WO2000050559A1 - Corps moules de produits de lavage et de nettoyage stables a l'abrasion et contenant des additifs solides - Google Patents

Corps moules de produits de lavage et de nettoyage stables a l'abrasion et contenant des additifs solides Download PDF

Info

Publication number
WO2000050559A1
WO2000050559A1 PCT/EP2000/001247 EP0001247W WO0050559A1 WO 2000050559 A1 WO2000050559 A1 WO 2000050559A1 EP 0001247 W EP0001247 W EP 0001247W WO 0050559 A1 WO0050559 A1 WO 0050559A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
acid
surfactant
premix
nonionic surfactants
Prior art date
Application number
PCT/EP2000/001247
Other languages
German (de)
English (en)
Inventor
Andreas Lietzmann
Birgit Burg
Peter Schmiedel
Markus Semrau
Monika Böcker
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to AU25490/00A priority Critical patent/AU2549000A/en
Publication of WO2000050559A1 publication Critical patent/WO2000050559A1/fr

Links

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
    • C11D1/72—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 cleaning hard surfaces, bleach tablets for use in washing machines or dishwashers, water softening tablets or stain remover tablets.
  • the invention relates to detergent tablets which are used for washing textiles in a household washing machine and are briefly referred to as detergent tablets.
  • Detergent tablets are widely described in the prior art and are becoming increasingly popular with consumers because of the 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.
  • European patent application EP 355 626 (Henkel KGaA) discloses a process for producing detergent tablets which are free or low in phosphate, in which at least two powdery to granular components (A) and (B) are produced, which are mixed and tabletted.
  • Component (A) contains the total amount of anionic surfactants, component (B) 75 to 100% of the total amount of nonionic surfactants.
  • European patent application EP 466 485 (Unilever) also describes detergent tablets which contain builders and anionic and nonionic surfactants.
  • the premix to be pressed consists here of particles which consist of 20 to 100% anionic surfactant and preferably of anionic surfactant-free particles which may contain nonionic surfactant. This document does not disclose a ratio to be maintained between nonionic and anionic surfactants. The problem of insufficient abrasion stability is also not mentioned.
  • Detergent tablets which in addition to high amounts of nonionic surfactant necessarily contain potassium carbonate, are described in European patent application EP 482 627 (Kao Corp.). According to the teaching of this document, the solubility of the tablets is improved by a special weight ratio between nonionic surfactant and potassium carbonate. In this document too, neither anion / nonionic surfactant ratios are disclosed, nor is the problem of abrasion stability dealt with.
  • the present invention was based on the object of providing moldings which, given a given hardness, are distinguished by short disintegration times and can therefore also be metered via the dispensing chamber of household washing machines.
  • the moldings should have an increased stability against falling and rubbing loads, ie they should have an improved, ie a reduced friability and a reduced abrasion behavior.
  • the advantageous properties should be based on the assembly of washing and cleaning medium ingredients can be achieved in order to be able to dispense with the addition of "non-recipe" auxiliaries that do not perform any washing and cleaning work. It has now been found that highly alkoxy-containing nonionic surfactants give the moldings increased stability against abrasion when they are added to the premix to be pressed.
  • the present invention relates to a process for the production of detergent tablets by mixing a surfactant-containing granulate with pulverulent preparation components and subsequent molding, which is characterized in that the mixture to be compressed is a solid preparation component based on the weight of the molding OJ up to 20% by weight of one or more highly alkoxylated nonionic surfactants with more than 10 alkylene oxide units are admixed.
  • the highly alkoxylated nonionic surfactant (s) are added separately to the premix in the process according to the invention, i.e. they are not completely part of the surfactant granulate.
  • the surfactant-containing granules also contain compounds which meet the criteria mentioned above, the granules are preferably free of these compounds.
  • the amount in which the highly alkoxylated nonionic surfactants are added to the premix and on the other hand the number of alkylene oxide units is within a narrower range.
  • Preferred processes are characterized in that the mixture to be pressed is 0J5 to 10% by weight, preferably 0.2 to 5% by weight, particularly preferably 0.25 to 4% by weight and in particular 0.4 to 2% by weight.
  • % of one or more highly alkoxylated nonionic surfactants with 10 to 100, preferably 20 to 80 and in particular 25 to 50 alkylene oxide units are admixed.
  • alkylene oxide units denotes the statistical mean value of AO groups in a molecule of the nonionic surfactant in other words, the statistical mean of the moles of alkylene oxide present per mole of alcohol.
  • ethylene oxide (EO) and propylene oxide (PO) units are of technical interest as alkylene oxide units.
  • the alkoxylates in question can be obtained in a known manner from the alcohols and ethylene or propylene oxide.
  • EO / PO mixtures can also be used in the context of the present invention.
  • the structure of the highly alkoxylated nonionic surfactants can be varied within wide limits.
  • the alkyl radical is determined by the selection of the long-chain alcohol.
  • the industrially accessible alcohols having 8 to 24 carbon atoms, in particular native alcohols from the hydrogenation of carboxylic acids or carboxylic acid derivatives are preferred.
  • the alcohols obtainable from technical alcohol syntheses, such as oxo alcohols and Ziegleral alcohols, can also be used.
  • fatty alcohols which can be used as the alkyl radical of the highly alkoxylated nonionic surfactants are, for example, hexanol (capro alcohol), heptanol (enanthal alcohol), octanol (caprylic alcohol), nonanol (pelargon alcohol), decanol (capric alcohol), undecanol, etc.
  • fatty alcohols such as dodecanol (laurinyl alcohol), tetradecanol (myristinyl alcohol), hexadecanol (palmitinyl alcohol), octadecanol (stearinyl alcohol), eicosanol (arachinyl alcohol), docosanol (behenyl alcohol), tetracosanol (lignocerinyl alcohol), tricotinyl alcohol (cerotinyl alcohol), cerotinyl alcohol (cerotinyl alcohol), cerotinyl alcohol (cerotinyl alcohol), tricotinyl alcohol (cerotanol alcohol), trotanol alcohol (Melissinyl alcohol) and the unsaturated species 9c-hexadecenol (palmitoleyl alcohol), 6c-octadecenol (petroselinyl alcohol), 6t-octadecenol (petroselaidin
  • Such mixtures are, for example Koskos- oil alcohol (about 6 wt .-% C g, 6 wt .-% C, 0, 48 wt .-% C I2, 18 wt .-% C14, 10 wt .-% C I6 , 2% by weight C 18 , 8% by weight C, 8 , 1% by weight C 18 ), palm kernel oil alcohol (approx.
  • the alcohol radical of the highly alkoxylated nonionic surfactants is derived from fatty alcohols and / or oxo alcohols and has chain lengths of 8 to 24, preferably 10 to 20, particularly preferably 12 to 18 and in particular 16 to 18 carbon atoms.
  • fatty alcohol ethoxylates are particularly preferred as highly alkoxy-hardened nonionic surfactants.
  • Preferred processes according to the invention are therefore characterized in that alcohol ethoxylates of the general formula are used as highly alkoxy-containing nonionic surfactants
  • C n H 2n + 1 O- (CH 2 CH 2 O) m H are used in which n values from 8 to 24, preferably from 10 to 20, particularly preferably from 12 to 18 and in particular from 16 to 18 and m values from over 10, preferably from 10 to 100, particularly preferably from 20 to 80 and especially from 25 to 50.
  • the particularly preferred chain length range from 16 to 18 carbon atoms and the particularly preferred degrees of ethoxylation from 25 to 50, the following compounds or mixtures (the technical mixtures) of these compounds are particularly suitable for use in the context of the present invention:
  • the highly alkoxylated nonionic surfactants are added to the premix in solid form, which is not a problem in view of the melting or softening point of these substances.
  • Compounds or technical mixtures of the type mentioned often do not have a clearly defined melting point, but instead have a melting range or softening point which can extend over one to two degrees Celsius.
  • the highly alkoxylated nonionic surfactants have melting points between 30 and 100 ° C., preferably between 30 and 75 ° C. and in particular between 30 and 50 ° C.
  • the premix to be pressed contains granulate (s) containing surfactant and further preparation components.
  • the granules containing surfactant can be produced by conventional industrial granulation processes such as compacting, extrusion, mixer granulation, pelletization or fluidized bed granulation. It is advantageous for the later detergent tablets if the premix to be pressed has a bulk density that comes close to that of conventional compact detergents. In particular, it is preferred that the premix to be pressed has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1. In preferred process variants, the surfactant-containing granulate satisfies certain particle size criteria.
  • the surfactant-containing granules have particle sizes between 100 and 2000 ⁇ m, preferably between 200 and 1800 ⁇ m, particularly preferably between 400 and 1600 ⁇ m and in particular between 600 and 1400 ⁇ m.
  • the surfactant granules preferably also contain carriers which particularly preferably come from the group of builders.
  • the premix to be pressed contains a surfactant-containing granulate which contains anionic and / or nonionic surfactants and builders and whose total surfactant content is 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 40% by weight, based in each case on the surfactant granulate, is.
  • the surfactant granules contain surface-active substances from the group of anionic, nonionic, zwitterionic or cationic surfactants, anionic surfactants being clearly preferred for economic reasons and because of their performance spectrum.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are preferably C 9 .
  • alkanesulfonates obtained from C 12.18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • Other suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
  • Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) yl sulfates Talgfettalko- alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C, the alkali and especially the sodium salts of the Schwefelhoffregurester C I2 -C 18 fatty alcohols, for example coconut fatty alcohol, C 20 10 -Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical which is produced on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • the C 2 -C 16 alkyl sulfates and C, 2 -C 15 alkyl sulfates and C ! 4 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
  • 2,3-alkyl sulfates which are produced for example according to US -Patentschriften 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • 21 alcohols such as 2-methyl-branched C 9 . -Alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 . 18 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and represent especially ethoxyherten fatty alcohols.
  • Preferred sulfosuccinates contain C.sub.g.lg fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated eraacic 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 which contain 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 10 to 20% by weight of anionic surfactant (s), based in each case on the Molded body weight included.
  • preferred detergent tablets have a soap content which exceeds 0.2% by weight, based on the total weight of the tablet.
  • the preferred anionic surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates, preferred detergent tablets 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular contain in particular 5 to 10% by weight of fatty alcohol sulfate (s), based in each case on the weight of the shaped body.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical has a methyl or linear branching in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 . 14 -alcohols with 3 EO or 4 EO, C,. ,, -alcohol with 7 EO, C 13 . 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C I2 . 18 - alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ! 2.14 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.
  • Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG).
  • Alkypolyglycosides that can be used satisfy the general formula RO (G) z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is Is a symbol which stands for a 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 1J 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.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • 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 is an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms
  • C M alkyl or phenyl radicals being preferred
  • [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this rest.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the nonionic and anionic surfactants can be incorporated into the detergent tablets according to the invention in a wide variety of ways.
  • detergent tablets 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 shaped body, is contained in the shaped bodies.
  • the premix contains a surfactant-containing granulate which contains from 5 to 60% by weight, preferably from 10 to 50% by weight and in particular from 15 to 40% by weight, based in each case on the weight of the surfactant granules (see above).
  • 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.
  • the surfactant granules are mixed with further ingredients of detergents and cleaning agents to form a compressible premix and then tabletted.
  • the production of detergent tablets is preferred according to the invention, so that preferred variants of the process according to the invention are characterized in that the proportion of the surfactant-containing granules in the premix to be compressed and thus in the detergent tablets is 40 to 95% by weight, preferably 45 to 85 % By weight and in particular 55 to 75% by weight, in each case based on the weight of the detergent tablets.
  • builders are important ingredients of detergents and cleaning agents. In addition to the wash-active substances, builders are the most important ingredients in detergents and cleaning agents.
  • the detergent tablets according to the invention can contain all of the builders usually used in detergents, especially zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - the phosphates.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
  • 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.
  • Crystalline, layered sodium silicates suitable as builders have the general formula NaMSi x O 2x + 1 ⁇ 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 is 2, 3 or 4.
  • M sodium or hydrogen
  • x is a number from 1.9 to 4
  • y is a number from 0 to 20
  • preferred values for x is 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na- > Si 2 O 5 'yH 2 O are preferred, whereby ⁇ -sodium disilicate can 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.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • zeolite of the P and / or X type 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. 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, adi pinic 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.
  • 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 .
  • 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 made from dialde hyden such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained 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 to the carboxylic acid function.
  • oxidizing agents capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608.
  • An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable.
  • a product oxidized at C 6 of the saccharide ring can be
  • Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycerol are also preferred in this context.
  • cerintrisuccinate. 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 ammoalkane phosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1J-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 ammoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues.
  • EDTMP hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the ammoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, especially if the agents also contain bleach, it may be preferred to use ammoalkane phosphonates, 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 ® mixer Series R or RV (trademark of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi ® Flexomix, the Fukae ® FS-G mixers (trade marks 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- Maschinene 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.
  • press agglomeration 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.
  • disintegration aids so-called tablet disintegrants
  • tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.
  • Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case based on the weight of the tablet.
  • Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets have such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 contain up to 6 wt .-%.
  • Pure cellulose has the formal gross composition (C 6 H ! 0 O 5 ) n and, formally speaking, is a ß-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
  • Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
  • Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted.
  • celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
  • the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose.
  • the content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the disintegrant based on cellulose.
  • the cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be pressed.
  • Detergent tablets which contain disintegrants in granular or optionally cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel). These writings are also detailed information on the The position of granulated, compacted or cogranulated cellulose disintegrants can be found.
  • the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
  • the above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ® TF-30-HG from Rettenmaier available in the present invention.
  • Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged.
  • a subsequent disaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 ⁇ m and can be compacted, for example, to granules with an average particle size of 200 ⁇ m.
  • the premix to be pressed additionally contains a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably of 3 to 7 wt .-% and in particular from 4 to 6 wt .-%, each based on the weight of the premix.
  • a disintegration aid preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably of 3 to 7 wt .-% and in particular from 4 to 6 wt .-%, each based on the weight of the premix.
  • the premix additionally contains one or more substances from the group of bleaching agents, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.
  • bleaching agents bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.
  • bleaching agents 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, irrespective of which other ingredients are contained in the shaped bodies.
  • 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 monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalonic acid operoxa [Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipinic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as IJ2-diperoxycarboxylic acid, 1, 9-diperoxyazoxybenoxy acid, Decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di
  • Chlorine or bromine-releasing substances can also be used as bleaching agents in moldings for automatic dishwashing.
  • Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid,
  • Dibromo isocyanuric acid and or dichloroisocyanuric acid (DICA) and / or their salts with Cations such as potassium and sodium are considered.
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • bleach activators can be incorporated into the premix.
  • 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.
  • polyacylated alkylenediamines especially tetraacetylethylene diamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially 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-dihydrofuran.
  • TAED
  • bleach catalysts can also be incorporated into the moldings.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures of cellulase containing particular interest.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules in the shaped bodies according to the invention can be, for example, approximately OJ to 5% by weight, preferably OJ to approximately 2% by weight.
  • laundry detergent and cleaning product tablets may also contain components which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • the moldings can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which 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 also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2- sulfostyryl) diphenyls. Mixtures of the aforementioned brighteners can also be used.
  • 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 washing and cleaning performance as well as a visually and sensorially "typical and unmistakable" product.
  • perfume oils or fragrances individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are e.g.
  • the ethers include, for example, benzyl ethyl ether, the aldehydes e.g.
  • the linear alkanals with 8-18 C atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, oc-isomethylionon and methylcedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance.
  • perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lentil flower oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the dye content of the laundry 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 entire 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 by 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 detergent tablets 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 towards textile fibers in order not to dye them.
  • 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 advantageous for the nature and physical properties of the premix (storage, pressing) as well as the finished detergent and cleaning agent moldings. 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 admixed processing components is a faujasite-type zeolite with particle sizes below 100 ⁇ m, is preferably below 10 ⁇ m and in particular below 5 ⁇ m and makes up at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1% by weight of the premix to be pressed.
  • the moldings according to the invention are first produced by dry mixing the constituents, which can be wholly or partially pregranulated, and then providing them, in particular pressing them into tablets, using conventional methods.
  • the premix is compressed in a so-called die between two punches to form a solid compressed product.
  • 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 molding being formed being determined by the position of the lower punch and the shape of the pressing tool.
  • the constant metering, even at high molding throughputs, is preferably achieved by volumetric metering 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 is conveyed away by subsequent transport devices. At this point, it's just that 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 correspondingly increased.
  • the throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table.
  • the number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available.
  • Each die on the die table is assigned an upper and lower punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps.
  • the die table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compaction, plastic deformation and ejection by means of rail-like cam tracks during the rotation.
  • these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks.
  • the die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix.
  • the pressure the pre-mix can be individually adjusted via the press 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.
  • All non-stick coatings known from the art are suitable for reducing stamp caking.
  • Plastic coatings are particularly advantageous, Plastic inlays or plastic stamps.
  • Rotating punches have also proven to be advantageous, with the upper and lower punches being designed to be rotatable if possible.
  • a plastic insert can generally be dispensed with.
  • the stamp surfaces should be electropolished here.
  • Tableting machines suitable within the scope of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and Courtoy NV, Halle (BE / LU).
  • the hydraulic double pressure press HPF 630 from LAEIS, D. is particularly suitable.
  • the molded body can be manufactured in a predetermined spatial shape and a predetermined size. Practically all practical configurations can be considered as the spatial form, for example the design as a board, 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. However, it is also possible to form compacts that have a plurality connect such mass units in a 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" molded article washing agent can also be realized in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the side.
  • the various components are not pressed into a uniform tablet, but that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous application properties of the molded body. If, for example, components are contained in the molded body that mutually influence each other negatively, it is possible to have one component in the more rapidly soluble layer to integrate and incorporate the other component in a slower 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 at least 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.
  • 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 2P ⁇ - ⁇ Dt
  • ⁇ 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 highly alkoxylated nonionic surfactants with more than 10 alkylene oxide units to improve the abrasion stability of detergent tablets.
  • This use according to the invention of the highly alkoxylated nonionic surfactants in the premix leads to shaped bodies with advantageous properties, as the examples below show.
  • preferred embodiments of the use according to the invention degrees of alkoxylation, chain lengths, melting points, composition of the premix, etc.
  • the surfactant granules were then processed with other components to give a compressible premix, the composition of which is given in Table 2.
  • the premixes El and E2 according to the invention contained highly ethoxylated nonionic surfactants, while the premix of comparative example V was free of such compounds.
  • the premixes were pressed in a Korsch eccentric press into 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 per molded body type varying by a maximum of 2 N or 2 s.
  • the hardness of the tablets was measured by deforming the tablet until it broke, the force acting on the side surfaces of the tablet and the maximum force which the tablet withstood being determined.
  • the washability was tested in a Miele Novotronic W918 washing machine (main wash program, 60 ° C). After washing in with three tablets and cold city water (10 ° C, 16 ° dH), the residues were dried and weighed out.
  • the abrasion stability was determined by placing a tablet on a sieve with a mesh size of 1.6 mm. This sieve was then placed in a Retsch analytical sieve machine and stressed with an amplitude of 2 mm over 120 seconds. By weighing the tablet lying on the sieve before and after the stress, the abrasion can be calculated in%.
  • Table 3 The experimental data are shown in Table 3:
  • the molded bodies E and V show a significantly better stability against the frictional load caused by the vibrating screen.
  • the application properties are consequently further improved by the use of the highly ethoxylated nonionic surfactants according to the invention.

Abstract

L'invention concerne des corps moulés de produits de lavage et de nettoyage qui se caractérisent non seulement par leur grande dureté et une bonne rinçabilité mais aussi par une grande stabilité à l'abrasion. On obtient ces moulés en mélangeant, comme composantes de préparation, au prémélange à comprimer 0,1 à 20 % en poids, par rapport au poids du corps moulé engendré, d'au moins un tensioactif non ionique hautement alcoxylé et plus de 10 unités d'oxyde d'alkylène.
PCT/EP2000/001247 1999-02-25 2000-02-16 Corps moules de produits de lavage et de nettoyage stables a l'abrasion et contenant des additifs solides WO2000050559A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU25490/00A AU2549000A (en) 1999-02-25 2000-02-16 Abrasion-resistant washing and cleaning agent shaped bodies containing solid additives

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1999108026 DE19908026A1 (de) 1999-02-25 1999-02-25 Abriebstabile Wasch- und Reinigungsmittelformkörper mit festen Additiven
DE19908026.7 1999-02-25

Publications (1)

Publication Number Publication Date
WO2000050559A1 true WO2000050559A1 (fr) 2000-08-31

Family

ID=7898739

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/001247 WO2000050559A1 (fr) 1999-02-25 2000-02-16 Corps moules de produits de lavage et de nettoyage stables a l'abrasion et contenant des additifs solides

Country Status (4)

Country Link
AU (1) AU2549000A (fr)
CA (1) CA2299445A1 (fr)
DE (1) DE19908026A1 (fr)
WO (1) WO2000050559A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2367830A (en) * 2000-10-12 2002-04-17 Procter & Gamble Process for preparing tablets
US8703111B2 (en) 2008-05-23 2014-04-22 Institut Quimic De Sarria Cets, Fundacio Privada Thermoplastic paste for repairing living tissues

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10163281A1 (de) * 2001-12-21 2003-07-03 Cognis Deutschland Gmbh Wasch- und reinigungsaktive Zubereitungen, enthaltend feste granuläre nichtion ische Tenside

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3104371A1 (de) * 1981-02-07 1982-11-11 Henkel KGaA, 4000 Düsseldorf "reinigungsmitteltablette"
EP0355626A1 (fr) * 1988-08-17 1990-02-28 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation de comprimés détergents à faible teneur en phosphate
DE19808758A1 (de) * 1998-03-02 1999-09-09 Henkel Kgaa Verfahren zur Herstellung von Wasch- und Reinigungsmittelformkörpern

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3104371A1 (de) * 1981-02-07 1982-11-11 Henkel KGaA, 4000 Düsseldorf "reinigungsmitteltablette"
EP0355626A1 (fr) * 1988-08-17 1990-02-28 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation de comprimés détergents à faible teneur en phosphate
DE19808758A1 (de) * 1998-03-02 1999-09-09 Henkel Kgaa Verfahren zur Herstellung von Wasch- und Reinigungsmittelformkörpern

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2367830A (en) * 2000-10-12 2002-04-17 Procter & Gamble Process for preparing tablets
US8703111B2 (en) 2008-05-23 2014-04-22 Institut Quimic De Sarria Cets, Fundacio Privada Thermoplastic paste for repairing living tissues
US9381251B2 (en) 2008-05-23 2016-07-05 Institut Quimic De Sarria Cets, Fundacio Privada Thermoplastic paste for repairing living tissues

Also Published As

Publication number Publication date
AU2549000A (en) 2000-09-14
CA2299445A1 (fr) 2000-08-25
DE19908026A1 (de) 2000-08-31

Similar Documents

Publication Publication Date Title
EP1138756B1 (fr) Détergents sous forme de comprimé comprenant des granules particuliers des agents tensioactifs
EP1037960B1 (fr) Corps moules de detergent a desintegration amelioree
EP1123378B1 (fr) Corps moules detergents et nettoyants munis d'un systeme granule effervescent exempt d'eau
WO2000044873A1 (fr) Pastilles detergentes a phases multiples
WO1999042556A1 (fr) Detergents et nettoyants sous forme de corps moules dont les proprietes presentent un profil renforce
WO2000014196A1 (fr) Pastilles de detergent renfermant des liants
WO2000050559A1 (fr) Corps moules de produits de lavage et de nettoyage stables a l'abrasion et contenant des additifs solides
EP1159392B2 (fr) Produits de lavage et de nettoyage moules contenant une association tensioactif/agent de blanchiment/adjuvant de lavage
EP1155111B1 (fr) Procede de production de corps moules de produits de lavage et de nettoyage de degradation rapide
WO2000029541A1 (fr) Corps moules nettoyants et detergents exempts de parfums
WO2000000581A1 (fr) Procede de preparation de detergents et de nettoyants sous forme de corps moules
WO1999055812A1 (fr) Corps moules detergents a proprietes de decomposition ameliorees
WO2000053716A1 (fr) Corps moules de lavage et de nettoyage contenant une association tensioactif/adjuvant de lavage
DE10129228B4 (de) Gelbildung verhindernde Zusätze zu Tensiden und Waschmittelformulierungen und ihre Anwendung in Wasch-und Reinigungsmitteln
WO2000022087A1 (fr) Corps moules detergents et nettoyants comprenant des acides oligocarboxyliques organiques
WO2000017305A1 (fr) Detergents et nettoyants sous forme de corps moules a constituants de preparation en gros morceaux
WO2000044871A1 (fr) Detergents et nettoyants sous forme de corps moules resistant a l'abrasion et a teneur elevee en tensioactifs non ioniques
WO2000027985A1 (fr) Corps moules d'agents nettoyants et detergents avec agents de solubilisation finement divises
WO2000000582A1 (fr) Procede de production de detergents et nettoyants sous forme de corps moules
WO2000027986A1 (fr) Corps moules d'agents nettoyants et detergents avec additifs
EP1112342A1 (fr) Corps moules de lavage et de nettoyage contenant des granules tensioactifs speciaux
WO2000044872A1 (fr) Detergents et nettoyants sous forme de corps moules, a rapport de detergent anionique defini
WO2000015753A1 (fr) Corps moules de lavage et de nettoyage contenant de l'alkyle benzene sulfonate
WO2000043487A1 (fr) Corps moules detergents et nettoyants stables a l'abrasion
WO2000060048A1 (fr) Detergents et nettoyants sous forme de corps moules, contenant des granules de tensioactifs speciaux

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AU AZ BA BB BG BR BY CN CR CU CZ DM EE GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LV MA MD MG MK MN MW MX NO NZ PL RO RU SD SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase