or Cleaning-Active Polymer 2)2 up to 185 from 16 to 168 from 15 to 158 from 15 to 15Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate0 up to 20 up to 10 from 0,5--MiscAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADSodium carbonate15 from 55 to 5525 from 55 to 5525 from 55 to 5530 50 to 50Sodium percarbonate8 from 32 to 3210 from 30 to 3010 from 30 to 3012 from 28 to 28Methyl glycine diacetic acid and its salts8 from 32 to 3225 from 55 to 5525 from 55 to 5525 from 55 to 55nonionic surfactant0,2 up to 80,4 up to 70,8 up to 60,8 up to 6Washing- or Cleaning-Active Polymer2 up to 185 from 16 to 168 from 15 to 158 from 15 to 15Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate0 up to 20 up to 10 from 0,5--Phosphate, phosphonate--------MiscAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADSodium carbonate15 from 55 to 5525 from 55 to 5525 from 55 to 5530 50 to 50Sodium percarbonate8 from 32 to 3210 from 30 to 3010 from 30 to 3012 from 28 to 28Methyl glycine diacetic acid and its salts8 from 32 to 3225 from 55 to 5525 from 55 to 5525 from 55 to 55Nonionic Surfactant 1)0,2 up to 80,4 up to 70,8 up to 60,8 up to 6Washing- or Cleaning-Active Polymer2 up to 185 from 16 to 168 from 15 to 158 from 15 to 15Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate0 up to 20 up to 10 from 0,5--Phosphate, phosphonate--------MiscAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADSodium carbonate15 from 55 to 5525 from 55 to 5525 from 55 to 5530 50 to 50Sodium percarbonate8 from 32 to 3210 from 30 to 3010 from 30 to 3012 from 28 to 28Methyl glycine diacetic acid and its salts8 from 32 to 3225 from 55 to 5525 from 55 to 5525 from 55 to 55nonionic surfactant0,2 up to 80,4 up to 70,8 up to 60,8 up to 6Washing- or Cleaning-Active Polymer 2)2 up to 185 from 16 to 168 from 15 to 158 from 15 to 15Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate0 up to 20 up to 10 from 0,5--Phosphate, phosphonate--------MiscAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADSodium carbonate15 from 55 to 5525 from 55 to 5525 from 55 to 5530 50 to 50Sodium percarbonate8 from 32 to 3210 from 30 to 3010 from 30 to 3012 from 28 to 28Methyl glycine diacetic acid and its salts8 from 32 to 3225 from 55 to 5525 from 55 to 5525 from 55 to 55Nonionic Surfactant 1)0,2 up to 80,4 up to 70,8 up to 60,8 up to 6Washing- or Cleaning-Active Polymer 2)2 up to 185 from 16 to 168 from 15 to 158 from 15 to 15Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate0 up to 20 up to 10 from 0,5--Phosphate, phosphonate--------MiscAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADSodium carbonate15 from 55 to 5525 from 55 to 5525 from 55 to 5530 50 to 50Sodium percarbonate8 from 32 to 3210 from 30 to 3010 from 30 to 3012 from 28 to 28Methyl glycine diacetic acid and its salts8 from 32 to 3225 from 55 to 5525 from 55 to 5525 from 55 to 55nonionic surfactant0,2 up to 80,4 up to 70,8 up to 60,8 up to 6Washing- or Cleaning-Active Polymer2 up to 185 from 16 to 168 from 15 to 158 from 15 to 15Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate0 up to 20 up to 10 from 0,5--Phosphate, phosphonate--------Polyethylene glycol0 up to 20 up to 10 from 0,1--Disintegration Aid0 up to 20 up to 10 from 0,1--MiscAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADSodium carbonate15 from 55 to 5525 from 55 to 5525 from 55 to 5530 50 to 50Sodium percarbonate8 from 32 to 3210 from 30 to 3010 from 30 to 3012 from 28 to 28Methyl glycine diacetic acid and its salts8 from 32 to 3225 from 55 to 5525 from 55 to 5525 from 55 to 55Nonionic Surfactant 1)0,2 up to 80,4 up to 70,8 up to 60,8 up to 6Washing- or Cleaning-Active Polymer2 up to 185 from 16 to 168 from 15 to 158 from 15 to 15Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate0 up to 20 up to 10 from 0,5--Phosphate, phosphonate--------Polyethylene glycol0 up to 20 up to 10 from 0,1--Disintegration Aid0 up to 20 up to 10 from 0,1--MiscAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADSodium carbonate15 from 55 to 5525 from 55 to 5525 from 55 to 5530 50 to 50Sodium percarbonate8 from 32 to 3210 from 30 to 3010 from 30 to 3012 from 28 to 28Methyl glycine diacetic acid and its salts8 from 32 to 3225 from 55 to 5525 from 55 to 5525 from 55 to 55nonionic surfactant0,2 up to 80,4 up to 70,8 up to 60,8 up to 6Washing- or Cleaning-Active Polymer 2)2 up to 185 from 16 to 168 from 15 to 158 from 15 to 15Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate0 up to 20 up to 10 from 0,5--Phosphate, phosphonate--------Polyethylene glycol0 up to 20 up to 10 from 0,1--Disintegration Aid0 up to 20 up to 10 from 0,1--MiscAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADSodium carbonate15 from 55 to 5525 from 55 to 5525 from 55 to 5530 50 to 50Sodium percarbonate8 from 32 to 3210 from 30 to 3010 from 30 to 3012 from 28 to 28Methyl glycine diacetic acid and its salts8 from 32 to 3225 from 55 to 5525 from 55 to 5525 from 55 to 55Nonionic Surfactant 1)0,2 up to 80,4 up to 70,8 up to 60,8 up to 6Washing- or Cleaning-Active Polymer 2)2 up to 185 from 16 to 168 from 15 to 158 from 15 to 15Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate Citrate0 up to 20 up to 10 from 0,5--Phosphate, phosphonate--------Polyethylene glycol0 up to 20 up to 10 from 0,1--Disintegration Aid0 up to 20 up to 10 from 0,1--MiscAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 ADAD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD 100 AD1) A nonionic surfactant selected from the group of compounds having the general formula C 4- 22- CH(OH)CH 2 O-(EO) 20-120- C 2-26, in particular from the group of compounds having the general formula C 8-12 fatty alcohol (EO) 22-2- hydroxydecyl ether or C 4-22 fatty alcohol (EO) 40-80-2- hydroxyalkyl ether2) A detergent or cleaning-active polymer selected from the group consisting of the homopolymeric polycarboxylates and the hydrophobically modified sulfonic acid group-containing copolymeric polycarboxylatesOne of the technical advantages of the process described consists in the direct transportability, meteringability and tabletability of the first pulverulent premix prepared in step i) by mixing its constituents. Because of higher process efficiency and reduced production costs, process variants are preferred in which the first pulverulent premix in step ii) is stored for a period of less than four hours, preferably less than two hours, particularly preferably less than 30 minutes and in particular less than 10 minutes. Very particular preference is given to process variants in the course of which the first pulverulent premix in step i) is provided by mixing its constituents and is fed directly to the metering device without storage.Even if storage of the pulverulent premix prior to pressing in step v) is not necessary owing to the advantageous properties of the premix, storage is nevertheless possible without these advantageous properties being lost. Depending on the process management or in the case of continuous process interruptions, for example during maintenance or repair, such a longer storage can be indicated. In a preferred alternative method, in step ii) storage takes place for a period of up to 24 hours, preferably for a period of four to 24 hours, in particular of eight to 24 hours.If the pulverulent premix is stored in step ii), storage is preferably carried out at a temperature of from 10 to 35° C.The tabletting can be carried out in commercially available tablet presses which can in principle be equipped with single or double punches. In the latter case, not only is the upper punch used for pressure build-up, but also the lower punch moves towards the upper punch during the pressing process, while the upper punch presses downward. For small production quantities, instead of the preferred rotary tablet press, eccentric tablet presses can also be used in which the punch or punches are fastened to an eccentric disk which is in turn mounted on an axis at a specific rotational speed. The movement of these rams is comparable to the operation of a conventional four-stroke motor. The pressing can be effected with one upper and lower punch each, but a plurality of punches can also be fastened to an eccentric disc, wherein the number of die bores is correspondingly increased. The throughput rates of eccentric presses vary, depending on the type, from a few hundred to a maximum of 3000 tablets per hour. Preferred methods use a rotary tablet press.In eccentric presses, the lower punch is generally not moved during the pressing process. As a result, the resulting tablet has a hardness gradient, i.e., is harder in the areas closer to the upper punch than in the areas closer to the lower punch.In rotary tablet presses, a larger number of matrices are arranged in a circle on a so-called die table. The number of matrices varies between 6 and 55, depending on the model, larger matrices also being commercially available. Each die on the die table is assigned an upper and lower punch, wherein the pressing pressure can in turn be actively built up only by the upper or lower punch, but also by both punches. The die table and the punches move about a common vertical axis, the punches being brought into the filling, compressing, plastic deformation and ejection positions during rotation by means of rail-like cam tracks. At the locations where a particularly severe raising or lowering of the punches is required (filling, compacting, ejection), these cam tracks are supported by additional low-pressure pieces, low-pressure drawing rails and raising tracks.The filling of the die in step iii) is preferably effected via a rigidly arranged metering device, for example the so-called filling shoe, which is connected to a storage container for the premix. The pressing pressure on the premix can be adjusted individually via the pressing paths for upper and lower punches, wherein the pressure build-up takes place by the rolling of the punch shaft heads past adjustable pressure rollers.The first pulverulent premix is fed to a filling shoe in step iii) of preferred process variants. Both in the feed lines and in the filling station itself, the premix is distinguished by low adhesion to bottom or side walls.The metered addition of the pulverulent premix in step iv) is preferably volumetric.The method is preferably used for the production of laundry or cleaning agent tablets or laundry or cleaning agent tablet phases which are suitable for metering via customary apparatuses in household washing machines or dishwashers, for example wash-in compartments or metering chambers. Against this background, process variants are preferred in which the die in step iv) has an opening area of from 7 to 15 cm 2, preferably from 8 to 12 cm 2.As stated above, the dies of preferably used tablet presses have movable, preferably vertically movable lower punches. These movable lower punches allow, on the one hand, the pressure build-up during the pressing of the premix, but also simplify the production of multi-phase tablets. For example, a plurality of, preferably different, pulverulent premix products can be compressed in a die one after the other and without expelling the intermediates to form a multi-phase detergent or cleaning agent tablet. When carrying out such a method variant, a movable lower punch makes it possible to adapt the die volume during the successive metering and tabletting processes.A preferred process variant for producing a two or more layered detergent or cleaning agent tablet comprises the steps: i) providing a first pulverulent premix comprising, based on its total weight a), 15 to 55% by weight of sodium carbonate; b) 8 to 32% by weight of sodium percarbonate; c) 8 to 30% by weight of methyl glycine diacetic acid (MGDA) and its salts; d) 0.2 to 8% by weight of nonionic surfactant; e) 2 to 18% by weight of detergent or cleaning-active polymer; f) 0 to 2% by weight of citrate; by mixing its constituents; ii) optionally storing the pulverulent premix; iii) supplying the pulverulent premix to a metering device of a tablet press; IV) Dosing of the pulverulent premix into the die of the die table of the tablet press onto a detergent tablet located in the die, which has been obtained by pressing at least one further pulverulent premix; v) Pressing the pulverulent premix in the die at a pressing force of 15 to 50 kN, with formation of a two-layer detergent tablet; vi) Expelling the detergent tablet or the detergent tablet phase from the die; vii) Packaging the detergent tablet or the detergent tablet phase or the detergent tablet phase.An alternative process variant comprises the steps: i) providing a first pulverulent premix comprising, based on its total weight a), 15 to 55% by weight of sodium carbonate; b) 8 to 32% by weight of sodium percarbonate; c) 8 to 30% by weight of methylglycinediacetic acid (MGDA) and its salts; d) 0.2 to 8% by weight of nonionic surfactant; e) 2 to 18% by weight of detergent-active polymer; f) 0 to 2% by weight of citrate; by mixing its constituents; ii) optionally storing the pulverulent premix; iii) feeding the pulverulent premix to a metering device of a tablet press; iv) metering the pulverulent premix into the die of the die table of the tablet press; v) compressing the pulverulent premix in the die with a compression force of 15 to 50 kN and metering a second pulverulent premix onto the compressed first pulverulent premix in the die and subsequent compressing to form a two-layer tablet; vi) expelling the detergent tablet or the detergent tablet phase from the die; vii) optionally packaging the detergent tablet or the detergent tablet phase.The tableting of the first pulverulent premix in step v) is preferably carried out with a compression force of from 16 to 36 kN, more preferably from 17 to 28 kN. These pressing forces ensure adequate tablet hardness with simultaneously good disintegration properties of the tablets or tablet phases.As described above, when the tabletting process is carried out, there is reduced adhesion of pulverulent premix to the surfaces of components used. This technical advantage is not limited to the bottom or side walls of feed lines, metering devices or matrices, but also includes the surfaces of the lower and upper punches which are in direct contact with the premix during the pressing of the premix.To further reduce these adhesions, it may be advantageous if the die has a rotatable lower punch in step iv). Alternatively or in combination with a rotatable lower punch, at least one of the punches between which the first powdery premix is pressed in step v) can have an adhesion-reducing coating.In a further preferred alternative method, at least one of the punches, between which the first powdery premix is pressed in step v), has an insert, preferably an exchangeable insert (insert). This preferably replaceable insert serves, for example, for modifying the surface properties of lower or upper punches. In particular, it is preferred to provide replaceable inserts on the wear-prone surfaces of the lower and upper punches. The mechanically particularly stressed, wear-prone surfaces of the lower and upper punches include in particular those surfaces which are in direct contact with the pulverulent premix during the pressing in step v). In preferred process variants, at least one of the punches, which is in direct contact with the pulverulent premix during the pressing in step v), has an exchangeable insert, preferably an exchangeable walkable insert.In addition to modifications of the surface properties, the punches used for pressing the pulverulent premix, in particular the upper punch used, can have different shapes, which deviate from the usual planar surface. In a preferred method variant, the upper punch has a protrusion. Such a protrusion enables, for example, the production of tablets with surface patterns or depressions.After the pressing in step v), the detergent tablet or the detergent tablet phase in step vi) is ejected from the die and can subsequently be packaged.Suitable for packaging are primary and secondary packaging agents, primary packaging agents being understood to mean those agents which are used for packaging individual laundry or cleaning agent tablets or laundry or cleaning agent tablet phases, while secondary packaging agents serve for packaging a plurality of laundry or cleaning agent tablets or laundry or cleaning agent tablet phases in one package. Primary packaging means are, for example, films, the secondary packaging means include cardboard boxes, plastic containers or standing-floor bags.The laundry or cleaning agent tablets ejected from the die in step vi) or the laundry or cleaning agent tablet phases do not require intermediate storage and are suitable for immediate packaging. Preferably, the packaging of the washing or cleaning agent tablet or of the washing or cleaning agent tablet phase in step vii) takes place within 60 minutes, preferably within 20 minutes and in particular within 5 minutes after the ejection of the washing or cleaning agent tablet or of the washing or cleaning agent tablet phase from the die in step vi).Even if storage of the laundry or cleaning agent tablet or the laundry or cleaning agent tablet phase before packaging is not necessary because of the advantageous properties of the laundry or cleaning agent tablet or the laundry or cleaning agent tablet phase, storage is nevertheless possible without these advantageous properties being lost. Depending on the process management or in the case of continuous process interruptions, for example during maintenance or repair, such a longer storage can be indicated. In a preferred alternative method, the packaging of the detergent tablet or detergent tablet phase in step vii) takes place within a period of 48 hours, preferably within a period of 36, particularly preferably within a period of one hour to 24 hours.In a preferred process variant, the detergent tablet or the detergent tablet phase in step vii) is enclosed by means of a film, for example a water-insoluble or a water-soluble film. To improve the aesthetic nature and the mechanical stability of the product, a detergent tablet or detergent tablet phase enclosed by a water-soluble film is preferably transported by means of a transport device through a shrink tunnel and the water-soluble film is shrunk in the shrink tunnel.Preferably, the laundry or cleaning agent tablet or the laundry or cleaning agent tablet phase following step vi) is packaged together with further laundry or cleaning agent tablets or laundry or cleaning agent tablet phases in bulk in an outer packaging. As an alternative to the loose packing, ordered preparation in the outer packaging is also possible. The ordered formulation may be suitable for reducing the amount of packaging material used for the outer packaging. Suitable outer packaging is, for example, the previously described cardboard boxes, plastic containers or stand-alone bags. The washing or cleaning agent tablet or washing or cleaning agent tablet phase ready-made in the outer packaging can have a primary packaging, for example a previously described film packaging. To reduce the packaging complexity, it may alternatively be preferred that the laundry or cleaning agent tablet or the laundry or cleaning agent tablet phase, following step vi), is packaged together with further laundry or cleaning agent tablets or laundry or cleaning agent tablet phases in loose bulk in an outer packaging without further packaging. As an alternative to the loose packing, ordered preparation in the outer packaging is also possible. In this case too, ordered formulation in the outer packaging is alternatively possible.This application provides, inter alia, the following articles: 1. process for preparing a detergent tablet or a detergent tablet phase, comprising the steps of: i) providing a first pulverulent premix comprising, based on its total weight a), 15 to 55% by weight of sodium carbonate; b) 8 to 32% by weight of sodium percarbonate; c) 8 to 30% by weight of methylglycinediacetic acid (MGDA) and its salts; d) 0.2 to 8% by weight of nonionic surfactant; e) 2 to 18% by weight of detergent or detergent-active polymer; f) 0 to 2% by weight of citrate; by mixing its constituents; ii) optionally storage of the pulverulent premix; iii) Feeding the pulverulent premix to a metering device of a tablet press; iv) Metering the pulverulent premix into the die of the die table of the tablet press; v) Compressing the pulverulent premix in the die with a compression force of 15 to 50 kN. vi) Expelling the detergent tablet or the detergent tablet phase from the die; vii) Optionally Packaging the detergent tablet or the detergent tablet phase or the detergent tablet phase. 2. process according to item 1, wherein the first pulverulent premix contains 25 to 55% by weight, preferably 30 to 50% by weight, of sodium carbonate, based on its total weight. 3.The method according to any one of the preceding points, wherein the weight proportion of the particles of sodium carbonate having a particle diameter of 125 to 2000 μm in the first pulverulent premix is more than 70% by weight, preferably more than 80% by weight and in particular more than 85% by weight. 4. the method according to any one of the preceding items, wherein the weight proportion of the particles of the sodium carbonate having a particle diameter of 200 to 1600 μm in the first powdery premix is more than 85 wt %. 5. process according to one of the preceding points, wherein the first pulverulent premix comprises, based on its total weight, 10 to 30% by weight, preferably 12 to 28% by weight, of sodium percarbonate. 6.The process according to any of the preceding points, wherein the proportion by weight of the particles of sodium percarbonate having a particle diameter of 125 to 2000 μm in the pulverulent premix is more than 70% by weight, preferably more than 80% by weight and in particular more than 85% by weight. 7. the method according to any of the preceding points, wherein the weight fraction of the particles of sodium percarbonate having a particle diameter of 200 to 1600 μm in the pulverulent premix is more than 85% by weight. 8 The process according to any one of the preceding items, wherein the first powdery premix contains, based on its total weight, 10 to 32 wt.%, preferably 12 to 30 wt.% of methyl glycine diacetic acid (MGDA) and its salts. 9. The method according to any one of the preceding points, wherein the first powdery premix contains, based on its total weight, 0.4 to 7 wt.%, preferably 0.8 to 6 wt.% of nonionic surfactant. 10. The method according to any one of the preceding points, wherein the non-ionic surfactant is selected from the group of the compounds having the general formula C 4-22- CH(OH)CH 2 O-(EO) 20-120- C 2-26, in particular from the group of the compounds having the general formula C 8-12 fatty alcohol (EO) 22-2- hydroxydecyl ether or C 4-22 fatty alcohol (EO) 40-80-2- hydroxyalkyl ether. 11 The process according to any of the preceding items, wherein the first pulverulent premix has a weight ratio of sodium carbonate and sodium percarbonate and methyl glycine diacetic acid (MGDA) and its salts to nonionic surfactant above 6:1, preferably above 12:1 and in particular above 18:1. 12.The method according to any one of the preceding points, wherein the first powdery premix contains, based on its total weight, less than 1 wt.%, preferably less than 0.5 wt.%, particularly preferably less than 0.1 wt.% and in particular no anionic surfactant. 13.The process according to any of the preceding points, wherein the first pulverulent premix contains, based on its total weight, 5 to 16% by weight, preferably 8 to 15% by weight, of active washing or cleaning polymer. 14. The process according to any of the preceding points, wherein the detergent or cleaning-active polymer is selected from the group of polycarboxylates, preferably from the group of homopolymeric polycarboxylates. 15. The process according to any of the preceding items, wherein the detergent- or cleaning-active polymer is selected from the group of polycarboxylates, preferably from the group of copolymeric polycarboxylates, more preferably from the group of copolymeric polycarboxylates containing sulphonic acid groups and in particular from the group of hydrophobically modified copolymeric polycarboxylates containing sulphonic acid groups. 16.The process according to any of the preceding points, wherein the first pulverulent premix comprises, based on its total weight, less than 1% by weight, preferably less than 0.5% by weight, more preferably less than 0.1% by weight and in particular no citrate. 17. The method of any of the preceding items, wherein the first powdered premix does not contain a phosphate. 18. The method according to any of the preceding items, wherein the first powdery premix does not contain a phosphonate. 19.The process according to any of the preceding points, wherein the first pulverulent premix comprises, based on its total weight, less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.1% by weight and in particular no tableting aid from the group of the polyethylene glycols. 20.The method according to any of the preceding points, wherein the first pulverulent premix, based on its total weight, comprises less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.1% by weight and in particular no disintegration aid from the group of disintegrants, in particular cellulose-based disintegrants, and of the spray systems. 21.The method according to any one of the preceding points, wherein the first powdery premix contains, based on its total weight, 0.2 to 4 wt.%, preferably 0.4 to 3 wt.% and in particular 0.8 to 2.5 wt.% enzyme preparation. 22.The method according to any of the preceding points, wherein the first pulverulent premix in step ii) is stored for a period of less than four hours, preferably less than two hours, particularly preferably less than 30 minutes and in particular less than 10 minutes. 23.The process according to any of the preceding points, wherein the first pulverulent premix in step i) is provided by mixing its constituents and is fed directly to the metering device without storage. 24th The method according to any one of the preceding items, wherein the first powdery premix in step ii) is stored at a temperature of 10 to 35°C. 25.Method according to one of the preceding points, wherein a rotary tablet press is used as the tablet press. 26.The method according to any one of the preceding points, wherein the first powdery premix in step iii) is fed to a filling shoe. 27. The method according to any of the preceding points, wherein the first pulverulent premix is metered in in step iv) by volumetric metering. 28.The method according to any of the preceding points, wherein the die in step iv) has an opening area of 7 to 15 cm 2, preferably of 8 to 12 cm 2. 28. Method according to one of the preceding points, wherein the die in step iv) has a movable, preferably vertically movable, lower punch. 30th The method of any of the preceding items, wherein the die comprises a rotatable lower punch in step iv). 31.A process for the preparation of a two or more layered detergent or cleaning agent tablet comprising the steps of: i) providing a first pulverulent premix containing, based on its total weight a), 15 to 55 wt.% sodium carbonate; b) 8 to 32 wt.% sodium percarbonate; c) 8 to 30 wt.% methyl glycine diacetic acid (MGDA) and its salts; d) 0.2 to 8 wt.% non-ionic surfactant; e) 2 to 18 wt.% detergent or cleaning active polymer; f) 0 to 2 wt.% citrate; by mixing its constituents; ii) optionally storing the pulverulent premix; iii) feeding the pulverulent premix to a metering device of a tablet press; IV) Dosing the pulverulent premix into the die of the die table of the tablet press onto a detergent tablet located in the die, which has been obtained by pressing at least one further pulverulent premix. v) Pressing the pulverulent premix in the die at a pressing force of 15 to 50 kN, with formation of a two-layer detergent tablet; vi) Expelling the detergent tablet or the detergent tablet phase from the die; vii) Optionally packaging the detergent tablet or the detergent tablet or the detergent tablet phase. 32. method according to one of the preceding points, wherein the first pulverulent premix in step v) is compressed with a compression force of 16 to 36 kN, preferably of 17 to 28 kN. 33. Method according to one of the preceding points, wherein the first pulverulent premix is pressed in step v) between the lower punch and the upper punch, and at least one of the punches has an exchangeable insert, preferably a walkable insert, which is in direct contact with the pulverulent premix during the pressing in step v). 34.Method according to one of the preceding points, wherein the first pulverulent premix in step v) is pressed between the lower die and the upper die and at least one of the dies has an adhesion-reducing coating. 35. Method according to one of the preceding points, wherein the first pulverulent premix is pressed in step v) between the lower die and the upper die, and at least one of the dies has an insert, preferably an exchangeable insert. 36. method according to one of the preceding points, wherein the first pulverulent premix is pressed in step v) between the lower punch and the upper punch and the upper punch has a protrusion. 37 A process for the production of a two-layer laundry or cleaning agent tablet, comprising the steps: i) providing a first pulverulent premix comprising, based on its total weight a), 15 to 55 wt.% sodium carbonate; b) 8 to 32 wt.% sodium percarbonate; c) 8 to 30 wt.% methyl glycine diacetic acid (MGDA) and its salts; d) 0.2 to 8 wt.% non-ionic surfactant; e) 2 to 18 wt.% laundry or cleaning active polymer; f) 0 to 2 wt.% citrate; by mixing its constituents; ii) optionally storing the pulverulent premix; iii) supplying the pulverulent premix to a metering device of a tablet press; iv) Metering the pulverulent premix into the die of the die table of the tablet press; v) Compressing the pulverulent premix in the die with a compression force of 15 to 50 kN and metering a second pulverulent premix onto the compressed first pulverulent premix in the die and subsequent compressing to form a two-layer tablet; vi) Expelling the detergent tablet or the detergent tablet phase from the die; vii) Optionally packaging the detergent tablet or the detergent tablet phase or the detergent tablet phase. 38.The method according to any of the preceding items, wherein the detergent tablet or the detergent tablet phase in step vii) is enclosed by means of a water-soluble film. 39. Method according to item 38, wherein the detergent tablet enclosed by a water-soluble film or the detergent tablet phase is transported by means of a transport device through a shrink tunnel and the water-soluble film is shrunk in the shrink tunnel. 40th The method according to any one of the items 1 to 37, wherein the detergent tablet or the detergent tablet phase in step vii) is enclosed by means of a water-insoluble film. 41. Method according to one of the preceding points, wherein the packaging of the washing or cleaning agent tablet or the washing or cleaning agent tablet phase in step vii) takes place within 60 minutes, preferably within 20 minutes and in particular within 5 minutes after the ejection of the washing or cleaning agent tablet or the washing or cleaning agent tablet phase from the die in step vi). 42. Method according to one of the preceding points, wherein the washing or cleaning agent tablet or the washing or cleaning agent tablet phase following step vi) is packaged together with further washing or cleaning agent tablets or washing or cleaning agent tablet phases in bulk in an outer packaging. 43. Method according to one of the preceding points, wherein the washing or cleaning agent tablet or the washing or cleaning agent tablet phase is packaged in a bulk package together with further washing or cleaning agent tablets or washing or cleaning agent tablet phases in a bulk package after step vi) without further packaging.References included in the specificationThis list of documents cited by the applicant has been produced in an automated manner and is only included for the better information of the reader. The list is not part of the German patent application or utility model application. The DPMA does not take any adhesion for any faults or omissions.Patent Literature citedEP 711 828 A2

[0005]

Claims

A process for the preparation of a laundry or cleaning agent tablet or a laundry or cleaning agent tablet phase, comprising the steps of: i) providing a first pulverulent premix containing, based on its total weight a), 15 to 55% by weight of sodium carbonate; b) 8 to 32% by weight of sodium percarbonate; c) 8 to 30% by weight of methyl glycine diacetic acid (MGDA) and its salts; d) 0.2 to 8% by weight of nonionic surfactant; e) 2 to 18% by weight of laundry or cleaning active polymer; f) 0 to 2% by weight of citrate; by mixing its constituents; ii) optionally storing the pulverulent premix; iii) supplying the pulverulent premix to a metering device of a tablet press; iv) Metering the pulverulent premix into the die of the die table of the tablet press; v) Compressing the pulverulent premix in the die with a compression force of 15 to 50 kN; vi) Expelling the washing or cleaning agent tablet or the washing or cleaning agent tablet phase from the die; vii) Optionally Packaging the washing or cleaning agent tablet or the washing or cleaning agent tablet phase.The process according to claim 1, wherein the first powdery premix contains 25 to 55 wt.%, preferably 30 to 50 wt.%, of sodium carbonate, based on its total weight.The process according to any of the preceding claims, wherein the first pulverulent premix comprises, based on its total weight, 10 to 30% by weight, preferably 12 to 28% by weight, of sodium percarbonate.The method according to any one of the preceding claims, wherein the first powdery premix contains, based on its total weight, 10 to 32 wt.%, preferably 12 to 30 wt.% methyl glycine diacetic acid (MGDA) and its salts.The method according to any one of the preceding claims, wherein the first powdery premix contains, based on its total weight, 0.4 to 7 wt.%, preferably 0.8 to 6 wt.% of non-ionic surfactant.The method according to any one of the preceding claims, wherein the first powdery premix has a weight ratio of sodium carbonate and sodium percarbonate and methyl glycine diacetic acid (MGDA) and its salts to nonionic surfactant above 6:1, preferably above 12:1 and in particular above 18:1.The method according to any one of the preceding claims, wherein the first pulverulent premix contains, based on its total weight, 5 to 16% by weight, preferably 8 to 15% by weight, of washing- or cleaning-active polymer.The method according to any one of the preceding claims, wherein the first powdery premix in step ii) is stored for a period of less than four hours, preferably less than two hours, particularly preferably less than 30 minutes and in particular less than 10 minutes.The method according to any one of the preceding claims, wherein the die in step iv) has an opening area of 7 to 15 cm 2, preferably of 8 to 12 cm 2.Method according to one of the preceding claims, wherein the first pulverulent premix in step v) is pressed with a pressing force of 16 to 36 kN, preferably of 17 to 28 kN.