EP1123378B1 - Corps moules detergents et nettoyants munis d'un systeme granule effervescent exempt d'eau - Google Patents

Corps moules detergents et nettoyants munis d'un systeme granule effervescent exempt d'eau Download PDF

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Publication number
EP1123378B1
EP1123378B1 EP99947459A EP99947459A EP1123378B1 EP 1123378 B1 EP1123378 B1 EP 1123378B1 EP 99947459 A EP99947459 A EP 99947459A EP 99947459 A EP99947459 A EP 99947459A EP 1123378 B1 EP1123378 B1 EP 1123378B1
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EP
European Patent Office
Prior art keywords
weight
acid
process according
effervescent system
granulated
Prior art date
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EP99947459A
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German (de)
English (en)
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EP1123378A1 (fr
Inventor
Andreas Lietzmann
Christian Block
Monika Böcker
Markus Semrau
Katrin Schnepp-Hentrich
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0052—Gas evolving or heat producing compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof

Definitions

  • the present invention is in the field of compact molded articles that are washable have cleaning-active properties.
  • Such detergent tablets include for example detergent tablets for washing textiles, Molded detergent for machine dishwashing or hard cleaning Surfaces, bleach tablets for use in washing machines or dishwashers, Water softening tablets or stain tablets.
  • the invention relates Detergent tablets that are used to wash textiles in one Household washing machine used and briefly referred to as detergent tablets.
  • Detergent tablets are widely described in the prior art are becoming increasingly popular with consumers because of the simple dosage.
  • Tableted detergents and cleaning agents have a number of powdered detergents Advantages: They are easier to dose and to handle and because of their compact structure Advantages in storage and transport. Also in the patent literature detergent tablets are therefore comprehensively described.
  • the delayed Disintegration of the moldings also has the disadvantage that they are customary Detergent tablets not through the induction chamber of household washing machines Allow to be flushed in, as the tablets do not get in quickly enough Secondary particles disintegrate, which are small enough to enter the induction chamber Washing drum to be washed in.
  • US 5, 114, 647 discloses cleaning particles which contain about 38% by weight of an effervescent system composed of Na 2 CO 3 and organic acid and more than 5% by weight of anionic surfactant.
  • the unpublished EP 881 282 A1 discloses tablets which also contain effervescent systems made of Na 2 CO 3 and organic acid as well as anionic surfactants. No information is given in these documents on water-free production or particle sizes of the shower system.
  • a method for producing a cogranulate which can be used in detergent tablets is described in WO98 / 14548 (Schmitz).
  • a citric acid solution is placed on a solid bed of soda moved in the mixer in order to produce granules which contain sodium bicarbonate, sodium citrate and a portion of residual soda.
  • the process disclosed in this document neither provides an effervescent system, nor is the granulation carried out without water.
  • the surfactant (s), builder and optionally contain further detergent and cleaning agent components are disclosed, the surfactant (s), builder and optionally contain further detergent and cleaning agent components.
  • the moldings disclosed here contain 1 to 10% by weight of one or more swellable, water-insoluble disintegration aid and 3 to 60 wt .-% of a gas-generating shower system, the swellable agent or the components of the shower systems compounded with other ingredients of the detergent and cleaning agent can also be mixed separately.
  • Information on a co-granulated shower system or for the water-free production of shower granules are this document not to be removed.
  • the present invention was based on the object of providing moldings which are characterized by short disintegration times with a given hardness and thus also dispense via the induction chamber of household washing machines. there should also be a simple and inexpensive method for producing such advantageous Shaped bodies are provided.
  • the invention relates to detergent tablets made of compressed, Particulate detergents and cleaning agents containing 5 to 50% by weight of anionic (s) Surfactant (s), which is an anhydrous granulated spray system in amounts of 1 to 20% by weight, each based on the molded article, containing at least 80 wt .-% of the particles of the water-free granulated shower system have particle sizes above 600 ⁇ m.
  • anionic (s) Surfactant (s) which is an anhydrous granulated spray system in amounts of 1 to 20% by weight, each based on the molded article, containing at least 80 wt .-% of the particles of the water-free granulated shower system have particle sizes above 600 ⁇ m.
  • a shower system generally consists of two components that are exposed to water can react with one another to release one or more gases. Although it is here shower systems are based on a multitude of technical possibilities Carbonates or bicarbonates mixed with acidic components (so-called acidifiers) most widespread. As part of the In the present invention, the ingredients of the effervescent system become a cogranulate processed, using an anhydrous granulation process. The effervescent granules obtained give the washing and Detergent tablets advantageous compared to the use of raw materials alone Characteristics.
  • the washing and Detergent tablets the water-free granulated shower system in quantities from 1 to 20% by weight, preferably from 2 to 18% by weight, particularly preferably from 3 to 15% by weight and in particular from 5 to 10% by weight, in each case based on the shaped body.
  • the contained in the detergent tablets according to the invention water-free granulated shower system is used in a coarser form. Although one could assume that a fine incorporation due to the more homogeneous distribution and the higher reaction surface leads to better results, it has been shown that exceeding a certain particle size the decay times at the desired Hardness further minimized.
  • Particularly preferred detergent tablets are characterized in that at least 90% by weight and in particular that Total amount of particles in the water-free granulated shower system have above 600 ⁇ m.
  • shower systems mostly consist of carbonates and / or Hydrogen carbonates and acidic components (acidifying agents) which are suitable To release carbon dioxide from them.
  • carbonates and / or hydrogen carbonates in the context of the present invention are the alkali metal salts and among them the sodium salts particularly preferred.
  • the relevant ones do not have to be pure Alkali metal carbonates or bicarbonates are used; rather mixtures different carbonates and hydrogen carbonates from washing technology interest or be preferred for economic reasons.
  • acidifying agents that release carbon dioxide from the alkali salts in aqueous solution are, for example, boric acid and alkali metal bisulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used.
  • organic acidifiers are used, with citric acid being a particularly preferred Acidifier is.
  • the other fixed ones can also be used in particular Mono-, oligo- and polycarboxylic acids. From this group tartaric acid is preferred, Succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid as well Polyacrylic acid.
  • Organic sulfonic acids such as amidosulfonic acid can also be used.
  • Sokalan® DCS Commercially available and as an acidifying agent in the context of the present Sokalan® DCS (trademark of BASF) is also preferably used according to the invention Mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight).
  • detergent tablets which as a water-free granulated shower system is a granulate made of carbonate (s) and / or hydrogen carbonate (s) with acidifying agent (s) in a weight ratio of 1:20 to 20: 1, preferably 1: 9 to 9: 1.
  • the components of the shower system carbonate (s) and / or granulate hydrogen carbonate (s) and acidifying agent
  • the components of the shower system carbonate (s) and / or granulate hydrogen carbonate (s) and acidifying agent
  • the above usable shower system compounds with at least 60 wt .-% shower system the above as the preferred particle size distribution.
  • water-free contain granulated, shower system-containing compounds which have at least 60% by weight shower system (carbonate (s) and / or hydrogen carbonate (s) and acidifying agent), each based on the weight of the compound, preferably at least 80% by weight, preferably at least 90% by weight and in particular the total amount of the compounds have particle sizes above 600 ⁇ m.
  • shower system carbonate (s) and / or hydrogen carbonate (s) and acidifying agent
  • Disintegrants based on cellulose are used as preferred additional 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 to 6 wt .-% included.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, viewed formally, 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 by 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 pressed.
  • Detergent tablets which contain disintegrants in granular or, if appropriate, cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants.
  • the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
  • the above-mentioned coarser disintegration aids based on cellulose and described in more detail in the cited documents are preferably to be used as disintegration aids in the context of the present invention and are commercially available, for example, under the name Arbocel® TF-30-HG from Rettenmaier.
  • Particularly preferred detergent tablets in the context of the present invention additionally contain a disintegration aid, preferably a Disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 wt .-%, 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 Disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 wt .-%, 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.
  • 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, the primary particle sizes of approx. 5 ⁇ m have and for example to granules with an average particle size of 200 microns are compactable.
  • Such coated washing and Detergent tablets can by spraying a melt or solution of the Coating material on the molded body or immersing the molded body in the melt or solution can be prepared.
  • the laundry detergent and cleaning product tablets are not one Coating, which covers the entire molded body, coated.
  • detergent tablets can be produced according to the invention, which disintegrate into their constituents extremely quickly in water. Washing and washing are particularly preferred in the context of the present invention Detergent tablets that are in water at 30 ° C in less than 60 seconds completely disintegrate into their secondary particles, which are so small that they overlap Have the washing-in chamber of a household washing machine wash in.
  • Disintegration aids to be used optionally contain the Detergent tablets according to the invention further detergents and Detergent ingredients, especially from the groups of surfactants, builders, Bleaches, bleach activators, optical brighteners, dyes and fragrances etc. These Substances are described below.
  • the first process step is the production of a water-free granulated shower system, its presence in the detergent tablets according to the invention gives the beneficial properties.
  • granulation aids so-called Granulating liquids
  • the granulating liquid being liquid bridges forms between the individual particles and thus to form agglomerates with a "raspberry structure" contributes.
  • Water or aqueous solutions are often used as the granulation liquid used, which is to be expressly avoided in the process according to the invention in order to to avoid a premature reaction of the components of the shower system.
  • the components of the shower system to mix dry together and a press agglomeration submit.
  • the press agglomeration process which is the mixture of the components the shower system is subjected to, can be realized in various devices become. Depending on the type of agglomerator used, different press agglomeration processes are used distinguished. The three most common and within the scope of the present The preferred press agglomeration process is extrusion Roller pressing or compacting and hole pressing (pelleting), so that in the frame preferred press agglomeration operations of the present invention extrusion, roll compacting and pelleting processes.
  • the The method according to the invention is carried out by means of roller compaction.
  • the mixture of the components of the shower system is targeted between two smooth or metered rollers provided with depressions of a defined shape and between the two rollers under pressure to form a leaf-shaped compact, the so-called Schülpe, rolled out.
  • the rollers exert a high line pressure on the premix and can be additionally heated or cooled as required.
  • smooth rollers one obtains smooth, unstructured sash bands, while through the Structured slugs are generated using structured rollers can, in which, for example, certain forms of the later effervescent granules are specified can be.
  • the cuff belt is subsequently subjected to a knock-off and crushing process broken into smaller pieces and can thus become granules are processed by further known surface treatment processes can be refined.
  • the method according to the invention is carried out by means of pelleting.
  • the mixture of the components of the shower system is applied to a perforated surface and pressed through the holes by means of a pressure-generating body.
  • the premix is compressed under pressure, pressed through a perforated surface by means of a rotating roller in the form of fine strands, and finally comminuted into granules using a knock-off device.
  • the most varied configurations of the pressure roller and perforated die are conceivable here. For example, flat perforated plates are used as well as concave or convex ring matrices through which the material is pressed using one or more pressure rollers.
  • the press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation.
  • An apparatus suitable for carrying out the method according to the invention is described, for example, in German laid-open specification DE 38 16 842 (Schlüter GmbH).
  • the ring die press disclosed in this document consists of a rotating ring die interspersed with press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge.
  • the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved.
  • the granulation capacity of the shower system can be adjusted or improved by auxiliary substances become. All raw materials common in detergents and cleaning agents can be used for this are used, whereby fatty alcohol ethoxylates with different degrees of ethoxylation, Polyethylene glycols or paraffins are preferred.
  • one or more are / are carried out in process step a) Carbonate (s) and / or bicarbonate (s) with one or more acidifying agent (s) dry mixed together and a press agglomeration, preferably one Roll compaction, subjected.
  • the detergent tablets according to the invention are also certain weight ratios in the method according to the invention particularly advantageous between the individual components of the shower system. So are Preferred processes in which the carbonate (s) and / or hydrogen carbonate (s) with the acidifying agent (s) in a weight ratio of 1:20 to 20: 1, preferably 1: 9 to 9: 1, mixed and press agglomerated.
  • the alkali metal salts preferably the Sodium salts used, with sodium hydrogen carbonate and sodium carbonate especially are preferred.
  • One or more substances are preferably used as acidifying agents from the group of solid organic di-, tri- and Oligocarboxylic acids are used, with citric acid being particularly preferred. In terms of Further applicable acidifying agents are referred to the above statements.
  • the particle sizes of the water-free granulated shower system and the amounts in which the water-free granulated shower system in the process according to the invention is used, are completely analogous to the above information.
  • Step a) So point in preferred method at least 90 wt .-% and in particular the total amount of in Step a) produced shower system particle sizes above 600 microns.
  • Further preferred processes are characterized in that the one produced in step a) Effervescent granules 1 to 20% by weight, preferably 2 to 18% by weight, particularly preferably 3 up to 15% by weight and in particular 5 to 10% by weight of the premix to be pressed accounts.
  • the washing and Detergent tablets in addition to the water-free granulated shower system Detergent and cleaning agent ingredients.
  • the effervescent granules produced in step a) are processed in step b) with at least a surfactant-containing granulate to a premix to be pressed with a Bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l combined.
  • the production of the surfactant-containing granules can be done by conventional technical means Granulation processes such as compacting, extrusion, mixer granulation, pelleting or fluidized bed granulation. It is there for later washing and Detergent tablets are advantageous if the premix to be pressed is a Has bulk density that comes close to the usual compact detergent. In particular it is preferred that the premix to be compressed has a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l.
  • the granules containing surfactant also suffice in certain preferred process variants
  • sectionchen relienkriterien Methods according to the invention are preferred in which the surfactant-containing granules particle sizes between 100 and 2000 microns, preferably between 200 and 1800 ⁇ m, particularly preferably between 400 and 1600 ⁇ m and in particular between 600 and 1400 ⁇ m.
  • the surfactant granules preferably also contain carriers, which particularly preferably come from the group of builders.
  • Particularly advantageous Processes are characterized in that the surfactant-containing granules are anionic and / or non-ionic surfactants and builders and total surfactant contents of at least 10% by weight, preferably at least 20% by weight and in particular at least 25% by weight.
  • the surfactant granules contain surface-active substances from the group of anionic, nonionic, zwitterionic or cationic Surfactants, anionic surfactants for economic reasons and because of their Range of services are clearly preferred.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are preferably 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 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 especially the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty 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, petrochemical-based straight-chain alkyl radical 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 in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular 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).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use 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 detergent tablets contain 5 to 50% by weight anionic surfactant (s).
  • anionic surfactant s
  • washing and Preferred detergent tablets the 7.5 to 40 wt .-% and in particular 10 to 20 % By weight of anionic surfactant (s), based in each case on the molding weight.
  • anionic surfactants When selecting the anionic surfactants that are used in the washing and Detergent tablets are used, freedom of formulation no framework conditions to be observed in the way.
  • Preferred washing and However, detergent tablets have a soap content of 0.2% by weight, based on the total weight of the molded body.
  • Preferred to use Anionic surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates preferred detergent tablets 2 to 20 wt .-%, preferably 2.5 up to 15% by weight and in particular 5 to 10% by weight of fatty alcohol sulfate (s), in each case based on the molded body weight.
  • 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 can 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 with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 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.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, such as them are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG).
  • Alkypolyglycosides that can be used satisfy the general formula RO (G) z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
  • Linear alkyl polyglucosides ie alkyl polyglycosides, are preferably used in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.
  • the detergent tablets according to the invention can preferably alkyl polyglycosides included, with APG contents of the molded articles being above 0.2% by weight on the entire molded body, are preferred.
  • Particularly preferred washing and Detergent tablets contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5 wt .-% and in particular from 0.5 to 3 wt .-%.
  • 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 the 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 the 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.
  • builders are the most important ingredients of Detergents and cleaning agents.
  • Detergent tablets can all be used in washing and cleaning agents
  • Builders may be included, in particular thus zeolites, which according to the invention are within a certain particle size range used silicates, carbonates, organic Cobuilder and - where there are no ecological prejudices against their use - also the Phosphates.
  • the builders mentioned can also be used in surfactant-free moldings are, so that it is possible according to the invention to produce moldings which for Water softening or as bleach tablets can be used.
  • processes use surfactant granules which, in addition to surfactant (s) as a carrier, builders (e) contain.
  • Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 ⁇ H 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, 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, 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 disilicates Na 2 Si 2 O 5 ⁇ yH 2 O are preferred, with ⁇ -sodium disilicate being obtainable for example by the method / described in the international patent application WO-A-91 08,171th
  • 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 provide 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.
  • zeolite X and zeolite A (about 80% by weight of zeolite X)
  • VEGOBOND AX® sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula nNa 2 O ⁇ (1-n) K 2 O ⁇ Al 2 O 3 ⁇ (2 - 2.5) SiO 2 ⁇ (3.5 - 5.5) H 2 O
  • the zeolite can be used both as a builder in a granular compound, and can also be used for a kind of "purging" of the entire mixture to be pressed, 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, provided that 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 differentiate 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 fabrics 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 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white, water-soluble powders that 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 arises 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 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light 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 mol. (Density 2.066 gcm -3 , water loss at 95 °), 7 mol. (Density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. Water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and changes to diphosphate Na 4 P 2 O 7 when heated more strongly. 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 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when Thomas slag is heated 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 °, also stated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with 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 ° 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 ° 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 Na 5 P 3 O 10 (sodium tripolyphosphate)
  • sodium tripolyphosphate sodium tripolyphosphate
  • n 3
  • Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
  • 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 can be used in the laundry 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 relative molecular mass 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), a UV detector being used.
  • GPC gel permeation chromatography
  • the measurement was carried out 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 relative molecular mass, 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 either be 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 which 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 and 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 can be
  • 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 present in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and at most contain two acid groups.
  • Such cobuilders are used, for example, in the international Patent application WO 95/20029 described.
  • 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 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 can 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).
  • premix in addition to the surfactant granulate and the water-free granulated shower system, this can also be done Compressing premix in the process according to the invention contain further ingredients.
  • the premix additionally contains 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 weight of the premix.
  • the premix additionally contains one or more Substances from the group of bleaching agents, bleach activators, enzymes, pH regulators, fragrances, Perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors. These substances are described below.
  • bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxyaloacidoperoxycaproic acid (P ⁇ ) )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipinic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxydiperoxybiperyldoxybiperyldiacyldiperoxy-diper
  • Chlorine or. Can also be used as bleaching agents in moldings for automatic dishwashing
  • Bromine-releasing substances are used.
  • appropriate chlorine or bromine releasing materials come, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with Cations such as potassium and sodium are considered.
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • bleach activators can be used as the sole component or be incorporated as an ingredient of component b).
  • Can be used as bleach activators Compounds containing aliphatic peroxocarboxylic acids under perhydrolysis conditions preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally result in substituted perbenzoic acid can be used. Suitable substances are the O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted Wear benzoyl groups.
  • Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
  • TAED Tetraacetylethylenediamine
  • 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.
  • 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 positively influence 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.
  • the moldings can, as optical brighteners, 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 similarly constructed Compounds which, instead of the morpholino group, have a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, e.g.
  • Dyes and fragrances become the detergent tablets according to the invention added to improve the aesthetic impression of the products and the Consumers in addition to performance a visually and sensory "typical and distinctive" To provide product.
  • Individual as perfume oils or fragrances Fragrance compounds e.g. synthetic products of the ester, ether, aldehyde type, Ketones, alcohols and hydrocarbons can be used.
  • fragrance compounds of the ester type are e.g.
  • the ethers include, for example, benzyl ethyl ether, to aldehydes e.g.
  • the linear alkanals with 8-18 C atoms citral, citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. the Jonone, ⁇ -isomethyl ionone and methyl cedryl ketone, to the Alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol,
  • the hydrocarbons mainly include terpenes such as limonene and Pinene. However, mixtures of different odoriferous substances are preferably used create an appealing fragrance together.
  • perfume oils can also be natural Fragrance mixtures contain, as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • Muscatel sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, Juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well Orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the content of the detergent tablets according to the invention is usually in the range of dyes below 0.01% by weight, while fragrances up to 2% by weight of the total Can make up wording.
  • the fragrances can be incorporated directly into the agents according to the invention but it can also be advantageous to apply the fragrances to the carrier, which have the liability of the perfume on the laundry and by a slower fragrance release for long-lasting fragrance of the textiles.
  • Such carrier materials have, for example Cyclodextrins have proven themselves, with the cyclodextrin-perfume complexes additionally can be coated with other auxiliaries.
  • 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, um not to stain them.
  • the moldings according to the invention are first produced by dry Mixing the components, which can be partially or completely pre-granulated, and then Inform, in particular pressing into tablets, whereby conventional Procedure can be used.
  • the premix is molded in a so-called die between two stamps compacted into a solid compressed. This process, hereinafter briefly referred to as tableting is divided into four sections: dosage, compression (elastic Deformation), plastic deformation and ejection.
  • the premix is introduced into the die, the filling quantity and thus the weight and shape of the resulting molded body by the position of the lower one Stamp and the shape of the press tool can be determined.
  • the constant dosage even with high throughputs of shaped bodies, a volumetric flow rate is preferably used Dosage of the premix reached.
  • the Upper stamp the premix and continues to lower towards the lower stamp. at this compression, the particles of the premix are pressed closer together, whereby the void volume within the filling between the punches is continuous decreases. From a certain position of the upper stamp (and thus from a certain Pressure on the premix) begins the plastic deformation at which the particles flow together and the molded body is formed.
  • the phase of elastic Deformation is shortened further and further, so that the resulting shaped body more or may have smaller cavities.
  • the Finished moldings are pressed out of the die by the lower punch and through subsequent transport devices transported away. At this point, it's just that Weight of the molded body finally determined, because the compacts due to physical Processes (stretching, crystallographic effects, cooling etc.) their shape and size can still change.
  • 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 stamp or stamps are attached to an eccentric disc, 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.
  • Matrix table For larger throughputs, 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 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 cam 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 the 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-shell-like structure have, in the case of the point tablets the top of the core or 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 size become. Practically all useful configurations come as a spatial form into consideration, for example the formation as a board, the shape of bars or bars, Cubes, cuboids and corresponding room elements with flat side surfaces as well in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to 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 appropriate, 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 and within the present invention preferred.
  • Another preferred molded body that can be produced has a plate or panel-like structure with alternating thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, the short thin Display segments, can be canceled and entered into the machine.
  • This The principle of the "bar-shaped" shaped body detergent can also be used in other geometric Shapes, for example vertical triangles that only on one of their Pages are connected alongside each other, can be realized.
  • the layer structure of the moldings can be done in a stack-like manner, with one dissolution process the inner layer (s) on the edges of the molded body already takes place, if the outer layers are not yet completely detached, it can also be one complete covering of the inner layer (s) by the outer layer (s) Layer (s) can be achieved, which prevents the premature dissolution of components the inner layer (s).
  • a molded body consists of at least three layers, ie two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleach, while in the case of the stacked shaped body, the two outer layers and in the case of the shell-shaped one Moldings, the outermost layers, however, are free of peroxy bleach.
  • the bodies to be coated can be coated with, for example aqueous solutions or emulsions are sprayed, or via the process of Get a coating on the melt coating.
  • multiphase molded articles can also be in the form of ring core tablets, Core coated tablets or so-called "bulleye” tablets are produced.
  • An overview of such embodiments of multi-phase tablets is in EP 055 100 (Jeyes Group).
  • This document discloses blocks of toilet detergent, which is a molded body made from a slowly soluble detergent composition include in which a bleach tablet is embedded. This document reveals at the same time the most diverse designs of multiphase molded bodies from from simple multi-phase tablets to complicated multi-layer systems Insoles.
  • ⁇ 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 molded body causes
  • D is the molded body diameter in meters
  • t is the Height of the molded body.
  • Granulation in a 50-liter ploughshare mixer from Lödige resulted in a surfactant-containing Granules (composition see Table 1), which is the basis for a particulate premix was used.
  • composition see Table 1 which is the basis for a particulate premix was used.
  • a tablettable premix was produced.
  • a shower system was incorporated into the premix as a further treatment component, that in the case of the shaped bodies E1 and E2 according to the invention in the form of a homogeneous Co-granules and in the comparative examples V1 and V2 in the form of a mixture of the two finely divided powders.
  • effervescent granules to be used according to the invention sodium bicarbonate, sodium carbonate and citric acid were mixed dry (see Table 3) and compacted on a Alexanderwerk compacting roller to form a slug. Then the slugs were ground on a sieve granulator. The ground slug was sieved between 0.6 and 1.6 mm. The effervescent system was added at 5% by weight to the premix to be pressed, after which the premixes were compressed into tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g) in a Korsch eccentric press.
  • the pressure was adjusted so that two series of molded bodies were obtained (E1, E1 ', E2, E2' or V1, V1 'and V2, V2'), which differ in their hardness.
  • the composition of the premixes to be pressed (and thus the shaped body) is shown in Table 2, the composition and particle size distribution of the added spray systems is given in Table 3, and the particle size distribution of the other treatment components is shown in Table 4.
  • composition of the surfactant granules [% by weight] C 9-13 alkyl benzene sulfonate 18.4 C 12-18 fatty alcohol with 7 EO 4.9 C 12-18 fatty alcohol sulfate 4.9 Soap 1.6 optical brightener 0.3 sodium 18.8 sodium silicate 5.5 Acrylic acid-maleic acid copolymer 5.5 Zeolite A (anhydrous active substance) 31.3 Na-hydroxyethane-1,1-diphosphonate 0.8 Water, salts rest Composition of the premixes [% by weight]: Granular surfactant (Table 1) 62.5 Shower system (Table 3) 5.0 Sodium perborate monohydrate 15.0 TAED 5.0 foam inhibitor 3.0 polyacrylate 1.0 enzymes 2.0 Perfume 0.5 Wessalith® P (Zeolite A) 1.0 Disintegration aid (cellulose) 5.0 Composition and particle size of the shower systems [% by weight, mm] citric acid Na-bicarbonate sieve fraction Granules (G) / powder mixture
  • the hardness of the tablets became after two days of storage by deforming 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 placed (600ml water, temperature 30 ° C) and the time to complete tablet disintegration measured.

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Claims (19)

  1. Corps façonnés d'agent(s) de lavage et de nettoyage constitués d'agent(s) de lavage et de nettoyage compacté(s), en forme de particules, contenant 5 à 50% en poids d'agent(s) tensioactif(s) anionique(s), caractérisés en ce qu'ils contiennent un système effervescent granulé exempt d'eau, en des quantités de 1 à 20% en poids, à chaque fois par rapport aux corps façonnés, au moins 80% en poids des particules du système effervescent granulé exempt d'eau présentant des granulométries supérieures à 600 µm.
  2. Corps façonnés d'agent(s) de lavage et de nettoyage selon la revendication 1, caractérisés en ce qu'ils contiennent le système effervescent granulé exempt d'eau en des quantités de 2 à 18% en poids, de préférence de 3 à 15% en poids et en particulier de 5 à 10% en poids, à chaque fois par rapport aux corps façonnés.
  3. Corps façonnés d'agent(s) de lavage et de nettoyage selon l'une quelconque des revendications 1 ou 2, caractérisés en ce qu'au moins 90% en poids et en particulier la quantité totale des particules du système effervescent granulé exempt d'eau présente des granulométries supérieures à 600 µm.
  4. Corps façonnés d'agent(s) de lavage et de nettoyage selon l'une quelconque des revendications 1 à 3, caractérisés en ce qu'ils contiennent en tant que système effervescent granulé exempt d'eau un granulat de carbonate(s) et/ou d'hydrogénocarbonate(s) avec un ou des agents d'acidification dans un rapport pondéral de 1:20 à 20:1, de préférence de 1:9 à 9:1.
  5. Corps façonnés d'agent(s) de lavage et de nettoyage selon l'une quelconque des revendications 1 à 4, caractérisés en ce qu'ils contiennent des corps composites contenant un système effervescent granulé exempt d'eau qui contiennent au moins 60% en poids de système effervescent (carbonate(s) et/ou hydrogénocarbonate(s) et agent(s) d'acidification), à chaque fois par rapport au poids du corps composite, de préférence au moins 80%, de préférence au moins 90% et en particulier la quantité totale des corps composites présentant des granulométries supérieures à 600 µm.
  6. Corps façonnés d'agent(s) de lavage et de nettoyage selon l'une quelconque des revendications 1 à 5, caractérisés en ce qu'ils contiennent en outre un adjuvant de désintégration, de préférence un adjuvant de désintégration à base de cellulose, de préférence sous forme granulée, co-granulée ou compactée, en des 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, à chaque fois par rapport au poids des corps façonnés.
  7. Procédé pour la préparation de corps façonnés d'agent(s) de lavage et de nettoyage, caractérisé par les étapes
    a) de préparation d'un système effervescent par granulation exempte d'eau, au moins 80% des particules du système effervescent granulé exempt d'eau présentant des granulométries supérieures à 600 µm,
    b) de mélange du granulat préparé dans l'étape a) avec d'autres constituants d'agents de lavage et de nettoyage de manière à former un prémélange à comprimer,
    c) de compression en des corps façonnés, qui contiennent 5 à 50% en poids d'agent(s) tensioactif(s) anionique(s).
  8. Procédé selon la revendication 7, caractérisé en ce que, dans l'étape de procédé a), un ou plusieurs carbonates et/ou hydrogénocarbonates sont mélangés à sec avec un ou plusieurs agents d'acidification et sont soumis à une agglomération par compression, de préférence un compactage par laminage.
  9. Procédé selon la revendication 8, caractérisé en ce que le ou les carbonate(s) et/ou hydrogénocarbonate(s) sont mélangés et agglomérés par compression avec le ou les agents d'acidification dans un rapport pondéral de 1:20 à 20:1, de préférence de 1:9 à 9:1.
  10. Procédé selon l'une quelconque des revendications 8 ou 9, caractérisé en ce qu'on utilise en tant que carbonates et/ou hydrogénocarbonates les sels de métal alcalin, de préférence les sels sodiques, l'hydrogénocarbonate sodique et le carbonate sodique étant particulièrement préférés.
  11. Procédé selon l'une quelconque des revendications 8 à 10, caractérisé en ce qu'on utilise en tant qu'agent d'acidification une ou plusieurs substances du groupe des acides dicarboxyliques, tricarboxyliques et oligocarboxyliques organiques solides à température ambiante, l'acide citrique étant particulièrement préféré.
  12. Procédé selon l'une quelconque des revendications 7 à 11, caractérisé en ce qu'au moins 90% en poids et en particulier la quantité totale du système effervescent préparé dans l'étape a) présente des granulométries supérieures à 600 µm.
  13. Procédé selon l'une quelconque des revendications 7 à 12, caractérisé en ce que le granulat effervescent préparé dans l'étape a) représente 1 à 20% en poids, de préférence 2 à 18% en poids, de manière particulièrement préférée 3 à 15% en poids et en particulier 5 à 10% en poids du prémélange à comprimer.
  14. Procédé selon l'une quelconque des revendications 7 à 13, caractérisé en ce que le granulat effervescent préparé dans l'étape a) est rassemblé dans l'étape b) avec au moins un granulat contenant un ou des agents tensioactifs de manière à former un prémélange à comprimer présentant une densité apparente d'au moins 500 g/l, de préférence d'au moins 600 g/l et en particulier d'au moins 700 g/l.
  15. Procédé selon la revendication 14, caractérisé en ce que le granulat contenant un ou des agents tensioactifs présente des granulométries entre 100 et 2000 µm, de préférence entre 200 et 1800 µm, de manière particulièrement préférée entre 400 et 1600 µm et en particulier entre 600 et 1400 µm.
  16. Procédé selon l'une quelconque des revendications 14 ou 15, caractérisé en ce que le granulat contenant un ou des agents tensioactifs contient des agents tensioactifs anioniques et/ou non ioniques ainsi que des adjuvants et la teneur totale en agents tensioactifs est d'au moins 10% en poids, de préférence d'au moins 20% en poids et en particulier d'au moins 25% en poids.
  17. Procédé selon la revendication 16, caractérisé en ce que le granulat contenant un ou des agents tensioactifs présente des granulométries entre 100 et 2000 µm, de préférence entre 200 et 1800 µm, de manière particulièrement préférée entre 400 et 1600 µm et en particulier entre 600 et 1400 µm.
  18. Procédé selon l'une quelconque des revendications 7 à 17, caractérisé en ce que le prémélange contient en outre un adjuvant de désintégration, de préférence un adjuvant de désintégration à base de cellulose, de préférence sous forme granulée, co-granulée ou compactée, en des 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, à chaque fois par rapport au poids du prémélange.
  19. Procédé selon l'une quelconque des revendications 7 à 18, caractérisé en ce que le prémélange contient en outre une ou plusieurs substances du groupe des agents de blanchiment, des activateurs de blanchiment, des enzymes, des agents de réglage du pH, des parfums, des supports de parfum, des agents fluorescents, des colorants, des inhibiteurs de mousse, des huiles de silicone, des agents anti-redépôt, des azurants optiques, des inhibiteurs de jaunissement, des inhibiteurs de transfert de couleur et des inhibiteurs de corrosion.
EP99947459A 1998-10-14 1999-10-05 Corps moules detergents et nettoyants munis d'un systeme granule effervescent exempt d'eau Expired - Lifetime EP1123378B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19847283 1998-10-14
DE19847283A DE19847283A1 (de) 1998-10-14 1998-10-14 Wasch- und Reinigungsmittelformkörper mit wasserfrei granuliertem Brausesystem
PCT/EP1999/007361 WO2000022085A1 (fr) 1998-10-14 1999-10-05 Corps moules detergents et nettoyants munis d'un systeme granule effervescent exempt d'eau

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EP1123378A1 EP1123378A1 (fr) 2001-08-16
EP1123378B1 true EP1123378B1 (fr) 2004-02-11

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2002224833A1 (en) * 2000-11-24 2002-06-03 Ijdo, Wouter Laurens Cleaning compositions
DE10123621B4 (de) * 2001-05-15 2006-12-07 Henkel Kgaa Verfahren zur Herstellung einer Wasserenthärtertablette
DE102009011928A1 (de) * 2009-03-10 2010-09-23 Licciardi, Natale, Dipl.-Ing. Verfahren zur Herstellung von Reinigungstabletten
DE102010051226A1 (de) 2010-11-12 2012-05-31 Dental Care Innovation Gmbh Ausspültablete mit abrasiven Bestandteilen
ES2586461B1 (es) * 2015-03-12 2017-12-01 Lorena MARTÍ COMA Composición detergente en forma de pastilla efervescente
CN110505867A (zh) 2017-02-02 2019-11-26 洁碧有限公司 用于牙齿清洁的包括研磨剂的片剂
CN108841469B (zh) * 2018-07-19 2023-09-01 河南城建学院 洗衣泡腾片包衣剂和耐潮洗衣泡腾片及其制备方法

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US4217234A (en) * 1978-02-16 1980-08-12 Werner Krisp Denture cleansing tablet and method of manufacturing the same
DE3535516A1 (de) * 1985-10-04 1987-04-09 Fritz Buchner Tablettenfoermiges wasch- und reinigungsmittel, verfahren zu seiner herstellung und seine verwendung
EP0248936A1 (fr) * 1986-06-13 1987-12-16 Richardson GmbH Tablette de nettoyage pour dentier et son procédé de fabrication
EP0253772A3 (fr) * 1986-07-15 1989-07-19 Warner-Lambert Company Compositions contenant un agent blanchissant pour le nettoyage et/ou le lavage des dentiers
US5114647A (en) * 1991-02-01 1992-05-19 Olin Corporation Effervescent tablets having increased disintegration rates
GB9622845D0 (en) * 1996-11-01 1997-01-08 Procter & Gamble Effervescent bleaching compositions
MA24525A1 (fr) * 1997-04-14 1998-12-31 Procter & Gamble Particule detergente
DE69731189T3 (de) * 1997-05-27 2009-12-24 The Procter & Gamble Company, Cincinnati Tabletten und Verfahren zu deren Herstellung
DE19722832A1 (de) * 1997-05-30 1998-12-03 Henkel Kgaa Waschmittelformkörper mit verbesserten Auflöseeigenschaften

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DE19847283A1 (de) 2000-04-20
DE59908529D1 (de) 2004-03-18
WO2000022085A1 (fr) 2000-04-20
EP1123378A1 (fr) 2001-08-16
ATE259414T1 (de) 2004-02-15

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