WO2000044872A1 - Detergents et nettoyants sous forme de corps moules, a rapport de detergent anionique defini - Google Patents

Detergents et nettoyants sous forme de corps moules, a rapport de detergent anionique defini Download PDF

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Publication number
WO2000044872A1
WO2000044872A1 PCT/EP2000/000384 EP0000384W WO0044872A1 WO 2000044872 A1 WO2000044872 A1 WO 2000044872A1 EP 0000384 W EP0000384 W EP 0000384W WO 0044872 A1 WO0044872 A1 WO 0044872A1
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Prior art keywords
weight
surfactant
detergent
acid
granules
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PCT/EP2000/000384
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German (de)
English (en)
Inventor
Andreas Lietzmann
Birgit Burg
Gerhard Blasey
Markus Semrau
Fred Schambil
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Henkel Kommanditgesellschaft Auf Aktien
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Priority to AU27976/00A priority Critical patent/AU2797600A/en
Publication of WO2000044872A1 publication Critical patent/WO2000044872A1/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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

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 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 simple dosage. Tableted detergents and cleaning agents have a number of advantages over powdered ones: They are easier to dose and handle and, thanks to their compact structure, have advantages in terms of storage and transport. Detergent tablets are therefore also comprehensively described in the patent literature. A problem that occurs again and again when using shaped articles which are active in washing and cleaning is the insufficient rate of disintegration and dissolution of the shaped articles under conditions of use.
  • the washing performance of shaped articles that are active in washing and cleaning is ensured by the use of surfactants, alkylbenzenesulfonates occupying an important position due to their high cleaning performance and large-scale availability and fatty alcohol sulfates due to their native raw material base with good cleaning performance. It was therefore one of the objects of the present invention to provide a laundry detergent and cleaning product tablet in which the preparation of the surfactant portion alone leads to it disintegrating more quickly with predetermined hardness. Another object of the present invention was to provide surfactant granules as a raw material base for detergent tablets, the use of the surfactant granules being intended to impart advantageous physical properties, in particular short disintegration times and high hardness, to the tablets.
  • Detergent tablets which contain fatty alcohol sulfate compounds are described in the older German patent application DE 198 49 630.3 (Henkel KGaA).
  • the FAS compounds disclosed herein have fatty alcohol sulfate contents above 60% by weight, based on the compound, and consist of at least 60% by weight of particles with particle sizes between 600 and 1600 ⁇ m.
  • Detergent tablets containing fatty alcohol sulfate and processes for their production are described, for example, in the unpublished German patent application DE 198 31 707.7 (Henkel KGaA).
  • a method is disclosed in which a surfactant-containing granulation batch is placed in a mixer / granulator and granulated with the addition of a fatty alcohol sulfate paste, after which the fatty alcohol sulfate-containing surfactant granules are mixed with powdered processing components and pressed into shaped bodies.
  • the invention relates to detergent tablets made of compressed, particulate detergent and detergent, containing builders, alkylbenzenesulfonates, fatty alcohol sulfates and optionally further surfactants and ingredients of detergents and cleaning agents, in which the ratio of alkylbenzenesulfonates to fatty alcohol sulfates is in the range from 3: 1 to 1: 100 lies.
  • ratio denotes the quotient of the percentages by weight of alkylbenzenesulfonate and fatty alcohol sulfate, the % By weight data relate to the entire molded body. It is not relevant here whether these anionic surfactants have been incorporated into the detergent tablets in different ways, or whether they are present in different phases or regions of the tablet.
  • the ratio is in an even narrower range, so that detergent tablets are preferred in which the ratio of alkylbenzenesulfonates to fatty alcohol sulfates is in the range from 2: 1 to 1:75, preferably from 1.5: 1 to 1: 50, particularly preferably from 1: 1 to 1:25 and in particular from 1: 2 to 1:10.
  • the detergent tablets according to the invention contain builders as well as alkylbenzenesulfonates and fatty alcohol sulfates as mandatory constituents. These are described below.
  • alkylbenzenesulfonates as powerful anionic surfactants have been known since the 1930s. At that time, alkylbenzenes were produced by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation, which were sulfonated with oleum and neutralized with sodium hydroxide solution.
  • propylene was tetramerized to give branched ⁇ -dodecylene and the product was converted to tetrapropylenebenzene via a Friedel-Crafts reaction using aluminum trichloride or hydrogen fluoride, which was subsequently sulfonated and neutralized.
  • Linear alkylbenzenesulfonates are made from linear alkylbenzenes, which in turn are accessible from linear olefms.
  • the resulting olefins are then reacted with benzene in the presence of acidic catalysts to give the alkylbenzenes, the choice of Friedel-Crafts catalyst having an influence on the isomer distribution of the resulting linear arene alkylbenzenes:
  • the choice of Friedel-Crafts catalyst having an influence on the isomer distribution of the resulting linear arene alkylbenzenes:
  • the detergent and cleaning agent forms contain the alkali metal, preferably sodium, salts of C 8 . 16 -, preferably C 9. , 3 - Contain alkylbenzenesulfonic acids which are derived from alkylbenzenes and which have a tetralin content below 5% by weight, based on the alkylbenzene.
  • alkylbenzenesulfonates whose alkyl benzenes HF method were prepared by the so that washing and cleaning composition shaped bodies are preferred, as the alkylbenzene sulfonates, the alkali metal, preferably sodium salts, of C G.16 -, preferably C. 9 13 - Alkylbenzenesulfonic acids, which have a 2-phenyl isomer content below 22% by weight, based on the alkylbenzenesulfonic acid.
  • the alkali metal preferably sodium salts
  • detergent tablets are preferred whose content of alkylbenzenesulfonates is between 0.5 and 25% by weight, preferably between 0.75 and 20% by weight, particularly preferably between 1 and 15% by weight. % and in particular between 1.25 and 12.5% by weight, based in each case on the weight of the shaped body.
  • Fatty alcohol sulfates the alkali metal, in particular sodium salts of the sulfuric acid half-esters of longer-chain alcohols, are commercially available from fatty alcohols which are reacted with sulfuric acid, chlorosulfonic acid, amidosulfonic acid or sulfur trioxide to give the alkyl sulfuric acids concerned and are subsequently neutralized.
  • the fatty alcohols are obtained from the fatty acids or fatty acid mixtures concerned by high-pressure hydrogenation of the fatty acid methyl esters.
  • the most important industrial process for the production of fatty alkyl sulfuric acids is the sulfonation of the alcohols with SO 3 / air mixtures in special cascade, falling film or tube bundle reactors.
  • the fatty acids are technically largely obtained from native fats and oils by hydrolysis. While the alkaline saponification which was carried out in the past century led directly to the alkali salts (soaps), only water is used on an industrial scale to split the fats into glycerol and the free fatty acids. Alternatively, the cleavage can be carried out with methanol, the methyl esters and glycerol being obtained directly. Large-scale processes are, for example, the split in the auto ven or the continuous high pressure gap.
  • Carboxylic acids which can be used as the basis for the fatty alcohol sulfates in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc.
  • fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanic acid (behenic acid), tetracosanoic acid (lignoceric acid), triacotonic acid (melotonic acid), triacotanoic acid (cerotonic acid) the unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidic acid), 9c, 12c-linadol acid) 9
  • Such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C 8, 6 wt .-% C 10 48 wt .-% C! 2, 18 wt .-% C14, 10 wt .-% C 16, 2 wt .-% C18, 8 wt .-% of C 18., 1 wt .-% C lg ⁇ •), palm kernel oil fatty acid (about 4 wt .-% C 8, 5 wt .-% C 10, 50 wt.
  • soybean oil fatty acid (approx. 2% by weight C 14 , 15 wt .-% C 16, 5 wt .-% C 18, 25 wt .-% C, 8, 45 wt .-% C, 8, 7 wt .-% C 18 -).
  • the alk (en) yl sulfates are preferably the alkali and in particular the sodium salts of the sulfuric acid half-esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C, 0 -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 can also be used, which are synthetic, petrochemical-based. ten straight-chain alkyl radical, which have a degradation behavior analogous to the adequate compounds based on oleochemical raw materials.
  • the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C 14 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
  • Preferred detergent tablets in the context of the present invention contain the alkali metal, preferably sodium salts of C 8 . 22 -, preferably C 10 - 20 - and especially C 12 . 18 - fatty alkyl sulfuric acids.
  • detergent tablets are preferred in which the content of the foam body in fatty alcohol sulfates is between 1 and 30% by weight, preferably between 1.5 and 25% by weight, particularly preferably between 2 and 20 % By weight and in particular between 2.5 and 15% by weight, in each case based on the weight of the shaped body.
  • the washing and cleaning agent film bodies according to the invention preferably contain the total amount of alkylbenzenesulfonates and fatty alcohol sulfates in the form of a surfactant granulate which contains both alkylbenzenesulfonates and fatty alcohol sulfates.
  • a surfactant granulate which contains both alkylbenzenesulfonates and fatty alcohol sulfates.
  • further anionic and nonionic surfactants can be contained in the shaped bodies, it being possible for these to be introduced into the shaped bodies both via the surfactant granules and in some other way.
  • the detergent tablets according to the invention can contain further surfactants from the groups of anionic, nonionic, cationic and zwitterionic surfactants, anionic surfactants being clearly preferred for economic reasons and on the basis of their performance spectrum.
  • anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type include, for example, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates such as are obtained, for example, from C 12 .
  • 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 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.
  • 2,3-alkyl sulfates which are produced for example in accordance with US Patent No. 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 . 18 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also known as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 . 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • 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 from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • 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.
  • detergent tablets are preferred whose total anionic surfactant content is above 5% by weight, preferably above 7.5% by weight and in particular above 10% by weight, based in each case on the weight of the tablet , lies.
  • the optionally used nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with 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 branches linearly or preferably in the 2-position methyl may be 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 or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12.14 alcohols with 3 EO or 4 EO, C 9 "alcohol with 7 EO, C 13 . 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C, 2 . Ig alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 . 14 alcohol with 3 EO and C 12 . 18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples 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 is a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
  • Linear alkyl polyglucosides ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.
  • the detergent tablets according to the invention can preferably contain alkyl polyglycosides, APG contents of the tablets more than 0.2% by weight, based on the entire tablet, 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 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 are usually obtained by reductive amination of a reducing sugar. can be obtained 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)
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 represents a linear, branched or cyclic alkyl radical or represents an aryl radical or an oxy-alkyl radical with 1 to 8 carbon atoms
  • C M - alkyl or phenyl radicals being preferred
  • [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this rest.
  • [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.
  • detergent tablets are preferred which additionally contain nonionic surfactant (s) and in which the nonionic surfactant content of the tablets is above 2% by weight, preferably above 5% by weight and is in particular above 7.5% by weight, based in each case on the molded body weight.
  • nonionic surfactants from all of the above-mentioned groups can be used. Regardless of the chemical nature of the nonionic surfactants used, it is preferred that the nonionic surfactants contained in the detergent tablets have a melting point below 40 ° C., preferably below 30 ° C. and in particular below 20 ° C.
  • the nonionic and anionic surfactants can be incorporated into the detergent tablets according to the invention in a wide variety of ways. They can be added to the premix to be treated, for example in solid form, or sprayed out of the premix in liquid form. It has proven to be advantageous to produce surfactant granules which are mixed with other powdery components to form the premix to be tabletted and pressed.
  • detergent tablets are preferred which contain the surfactants in the form of a surfactant-containing granulate in amounts of from 40 to 95% by weight, preferably from 45 to 85% by weight and in particular from 55 to 75% by weight. , each based on the weight of the molded body, is contained in the molded bodies.
  • detergent tablets are preferred in which the surfactant granules contain from 5 to 60% by weight, preferably from 10 to 50% by weight and in particular from 15 up to 40% by weight, based in each case on the weight of the surfactant granules.
  • detergent tablets in which the anionic surfactant content of the surfactant granules is 5 to 45% by weight, preferably 10 to 40% by weight and in particular 15 to 35% by weight, based in each case on the weight of the surfactant granules and detergent tablets, in which the content of the surfactant granules of nonionic surfactants is 1 to 30% by weight, preferably 5 to 25% by weight and in particular 7.5 to 20% by weight, in each case based on the weight of the surfactant granules , is preferred according to the invention.
  • surfactant granules In order to obtain storage-stable and free-flowing surfactant granules, it is preferred if carrier substances are added in the preparation of the surfactant granules, ie the surfactant granules contain builders. Other ingredients of detergents and cleaning agents, in particular so-called small components such as optical brighteners, polymers, defoamers, phosphonates, colorants and fragrances, can also be part of the surfactant granules. These substances are described below.
  • builders are the most important ingredients in detergents and cleaning agents.
  • the washing and cleaning agent shaped bodies according to the invention can contain all builders normally used in washing and cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also the phosphates.
  • These builders can be added to the mixtures to be tabletted, but they can also be wholly or partly a component of surfactant granules.
  • Crystalline, layered sodium silicates suitable as builders have the general formula NaMSi x O 2x + , ⁇ 2 O, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • M sodium or hydrogen
  • x is a number from 1, 9 to 4
  • y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 "yH 2 O are preferred, with ⁇ -sodium disilicate being able to be obtained, for example, by the method described in international patent application WO-A-91/08171.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention is under the term “amo ⁇ h” also understood “roentgenamo ⁇ h".
  • 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 integrated in such a way that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray silicates.
  • zeolite of the P and / or X type that is usually introduced by the surfactant granules
  • further zeolite 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.
  • Organic cobuilders which can be used in the detergent tablets according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances are described below.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), 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 acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used.
  • the measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard.
  • the molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of 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 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • biodegradable polymers composed of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers .
  • Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
  • DE dextrose equivalent
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring for carboxylic acid function.
  • oxidizing agents capable of oxidizing at least one alcohol function of the saccharide ring for carboxylic acid function.
  • Such oxidized dextrins and processes for their production are, for example, from the European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as the international patent applications WO 92/18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known.
  • An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable.
  • a product oxidized at C 6 of the saccharide ring can be
  • Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are 3 to 15% by weight in formulations containing zeolite and / or silicate.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such cobuilders are described, for example, in international patent application WO 95/20029.
  • phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
  • hydroxyalkane phosphonates l-hydroxyethane-l, l-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9).
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal de assets. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • the granules containing surfactant are not produced by spray drying, but rather by means of a granulation process.
  • press agglomeration processes can also be used, for example. Methods in which the surfactant-containing granules are produced by granulation, agglomeration, press agglomeration or a combination of these methods are therefore preferred.
  • the granulation can be carried out in a large number of apparatuses customarily used in the detergent and cleaning agent industry. For example, it is possible to use the rounding agents commonly used in pharmacy. In such turntable devices, the residence time of the granules is usually less than 20 seconds.
  • Conventional mixers and mixing granulators are also suitable for granulation. Both high-intensity mixers (“high-shear mixers”) and normal mixers with lower circulation speeds can be used as mixers.
  • Suitable mixers are, for example, Eirich ® mixers from the R or RV series (trademark of Maschinenfabrik Gustav Eirich, Hardheim), Schugi ® Flexomix, and Fukae ® FS-G mixers (Trademark of Fukae Powtech, Kogyo Co., Japan), the Lödige ® FM, KM and CB mixers (trademark of Lödige Maschinenbau GmbH, Paderborn) or the Drais ® series T or KT (trademark of Drais-Werke GmbH , Mannheim).
  • the residence times of the granules in the mixers are in the range of less than 60 seconds, the residence time also being dependent on the circulation speed of the mixer. The dwell times are reduced accordingly the faster the mixer runs.
  • the residence times of the granules in the mixer / rounder are preferably less than one minute, preferably less than 15 seconds. Dwell times of up to 20 minutes are set in slow-running mixers, for example a Lödige KM, dwell times below 10 minutes being preferred because of the process economy.
  • the surfactant-containing granules are compressed under pressure and under the action of shear forces, homogenized in the process and then discharged from the apparatus in a shaping manner.
  • the technically most important press agglomeration processes are extrusion, roller compaction, pelleting and tableting.
  • preferred press agglomeration processes used to produce the surfactant-containing granules are extrusion, roller compaction and pelletization.
  • the surfactant-containing granulate is preferably fed continuously to a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guide, the housing and the extruder granulating head of which are heated to the predetermined extrusion temperature could be.
  • the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally, under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating cutting knife.
  • the hole diameter of the perforated nozzle plate and the length of the cut gate are matched to the selected granule size.
  • Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.8 to 5 mm and in particular in the range from approximately 1.0 to 3 mm.
  • the length / diameter ratio of the chopped-off primary granules is in the range from about 1: 1 to about 3: 1.
  • extrusions / readings can also be carried out in low-pressure extruders, in the Kahl press or in the extruder.
  • the production process for the surfactant-containing granules is carried out by means of roller compaction.
  • the granules containing surfactant are metered in between two smooth rollers or with depressions of a defined shape and rolled out under pressure between the two rollers to form a sheet-like compact, the so-called Schülpe.
  • the rollers exert a high line pressure on the premix and can be additionally heated or cooled as required.
  • smooth rollers smooth, unstructured sliver belts are obtained, while by using structured rollers, correspondingly structured slugs or individual pellets can be produced, in which, for example, certain shapes of the later granules or moldings can be specified.
  • the sliver belt is subsequently broken down into smaller pieces by a knocking-off and comminution process and can be processed into granules in this way, which can be further tempered by further surface treatment methods known per se, in particular in an approximately spherical shape.
  • the preparation of the surfactant-containing granules is carried out by means of pelleting.
  • the surfactant-containing granules are applied to a perforated surface and pressed through the holes by means of a pressure-producing body.
  • the surfactant-containing granules are compressed under pressure, plasticized, pressed through a perforated surface in the form of fine strands by means of a rotating roller and finally comminuted to granules with a knock-off device.
  • the most varied configurations of the pressure roller and perforated die are conceivable here.
  • the press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation.
  • An apparatus suitable for carrying out the method according to the invention is described, for example, in German laid-open specification DE 38 16 842 (Schlüter GmbH).
  • the ring die press disclosed in this document consists of a rotating ring die penetrated by press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge.
  • the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved.
  • the detergent tablets of the present invention may contain further detergent ingredients.
  • the premix to be ve ⁇ ressed can contain other ingredients customary in washing and cleaning agents, in particular from the group of disintegration aids, 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 included.
  • all or part of the substances mentioned can already be part of the surfactant granules.
  • tablet disintegrants In order to facilitate the disintegration of highly compressed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, in order to shorten the disintegration times.
  • tablet disintegrants or disintegration accelerators are understood as auxiliary substances which are necessary for the 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 molded article weight.
  • Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred washing and cleaning agent shaped bodies 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 I0 O 5 ) n and, formally speaking, represents a ß-1,4-polyacetal of cellobiose, which in turn consists of two Molecules of glucose is built up. 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 esters 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 treated.
  • Detergent tablets which contain disintegrants in granular or optionally granulated form, are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants.
  • the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
  • the coarser disintegration aids based on cellulose that are mentioned above and described in more detail in the cited documents are preferred as disintegration aids in the context of the present invention used and commercially available, for example, under the name Arbocel ® TF-30-HG from Rettenmaier.
  • 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.
  • Coated detergent tablets of this type can be produced by spraying a melt or solution of the coating material onto the molded article or by 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 that 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.
  • Particularly preferred in the context of the present invention are detergent tablets which in water at 30 ° C. in less than 60 seconds completely disintegrate into their seconds articles which are so small that they can be washed in via the washing-up chamber of a household washing machine.
  • the compounds which serve as bleaching agents and supply H 2 O 2 in water sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid 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. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, regardless of which other ingredients are contained in the molded articles.
  • 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-diperoxyazelaic acid diperoxyacid, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-
  • 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,
  • Dibromisocy.anurklare 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-dimethylhyd.anthoin are also suitable.
  • bleach activators can be incorporated into the molded body.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having 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.
  • Multi-acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular l, 5-diacetyl-2,4-dioxohexahydro-l, 3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetoxy and 2,5-diacetyloxy and 2,5-glycolacetyl, ethylene glycol 2,5-dihydrofur
  • 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.
  • Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hy- By removing pilling and microfibrils, drolasen can also help to maintain color and increase the softness of the textile. Oxidoreductases can also be used for bleaching or for inhibiting color transfer.
  • hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hy
  • Bacillus subtilis Bacillus licheniformis
  • Streptomyceus griseus Streptomyceus griseus
  • Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants.
  • Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest.
  • Known cutinases are examples of such lipolytically active enzymes.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes can be adsorbed on carriers or embedded in coating substances 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 0.5 to about 4.5% 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.
  • 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, based in each case on the nonionic cellulose ether
  • the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • the moldings can contain derivatives of diammostilbenedisulfonic 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 to provide the consumer with a visually and sensorially "typical and distinctive" product in addition to performance.
  • Individual fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexylpropyl pentylpionate and stally.
  • the ethers include, for example, benzyl ethyl ether
  • the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronel lal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal
  • the ketones include, for example, the jonones, oc-isomethylionone and methylcedryl ketone
  • the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and hydrocarbons belong to the hydrocarbons mainly the tezenes like limes 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, linden blossom 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 is not difficult for the 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 to textile fibers, in order not to dye them.
  • Another object of the present invention is a method for producing detergent tablets by mixing granules containing surfactant with finely divided preparation components and subsequent shaping in a manner known per se, the ratio of alkylbenzenesulfonates to fatty alcohol sulfates being in the range from 3: 1 to 1: 100.
  • Variants in which the ratio is within a narrower range are also preferred in the method according to the invention.
  • Preferred processes are characterized in that the ratio of alkylbenzenesulfonates to fatty alcohol sulfates is in the range from 2: 1 to 1:75, preferably from 1.5: 1 to 1:50, particularly preferably from 1: 1 to 1:25 and in particular from 1 : 2 to 1:10
  • the surfactants can be introduced into the moldings in different ways, the incorporation via surfactant granules being particularly advantageous.
  • process engineering advantages can result from a separation of alkylbenzenesulfonates and fatty alcohol sulfates, so that processes in which two surfactant-containing granules are mixed with finely divided processing components and subsequently molded in a manner known per se, one surfactant granulate containing the alkylbenzenesulfonate surfactants and the other surfactant granules contains, are preferred according to the invention.
  • surfactant granulate containing both alkylbenzenesulfonates and fatty alcohol sulfates.
  • the surfactant-containing granules have total anionic surfactant contents of 5 to 40% by weight, preferably 10 to 35% by weight and in particular 15 to 30% by weight, based in each case on the Weight of the surfactant granules, the content of the surfactant granules of alkylbenzenesulfonates preferably 1 to 30% by weight, particularly preferably 2 to 25% by weight and in particular 3 to 20% by weight, and the content of the surfactant granules in fatty alcohol sulfates preferably 1 to 35 % By weight, particularly preferably 2.5 to 30% by weight and in particular 5 to 25% by weight, in each case based on the weight of the surfactant granules.
  • the addition of nonionic surfactants is often advantageous.
  • 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 quality and physical properties of both the premix (storage, molding) as well as 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 (compare Donald W.
  • the or one of the subsequently admixed finely divided processing components comprises a zeolite of the faujasite type with partial Chen sizes below 100 microns, preferably below 10 microns and in particular below 5 microns and is at least 0.2 wt .-%, preferably at least 0.5 wt .-% and in particular more than 1 wt .-% of the premix to be ve ⁇ resses.
  • the premix to be ve ⁇ resses has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular above 700 g / 1, and furthermore one or more substances from the group of disintegration aids, bleaching agents, bleach activators , Enzymes, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.
  • 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 point in time, only the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.).
  • 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 disk, the number of die holes being increased accordingly.
  • the throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses are selected 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 pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch 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 sensibly manageable designs come as a room shape were considered, for example, the design as a table, the rod 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 as tablets, in cylinder or cuboid form can be expedient, 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 used in other geometric Shapes, for example vertically standing triangles, which are connected to one another only on one of their sides, are realized.
  • 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, for example, components are contained in the moldings that mutually influence each other negatively, 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.
  • 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, that is to say two outer and at least one inner layer, at least one peroxy bleaching agent being contained in one of the inner layers, while in the case of the stacked molded body the two cover layers and in the case of the molded body the outermost layers, however, 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. Similar effects can also be achieved by coating individual constituents of the detergent and cleaning agent composition to be treated or the entire molded article.
  • 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.
  • 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.
  • Another object of the present invention is the use of surfactant-containing granules which, after mixing with finely divided processing components, are pressed in a manner known per se to form detergent tablets and in which the ratio of alkylbenzenesulfonates to fatty alcohol sulfates is in the range from 3: 1 to 1 : 100, is to improve the hardness and disintegration time of detergent tablets.
  • the surfactants in a defined weight ratio, the physical properties of the molded body can be improved, as the following examples show: Examples:
  • Various surfactant granules were produced by wet granulation in a 130-liter ploughshare mixer from Lödige, the contents of which varied in alkylbenzenesulfonate and fatty alcohol sulfate. Following the granulation, the granules were dried in an Aeromatic fluidized bed apparatus at an inlet air temperature of 60 ° C. for 30 minutes. After drying, the granules were sieved to remove the fine particles ⁇ 0.6 mm and coarse particles> 1.6 mm.
  • the surfactant granules E1 to E4 or V were then prepared with further components to form a compressible premix, after which the Koring eccentric was used to form tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g).
  • the measured values of the tablet hardness and disintegration times are in each case the mean values of a double determination, the individual values varying by type of molded body by a maximum of 2 N or 2 s.
  • the composition of the surfactant granules is shown in Table 1, the composition of the premixes to be treated (and thus the molded article) is shown in Table 2.
  • Table 3 shows that the disintegration times of detergent tablets are significantly reduced by the use of ABS and FAS in a certain ratio.

Abstract

L'invention concerne des détergents et nettoyants sous forme de corps moulés, se caractérisant par des temps de désintégration réduits pour un niveau de durcissement élevé et une bonne aptitude à l'injection. On obtient ce type de détergents et de nettoyants si le rapport des alkylbenolsulfonates et des sulfates d'alcool gras contenus dans les corps moulés se situe entre 3:1 et 1:100.
PCT/EP2000/000384 1999-01-28 2000-01-19 Detergents et nettoyants sous forme de corps moules, a rapport de detergent anionique defini WO2000044872A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU27976/00A AU2797600A (en) 1999-01-28 2000-01-19 Moulded detergent and cleaning agent articles with defined anionic detergent ratio

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1999103290 DE19903290A1 (de) 1999-01-28 1999-01-28 Wasch- und Reinigungsmittelformkörper mit definiertem Aniontensidverhalten
DE19903290.4 1999-01-28

Publications (1)

Publication Number Publication Date
WO2000044872A1 true WO2000044872A1 (fr) 2000-08-03

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AU (1) AU2797600A (fr)
CA (1) CA2297453A1 (fr)
DE (1) DE19903290A1 (fr)
WO (1) WO2000044872A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104371838A (zh) * 2014-10-29 2015-02-25 国家电网公司 一种清洗电路板的清洗剂及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997034994A1 (fr) * 1996-03-21 1997-09-25 Henkel Kommanditgesellschaft Auf Aktien Detergent et nettoyant solide a masse volumique apparente elevee contenant des tensioactifs et des adjuvants, et compose approprie
WO1999029825A1 (fr) * 1997-12-08 1999-06-17 Henkel Kommanditgesellschaft Auf Aktien Corps moules de detergent a desintegration amelioree
DE19841362A1 (de) * 1998-09-10 2000-03-16 Henkel Kgaa ABS-haltige Wasch- und Reinigungsmittelformkörper

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997034994A1 (fr) * 1996-03-21 1997-09-25 Henkel Kommanditgesellschaft Auf Aktien Detergent et nettoyant solide a masse volumique apparente elevee contenant des tensioactifs et des adjuvants, et compose approprie
WO1999029825A1 (fr) * 1997-12-08 1999-06-17 Henkel Kommanditgesellschaft Auf Aktien Corps moules de detergent a desintegration amelioree
DE19841362A1 (de) * 1998-09-10 2000-03-16 Henkel Kgaa ABS-haltige Wasch- und Reinigungsmittelformkörper

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104371838A (zh) * 2014-10-29 2015-02-25 国家电网公司 一种清洗电路板的清洗剂及其制备方法
CN104371838B (zh) * 2014-10-29 2017-10-13 国家电网公司 一种清洗电路板的清洗剂及其制备方法

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AU2797600A (en) 2000-08-18
CA2297453A1 (fr) 2000-07-28
DE19903290A1 (de) 2000-08-03

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