EP1123380B1 - Combinaison de corps faconnes d'agents de lavage et de nettoyage avec un emballage - Google Patents

Combinaison de corps faconnes d'agents de lavage et de nettoyage avec un emballage Download PDF

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Publication number
EP1123380B1
EP1123380B1 EP99952556A EP99952556A EP1123380B1 EP 1123380 B1 EP1123380 B1 EP 1123380B1 EP 99952556 A EP99952556 A EP 99952556A EP 99952556 A EP99952556 A EP 99952556A EP 1123380 B1 EP1123380 B1 EP 1123380B1
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EP
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Prior art keywords
acid
weight
tablet
detergent
combination
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Revoked
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EP99952556A
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German (de)
English (en)
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EP1123380A1 (fr
Inventor
Andreas Lietzmann
Markus Semrau
Wolfgang Barthel
Werner Künzel
Heinke Jebens
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D2565/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D2565/38—Packaging materials of special type or form
    • B65D2565/381—Details of packaging materials of special type or form
    • B65D2565/388—Materials used for their gas-permeability

Definitions

  • the present invention relates to detergent tablets, which are percarbonate included and to ensure better disintegration times with high Hardening can be combined with a special packaging system.
  • the invention includes such specially packaged shaped articles such as detergent tablets, detergent tablets, Bleaching tablets or water softening tablets with percarbonate.
  • the dichotomy between a sufficiently hard molded body and a sufficient one Rapid disintegration is a key problem. Since sufficiently stable, i.e. Shaped and unbreakable molded body only produced by relatively high compression pressures can, there is a strong compression of the molded parts and a consequent delayed disintegration of the shaped body in the aqueous Liquor and thus too slow a release of the active substances in the washing machine or cleaning process.
  • the delayed disintegration of the molded body continues to have Disadvantage that conventional detergent tablets do not have the induction chamber Have it washed in by household washing machines as the tablets are not in decay into secondary particles that are small enough to escape from the Detergent dispenser to be washed into the washing drum.
  • Detergent tablets contain for bleaching and cleaning performance Bleach, with sodium perborate monohydrate and tetrahydrate so far have the greatest importance.
  • sodium percarbonate is of outstanding importance.
  • Sodium percarbonate is a good choice for use in detergents and cleaning agents Bleach, because it dissolves quickly and completely in water, based on its weight can release a lot of oxygen and after the release of oxygen as a carbonate source an additional builder function takes over.
  • EP-A-0 481 793 (Unilever) describes detergent tablets in which individual ingredients are present separately from others.
  • the detergent tablets disclosed in this document contain sodium percarbonate, which is spatially separated from all other components that could influence its stability. This document does not contain any information on the packaging of the moldings.
  • the international patent application WO98 / 4046 (Unilever) describes a combination of at least one tablet of compressed particulate detergent, which is stored at least 24 hours h in a packaging system having a moisture permeability rate of less than 20 g / m 2/24 h. According to the information in this document, this combination increases the hardness of the tablets during storage, while the dissolution times decrease. Although the disintegration time of the tablets is measured under mechanical influence (stirring) according to the information in this document, all disintegration times are in some cases well over 2 minutes. Such high disintegration times render the moldings disclosed in this document unusable for metering through the washing-in chamber of household washing machines, since they do not disintegrate sufficiently quickly and therefore cannot be washed in. The use of sodium percarbonate is also not mentioned in this document.
  • European patent application EP-A-0 634 485 (Procter & Gamble) relates to combinations of granular detergent compositions which contain a percarbonate bleach and a packaging system containing the compositions to ensure better stability of the bleach over longer storage times. In this document too there is no information on detergent tablets, nor is the problem of excessive disintegration times with high hardness mentioned.
  • the present invention was based on the object, the advantages of using To use sodium percarbonate in detergent tablets and thereby To provide moldings that are characterized by high hardness with short disintegration times distinguished. In addition to overcoming this dichotomy between hardness and decay time the moldings should have such short disintegration times that a dosage over the Detergent dispenser of household washing machines easily and without residue possible is.
  • the present invention relates to a combination of (a) detergent tablet (s); which contains sodium percarbonate and a packaging system containing the detergent tablets, the tablet (s) containing the sodium percarbonate in amounts of 5 to 50% by weight and the packaging system having a moisture vapor transmission rate of 0.1 g / m 2 / day to less than 20 g / m 2 / day if the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%.
  • the detergent tablets of the present invention contain sodium percarbonate to develop the desired bleaching performance.
  • Sodium percarbonate is a non-specific term for sodium carbonate peroxohydrates which, strictly speaking, are not “percarbonates” (ie salts of percarbonic acid) but hydrogen peroxide adducts with sodium carbonate.
  • the merchandise has the average composition 2 Na 2 CO 3 .3 H 2 O 2 and is therefore not peroxycarbonate.
  • Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm -3 , which easily breaks down into sodium carbonate and bleaching or oxidizing oxygen.
  • the industrial production of sodium percarbonate is mainly produced by precipitation from an aqueous solution (so-called wet process).
  • aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate is precipitated by salting-out agents (predominantly sodium chloride), crystallization aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg 2+ ions).
  • the precipitated salt which still contains 5 to 12% by weight of mother liquor, is then centrifuged off and dried at 90 ° C. in a fluid bed dryer.
  • the bulk density of the finished product can vary between 800 and 1200 g / l depending on the manufacturing process.
  • the percarbonate is stabilized by an additional coating.
  • the sodium percarbonate bleach is in depending on the desired product varying amounts in the combinations of detergent tablets (s) according to the invention and packaging system used. Usual salaries are included between 5 and 50% by weight, preferably between 10 and 40% by weight and in particular between 15 and 35% by weight, based in each case on the entire molded article.
  • the content of the moldings in this substance is also of the intended use the shaped body depends. While common universal detergent in tablet form between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular contain between 12.5 and 22.5 wt .-% sodium percarbonate, the contents for bleach or bleach booster tablets between 15 and 50 wt .-%, preferably between 22.5 and 45% by weight and in particular between 30 and 40% by weight.
  • the detergent tablets further usual ingredients detergents and cleaning agents, which are described below.
  • the packaging system of the combination of detergent tablets (s) and packaging system according to the invention has a moisture vapor transmission rate of 0.1 g / m 2 / day to less than 20 g / m 2 / day when the packaging system is at 23 ° C. and a relative Equilibrium moisture of 85% is stored.
  • the specified temperature and humidity conditions are the test conditions that are mentioned in DIN standard 53122, whereby according to DIN 53122 minimal deviations are permissible (23 ⁇ 1 ° C, 85 ⁇ 2% relative humidity).
  • the moisture vapor permeability rate of a given packaging system or material can be determined by further standard methods and is, for example, also in the ASTM standard E-96-53T ("Test for measuring Water Vapor transmission of Materials in Sheet form") and in the TAPPI standard T464 m-45 ("Water Vapor Permeability of Sheet Materials at high temperature an Humidity").
  • the measuring principle of current methods is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, the container being closed at the top with the material to be tested.
  • the relative equilibrium humidity is 85% at 23 ° C. when measuring the moisture vapor transmission rate in the context of the present invention.
  • the absorption capacity of air for water vapor increases with the temperature up to a respective maximum content, the so-called saturation content, and is given in g / m 3 .
  • saturation content For example, 1 m 3 of air at 17 ° C is saturated with 14.4 g of water vapor; at a temperature of 11 ° C, saturation is already present with 10 g of water vapor.
  • the relative humidity is the ratio of the actual water vapor content to the saturation content corresponding to the prevailing temperature.
  • the relative equilibrium humidity of 85% at 23 ° C can be found, for example, in laboratory chambers with humidity control depending on the device type to +/- 2% r.L. adjust exactly. Even over saturated solutions of certain salts form in closed systems constant and well-defined relative humidity at a given temperature, that on the phase equilibrium between partial pressure of water, saturated solution and soil body are based.
  • Packaging systems preferred in the context of the present invention have a moisture vapor permeability rate of 0.5 g / m 2 / day to less than 15 g / m 2 / day.
  • the packaging system of the combination according to the invention encloses the invention one or more detergent tablets. It is preferred according to the invention either to design a shaped body such that it comprises an application unit of the detergent and cleaning agent, and this molded body to be packed individually, or the number of moldings in one packaging unit to pack, which in total comprises an application unit.
  • a target dosage of According to the invention 80 g of detergent and cleaning agent is possible, a 80 g weight Manufacture detergent tablets and pack them individually, it is but also possible according to the invention, two shaped tablets weighing 40 g each to pack in a packaging to form a combination according to the invention to get.
  • the packaging system of the combination according to the invention can be of the most varied Materials exist and take on any external shape. From economic However, packaging systems are reasons and for reasons of easier processability preferred, where the packaging material is light in weight, easily process and is inexpensive. In combinations preferred according to the invention the packaging system consists of a sack or pouch made of single-layer or laminated Paper and / or plastic film.
  • the detergent tablets can be unsorted, i.e. as a loose fill, be filled into a bag made of the materials mentioned. But it is aesthetic Preferred and for sorting the combinations in secondary packaging preferred, the detergent tablets are sorted individually or in groups Fill sacks or bags. For individual application units of the detergent tablets, that are in a sack or pouch has been in technology the term "flow pack" is naturalized. Such "flow packs” can then - again preferably sorted - optionally packed in outer packaging, what the compact Offer form of the molded body underlines.
  • the sacks or bags made of single-layer or laminated paper or plastic film which are preferably used as a packaging system, can be designed in a wide variety of ways, for example as a blown-up bag without a central seam or as a bag with a central seam, which is sealed by heat (hot fusion), adhesives or adhesive tapes become.
  • Single-layer bag or sack materials are the known papers, which can optionally be impregnated, and plastic films, which can optionally be co-extruded.
  • Plastic films that can be used as a packaging system in the context of the present invention are specified , for example, in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI Verlag, Düsseldorf, 1988, page 193 .
  • Figure 111 shown there also provides information on the water vapor permeability of the materials mentioned.
  • packaging system in the context of the present invention always the primary packaging of the moldings, i.e. the packaging that is on the inside is in direct contact with the molded body surface. An optional secondary packaging no requirements are made, so that all common materials and Systems can be used.
  • the detergent tablets contain molded articles the combination according to the invention, depending on its intended use, further ingredients of detergents and cleaning agents in varying amounts. Regardless of the purpose the shaped body, it is preferred according to the invention that the or Detergent tablets have a relative equilibrium moisture content of less than 30% at 35 ° C.
  • the relative equilibrium moisture content of the detergent tablets can are determined according to common methods, whereby within the scope of the present The following procedure was chosen: A water-impermeable 1 liter container with a lid, which has a closable opening for insertion of samples, was with a total of 300 g detergent tablets filled and kept at a constant 23 ° C for 24 h in order to maintain a constant temperature of Ensure vessel and substance. The water vapor pressure in the room above the moldings can then be determined with a hygrometer (Hygrotest 6100, Testoterm Ltd., England) become. The water vapor pressure is now measured every 10 minutes, until two successive ones Values show no deviation (equilibrium moisture). The above Hygrometer allows a direct display of the recorded values in% relative humidity.
  • Bleach activators are incorporated into detergents and cleaning agents to aid in washing to achieve an improved bleaching effect at temperatures of 60 ° C. and below.
  • bleach activators can be compounds that are under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms and / or optionally substituted perbenzoic acid are used become.
  • Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines especially tetraacetylethylenediamine (TAED), acylated Triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, in particular Triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
  • TAED tetraacetylethylene
  • bleaching catalysts can be incorporated into the moldings.
  • these fabrics are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing ones Tripod ligands as well as Co, Fe, Cu and Ru amine complexes are used as bleaching catalysts usable.
  • the moldings according to the invention contain, based in each case on the entire moldings, between 0.5 and 30% by weight, preferably between 1 and 20% by weight and in particular between 2 and 15% by weight of one or more bleach activators or bleach catalysts. Depending on the intended use of the moldings produced, these amounts can vary.
  • bleach activator contents in typical universal detergent tablets between 0.5 and 10% by weight, preferably between 2 and 8% by weight and in particular between 4 and 6% by weight usual, while bleach tablets definitely have higher contents, for example between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular can have between 10 and 20% by weight.
  • the specialist is there not restricted in its freedom of formulation and can be stronger or weaker bleaching detergent tablets, detergent tablets or bleach tablets by varying the bleach activator and bleach content.
  • a particularly preferred bleach activator is N, N, N ', N'-tetraacetylethylenediamine, which is widely used in washing and cleaning agents. Accordingly, preferred detergent tablets are characterized in that that as a bleach activator tetraacetylethylenediamine in the above Amounts are used.
  • the detergent tablets according to the invention can contain other ingredients, the amounts of which vary according to the intended use straighten the molded body.
  • substances from the groups of Surfactants, builders and polymers for use in the invention Detergent tablets are suitable. The expert will not be here either Difficulties in selecting the individual components and their quantities. So a universal detergent tablet will contain higher amounts of surfactant (s), while in the case of bleach tablets, they may even be completely omitted can be.
  • the amount of builder (s) used also varies depending on intended use.
  • the or is the detergent tablets (a) detergent tablet (s), which surfactant (s) and contains builder (s).
  • laundry detergent tablets according to the invention all can usually builders used in washing and cleaning agents, in particular So zeolites, silicates, carbonates, organic cobuilders and wherever no ecological ones There are prejudices against their use - including phosphates.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • M sodium or hydrogen
  • x is a number from 1.9 to 4
  • y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514 .
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171 .
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 .
  • Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (approx ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula Na 2 O.
  • zeolite (1-n) K 2 O ⁇ Al 2 O 3 ⁇ (2 to 2.5) SiO 2 ⁇ (3.5 to 5.5) H 2 O can be described.
  • the zeolite can be used both as a builder in a granular compound and can also be used for a kind of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating the zeolite into the premix.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • phosphates are also used as builder substances possible if such use is not avoided for ecological reasons should be.
  • alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (Sodium or potassium tripolyphosphate) in the detergent and cleaning agent industry the greatest importance.
  • Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 ° C) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
  • NaH 2 PO 4 is acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate primary or monobasic potassium phosphate, potassium biphosphate, KDP
  • KH 2 PO 4 is a white salt with a density of 2.33 gcm -3 , has a melting point of 253 ° C [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is easily soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm -3 , water loss at 95 ° C), 7 moles (density 1.68 gcm -3 , melting point 48 ° C with loss of 5 H 2 O) and 12 moles. Water (density 1.52 gcm -3 , melting point 35 ° C with the loss of 5 H 2 O), becomes anhydrous at 100 ° C and changes to diphosphate Na 4 P 2 O 7 when heated. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is easily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm -3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
  • Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH.
  • Tripotassium phosphate (tertiary or triphase potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 gcm -3 , has a melting point of 1340 ° C and is easily soluble in water with an alkaline reaction. It arises, for example, when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 ° C also given 880 ° C) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° C below loss of water). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na 4 P 2 O 7 is formed by heating disodium phosphate to> 200 ° C or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
  • the decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water.
  • Potassium diphosphate potassium pyrophosphate
  • K 4 P 2 O 7 exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH value being 1% Solution at 25 ° C is 10.4.
  • Sodium and potassium phosphates in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P 2 O 5 , 25% K 2 O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry.
  • sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
  • these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.
  • Organic cobuilders which can be used in the detergent tablets according to the invention in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, Aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances are described below.
  • Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such polycarboxylic acids being among polycarboxylic acids can be understood that carry more than one acid function.
  • these are citric acid, Adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, Fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if one such use is not objectionable for ecological reasons, as well as mixtures from these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the acids themselves can also be used.
  • the acids have a builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents.
  • citric acid succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.
  • Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, this can Group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.
  • copolymeric polycarboxylates especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
  • the 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid As special copolymers of acrylic acid with maleic acid have proven suitable, the 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid.
  • Your molecular weight, based on free acids is generally from 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution be used.
  • the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers can also allylsulfonic acids, such as for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
  • allylsulfonic acids such as for example, allyloxybenzenesulfonic acid and methallylsulfonic acid
  • biodegradable polymers made from more than two different ones Monomer units, for example those which are salts of acrylic acid as monomers and the maleic acid and vinyl alcohol or vinyl alcohol derivatives or as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives contain.
  • copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
  • polyacetals which are obtained by reacting dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups can be obtained.
  • Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from Obtained polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be.
  • the hydrolysis can be carried out according to customary methods, for example acid-catalyzed or enzyme-catalyzed Procedures are carried out. They are preferably hydrolysis products with average molecular weights in the range of 400 to 500000 g / mol.
  • DE dextrose equivalent
  • Both maltodextrins with a DE between 3 and 20 and dry glucose syrups can be used with a DE between 20 and 37 as well as so-called yellow dextrins and White dextrins with higher molar masses in the range from 2000 to 30000 g / mol.
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • oxidizing agents capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608 .
  • An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable.
  • a product oxidized at C 6 of the saccharide ring
  • Oxydisuccinates and other derivatives of disuccinates are other suitable cobuilders.
  • ethylenediamine-N, N'disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are those containing zeolite and / or silicate Formulations at 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such cobuilders are described, for example, in international patent application WO 95/20029 .
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of the neutral sodium salts, z. B.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, especially if the agents also contain bleach, be preferred to use aminoalkanephosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.
  • the amount of builder is usually between 10 and 70 wt .-%, preferably between 15 and 60% by weight and in particular between 20 and 50% by weight.
  • the amount of builders used depends on the intended use, so that Bleach tablets may have higher amounts of builders (for example between 20 and 70% by weight, preferably between 25 and 65% by weight and in particular between 30 and 55% by weight), for example detergent tablets (usually 10 to 50% by weight, preferably 12.5 to 45% by weight and in particular between 17.5 and 37.5% by weight).
  • Preferred detergent tablets furthermore contain one or more Surfactant (s).
  • anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these are used. Mixtures are preferred from an application point of view from anionic and nonionic surfactants.
  • the total surfactant content of the moldings is 5 to 60 wt .-%, based on the weight of the shaped body, with surfactant contents above 15% by weight are preferred.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Preferred surfactants of the sulfonate type are C 9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C 12-18 monoolefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent ones receives alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they are the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol.
  • preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, Myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C 14 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
  • 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural Fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants including the soaps can be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or Triethanolamine.
  • the anionic surfactants are preferably in the form of their Sodium or potassium salts, especially in the form of the sodium salts.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C12-18 alcohol containing 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants either as the sole nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in the Japanese patent application JP 58/217598 are described or which preferably according to that in the international Patent application WO-A-90/13533 can be prepared.
  • nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of ethoxylated fatty alcohols, especially not more than half of it.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this rest.
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cyclic alkyl radical or an aryl
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example, according to the teaching of international application WO-A-95/07331 by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides be transferred.
  • detergent tablets are shaped preferred, which contain anionic (s) and nonionic (s) surfactant (s), with application technology Advantages from certain proportions in which the individual surfactant classes used, can result.
  • detergent tablets are particularly preferred which the ratio of anionic surfactant (s) to nonionic surfactant (s) between 10: 1 and 1:10, preferably is between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2.
  • the present invention therefore provides that at least one phase of the shaped body is free of non-ionic surfactants.
  • detergent tablets are also conceivable, in which at least one phase of the shaped body is free from anionic surfactants.
  • disintegration aids so-called tablet disintegrants
  • tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.
  • Swelling these substances, which are also called “explosives” due to their effect, enlarge their volume when water enters, whereby on the one hand the volume increases (Swelling), on the other hand, a pressure can be generated via the release of gases which can break the tablet into smaller particles.
  • Well-known disintegration tools are, for example, carbonate / citric acid systems, but also other organic ones Acids can be used.
  • Swelling disintegration aids are, for example synthetic polymers such as polyvinyl pyrrolidone (PVP) or natural polymers or modified Natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
  • PVP polyvinyl pyrrolidone
  • Natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
  • Preferred detergent tablets also contain a disintegration aid, preferably a cellulose-based disintegration aid, in quantities from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6 % By weight, in each case based on the weight of the shaped body.
  • a disintegration aid preferably a cellulose-based disintegration aid
  • Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets have such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 contain up to 6 wt .-%.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, formally speaking, is a ⁇ -1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
  • Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
  • Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
  • the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose.
  • the content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant.
  • Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.
  • the cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be compressed.
  • the detergent tablet (s) is a detergent tablet (s) which are a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the molding weight, contains.
  • microcrystalline cellulose As another disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions that only attack the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses and dissolve completely, but leave the crystalline areas (approx. 70%) undamaged.
  • a subsequent disaggregation of the microfine celluloses resulting from the hydrolysis delivers the microcrystalline celluloses, which have primary particle sizes of approx. 5 ⁇ m and compactible, for example, into granules with an average particle size of 200 ⁇ m are.
  • Disintegration-promoting systems are used in detergent tablets often so-called "shower systems" used.
  • oligomeric oligocarboxylic acids such as succinic acid, maleic acid and in particular Citric acid used in combination with carbonates or hydrogen carbonates.
  • the detergent tablet however not an "effervescent tablet", i.e. preferred washing and Detergent tablets are free of oligomeric oligocarboxylic acids, in particular Citric acid.
  • the molded body It is also technically possible to coat the molded body with a coating that covers the entire molded body.
  • Such coated detergent tablets can by spraying on a melt or solution of the coating material the molded body or immersing the molded body in the melt or solution become.
  • the or is the detergent tablets (a) detergent tablet (s), which not is / are coated with a coating that covers the entire molded body.
  • detergent tablets can be produced according to the invention, which disintegrate extremely quickly into their constituents at high hardnesses in water. Combinations are particularly preferred in the context of the present invention which the detergent tablet (s) (or detergent tablets) which is / are completely in their secondary particles in water at 30 ° C in less than 60 seconds disintegrates / disintegrate.
  • bleach, bleach activator, builder, surfactant and Disintegration aids can be the detergent tablets according to the invention other ingredients from the group that are common in washing and cleaning agents of dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, Anti-redeposition agents, graying inhibitors, color transfer inhibitors and corrosion inhibitors contain.
  • the aesthetic impression of the detergent tablets according to the invention can be colored with suitable dyes.
  • suitable dyes preferred Dyes, the selection of which is not difficult for the person skilled in the art a high storage stability and insensitivity to the other ingredients of the Medium and against light and no pronounced substantivity towards textile fibers in order not to stain them.
  • Preferred for use in the detergent tablets according to the invention are all colorants that can be oxidatively destroyed in the washing process as well Mixtures of these with suitable blue dyes, so-called blue tones. It turned out to be proven to use colorants that are in water or at room temperature liquid organic substances are soluble.
  • anionic ones are suitable Colorants, e.g. anionic nitroso dyes.
  • a possible colorant is, for example Naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020), which is a commercial product available for example as Basacid® Green 970 from BASF, Ludwigshafen is, and mixtures of these with suitable blue dyes.
  • Pigmosol® Blue 6900 (CI 74160), Pigmosol® Green 8730 (CI 74260), Basonyl® Red 545 FL (CI 45170), Sandolan® Rhodamine EB400 (CI 45100), Basacid® Yellow 094 (CI 47005), Sicovit® Patent Blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI 74160), Supranol® Blau GLW (CAS 12219-32-8, CI Acidblue 221)), Nylosan® Yellow N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan® Blue (CI Acid Blue 182, CAS 12219-26-0).
  • colorants When choosing the colorant, care must be taken to ensure that the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the washing or cleaning agents varies. In the case of colorants which are readily water-soluble, for example the above-mentioned Basacid® green or the above-mentioned Sandolan® blue, colorant concentrations are typically selected in the range from a few 10 -2 to 10 -3 % by weight.
  • the suitable concentration of the colorant in washing or cleaning agents is typically a few 10 -3 to 10 -4 % by weight.
  • the moldings can be optical brighteners of the type of derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar built-up compounds that instead of the morpholino group a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group wear. Brighteners of the substituted diphenylstyryl type may also be present be, e.g.
  • the optical brighteners are in the detergent tablets according to the invention in concentrations between 0.01 and 1 wt .-%, preferably between 0.05 and 0.5 wt .-% and in particular between 0.1 and 0.25% by weight, based in each case on the entire molded body.
  • Fragrances are added to the agents according to the invention to give the aesthetic impression to improve the products and give the consumer a visual and to provide sensory "typical and distinctive" product.
  • perfume oils or fragrances can individual fragrance compounds, e.g. the synthetic Products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type be used. Fragrance compounds of the ester type are e.g.
  • benzyl acetate Phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
  • To the etheme include, for example, benzyl ethyl ether, the aldehydes e.g.
  • the linear alkanals with 8-18 C atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, Lilial and Bourgeonal
  • ketones e.g. the Jonone, ⁇ -isomethylionon and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, belong to the hydrocarbons mainly the terpenes like limes and pinene.
  • mixtures are preferred different fragrances are used, which together make an appealing Generate fragrance.
  • perfume oils can also contain natural fragrance mixtures, as they are accessible from plant sources, e.g. Pine, citrus, jasmine, patchouly, Rose or ylang-ylang oil.
  • plant sources e.g. Pine, citrus, jasmine, patchouly, Rose or ylang-ylang oil.
  • the content of the detergent tablets according to the invention is usually in the range of fragrances up to 2% by weight of the total formulation.
  • the fragrances can can be incorporated directly into the agents according to the invention, but it can also be advantageous be to apply the fragrances to carriers that will adhere the perfume to the laundry intensify and through a slower fragrance release for long-lasting fragrance of the textiles to care.
  • Cyclodextrins for example, have proven useful as such carrier materials, the cyclodextrin-perfume complexes additionally with other auxiliaries can be coated.
  • Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question.
  • Bacterial strains or are particularly well suited Mushrooms such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents.
  • Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or Protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, but especially mixtures containing cellulase of special interest.
  • Peroxidases or oxidases have also been found in some Cases proved to be suitable.
  • the enzymes can be adsorbed on carriers and / or be embedded in coating substances to protect them against premature decomposition.
  • the Proportion of the enzymes, enzyme mixtures or enzyme granules in the inventive Shaped bodies can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 % By weight.
  • the detergent tablets can also contain components which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect is particularly evident when a textile is dirty is already several times with a detergent according to the invention, this contains oil and fat-dissolving component, was washed.
  • nonionic cellulose ethers such as methyl cellulose and methylhydroxy-propyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and of hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether, as well as those known from the prior art Polymers of phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.
  • Preferred detergent tablets in the context of the present invention are obtained by compressing a particulate premix from at least one Granules containing surfactant and at least one powdered powder added afterwards Component received.
  • the surfactant-containing granules can be made using conventional granulation processes such as mixer and plate granulation, fluidized bed granulation, extrusion, Pelleting or compacting can be made. It is there for the later washing and Detergent tablets are advantageous if the premix to be pressed is Bulk density of at least 500 g / l, preferably at least 600 g / l and in particular above 700 g / l. Another benefit can come from a narrower particle size distribution of the surfactant granules used result.
  • detergent tablets are preferred in which the granules Particle sizes between 10 and 4000 ⁇ m, preferably between 100 and 2000 ⁇ m and in particular between 600 and 1400 microns.
  • the premix with finely divided surface treatment agents be "powdered". This can affect the nature and physical properties both the premix (storage, pressing) and the finished detergent tablets be an advantage.
  • Fine powdering agents are in the stand well-known in the art, mostly zeolites, silicates or other inorganic salts be used.
  • the premix is preferred with finely divided zeolite "powdered", with zeolites of the faujasite type being preferred.
  • zeolites of the faujasite type As part of the present Invention characterizes the term "faujasite type zeolite" all three zeolites, which form the faujasite subgroup of zeolite structure group 4 (compare Donald W.
  • zeolites Mixtures or cocrystallizates of faujasite-type zeolites with other zeolites, which do not necessarily have to belong to the zeolite structure group 4 are used as powdering agents can be used, it being advantageous if at least 50% by weight of the powdering agent consist of a zeolite of the faujasite type.
  • detergent tablets are shaped preferred, which consist of a particulate premix, the granular components and subsequently mixed powdered substances, the or one of the subsequently mixed powdered components a zeolite of the faujasite type with particle sizes below 100 ⁇ m, preferably below 10 ⁇ m and in particular is below 5 ⁇ m and is at least 0.2% by weight, preferably at least 0.5% by weight and makes up in particular more than 1% by weight of the premix to be pressed.
  • the finely divided processing components with the particle sizes mentioned above can be mixed dry with the premix to be pressed. It is also possible and preferred, by adding small amounts of liquid substances to the surface to "glue" the coarser particles.
  • These powdering processes are in the prior art Technology described broadly and familiar to the expert.
  • liquid components that are suitable for promoting the adhesion of the powdering agents for example nonionic Surfactants or aqueous solutions of surfactants or other detergents and cleaning agents be used. It is within the scope of the present invention preferred, as a liquid coupling agent between finely divided powdering agent and use coarse-grained particles of perfume.
  • the premixes are produced in a so-called The die is compacted between two punches to form a solid compact.
  • This The process which is briefly referred to below as tableting, is divided into four Sections: dosage, compression (elastic deformation), plastic deformation and Ejection.
  • Tableting takes place in commercially available tablet presses, which are basically single or Double stamps can be equipped. In the latter case, it is not only the upper stamp used to build up pressure, also the lower stamp moves during the Pressing process towards the upper punch, while the upper punch presses down.
  • eccentric tablet presses which the one or more stamps are attached to an eccentric, which in turn on one Axis is mounted with a certain rotational speed. The movement of this Press ram is comparable to the way a conventional four-stroke engine works.
  • the pressing can be done with one upper and one lower stamp, but several can also be used Stamp be attached to an eccentric disc, the number of die holes is expanded accordingly.
  • the throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses are selected, on which a so-called Matrix table a larger number of matrices is arranged in a circle.
  • the number of matrices varies between 6 and 55, depending on the model, with larger matrices also are commercially available.
  • Each die on the die table is an upper and lower stamp assigned, with the pressing pressure again being active only through the upper or lower stamp, but can also be built using both stamps.
  • the matrix table and the Stamps move around a common vertical axis, the stamp with the help of rail-like curved tracks during the circulation in the positions for filling, Compression, plastic deformation and discharge are brought.
  • Rotary presses can also be equipped with two filling shoes to increase throughput be, whereby only a semicircle is run through to produce a tablet got to.
  • Several filling shoes are used to produce two- and multi-layer molded articles arranged one behind the other without the slightly pressed first layer in front of the further filling is ejected.
  • By appropriate process control are in this way also coated and dot tablets can be produced, which have an onion skin-like structure have, whereby in the case of the point tablets the top of the core or the core layers is not covered and therefore remains visible.
  • Rotary tablet presses are also included Single or multiple tools can be equipped, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing.
  • the throughputs of modern rotary tablet presses are over a million tablets per hour.
  • Tableting machines suitable for the purposes of the present invention are, for example available from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMAmaschinessysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms.
  • Other providers are, for example Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy N.V., Halle (BE / LU) and Mediopharm Kamnik (SI).
  • the hydraulic double-pressure press is particularly suitable HPF 630 from LAEIS, D.
  • Tableting tools are for example from the company Adams Tablettierwerkmaschinen, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter negligencebau, Tamm available.
  • Other providers are e.g. the Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).
  • the moldings can be made in a predetermined spatial shape and a predetermined size being made up of several phases, i.e. Layers, inclusions or Cores and rings exist. Practically all sensibly manageable come as a room shape Configurations into consideration, for example, the training as a board, the staff or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces as well as in particular cylindrical configurations with circular or oval cross section. This last embodiment covers the presentation form of the Tablet up to compact cylinder pieces with a ratio of height to diameter above 1.
  • the portioned compacts can each be separate individual elements be formed, the predetermined dosage of detergents and / or cleaning agents equivalent. However, it is also possible to form compacts that have a plurality connect such mass units in a compact, in particular by predetermined The easy separation of portioned smaller units is provided for predetermined breaking points is.
  • the formation of the portioned compacts as Tablets, in the shape of a cylinder or cuboid, are expedient, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred.
  • Commercial hydraulic presses, Eccentric presses or rotary presses are suitable devices in particular for the production of such compacts.
  • the spatial shape of another embodiment of the shaped body is in its dimensions the induction chamber of commercial household washing machines adapted so that the Shaped bodies can be metered directly into the induction chamber without a metering aid, where it dissolves during the induction process.
  • a metering aid where it dissolves during the induction process.
  • the detergent tablets are easily possible via a dosing aid.
  • Another preferred multi-phase molded body that can be produced has one plate-like or plate-like structure with alternating thick long and thin short segments, so that individual segments of this "multi-phase bar" at the predetermined breaking points, which represent the short thin segments, broken off and entered into the machine can be.
  • This principle of the "bar-shaped" shaped body detergent can also be in other geometric shapes, for example vertically standing triangles, which are connected to each other only on one of their sides, realized become.
  • multi-phase shaped bodies can also be produced in the form of toroidal core tablets, core jacket tablets or so-called "bulleye" tablets.
  • An overview of such embodiments of multi-phase tablets is described in EP 055 100 (Jeyes Group).
  • This document discloses toilet block detergents which comprise a molded body of a slowly soluble detergent composition in which a bleach tablet is embedded.
  • this document discloses the most varied designs of multi-phase tablets, from simple multi-phase tablets to complicated multi-layer systems with inlays.
  • ⁇ stands for diametral fracture stress (DFS) in Pa
  • P is the force in N which leads to the pressure exerted on the molded body, which is the Breakage of the shaped body causes
  • D is the shaped body diameter in meters
  • t is the Height of the molded body.
  • a surfactant granulate was mixed with further processing components and pressed to give tablets on an eccentric tablet press.
  • the composition of the surfactant granules is given in Table 1 below, the composition of the premix to be pressed (and thus the composition of the moldings) can be found in Table 2.
  • Granular surfactant [% by weight] C 9-13 alkyl benzene sulfonate 19.4 C 12-18 fatty alcohol sulfate 5.2 C 12-18 fatty alcohol with 7 EO 4.8 C 12-16 alkyl 1,4-glycoside 1.0 Soap 1.6 sodium 17 sodium silicate 5.6 Zeolite A (anhydrous active substance) 28.5 optical brightener 0.3 Na-hydroxyethane-1,1-diphosphonate 0.8 Acrylic acid-maleic acid copolymer 5.6 Water, salts rest Premix [wt%] Surfactant granules 62.6 Sodium percarbonate 17.4 tetraacetylethylenediamine 7.3 foam inhibitor 3.5 enzymes 1.7 Perfume 0.5 Zeolite A (Wessalith® P, Degussa) 1.0 cellulose 5.0
  • the tablettable premixes were compressed in a Korsch eccentric press into tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g).
  • the pressure was adjusted so that three series of molded bodies were obtained (E, E ', E "and V, V', V"), which differ in their hardness.
  • the shaped bodies E according to the invention were packaged after manufacture for a combination of the invention by two tablets in a flow pack of laminate foil (aluminized film, thickness: 35 microns, the water vapor permeability of 1 g / m 2/24 hr) were packed; Comparative Examples V were stored open. The hardness and disintegration time of all molded body series were measured before packaging.
  • Both shaped bodies (combination E according to the invention and comparative shaped body V) were stored for 14 days in a climatic cell at 23 ° C. and 85% relative atmospheric humidity (test conditions according to DIN 53122), after which the hardness and disintegration times were determined again.
  • the hardness of the tablets was determined by deformation of the tablet measured to break, the force acting on the side surfaces of the tablet and the maximum force that the tablet withstood was determined.
  • the tablet was placed in a beaker with water (600 ml of water, temperature 30 ° C.) and the time until the tablet disintegrated completely.
  • 3 tablets were placed in the washdown chamber of a household washing machine (AEG ⁇ ko Lavamat) and a 40 ° C program was started without prewashing. After the induction process was completed, the residues in the induction chamber were dried and weighed.
  • Table 3 shows impressively that the hardness and disintegration times of the detergent tablets change only slightly in the combinations according to the invention, while the moldings of comparative example V unacceptably harden and extremely bad or no longer decay.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Packages (AREA)

Claims (10)

  1. Combinaison d'un(de) corps façonné(s) de produit de lavage et de nettoyage et d'un système de conditionnement contenant le ou les corps façonnés de produit de lavage et de nettoyage,
    caractérisée en ce que
    le/les corps façonné(s) contient/contiennent du percarbonate de sodium en quantités de 5 à 50 % en poids, et le système de conditionnement présente un taux de perméabilité à la vapeur d'eau de 0,1 g/m2/jour à moins de 20 g/m2/jour, lorsque le système de conditionnement est conservé à 23°C et à une humidité relative à l'équilibre de 85 %.
  2. Combinaison selon la revendication 1,
    caractérisée en ce que
    le système de conditionnement présente un taux de perméabilité à la vapeur d'eau de 0,5 g/m2/jour à moins de 15 g/m2/jour.
  3. Combinaison selon la revendication 1 ou 2,
    caractérisée en ce que
    le ou les corps façonnés de produit de lavage et de nettoyage présente/présentent une humidité relative à l'équilibre de moins de 30 % à 35°C.
  4. Combinaison selon l'une quelconque des revendications 1 à 3,
    caractérisée en ce que
    le système de conditionnement consiste en un sachet ou une poche en une pellicule de matière plastique et/ou en papier stratifiés ou mono-couches.
  5. Combinaison selon la revendication 4,
    caractérisée en ce que
    le système de conditionnement consistant en un sachet ou une poche est constitué d'une pellicule de matiére plastique monocouche ou stratifiée ayant une épaisseur de 10 à 200 µm, de préférence de 20 à 100 µm, et en particulier de 25 à 50 µm.
  6. Combinaison selon l'une quelconque des revendications 1 à 5,
    caractérisée en ce que
    le système de conditionnement ne comprend pas de carton à base de papier revêtu de cire.
  7. Combinaison selon l'une quelconque des revendications 1 à 6
    caractérisée en ce que
    le ou les corps façonnés de produit de lavage et de nettoyage est/sont un(des) comprimé(s) de produit de lavage contenant un(des) tensio-actif(s) et un(des) adjuvant(s) actif(s) de détergence.
  8. Combinaison selon l'une quelconque des revendications 1 à 7,
    caractérisée en ce que
    le ou les corps façonnés de produit de lavage et de nettoyage est/sont un(des) comprimé(s) de produit de lavage qui contient(contiennent) un adjuvant de désintégration, de préférence un adjuvant de désintégration à base de cellulose, de préférence sous forme granulaire, co-granulée ou compactée, en quantités de 0,5 à 10 % en poids, de préférence de 3 à 7 % en poids, et en particulier de 4 à 6 % en poids, dans chaque cas par rapport au poids du corps façonné.
  9. Combinaison selon l'une quelconque des revendications 1 à 8,
    caractérisé en ce que
    le ou les corps façonnés de produit de lavage et de nettoyage est/sont un(des) comprimé(s) de produit de lavage qui n'est/ne sont pas enrobé(s) avec un enrobage qui recouvre la totalité des corps façonnés.
  10. Combinaison selon l'une quelconque des revendications 1 à 9,
    caractérisée en ce que
    le ou les corps façonnés de produit de lavage et de nettoyage est/sont un(des) comprimé(s) de produit de lavage qui se désintègre(nt) complètement en ses(leurs) particules secondaires en moins de 60 secondes dans de l'eau à 30°C.
EP99952556A 1998-10-21 1999-10-12 Combinaison de corps faconnes d'agents de lavage et de nettoyage avec un emballage Revoked EP1123380B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19848457 1998-10-21
DE19848457A DE19848457A1 (de) 1998-10-21 1998-10-21 Wasch- und Reinigungsmittelformkörper/Verpackung-Kombination
PCT/EP1999/007665 WO2000023557A1 (fr) 1998-10-21 1999-10-12 Combinaison de corps façonnes d'agents de lavage et de nettoyage avec un emballage

Publications (2)

Publication Number Publication Date
EP1123380A1 EP1123380A1 (fr) 2001-08-16
EP1123380B1 true EP1123380B1 (fr) 2002-12-18

Family

ID=7885139

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Application Number Title Priority Date Filing Date
EP99952556A Revoked EP1123380B1 (fr) 1998-10-21 1999-10-12 Combinaison de corps faconnes d'agents de lavage et de nettoyage avec un emballage

Country Status (5)

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EP (1) EP1123380B1 (fr)
AT (1) ATE230015T1 (fr)
DE (2) DE19848457A1 (fr)
ES (1) ES2190665T3 (fr)
WO (1) WO2000023557A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000077151A1 (fr) * 1999-06-16 2000-12-21 Henkel Kommanditgesellschaft Auf Aktien Detergents et nettoyants sous forme de corps moules
WO2000078910A1 (fr) * 1999-06-19 2000-12-28 Henkel Kommanditgesellschaft Auf Aktien Procede de pressage pour comprimes d'agents de lavage et de nettoyage
DE19937428A1 (de) * 1999-08-07 2001-02-08 Henkel Kgaa Reinigungs- und Waschmittelformkörper
DE10044495A1 (de) * 2000-09-08 2002-10-24 Henkel Kgaa Formkörper
GB2386122A (en) 2002-03-06 2003-09-10 Reckitt Benckiser Nv Improvements in or relating to packaging
EP2270123A1 (fr) * 2009-06-30 2011-01-05 The Procter and Gamble Company Compositions de blanchiment de particules emballées

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9021761D0 (en) * 1990-10-06 1990-11-21 Procter & Gamble Detergent compositions
DK0634484T3 (da) * 1993-07-14 1999-05-10 Procter & Gamble Detergentemballeringskombination
EP0634485B1 (fr) * 1993-07-14 2001-09-05 The Procter & Gamble Company Combinaison détergent-conditionnement
EP0899208B1 (fr) * 1997-09-01 2000-12-27 The Procter & Gamble Company Dispositif d'emballage de tablettes détergentes

Also Published As

Publication number Publication date
ES2190665T3 (es) 2003-08-01
DE19848457A1 (de) 2000-04-27
ATE230015T1 (de) 2003-01-15
DE59903872D1 (de) 2003-01-30
EP1123380A1 (fr) 2001-08-16
WO2000023557A1 (fr) 2000-04-27

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