EP1004656B1 - Densified granulate, its manufacturing process and its use as disintegrant for compacted mouldings - Google Patents

Densified granulate, its manufacturing process and its use as disintegrant for compacted mouldings Download PDF

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Publication number
EP1004656B1
EP1004656B1 EP98121397A EP98121397A EP1004656B1 EP 1004656 B1 EP1004656 B1 EP 1004656B1 EP 98121397 A EP98121397 A EP 98121397A EP 98121397 A EP98121397 A EP 98121397A EP 1004656 B1 EP1004656 B1 EP 1004656B1
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EP
European Patent Office
Prior art keywords
cellulose
granulate
meth
acrylic acid
copolymers
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.)
Expired - Lifetime
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EP98121397A
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German (de)
French (fr)
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EP1004656A1 (en
Inventor
Sascha Casteel
Elke Dr. Philippsen-Neu
Hans-Georg Dr. Hartan
Rainer Pöschmann
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Dalli Werke GmbH and Co KG
Original Assignee
Dalli Werke Waesche und Korperpflege GmbH and Co KG
Stockhausen GmbH and Co KG
Chemische Fabrik Stockhausen GmbH
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Application filed by Dalli Werke Waesche und Korperpflege GmbH and Co KG, Stockhausen GmbH and Co KG, Chemische Fabrik Stockhausen GmbH filed Critical Dalli Werke Waesche und Korperpflege GmbH and Co KG
Priority to ES98121397T priority Critical patent/ES2153229T3/en
Priority to DK98121397T priority patent/DK1004656T3/en
Priority to DE59800410T priority patent/DE59800410D1/en
Priority to PT79100995T priority patent/PT1004656E/en
Priority to EP98121397A priority patent/EP1004656B1/en
Priority to AT98121397T priority patent/ATE198348T1/en
Priority to HU9903991A priority patent/HU228025B1/en
Priority to TR1999/02772A priority patent/TR199902772A3/en
Priority to CZ19993977A priority patent/CZ290160B6/en
Priority to PL336514A priority patent/PL191104B1/en
Priority to US09/438,657 priority patent/US6232285B1/en
Publication of EP1004656A1 publication Critical patent/EP1004656A1/en
Publication of EP1004656B1 publication Critical patent/EP1004656B1/en
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    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • the invention is directed to granules that are particularly good at water records and forwards inside, which in some cases increases the volume takes place, so that the granules as disintegrants for pressed moldings, such as tablets.
  • Disintegrants for tablets or granules are auxiliary substances that disintegrate tablets or granules in contact with liquids, in particular Influence water positively.
  • the decay of Tablets in large parts and then a disintegration into smaller ones Particles are caused and accelerated.
  • inorganic and organic disintegrants for tablets are Substances known, for example inorganic substances such as bentonites, also persalts, acetates, alkali carbonates / hydrogen carbonates and citric acid.
  • organic compounds include starch, modified Starch and starch degradation products, cellulose, cellulose ethers, such as Methyl cellulose hydroxypropyl cellulose and carboxymethyl cellulose, poly (meth) acrylates, Polyvinyl pyrrolidone and cross-linked polyvinyl pyrrolidone, Alginates, gelatin and pectins.
  • an explosive granulate and its use in washing or cleaning-active moldings such as tablets, known a high adsorption capacity for water and a grain size distribution in which at least 90% by weight has a particle size of at least 0.2 mm and a maximum of 3 mm.
  • the granules preferably contain 25-100% by weight of disintegrants, such as starch, starch derivatives, cellulose, cellulose derivatives, Alginic acid, carboxylmethylamylopectin, polyacrylic acid, polyvinylpyrrolidone and polyvinyl polypyrrolidone.
  • disintegrants such as starch, starch derivatives, cellulose, cellulose derivatives, Alginic acid, carboxylmethylamylopectin, polyacrylic acid, polyvinylpyrrolidone and polyvinyl polypyrrolidone.
  • Citric acid is used as a disintegrant or citrates, bicarbonates and carbonates, bisulfate and percarbonate, microcrystalline Cellulose, sugar, sorbitol or swellable layered silicates called the type of bentonite or smectite.
  • the explosives are used in quantities of 1 to 25% by weight as a single raw material or as a compound.
  • DE-A-44 04 279 describes the following disintegrants for washing or cleaning tablets: starch, starch derivatives, cellulose, cellulose derivatives, microcrystalline cellulose, salts of polymeric polyacrylates or polymethacrylates, methyl celluloses, hydroxypropyl celluloses or methyl hydroxypropyl celluloses. Acetates or percarbonates are also mentioned as disintegrants.
  • the application amounts are up to 15% by weight. Since water-soluble silicates are used as builders, a combination of poly (meth) acrylates and nonionic cellulose ethers can Amounts of 1% by weight lead to very good results.
  • Detergent tablets are known from EP-A-522 766 which contain disintegrants which function according to four different mechanisms: swelling, porosity / capillary action, deformation and chemical reaction.
  • Starch, starch derivatives, carboxymethyl starch, sodium starch glycolates, cellulose and cellulose derivatives, carboxymethyl cellulose, crosslinked modified cellulose, microcrystalline cellulose and various organic polymers such as polyethylene glycol, and crosslinked polyvinypyrrolidones and inorganic swelling agents such as bentonites are described. Combinations of organic acids and bicarbonates of the carbonates of alkali metals are also mentioned.
  • EP 0 628 627 A1 describes a water-soluble, water-softening agent Builder in the form of a tablet. Combinations are used as explosives from citric acid and / or partially neutralized polymers and carbonate and / or bicarbonate or an insoluble polyvinylpyrrolidone.
  • detergent tablets are described as disintegrants Starch derivatives, cellulose compounds, polyvinylpyrrolidone compounds, polyvinylpolypyrrolidone compounds, Bentonite compounds, alginate gelatin and may contain pectins.
  • a polyfunctional organic carboxylic acid such as maleic acid Malic acid citric acid or tartaric acid together with carbonates or Bicarbonates recommended.
  • 95/06 109 is a method for producing detergent granules known high density from anhydrous material.
  • the agglomerates are free fluent and have a high content of detergent substances.
  • the object of the invention is to swell quickly and strongly in water
  • To create granules so that it can be used as a disintegrant for molded articles is suitable to promote their decay on contact with water.
  • This task is solved by a compacted explosive granulate for pressed molded articles containing non-water-soluble, water-swellable high-purity cellulose and / or cellulose derivatives and finely divided polymers or copolymers of (meth) acrylic acid or mixtures of these polymers or copolymers and one or more liquid nonionic and / or anionic and / or amphoteric surfactant (s) used for gel formation or thickening incline with water, the weight ratio of the combined in Water-swellable cellulose / cellulose derivatives and the polymers / copolymers of (meth) acrylic acid: liquid surfactant (s) is from 100: 1 to 10: 1.
  • the anisotropic cellulose was aligned by the compression or cellulose derivatives.
  • the water-swellable, high-purity cellulose becomes microcrystalline in form Structure used, the super-molecular structural elements Have the shape of fibrils, in the longitudinal direction of which crystalline and can alternate amorphous areas. Have proven to be particularly suitable Fibrils of native cellulose with a maximum length of 300 ⁇ m have been proven. Both microcrystalline and amorphous fine cellulose can be used and mixtures thereof can be used.
  • the finely divided cellulose preferably has bulk densities of 40 g / l up to 300 g / l, very particularly preferably from 65 g / l to 170 g / l. Become already used granulated types, their bulk density is higher and can be from 350 g / l to 550 g / l.
  • the bulk weights of the cellulose derivatives can range from 50 g / l to 1000 g / l, preferably in the range of 100 g / l and 800 g / l.
  • the particle size of the finely divided cellulose can be between 30 ⁇ m and 300 ⁇ m, preferably between 30 ⁇ m and 200 ⁇ m, in the case of granulated types the average particle size is between 350 ⁇ m and 800 ⁇ m.
  • the particle size of the finely divided Cellulose derivatives can be between 30 ⁇ m and 1000 ⁇ m.
  • cellulose derivatives that are swellable in water such as cellulose ethers and cellulose esters and mixed modifications the same can also be used.
  • Suitable cellulose ethers are e.g. Methyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose, as well modified carboxymethyl cellulose.
  • Granules are present.
  • finely divided polymers of (meth) acrylic acid or copolymers of (Meth) acrylic acid or salts thereof or mixtures of such polymers or copolymers or salts thereof with high water absorption contained in the granulate Linear ones have proven to be particularly suitable Polymers of (meth) acrylic acid, copolymers of (meth) acrylic acid or salts the same with weight average molecular weights of 5,000 to 70,000 and cross-linked polymers of (meth) acrylic acid, copolymers of (Meth) acrylic acid or salts thereof with weight average molecular weights proven from 1,000,000 to 5,000,000.
  • the copolymers are concerned it is preferably a copolymer of (meth) acrylic acid and maleic acid or maleic anhydride, for example 40 to 90% by weight (Meth) acrylic acid and 60 to 10% by weight of maleic acid or maleic anhydride contain, whose relative molar mass, based on free acids, between 3,000 and 100,000, preferably 3,000 to 70,000 and very particularly preferred Is 5,000 to 50,000.
  • Ter- and quattropolymeric polycarboxylates have also proven to be very suitable proven, made from (meth) acrylic acid, maleic acid and vinyl alcohol or vinyl alcohol derivatives, or those of (meth) acrylic acid, ethylenically unsaturated sulfonic acids and sugar derivatives, or such (Meth) acrylic acid, maleic acid, vinyl alcohol derivatives and sulfonic acid groups Monomers
  • Salt formation is preferably carried out with cations of alkali metals, Ammonia and amines, or their mixtures.
  • the finely divided polymers / copolymers of (meth) acrylic acid or salts preferably have the same of the cross-linked derivatives described above an average particle size of 45 ⁇ m to 150 ⁇ m. Most notably particle sizes from 45 ⁇ m to 90 ⁇ m are preferred.
  • Particles with average particle sizes over 150 ⁇ m show a good one Explosive effects, but are too large after swelling, become when washing filtered off and are visually as particles on the textile after washing visible.
  • Cellulose / cellulose derivatives are made with polymers / copolymers from (Meth) acrylic acid or salts thereof combined in the granulate, the weight ratio can be from 100: 0.5 to 100: 30, preferably from 100: 1 to 100: 20, a weight ratio of is very particularly preferred 100: 1 to 100: 10, the most favorable is a weight ratio of 100: 3.
  • the granulate contains one or more other essential constituents liquid, water-forming or thickening surfactants from the group of nonionic, anionic or amphoteric surfactants.
  • the nonionic surfactants are selected from alkyl polyglucosides, fatty acid alkylolamides, Fatty acid polyethylene glycol esters, fatty amine oxethylates, Fatty alcohol ethoxylates with 3-15 mol ethylene oxide or propylene oxide, Fatty acid glycerides, sorbitan esters, sucrose esters, e.g. Sucrose palmitate, Pentaerythritol partial esters, which can also be ethoxylated, as well as alkylphenol polyethylene glycol ethers and phenol poly - ethylene glycol ethers (if they can be used in the respective country)
  • the anionic surfactants are selected from alkyl sulfates, linear and branched alkylbenzenesulfonates, alkylglycerol ethers, fatty alcohol polyethylene glycol ether sulfates, Paraffin sulfonates, alpha olefin sulfonates, Sulfosuccinates, phosphoric acid esters and fatty alcohol ether carboxylates.
  • amphoteric surfactants are selected from coconut fatty acid amidopropyl betaine, modified imidazolines and fatty acid amide derivatives with betaine structure.
  • the quantitative ratio of cellulose / cellulose derivatives and / or polymers / copolymers of (meth) acrylic acid or salts thereof: surfactant can from 100: 1 to 10: 1. Quantities of 100: 2 are preferred up to 100: 5
  • the gel-forming or water-thickening surfactants can be anionic, be amphoteric or nonionic, particularly preferred are nonionic Surfactants.
  • liquid Surfactants initially in direct contact with the cellulose / cellulose derivatives to bring and attach to it and then the finely divided polymers / Copolymers of (meth) acrylic acid or its salts in the mixture to be introduced in such a way that the polymer particles on the fibrils of the cellulose be liable.
  • the mixture of the granulate components according to the invention, cellulose / cellulose derivatives and polymers / copolymers of (meth) acrylic acid and nonionic surfactants are then granulated using conventional methods.
  • mixers from Vomm, Lödige, Schugi, Eirich, Henschel or Fukae can be used.
  • the final compression is essential.
  • Compacting under Pressure can be applied in various ways.
  • Compaction on rolling mills has proven to be particularly suitable whose rollers run at different speeds, so that the pressure on the granules in the nip is still due to friction is added. This leads to the formation of a scale-like structure and alignment of the anisotropic cellulose / cellulose derivatives in the granulate.
  • This orientation can be one of the reasons for the particularly cheap source kinetic behavior of this embodiment of the invention Be granules.
  • the compression of the granules should preferably be such that the compression Granules a bulk density of 100 g / l to 800 g / l, preferred from 200 g / l to 600 g / l, very particularly preferably from 300 g / l to 500 g / l having.
  • the disintegrant granules according to the invention are in the moldings in Contain amounts of 0.5 wt.% To 10 wt.%, Preferably 2 wt.% To 7 % By weight and particularly preferably 3% by weight to 6% by weight.
  • the specific water absorption capacity of the granules according to the invention can be determined gravimetrically as follows: A defined amount of granules (eg 2.00 g) is sealed in a thin paper bag, such as a tea bag, and immersed in a vessel with an excess of water. After 3 minutes of immersion, the bag is removed from the water and hung for 10 minutes to drain. The bag is weighed and the water absorption is determined from the weight difference of a wet bag with and without granules. Distilled water or water with a defined hardness can be used for the determination.
  • a defined amount of granules eg 2.00 g
  • a thin paper bag such as a tea bag
  • the water absorption which can be determined in this way is preferably 500 until 2000 %
  • the compacted granulate according to the invention is distinguished by a special one Swelling kinetics, the expansion changes depending on the Time is not linear and should reach a certain level after the shortest possible time to reach.
  • the increase in volume after 5 seconds is preferably 55% by volume to 225% by volume, the increase in volume being greater with higher compaction, ie higher bulk density.
  • the increase in volume is preferably 75% by volume to 270% by volume, the increase in volume likewise increasing with increasing bulk density.
  • the volume increases after 5 seconds contact with water from 55 vol.% to 100 vol.% and after 10 seconds from 75 vol.% to 130 vol.%.
  • a bulk density of 400 g / l to 500 g / l the volume increase of 200 after 5 seconds Vol.% To 225 vol.% And after 10 seconds from 230 vol.% To 270 vol.%.
  • Figure 1 shows a diagram for the swelling kinetics of known explosives and granules according to the invention.
  • Table 1 contains the corresponding measured values. Swelling kinetics of different materials Bulk density [g / l] 70 90 90 300 300 450 450 Cellulose V 1 M1 V2 M2 V3 M3 Time [sec] Way [mm] Way [mm] Way [mm] Way [mm] Way [mm] Way [mm] Way [mm] Way [mm] 0 0 0 0 0 1 0.10 0.20 0.25 0.30 0.50 0.80 1.20 2nd 0.20 0.40 0.40 0.60 1.05 1.20 1.80 3rd 0.30 0.60 0.65 0.90 1.35 1.50 2.20 4th 0.35 0.70 0.80 1.00 1.58 1.60 2.40 5 0.40 0.85 0.95 1.10 1.75 1.70 2.50 6 0.42 1.00 1.15 1.15 1.83 1.72 2.58 7 0.44 1.10 1.25 1.20 1.93 1.80 2.65 8th 0.46 1.20 1.40 1.25 2.00 1.82 2.70 9 0.48 1.35 1.55 1.40 2.05 1.82 2.72 10th 0.48 1.40 1.65 1.50 2.15 1.85 2.
  • composition of the samples V1 to V3 is as in Table 3, example 2.1.
  • composition of the samples M1 to M3 is as in Table 3, example. 2.3: Does not fall under the scope of protection; but supports the concept of the present invention. Volume expansion in vol.% Cellulose V1 M1 V2 M2 V3 M3 Bulk density in g / l 70 90 90 300 300 450 450 Volume increase after 5 sec vol.% 5 14 16 55 100 200 225 after 10 sec vol.% 6 23 28 75 130 230 270
  • Formulation V1 has the composition of Example 2.1 in undensified form.
  • Formulation M1 has the composition of Example 2.3 in undensified form.
  • V2, M2 denote samples that were compressed to a bulk density of 300 g / l after mixing in a roller press.
  • V3 and M3 refer to samples which, after mixing, were compressed to a bulk density of 450 g / l using a roller press.
  • the increase in volume after 5 seconds is preferably at least 95%, particularly preferred> 150%.
  • Another object of the invention is a method for manufacturing a compacted granulate that is insoluble in water but swellable high-purity cellulose and / or cellulose derivatives and finely divided polymers / copolymers of (meth) acrylic acid or its salts and one or more contains liquid surfactants by mixing high-purity cellulose / cellulose derivative with the surfactant (s) according to the invention and mixing the polymers / copolymers, granulating and then compressing the Granules aligned with anisotropic cellulose / cellulose derivatives.
  • the first step of the process involves a mixing and granulating process, in the pre-compounds produced by agglomeration processes become. These precompounds form a free-flowing and coarse-grained Goods that have a certain degree of moisture.
  • the next step will be these precompounds are mechanically compressed.
  • the products can be between two pressure areas in roller compressors, e.g. B. smooth or profiled, compressed become. If certain sliding properties are available, the Compression in extruders or flat die presses to form dies.
  • the compactate is ejected as a strand. Compression methods in Matrices with stamps or pillow rollers produce compact forms such as tablets or briquettes. Roller compactors, Extruders, roller or cube presses, but also granulating presses be used. Below are the coarse, densified particles crushed, e.g. Suitable for mills, shredders or roller mills are.
  • the granulate according to the invention takes this quickly in contact with water with volume increase and is therefore suitable as a so-called Disintegrant for pressed moldings so that they quickly disintegrate in water.
  • the invention includes the use of the compacted granules as Disintegrants for pressed molded articles, for example tablets, cubes, Bullets and the like.
  • disintegrant for detergent formulations is particularly preferred, Detergent formulations, stain salts, water softeners in tablet or cube form.
  • Detergent tablets and detergent tablets for different Purposes, in the sanitary area or for dishwashers are generally known.
  • Such moldings must have sufficient stability and strength to enable handling, packaging and storage however, quickly disintegrate on contact with water, so that the components can have the desired effect.
  • the pressed moldings often contain so-called Disintegrants that due to the swelling behavior and the increase in volume Remove the cohesion of the shaped bodies and accelerate the disintegration.
  • Detergent formulations usually contain builders, bleaches and bleach activators, surfactants, tabletting aids, disintegrants and other common additives and auxiliaries.
  • Fillers can also form part of the builder system such as alkali carbonates, bicarbonates e.g. Sodium carbonate or sodium hydrogen carbonate, Sesquiocarbonates, sodium sulfate, magnesium sulfate, or citrate, citric acid, succinic acid, tartaric acid and malic acid his.
  • Cobuilders and dispersants are often used as auxiliary builders. Such cobuilders or dispersants can be polyacrylic acids and their sodium salts.
  • Copolymers of (meth) acrylic acid and maleic acid terpolymers and Quattropolymers of (meth) acrylic acid, maleic acid, vinyl alcohol and sulfo groups Vinyl compounds can be used.
  • Ter- and quattropolymeric polycarboxylates are also particularly preferred, made from (meth) acrylic acid, maleic acid and vinyl alcohol or Vinyl alcohol derivatives (as described in DE 43 00 772 C2) or those from (meth) acrylic acid, 2-alkylallylsulfonic acid and sugar derivatives (as described in DE 42 21 381 C1) or those made from (meth) acrylic acid, Maleic acid, vinyl alcohol derivatives and monomers with sulfonic acid groups (described in DE 19 516 957 A).
  • polyethylene glycol and / or polypropylene glycol with a Suitable molecular weight from 900 to 30,000, as well as carboxylated polysaccharides, Polyaspartates and polyglutamate.
  • Customary bleaching agents are sodium perborate tetrahydrate and sodium perborate monohydrate, sodium percarbonate, peroxypyrophosphates, citrate perhydrates, as well as H 2 O 2 -producing peracidic salts, peracids such as perbenzoates, peroxyphthalates, diperazelaic acid and diperdodecanedioic acids.
  • the bleach content in tablets is preferably 10-60% by weight and in particular 15-50% by weight.
  • activators can be incorporated.
  • Suitable bleach activators are the N-acyl and O-acyl compounds forming with H 2 O 2 organic peracids, preferably N, N'-tetraacylated diamines, carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. Acetylated mixtures of sorbitol and mannitol can also be used.
  • bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,2,5-triazine (DADHT) and acetylated sorbitol mannitol Mixtures (SORMAN).
  • TAED N, N, N ', N'-tetraacetylethylene diamine
  • DADHT 1,5-diacetyl-2,4-dioxo-hexahydro-1,2,5-triazine
  • SORMAN acetylated sorbitol mannitol Mixtures
  • cationic surfactants can also be present in detergent formulations, for example quaternary ammonium compounds with C 8 -C 16 N-alkyl or N-alkenyl groups and N-substituents such as methyl, hydroxyethyl or hydroxypropyl groups.
  • Polyalkylene glycols and magnesium stearates come as tableting aids into consideration.
  • Examples of other common detergent additives and auxiliaries are Enzymes, magnesium silicates, aluminum aluminates, benzotriazole, glycerin, Magnesium stearate, polyalkylene glycols, hexametaphosphate, phosphonates, bentonites, Soil release polymers, carboxymethyl celluloses.
  • Dishwashing tablets as an educational form of detergent formulations usually contain polyphosphates, pyrophosphates, Metaphosphates or phosphonates, layered silicates, amorphous silicates, amorphous disilicates and zeolites, as well as fillers such as sodium carbonate, Sodium sulfate, magnesium sulfate, sodium hydrogen carbonate, citrate as well Citric acid, succinic acid, tartaric acid and malic acid. Frequently are also used as auxiliary builders, cobuilders and dispersants. Such Cobuilders or dispersants can be polyacrylic acids or copolymers with polyacrylic acid and its sodium salts.
  • Customary bleaching agents are sodium perborate tetrahydrate and sodium perborate monohydrate, sodium percarbonate, peroxypyrophosphates, citrate perhydrates, as well as H 2 O 2 -producing peracidic salts, peracids such as perbenzoates, peroxyphthalates, diperazelaic acid and diperdodecanedioic acids.
  • the content in the tablets is preferably 10-60% by weight and in particular 15-50% by weight.
  • Low-foaming non-ionic surfactants of the polyalkylene glycol and alkyl polyglucoside type are also used.
  • Examples of other common detergent additives and auxiliaries are here too enzymes, magnesium silicates, aluminum aluminates, benzotriazole, Glycerin, magnesium stearate, polyalkylene glycols, hexametaphosphate as well Phosphonates.
  • Water softening tablets usually consist of builders such as Layered silicates, amorphous silicates, amorphous disilicates and zeolites, as well as fillers such as sodium carbonate, sodium sulfate, magnesium sulfate, Sodium bicarbonate, citrate and citric acid. Often called Auxiliary builders cobuilders and dispersants also used. Such cobuilders or dispersants can be polyacrylic acids or copolymers with polyacrylic acid and their sodium salts.
  • Low-foaming non-ionic surfactants of the polyalkylene glycol and alkyl polyglucoside type are also used.
  • Examples of other common detergent additives and auxiliaries are Magnesium silicates, polyalkylene glycols and phosphonates.
  • disintegrant compositions according to the teaching of the invention (all amounts in% by weight) .
  • Detergent tablet containing phosphate strength of the tablet and its Disintegration time using the granules of the above examples:
  • Phosphate-containing detergent tablets with the composition described in Table 3 were examined for their disintegration time and strength.
  • Table 5 shows the strength and disintegration time of the individual detergent tablets when using the different disintegrants: Disintegrant composition according to example Disintegration time in sec Strength in N 2.1 35 62 2.2 28 61 2.3 25th 63 2.4 28 70 2.5 22 53 2.6 19th 64 2.7 21 63 2.8 29 58
  • Phosphate-free detergent tablet strength of the tablet and its disintegration time using one of the granules of the aforementioned examples:
  • Amorphous disilicate 36 30th Fatty alcohol ethoxylate 2nd 7 Fatty alcohol sulfate 11 15 Linear alkyl benzene sulphonate 4th 2nd Sodium percarbonate 16 16 TAED 4th 4th Acrylate-maleate copolymer - 3rd soda 7 4th Sodium citrate 5 5 Microcrystalline cellulose (200 ⁇ m) 4th 4th Defoamer, optical brightener, CMC, phosphonate 5 4th Enzyme mix 1 1 Disintegrant preparation according to example 2.3 5 5 5 Recipe Disintegration time in sec Strength in N a) 40 68 b) 15 48
  • Example 11 Pressed molded articles with the intended use as

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Abstract

Verdichtetes Granulat aus in Wasser quellbarer Cellulose und/oder Cellulosederivaten und feinteiligen Polymeren/Copolymeren von (Meth)acrylsäure oder Salzen derselben und ein oder mehreren flüssigen Tensiden und dessen Verwendung als Sprengmittel für Waschmitteltabletten, Reinigungsmitteltabletten, Wasserenthärtungstabletten Fleckensalztabletten, sowie ein Verfahren zum Herstellen des verdichteten Granulats durch Mischen der Bestandteile, Granulieren und Verdichten.Compacted granules of water-swellable cellulose and / or cellulose derivatives and finely divided polymers / copolymers of (meth) acrylic acid or salts thereof and one or more liquid surfactants and their use as disintegrants for detergent tablets, detergent tablets, water softening tablets, stain remover tablets, and a process for producing the compressed tablets Granules by mixing the components, granulating and compacting.

Description

Die Erfindung richtet sich auf ein Granulat, das besonders gut Wasser aufnimmt und im Innern weiterleitet wodurch zum Teil eine Volumenzunahme erfolgt, so daß das Granulat als Sprengmittel für gepreßte Formkörper, wie Tabletten, geeignet ist.The invention is directed to granules that are particularly good at water records and forwards inside, which in some cases increases the volume takes place, so that the granules as disintegrants for pressed moldings, such as tablets.

Sprengmittel für Tabletten oder Granulate sind Hilfsstoffe, die den Zerfall von Tabletten oder des Granulats bei Kontakt mit Flüssigkeiten, insbesondere Wasser positiv beeinflussen. Dabei soll sowohl der Zerfall von Tabletten in grobe Teile als auch nachfolgend ein Zerfall in kleinere Partikel bewirkt und beschleunigt werden.Disintegrants for tablets or granules are auxiliary substances that disintegrate tablets or granules in contact with liquids, in particular Influence water positively. The decay of Tablets in large parts and then a disintegration into smaller ones Particles are caused and accelerated.

Als Sprengmittel für Tabletten sind eine Vielzahl anorganischer und organischer Substanzen bekannt, zum Beispiel anorganische Stoffe wie Bentonite, auch Persalze, Acetate, Alkalicarbonate/Hydrogencarbonate und Zitronensäure. Zu den bekannten organischen Verbindungen gehören Stärke, modifizierte Stärke und Stärkeabbauprodukte, Cellulose, Celluloseether, wie Methylcellulose Hydroxypropylcellulose und Carboxymethylcellulose, Poly(meth)acrylate, Polyvinylpyrrolidon und quervernetztes Polyvinylpyrrolidon, Alginate, Gelatine und Pectine.A large number of inorganic and organic disintegrants for tablets are Substances known, for example inorganic substances such as bentonites, also persalts, acetates, alkali carbonates / hydrogen carbonates and citric acid. Known organic compounds include starch, modified Starch and starch degradation products, cellulose, cellulose ethers, such as Methyl cellulose hydroxypropyl cellulose and carboxymethyl cellulose, poly (meth) acrylates, Polyvinyl pyrrolidone and cross-linked polyvinyl pyrrolidone, Alginates, gelatin and pectins.

Bei Tabletten, die aus vorgefertigten Compounds gepreßt werden, besteht die Notwendigkeit, den Zerfall in die ursprünglichen Compounds und nachfolgend auch in Einzelbestandteile zu beschleunigen.For tablets that are made from pre-made compounds the need to disintegrate into the original compounds and subsequent to accelerate even in individual components.

Bei Tabletten, die aus nicht vorgefertigten Compounds gepreßt werden, entsteht beim Verpressen häufig eine sehr hohe Dichte, die bei Kontakt mit Wasser den gewünschten Zerfall der Tablette verzögert. Dies ist häufig unerwünscht, weil sich Bestandteile dann nur mit Verzögerung lösen. For tablets that are pressed from non-prefabricated compounds, A very high density often arises when pressing, that in contact delayed the desired disintegration of the tablet with water. This is common undesirable, because components then only come off with a delay.

Aus W098/40463 ist ein Sprengmittelgranulat und seine Verwendung in wasch- oder reinigungsaktiven Formkörpern, wie Tabletten, bekannt, welches ein hohes Adsorptionsvermögen für Wasser und eine KorngröBenverteilung aufweist, bei der mindestens 90 Gew.% eine Partikelgröße von mindestens 0,2 mm und maximal 3 mm haben. Das Granulat enthält vorzugsweise 25-100 Gew.% Sprengmittel, wie Stärke, Stärkederivate, Cellulose, Cellulosederivate, Alginsäure, Carboxylmethylamylopectin, Polyacrylsäure, Polyvinylpyrrolidon und Polyvinylpolypyrrolidon. Nach der Lehre dieses Patentes wirkt sich das Vorhandensein von anionischen oder nichtionischen Tensiden negativ auf die Tablettenzerfallszeit aus. Das Granulat wird durch herkömmliche Weise hergestellt, wie Sprühtrocknung, Heißdampftrocknung wässriger Zubereitungen oder durch Granulieren, Pelletierung, Extrusion oder Walzenkompaktierung pulverförmiger Bestandteile.From W098 / 40463 an explosive granulate and its use in washing or cleaning-active moldings, such as tablets, known a high adsorption capacity for water and a grain size distribution in which at least 90% by weight has a particle size of at least 0.2 mm and a maximum of 3 mm. The granules preferably contain 25-100% by weight of disintegrants, such as starch, starch derivatives, cellulose, cellulose derivatives, Alginic acid, carboxylmethylamylopectin, polyacrylic acid, polyvinylpyrrolidone and polyvinyl polypyrrolidone. After teaching this Patentes affects the presence of anionic or nonionic Surfactants negatively affect the tablet disintegration time. The granules will made by conventional means, such as spray drying, steam drying aqueous preparations or by granulating, pelleting, Extrusion or roller compaction of powdery components.

In WO 96/06156 wird ein Verfahren zur Herstellung von Wasch- oder Reinigungsmitteltabletten beschrieben. Als Sprengmittel werden Citronensäure bzw. Citrate, Bicarbonate und Carbonate, Bisulfat und Percarbonat, mikrokristalline Cellulose, Zucker, Sorbit oder quellfähige Schichtsilikate von der Art der Bentonite oder Smektite genannt. Die Sprengmittel werden in Mengen von 1 bis 25 Gew.% als Einzelrohstoff oder als Compound eingesetzt.WO 96/06156 describes a method for producing detergent tablets described. Citric acid is used as a disintegrant or citrates, bicarbonates and carbonates, bisulfate and percarbonate, microcrystalline Cellulose, sugar, sorbitol or swellable layered silicates called the type of bentonite or smectite. The explosives are used in quantities of 1 to 25% by weight as a single raw material or as a compound.

DE-A-44 04 279 beschreibt folgende Sprengmittel für Wasch- oder Reinigungstabletten: Stärke, Stärkederivate, Cellulose, Cellulosederivate, mikrokristalline Cellulose, Salze polymerer Polyacrylate oder Polymethacrylate, Methylcellulosen, Hydroxypropylcellulosen bzw. Methylhydroxypropylcellulosen. Auch Acetate oder Percarbonate werden als Sprengmittel genannt. Die Anwendungsmengen betragen bis zu 15 Gew.%. Da als Builder wasserlösliche Silikate eingesetzt werden, können mit einer Kombination aus Poly(meth)acrylaten und nichtionischen Celluloseethern schon
Mengen von 1 Gew.% zu sehr guten Ergebnissen führen. DE-A-44 04 279 describes the following disintegrants for washing or cleaning tablets: starch, starch derivatives, cellulose, cellulose derivatives, microcrystalline cellulose, salts of polymeric polyacrylates or polymethacrylates, methyl celluloses, hydroxypropyl celluloses or methyl hydroxypropyl celluloses. Acetates or percarbonates are also mentioned as disintegrants. The application amounts are up to 15% by weight. Since water-soluble silicates are used as builders, a combination of poly (meth) acrylates and nonionic cellulose ethers can
Amounts of 1% by weight lead to very good results.

In der europäischen Patentanmeldung EP 0 846 756 A1 werden Tablettensprengmittel in die Tablette und bevorzugt in die äußere feste Hülle der Tablette eingearbeitet. Bevorzugt werden Kombinationen aus löslichen Säuren und Alkalicarbonaten verwendet. Weitere mögliche Sprengmittel können dem "Handbook of Pharmaceutical Excipients (1986) entnommen werden. Als Beispiele werden genannt: Stärke (modifizierte Stärke Natrium-Stärke-Gluconate), Gummi (Agar, Guar, und andere), Cellulose, Carboxymethylcellulose, Alginate, Siliziumdioxid, Ton, Polyvinylpyrrolidon, Polysaccharide und Ionenaustauscherharze.In the European patent application EP 0 846 756 A1 tablet disintegrants into the tablet and preferably into the outer hard shell of the Tablet incorporated. Combinations of soluble acids are preferred and alkali carbonates used. Other possible explosives can from the "Handbook of Pharmaceutical Excipients (1986). As Examples are: starch (modified starch sodium starch gluconate), Gum (agar, guar, and others), cellulose, carboxymethyl cellulose, Alginates, silicon dioxide, clay, polyvinylpyrrolidone, polysaccharides and ion exchange resins.

Aus EP-A-522 766 sind Waschmitteltabletten bekannt, die Sprengmittel enthalten, die nach vier verschiedenen Mechanismen funktionieren: Quellung, Porosität / Kapillarwirkung, Deformation und chemische Reaktion. Beschrieben werden Stärke, Stärkederivate, Carboxymethylstärke, Natrium-Stärke-Glycolate, Cellulose und Cellulosederivate, Carboxymethylcellulose, vernetzte modifizierte Cellulose, mikrokristalline Cellulose und verschiedene organische Polymere wie Polyethylenglykol, und vernetzte Polyvinypyrrolidone und anorganische Quellungsmittel wie Bentonite.
Ebenso genannt werden Kombinationen aus organischen Säuren und Bicarbonaten der Carbonate von Alkalimetallen.Detergent tablets are known from EP-A-522 766 which contain disintegrants which function according to four different mechanisms: swelling, porosity / capillary action, deformation and chemical reaction. Starch, starch derivatives, carboxymethyl starch, sodium starch glycolates, cellulose and cellulose derivatives, carboxymethyl cellulose, crosslinked modified cellulose, microcrystalline cellulose and various organic polymers such as polyethylene glycol, and crosslinked polyvinypyrrolidones and inorganic swelling agents such as bentonites are described.
Combinations of organic acids and bicarbonates of the carbonates of alkali metals are also mentioned.

EP 0 628 627 A1 beschreibt einen wasserlöslichen, wasserenthärtenden Builder in Form einer Tablette. Dabei werden als Sprengmittel Kombinationen aus Citronensäure und/oder teilneutralisierten Polymeren und Carbonat und /oder Bicarbonat oder ein unlösliches Polyvinylpyrrolidon eingesetzt.EP 0 628 627 A1 describes a water-soluble, water-softening agent Builder in the form of a tablet. Combinations are used as explosives from citric acid and / or partially neutralized polymers and carbonate and / or bicarbonate or an insoluble polyvinylpyrrolidone.

In einer weiteren veröffentlichten europäischen Patentanmeldung (EP 0 799 886 A2), werden Waschmitteltabletten beschrieben, die als Sprengmittel Stärkederivate, Cellulose-Compounds, Polyvinylpyrrolidon-Compounds, Polyvinylpolypyrrolidon-Compounds, Bentonit-Compounds, Alginate Gelatine und Pectine enthalten können. Zur weiteren Verbesserung der Lösezeit wird der Zusatz einer polyfunktionalen organischen Carbonsäure, wie Maleinsäure Äpfelsäure Citronensäure oder Weinsäure zusammen mit Carbonaten oder Bicarbonaten empfohlen.In another published European patent application (EP 0 799 886 A2), detergent tablets are described as disintegrants Starch derivatives, cellulose compounds, polyvinylpyrrolidone compounds, polyvinylpolypyrrolidone compounds, Bentonite compounds, alginate gelatin and may contain pectins. To further improve the release time the addition of a polyfunctional organic carboxylic acid such as maleic acid Malic acid citric acid or tartaric acid together with carbonates or Bicarbonates recommended.

Aus WO)95/06 109 ist ein Verfahren zum Herstellen von Waschmittelgranulat hoher Dichte aus wasserfreiem Material bekannt. Die Agglomerate sind frei fließend und weisen einen hohen Gehalt an waschaktiven Substanzen auf. Als wasserfreie Stoffe sind Carbonate, Sulfate, Carbonat/Sulfatkomplexe, Tripolyphosphate, Tetra-natrium-pyrophosphate, Citrate, Aluminosilikate, Cellulose und absorbierende synthetische organische Polymere genannt.From WO) 95/06 109 is a method for producing detergent granules known high density from anhydrous material. The agglomerates are free fluent and have a high content of detergent substances. Carbonates, sulfates, carbonate / sulfate complexes, Tripolyphosphates, tetra-sodium pyrophosphates, citrates, aluminosilicates, Called cellulose and absorbent synthetic organic polymers.

Aus dem Stand der Technik ist kein Sprengmittel bekannt, das sich durch eine nichtlineare Quellkinetik auszeichnet und es ist nirgends die Verwendung von Tensiden, bevorzugt gelbildende oder mit Wasser verdickende Tenside, im Sprengmittel erwähnt. Die Verlängerung der Tablettenzerfallszeit durch bestimmte Tenside wird bisher als Nachteil beschrieben.No disintegrant is known from the prior art, which is characterized by is characterized by a non-linear source kinetics and the use is nowhere of surfactants, preferably gel-forming or water-thickening Surfactants, mentioned in the disintegrant. The prolongation of the tablet disintegration time Certain surfactants have so far been described as a disadvantage.

Aufgabe der Erfindung ist es, ein in Wasser schnell und stark quellendes Granulat zu schaffen, so daß es als Sprengmittel für gepreßte Formkörper geeignet ist, um deren Zerfall bei Kontakt mit Wasser zu fördern.The object of the invention is to swell quickly and strongly in water To create granules so that it can be used as a disintegrant for molded articles is suitable to promote their decay on contact with water.

Diese Aufgabe wird gelöst durch ein verdichtetes Sprengmittelgranulat für gepreßte Formkörper, enthaltend nicht wasserlösliche, in Wasser quellbare hochreine Cellulose und/oder Cellulosederivate und feinteilige Polymere oder Copolymere von (Meth)acrylsäure oder Mischungen dieser Polymeren oder Copolymeren und ein oder mehrere flüssige nichtionische und/oder anionische und/oder amphotere Tensid(e),die zur Gelbildung oder Verdikkung mit Wasser neigen, wobei das Gewichtsverhältnis der kombinierten in Wasser quellbaren Cellulose/Cellulosederivate und der Polymere/Copolymere von (Meth)acrylsäure : flüssigen Tensid(en) von 100:1 bis 10:1 beträgt. Durch das Verdichten wurde eine Ausrichtung der anisotropen Cellulose bzw. Cellulosederivate erzeugt. This task is solved by a compacted explosive granulate for pressed molded articles containing non-water-soluble, water-swellable high-purity cellulose and / or cellulose derivatives and finely divided polymers or copolymers of (meth) acrylic acid or mixtures of these polymers or copolymers and one or more liquid nonionic and / or anionic and / or amphoteric surfactant (s) used for gel formation or thickening incline with water, the weight ratio of the combined in Water-swellable cellulose / cellulose derivatives and the polymers / copolymers of (meth) acrylic acid: liquid surfactant (s) is from 100: 1 to 10: 1. The anisotropic cellulose was aligned by the compression or cellulose derivatives.

Die in Wasser quellbare hochreine Cellulose wird in Form mikrokristalliner Gefüge eingesetzt, wobei die übermolekularen Strukturelemente die Form von Fibrillen aufweisen, in deren Längsrichtung sich kristalline und amorphe Bereiche abwechseln können. Als besonders geeignet haben sich Fibrillen nativer Cellulose mit einer maximalen Länge von 300 µm erwiesen. Es können sowohl mikrokristalline als auch amorphe feinteilige Cellulose und Mischungen derselben verwendet werden.The water-swellable, high-purity cellulose becomes microcrystalline in form Structure used, the super-molecular structural elements Have the shape of fibrils, in the longitudinal direction of which crystalline and can alternate amorphous areas. Have proven to be particularly suitable Fibrils of native cellulose with a maximum length of 300 µm have been proven. Both microcrystalline and amorphous fine cellulose can be used and mixtures thereof can be used.

Die feinteilige Cellulose weist vorzugsweise Schüttgewichte von 40 g/l bis 300 g/l, ganz besonders bevorzugt von 65 g/l bis 170 g/l auf. Werden bereits aufgranulierte Typen verwendet, liegt deren Schüttgewicht höher und kann von 350 g/l bis 550 g/l betragen. Die Schüttgewichte der Cellulosederivate können im Bereich von 50 g/l bis 1000 g/l, bevorzugt im Bereich von 100 g/l und 800 g/l liegen.The finely divided cellulose preferably has bulk densities of 40 g / l up to 300 g / l, very particularly preferably from 65 g / l to 170 g / l. Become already used granulated types, their bulk density is higher and can be from 350 g / l to 550 g / l. The bulk weights of the cellulose derivatives can range from 50 g / l to 1000 g / l, preferably in the range of 100 g / l and 800 g / l.

Die Teilchengröße der feinteiligen Cellulose kann zwischen 30 µm bis 300 µm, vorzugsweise zwischen 30 µm und 200 µm betragen, im Falle von aufgranulierten Typen liegt die mittlere Teilchengröße zwischen 350 µm und 800 µm. Die Teilchengröße der feinteiligen Cellulosederivate kann zwischen 30 µm und 1000 µm betragen.The particle size of the finely divided cellulose can be between 30 μm and 300 μm, preferably between 30 μm and 200 µm, in the case of granulated types the average particle size is between 350 µm and 800 µm. The particle size of the finely divided Cellulose derivatives can be between 30 µm and 1000 µm.

Aufgrund ihres Wasseraufnahmevermögens sind in Wasser quellbare Cellulosederivate, wie Celluloseether und Celluloseester und gemischte Modifizierungen derselben ebenso verwendbar. Geeignete Celluloseether sind z.B. Methylcellulose, Hydroxypropylcellulose und Carboxymethylcellulose, sowie modifizierte Carboxymethylcellulose.Due to their water absorption capacity, cellulose derivatives that are swellable in water, such as cellulose ethers and cellulose esters and mixed modifications the same can also be used. Suitable cellulose ethers are e.g. Methyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose, as well modified carboxymethyl cellulose.

Es können auch reine Cellulose und Cellulosederivate zusammen im erfindungsgemäßen Granulat vorhanden sein.Pure cellulose and cellulose derivatives can also be used together in the invention Granules are present.

In Kombination mit reiner feinteiliger Cellulose/Cellulosederivaten sind feinteilige Polymere von (Meth)acrylsäure oder Copolymere von (Meth)acrylsäure oder Salze derselben oder Mischungen von derartigen Polymeren oder Copolymeren oder Salzen derselben mit hohem Wasseraufnahmevermögen im Granulat enthalten. Als besonders geeignet haben sich lineare Polymere von (Meth)acrylsäure, Copolymere von (Meth)acrylsäure oder Salze derselben mit gewichtsmittleren Molekulargewichten von 5.000 bis 70.000 und quervernetzte Polymere von (Meth)acrylsäure, Copolymere von (Meth)acrylsäure oder Salze derselben mit gewichtsmittleren Molekulargewichten von 1.000.000 bis 5.000.000 erwiesen. Bei den Copolymeren handelt es sich vorzugsweise um Copolymere von (Meth)acrylsäure und Maleinsäure oder Maleinsäureanhydrid, die beispielsweise 40 bis 90 Gew.% (Meth)acrylsäure und 60 bis 10 Gew.% Maleinsäure oder Maleinsäureanhydrid enthalten, deren relative Molmasse, bezogen auf freie Säuren, zwischen 3.000 und 100.000, vorzugsweise 3.000 bis 70.000 und ganz besonders bevorzugt 5.000 bis 50.000 beträgt.In combination with pure fine cellulose / cellulose derivatives finely divided polymers of (meth) acrylic acid or copolymers of (Meth) acrylic acid or salts thereof or mixtures of such polymers or copolymers or salts thereof with high water absorption contained in the granulate. Linear ones have proven to be particularly suitable Polymers of (meth) acrylic acid, copolymers of (meth) acrylic acid or salts the same with weight average molecular weights of 5,000 to 70,000 and cross-linked polymers of (meth) acrylic acid, copolymers of (Meth) acrylic acid or salts thereof with weight average molecular weights proven from 1,000,000 to 5,000,000. The copolymers are concerned it is preferably a copolymer of (meth) acrylic acid and maleic acid or maleic anhydride, for example 40 to 90% by weight (Meth) acrylic acid and 60 to 10% by weight of maleic acid or maleic anhydride contain, whose relative molar mass, based on free acids, between 3,000 and 100,000, preferably 3,000 to 70,000 and very particularly preferred Is 5,000 to 50,000.

Als gut geeignet haben sich auch ter- und quattropolymere Polycarboxylate erwiesen, hergestellt aus (Meth)acrylsäure, Maleinsäure und Vinylalkohol oder Vinylalkoholderivaten, oder solche aus (Meth)acrylsäure, ethylenisch ungesättigen Sulfonsäuren und Zuckerderivaten, oder solche aus (Meth)acrylsäure, Maleinsäure, Vinylalkoholderivaten und sulfonsäuregruppenhaltigen MonomerenTer- and quattropolymeric polycarboxylates have also proven to be very suitable proven, made from (meth) acrylic acid, maleic acid and vinyl alcohol or vinyl alcohol derivatives, or those of (meth) acrylic acid, ethylenically unsaturated sulfonic acids and sugar derivatives, or such (Meth) acrylic acid, maleic acid, vinyl alcohol derivatives and sulfonic acid groups Monomers

Die Salzbildung erfolgt vorzugsweise mit Kationen von Alkalimetallen, Ammoniak und Aminen, bzw. deren Mischungen.Salt formation is preferably carried out with cations of alkali metals, Ammonia and amines, or their mixtures.

Die feinteiligen Polymeren/Copolymeren von (Meth)acrylsäure oder Salzen derselben der vorstehend beschriebenen vernetzten Derivate haben vorzugsweise eine mittlere Teilchengröße von 45 µm bis 150 µm. Ganz besonders bevorzugt sind Teilchengrößen von 45 µm bis 90 µm.The finely divided polymers / copolymers of (meth) acrylic acid or salts preferably have the same of the cross-linked derivatives described above an average particle size of 45 µm to 150 µm. Most notably particle sizes from 45 μm to 90 μm are preferred.

Teilchen mit mittleren Teilchengrößen über 150 µm zeigen zwar eine gute Sprengwirkung, sind nach dem Quellen jedoch zu groß, werden beim Waschen abfiltriert und sind auf dem Textilgut nach der Wäsche visuell als Teilchen sichtbar.Particles with average particle sizes over 150 µm show a good one Explosive effects, but are too large after swelling, become when washing filtered off and are visually as particles on the textile after washing visible.

Cellulose/Cellulosederivate werden mit Polymeren/Copolymeren von (Meth)acrylsäure oder Salzen derselben im Granulat kombiniert, das Gewichtsverhältnis kann von 100:0,5 bis 100:30, vorzugsweise von 100:1 bis 100:20 betragen, ganz besonders bevorzugt ist ein Gewichtsverhältnis von 100:1 bis 100:10, am günstigsten ist ein Gewichtsverhältnis von 100:3.Cellulose / cellulose derivatives are made with polymers / copolymers from (Meth) acrylic acid or salts thereof combined in the granulate, the weight ratio can be from 100: 0.5 to 100: 30, preferably from 100: 1 to 100: 20, a weight ratio of is very particularly preferred 100: 1 to 100: 10, the most favorable is a weight ratio of 100: 3.

Als weiteren wesentlichen Bestandteil enthält das Granulat ein oder mehrere flüssige, mit Wasser gelbildende oder verdickende Tenside, ausgewählt aus der Gruppe der nichtionischen, anionischen oder amphoteren Tenside.The granulate contains one or more other essential constituents liquid, water-forming or thickening surfactants from the group of nonionic, anionic or amphoteric surfactants.

Die nichtionischen Tenside sind ausgewählt aus Alkylpolyglucosiden, Fettsäure-Alkylolamiden, Fettsäure-Polyethylenglykolestern, Fettaminoxethylaten, Fettalkoholethoxylaten mit 3-15 Mol Ethylenoxid oder Propylenoxid, Fettsäureglyceriden, Sorbitanestern, Saccharoseestern, z.B. Saccharosepalmitat, Pentaaerythrit-Partialester, die auch ethoxyliert sein können, sowie Alkylphenol-Polyethylenglykolethern und Phenolpoly - ethylenglykolethern (wenn diese im jeweiligen Land eingesetzt werden dürfen)The nonionic surfactants are selected from alkyl polyglucosides, fatty acid alkylolamides, Fatty acid polyethylene glycol esters, fatty amine oxethylates, Fatty alcohol ethoxylates with 3-15 mol ethylene oxide or propylene oxide, Fatty acid glycerides, sorbitan esters, sucrose esters, e.g. Sucrose palmitate, Pentaerythritol partial esters, which can also be ethoxylated, as well as alkylphenol polyethylene glycol ethers and phenol poly - ethylene glycol ethers (if they can be used in the respective country)

Die anionische Tenside sind ausgewählt aus Alkylsulfaten, linearen und verzweigten Alkybenzolsulfonaten, Alkylglycerolethern, Fettalkoholpolyethylenglycolethersulfaten, Paraffinsulfonaten, Alpha-Olefinsulfonaten, Sulfosuccinaten, Phosphorsäureestern und Fettalkoholethercarboxylaten.The anionic surfactants are selected from alkyl sulfates, linear and branched alkylbenzenesulfonates, alkylglycerol ethers, fatty alcohol polyethylene glycol ether sulfates, Paraffin sulfonates, alpha olefin sulfonates, Sulfosuccinates, phosphoric acid esters and fatty alcohol ether carboxylates.

Die amphoteren Tenside sind ausgewählt aus Cocosfettsäureamidopropylbetain, modifizierten Imidazolinen und Fettsäureamidderivaten mit Betainstruktur.The amphoteric surfactants are selected from coconut fatty acid amidopropyl betaine, modified imidazolines and fatty acid amide derivatives with betaine structure.

Das Mengenverhältnis von Cellulose/Cellulosederivaten und/oder Polymeren/Copolymeren von (Meth)acrylsäure oder Salzen derselben : Tensid kann von 100:1 bis 10:1 betragen. Bevorzugt sind Mengenverhältnisse von 100:2 bis 100:5The quantitative ratio of cellulose / cellulose derivatives and / or polymers / copolymers of (meth) acrylic acid or salts thereof: surfactant can from 100: 1 to 10: 1. Quantities of 100: 2 are preferred up to 100: 5

Völlig überraschend wurde gefunden, daß bei Anlagerung der erfindungsgemäßen Tenside an Cellulose bzw. deren Derivaten die Quellwirkung der erfindungsgemäßen Sprengmittelgranulate deutlich verbessert wird. Dies ist besonders überraschend, da viele konzentrierte Tenside bei Kontakt mit Wasser zur Gelbildung neigen und die Benetzung und Quellung des Sprengmittelgranulates eher behindert sein sollte. Gelbildung oder verdickende Wirkungen hat man z.B. bei Fettalkoholethoxylaten, Seifen, Fettalkylethersulfaten und Fettalkylsulfaten beobachtet.Completely surprisingly, it was found that when the inventive compounds were added Surfactants on cellulose or their derivatives have the swelling effect of the invention Disintegrant granules is significantly improved. This is Particularly surprising, since many concentrated surfactants come into contact with Water tend to gel and wetting and swelling of the disintegrant granules should be rather disabled. Gelation or thickening One has effects e.g. for fatty alcohol ethoxylates, soaps, fatty alkyl ether sulfates and fatty alkyl sulfates were observed.

Die gelbildenden oder mit Wasser verdickenden Tenside können anionisch, amphoter oder nichtionisch sein, besonders bevorzugt sind nichtionische Tenside.The gel-forming or water-thickening surfactants can be anionic, be amphoteric or nonionic, particularly preferred are nonionic Surfactants.

Es hat sich deshalb als besonders vorteilhaft erwiesen, die flüssigen Tenside zunächst in direktem Kontakt mit der Cellulose / den Cellulosederivaten zu bringen und daran anzulagern und dann die feinteiligen Polymere / Copolymere von (Meth)acrylsäure oder deren Salze in die Mischung derart einzubringen, daß die Polymerteilchen an den Fibrillen der Cellulose haften.It has therefore proven to be particularly advantageous to use the liquid Surfactants initially in direct contact with the cellulose / cellulose derivatives to bring and attach to it and then the finely divided polymers / Copolymers of (meth) acrylic acid or its salts in the mixture to be introduced in such a way that the polymer particles on the fibrils of the cellulose be liable.

Die Mischung der erfindungsgemäßen Granulatbestandteile, Cellulose/Cellulosederivate und Polymere/Copolymere von (Meth)acrylsäure und nichtionische Tenside wird dann mit üblichen Verfahren granuliert. Beispielsweise können Mischer der Firmen Vomm, Lödige, Schugi, Eirich, Henschel oder Fukae eingesetzt werden.The mixture of the granulate components according to the invention, cellulose / cellulose derivatives and polymers / copolymers of (meth) acrylic acid and nonionic surfactants are then granulated using conventional methods. For example can mixers from Vomm, Lödige, Schugi, Eirich, Henschel or Fukae can be used.

Für das Quell- und Wasseraufnahmeverhalten des erfindungsgemäßen Granulats ist die abschließende Verdichtung wesentlich. Das Verdichten unter Anwendung von Druck kann auf verschiedene Weise erfolgen.For the swelling and water absorption behavior of the granules according to the invention the final compression is essential. Compacting under Pressure can be applied in various ways.

Als besonders geeignet hat sich die Verdichtung auf Walzwerken erwiesen, deren Walzen mit unterschiedlicher Umdrehungsgeschwindigkeit laufen, so daß die Druckeinwirkung auf das Granulat im Walzenspalt noch durch Friktion ergänzt wird. Dies führt zur Ausbildung von schuppenartiger Struktur und Ausrichtung der anisotropen Cellulose/Cellulosederivate im Granulat. Compaction on rolling mills has proven to be particularly suitable whose rollers run at different speeds, so that the pressure on the granules in the nip is still due to friction is added. This leads to the formation of a scale-like structure and alignment of the anisotropic cellulose / cellulose derivatives in the granulate.

Diese Ausrichtung kann eine der Ursachen für das besonders günstige quellkinetische Verhalten dieser Ausführungsform der erfindungsgemäßen Granulate sein.This orientation can be one of the reasons for the particularly cheap source kinetic behavior of this embodiment of the invention Be granules.

Die Verdichtung des Granulats soll vorzugsweise derart sein, daß das verdichtete Granulat eine Schüttdichte von 100 g/l bis 800 g/l, bevorzugt von 200 g/l bis 600 g/l, ganz besonders bevorzugt von 300 g/l bis 500 g/l aufweist.The compression of the granules should preferably be such that the compression Granules a bulk density of 100 g / l to 800 g / l, preferred from 200 g / l to 600 g / l, very particularly preferably from 300 g / l to 500 g / l having.

Die erfindungsgemäßen Sprengmittelgranulate sind in den Formkörpern in Mengen von 0,5 Gew.% bis 10 Gew.% enthalten, vorzugsweise 2 Gew.% bis 7 Gew.% und besonders bevorzugt 3 Gew.% bis 6 Gew.%.The disintegrant granules according to the invention are in the moldings in Contain amounts of 0.5 wt.% To 10 wt.%, Preferably 2 wt.% To 7 % By weight and particularly preferably 3% by weight to 6% by weight.

Das spezifische Wasseraufnahmevermögen des erfindungsgemäßen Granulats kann gravimetrisch wie folgend bestimmt werden:
Eine definierte Granulatmenge (z.B. 2.00 g) wird in einen dünnen Papierbeutel, wie einem Teebeutel eingeschweißt und in ein Gefäß mit einem Überschuß an Wasser getaucht. Nach 3 Minuten Eintauchzeit wird der Beutel aus dem Wasser herausgenommen und 10 Minuten zum Abtropfen aufgehängt. Der Beutel wird gewogen und aus der Gewichtsdifferenz eines nassen Beutels mit und ohne Granulat die Wasseraufnahme bestimmt. Für die Bestimmung kann destilliertes Wasser oder Wasser mit definierter Härte verwendet werden.The specific water absorption capacity of the granules according to the invention can be determined gravimetrically as follows:
A defined amount of granules (eg 2.00 g) is sealed in a thin paper bag, such as a tea bag, and immersed in a vessel with an excess of water. After 3 minutes of immersion, the bag is removed from the water and hung for 10 minutes to drain. The bag is weighed and the water absorption is determined from the weight difference of a wet bag with and without granules. Distilled water or water with a defined hardness can be used for the determination.

Die auf diese Weise bestimmbare Wasseraufnahme beträgt vorzugsweise 500 bis 2000 %The water absorption which can be determined in this way is preferably 500 until 2000 %

Das erfindungsgemäße verdichtete Granulat zeichnet sich durch eine besondere Quellkinetik aus, die Ausdehnung ändert sich in Abhängigkeit von der Zeit nicht linear und soll nach möglichst kurzer Zeit ein bestimmtes Niveau erreichen. Besonders von Interesse ist das Quellverhalten in den ersten 10 Sekunden nach Berührung mit Wasser, wenn das Granulat als Sprengmittel für Formkörper verwendet werden soll.The compacted granulate according to the invention is distinguished by a special one Swelling kinetics, the expansion changes depending on the Time is not linear and should reach a certain level after the shortest possible time to reach. The swelling behavior in the first 10 seconds after contact with water when the granules as Explosives should be used for moldings.

Vorzugsweise beträgt die Volumenzunahme nach 5 Sekunden 55 Vol.% bis 225 Vol.%, wobei bei höherer Verdichtung, d.h. höherem Schüttgewicht, die Volumenzunahme größer ausfällt.
Nach 10 Sekunden beträgt die Volumenzunahme vorzugsweise 75 Vol.% bis 270 Vol.%, wobei ebenfalls die Volumenzunahme mit steigendem Schüttgewicht zunimmt.The increase in volume after 5 seconds is preferably 55% by volume to 225% by volume, the increase in volume being greater with higher compaction, ie higher bulk density.
After 10 seconds, the increase in volume is preferably 75% by volume to 270% by volume, the increase in volume likewise increasing with increasing bulk density.

Bei einem Schüttgewicht von 250 g/l bis 350 g/l beträgt die Volumenzunahme nach 5 Sekunden Berührung mit Wasser von 55 Vol.% bis 100 Vol.% und nach 10 Sekunden von 75 Vol.% bis 130 Vol.%. Bei einem Schüttgewicht von 400 g/l bis 500 g/l beträgt die Volumenzunahme nach 5 Sekunden von 200 Vol.% bis 225 Vol.% und nach 10 Sekunden von 230 Vol.% bis 270 Vol.%.With a bulk density of 250 g / l to 350 g / l, the volume increases after 5 seconds contact with water from 55 vol.% to 100 vol.% and after 10 seconds from 75 vol.% to 130 vol.%. With a bulk density of 400 g / l to 500 g / l, the volume increase of 200 after 5 seconds Vol.% To 225 vol.% And after 10 seconds from 230 vol.% To 270 vol.%.

Zur Bestimmung der Quellgeschwindigkeit und der Quellhöhe unter Belastung werden 3,00 g Granulat in ein zylindrisches Kunststoffgefäß mit einem Innendurchmesser von 60 mm gegeben und mit einem wasserdurchlässigen Vlies abgedeckt. Die Schichtdicke des Granulates beträgt je nach Schüttgewicht 1- 3 mm . Auf das Vlies wird ein beweglicher, durchbohrter Stempel mit einem Gewicht von 58 g aufgesetzt und mit einem Wegmeßinstrument verbunden das den Weg des Stempels in Abhängigkeit von der Zeit aufzeichnet. Durch Zugabe von 50 ml Wasser wird das Granulat zum Aufquellen gebracht und die dadurch ausgelöste Verschiebung des Stempels (Weglänge) in Abhängigkeit von der Zeit bestimmt und graphisch ausgewertet.To determine the swelling speed and the swelling height under load 3.00 g of granules are placed in a cylindrical plastic container with a Given an inner diameter of 60 mm and with a water-permeable Fleece covered. The layer thickness of the granules is depending on the bulk density 1-3 mm. A movable, pierced stamp is placed on the fleece put on with a weight of 58 g and with a displacement measuring instrument connected that records the path of the stamp depending on the time. The granules are made to swell by adding 50 ml of water and the resulting displacement of the stamp (path length) in Determined as a function of time and evaluated graphically.

Abbildung 1 zeigt ein Diagramm für die Quellkinetik von bekannten Sprengmitteln und erfindungsgemäßen Granulaten.Figure 1 shows a diagram for the swelling kinetics of known explosives and granules according to the invention.

Tabelle 1 enthält die entsprechenden Meßwerte. Quellkinetik verschiedener Materialien Schüttdichte [g/l] 70 90 90 300 300 450 450 Cellulose V 1 M1 V2 M2 V3 M3 Zeit [Sec] Weg [mm] Weg [mm] Weg [mm] Weg [mm] Weg [mm] Weg [mm] Weg [mm] 0 0 0 0 0 0 0 0 1 0,10 0,20 0,25 0,30 0,50 0,80 1,20 2 0,20 0,40 0,40 0,60 1,05 1,20 1,80 3 0,30 0,60 0,65 0,90 1,35 1,50 2,20 4 0,35 0,70 0,80 1,00 1,58 1,60 2,40 5 0,40 0,85 0,95 1,10 1,75 1,70 2,50 6 0,42 1,00 1,15 1,15 1,83 1,72 2,58 7 0,44 1,10 1,25 1,20 1,93 1,80 2,65 8 0,46 1,20 1,40 1,25 2,00 1,82 2,70 9 0,48 1,35 1,55 1,40 2.05 1,82 2,72 10 0,48 1,40 1,65 1,50 2,15 1,85 2,75 11 0,49 1,45 1,75 1,60 2,20 1,90 2,80 12 0,50 1,50 1,80 1,65 2,25 1,92 2,83 Table 1 contains the corresponding measured values. Swelling kinetics of different materials Bulk density [g / l] 70 90 90 300 300 450 450 Cellulose V 1 M1 V2 M2 V3 M3 Time [sec] Way [mm] Way [mm] Way [mm] Way [mm] Way [mm] Way [mm] Way [mm] 0 0 0 0 0 0 0 0 1 0.10 0.20 0.25 0.30 0.50 0.80 1.20 2nd 0.20 0.40 0.40 0.60 1.05 1.20 1.80 3rd 0.30 0.60 0.65 0.90 1.35 1.50 2.20 4th 0.35 0.70 0.80 1.00 1.58 1.60 2.40 5 0.40 0.85 0.95 1.10 1.75 1.70 2.50 6 0.42 1.00 1.15 1.15 1.83 1.72 2.58 7 0.44 1.10 1.25 1.20 1.93 1.80 2.65 8th 0.46 1.20 1.40 1.25 2.00 1.82 2.70 9 0.48 1.35 1.55 1.40 2.05 1.82 2.72 10th 0.48 1.40 1.65 1.50 2.15 1.85 2.75 11 0.49 1.45 1.75 1.60 2.20 1.90 2.80 12th 0.50 1.50 1.80 1.65 2.25 1.92 2.83

Die Zusammensetzung der Muster V1 bis V3 ist wie in Tabelle 3, Beispiel 2.1.The composition of the samples V1 to V3 is as in Table 3, example 2.1.

Die Zusammensetzung der Muster M1 bis M3 ist wie in Tabelle 3, Beispiel. 2.3 : Fällt nicht unter den Schutzbereich ; unterstükt aber das Konzept der vorliegenden Erfindung. Volumenausdehnung in Vol.% Cellulose V1 M1 V2 M2 V3 M3 Schüttdichte in g/l 70 90 90 300 300 450 450 Volumenzunahme nach 5 Sec Vol.% 5 14 16 55 100 200 225 nach 10 Sec Vol.% 6 23 28 75 130 230 270 The composition of the samples M1 to M3 is as in Table 3, example. 2.3: Does not fall under the scope of protection; but supports the concept of the present invention. Volume expansion in vol.% Cellulose V1 M1 V2 M2 V3 M3 Bulk density in g / l 70 90 90 300 300 450 450 Volume increase after 5 sec vol.% 5 14 16 55 100 200 225 after 10 sec vol.% 6 23 28 75 130 230 270

Die Formulierung V1 hat die Zusammensetzung von Beispiel 2.1 in unverdichteter Form. Die Formulierung M1 hat die Zusammensetzung von Beispiel 2.3 in unverdichteter Form.
Mit V2, M2 sind Proben bezeichnet, die nach dem Mischen in einer Walzenpresse auf ein Schüttgewicht von 300 g/l verdichtet wurden. Mit V3 und M3 sind Proben bezeichnet, die nach dem Mischen auf ein Schüttgewicht von 450 g/l mittels Walzenpresse verdichtet wurden.Formulation V1 has the composition of Example 2.1 in undensified form. Formulation M1 has the composition of Example 2.3 in undensified form.
V2, M2 denote samples that were compressed to a bulk density of 300 g / l after mixing in a roller press. V3 and M3 refer to samples which, after mixing, were compressed to a bulk density of 450 g / l using a roller press.

Man erkennt deutlich die verbesserte Performance der verdichteten Proben, wobei die Volumenzunahme nach 5 Sec vorzugsweise mindestens 95% beträgt, besonders bevorzugt > 150%.You can clearly see the improved performance of the compressed samples, the increase in volume after 5 seconds is preferably at least 95%, particularly preferred> 150%.

Ein weiterer Gegenstand der Erfindung ist auch ein Verfahren zum Herstellen eines verdichteten Granulats, das in Wasser unlösliche, jedoch quellbare hochreine Cellulose und/oder Cellulosederivate und feinteilige Polymere/Copolymere von (Meth)acrylsäure oder deren Salze und ein oder mehrere flüssige Tenside enthält, durch Mischen von hochreiner Cellulose/Cellulosederivat mit den erfindungsgemäßen Tensid(en) und Einmischen der Polymeren/Copolymeren, Granulieren und anschließendes Verdichten des Granulats unter Ausrichtung anisotroper Cellulose/Cellulosederivate.Another object of the invention is a method for manufacturing a compacted granulate that is insoluble in water but swellable high-purity cellulose and / or cellulose derivatives and finely divided polymers / copolymers of (meth) acrylic acid or its salts and one or more contains liquid surfactants by mixing high-purity cellulose / cellulose derivative with the surfactant (s) according to the invention and mixing the polymers / copolymers, granulating and then compressing the Granules aligned with anisotropic cellulose / cellulose derivatives.

Der erste Schritt des Verfahrens beinhaltet einen Misch- und Granulierungsvorgang, bei dem Vorcompounds durch Agglomerationsverfahren hergestellt werden. Diese Vorcompounds bilden eine rieselfähige und grobkörnige Ware, die einen bestimmten Feuchtegrad hat. Im nächsten Schritt werden diese Vorcompounds mechanisch verdichtet. Die Produkte können zwischen zwei Druckflächen in Walzenverdichtern, z. B. glatt oder profiliert, verdichtet werden. Sind bestimmte Gleiteigenschaften vorhanden, so kann die Verdichtung in Extrudern oder Flachmatrizenpressen zu Matrizen erfolgen. Der Ausstoß des Kompaktates erfolgt als Strang. Verdichtungsmethoden in Matrizen mit Stempeln oder Kissenwalzen ergeben Kompaktatformen wie Tabletten bzw. Briketts. Als Verdichtungsmaschinen können Walzenkompaktoren, Extruder, Walzen- oder Würfelpressen, aber auch Granulierpressen eingesetzt werden. Nachfolgend werden die groben, verdichteten Teilchen zerkleinert, wobei z.B. Mühlen, Schnitzler oder Walzenstühle geeignet sind.The first step of the process involves a mixing and granulating process, in the pre-compounds produced by agglomeration processes become. These precompounds form a free-flowing and coarse-grained Goods that have a certain degree of moisture. The next step will be these precompounds are mechanically compressed. The products can be between two pressure areas in roller compressors, e.g. B. smooth or profiled, compressed become. If certain sliding properties are available, the Compression in extruders or flat die presses to form dies. The compactate is ejected as a strand. Compression methods in Matrices with stamps or pillow rollers produce compact forms such as tablets or briquettes. Roller compactors, Extruders, roller or cube presses, but also granulating presses be used. Below are the coarse, densified particles crushed, e.g. Suitable for mills, shredders or roller mills are.

Das erfindungsgemäße Granulat nimmt bei Kontakt mit Wasser dieses rasch unter Volumenvergrößerung auf und eignet sich deshalb als sogenanntes Sprengmittel für gepreßte Formkörper, so daß diese in Wasser rasch zerfallen.The granulate according to the invention takes this quickly in contact with water with volume increase and is therefore suitable as a so-called Disintegrant for pressed moldings so that they quickly disintegrate in water.

Die Erfindung schließt die Verwendung der verdichteten Granulate als Sprengmittel für gepreßte Formkörper, beispielsweise Tabletten, Würfel, Kugeln und dergleichen ein.The invention includes the use of the compacted granules as Disintegrants for pressed molded articles, for example tablets, cubes, Bullets and the like.

Besonders bevorzugt ist die Verwendung als Sprengmittel für Reinigungsmittelformulierungen, Waschmittelformulierungen, Fleckensalze, Wasserenthärter in Tabletten- oder Würfelform.The use as disintegrant for detergent formulations is particularly preferred, Detergent formulations, stain salts, water softeners in tablet or cube form.

Waschmitteltabletten und Reinigungsmitteltabletten für unterschiedliche Zwecke, im Sanitärbereich oder für Geschirrspüler sind grundsätzlich bekannt. Detergent tablets and detergent tablets for different Purposes, in the sanitary area or for dishwashers are generally known.

Derartige Formkörper müssen eine ausreichende Stabilität und Festigkeit aufweisen, um Handhabung, Verpackung und Lagerung zu ermöglichen, sollen jedoch bei Kontakt mit Wasser rasch zerfallen, so daß die Bestandteile die gewünschte Wirkung entfalten können.Such moldings must have sufficient stability and strength to enable handling, packaging and storage however, quickly disintegrate on contact with water, so that the components can have the desired effect.

Aus diesem Grunde enthalten die gepreßten Formkörper häufig sogenannte Sprengmittel, die aufgrund des Quellverhaltens und der Volumenzunahme den Zusammenhalt der Formkörper aufheben und den Zerfall beschleunigen.For this reason, the pressed moldings often contain so-called Disintegrants that due to the swelling behavior and the increase in volume Remove the cohesion of the shaped bodies and accelerate the disintegration.

Derartige als Formkörper, wie beispielsweise Tabletten, ausgebildete Waschmittelformulierungen enthalten in der Regel Gerüststoffe, Bleichmittel und Bleichaktivatoren, Tenside, Tablettierhilfsmittel, Sprengmittel und weitere übliche Zusätze und Hilfsstoffe.Such designed as shaped bodies, such as tablets Detergent formulations usually contain builders, bleaches and bleach activators, surfactants, tabletting aids, disintegrants and other common additives and auxiliaries.

Als Gerüststoffe kommen Polyphosphate, Pyrophosphate, Metaphosphate oder Phosphonate, Schichtsilikate, amorphe Silikate, amorphe Disilikate und Zeolith in Betracht. Weitere Bestandteile des Buildersystems können Füllstoffe wie Alkalicarbonate, Bicarbonate z.B. Natriumcarbonat oder Natriumhydrogencarbonat, Sesquiocarbonate, Natriumsulfat, Magnesiumsulfat, oder Citrat, Citronensäure, Bernsteinsäure, Weinsteinsäure und Äpfelsäure sein. Häufig werden als Hilfsgerüststoff Cobuilder und Dispergatoren mitverwendet. Solche Cobuilder oder Dispergatoren können Polyacrylsäuren und deren Natriumsalze sein.Polyphosphates, pyrophosphates, metaphosphates or come as builders Phosphonates, layered silicates, amorphous silicates, amorphous disilicates and Zeolite into consideration. Fillers can also form part of the builder system such as alkali carbonates, bicarbonates e.g. Sodium carbonate or sodium hydrogen carbonate, Sesquiocarbonates, sodium sulfate, magnesium sulfate, or citrate, citric acid, succinic acid, tartaric acid and malic acid his. Cobuilders and dispersants are often used as auxiliary builders. Such cobuilders or dispersants can be polyacrylic acids and their sodium salts.

Auch Copolymere aus (Meth)acrylsäure und Maleinsäure, Terpolymere und Quattropolymere aus (Meth)acrylsäure, Maleinsäure, Vinylalkohol und sulfogruppenhaltigen Vinylverbindungen können verwendet werden.Copolymers of (meth) acrylic acid and maleic acid, terpolymers and Quattropolymers of (meth) acrylic acid, maleic acid, vinyl alcohol and sulfo groups Vinyl compounds can be used.

Insbesondere bevorzugt sind auch ter- und quattropolymere Polycarboxylate, hergestellt aus (Meth)acrylsäure, Maleinsäure und Vinylalkohol oder Vinylalkoholderivaten (wie sie in DE 43 00 772 C2 beschrieben sind) oder solche aus (Meth)acrylsäure, 2-Alkylallylsulfonsäure und Zuckerderivaten (wie in DE 42 21 381 C1 beschrieben) oder solche aus (Meth)acrylsäure, Maleinsäure, Vinylalkoholderivaten und Monomeren mit Sulfonsäuregruppen (beschrieben in DE 19 516 957 A).Ter- and quattropolymeric polycarboxylates are also particularly preferred, made from (meth) acrylic acid, maleic acid and vinyl alcohol or Vinyl alcohol derivatives (as described in DE 43 00 772 C2) or those from (meth) acrylic acid, 2-alkylallylsulfonic acid and sugar derivatives (as described in DE 42 21 381 C1) or those made from (meth) acrylic acid, Maleic acid, vinyl alcohol derivatives and monomers with sulfonic acid groups (described in DE 19 516 957 A).

Des weiteren sind Polyethylengkykol und/oder Polypropylenglykol mit einem Molekulargewicht von 900 bis 30.000 geeignet, sowie carboxylierte Polysaccharide, Polyaspartate und Polyglutamat.There are also polyethylene glycol and / or polypropylene glycol with a Suitable molecular weight from 900 to 30,000, as well as carboxylated polysaccharides, Polyaspartates and polyglutamate.

Auch Mischungen mit verschiedenen organischen Buildern wie z.B. Zitronensäure sind möglich.Mixtures with various organic builders such as citric acid are possible.

Übliche Bleichmittel sind Natriumperborattetrahydrat und Natriumperboratmonohydrat, Natriumpercarbonat, Peroxypyrophosphate, Citratperhydrate, sowie H2O2 liefernde persaure Salze, Persäuren, wie Perbenzoate, Peroxyphthalate, Diperazelainsäure und Diperdodecandisäuren.
Der Gehalt an Bleichmitteln in Tabletten beträgt vorzugsweise 10-60 Gew.% und insbesondere 15-50 Gew.%.Customary bleaching agents are sodium perborate tetrahydrate and sodium perborate monohydrate, sodium percarbonate, peroxypyrophosphates, citrate perhydrates, as well as H 2 O 2 -producing peracidic salts, peracids such as perbenzoates, peroxyphthalates, diperazelaic acid and diperdodecanedioic acids.
The bleach content in tablets is preferably 10-60% by weight and in particular 15-50% by weight.

Um beim Waschen unter 60°C und darunter eine gute Bleichwirkung zu erzielen, können Aktivatoren eingearbeitet werden. Geeignete Bleichaktivatoren sind die mit H2O2 organische Persäuren bildenden N-Acyl und O-Acylverbindungen, vorzugsweise N,N'-tetraacylierte Diamine, Carbonsäureanhydride und Ester von Polyolen wie Glucosepentaacetat. Ferner können acetylierte Mischungen aus Sorbitol und Mannitol verwendet werden. Besonders geeignet als Bleichaktivatoren sind N,N,N',N'-Tetraacetylethylendiamin (TAED), 1,5- Diacetyl-2,4-dioxo-hexahydro-1,2,5-triazin (DADHT) und acetylierte Sorbitol-Mannitol-Mischungen (SORMAN).In order to achieve a good bleaching effect when washing below 60 ° C and below, activators can be incorporated. Suitable bleach activators are the N-acyl and O-acyl compounds forming with H 2 O 2 organic peracids, preferably N, N'-tetraacylated diamines, carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. Acetylated mixtures of sorbitol and mannitol can also be used. Particularly suitable bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,2,5-triazine (DADHT) and acetylated sorbitol mannitol Mixtures (SORMAN).

Neben nichtionischen, anionischen und amphoteren Tensiden können in Waschmittelformulierungen auch kationische Tenside anwesend sein, beispielsweise quaternäre Ammoniumverbindungen mit C8 - C16 N-Alkyl- bzw. N-Alkenylgruppen und N-Substituenten wie Methyl-, Hydroxyethyl- bzw. Hydroxypropylgruppen.In addition to nonionic, anionic and amphoteric surfactants, cationic surfactants can also be present in detergent formulations, for example quaternary ammonium compounds with C 8 -C 16 N-alkyl or N-alkenyl groups and N-substituents such as methyl, hydroxyethyl or hydroxypropyl groups.

Als Tablettierhilfsmittel kommen Polyalkylenglykole und Magnesiumstearate in Betracht.Polyalkylene glycols and magnesium stearates come as tableting aids into consideration.

Beispiele für weitere übliche Waschmittelzusätze und Hilfsstoffe sind Enzyme, Magnesiumsilikate, Aluminiumaluminate, Benzotriazol, Glycerin, Magnesiumstearat, Polyalkylenglykole, Hexametaphosphat, Phosphonate, Bentonite, Soil Release Polymere, Carboxymethylcellulosen.Examples of other common detergent additives and auxiliaries are Enzymes, magnesium silicates, aluminum aluminates, benzotriazole, glycerin, Magnesium stearate, polyalkylene glycols, hexametaphosphate, phosphonates, bentonites, Soil release polymers, carboxymethyl celluloses.

Geschirrspültabletten als eine Ausbildungsform von Reinigungsmittelformulierungen enthalten in der Regel als Gerüststoffe Polyphosphate, Pyrophosphate, Metaphosphate oder Phosphonate, Schichtsilikate, amorphe Silikate, amorphe Disilikate und Zeolithe, sowie Füllstoffe wie Natriumcarbonat, Natriumsulfat, Magnesiumsulfat, Natriumhydrogencarbonat, Citrat sowie Citronensäure, Bernsteinsäure, Weinsteinsäure und Äpfelsäure. Häufig werden als Hilfgerüststoff Cobuilder und Dispergatoren mitverwendet. Solche Cobuilder oder Dispergatoren können Polyacrylsäuren oder Copolymere mit Polyacrylsäure und deren Natriumsalze sein.Dishwashing tablets as an educational form of detergent formulations usually contain polyphosphates, pyrophosphates, Metaphosphates or phosphonates, layered silicates, amorphous silicates, amorphous disilicates and zeolites, as well as fillers such as sodium carbonate, Sodium sulfate, magnesium sulfate, sodium hydrogen carbonate, citrate as well Citric acid, succinic acid, tartaric acid and malic acid. Frequently are also used as auxiliary builders, cobuilders and dispersants. Such Cobuilders or dispersants can be polyacrylic acids or copolymers with polyacrylic acid and its sodium salts.

Übliche Bleichmittel sind Natriumperborattetrahydrat und Natriumperboratmonohydrat, Natriumpercarbonat, Peroxypyrophosphate, Citratperhydrate, sowie H2O2 liefernde persaure Salze, Persäuren, wie Perbenzoate, Peroxyphthalate, Diperazelainsäure und Diperdodecandisäuren. Der Gehalt in den Tabletten beträgt vorzugsweise 10-60 Gew.% und insbesondere 15-50 Gew.%.Customary bleaching agents are sodium perborate tetrahydrate and sodium perborate monohydrate, sodium percarbonate, peroxypyrophosphates, citrate perhydrates, as well as H 2 O 2 -producing peracidic salts, peracids such as perbenzoates, peroxyphthalates, diperazelaic acid and diperdodecanedioic acids. The content in the tablets is preferably 10-60% by weight and in particular 15-50% by weight.

Schaumarme nichtionische Tenside vom Typ Polyalkylenglykol und Alkylpolyglucoside werden ebenfalls eingesetzt. Low-foaming non-ionic surfactants of the polyalkylene glycol and alkyl polyglucoside type are also used.

Beispiele für weitere übliche Waschmittelzusätze und Hilfsstoffe sind auch hier Enzyme, Magnesiumsilikate, Aluminiumaluminate, Benzotriazol, Glycerin, Magnesiumstearat, Polyalkylenglykole, Hexametaphosphat sowie Phosphonate.Examples of other common detergent additives and auxiliaries are here too enzymes, magnesium silicates, aluminum aluminates, benzotriazole, Glycerin, magnesium stearate, polyalkylene glycols, hexametaphosphate as well Phosphonates.

Wasserenthärtungstabletten bestehen in der Regel aus Gerüststoffen wie Schichtsilikaten, amorphen Silikaten, amorphen Disilikaten und Zeolithen, sowie Füllstoffen wie Natriumcarbonat, Natriumsulfat, Magnesiumsulfat, Natriumhydrogencarbonat, Citrat sowie Citronensäure. Häufig werden als Hilfgerüststoff Cobuilder und Dispergatoren mitverwendet. Solche Cobuilder oder Dispergatoren können Polyacrylsäuren oder Copolymere mit Polyacrylsäure und deren Natriumsalze sein.Water softening tablets usually consist of builders such as Layered silicates, amorphous silicates, amorphous disilicates and zeolites, as well as fillers such as sodium carbonate, sodium sulfate, magnesium sulfate, Sodium bicarbonate, citrate and citric acid. Often called Auxiliary builders cobuilders and dispersants also used. Such cobuilders or dispersants can be polyacrylic acids or copolymers with polyacrylic acid and their sodium salts.

Schaumarme nichtionische Tenside vom Typ Polyalkylenglykol und Alkylpolyglucoside werden ebenfalls eingesetzt.Low-foaming non-ionic surfactants of the polyalkylene glycol and alkyl polyglucoside type are also used.

Beispiele für weitere übliche Waschmittelzusätze und Hilfsstoffe sind Magnesiumsilikate, Polyalkylenglykole und Phosphonate.Examples of other common detergent additives and auxiliaries are Magnesium silicates, polyalkylene glycols and phosphonates.

Die Erfindung wird nachfolgend anhand von Ausführungsbeispielen noch weiter erläutert. Alle Angaben beziehen sich auf Gewicht, es sei denn, es ist im Einzelfalle etwas anderes angegeben. The invention is further elucidated below on the basis of exemplary embodiments explained. All data refer to weight, unless it something else is specified in individual cases.

BeispieleExamples Beispiele 1-8Examples 1-8

Beispiele für Sprengmittelzusammensetzungen entsprechend der Lehre der Erfindung (alle Mengen in Gew.%) .Examples of disintegrant compositions according to the teaching of the invention (all amounts in% by weight) . Beispielexample 2.1 Vergleich2.1 comparison 2.2 Vergleich2.2 comparison 2.32.3 2.42.4 2.52.5 2.62.6 2.72.7 2.82.8 Bestandteil:Component: Cellulose Cellulose 8585 5050 8080 4848 8585 9494 8888 6565 Lineares PAA Linear PAA 1515 55 1010th 55 88th -- 99 77 Vernetztes PPA Networked PPA -- -- -- -- 55 44th -- -- CMC CMC -- -- -- -- -- -- 11 -- MikrokristallineMicrocrystalline -- -- -- -- -- -- -- 2626 Cellulose Cellulose Nio-Tensid Nio surfactant -- -- 1010th 55 22nd 22nd 22nd 22nd Wasser ad 100%Water ad 100% -- 4545 -- 4242 -- -- -- --

Beispiel 9:Example 9:

Phosphathaltige Waschmitteltablette: Festigkeit der Tablette und ihre Zerfallszeit unter Verwendung der Granulate der vorgenannten Beispiele:Detergent tablet containing phosphate: strength of the tablet and its Disintegration time using the granules of the above examples:

Phosphathaltige Waschmitteltabletten mit den in Tabelle 3 beschriebenen Zusammensetzung wurden auf ihre Zerfallszeit und Festigkeit untersucht. Zusammensetzung Waschmitteltablette: Rohstoff Einsatzmenge in % Natriumtripolyphosphat 35 Natriumpercarbonat 19 TAED 4 Fettalkoholsulfat 14 Lineares Alkylbenzolsulphonat 4 Soda 8 Entschäumer, optischer Aufheller, CMC, Phosphonat 6 Mikrokristalline Cellulose (200 µm) 2 Enzymmix 1 Fettalkoholethoxilat (C12/14, EO=4,7) 2 Sprengmittelzubereitung gemäß Beispielen 2.1 bis 2.8 5 Phosphate-containing detergent tablets with the composition described in Table 3 were examined for their disintegration time and strength. Composition of detergent tablet: raw material Amount used in% Sodium tripolyphosphate 35 Sodium percarbonate 19th TAED 4th Fatty alcohol sulfate 14 Linear alkyl benzene sulphonate 4th soda 8th Defoamer, optical brightener, CMC, phosphonate 6 Microcrystalline cellulose (200 µm) 2nd Enzyme mix 1 Fatty alcohol ethoxylate (C12 / 14, EO = 4.7) 2nd Disintegrant preparation according to Examples 2.1 to 2.8 5

Tabelle 5 zeigt die Festigkeit und Zerfallszeit der einzelnen Waschmitteltabletten bei Verwendung der verschiedenen Sprengmittel: Sprengmittelzusammensetzung entspr. Beispiel Zerfallszeit in sec Festigkeit in N 2.1 35 62 2.2 28 61 2.3 25 63 2.4 28 70 2.5 22 53 2.6 19 64 2.7 21 63 2.8 29 58 Table 5 shows the strength and disintegration time of the individual detergent tablets when using the different disintegrants: Disintegrant composition according to example Disintegration time in sec Strength in N 2.1 35 62 2.2 28 61 2.3 25th 63 2.4 28 70 2.5 22 53 2.6 19th 64 2.7 21 63 2.8 29 58

Beispiel 10:Example 10:

Phosphatfreie Waschmitteltablette: Festigkeit der Tablette und ihre Zerfallszeit unter Verwendung eines der Granulate der vorgenannten Beispiele:Phosphate-free detergent tablet: strength of the tablet and its disintegration time using one of the granules of the aforementioned examples:

10.1.: Granulat aus Beispiel 2.3 in Zeolith-basierten Rezepturen Rohstoff Einsatzmenge in % a) b) Zeolith P 39 35 Fettalkoholethoxilat (C12/14, E0=4,7) 4 7 Natriumpercarbonat 16 16 TAED 4 4 Fettalkoholsulfat 10 11 Lineares Alkylbenzolsulphonat 3 3 Soda 4 4 Entschäumer, optischer Aufheller, CMC, Phosphonat 5 5 Enzymmix 1 1 Mikrokristalline Cellulose (200 µm) 4 4 Sprengmittelzubereitung gemäß Beispiel 2.3 5 5 Natriumcitrat 5 5 Rezeptur Zerfallszeit in sec Festigkeit in N a) 40 57 b) 60 51 10.1 .: Granules from example 2.3 in zeolite-based formulations raw material Amount used in% a) b) Zeolite P 39 35 Fatty alcohol ethoxylate (C12 / 14, E0 = 4.7) 4th 7 Sodium percarbonate 16 16 TAED 4th 4th Fatty alcohol sulfate 10th 11 Linear alkyl benzene sulphonate 3rd 3rd soda 4th 4th Defoamer, optical brightener, CMC, phosphonate 5 5 Enzyme mix 1 1 Microcrystalline cellulose (200 µm) 4th 4th Disintegrant preparation according to example 2.3 5 5 Sodium citrate 5 5 Recipe Disintegration time in sec Strength in N a) 40 57 b) 60 51

10.2: Granulat aus in Disilikat-basierten Rezepturen10.2: Granules from formulations based on disilicate

Rohstoffraw material Einsatzmenge in %Amount used in% a)a) b)b) Amorphes DisilikatAmorphous disilicate 3636 3030th FettalkoholethoxilatFatty alcohol ethoxylate 22nd 77 FettalkoholsulfatFatty alcohol sulfate 1111 1515 Lineares AlkylbenzolsulphonatLinear alkyl benzene sulphonate 44th 22nd NatriumpercarbonatSodium percarbonate 1616 1616 TAEDTAED 44th 44th Acrylat-Maleat-CopolymerAcrylate-maleate copolymer -- 33rd Sodasoda 77 44th NatriumcitratSodium citrate 55 55 Mikrokristalline Cellulose (200 µm)Microcrystalline cellulose (200 µm) 44th 44th Entschäumer, optischer Aufheller, CMC, PhosphonatDefoamer, optical brightener, CMC, phosphonate 55 44th EnzymmixEnzyme mix 11 11 Sprengmittelzubereitung gemäß Beispiel 2.3Disintegrant preparation according to example 2.3 55 55 RezepturRecipe Zerfallszeit in secDisintegration time in sec Festigkeit in NStrength in N a)a) 4040 6868 b)b) 1515 4848

Beispiel 11: Gepreßte Formkörper mit dem Verwendungszweck alsExample 11: Pressed molded articles with the intended use as

  • a) Fleckensalz der folgenden Zusammensetzung: Rohstoff Einsatzmenge in % Soda -Disiklikat Cogranulat 20 Soda 41 Nichtionisches Tensid 4 TAED 7 Enzymmix 1 Natriumpercarbonat 24 Sprengmittelzubereitung gemäß Beispiel 2.4 3 a) Stain remover of the following composition: raw material Amount used in% Soda disiccate cogranulate 20th soda 41 Nonionic surfactant 4th TAED 7 Enzyme mix 1 Sodium percarbonate 24th Disintegrant preparation according to example 2.4 3rd
  • b) Wasserenthärter der folgenden Zusammensetzung: Rohstoff Einsatzmenge in % Zeolith 15 Natriumhydrogencarbonat 32 Zitronensäure 20 Polycarboxylat 17 Schichtsilikat 8 Prozeßhilfsmittel 5 Sprengmittelzubereitung gemäß Beispiel 2.5 3 b) water softener of the following composition: raw material Amount used in% Zeolite 15 Sodium bicarbonate 32 citric acid 20th Polycarboxylate 17th Layered silicate 8th Process aids 5 Disintegrant preparation according to example 2.5 3rd
  • c) Maschinen-Geschirr-Reiniger der folgenden Zusammensetzung: Rohstoff Einsatzmenge in % Soda-Silikat Cogranulat 20 Tripolyphosphat 35 Soda 20 Natriumperborat 12 TAED 4 Enzymmix 2 Prozeßhilfsmittel 3 Parfum, Farbstoffe 2 Sprengmittelzubereitung gemäß Beispiel 2.7 2 c) Machine dishwashing detergent of the following composition: raw material Amount used in% Soda-silicate cogranulate 20th Tripolyphosphate 35 soda 20th Sodium perborate 12th TAED 4th Enzyme mix 2nd Process aids 3rd Perfume, dyes 2nd Disintegrant preparation according to example 2.7 2nd

    • Ergebnisse zur Festigkeit und Zerfallszeit der ReinigungstablettenResults on the strength and disintegration time of the cleaning tablets

    Physikalische ParameterPhysical parameters Fleckensalz gemäß Zusammensetzung a)Stain remover according to composition a) Wasserenthärter gemäß Zusammensetzung b)Water softener according to composition b) Maschinengeschirr-Reiniger gemäß Zusammensetzung c)Machine dish cleaner according to composition c) Festigkeit in NStrength in N 188188 210210 186186 Zerfallszeit ohne SprengmittelDisintegration time without explosives 224 s224 s 147 s147 s 240 s240 s Zerfallszeit mit SprengmittelDisintegration time with disintegrant 100 s100 s 73 s73 s 70 s70 s

    Claims (21)

    1. Compacted disintegrating granulate for pressed molded bodies comprising water-insoluble, water-swellable high purity cellulose and/or cellulose derivatives, and finely divided polymers/copolymers of (meth)acrylic acid or salts thereof, and one or more liquid nonionic and/or anionic and/or amphoteric surfactant(s) forming a gel or thickening when contacted with water wherein the weight ratio of the combined amount of the water-swellable cellulose/cellulose derivatives and polymers/copolymers of (meth)acrylic acid to the liquid surfactant(s) is 100:1 to 10:1.
    2. Granulate of claim 1, characterized in that the compaction results in an orientation of the anisotropic cellulose or cellulose derivatives, respectively.
    3. Granulate of claim 1 or 2, characterized in that the water-swellable celulose/cellulose derivatives and the finely divided polymers/copolymers of (meth)acrylic acid are present in a weight ratio of 100:0,5 to 100:30, preferably 100:1 to 100:20, most preferred 100:1 to 100:10.
    4. Granulate of any of claims 1 to 3, characterized in that the apparent density is 100 g/l to 800 g/l, preferably 200 g/l to 600 g/l, and most preferred 300 g/l to 500 g/l.
    5. Granulate of any of claims 1 to 4, characterized in that the specific water absorption is 500 to 2,000 wt-%.
    6. Granulate of any of claims 1 to 5, characterized by exhibiting nonlinear swelling kinetics.
    7. Granulate of any of claims 1 to 6, characterized in that the finely divided polymers/copolymers of (meth)arcylic acid are selected from linear polymers/copolymers of (meth)acrylic acid, crosslinked polymers/copolymers of (meth)acrylic acid, copolymers of (meth)acrylic acid and maleic acid, terpolymeric and quaterpolymeric copolymers prepared from (meth)acrylic acid, maleic acid and vinyl alcohol or vinyl alcohol derivatives, or such from (meth)acrylic acid, sulfonic acids with ethylenic unsaturation and sugar derivatives, or such from (meth)acrylic acid, maleic acid, or maleic anhydride, vinyl alcohol derivatives, and monomers containing sulfonic acid groups, and mixtures thereof.
    8. Granulate of any of claims 1 to 7, characterized in that the finely divided cellulose has a mean particle size of between 30 µm and 300 µm and/or an apparent density of 40 g/l to 300 g/l, preferably 65 g/l to 170 g/l.
    9. Granulate of any of claims 1 to 8, characterized in that the cellulose derivatives are selected from cellulose ethers, cellulose esters and mixed modifications thereof.
    10. Granulate of claim 9, characterized in that the cellulose derivatives have a mean particle size of between 30 µm and 1.000 µm and/or an apparent density of 50 g/l to 1,000 g/l, preferably 100 g/l to 800 g/l.
    11. Granulate of any of claims 1 to 10, characterized in that the liquid anionic and/or nonionic surfactant(s) is (are) selected from fatty alcohol ethoxylates with 3 to 15 moles of ethylene oxide, anionics of the fatty alcohol sulfate type and linear alkylbenzene sulfonates as well as alkylether sulfates, and mixtures thereof.
    12. Process for preparing a compacted disintegrating granulate of any of claims 1 to 11 by mixing the high purity cellulose/cellulose derivatives with the nonionic, anionic and amphoteric surfactant(s) and intermixing the finely divided polymers/copolymers of (meth)acrylic acid or salts thereof wherein the weight ratio of the combined amount of the water-swellable cellulose/cellulose derivatives and polymers/copolymers of (meth)acrylic acid to the liquid surfactant(s) is 100:1 to 10:1, and granulating and subsequent compacting the granulate.
    13. Process of claim 12, wherein compacting of the granulate results from orientation of anisotropic cellulose/cellulose derivatives.
    14. Process of claim 12 or 13, characterized in that compacting is accomplished by means of rolls with friction.
    15. Process of claim 12 or 13, characterized in that compacting is accomplished by means of roll compactors, roll presses or cube presses, or extruders.
    16. Use of the disintegrating granulate of any of claims 13 to 11 as disintegrating agent for pressed molded bodies wherein the disintegrating granulate is present in the pressed molded bodies in amounts from 0.5 wt-% to 10 wt-%, preferably 2 wt-% to 7 wt-%, and most preferred 3 wt-% to 6 wt-%.
    17. Use according to claim 16 as disintegrating agent for detergent tablets.
    18. Use according to claim 16 as disintegrating agent for cleaning tablets.
    19. Use according to claim 18 as disintegrating agent for cleaning tablets suitable for dishwashers.
    20. Use according to claim 16 as disintegrating agent for water softening tablets.
    21. Use according to claim 16 as disintegrating agent for scouring salt tablets.
    EP98121397A 1998-11-11 1998-11-11 Densified granulate, its manufacturing process and its use as disintegrant for compacted mouldings Expired - Lifetime EP1004656B1 (en)

    Priority Applications (11)

    Application Number Priority Date Filing Date Title
    ES98121397T ES2153229T3 (en) 1998-11-11 1998-11-11 DENSIFIED GRANULATE, PROCEDURE FOR ITS MANUFACTURING AND ITS USE AS A DETREAGENT AGENT FOR COMPACTED MOLDED BODIES.
    DK98121397T DK1004656T3 (en) 1998-11-11 1998-11-11 Compressed granules, manufacturing process and use as explosives for pressed molds
    DE59800410T DE59800410D1 (en) 1998-11-11 1998-11-11 Compacted granules, manufacturing process and use as disintegrant for molded articles
    PT79100995T PT1004656E (en) 1998-11-11 1998-11-11 PROCESS FOR MANUFACTURING AND USING COMPACTED GRANULATED AS DISINTEGRANT IN PRESSED MOLDED BODIES
    EP98121397A EP1004656B1 (en) 1998-11-11 1998-11-11 Densified granulate, its manufacturing process and its use as disintegrant for compacted mouldings
    AT98121397T ATE198348T1 (en) 1998-11-11 1998-11-11 COMPACTED GRANULES, PRODUCTION PROCESS AND USE AS EXPLOSIVES FOR PRESSED MOLDINGS
    HU9903991A HU228025B1 (en) 1998-11-11 1999-11-01 Caulked granulate, process for producing it and its use as a material for promoting decomposition
    TR1999/02772A TR199902772A3 (en) 1998-11-11 1999-11-10 Compressed granules, production and use as irrigation agent
    CZ19993977A CZ290160B6 (en) 1998-11-11 1999-11-10 Compacted granulation product, process for producing thereof and its use as swelling agent for pressed shaped bodies
    PL336514A PL191104B1 (en) 1998-11-11 1999-11-10 Pelletised material of increased density, method of obtaining same and method of making press-formed mouldings
    US09/438,657 US6232285B1 (en) 1998-11-11 1999-11-12 Compacted granulate, process for making same and use as disintegrating agent for pressed detergent tablets, cleaning agent tablets for dishwashers, water softening tablets and scouring salt tablets

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    EP98121397A EP1004656B1 (en) 1998-11-11 1998-11-11 Densified granulate, its manufacturing process and its use as disintegrant for compacted mouldings

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    EP1004656B1 true EP1004656B1 (en) 2000-12-27

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    EP (1) EP1004656B1 (en)
    AT (1) ATE198348T1 (en)
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    DE (1) DE59800410D1 (en)
    DK (1) DK1004656T3 (en)
    ES (1) ES2153229T3 (en)
    HU (1) HU228025B1 (en)
    PL (1) PL191104B1 (en)
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    CZ290160B6 (en) 2002-06-12
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