EP0777721A1 - Procede de production de produits de lavage et de nettoyage en comprimes - Google Patents

Procede de production de produits de lavage et de nettoyage en comprimes

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Publication number
EP0777721A1
EP0777721A1 EP95929834A EP95929834A EP0777721A1 EP 0777721 A1 EP0777721 A1 EP 0777721A1 EP 95929834 A EP95929834 A EP 95929834A EP 95929834 A EP95929834 A EP 95929834A EP 0777721 A1 EP0777721 A1 EP 0777721A1
Authority
EP
European Patent Office
Prior art keywords
weight
compounds
acid
anionic surfactants
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.)
Granted
Application number
EP95929834A
Other languages
German (de)
English (en)
Other versions
EP0777721B1 (fr
Inventor
Georg Assmann
Hans-Friedrich Kruse
Jochen Jacobs
Volker Bauer
Günther VOGT
Heinz-Manfred Wilsberg
Sandra Witt
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0777721A1 publication Critical patent/EP0777721A1/fr
Application granted granted Critical
Publication of EP0777721B1 publication Critical patent/EP0777721B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • 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
    • C11D17/0082—Coated tablets
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S159/00—Concentrating evaporators
    • Y10S159/26—Electric field

Definitions

  • the invention relates to a method for producing detergent tablets containing surfactants using microwave technology.
  • microwaves is understood to mean the entire frequency range between 3 and 300,000 MHz, which thus also includes the radio wave range from 3 to 300 MHz in addition to the actual microwave range of above 300 MHz.
  • This technique can be used to produce so-called macrosolids, which in addition to tablets also include blocks, for example, which can usually contain up to 40% by weight of surfactants.
  • one of the raw materials used in substantial amounts is a crystalline layered silicate, in particular of the type SKS- ⁇ W (crystalline sodium disilicate commercial product from Hoechst AG, Germany)
  • the surfactant content can even be up to 60% by weight.
  • Further possible ingredients are on the one hand the microwave-active hydrated inorganic or organic salts such as alkali phosphate, alkali carbonate, alkali bicarbonate, alkali sulfate and O 96/0615
  • Citrate but also zeolite and even peroxy bleaching agents such as perborate or percarbonate. These are preferably used in encased form.
  • the invention accordingly relates to a process for the preparation of detergent tablets containing anionic surfactants, the tablets being produced using microwave technology and the anionic surfactants being introduced into the process in the form of one or more compounds.
  • surfactant compounds including highly concentrated surfactant compounds with contents of up to about 95% by weight of surfactants, results in local surfactant concentration differences in the tablet, which is not only an advantage in processing, but also in the later disintegration of the tablet in the wash liquor affects.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are preferably C 1 -C 3 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 1 -C 8 -monoolefins with a terminal or internal double bond Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
  • alkanesulfonates obtained from C12-Ciss alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as the mono-, di- and triesters as well as their mixtures, as they are in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the esterification of triglycerides with 0.3 to 2 moles of glycerol be preserved.
  • Preferred sulfated 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. If one starts from fats and oils, that is to say natural mixtures of different fatty acid glycerol esters, it is necessary to largely saturate the starting products with hydrogen in a manner known per se, ie to harden them to iodine numbers less than 5, advantageously less than 2.
  • Suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, turnip oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, lard oil or lard. Because of their high natural proportion of saturated fatty acids, it has proven to be particularly advantageous to start from coconut oil, palm kernel oil or beef tallow.
  • the sulfonation of the saturated fatty acids with 6 to 22 carbon atoms or the mixtures of fatty acid glycerol esters with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, is preferably carried out by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases, as described in the international context Patent application WO-A-91/09009 is specified.
  • the sulfonation products are a complex mixture which contains mono-, di- and triglyceride sulfonates with oc and / or internal sulfonic acid groups.
  • Sulfonated fatty acid salts glyceride sulfates, glycerine sulfates, glycerin and soaps are formed as by-products. If one starts with the sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures, the proportion of ⁇ -sulfonated fatty acid disalts can, depending on the procedure, be up to about 60% by weight.
  • Suitable sulfate-type surfactants 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 semiesters of the Ci2-Ci8- fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Cio- C2 ⁇ ⁇ 0xoalcohols 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.
  • Ci6-Ci8-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-wash detergents, to use Ci6-C ⁇ 8-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 Ci2-Ci8-fatty alkyl sulfates or mixtures of Ci2-Ci4-fatty alkyl sulfates or Ci2-Ci8-fatty alkyl sulfates with Ci6-C ⁇ 8-fatty alkyl sulfates and in particular Ci2- Ci6-fatty alkyl sulfates with Ci6-Ci8-fatty alkyl sulfates.
  • fatty alkyl sulfates preferably Ci2-Ci8-fatty alkyl sulfates or mixtures of Ci2-Ci4-fatty alkyl sulfates or Ci2-Ci8-fatty alkyl sulfates with Ci6-C ⁇ 8-fatty alkyl sulfates and in particular Ci2- Ci6-fatty alkyl sulfates with Ci6-Ci8-fatty alkyl sulfates.
  • saturated alkyl sulfates not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably CIOE to C22 are used.
  • Mixtures of saturated sulfated fatty alcohols predominantly consisting of C15 and unsaturated sulfated fatty alcohols predominantly consisting of CQ are particularly preferred, for example those derived from solid or liquid HD-Ocenol ( R ) fatty alcohol mixtures (commercial product of the applicant) ).
  • Weight ratios of alkyl sulfates are too Alkenyl sulfates of 10: 1 to 1: 2 and in particular of about 5: 1 to 1: 1 are preferred.
  • the sulfuric acid monoesters of the straight-chain or branched C7-C2i alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 moles of ethylene oxide (EO) or Ci2-Ci8 -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 in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain Cg to Cj8 fatty alcohol residues or mixtures thereof.
  • Preferred sulfosuccinates in particular contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, viewed in isolation, are nonionic surfactants (for a 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, myric acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated Ci2-C24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
  • the anionic surfactants and soaps can be present 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 are preferably located Surfactants in the form of their sodium or potassium salts, especially in the form of the sodium salts.
  • nonionic, cationic, zwitterionic or amphoteric surfactants can also be used in the tablets, optionally also in the compounds containing anionic surfactants.
  • Nonionic surfactants are particularly 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 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.
  • the preferred ethoxylated alcohols include, for example, Ci2-Ci4 alcohols with 3 EO or 4 EO, Cg-Cn alcohol with 7 EO, Ci3-Ci5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2-Ci8- Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-Ci4 alcohol with 3 EO and Ci2-Ci8 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.
  • alkyl glycosides of the general formula R0 (G) can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms. Atoms means 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, indicating the distribution of monoglycosides and oligoglycosides is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • 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.
  • 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 non-ionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • R2C0 for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 Hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • compounds containing anionic surfactants which contain various anionic surfactants - for example alkyl sulfates and alkylbenzenesulfonates and / or soap or alkyl sulfates and sulfated fatty acid glycerol esters - and / or anionic surfactants in combination with nonionic surfactants - for example alkyl sulfates and ethoxylated Fatty alcohols or alkyl sulfates, alkyl benzene sulfonates, ethoxylated fatty alcohols and / or alkyl glycosides or alkyl sulfates, soap, ethoxylated fatty alcohols and glucamides - contain. These are preferably compounds which contain anionic surfactants and nonionic surfactants in a weight ratio of 10: 1 to 1: 1.
  • Compounds used with preference have a surfactant content of at least 10% by weight.
  • compounds which have at least 40% by weight, preferably 60 to 95% by weight, based on the compound, of anionic surfactants.
  • a further preferred embodiment of the invention provides that at least two different types of compounds are used in the process.
  • anionic surfactants and nonionic surfactants can contain, for example, 40 to 70% by weight of the nonionic surfactants mentioned and silicates of the known type, organic builder substances such as polymeric polycarboxylates and / or phosphonates.
  • Particularly advantageous embodiments of the invention provide that at least 35% by weight, preferably at least 50% by weight and in particular at least 70% by weight, of the total formulation of the detergent or cleaning tablet consists of one or more different types of compounds ⁇ stand.
  • a method can be particularly advantageous in which even at least 75% by weight and up to 100% by weight of the total formulation are presented as a compound, which has optionally been post-treated.
  • washing or cleaning agents which contain at least one compound containing anionic surfactants can be converted into tablets in the manner according to the invention.
  • spray-dried detergents with bulk densities of about 300 to 600 g / l, which preferably contain 5 to 40% by weight of anionic surfactants in the spray-dried proportions.
  • These spray-dried granules can also be subsequently sprayed or powdered with further ingredients of washing or cleaning agents under granulating conditions, which increases the bulk density.
  • Non-ionic surfactants are to be mentioned as preferred liquid constituents, for example fine zeolites, silicas, sulfates and / or calcium stearates as powdering agents.
  • spray-dried granules containing anionic surfactant are present in addition to spray-dried or granulated compounds which consist of carrier materials such as zeolite, crystalline sheet silicates, polymeric polycarboxylates, carbonates and optionally also silicates and with liquid to pasty or wax-like ingredients such as are impregnated with nonionic surfactants and / or foam inhibitors or conventional textile plasticizers.
  • carrier materials such as zeolite, crystalline sheet silicates, polymeric polycarboxylates, carbonates and optionally also silicates and with liquid to pasty or wax-like ingredients such as are impregnated with nonionic surfactants and / or foam inhibitors or conventional textile plasticizers.
  • Spray-dried granules containing anionic surfactants can be tabletted with zeolite-containing granules which are sprayed with nonionic surfactants and / or individual extrudates, for example extrudates containing enzyme or bleach activator, but also peroxy bleaching agents, using microwave technology. It is also possible to use various extrudates, for example those which have been produced by the process according to the earlier German application P 44 06 210.9, for microwave tableting to use. Compounds which have been produced by means of superheated steam drying or drying by means of microwave radiation can also be used as compounds.
  • At least one of several compounds with high anionic surfactant compounds is used which has anionic surfactant contents above 40% by weight, preferably up to above 90% by weight, and in particular advantageously by granulation with simultaneous drying possibility by a process which takes place in a fluidized bed, as described in international application W093 / 04162.
  • the compounds are connected to one another by local melting / sintering at the contact points.
  • the cavities that exist between the individual compounds before irradiation with microwaves bring about a high porosity of the resulting tablet and thus contribute to improving the dissolving properties of the tablet.
  • compounds which contain proportions of starting materials which are present in hydrated form. If these water-containing components are not present in the compounds or are not available in sufficient quantities for sintering, then so The compounds can be partially or completely coated with such substances in sufficient quantity before tabletting using microwave technology.
  • Enveloping substances used with particular preference are amorphous silicates such as metasilicates or water glasses, alkali carbonates and alkali sulfates, zeolites such as zeolite A, X, Y or P, in particular zeolite A and P or mixtures of these, but also organic components such as water-containing citrates, for example sodium citrate. dihydrate, or water-containing acetates, for example sodium acetate trihydrate.
  • These coating substances are advantageously introduced into the process in amounts of 1 to 30% by weight, based on the overall formulation.
  • the overall formulation consisting of the individual compounds and possibly further individual non-surfactant raw materials, which do not have to be present as a compound, is filled into a shaped body and irradiated with microwaves.
  • the irradiation leads to elevated temperatures and to the local sintering of the compounds at the contact points, the cavities in the molded body being retained, ie complete fusion of the compounds with one another is avoided.
  • the compounds themselves are therefore not burdened by higher temperatures.
  • This type of sintering leads to a surprisingly high breaking strength of the tablet, so that it can be handled and in particular transported without problems.
  • the invention provides that disintegrants are incorporated into the tablets, which cause the tablet to break open after it has come into contact with water.
  • Typical disintegrants which are preferably used in this process are, for example, citric acid or citrates, bicarbonates and carbonates, bisulfate, but also percarbonate. Due to the relatively low temperatures occurring in this process, it is possible to incorporate peroxy bleaching agents such as perborate and even percarbonate into the tablets.
  • Other preferred disintegrants are microcrystalline cellulose, sugar, in particular sorbitol, but also sheet silicates, in particular finely divided and swellable sheet silicates of the bentonite or sectite type. Disintegrants of the type described can be used in amounts of from 0.5 to 30% by weight, preferably from 1 to 25% by weight, based on the overall formulation. It is possible to use the explosives as a single raw material or also as a compound.
  • disintegrants are therefore used which were coated with known hydrophobic components before they were used.
  • paraffin oil or silicone oil are mentioned as coating substances, the use of which is also preferred.
  • the tablets can be post-treated with further substances, preferably ingredients of detergents or cleaning agents, and in particular ingredients that are sensitive to microwaves.
  • Enzymes and perfumes should be mentioned in particular.
  • the tablets can contain all of the usual ingredients of washing or cleaning agents in their overall formulation.
  • surfactants already described in detail, in particular inorganic and organic builder substances, components which prevent the textile fabric from being soiled again (soil repellents), and graying inhibitors, alkaline salts, bleaching agents and bleach activators, foam inhibitors, textile-softening substances, neutral salts and dyes and Contain fragrances.
  • aluminosilicates of the zeolite type are particularly suitable as inorganic builder substances.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality.
  • zeolite X and zeolite P and mixtures of A, X and / or P are also suitable.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x 02 ⁇ + i'yH20, 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 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 represents sodium and x assumes the values 2 or 3.
  • Usable organic builders are, for example, the polycarboxylic acids preferably 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), provided that 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.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, 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.
  • Biodegradable terpolymers are also particularly preferred, for example those which, as monomers, contain salts of acrylic acid and maleic acid and vinyl alcohol or Contain vinyl alcohol derivatives (P 4300772.4) or the salts of acrylic acid and 2-alkylallylsulfonic acid as monomers and sugar derivatives (DE 4221 381).
  • oxidation products of carboxyl group-containing polyglucosans and / or their water-soluble salts are described, for example, in international patent application WO-A-93/08251 or whose preparation is described, for example, in international patent application WO-A-93/16110.
  • polyaspartic acids or their salts and derivatives are also to be mentioned as further preferred builder substances.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223 .
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the inorganic and / or organic builder substances are preferably used in the tablets in amounts of about 10 to 60% by weight, in particular 15 to 50% by weight.
  • the agents can also contain components which have a positive influence on the oil and fat washability from textiles. This effect is particularly evident when a textile is soiled, which has previously been washed several times with a detergent according to the invention and which is oil and contains 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 from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight, in each case based on the non-ionic cellulose ether, and also 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 anionic and / or nonionic mo ⁇ differentiated derivatives of these. They can take effect in small quantities. 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 keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying.
  • Water-soluble colloids of mostly organic nature are suitable for this, 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 polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), 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% by weight, based on the detergent, are preferred used.
  • Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these;
  • alkali carbonate and amorphous alkali silicate especially sodium silicate with a molar ratio Na2 ⁇ : Si ⁇ 2 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used.
  • the sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight.
  • the content of sodium silicate in the compositions is generally up to 10% by weight and preferably between 2 and 8% by weight.
  • amorphous is also understood to mean “X-ray amorphous”. This means that the 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. However, it is very well possible and can even lead to particularly good image properties that 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 regions of the size 10 to a few hundred n.
  • X-ray amorphous silicates like some commercially available compounds made of carbonates and amorphous silicates, are suitable for partially or completely replacing the usual builder substances such as phosphate, zeolite and crystalline layer silicates. If such substances are used, their content can also exceed the amounts given above for carbonates and amorphous silicates. Contents of up to 40% by weight or even 60% by weight are entirely within the scope of the invention.
  • alkali metal carbonates can also be replaced by sulfur-free, 2 to 11 carbon atoms and, if appropriate, a further carboxyl and / or amino group and / or salts thereof.
  • the alkali metal carbonates be partially or completely replaced by glycine or glycinate.
  • 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 H2O2-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the salary of the The amount of bleaching agent 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 H2O2, 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 activator content of the bleach-containing agents is 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'-tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,5,5-triazine (DADHT) and acetylated sorbitol mannitol Mixtures (S0RMAN).
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of Ci8-C24 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, e.g. those made of silicone, 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 bistearylethylene diamides are particularly preferred.
  • the salts of polyphosphonic acids which are preferably used are the neutral sodium salts of, for example, l-hydroxyethane-l, l-diphosphonate, Diethylenetriamine pentamethylene phosphonate or ethylenediaminetetramethylene phosphonate is used in amounts of 0.1 to 1.5% by weight.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active ingredients 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.
  • Peroxides 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 the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • the tablets or compounds 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-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly structured compounds which are used instead of the morpholino group carry 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.
  • tablets are produced which contain 15 to 40% by weight, preferably 18 to 35% by weight and in particular 20 to 30% by weight of anionic or anionic and nonionic surfactants, the Anionic surfactant content preferred is above 10% by weight and the weight ratio of anionic surfactants: nonionic surfactants is 5: 1 to 1: 2.
  • Particularly preferred anionic surfactants are alkyl benzene sulfonates and alkyl sulfates and soaps.
  • Preferred nonionic surfactants are ethoxylated Ci2-Ci8 fatty alcohols or oxo-alcohols and alkyl glycosides.
  • preferably manufactured tablets contain 10 to 60% by weight, preferably 15 to 50% by weight and in particular 20 to 40% by weight of builder substances such as zeolite A and / or zeolite P, crystalline layered silicates of the SKS-6 type ( R ) or amorphous or X-ray amorphous silicates and carbonate-silicate compounds with a correspondingly high calcium binding.
  • builder substances such as zeolite A and / or zeolite P, crystalline layered silicates of the SKS-6 type ( R ) or amorphous or X-ray amorphous silicates and carbonate-silicate compounds with a correspondingly high calcium binding.
  • tablets are produced which contain 40 to 60% by weight of compounds, 10 to 90% by weight of anionic surfactants, advantageously alkylbenzenesulfonates and / or alkyl sulfates, and 10 to 90% by weight .-% consist of builder substances, hydrated salts and / or disintegrants.
  • Further advantageous tablets additionally have compounds which are free of anionic surfactants and contain builder substances, advantageously zeolite A and / or zeolite P and 10 to 40% by weight of nonionic surfactants.
  • a tablet was produced from the compounds, powders and liquids listed below in accordance with the teaching of the international patent application PCT / EP94 / 01330.
  • a homogeneous overall mixture was produced from the components in a mixer, 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 surface was 35 N on one surface of 2.7 cm 2 ).
  • the microwave radiation was then carried out at 2450 MHz and 700 watts. The radiation lasted 7 seconds. A temperature of 60 ° C was not exceeded during the irradiation process.
  • the tablet had good breaking strength at pressures between 7.4 to 37 N / cm 2 .
  • the tablet also had a high rate of disintegration in water: Large parts of the tablet had disintegrated after only 1 minute; after 5 minutes the tablet was 100% disintegrated.
  • Percarbonate could also be used instead of the perborate. It was also possible to use the soap as separate soap granules containing more than 80% by weight of soap and also soda and polymeric polycarboxylates.
  • a tablet was produced from the compounds, powders and liquids listed below in accordance with the teaching of the international patent application PCT / EP94 / 01330.
  • a homogeneous total mixture was produced from the components in a mixer, which was then filled into a shaped body and pre-pressed for 10 seconds with a pressure of 2.6 N / cm 2 (the force exerted on the circular surface was 7 N on one surface of 2.7 cm 2 ).
  • the microwave radiation was then carried out at 2450 MHz and 700 watts. The radiation lasted 7 seconds. A temperature of 65 ° C was not exceeded during the irradiation process.
  • anionic surfactant compound consisting of 90.5% by weight
  • sodium silicate Na2 ⁇ : SO2, 1: 2.0 with 18% by weight water.
  • the tablet had good breaking strength at pressures between 7.4 to 22 N / cm 2 .
  • the tablet also had a high rate of disintegration in water: Large parts of the tablet had disintegrated after only 0.5 minutes; after 4 minutes the tablet was 100% disintegrated.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP95929834A 1994-08-19 1995-08-10 Procede de production de produits de lavage et de nettoyage en comprimes Expired - Lifetime EP0777721B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4429550A DE4429550A1 (de) 1994-08-19 1994-08-19 Verfahren zur Herstellung von Wasch- oder Reinigungsmitteltabletten
DE4429550 1994-08-19
PCT/EP1995/003169 WO1996006156A1 (fr) 1994-08-19 1995-08-10 Procede de production de produits de lavage et de nettoyage en comprimes

Publications (2)

Publication Number Publication Date
EP0777721A1 true EP0777721A1 (fr) 1997-06-11
EP0777721B1 EP0777721B1 (fr) 1998-11-25

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EP (1) EP0777721B1 (fr)
JP (1) JPH10504349A (fr)
KR (1) KR970705629A (fr)
AT (1) ATE173758T1 (fr)
DE (2) DE4429550A1 (fr)
ES (1) ES2126310T3 (fr)
WO (1) WO1996006156A1 (fr)

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KR970705629A (ko) 1997-10-09
ATE173758T1 (de) 1998-12-15
JPH10504349A (ja) 1998-04-28
US5866531A (en) 1999-02-02
ES2126310T3 (es) 1999-03-16
DE4429550A1 (de) 1996-02-22
WO1996006156A1 (fr) 1996-02-29
DE59504349D1 (de) 1999-01-07
EP0777721B1 (fr) 1998-11-25

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