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WO2000027959A1 - Corps moules de lessive et de detergent a granulat antimousse - Google Patents

Corps moules de lessive et de detergent a granulat antimousse Download PDF

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Publication number
WO2000027959A1
WO2000027959A1 PCT/EP1999/008086 EP9908086W WO0027959A1 WO 2000027959 A1 WO2000027959 A1 WO 2000027959A1 EP 9908086 W EP9908086 W EP 9908086W WO 0027959 A1 WO0027959 A1 WO 0027959A1
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WO
WIPO (PCT)
Prior art keywords
weight
foam inhibitor
granules
foam
detergent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1999/008086
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German (de)
English (en)
Inventor
Rene-Andres Artiga-Gonzalez
Stefan Hammelstein
Ingrid Kraus
Andreas Lietzmann
Maria Liphard
Adolf Wiche
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of WO2000027959A1 publication Critical patent/WO2000027959A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating 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
    • 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

Definitions

  • the present invention is in the field of compact moldings which have washing and cleaning properties.
  • Such detergent tablets comprise, for example, detergent tablets for washing textiles, detergent tablets for machine dishwashing or hard surface cleaning, bleach tablets for use in washing machines or dishwashers, water softening tablets or stain remover tablets.
  • the invention relates to detergent tablets which are used for washing textiles in a household washing machine and are briefly referred to as detergent tablets.
  • Detergent tablets are widely described in the prior art and are becoming increasingly popular with consumers because of the ease of dosing and handling, so that this type of product is becoming increasingly established in the market for detergents and cleaning agents in addition to the conventional powder products.
  • a fundamental problem in the form of high-density molded articles is their reduced disintegration time, which is accompanied by increasing hardness, and thus deteriorated solubility.
  • the disintegration times of the detergent tablets are so high that the tablets cannot be washed in via the induction chests of household washing machines because they do not pass into secondary particles sufficiently quickly that are small enough to be washed in.
  • Such moldings must either be put directly into the laundry, with or without a metering aid (for example a sachet), where the contact between the laundry and the slowly dissolving molding can lead to textile damage due to high local concentrations of bleaching agent and enzymes.
  • a metering aid for example a sachet
  • EP-A-0 466 484 discloses detergent tablets in which the premix to be compressed has particle sizes between 200 and 1200 ⁇ m, the upper and lower limits of the particle sizes not differing by more than 700 ⁇ m. None is said in this document about the surface treatment of individual ingredients.
  • EP-A-0 522 766 also relates to moldings made from a compacted, particulate detergent composition containing surfactants, builders and disintegration aids, at least some of the particles being coated with the disintegration agent which has both binder and disintegration activity Dissolving the molded body in water shows.
  • This document also indicates the general difficulty of producing moldings with adequate stability and good solubility at the same time.
  • the particle size in the mixture to be pressed should be above 200 ⁇ m, the upper and lower limits of the individual particle sizes should not differ from one another by more than 700 ⁇ m.
  • a premix to be compressed should have a relatively homogeneous particle size distribution on the one hand and should be relatively coarse-grained on the other.
  • the large-scale use in tableting premixes is not possible without problems, since the performance of the ingredients is reduced as a result.
  • foam inhibitors are added to the detergents and cleaning agents in finely divided form in order to control the foam formation even at low washing temperatures and thus prevent the washing liquor from overflowing.
  • the use of coarser foam inhibitor compounds therefore leads especially at the washing temperatures of 30 and 40 ° C to undesirably high foaming.
  • a further object of the present invention was therefore to find an incorporation form for foam inhibitors in detergent tablets, in which on the one hand the above-mentioned requirements for the molded article are met, but on the other hand the defoamer performance is not impaired.
  • the invention relates to detergent tablets made of compressed particulate detergents and cleaning agents which contain a wet-granulated foam inhibitor granulate.
  • foam inhibitors are understood to be substances which are added to foaming liquids in order to reduce or prevent their foaming.
  • the foam inhibitors are either surface-active substances that displace the foaming agents from the interface without generating foam themselves (e.g. soaps), or products that increase the surface tension of the water, e.g. natural fats and oils or fatty alcohols.
  • the use of foam inhibitors is indispensable both in the household (machine dishwashing detergent, detergent) and in industry (manufacture of paper, sugar, etc.).
  • the high foaming power of the anionic surfactants contained therein is generally achieved by using long-chain soaps, e.g. Sodium behenate reduced;
  • defoamers based on paraffin or silicone have become more important because the defoaming performance of the soaps is heavily dependent on the water hardness.
  • foam inhibitor active substance characterizes the substance or the compound which the desired foam-reducing or -controlling properties Has shafts, for example the paraffin or silicone oil.
  • the foam inhibitors are usually not added to the washing and cleaning agents as a pure active substance, but in the form of compounds in which the foam inhibitor active substance is present together with other substances. In the case of liquid foam inhibitor active substances in particular, such "foam inhibitor compounds" of active substance and carrier material are present.
  • foam inhibitor active substances or foam inhibitor compounds are converted by wet granulation into a "foam inhibitor granulate" which, according to the invention, is contained in the detergent tablets.
  • the term "granulate” always denotes a product in connection with foam inhibitors wet granulation, ie a compression process using a liquid granulation aid.
  • Foam inhibitors or foam inhibitor compounds compacted on dry paths are not referred to in the context of the present application as “granules” but rather as “agglomerates” or “compactates”.
  • Paraffins and silicones are preferably used as foam inhibitor active substances in the context of the present invention, which can be present in a known manner in a mixture with finely divided bisfatty acid amides and / or silicas, paraffins and silicones largely liquid at room temperature being preferred.
  • the content of foam inhibitor active substance is 1 to 30% by weight, based on the granulate, so that detergent tablets are preferred in which the foam inhibitor granules are 1 to 30% by weight based on the weight of the granules .-%, preferably 2 to 25 wt .-% and in particular 3 to 20 wt .-% foam inhibitors from the group of paraffins and / or silicones.
  • the foam inhibitor granules can be obtained by wet granulation of pure foam inhibitor active substances or from foam inhibitor compounds. Usually foam inhibitor compounds are used, which are granulated. In addition to the foam inhibitor active substances, the foam inhibitor granules used according to the invention preferably contain further substances, in particular carriers. germ materials. Detergent tablets in which the foam inhibitor granules as carrier material for the paraffin (s) and / or silicone (s) contain one or more substances from the group of sulfates, carbonates, bicarbonates, silicates and citrates, the Alkali metal salts are preferred and the sodium salts are particularly preferred are preferred in the context of the present invention.
  • foam inhibitor granules When the foam inhibitor granules are produced by wet granulation, further ingredients of detergents and cleaning agents can be incorporated into the foam inhibitor granules via the granulation aid (“granulating liquid”) or via additives.
  • the foam inhibitor granules contain substances from the group of polymers as further ingredients of detergents and cleaning agents, These polymers can contribute to improving the primary washability by inhibiting the color transfer or by repositioning the dirt prevent the liquor from spilling onto the textile, but polymers with cobuilder properties can also improve the secondary washability, disilicate, carboxymethyl cellulose (CMC) and polycarboxylates are considered as preferred polymers
  • CMC carboxymethyl cellulose
  • polycarboxylates are considered as preferred polymers Examples are homo- and copolymers of acrylic acid.
  • Polyacrylates acrylic acid / maleic acid copolymers and acrylic phosphinates are particularly preferred.
  • Polyacrylates are, for example, under the names Versicol ® E5, Versicol ® E7 and Versicol ® E9 (trademark of the Allied Colloids), Narlex ® LD 30 and Narlex ® LD 34 (trademark of the national adhesives), Acrysol ® LMW-10, Acrysol ® LMW-20, Acrysol LMW-45 ® and Acrysol ® Al-N (trademark of Rohm & Haas), and Sokalan ® PA-20, PA-40 Sokalan ®, Sokalan ® PA 70 and Sokalan ® PA-110 (trademark of BASF) commercially available.
  • Ethylene / maleic acid copolymers are sold under the name EMA ® (trademark of Monsanto), methyl vinyl ether / maleic acid copolymers under the name Gantrez ® AN 119 (trademark of GAF Corp.) and acrylic acid / maleic acid copolymers under the names Sokalan ® CP5 and Sokalan ® CP7 (trademark of BASF).
  • Acrylic phosphates are available as DKW ® (trademark of National Adhesives) and Belperse ® types (trademark of Ciba-Geigy).
  • graft copolymers which are obtained by grafting polyalkylene oxides with molecular weights between 2000 and 100000 with vinyl acetate.
  • the acetate groups can optionally be saponified up to 15%.
  • Polymers of this type, as EP-A-0219048 (BASF) are described in European patent application, under the name Sokalan ® HP22 (trademark of BASF).
  • silicate solutions sodium silicate solutions
  • polycarboxylate solutions mixtures of CMC / water and water are particularly suitable as granulating liquids, the first-mentioned granulating liquids being preferred over the latter two.
  • Preferred detergent tablets in the context of the present invention are characterized in that the foam inhibitor granules contain further ingredients of detergents and cleaning agents, in particular polymers, in amounts of 0.5 to 20% by weight, preferably of 1 to 10 Wt .-% and in particular from 2.5 to 7.5 wt .-%, each based on the foam inhibitor granules.
  • the detergent tablets contain a wet-granulated foam inhibitor granulate.
  • the foam inhibitor active substance (s) only partially via the granules used according to the invention and to a further extent in the conventional way, it is preferred according to the invention if the detergent tablets are at least 80% by weight, preferably at least 90 % By weight and particularly preferably the total amount of the defoamer contained in the shaped body in the form of wet-granulated foam inhibitor granules.
  • Foam inhibitor active substance can contain the wet-granulated foam inhibitor granules in the detergent tablets according to the invention in varying amounts, the person skilled in the art having no limits with regard to his freedom from formulations.
  • Preferred detergent tablets contain 1 to 15% by weight, preferably 2 to 10% by weight and in particular 2.5 to 7.5% by weight, of the wet-granulated foam inhibitor granules as a general formulation.
  • detergent tablets are preferred which, based on the weight of the body, comprise 0.01 to 5% by weight, preferably 0.1 to 2.5% by weight and in particular 0.5 to 1% by weight of foam inhibitor - Contain active substance.
  • 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.
  • Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case based on the weight of the tablet.
  • 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 ⁇ oO 5 ) n and, formally speaking, is a ß-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 hydroxyl 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 disintegrant based on cellulose.
  • 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 optionally 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 writings are also detailed information on the The position of granulated, compacted or cogranulated cellulose disintegrants can be found.
  • 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 and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ® TF-30-HG from Rettenmaier available in the present invention.
  • Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged.
  • a subsequent disaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 ⁇ m and can be compacted, for example, to granules with an average particle size of 200 ⁇ m.
  • Detergent tablets preferred in the context of the present invention additionally contain 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 3 to 7% by weight. -% and in particular from 4 to 6 wt .-%, each based on the weight of the molded body.
  • 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 3 to 7% by weight. -% and in particular from 4 to 6 wt .-%, each based on the weight of the molded body.
  • Such coated detergent tablets can be produced by spraying a melt or solution of the coating material onto the molded article or immersing the molded article in the melt or solution. In preferred embodiments of the present invention, however, the detergent tablets are not coated with a coating which covers the entire tablet.
  • detergent tablets can be produced according to the invention which disintegrate into their constituents extremely quickly in water at high hardness. In the context of the present invention, particular preference is given to detergent tablets which disintegrate completely in water at 30 ° C. in less than 60 seconds into their secondary particles, which are so small that they can be washed in via the washing-in chamber of a household washing machine.
  • Another object of the present invention is a method for producing detergent tablets, characterized by the steps
  • step a) production of a foam inhibitor granulate by wet granulation, b) mixing of the granulate produced in step a) with further ingredients of detergents and cleaning agents to form a premix to be pressed, c) pressing into shaped bodies.
  • a foam inhibitor granulate is produced by wet granulation.
  • the person skilled in the art can fall back on machines and apparatuses known from the literature as well as process engineering operations, as described, for example, in W. Pietsch, "Size Enlargement by Agglomeration", Verlag Wiley, 1991, and the literature cited therein are.
  • process step a) is carried out in the following substeps:
  • Process step a1) corresponds to the above-described production of foam inhibitor compounds from foam inhibitor active substance (s).
  • process step a1) is carried out as spraying or spraying on a melt, an emulsion or a solution of solid foam inhibitor active substance or as spraying or spraying liquid foam inhibitor active substance onto moving carrier material particles or as spray drying of a carrier material foam inhibitor slurry.
  • foam inhibitor active substances are those from the group of paraffins and / or silicones.
  • foam inhibitors from the group of paraffins and / or silicones preferably paraffins and / or silicones which are liquid at room temperature, in amounts of 1 to 30% by weight, preferably 5, as the foam inhibitor active substance up to 25% by weight and in particular from 10 to 20% by weight, based in each case on the weight of the compound, are preferred.
  • one or more substances from the group of the sulfates, carbonates, bicarbonates, silicates and citrates are preferably used as the carrier material for the foam inhibitor active substance, the alkali metal salts being preferred and the sodium salts being particularly preferred.
  • the foam inhibitor compound is optionally mixed with further ingredients of detergents and cleaning agents.
  • Substances from the group of builders, cobuilders and polymers are preferably used here in amounts of 5 to 40% by weight, preferably 10 to 35% by weight and in particular 15 to 30% by weight, in each case based on the mixture of Foam inhibitor compound and other ingredients used. These builders, cobuilders and polymers are described below.
  • the solid mixture is granulated with the addition of a granulating liquid.
  • granulation aids with both for example, nonionic surfactants, polyethylene glycols or other liquids can be used.
  • the process for producing the detergent tablets comprises mixing the foam inhibitor granules with further components to form a premix, which is pressed in the last process step.
  • the foam inhibitor granulate produced in step a) makes up 1 to 15% by weight, preferably 2 to 10% by weight and in particular 2.5 to 7.5% by weight of the premix to be pressed.
  • the foam inhibitor granulate produced in step a) is combined in step b) with at least one surfactant-containing granulate to form a premix to be pressed with a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1 .
  • a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1 include preferred method, therefore, the compression of a teilchenfb 'RMI gen premixture of at least one foam inhibitor granules, at least one surfactant-sid restroomn granules and at least one blended powder component.
  • the granules containing surfactant can be produced by conventional industrial granulation processes such as compacting, extrusion, mixer granulation, pelletization or fluidized bed granulation.
  • the surfactant-containing granulate satisfies certain particle size criteria.
  • Methods according to the invention are preferred in which the surfactant-containing granules have particle sizes between 100 and 2000 ⁇ m, 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.
  • surfactant-containing granules contain anionic and / or nonionic surfactants and builders and have total surfactant contents of at least 10% by weight, preferably at least 20% by weight and in particular at least 25% by weight.
  • anionic surfactants come from the group of anionic, nonionic, zwitterionic or cationic surfactants, anionic surfactants being clearly preferred for economic reasons and because of their range of services.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Suitable surfactants of the sulfonate type are preferably C 9-13 - alkyl benzene sulfonates, Olef ⁇ nsulfonate, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from 2- C ⁇ ⁇ 8 -Monoolefmen with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates which are for example obtained from 2- C ⁇ ⁇ 8 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids (ester sulfonates), 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 are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
  • Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 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 semiesters of the -C 8 -C fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the CIO-C o-oxo alcohols and those Half-secondary alcohols of this chain length are preferred.
  • 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 ⁇ -C 6 alkyl sulfates and C 12 - Cis alkyl sulfates and C ⁇ 4 -C ⁇ 5 alkyl sulfates are preferred for washing technology reasons.
  • 2,3-alkyl sulfates which are produced for example according to US -Patentschriften 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • 21 alcohols such as 2 -methyl-branched C 9 ⁇ alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 i 8 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.
  • Preferred sulfosuccinates contain C 8- ⁇ 8 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 whose fatty alcohol residues 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 are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also 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, in particular in the form of the sodium salts.
  • surfactant granules are preferred as process end products of intermediate step a), which each contain 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 10 to 20% by weight of anionic surfactant (s) based on the granules.
  • the preferred anionic surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates, preferred detergent tablets 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight of fatty alcohol sulfate (s) in each case based on the weight of the detergent tablets
  • 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 has a methyl or linear branching in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm or tallow fat, are or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol is preferred.
  • the preferred ethoxylated alcohols include, for example, C 2-1 alcohols with 3 EO or 4 EO, C 9- 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 2- C ⁇ ⁇ 4 alcohol containing 3 EO and C ⁇ 2-18 - 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 of this are 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 as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared 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, C atoms and G is Is a symbol which stands for a glycosine 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, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.
  • the end products of the process of intermediate step a) can preferably contain alkyl polyglycosides, with APG contents of more than 0.2% by weight, based on the total molded body, being preferred.
  • Particularly preferred detergent tablets contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 to 3% by weight.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • surfactants are polyhydroxy fatty acid amides of the formula (II),
  • 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
  • [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 (III)
  • [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, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the surfactant content of the surfactant-containing granules produced in step a) is 5 to 60% by weight. %, preferably 10 to 50% by weight and in particular 15 to 40% by weight, in each case based on the surfactant granules.
  • the surfactant granules can be used in the detergent tablets in varying amounts.
  • builders are the most important ingredients in detergents and cleaning agents.
  • surfactant granules but also as part of the Premix or as a component in the foam inhibitor granules used according to the invention can contain all builders normally used in detergents and cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - the phosphates.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O x + ⁇ ⁇ 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 Si 2 O 5 ' yH O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.
  • Amorphous sodium silicates with a modulus Na O: SiO from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are delayed in dissolution, can also be used and have secondary washing properties.
  • 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 have serge 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.
  • zeolite of the P and / or X type introduced by the surfactant granules can be incorporated into the premix by adding zeolite as a treatment component.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably a type A, P, X or Y zeolite.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • 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 as builder substances, provided that such use should not be avoided for ecological reasons.
  • the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.
  • Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of 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 detergent tablets according to the invention can also contain, as additional cobuilders and graying inhibitors, 0.5 to 5% by weight, preferably 1 to 3% by weight, of a polycarboxylate polymer which contains (meth) acrylate and / or maleate Contains units.
  • a polycarboxylate polymer which contains (meth) acrylate and / or maleate Contains units.
  • anionic polymers can be used in their acid form or in the partially or completely neutralized salt form.
  • Preferred polymers are homo- and copolymers of acrylic acid. Polyacrylates are particularly preferred here, Acrylic acid / maleic acid copolymers and acrylic phosphinates.
  • Polyacrylates are, for example, under the names Versicol ® E5, Versicol ® E7 and Versicol ® E9 (trademark of Allied Colloids), Narlex ® LD 30 and Narlex ® LD 34 (trademark of national adhesives), Acrysol ® LMW-10, Acrysol ® LMW- 20, Acrysol ® LMW-45 and Acrysol ® Al-N (trademark of Rohm & Haas) as well as Sokalan ® PA-20, Sokalan ® PA-40, Sokalan ® PA-70 and Sokalan ® PA-110 (trademark of BASF) available in the stores.
  • Ethylene / maleic acid copolymers are sold under the name EMA ® (trademark of Monsanto), methyl vinyl ether / maleic acid copolymers under the name Gantraz ® AN 119 (trademark of GAF Co ⁇ .) And acrylic acid / maleic acid copolymers under the name Sokalan ® CP5 and Sokalan ® CP7 (trademark of BASF).
  • Acrylic phosphinates are available as DKW ® (trademark of National Adhesives) and Belperse ® - types (trademark of Ciba-Geigy).
  • graft copolymers which are obtained by grafting polyalkylene oxides with molecular weights between 2000 and 100,000 with vinyl acetate.
  • the acetate groups can optionally be saponified up to 15%.
  • Polymers of this type, as EP-A-0219048 (BASF) are described in European patent application, under the name Sokalan ® HP22 (trademark of BASF).
  • the premix Before the particulate premix is pressed into detergent tablets, the premix can be "powdered” with finely divided surface treatment agents. This can be of advantage for the nature and physical properties of both the premix (storage, pressing) and the finished detergent tablets. Finely divided powdering agents are well known in the art, mostly zeolites, silicates or other inorganic salts being used. However, the premix is preferably “powdered” with finely divided zeolite, zeolites of the faujasite type being preferred. In the context of the present invention, the term “faujasite-type zeolite” denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4 (see Donald W.
  • zeolite Y and faujasite and mixtures of these compounds can also be used, the pure zeolite X being preferred.
  • Mixtures or cocrystallisates of zeolites of the faujasite type with other zeolites which do not necessarily have to belong to the zeolite structural group 4 can also be used as powdering agents, it being advantageous if at least 50% by weight of the Powder consist of a zeolite of the faujasite type.
  • detergent tablets consist of a particulate premix which contains granular components and subsequently admixed powdery substances, the or one of the subsequently admixed powdery components being a zeolite of the faujasite type with particle sizes below 100 ⁇ m, is preferably below 10 ⁇ m and in particular below 5 ⁇ m and is at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1% by weight of the premix to be treated.
  • detergent tablets are preferred which additionally contain a disintegration aid.
  • 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 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the weight of the premix, are preferred.
  • the particulate premixes to be treated can additionally contain 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.
  • bleaching agents sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O-providing peracidic salts or peracids, such as peracids. benzoates, 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) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monophthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidopercapid [Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1, 9-diperoxyacelic acid oxyacid, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di
  • Chlorine or bromine-releasing substances can also be used as bleaching agents in molded articles for automatic dishwashing.
  • Suitable materials which release chlorine or bromine include, 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 incorporated as the sole component or as an ingredient of component b).
  • Can be used as bleach activators Compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate, ethylene glycol, Diacetoxy-2,5-dihydrofuran.
  • TAED tetraacetylethylene diamine
  • DADHT 1,5-
  • bleach catalysts can also be incorporated into the moldings.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules in the inventive Molded bodies can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • the detergent tablets can also contain components that positively influence the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • the shaped bodies can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-mo ⁇ holino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which, instead of the Mo ⁇ holino group, have a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyryl type may be present, e.g.
  • Dyes and fragrances are added to the detergent tablets according to the invention in order to improve the aesthetic impression of the products and, in addition to the softness, to provide the consumer with a visually and sensorially "typical and unmistakable" product.
  • perfume oils or fragrances NEN single fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexylproylatepyll-propyll-propyl-allyl-propyl-allyl-propyl-allyl-propyl-allyl-propyl-allyl-propyl-allyl-propyl-allyl-propyl-allyl-propyl-allyl-propyl-allyl-propyl-allyl-propyl-allyl-propyl-allyl-propyl-allyl-propyl-allyl-propyl-allyl-propyl-ally
  • the ethers include, for example, benzylethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the ionone, c -Isomethyl ionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and te ⁇ ineol, the hydrocarbons mainly include tephenols such as limonene and pinene.
  • Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lentil flower oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the dye content of the detergent tablets according to the invention is usually less than 0.01% by weight, while fragrances can make up up to 2% by weight of the total formulation.
  • the fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
  • the agents according to the invention can be colored with suitable dyes.
  • Preferred dyes the selection of which No problem for a person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity towards textile fibers in order not to dye them.
  • the molded articles according to the invention are first produced by dry mixing the constituents, which can be wholly or partially pregranulated, and then providing information, in particular feeding them into tablets, whereby conventional methods can be used.
  • the premix is compacted in a so-called die between two punches to form a solid compact. This process, which is briefly referred to as tableting in the following, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.
  • the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molded body being formed being determined by the position of the lower punch and the shape of the pressing tool.
  • the constant dosing, even at high mold throughputs, is preferably achieved by volumetric dosing of the premix.
  • the upper punch touches the premix and lowers further in the direction of the lower punch.
  • the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix), the plastic deformation begins, in which the particles flow together and the molded body is formed.
  • the premix particles are also crushed and sintering of the premix occurs at even higher pressures.
  • the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities.
  • the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this time, only the weight of the molded body is finally determined, because the compacts are due to physical Processes (stretching, crystallographic effects, cooling etc.) can still change their shape and size.
  • Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down.
  • eccentric tablet presses are preferably used, in which the punch or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine.
  • the pressing can take place with one upper and one lower punch, but several punches can also be attached to one eccentric disc, the number of die holes being correspondingly increased.
  • 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 in which a larger number of dies is arranged in a circle on a so-called die table.
  • the number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available.
  • Each die on the die table is assigned an upper and lower punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps.
  • the die table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compaction, plastic deformation and ejection by means of rail-like cam tracks during the rotation.
  • these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks.
  • the die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix.
  • the pressure on the premix is individual via the press paths for the upper and lower punches adjustable, whereby the pressure builds up by rolling the stamp shaft heads past adjustable pressure rollers.
  • Rotary presses can also be provided with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet.
  • several filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before further filling.
  • jacket and dot tablets can also be produced in this way, which have an onion-shell-like structure, the top side of the core or the core layers not being covered in the case of the dot tablets and thus remaining visible.
  • Rotary tablet presses can also be equipped with single or multiple tools, 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 one million molded articles per hour.
  • Tableting machines suitable within the scope of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and Courtoy NV, Halle (BE / LU).
  • the hydraulic double pressure press HPF 630 from LAEIS, D. is particularly suitable.
  • the molded body can be manufactured in a predetermined spatial shape and a predetermined size. Practically all practical configurations can be considered as the spatial shape, for example, the design as a board, the bar or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section.
  • This last embodiment covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.
  • the portioned compacts can each be designed as separate individual elements that correspond to the predetermined dosage of the detergents and / or cleaning agents. It is also possible, however, to form compacts which connect a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined predetermined breaking points.
  • the portioned compacts can be designed as tablets, in cylindrical or cuboid form, with a diameter / height ratio in the range from 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 pressed articles.
  • the spatial shape of another embodiment of the molded body is adapted in its dimensions to the detergent dispenser of commercially available household washing machines, so that the molded body can be metered directly into the dispenser without metering aid, where it dissolves during the dispensing process.
  • the detergent tablets without problems using a metering aid and is preferred in the context of the present invention.
  • Another preferred molded body that can be produced has a plate-like or plate-like structure with alternating thick long and thin short segments, so that individual segments of this "bolt" at the predetermined breaking points, which represent the short thin segments, broken off and into the Machine can be entered.
  • This principle of the "bar-shaped" shaped body detergent can also be realized in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the side.
  • the various components are not pressed into a uniform tablet, but that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous application properties of the molded body. If both for example, components are contained in the moldings that mutually influence each other negatively, so it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the first component has already reacted if the second goes into solution.
  • the layer structure of the molded body can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the molded body when the outer layers have not yet been completely removed, but it is also possible for the inner layer (s) to be completely encased ) can be achieved by the layer (s) lying further outwards, which leads to the premature dissolution of components of the inner layer (s).
  • a molded body consists of at least three layers, i.e. two outer and at least one inner layer, at least one peroxy bleaching agent being contained in at least one of the inner layers, while in the case of the stap egg-shaped molded body, the two outer layers and in the case of the shaped body however, the outermost layers are free of peroxy bleach. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes that may be present in a molded body.
  • Such multilayer molded bodies have the advantage that they can be used not only via a dispensing chamber or via a metering device which is added to the washing liquor; rather, in such cases it is also possible to put the molded body into direct contact with the textiles in the machine without the risk of bleaching from bleaching agents and the like.
  • the bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions, or else they can be coated using the melt coating method. After pressing, the detergent tablets have a high stability.
  • the breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to
  • ⁇ stands for diametral fracture stress (DFS) in Pa
  • P is the force in N that leads to the pressure exerted on the molded body that causes the molded body to break
  • D is the molded body diameter in meters and t the height of the molded body.
  • the present invention furthermore relates to the use of wet-granulated foam inhibitor granules which, after mixing with finely divided processing components, are pressed in a manner known per se to form detergent tablets, for improving the stability and solubility of detergent tablets.
  • foam inhibitor granules mentioned which are mixed after mixing with other components to form detergent tablets, the physical properties of the molded articles can be significantly improved, as the examples below demonstrate.
  • Granulation in a 50-liter ploughshare mixer from Lödige produced granules containing tensides (for composition, see Table 1), which was used as the basis for a particulate premix. Following the granulation, the granules were dried in a fluidized bed apparatus from Glatt at a supply air temperature of 60 ° C. over a period of 30 minutes. After drying, fine particles ⁇ 0.4 mm and coarse particles> 1.6 mm were screened off.
  • the particulate premix was produced by blending the surfactant-containing granules with bleach, bleach activator and other processing components.
  • the particulate premix contained a foam inhibitor concentrate which was used in the form of wet granules in the case of the molded bodies E according to the invention, in the form of a compact in the case of comparative example VI and in the form of non-granulated powder in the case of comparative example V2.
  • a mixture of paraffin on carrier material and a polymer on carrier material was used as the foam inhibitor concentrate.
  • the first-mentioned mixture was produced according to the teaching of international patent application WO97 / 34983 (Henkel) and had an active substance content (paraffin) of 15% by weight, the powdery product having a bulk density of 700 g / l.
  • the polymer on a carrier material is a terephthalic acid-ethylene glycol-polyethylene glycol ester which has been applied to sodium sulfate as a carrier.
  • the powdery product with 70 wt .-% polymer and 30 wt .-% sodium sulfate, which has a bulk density of 1020 g / 1, is commercially available under the name Repelotex ® -SRP-4 (trademark of Rhodia, Rhone-Poulenc) .
  • a mixture of the two powdery products was used, the proportions of which are shown in the table in the ready-to-press premix.
  • a mixture of 76% by weight of the paraffm carrier powder and 24% by weight of the polymer carrier powder was compacted to form a slug on a compacting roller of the Alexanderwerk type. Then followed grinding the slug on a sieve granulator, the ground slug being sieved between 0.6 and 1.6 mm.
  • the two powder of a wet granulation were subjected by adding 5 kg of a mixture of 76 wt .-% of Paraffm carrier powder and 24 wt .-% of the polymer support powder with 1 kg of a polymer solution (Sokalan ® -CP 5: Acrylic acid-maleic acid copolymer, 40% in water) was granulated in a 20 liter Lödige ploughshare mixer with chopper. The granules were then dried in a smooth fluidized bed at a supply air temperature of 80 ° C. for 30 minutes and sieved between 0.6 and 1.6 mm after drying.
  • Sokalan ® -CP 5 Acrylic acid-maleic acid copolymer, 40% in water
  • the premixes to be contained contained 4.6% by weight of the defoaming powder (V2) or compactate (VI) or granulate (E).
  • the premixes were pressed in a Korsch eccentric tablet (diameter: 44 mm, height: 22 mm, weight: 37.5 g). The pressure was adjusted so that two series of molded bodies were obtained (E, E 'or VI, VI' and V2, V2 '), which differ in their hardness.
  • Table 2 shows the composition of the premixes to be treated (and thus the shaped body).
  • the hardness of the tablets was measured by deforming the tablet until it broke, the force acting on the side surfaces of the tablet and the maximum force which the tablet withstood being 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.
  • water 600 ml of water, temperature 30 ° C.
  • the defoamer performance two tablets were placed in the dispenser of a household washing machine (AEG ⁇ ko-Lavamat) and a 60 ° C main wash program was started. The foam formation was then assessed through the porthole or via the half-opened induction chamber, the grades 0 (“no foam”) to 6 (“foam standing in the induction chamber”) being used.
  • the experimental data are shown in Table 3:
  • Table 3 shows that the disintegration time of molded articles which contain a granulated or compacted foam inhibitor system (E, VI) is reduced compared to molded articles in which the foam inhibitor is used in finely divided form, with comparable hardness.
  • E, VI granulated or compacted foam inhibitor system
  • Table 3 shows that the disintegration time of molded articles which contain a granulated or compacted foam inhibitor system (E, VI) is reduced compared to molded articles in which the foam inhibitor is used in finely divided form, with comparable hardness.
  • the use of the compacted foam inhibitor system in the moldings of Comparative Example VI at low washing temperatures leads to unacceptable foam notes, i.e. at 40 ° C the defoamer performance is insufficient.
  • Only the granulated foam inhibitor according to the invention in the molded bodies E shows at the same time a very good defoamer performance and improved disintegration times at high hardness levels.

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Abstract

L'invention concerne des corps moulés de lessive et de détergent présentant une dureté élevée et un temps de désagrégation toutefois court pour un bon pouvoir antimousse. Les corps moulés selon l'invention contiennent des granulats inhibiteurs de mousse obtenus par granulation par voie humide. A cet effet, on produit un granulat inhibiteur de mousse par granulation par voie humide, on le mélange à d'autres constituants et on le comprime en corps moulés de lessive et de détergent.
PCT/EP1999/008086 1998-11-05 1999-10-26 Corps moules de lessive et de detergent a granulat antimousse Ceased WO2000027959A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1998150983 DE19850983A1 (de) 1998-11-05 1998-11-05 Wasch- und Reinigungsmittelformkörper mit Entschäumergranulat
DE19850983.9 1998-11-05

Publications (1)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4136045A (en) * 1976-10-12 1979-01-23 The Procter & Gamble Company Detergent compositions containing ethoxylated nonionic surfactants and silicone containing suds suppressing agents
US4362642A (en) * 1976-01-23 1982-12-07 Lever Brothers Company Alkyl phosphoric acid polyvalent salts-mineral oil lather controlled detergent compositions
DE19531690A1 (de) * 1995-08-29 1997-03-06 Henkel Kgaa Figurenhaft ausgestaltete feste und verdichtete Mehrkomponentengemische aus dem Bereich der Wasch- und Reinigungsmittel sowie Verfahren zu ihrer Herstellung
WO1997034983A1 (fr) * 1996-03-19 1997-09-25 Henkel Kommanditgesellschaft Auf Aktien Agent particulaire regulateur de mousse a base de paraffine
WO1998009701A1 (fr) * 1996-09-06 1998-03-12 Henkel Kommanditgesellschaft Auf Aktien Procede pour la fabrication de regulateurs de mousse contenant de la paraffine
WO1998055575A1 (fr) * 1997-06-03 1998-12-10 Henkel Kommanditgesellschaft Auf Aktien Granules adjuvants pour corps moules detergents et lavants

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4362642A (en) * 1976-01-23 1982-12-07 Lever Brothers Company Alkyl phosphoric acid polyvalent salts-mineral oil lather controlled detergent compositions
US4136045A (en) * 1976-10-12 1979-01-23 The Procter & Gamble Company Detergent compositions containing ethoxylated nonionic surfactants and silicone containing suds suppressing agents
DE19531690A1 (de) * 1995-08-29 1997-03-06 Henkel Kgaa Figurenhaft ausgestaltete feste und verdichtete Mehrkomponentengemische aus dem Bereich der Wasch- und Reinigungsmittel sowie Verfahren zu ihrer Herstellung
WO1997034983A1 (fr) * 1996-03-19 1997-09-25 Henkel Kommanditgesellschaft Auf Aktien Agent particulaire regulateur de mousse a base de paraffine
WO1998009701A1 (fr) * 1996-09-06 1998-03-12 Henkel Kommanditgesellschaft Auf Aktien Procede pour la fabrication de regulateurs de mousse contenant de la paraffine
WO1998055575A1 (fr) * 1997-06-03 1998-12-10 Henkel Kommanditgesellschaft Auf Aktien Granules adjuvants pour corps moules detergents et lavants

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