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EP0877791B1 - Procede de production de corps moules constitues d'un produit de lavage ou de nettoyage - Google Patents

Procede de production de corps moules constitues d'un produit de lavage ou de nettoyage Download PDF

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Publication number
EP0877791B1
EP0877791B1 EP97900991A EP97900991A EP0877791B1 EP 0877791 B1 EP0877791 B1 EP 0877791B1 EP 97900991 A EP97900991 A EP 97900991A EP 97900991 A EP97900991 A EP 97900991A EP 0877791 B1 EP0877791 B1 EP 0877791B1
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EP
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Prior art keywords
weight
acid
tablets
compounds
surfactants
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.)
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EP97900991A
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German (de)
English (en)
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EP0877791A1 (fr
Inventor
Heinz-Manfred Wilsberg
Sandra Witt
Günther VOGT
Hans-Friedrich Kruse
Volker Bauer
Georg Assmann
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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
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0086—Laundry tablets

Definitions

  • the invention relates to a method for producing surfactant-containing washing or Detergent tablets.
  • Microwave technology offers another possibility for the production of detergent tablets.
  • international application WO 94/25563 describes the production of washing and cleaning-active moldings using microwave technology, which have an extremely high dissolving rate or disintegration rate.
  • This technique can be used to produce so-called macrosolids, which can usually contain up to 40% by weight of surfactants.
  • one of the raw materials used in substantial quantities is a crystalline layered silicate, in particular of the type SKS-6 ® (crystalline sodium disilicate; commercial product from Hoechst AG, Germany), the surfactant content can even be up to 60% by weight.
  • the anionic surfactants in substantial quantities for example in amounts above 10% by weight, and inorganic salts in amounts contain below 60 wt .-%, can be prepared according to the teaching of older German application DE-A-4429550 can be prepared by the anionic Surfactants in the form of one or more compounds are introduced into the process.
  • the object of the present invention was therefore to provide an improved method for To provide production of detergent tablets, which regardless of the manufacturing process, both have a high dimensional stability as well also quickly dissolve in water.
  • the invention therefore relates to a process for producing detergent-containing washing or detergent tablets, the starting materials being amorphous sodium silicate, which has a water content of less than 15% by weight, in solid form is admixed and this mixture is then molded in a manner known per se is transferred.
  • the process according to the invention is characterized in that amorphous sodium silicate in solid form, which has a water content of less than 15% by weight, is added to the starting materials. It is advantageous to introduce the amorphous sodium silicate into the process as finely divided as possible, that is to say as a powder.
  • the amorphous sodium silicates used in the process according to the invention are preferably silicates in the module range (molar ratio SiO 2 / Na 2 O) 1.3 to 3.0, in particular 1.8 to 3.
  • the term "amorphous" is used in the context of Invention also understood “X-ray amorphous".
  • the water content of the amorphous sodium silicates used according to the invention is below 15% by weight, preferably between 0.5 and 13% by weight and in particular between 2 and 8% by weight.
  • amorphous silicates used according to the invention with a water content of less than 15% by weight can, for example, by the method of EP 542 131 Drying water glass solutions can be made with hot air or flue gas. It is also preferred to use dried amorphous sodium silicate, as described in German patent application DE 44 00 024 is described.
  • the detergent tablets produced according to the invention have a proportion of dried amorphous sodium silicate, based on the Total weight of the moldings, between 1 and 25% by weight, preferably between 3 and 15% by weight.
  • the moldings can be obtained in a manner known per se, for example by pressing or by pouring the components or with the help of Microwave technology.
  • the moldings are made using the Microwave technology manufactured.
  • the premixed ones are Ingredients placed in a mold and pressed under pressure. The height the pressure is dependent on the desired strength of the molded body chosen.
  • the moldings can be made by casting, if any or all Components, for example by melting or pressurization, into one Allow liquid form to be converted and all components stable under these conditions are.
  • the liquid mixture is poured into a mold and then it is left freeze.
  • the entire recipe consisting of: the individual ingredients, as well as any other individual non-surfactant raw materials, according to WO 94/25563 filled into a mold and irradiated with microwaves.
  • “Microwaves” in the context of the mentioned patent application is the entire Frequency range between 3 and 300,000 MHz understood, that is in addition to the actual microwave range of above 300 MHz also the radio wave range of 3 to 300 MHz.
  • the radiation leads to increased temperatures and to local sintering of the ingredients at the contact points, the cavities in the Shaped bodies are retained, i.e. a complete fusion of the ingredients among themselves is avoided.
  • the voids between the individual ingredients are present before irradiation with microwaves, cause a high porosity of the Shaped body and thus contribute to improving the release properties of the Molded body at.
  • the Present invention uses raw materials, some of which are in hydrated form available.
  • “hydrated” is used to mean “hydrated under certain conditions regarding temperature, pressure or relative humidity of the Atmosphere to which the raw material is exposed or with which the raw material is exposed Balance stands "understood.
  • molded body is not limited to one certain spatial form limited. In principle, any spatial shape is possible that the Starting materials can be forced due to an outer container. Preference is given to tablets in the conventional sense, i.e. cylindrical body, the The height of the cylinder is smaller than its diameter.
  • the spatial shape of a particularly preferred embodiment of the tablet is in its Dimensions of the induction bowl of standard household washing machines adjusted so that the tablet is metered directly into the dispenser without a metering aid where it dissolves during the induction process.
  • Another preferred shaped body that can be produced has a plate or panel-like structure with alternating thick long and thin short segments, see above that individual segments of this "bolt" at the predetermined breaking points, the short display thin segments, can be canceled and entered into the machine can.
  • This principle of "bar-shaped” tablet detergent can also be used in others geometric shapes, for example vertically standing triangles, which only appear one of its sides are connected to each other along the side, can be realized.
  • the individual Starting materials in the form of compounds that is, pre-made mixtures individual starting materials used.
  • Surfactant compounds are particularly preferred used, in particular compounds containing anionic surfactants, which also contain nonionic, can contain amphoteric or cationic surfactants.
  • the surfactant compounds have usually a surfactant content of at least 10% by weight, preferably at least 40% by weight, particularly preferably 60 to 95% by weight, based on the compound.
  • the use of such surfactant compounds, including highly concentrated surfactant compounds with contents of up to about 95% by weight of surfactants causes local Differences in surfactant concentration in the tablet, which is not only evident in the Processing, but also when the shaped body later disintegrates in the wash liquor Has shown an advantage.
  • the various components are not compressed into a uniform tablet, but that tablets 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 performance properties of the tablets. If, for example, components are contained in the tablets which have a mutually negative influence, 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. when the second goes into solution.
  • a tablet consists of at least three layers, that is to say two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleaching agent, while in the case of the stack-like tablet the two outer layers and the shell-like one However, the outermost layers of the tablet are free of peroxy bleach.
  • Such multilayer tablets have the advantage that they can be used not only via a dispenser or via a metering device which is added to the washing liquor; rather, in such cases it is also possible to place the tablet in direct contact with the textiles in the machine without fear of stains from bleaching agents and the like.
  • Another preferred embodiment of the invention provides that in the Process at least two different types of compounds are used.
  • washing or cleaning agents which have at least one contain compound containing anionic surfactant, in the manner of the invention in molded articles convict. Examples of this are spray-dried detergents with bulk weights of about 300 to 600 g / l, preferably 5 to 40% by weight in the spray-dried proportions Anionic surfactants included.
  • spray-dried granules can also be retrofitted with other ingredients of washing or cleaning agents under granulating Conditions are sprayed or powdered, which increases the bulk weight.
  • the preferred liquid constituents here are nonionic surfactants, as powdering agents for example finely divided zeolites, silicas, sulfates and / or calcium stearates to call.
  • Spray-dried granules containing anionic surfactant in addition to spray-dried or granulated Compounds which are made of carrier materials such as zeolite, crystalline Layered silicates, polymeric polycarboxylates, carbonates and optionally also Silicates exist and with liquid to pasty or waxy ingredients such as nonionic surfactants and / or foam inhibitors or conventional Textile softeners are impregnated.
  • carrier materials such as zeolite, crystalline Layered silicates, polymeric polycarboxylates, carbonates and optionally also Silicates
  • liquid to pasty or waxy ingredients such as nonionic surfactants and / or foam inhibitors or conventional Textile softeners are impregnated.
  • the shaped articles produced according to the invention with other substances, especially ingredients of washing or cleaning agents aftertreated.
  • substances that are subject to the conditions of Manufacturing how high temperatures or pressures are not stable.
  • This includes for example enzymes and perfumes.
  • microwave technology it may be advantageous that enzymes due to the better possible Temperature control or the lower temperature load of the overall mixture with be irradiated.
  • those produced according to the invention Shaped body according to the teaching of European patent application EP-A-0 002 293 with a Shell made of hydrated salts, such as sodium acetate trihydrate or the di-, Provide hepta or dodecahydrates of the disodium hydrogen phosphate.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are preferably C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as those obtained from C 12 -C 18 monoolefins with an end or internal double bond by sulfonation Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates obtained from C 12 -C 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.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are the mono-, di- and triesters as well as their mixtures understand how they are produced by esterification of a monoglycerin with 1 up to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerin be preserved.
  • Preferred sulfonated fatty acid glycerol esters are Sulfation 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.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
  • alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid half-esters of the 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.
  • 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 16 -C 18 alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C 16 -C 18 -alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and relatively low ones Washing temperatures of, for example, room temperature to 40 ° C.
  • the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably C 12 -C 18 fatty alkyl sulfates or mixtures of C 12 -C 14 fatty alkyl sulfates or C 12 -C 18 fatty alkyl sulfates with C 16 -C 18 -Fatty alkyl sulfates and especially C 12 -C 16 fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates.
  • saturated alkyl sulfates not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C 16 to C 22 are used.
  • Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred. 2,3-alkyl sulfates are also suitable.
  • the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol ethylene oxide such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol ethylene oxide (EO) or C 12 - C 18 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps 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.
  • those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 12 -C 24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
  • 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.
  • non-ionic, cationic, zwitterionic or amphoteric surfactants are used.
  • nonionic surfactants preferred.
  • 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 linearly or preferably 2-branched methyl or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohol with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 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.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which either as sole nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the Alkyl chain, especially fatty acid methyl esters, such as those found in Japanese Patent application JP 58/217598 are described or preferably according to the in the international patent application WO-A-90/13533 become.
  • 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 the R-CO 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 stands.
  • 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 2 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 3 is a linear, branched or cyclic alkyl radical or an aryl radical is 2 to 8 carbon atoms and R 4 is a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • R 2 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 3 is a linear, branched or cyclic alkyl radical or an
  • [Z] is preferably obtained by reductive amination of a sugar, for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a 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 the international application WO-A-95/07331 by implementation with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.
  • the moldings can contain all the usual ingredients of washing or cleaning agents contain their total recipe. These include, in addition to those already detailed described surfactants, in particular inorganic and organic builder substances, Components that prevent the textile fabric from being soiled again (should repellents), and graying inhibitors, alkaline salts, bleaches and Bleach activators, foam inhibitors, fabric softeners, neutral salts and Dyes and fragrances.
  • suitable inorganic builders are suitable in particular zeolite-type aluminosilicates.
  • the fine crystalline, synthetic and bound water containing zeolite is preferably zeolite A and / or P in Detergent quality.
  • zeolite X and mixtures of A, X are also suitable and / or P.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 , yH2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to Is 20 and preferred values for x are 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 are those in which M is sodium and x is 2 or 3. In particular, both ⁇ - and ⁇ -sodium Na 2 Si 2 O 5 ⁇ yH 2 O preferred.
  • Usable organic builders are, for example, the preferred ones in the form of their Sodium salts used polycarboxylic acids, such as citric acid, adipic acid Succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided that such use is not for ecological reasons objectionable, 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.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of Polyacrylic acid or polymethacrylic acid, for example those with a relative Molecular mass from 800 to 150,000 (based on acid).
  • Suitable copolymers Polycarboxylates are especially those of acrylic acid with methacrylic acid and Acrylic acid or methacrylic acid with maleic acid.
  • Have proven to be particularly suitable Copolymers of acrylic acid with maleic acid have proven to be 50 to 90% by weight of acrylic acid and contain 50 to 10% by weight of maleic acid.
  • Their relative molecular mass, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • Organic are also particularly preferred degradable polymers with more than two different monomer units, for example those used as monomers salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives (DE 43 00 772.) or the salts of acrylic acid as monomers and 2-alkylallylsulfonic acid and sugar derivatives (DE 42 21 381).
  • copolymers are those described in the German patent applications DE 43 03 320 and P 44 17 734.8 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or vinyl acetate.
  • Suitable builder systems are oxidation products of carboxyl group-containing ones Polyglucosans and / or their water-soluble salts, such as those in the international patent application WO-A-93/08251 or their Manufactured, for example, in international patent application WO-A-93/16110 is described.
  • polyacetals which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups, for example as in the European patent application EP-A-0 280 223 can be obtained.
  • Preferred polyacetals will be from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the inorganic and / or organic builder substances are preferably in Amounts from about 10 to 60 wt .-%, in particular from 15 to 50 wt .-%, in the Tablets used.
  • the agents can also contain components that the oil and Influencing fat washability from textiles positively. This effect becomes special clearly if a textile is soiled that has already been washed several times with one detergent according to the invention, which contains this oil and fat-dissolving component, is washed.
  • the preferred oil and fat dissolving components include for example nonionic cellulose ethers such as methyl cellulose and in particular Methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and on hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ethers, as well as the polymers known from the prior art phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers from ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these. You can already take effect in small amounts. Their content is therefore preferably 0.2 to 10 % By weight and in particular up to 5% by weight.
  • Graying inhibitors have the task of removing the dirt detached from the fiber in the To keep the fleet suspended and thus prevent graying.
  • water-soluble colloids mostly of an organic nature, for example the water soluble salts of polymeric carboxylic acids, glue, gelatin, salts of Ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble, acidic Group-containing polyamides are suitable for this purpose.
  • Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt) are preferred.
  • Methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and Polyvinylpyrrolidone, for example in amounts of 0.1 to 5 wt .-%, based on the Means used.
  • Suitable ingredients of the agents are water-soluble inorganic salts such as Bicarbonates and carbonates.
  • the content of sodium carbonate and / or bicarbonate in the agent is preferably up to 50% by weight, advantageously between 10 and 25% by weight
  • 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 or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate and / or percarbonate.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or O-acyl compounds which form organic peracids with H 2 O 2 , preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonate, also carboxylic anhydrides and esters of polyols, such as glucose pentaacetate.
  • Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239.
  • the bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED ), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 12 -C 18 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
  • the salts of polyphosphonic acids are preferably the neutral ones Sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, Diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylenephosphonate used in amounts of 0.1 to 1.5 wt .-%.
  • Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. Are particularly well suited Strains of bacteria or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic substances obtained. Preferably be Subtilisin-type proteases, and in particular proteases derived from Bacillus lentus won, used.
  • Enzyme mixtures are, 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 cellulase-containing mixtures 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, to protect them against premature decomposition.
  • the percentage of enzymes Enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2% by weight.
  • the tablets can be derivatives of diaminostilbenedisulfonic acid as optical brighteners 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 a diethanolamino group, a Carry a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, e.g.
  • a tablet was produced from the compounds, powders and liquids listed below in accordance with the teaching of international patent application WO 94/25563.
  • Granulated compounds were used as starting materials (Table 1), which were mixed in a mixer to form a homogeneous overall mixture, which was then filled into a shaped body and pre-pressed for 10 seconds at a pressure of 13 N / cm 2 (the force exerted on the circular area) 35 N on an area of 2.7 cm 2 ).
  • the microwave radiation was then carried out at 2450 MHz and 250 watts. The irradiation lasted 13.5 seconds.
  • the tablets had a diameter of 4 cm, a height of 2.5 cm and a weight of 20 g.
  • the amorphous sodium silicate used (module 2.0) had a water content of 13% by weight (measured as loss on ignition, produced by the process of DE 44 00 024).
  • the compressive strength of the tablets was measured using a SCHLEUNIGER model 6D tablet hardness tester. (Composition in% by weight) A B C.
  • a shaped body (20 g) was placed in a conventional Doser for dry laundry (3.5 kg) in a washing machine (type Miele Novotronic W 918). After water had run in, the dosing device with the Molded body weighed. Then a colored washing program (111 water, 16 ° d) carried out. After 5 and 10 minutes the washing program was interrupted and the Doser weighed with the remains of the molded body.
  • Table 1 The differences from the first measurement of the Dosers with shaped bodies can be found in Table 1.
  • Sokalan ® CP5 maleic acid-acrylic acid copolymer Na salt (from BASF)
  • Nonionic surfactant compound Dehydol ® LT 7 53.0 Silica 24.6 Sokalan ® CP5 22.4 Anionic surfactant granules Na 2 CO 3 2.0 Texapon ® LS 96.0 water 2.0 Soap granules Soap 89.8 Sokalan ® CP5 8.1 Na 2 CO 3 2.1
  • Tablets were produced by the same procedure as in Example 1.
  • the amorphous sodium silicate (module 2.0) had a water content of 8% by weight (measured as loss on ignition, produced by the process of DE 44 00 024).
  • the tablets produced in this way had a compressive strength of at least 20 N / cm 2 and disintegrated in cold water after no more than 60 seconds. (To measure the rate of disintegration, the tablets were placed in a beaker with 750 ml of water and the time at which the tablets had disintegrated was determined).
  • the recipes can be found in Table 2.

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Claims (12)

  1. Procédé de production de corps moulés constitués d'un produit de lavage ou de nettoyage renfermant un ou plusieurs tensioactifs, caractérisé en ce que, en se référant au poids total du corps moulé de produit de lavage ou de nettoyage, entre 1 et 25 % en poids, de préférence entre 3 et 15 % en poids de silicate de sodium amorphe possédant une teneur en eau inférieure à 15 % en poids sont mélangés sous forme solide aux matières de départ et que ce mélange est ensuite transformé en corps moulé d'une manière connue en soi
  2. Procédé selon la revendication 1, caractérisé en ce que les corps moulés sont produits à l'aide de la technique des micro-ondes.
  3. Procédé selon une des revendications 1 à 2, caractérisé en ce que les corps moulés sont produits à l'aide de procédés de chauffage conventionnels, par exemple à l'air chaud ou au rayonnement infrarouge, ou à l'aide de techniques combinées, par exemple par la technique des micro-ondes et la technique conventionnelle.
  4. Procédé selon une des revendications 1 à 3, caractérisé en ce que le silicate de sodium amorphe séché présente un module compris dans la plage de modules (rapport molaire SiO2/Na2O) de 1,3 à 3,0, de préférence de 1,8 à 3.
  5. Procédé selon une des revendications 1 à 4, caractérisé en ce que le silicate de sodium amorphe séché possède entre 0,5 et 13 % en poids, de préférence entre 2 et 8 % en poids d'eau.
  6. Procédé selon une des revendications 1 à 5, caractérisé en ce que le moule rempli des matières de départ fait l'objet d'un précompactage avant l'irradiation par les micro-ondes
  7. Procédé selon une des revendications 1 à 6, caractérisé en ce que les tensioactifs sont incorporés dans le procédé sous la forme de compounds.
  8. Procédé selon une des revendications 1 à 7, caractérisé en ce que l'on met en oeuvre des compounds renfermant des surfactifs anioniques, qui peuvent également contenir des tensioactifs non ioniques, amphotères ou cationiques.
  9. Procédé selon une des revendications 1 à 8, caractérisé en ce que l'on met en oeuvre au moins deux compounds différent, les tensioactifs actifs anioniques et non ioniques étant contenus séparément dans des compounds différents.
  10. Procédé selon une des revendications 1 à 9, caractérisé en ce qu'au moins 15 % en poids, de préférence au moins 35 % en poids et en particulier, au moins 50 % en poids de la formulation totale du corps moulé sont constitués d'un ou de plusieurs compounds différents.
  11. Procédé selon une des revendications 1 à 10, caractérisé en ce que les corps moulés prêts à l'emploi font l'objet d'un traitement postérieur par d'autres substances, par exemple des ingrédients de produits de lavage ou de nettoyage.
  12. Procédé selon une des revendications 1 à 11, caractérisé en ce que le corps moulé est un corps cylindrique dont la hauteur du cylindre est inférieure à son diamètre.
EP97900991A 1996-01-19 1997-01-10 Procede de production de corps moules constitues d'un produit de lavage ou de nettoyage Revoked EP0877791B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19601840 1996-01-19
DE19601840A DE19601840A1 (de) 1996-01-19 1996-01-19 Verfahren zur Herstellung von Wasch- oder Reinigungsmittelformkörpern
PCT/EP1997/000087 WO1997026317A1 (fr) 1996-01-19 1997-01-10 Procede de production de corps moules constitues d'un produit de lavage ou de nettoyage

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EP0877791A1 EP0877791A1 (fr) 1998-11-18
EP0877791B1 true EP0877791B1 (fr) 2000-05-31

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EP (1) EP0877791B1 (fr)
AT (1) ATE193548T1 (fr)
DE (2) DE19601840A1 (fr)
ES (1) ES2148923T3 (fr)
WO (1) WO1997026317A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4429550A1 (de) * 1994-08-19 1996-02-22 Henkel Kgaa Verfahren zur Herstellung von Wasch- oder Reinigungsmitteltabletten
DE4439679A1 (de) * 1994-11-07 1996-05-09 Henkel Ecolab Gmbh & Co Ohg Verfahren zur Herstellung von Wasch- und Reinigungsmitteltabletten durch Mikrowellen- und Heißluftbehandlung
DE19636036A1 (de) * 1996-09-05 1998-03-12 Henkel Kgaa Verfahren zur Herstellung tensidhaltiger Formkörper mit Mikrowellenstrahlung
DE19709411A1 (de) * 1997-03-07 1998-09-10 Henkel Kgaa Waschmittelformkörper
US5961663A (en) * 1997-05-29 1999-10-05 Colgate-Palmolive Co. Microwave-dried amorphous alkali metal silicate powders and their use as builders in detergent compositions
DE19841361A1 (de) * 1998-09-10 2000-03-16 Henkel Kgaa Verfahren zur Herstellung von Wasch- oder Reinigungsmittelformkörpern
DE19910819A1 (de) * 1999-03-11 2000-09-14 Henkel Kgaa Wasch- und Reinigungsmittelformkörper mit Tensid-Bleichmittel-Builderkombination
GB0005785D0 (en) * 2000-03-11 2000-05-03 Mcbride Robert Ltd Detergent tablets

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL278464A (fr) * 1961-05-15
GB1077067A (en) * 1963-10-18 1967-07-26 Unilever Ltd Detergent tablet
US3450494A (en) * 1967-07-18 1969-06-17 Conrad J Gaiser Amorphous sodium silicate having inherent binding properties and method of producing same
DE3315950A1 (de) * 1983-05-02 1984-11-15 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung von reinigungsmitteltabletten
ATE207109T1 (de) * 1993-05-05 2001-11-15 Henkel Ecolab Gmbh & Co Ohg Verfahren zum verfestigen von teilchenfoermigen feststoffen und reinigungsprodukte daraus
DE4400024A1 (de) * 1994-01-03 1995-07-06 Henkel Kgaa Silikatische Builder und ihre Verwendung in Wasch- und Reinigungsmitteln sowie Mehrstoffgemische für den Einsatz auf diesem Sachgebiet
DE4404279A1 (de) * 1994-02-10 1995-08-17 Henkel Kgaa Tablette mit Buildersubstanzen
DE4429550A1 (de) * 1994-08-19 1996-02-22 Henkel Kgaa Verfahren zur Herstellung von Wasch- oder Reinigungsmitteltabletten

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ES2148923T3 (es) 2000-10-16
DE59701807D1 (de) 2000-07-06
ATE193548T1 (de) 2000-06-15
EP0877791A1 (fr) 1998-11-18
WO1997026317A1 (fr) 1997-07-24

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