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WO2000058435A1 - Pastilles comportant un adjuvant - Google Patents

Pastilles comportant un adjuvant Download PDF

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Publication number
WO2000058435A1
WO2000058435A1 PCT/EP2000/002335 EP0002335W WO0058435A1 WO 2000058435 A1 WO2000058435 A1 WO 2000058435A1 EP 0002335 W EP0002335 W EP 0002335W WO 0058435 A1 WO0058435 A1 WO 0058435A1
Authority
WO
WIPO (PCT)
Prior art keywords
tablet
weight
tablets
acid
builder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2000/002335
Other languages
German (de)
English (en)
Inventor
Mike PÜTZ
Harald Volk
Peter Jeschke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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
Priority claimed from DE19942796A external-priority patent/DE19942796A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AU32903/00A priority Critical patent/AU3290300A/en
Publication of WO2000058435A1 publication Critical patent/WO2000058435A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0086—Laundry tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates

Definitions

  • the invention relates to builder-containing tablets which contain crystalline layered silicates and are suitable for washing or cleaning or for water softening.
  • Tablets have a number of advantages over powdered agents, such as simple dosing and low packaging volume requirements. Problems arise, however, in that relatively high compression pressures have to be used to achieve adequate dimensional stability and fracture resistance when pressing the powdery constituents. Because of the high degree of compaction, such tablets often have inadequate disintegration and dissolving properties during use. In order to get such problems under control, tableting aids are usually added to the actual active substances. These are, for example, polyethylene glycols, typically with molar masses of 1000 to 6000 g / mol, which usually make up 2 to 6% by weight of the total tablet formulation. So-called disintegrants are also added to enable the tablets to be dissolved quickly.
  • Such disintegrants which are usually used in amounts of 3 to 30% by weight of the tablets, are, for example, microcrystalline cellulose or swellable synthetic polymers such as polyvinylpyrrolidone. Both the tabletting aids and the disintegrants are additives which do not themselves contribute to the action of the respective tableted agents. Therefore, these additives reduce the active ingredient content of the tablets.
  • Tablets which contain crystalline layered silicates have long been known per se.
  • Patent application WO 95/21908 already describes tablets which are amorphous, partially stable and / or crystalline layered sodium silicates of the formula
  • a water softening tablet described in the application contains, for example, 20 to 80% by weight of the crystalline layered silicates, and if appropriate up to 80% by weight of zeolite and / or phosphate, possibly up to 50% by weight of polycarboxylate, up to 15% by weight of polymeric polycarboxylates and up to 30% by weight of surfactants
  • the tablet specified in an example contains methylhydroxypropyl cellulose as disintegrant
  • EP-A-812 808 discloses water softener tablets which can contain up to 45% by weight of crystalline layered silicates, in addition they contain a polyfunctional carboxylic acid or its salt, carbonate and / or bicarbonate and polymer. The tablets further contain 1 to 6 % By weight of binder and up to 15% by weight of disintegrant
  • tablets which, in addition to other ingredients, contain a granular additive which contains a crystalline layered silicate and (co) polymeric polycarboxylic acid as essential constituents, can also be prepared without the use of additional tabletting aids or disintegrants at moderate compression pressures and are readily soluble are
  • a first subject of the invention are tablets which contain builder substances and optionally further ingredients of washing or cleaning agents, or phases of such tablets which are characterized in that they contain a powdery to granular additive which as essential components is a crystalline layered silicate of the general formula (I)
  • M is sodium or hydrogen
  • x is a number from 1.9 to 22 and y is a number from 0 to 33, and contains (co) polymeric polycarboxylic acid, but the tablets do not contain any additional disintegrant which has no builder action, and contain a maximum of 2% by weight of additional tabletting aid
  • Such crystalline layered silicates of the formula (I) are sold by Cla ⁇ ant GmbH (Germany) under the trade name Na-SKS.
  • Na-SKS-1 Na 2 Si 22 O 45 xH 2 O, Kenyait
  • Na are to be mentioned here, for example -SKS-2 (Na 2 S ⁇ 14 O 29 xH 2 O, Magadnt), Na-SKS-3 (Na 2 S ⁇ 8 O 17 xH 2 O) or Na-SKS-4 (Na 2 S ⁇ 4 O 9 xH 2 O, makatite)
  • Agents which contain crystalline phyllosilicates of the formula (I) in which x is 2 are particularly suitable for the purposes of the present invention.
  • Na-SKS-5 ⁇ -Na 2 Si 2 O 5
  • Na are particularly suitable -SKS-7 (ß-Na 2 S ⁇ 2 O 5 , Natrosi t)
  • Na-SKS-9 NaHS ⁇ 2 O 5 H 2 O
  • Na-SKS-10 NaHS ⁇ 2 O 5 3H 2 O, Kanemit
  • Na-SKS-11 t-Na 2 S ⁇ 2 O 5
  • Na-SKS-13 Na-SKS-13
  • Na-SKS-6 ⁇ -Na 2 S ⁇ 2 O 5
  • An overview of crystalline layered silicates For example, the articles published in "Hoechst High Chem Magazin 14/1993" on pages 33 - 38 and in "Seifen-Ole-Fette-Wwachs, 116 vol., No.
  • the crystalline layered silicates of the formula (I) are introduced into the tablets according to the invention via the builder additive used in the invention.
  • the crystalline layered silicates of the formula (I) a introduced exclusively into the tablets according to the invention via the builder additive used according to the invention.
  • the tablets advantageously contain the crystalline layered silicate of the formula (I) in amounts of 2 to at most 50% by weight, preferably in amounts of 5 to 45% by weight and in particular in amounts of 10 to 40% by weight
  • a (co) polymeric polycarboxylic acid is understood to mean a homopolymer or copolymer which is not or only partially neutralized. These include the homopolymers of acrylic acid or methacrylic acid or their copolymers with further ethylenically unsaturated monomers such as, for example Acrolein, dimethylacrylic acid, ethylacrylic acid, vinyl acetic acid, allylacetic acid, maleic acid, fumaric acid, itaconic acid, meth (-allylsulfonic acid), vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid as well as monomers containing phosphorus groups such as vinylphosphonic acid, allylphosphoric acid and acrylate methacrylate, acrylate (meth) acrylate, acrylate (meth) acrylate, acrylate (meth) acrylate, Allyl alcohol sulfates and allyl
  • Preferred (co) polymers have an average molecular weight of 1000 to 100000 g / mol, preferably of 2000 to 75000 g / mol and in particular of 2000 to 35000 g / mol.
  • the degree of neutralization of the acid groups is advantageously from 0 to 90%, preferably from 10 to 80% and in particular from 30 to 70%.
  • Suitable polymers include above all homopolymers of acrylic acid and copolymers of (meth) acrylic acid with maleic acid or maleic anhydride.
  • copolymers are derived from terpolymers which are obtained by polymerizing 10 to 70% by weight of monoethylenically unsaturated dicarboxylic acids with 4 to 8 C atoms or salts thereof, 20 to 85% by weight of monoethylenically unsaturated monocarboxylic acids with 3 to 10 C atoms or their salts, 1 to 50% by weight of monounsaturated monomers which release hydroxyl groups on the polymer chain after saponification, and 0 to 10% by weight of further free-radically copolymerizable monomers.
  • saponification of the monounsaturated monomers which release a hydroxyl group on the polymer chain after saponification is preferred in an acidic environment. Products of the type mentioned above are described in German patent applications DE-A-43 00 772 and DE-A-195 16 957 and in WO-A-94/15978.
  • Graft polymers of monosaccharides, oligosaccharides, polysaccharides and modified polysaccharides are also suitable, as are described in German patent applications DE-A-40 03 172 and DE-A-44 15 623.
  • the graft polymers with proteins of animal or vegetable origin, in particular with modified proteins, disclosed in the European patent application are also well suited.
  • copolymers of sugar and other polyhydroxy compounds and a monomer mixture of the following composition are preferably used: 45 to 96% by weight of monoethylenically unsaturated C 3 to C 10 monocarboxylic acid or mixtures of C 3 to C 10 monocarboxylic acids and / or their salts with monovalent cations, monomers containing 4 to 55% by weight of monoethylenically unsaturated monosulfonic acid groups, monoethylenically unsaturated sulfuric acid esters, vinylphosphonic acid and / or the salts of these acids with monovalent cations and 0 to 30% by weight of water-soluble, monoethylenically unsaturated compounds, which are modified with 2 to 50 moles of alkylene oxide per mole of monoethylenically unsaturated compound.
  • Such compounds are described in DE-A-42 21 381 and in DE-A-43 43 993.
  • polyaspartic acids or their derivatives are polyaspartic acids or their derivatives in non-neutralized or only partially neutralized form.
  • the polyaspartic acids are usually obtained in the form of their alkali metal or ammonium salts.
  • the products which are not or only partially neutralized can be obtained from this by adding appropriate amounts of organic or inorganic acids and, if appropriate, separating off the salts formed.
  • Such products can also be obtained by the thermal reaction of maleic acid and ammonia or by the condensation of aspartic acid and the subsequent hydrolysis of the polysuccinimide formed.
  • the production of such products is described, for example, in DE-A-36 26 672, DE-A-43 07 114, DE-A-44 27 287, EP-A-0 612 784, EP-A-0 644 257 and WO -A-92/14753.
  • Graft polymers of acrylic acid, methacrylic acid, maleic acid and other ethylenically unsaturated monomers on salts of polyaspartic acid are also particularly suitable.
  • the otherwise necessary addition of acid to produce the only partially neutralized form of polyaspartic acid can be dispensed with here.
  • the amount of polyaspartate is usually chosen so that the degree of neutralization of all carboxyl groups incorporated in the polymer does not exceed 80%, preferably 60%. Products of the type mentioned are described in more detail in international patent application WO-A-94/01486.
  • the amounts in which the (co) polymeric polycarboxylates which are not or only partially neutralized are contained in the agents according to the invention are determined by the content of the builder additives used according to the invention and their content of these polymers.
  • the builder additive used according to the invention contains the crystalline layered silicate of the formula (I) and the (co) polymeric polycarboxylic acid preferably in weight ratios of (40 to 1): 1, in particular of (20 to 2): 1, ratios of 7 : 1 to about 3: 1, based in each case on the anhydrously calculated active substances, can be particularly advantageous.
  • the water content of the builder additives used according to the invention is preferably 4 to 20% by weight, the upper meaningful value for the water content being made dependent on the builder additive still being stable even after storage at elevated temperatures of, for example, 40 ° C. and should be free-flowing and should not clump together. It has been shown that the lower value for the water content influences the dissolving behavior of the builder additive. For reasons of the higher dissolution rate of the builder additive, additives are therefore preferred which have 5 to 15% by weight of water and in particular 7 to 12% by weight of water.
  • the water content is determined at a temperature of 140 ° C and a duration of 4 hours.
  • the builder additives used according to the invention can be prepared by simply bringing the crystalline layered silicate of the formula (I) into contact with an aqueous solution, preferably a concentrated aqueous solution of the (co) polymeric polycarboxylic acid and, if appropriate, then drying to the desired water content.
  • aqueous solution preferably a concentrated aqueous solution of the (co) polymeric polycarboxylic acid
  • Usual mixing and granulating devices such as the ploughshare mixer from Lödige or a Schugi mixer or an Eirich mixer or a Lödige recycler CB 30, as well as other apparatuses known to the person skilled in the art, which in particular allow a liquid to be sprayed onto a solid, are also suitable Fluidized bed apparatus.
  • the polymer solution serves as an agglomeration aid.
  • the builder additives used according to the invention have only a slightly reduced initial alkalinity, but a significantly lower residual alkalinity compared to the pure crystalline layered silicate of the formula (I).
  • the residual alkalinity can be adjusted accordingly by the polymeric acid content of the additives can be set.
  • the builder additive can therefore be used as a buffer substance in machine dishwashing detergents.
  • the builder additives can contain large amounts of (co) polymeric polycarboxylic acid, with amounts between 2 and 40% by weight being preferred and amounts between 5 and 30% by weight being particularly preferred and amounts between 10 and 25% by weight entirely are particularly preferred.
  • the content of the crystalline layered silicates of the formula (I) in the builder additives is preferably 50 to 90% by weight, particularly preferably 60 to 90% by weight and very particularly preferably 65 to 85% by weight.
  • the calcium binding capacity of the additives is preferably above 185 mg CaCO 3 / g.
  • the pH of a 0.1% by weight aqueous solution is preferably above 10 but below 12 at 20.degree. C.
  • the bulk density of the additives used according to the invention varies depending on the type of preparation and is usually in the range from above 400 to about 700 g / l. While pure crystalline layered silicate of the formula (I) such as SKS6® is usually obtained in very fine particles and also has large amounts of dust constituents, the builder additive used according to the invention is a coarser powder to agglomerate / granulate, which is more finely divided when it is produced in the fluidized bed and coarser when it was made, for example, in a high speed mixer.
  • Coarse-grained additives for example, have an average particle size (d 50 ) of approximately 450 to 900 ⁇ m, while more finely divided additives have an average particle size (d 50 ) of between approximately 280 and 330 ⁇ m. But even with the fine-particle additives, the dust content is significantly lower than with the commercially available pure crystalline layered silicates of the formula (I), in particular than with SKS6®.
  • the content of these builder additives in the tablets according to the invention can be varied within a wide range and depends on the desired function of the tablets. Typical levels of these builder additives are> approximately 20-60% by weight, levels of 25-55% by weight and in particular up to 45% by weight being preferred.
  • Disintegrants which, according to the invention, should not be contained in the tablets or the tablet phases are auxiliary substances which have a positive influence on the dissolving or disintegrating process in the aqueous application phase, but which otherwise have no effect in the sense of the tableted agent as a builder.
  • auxiliary substances which have a positive influence on the dissolving or disintegrating process in the aqueous application phase, but which otherwise have no effect in the sense of the tableted agent as a builder.
  • 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.
  • Well-known disintegrants are, for example, carbonate / citric acid systems, although other organic acids can also be used.
  • these systems have a builder action and are therefore expressly not among the disintegrants which have no action in the sense of the tableted agent, and may accordingly be present in the tablets or tablet phases according to the invention.
  • Preferred embodiments of the invention even contain large amounts of organic carboxylic acids and carbonates. These preferred embodiments are water softening tablets, which are described in detail below.
  • Swelling disintegrants which should not be included according to the invention are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
  • PVP polyvinylpyrrolidone
  • natural polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
  • the tablets or tablet phases according to the invention should not contain any cellulose-based disintegrants.
  • Pure cellulose has the formal gross composition (C 6 H 10 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 also mean cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products Esterifications or etherifications in which hydroxy 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, carboxymethyicellulose (CMC), cellulose esters and ethers and aminocelluloses.
  • CMC carboxymethyicellulose
  • cellulose esters and ethers and aminocelluloses Such compounds do indeed have effects in the sense of the tableted agent, but in particular if the agent is a laundry detergent, the tablets or tablet phases according to the invention are, however, preferably not present.
  • Microcrystalline cellulose can be mentioned as a further disintegrant based on cellulose 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.
  • microcrystalline celluloses which have primary particle sizes of approximately 5 ⁇ m and can be compacted, for example, into granules with an average particle size of 200 ⁇ m.
  • Tableting aids which are contained in the tablets or tablet phases according to the invention to a maximum of 2% by weight, are substances which ensure better cohesion of the individual powdery or granular constituents and thus contribute to the stability of the tablet.
  • the tablets or tablet phases preferably contain only dust binders as tableting aids.
  • the undesirable tabletting aids include, in particular, polyethylene glycols with molecular weights in the range from 1000 to 10,000 g / mol, starch, cellulose, starch and cellulose derivatives, but also gelatin and polyvinylpyrrolidone.
  • Some detergent ingredients such as certain liquid to pasty nonionic surfactants, also act as tableting aids. These can be contained in tablets according to the invention, if the intended action of the tablets as a detergent so requires However, they do not require tableting aids. Preferred embodiments of the invention are therefore also free from such nonionic surfactants.
  • Tablets or tablet phases with these ingredients can be pressed at moderate pressing presses and still show high edge abrasion resistance.
  • the tablets are readily soluble, the solubility of the tablets known from the prior art, which can contain both large amounts of tableting aids and the disintegrants described above, at least comparable.
  • the tablets or tablet phases according to the invention allow a very high active ingredient content, since it is precisely these disintegrants or the described tableting aids that are contained only in very small amounts.
  • the tablets can contain other ingredients. These can preferably be substances which have (co) builder properties.
  • the tablets may also contain the builders already listed, crystalline layered sodium silicates and polymeric polycarboxylic acids, in addition to the additive, and also in separate form. In particular, this can be the case if the tablets have several “phases” or “layers” which are composed in themselves homogeneously. In the case of such multi-phase tablets, it can be preferred if the different phases, which can contain different active substances, dissolve at different speeds. Accordingly, it may be preferred to use the additive only in one phase according to the invention, while the other phase contains no or another disintegrant. However, it may be desirable if the other phase (s) contain the same builder substances, but in a form that does not have the explosive effect of the additive.
  • the tablets according to the invention can also contain other builders and cobuilder substances:
  • aluminosilicates and phosphates are primarily aluminosilicates and phosphates.
  • the aluminosilicate is preferably finely crystalline, synthetic and bound water-containing zeolites, in particular Zeolite A, X and / or P.
  • Zeolite P for example, zeolite MAP (R) (commercial product from Crosfield) is used.
  • zeolite Y and mixtures of A, X, Y and / or P are also suitable.
  • Such a mixture of zeolite A and zeolite X is commercially available, for example, under the name Vegobond AX® (from Condea Augusta SpA).
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • 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.
  • the possible builder substances also include amorphous sodium silicates with a modulus Na 2 O: SiO 2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties.
  • the delay in dissolution compared to conventional amorphous sodium silicates can have been caused in various ways, for example by surface treatment, compounding, compaction / 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 provide 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.
  • compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • phosphates As builder substances, it is also possible to use the generally known 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. Their content is generally not more than 25% by weight, preferably not more than 20% by weight, based in each case on the finished composition. In some cases, it has been shown that tripolyphosphates in particular, even in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances lead to a synergistic improvement in the secondary washing ability. It may also be preferred to use phosphate in the form of the phosphate compound described in the earlier German patent application DE 198 59 807.6.
  • usable organic builders are, for example, also 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 value of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • polyacetals which are produced by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as in the European patent application EP-A-0 280 223 can be obtained.
  • 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.
  • Ethylenediamine N, N'-disuccinate (EDDS) whose synthesis is described for example in US 3,158,615, preferably in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP-A-0 150 930 and Japanese Patent Application JP 93/339896 become.
  • Suitable amounts for use in formulations containing zeolite and / or silicate are 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may 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 1-hydroxyethane-1 J-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 ethylenediamine tetramethylene phosphonate (EDTMP) and diethylene triamine pentamethylene phosphonate
  • DTPMP and their higher homologues in question. They are preferably in the form of the neutral sodium salts, e.g. B. as the 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 aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it is preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • the tablets are water softening tablets.
  • Such tablets contain a very high proportion of builder substances.
  • Preferred water softener tablets consist of 60 to 100% by weight, in particularly advantageous embodiments even more than 80% by weight, of builders and cobuilder substances.
  • active substance contents of more than 90% by weight, in particular more than 95% by weight, are also preferred in these builder tablets, these can only be achieved with difficulty since the individual ingredients also introduce water into the tablets.
  • Those water softening tablets which contain a carbonate / polycarboxylic acid system already described above are particularly preferred. Such water softening systems react bubbly with each other when they come into contact with water, thus contributing to the disintegration of the tablets, softening the water and also dissolving without residue. Any alkali carbonate, bicarbonate or sesquicarbonate, alone or in mixtures with others, can be used as the carbonate. However, the use of bi- and sesquicarbonates is particularly preferred.
  • polycarboxylic acids are 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.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof are particularly preferred. All or some of these acids can also be used in the form of their salts.
  • Preferred water softener tablets contain 10 to 40% by weight, in particular 15 to 30% by weight, of such polycarboxylic acids or Polycarboxylic acid salts and 10 to 50% by weight, in particular 20 to 45% by weight, of alkali carbonate, bicarbonate or sesquicarbonate.
  • the tablets are detergent tablets.
  • Such tablets can preferably contain surface-active substances.
  • These surface-active substances come from the group of anionic, nonionic, zwitterionic or cationic surfactants, anionic surfactants being clearly preferred for economic reasons and because of their range of services.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are preferably C 9 . 13 - alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained, for example, from C 12-18 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products, into consideration.
  • Alkanesulfonates which are derived from C 12 are also suitable.
  • 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.
  • 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.
  • the alk (en) yl sulfates are 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 the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 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.
  • 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.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 . 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • 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.
  • the preferred anionic surfactants to be used in detergent tablets are the alkylbenzenesulfonates and fatty alcohol sulfates, preferred detergent tablets being 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight of fatty alcohol sulfate (s) on the weight of the detergent tablets.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position 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 ⁇ alcohol with 7 EO, C 13 . 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 . 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of 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.
  • Another class of preferably used 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, such as them are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced 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).
  • APG alkyl polyglycosides
  • Usable alkyl polyglycosides 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 the Is 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 tablets can preferably contain alkylpolyglycosides, with APG contents of more than 0.2% by weight, based on the entire molded body, being preferred.
  • Particularly preferred detergent tablets contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 to 3% by weight.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), R
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (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 aikyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 represents a linear, branched or cyclic aikyl radical or Aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, where C 1 . 4 -alkyl or phenyl radicals are preferred and [Z] stands for a linear polyhydroxyalkyl radical, the alkyl chain of which is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of this radical.
  • [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, by reaction with Fatty acid methyl esters can be converted into the desired polyhydroxy fatty acid amides in the presence of an alkoxide as catalyst.
  • the surfactant content of detergent tablets is usually between 10 and 40% by weight, preferably between 12.5 and 30% by weight and in particular between 15 and 25% by weight, bleach tablets and water softener tablets are usually free of surfactants.
  • the tablets according to the invention can additionally contain one or more substances from the groups 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 and Color transfer inhibitors included. These substances are described below.
  • bleaching agents sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate are of particular importance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced.
  • bleaches from the group of organic bleaches 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) the 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, ⁇ -phthalimidoxy acid panoic acid (PAP) )], o- Carboxybenzämidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperocysebacic acid, diperoxydodiacodoxydiperylpiperyldiacyldiperoxybutyldiacid, 4-diperoxybutyld
  • bleach activators can be incorporated into the tablets according to the invention.
  • 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.
  • bleach catalysts can also be incorporated into the tablets.
  • 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.
  • Bakery terienstämmeri or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus, enzymatic active ingredients obtained.
  • Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules in the shaped bodies according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • the most commonly used enzymes include lipases, amylases, cellulases and proteases.
  • Preferred proteases are e.g. B. BLAP®140 from Biozym, Optimase®-M-440 and Opticlean®-M-250 from Solvay Enzymes; Maxacal®CX and Maxapem® or Esperase® from Gist Brocades or Savinase® from Novo.
  • Particularly suitable cellulases and lipases are Celluzym® 0.7 T and Lipolase® 30 T from Novo Nordisk.
  • the tablets can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-aniiino-4-morphoiino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly structured compounds which, instead of the morpholino 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 moldings according to the invention in order to improve the aesthetic impression of the products and to the consumer in addition to the Softness performance to provide a visually and sensorially "typical and distinctive" product.
  • 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, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl benzylatepylpionate, allyl cyclohexyl propyl pionate.
  • the ethers include, for example, benzylethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones include, for example, the jonones, Is-isomethylionone and methyl cedryl ketone , the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, 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 colorant content of the 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 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.
  • they 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.
  • Another object of the present invention is a process for the production of tablets containing builder substances and possibly other ingredients of detergents or cleaning agents, or phases of such tablets, characterized in that a powdery to granular additive, which as a constituent components is a crystalline layered Silicate of the general formula (I)
  • M represents sodium or hydrogen
  • x is a number from 1.9 to 2.2 and y is a number from 0 to 33, and contains (co) polymeric polycarboxylic acid, with further builder substances and, if appropriate, ingredients of washing and cleaning agents is mixed into a premix and this premix is pressed into tablets or phases of tablets without the addition of additional disintegrants which have no builder action and with a maximum of 2% by weight of tabletting aid.
  • the builder additive is the additive already described above. Since exactly those tablets or phases of tablets are to be obtained in the production process described here, as have also been described above, it goes without saying that the preferred embodiments already described for the tablets, correspondingly also preferably in the process getting produced.
  • the tablets according to the invention contain the builder additives according to the invention in varying amounts depending on the intended use.
  • Processes according to the invention in which the builder additive is used in amounts of 20 to 60% by weight, preferably in amounts of 25 to 55% by weight and in particular in amounts of up to 45% by weight, are also completely analogous.
  • the premixes containing the described builder additive already have advantages. These premixes have a very good flowability, which allows the filling shoe to be filled evenly, thus helping to ensure a uniform quality of the manufacturing tablets. Furthermore, the premix hardly clumps and accordingly does not bake on the walls of the tablet press.
  • the builder additive according to the invention allows the premix to be compressed at moderate pressures. This protects the tabletting tools and increases their service life.
  • the builder additive is mixed with other ingredients of detergents and cleaning agents and pressed into the molded body.
  • Processes according to the invention are preferred here, which are characterized in that the builder additive is mixed with at least one oxygen bleaching agent selected from the group of alkali perborates, alkali percarbonates, organic peracids and hydrogen peroxide.
  • the bleaches in question were described above.
  • the bleaching performance of moldings containing bleach is preferably increased by using bleach activators.
  • the builder additive with at least one bleach activator preferably from the group of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), the N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methylsulfate (MMA) and / or the bleach-enhancing transition metal complexes, especially with the central atoms Mn, Fe, Co, Cu, Mo, V , Ti and / or Ru, preferably from the group of manganese and / or cobalt
  • TAED tetraacetylethylenediamine
  • NOSI N-
  • the premix additionally contains one or more substances from the group of enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors and color transfer inhibitors.
  • the premix Before the particulate premix is pressed into shaped articles, the premix can be "powdered” with finely divided surface treatment agents. This can be advantageous for the nature and physical properties of both the premix (storage, compression) and the finished 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.
  • zeolite Y and faujasite and mixtures of these compounds can also be used, the pure zeolite X being preferred.
  • Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, which do not necessarily have to belong to the zeolite structural group 4 can be used as powdering agents, it being advantageous if at least 50% by weight of the powdering agent from a zeolite of faujasite -Type exist.
  • 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 compacted in a so-called die between two punches to form a solid compressed product. This process, which takes place in The following, briefly referred to as tableting, is divided into four sections: dosage, 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 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.
  • the lower stamp 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 be done with an upper and lower stamp
  • several punches can also be attached to an eccentric disk, the number of die holes being correspondingly expanded.
  • 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 stamp, with the pressing pressure being active only by the upper or lower die. Lower stamp, but can also be built up by both stamps.
  • the die table and the stamps move around a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like curved 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 after the other without the slightly pressed first layer being ejected before the 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 for pressing at the same time.
  • the throughputs of modern rotary tablet presses are over one million tablets 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 moldings can be manufactured in a predetermined spatial shape and a predetermined size. Practically all practical configurations can be considered as the spatial shape, for example, the design as a board, the bar or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.
  • the portioned compacts can each be designed as separate individual elements that correspond to the predetermined dosage of the detergents and / or cleaning agents. It is also possible, however, to form compacts which connect a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined predetermined breaking points.
  • the portioned compacts can be designed as tablets, in cylindrical or cuboid form, with a diameter / height ratio in the range from about 0.5: 2 to 2: 0.5 is preferred.
  • Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such compacts.
  • the spatial shape of another embodiment of the shaped bodies is adapted in its dimensions to the induction chamber of commercial household washing machines, so that the shaped bodies can be metered directly into the induction chamber without a metering aid, where it dissolves during the induction process.
  • a metering aid where it dissolves during the induction process.
  • water softener or detergent tablets via a dosing aid is also possible without any problems and is preferred in the context of the present invention.
  • Another preferred molded body that can be produced has a plate-like or sheet-like structure with alternating thick and short short segments, so that individual segments of this "Riege! at the predetermined breaking points, which represent the short, thin segments, can be broken off and entered into the machine.
  • This principle of the "bar-shaped" shaped body detergent can also be implemented 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 different components are not pressed into a uniform tablet, but that tablets are obtained which have several layers or “phases”, ie at least two layers. It is also possible for these different layers to be different This can preferably be achieved, in particular, if one of the layers now contains the builder additive according to the invention, while the other may contain no or any other disintegrant, which can result in advantageous performance properties of the shaped bodies, for example if components in the shaped bodies are contained, which 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 shaped bodies can be stacked, with the inner layer (s) already loosening at the edges of the shaped body when the outer layers have not yet been completely detached, 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 shaped body consists of at least three layers, that is to say two outer and at least one inner layer, a peroxy bleaching agent being contained in at least one of the inner layers, while the two outer layers in the case of the stacked shaped body and the outermost layers being free of peroxy bleaching agent in the case of the shell-shaped shaped body.
  • peroxy bleaching agents any bleach activators and / or enzymes that may be present in one molded body.
  • Such multilayered moldings have the advantage that they can not only be used via a dispensing chamber or via a metering device which is added to the wash 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 stains 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 method of melt coating.
  • 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
  • t is the Height of the molded body.
  • Water softener tablets were produced from the ingredients listed in Table 1 on a rotary press (from Fette). For this purpose, the individual components were mixed and pressed with a pressure according to Table 2. All tablets had a weight of 18 g, the compression pressure was chosen so that all tablets had the same height.
  • a layered silicate polymer compound was used in Examples E1 to E3 according to the invention. This compound was formed when SKS-6® (Clariant) was reacted with a terpolymer in accordance with the disclosure of patent application EP-A-849 355. The terpolymer used in accordance with the disclosure in WO 94/15978 was obtained from 80% by weight.
  • Acrylic acid and maleic acid in a weight ratio of 7: 3 and 20% by weight of vinyl acetate were produced and then saponified in an acidic environment (commercial product from Stockhausen).
  • the resulting builder additive contained 71% by weight of SKS-6, 20% by weight of the terpolymer and 9% by weight of water.
  • copolymer which is an acrylic acid / maleic acid copolymer, was also used (Sokalan CP5®; trade name from BASF).
  • Comparative examples V1 and V3 contained layered silicate in the form of SKS-6 powder.
  • the comparative examples also contained microcrystalline cellulose as disintegrant and a polyethylene glycol with a molecular weight of 4000 g / mol as tabletting aid.
  • paraffin oil used in the examples according to the invention like the polyethylene glycol used in the comparative examples with a molar mass of 400 g / mol, serves as a dust-binding agent. Differences from 100% by weight in Table 1 result from additionally contained water and salts.
  • tablets of greater hardness and edge breaking stability than in the comparative examples could be obtained at lower compression pressures.
  • the tablets according to the invention had dissolution times comparable to those of the comparative tests. Less caking on the filling shoes and in the die was also observed in the production of the tablets according to the invention (see Table 2).
  • the hardness of the tablets was measured by deforming the tablet to fracture, the force acting on the side surfaces of the tablet and the maximum force that the tablet was able to withstand.
  • the measurement was carried out on a hardness tester CT5 (Holland) with punch diameters of 8 mm.
  • the edge break test was carried out in a rectangular plastic container with edge lengths from 18 to 14 to 22 cm. 5 tablets were weighed into this container and rotated at 40 rpm for 1 minute. The tablets were then weighed again and, as a result, the weight of the tablets after the test was given as a percentage of the weight of the tablets before the test (Table 2).
  • the dissolution test in the beaker was carried out at 20 ° C.
  • a tablet with the dimensions 14.8 x 34.4 mm was placed on a sieve with a mesh size of 0.6 x 0.6 cm and this sieve was hung in a 1000 ml beaker filled with water. The time until the tablet fell through the sieve was measured with stirring.
  • For the dissolution test in the washing machine three tablets were placed in a washing machine drum filled with laundry. The machine was then started in the 30 ° C wash program without prewash. The time is stopped as soon as the drum begins to circulate. The washing process was then stopped after 1 or 2 or 3 or 4 or 5 min and the water was pumped out. The dissolution time was then the time after which no residues from the tablets could be found.
  • Table 2 are mean values from duplicate determinations.
  • the caking on the tablet press was assessed visually. The assessment was based on the following key: very good (++): no significant caking; good (+): visible caking, but does not affect the tableting; satisfactory (0): visible caking, minor impairment of the tableting; bad (-): massive impairment of tableting.

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  • Inorganic Chemistry (AREA)
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Abstract

Pastilles comportant un adjuvant, qui contiennent un additif renfermant un silicate de sodium cristallin sous forme de couches et un acide polycarboxylique (co)polymère. Lesdites pastilles peuvent être fabriquées sans adjonction d'adjuvants de pastillage ou de désintégration supplémentaires, et présentent cependant un comportement de dissolution comparable à celui de pastilles dans lesquelles des constituants de ce type sont ajoutés séparément, mais qui contiennent en plus des adjuvants de pastillage et de désintégration supplémentaires. En outre, ces pastilles peuvent être obtenues à des pressions de compression plus basses, pour une dureté comparable. En particulier des pastilles d'adoucissement d'eau peuvent ainsi présenter une teneur élevée en substances actives étant donné que l'utilisation d'adjuvants qui ne contribuent pas à l'effet d'adoucissement de l'eau est largement évitée.
PCT/EP2000/002335 1999-03-25 2000-03-16 Pastilles comportant un adjuvant Ceased WO2000058435A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU32903/00A AU3290300A (en) 1999-03-25 2000-03-16 Tablet containing a builder

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19913434 1999-03-25
DE19913434.0 1999-03-25
DE19942796A DE19942796A1 (de) 1999-03-25 1999-09-08 Builder-haltige Tablette
DE19942796.8 1999-09-08

Publications (1)

Publication Number Publication Date
WO2000058435A1 true WO2000058435A1 (fr) 2000-10-05

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PCT/EP2000/002335 Ceased WO2000058435A1 (fr) 1999-03-25 2000-03-16 Pastilles comportant un adjuvant

Country Status (3)

Country Link
AU (1) AU3290300A (fr)
CA (1) CA2302141A1 (fr)
WO (1) WO2000058435A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1113068A3 (fr) * 1999-12-16 2001-12-19 Clariant GmbH Composé de silicate en couches granulaires
DE10123621A1 (de) * 2001-05-15 2002-11-28 Henkel Kgaa Verfahren zur Herstellung einer Wasserenthärtertablette
EP1083216A3 (fr) * 1999-09-11 2003-01-22 Clariant GmbH Cogranulés comprenant de silicates de métaux alkalins en couche et de désintégrants
US6545147B1 (en) 1999-09-10 2003-04-08 Clariant Gmbh Bleaching-active metal complexes
WO2012069895A1 (fr) 2010-11-12 2012-05-31 Dental Care Innovation Gmbh Comprimé soluble contenant des éléments abrasifs
US10959931B2 (en) 2017-02-02 2021-03-30 Water Pik, Inc. Tablet including abrasive for dental cleaning

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0504091A1 (fr) * 1991-03-15 1992-09-16 Cleantabs A/S Composition pour le lavage machinal de la vaisselle sans phosphate
WO1995020030A1 (fr) * 1994-01-25 1995-07-27 Unilever N.V. Co-granules et pastilles detergentes produites a l'aide desdits co-granules
WO1995021908A1 (fr) * 1994-02-10 1995-08-17 Henkel Kommanditgesellschaft Auf Aktien Comprime contenant des adjuvants
EP0812808A1 (fr) * 1996-06-12 1997-12-17 Cleantabs A/S Comprimés pour adoucir l'eau
DE19819187A1 (de) * 1998-04-30 1999-11-11 Henkel Kgaa Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0504091A1 (fr) * 1991-03-15 1992-09-16 Cleantabs A/S Composition pour le lavage machinal de la vaisselle sans phosphate
WO1995020030A1 (fr) * 1994-01-25 1995-07-27 Unilever N.V. Co-granules et pastilles detergentes produites a l'aide desdits co-granules
WO1995021908A1 (fr) * 1994-02-10 1995-08-17 Henkel Kommanditgesellschaft Auf Aktien Comprime contenant des adjuvants
EP0812808A1 (fr) * 1996-06-12 1997-12-17 Cleantabs A/S Comprimés pour adoucir l'eau
DE19819187A1 (de) * 1998-04-30 1999-11-11 Henkel Kgaa Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6545147B1 (en) 1999-09-10 2003-04-08 Clariant Gmbh Bleaching-active metal complexes
EP1083216A3 (fr) * 1999-09-11 2003-01-22 Clariant GmbH Cogranulés comprenant de silicates de métaux alkalins en couche et de désintégrants
EP1113068A3 (fr) * 1999-12-16 2001-12-19 Clariant GmbH Composé de silicate en couches granulaires
DE10123621A1 (de) * 2001-05-15 2002-11-28 Henkel Kgaa Verfahren zur Herstellung einer Wasserenthärtertablette
DE10123621B4 (de) * 2001-05-15 2006-12-07 Henkel Kgaa Verfahren zur Herstellung einer Wasserenthärtertablette
WO2012069895A1 (fr) 2010-11-12 2012-05-31 Dental Care Innovation Gmbh Comprimé soluble contenant des éléments abrasifs
DE102010051226A1 (de) 2010-11-12 2012-05-31 Dental Care Innovation Gmbh Ausspültablete mit abrasiven Bestandteilen
US9493731B2 (en) 2010-11-12 2016-11-15 Dental Care Innovation Gmbh Soluble tablet, containing abrasive media
US10959931B2 (en) 2017-02-02 2021-03-30 Water Pik, Inc. Tablet including abrasive for dental cleaning
US11596587B2 (en) 2017-02-02 2023-03-07 Water Pik, Inc. Tablet including abrasive for dental cleaning

Also Published As

Publication number Publication date
CA2302141A1 (fr) 2000-09-25
AU3290300A (en) 2000-10-16

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