EP1043391B1 - High density disintegrating granulate for tablets; method for making it and its use - Google Patents
High density disintegrating granulate for tablets; method for making it and its use Download PDFInfo
- Publication number
- EP1043391B1 EP1043391B1 EP99106370A EP99106370A EP1043391B1 EP 1043391 B1 EP1043391 B1 EP 1043391B1 EP 99106370 A EP99106370 A EP 99106370A EP 99106370 A EP99106370 A EP 99106370A EP 1043391 B1 EP1043391 B1 EP 1043391B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- disintegrant
- weight
- granular material
- tablets
- material according
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
-
- 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
Definitions
- the invention relates to auxiliaries granules, composed of cellulose and optionally cellulose / starch derivatives, polymeric binders and gel-forming surfactants, which are used as disintegrating agents for tablets in u.a. Detergent and cleaning product is suitable. Furthermore, a method for producing the granules and their use is described.
- Disintegrating agents for tablets or granules are auxiliaries which positively influence the disintegration of tablets or of the granules on contact with liquids, in particular water. In this case, both the disintegration of tablets into coarse parts as well as subsequently a disintegration into smaller particles up to the dissolution / dispersion of all detergent components should be effected and accelerated.
- Tablets are made by pressing a starting granulate with certain pressures, the bulk density being e.g. for compact detergents is about 900g / l, after tableting to 1200 g / l increases.
- Such tablets with higher densities than the starting granules are naturally less soluble / divisible than the starting granules.
- the addition of decay-promoting explosives is appropriate.
- Addition to the dispenser is most convenient to the user and safest for the quality of the wash.
- very high Requirements placed on the rate of disintegration of the tablet In particular, the first step of the disintegration of the tablet in coarse parts must go very quickly, otherwise residues of the tablet remain in the dispenser and are not used for washing.
- a time of approximately 30 seconds is available for flushing in the tablets via the dispensing chamber.
- the tablets have to fulfill their function both in hot and cold rinsing water. In the washing drum are different conditions for the disintegration of the tablet, since both mechanical friction and increasing water temperatures affect the dissolution process of the tablet.
- tablet disintegrants in pharmaceutical practice. According to their mechanism of action, several models are discussed for tablet disintegrants, such as the development of gas bubbles (effervescent powder), the mutual particle repulsion, the water transport (wicking) and the swelling / expansion by water absorption.
- DE-OS 2,251,249 e.g. rapidly disintegrating drug tablets prepared by compressing drug granules and disintegrant granules.
- the use of granular starting materials results in a porous tablet structure.
- disintegrant granules based on starch with a particle size of 2.0 to 0.3 mm are used.
- Drug tablets are known from DE-OS 2 355 204, which are pressed from granular components, the granules are set for reasons of tablet stability prior to compression to a moisture content of less than 2%.
- US 3,629,393 claims sustained-release drug tablets which are pressed from granular ingredients using disintegrants of high molecular weight, water-swellable compounds such as cellulose derivatives in the form of granules.
- the granule dimensions move in the examples by 0.84 mm.
- US 4,072,535 describes the use of pre-compacted starch disintegrators for pharmaceuticals and detergents.
- the grain size of Kompaktates is 0.05 mm to 0.42 mm, the moisture content is 9-16%, preferably 11-13%.
- the disintegration times of the example tablets are several minutes.
- Detergent tablets are known from DE-OS 2 321 693, containing 1 to 25 wt.% Fibrous cellulose as disintegrant. In the examples, tablets having a strength of 15 to 19 N are prepared using compacted cellulose granules.
- EP 0170791 tablet-shaped washing additives which are pressed from granular components, wherein also 1 to 5 wt.% Granular tablet disintegrants based on crosslinked Polyvinylpyrrolidone and / or cellulose ethers are used.
- the granules should be free of dust particles.
- the tablets have breaking strengths of 50 to 120 N and have long dissolution times of several minutes.
- washing or cleaning active moldings are known, which are prepared using a disintegrant granules having a high water adsorption capacity and a particle size distribution, wherein at least 90 wt.% A particle size of at least 0.2 mm and a maximum of 3 mm to have.
- the dust content ⁇ 0.1 mm is less than 1%.
- the disintegrant granules contain at least 20% by weight of disintegrants, such as starch, starch derivatives, cellulose, cellulose derivatives. According to the teaching of this patent, the presence of anionic or nonionic surfactants adversely affects tablet disintegration time.
- the granules are prepared by conventional means, such as spray drying, hot steam drying of aqueous preparations, or by granulation, pelleting, extrusion or roll compaction of powdered ingredients. Detailed process information on the granulation process or on further process steps after the granulation of the disintegrant granules are not made.
- the detergent tablet prepared by way of example contains a disintegrant based on compacted cellulose from thermochanically treated wood pulp and has a tablet hardness of 45 N. Higher strength tablets, i. over 50 N are not described.
- WO 98/55575 describes an auxiliary granulate for washing and cleaning agent-active moldings.
- the claimed auxiliary granules contain 10 to 95% by weight of cellulose having particle sizes below 0.1 mm and 5 to 90% by weight of microcrystalline cellulose.
- the celluloses are partially combined with carboxymethyl cellulose, TAED and citric acid / bicarbonate.
- the particle sizes of Kompaktates be more than 90% by weight of 0.3 to 2.0 mm, less than 5% by weight less than 0.2 mm and have no dust content.
- roll compaction of the dry premix is preferred.
- Detailed process information for granule production are not made.
- the detergent tablets exemplified using the excipient granules have low strengths of 35 N or less. More stable, more compact tablets with higher strength from 50 N are not described.
- cellulose / cellulose derivatives or starch / starch derivatives are combined with thickening surfactants and finely divided polymers of (meth) acrylic acid in compacted granulated form as disintegrant granules for detergents and cleaners , Water softeners and stain salts in tablet form claimed.
- the granules have a non-linear source kinetics, wherein in relation to the entire swelling process in the initial phase of the swelling process, a very large increase in volume occurs. About the dissolution behavior of the tablets in the dispenser of a washing machine no information is given.
- the patent application WO 98/40462 describes a compact of powdered and / or granular ingredients, in particular detergent ingredients, which contains particles of cellulose-containing material which act as disintegrating agents and which can also be present in compacted form.
- cellulose component are thermomechanical (TMP) and chemical thermomechanical (CTMP) treated wood pulps.
- TMP thermomechanical
- CMP chemical thermomechanical
- the particle size of the compacted disintegrant may be 0.2 to 6 mm.
- Surfactant raw materials can also be fed to the compact via the cellulose component, with 0.5-5% surfactant / compact being mentioned.
- the prior art also includes sales products of the company Degussa AG with the name Elcema G250 and Elcema G 400, which consist of compacted pure cellulose and have been used since 1971 as a tablet disintegrant. These products are made by dry granulation and have a particle size of 0.03 to 0.40 mm. The moisture content is ⁇ 6%.
- the object of the invention is therefore to provide a comparison with the prior art improved disintegrant granules for tablets.
- it should swell so rapidly and strongly that tablets made using it are largely dissolved in the dispensing chamber of washing machines during the brief water scavenging time.
- the disintegrant granules should have a high Have abrasion resistance and are not limited in its effect by inevitably incurred in the course of its manufacturing process fine and dust in particular parts.
- the disintegrants in tablets with high strengths above 50 N should ensure a combination of good explosive action and good solubility and experience only minor signs of aging in the form of a weakening of the properties by storage of the tablets over several weeks.
- the object also includes the provision of a method for producing the disintegrant granules and their use in tablets for washing and cleaning processes.
- Component A is a compound having Component A:
- water-insoluble, swellable cellulose is used.
- Particularly suitable fibrils native cellulose with a maximum length of 0.30 mm proved.
- Both microcrystalline and amorphous particulate cellulose and mixtures thereof can be used.
- the finely divided cellulose preferably has apparent densities of from 40 g / l to 300 g / l, very particularly preferably from 65 g / l to 170 g / l. If already granulated types are used, their bulk density is higher and, in an advantageous embodiment, can be from 350 g / l to 550 g / l.
- the bulk densities of the cellulose derivatives are typically in the range of 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 is preferably between 0.030 mm and 0.20 mm, in the case of granulated types, the preferred average particle size is between 0.350 mm and 0.800 mm.
- the particle size of the finely divided cellulose derivatives is preferably 0.030 mm to 3.0 mm.
- the proportion of cellulose in disintegrant granules is between 60 to 99% by weight, preferably between 60 to 95% by weight.
- regenerated celluloses such as viscose are also used.
- regenerated celluloses in powder form are characterized by a very good water absorption.
- the viscose powder can be produced from cut viscose fiber or by precipitation of the dissolved viscose.
- Low molecular weight cellulose degraded by electron beam is also suitable, for example, for producing the disintegrant granulate.
- plasticized regenerated fibers are used.
- a typical plasticizer for such products may be mentioned here, for example, glycerol.
- the granules according to the invention may comprise water-swellable cellulose derivatives such as cellulose ethers and cellulose esters and starch or starch derivatives and other swellable polysaccharides and polygalactomannans, for example ionically modified celluloses and starches such as carboxymethyl-modified cellulose and starch, nonionically modified celluloses and starches such as alkoxylated celluloses and starches such as hydroxypropyl and hydroxyethyl starch or hydroxypropyl and hydroxyethyl cellulose and alkyletherified products such as methylcellulose, as well as mixed modified celluloses and starches from the aforementioned modifications, optionally combined with a modification to Networking leads.
- water-swellable cellulose derivatives such as cellulose ethers and cellulose esters and starch or starch derivatives and other swellable polysaccharides and polygalactomannans
- ionically modified celluloses and starches such as carboxymethyl-mod
- Suitable starches are also cold-swelling starches which are formed by mechanical or degrading reactions on the starch grain. These include, above all, swelling powders from extruder and drum dryer processes as well as enzymatically, oxidatively or acid-degrading modified products. Chemically derivatized starches preferably contain substituents attached to the polysaccharide chains in sufficient numbers by ester and ether groups
- Starches modified with ionic substituents such as carboxylate, hydroxyalkyl or phosphate groups have been found to be particularly advantageous and are therefore preferred. To improve the swelling behavior, the use of easily cross-linked starches has proven itself. Also alkaline treated starches can be used because of their good cold water swellability.
- the combination of cellulose with cellulose derivatives and / or starch and / or starch derivatives has been proven.
- the proportions can vary within wide limits, based on the combination, the proportion of cellulose derivatives and / or starch and / or starch derivatives preferably 0.1 to 85 wt.%, Particularly preferably 5 to 50 wt.%.
- Component B is a compound having Component B:
- Binders used are polymers or copolymers of (meth) acrylic acid or mixtures of such polymers or copolymers in the granules.
- the polymers are selected from the group of homopolymers of (meth) acrylic acid, from the group of copolymers with the following monomer components of ethylenically unsaturated dicarboxylic acids and / or their anhydrides and / or ethylenically unsaturated sulfonic acids and / or acrylic esters and / or vinyl esters and / or vinyl ethers or their saponification products and / or crosslinkers and / or graft bases based on polyhydroxy compounds.
- Non-crosslinked polymers or copolymers of (meth) acrylic acid having weight-average molecular weights of 5,000 to 70,000 have proved to be particularly suitable.
- the copolymers are preferably copolymers of (meth) acrylic acid and ethylenically unsaturated dicarboxylic acids or their anhydrides, such as maleic acid or maleic anhydride, which contain, for example, 40 to 90% by weight of (meth) acrylic acid and 60 to 10% by weight of maleic acid or Maleic anhydride whose relative molecular weight, based on free Acids, between 3,000 and 100,000, preferably 3,000 to 70,000 and most preferably 5,000 to 50,000.
- ter- and quattropolymere polycarboxylates composed of (meth) acrylic acid, maleic acid and optionally fully or partially saponified vinyl alcohol derivatives, or those of (meth) acrylic acid, ethylenically unsaturated sulfonic acids and polyhydroxy units, such as sugar derivatives, or such from (meth) acrylic acid, maleic acid, vinyl alcohol derivatives and monomers containing sulfonic acid groups.
- suitable polymers can be found in the patents DE 43 00 772, DE 42 21 371 and WO 95/17444.
- the polymeric binders are preferably used in the preparation in the form of their aqueous solutions, but can also be used in the form of finely divided powders.
- the binder polymers are preferably in part or fully neutralized form, the salt formation is preferably carried out with cations of alkali metals, ammonia and amines, or mixtures thereof.
- the proportion of polymers / copolymers in the disintegrant is between 1 and 40% by weight, preferably between 1 and 20% by weight, more preferably between 5 and 15% by weight. Polymer contents above 15% in the disintegrant result in harder disintegrant granules, while polymer contents below 1% tend to form soft granules that are less resistant to abrasion.
- Suitable polymer binders are also crosslinked polymers of (meth) acrylic acid. They are preferably used as finely divided powders and preferably have average particle sizes of 0.045 mm to 0.150 mm and are preferably used with 0.1 to 10 wt.%. Although particles having an average particle size of more than 0.150 mm also give good disintegrant granules, but after dissolution of the pellets produced with the granules visually visible as particles swelling bodies, which are clearly visible, for example, in the case of textile washes deposited on the textile material in a disturbing manner.
- a particular embodiment of the invention is the combination of soluble poly (meth) acrylate homo- and copolymers and the aforementioned finely divided crosslinked polymer particles.
- the disintegrant granules contain one or more liquid, water-gelling surfactants selected from the group of nonionic, anionic or amphoteric surfactants which are present in amounts of up to 7% by weight, preferably up to 3.5% by weight. If the surfactant content in the disintegrant is too high, in addition to an increased abrasion of the tablets produced therewith, also worse swelling properties result.
- the nonionic surfactants may include, for example, alkyl polyglucosides, fatty acid alkylolamides, fatty acid polyethylene glycol esters, fatty amine oxethylates, Fatty alcohol ethoxylates with 3-15 moles of ethylene oxide or propylene oxide, fatty acid glycerides, sorbitan esters, sucrose esters, for example sucrose palmitate, pentaerythritol partial esters, which may also be ethoxylated, and alkylphenol-polyethylene glycol ethers or phenol-poly-ethylene glycol ethers.
- the anionic surfactants may be, for example, alkyl sulfates, linear and branched alkyl benzene sulfonates, alkyl glycerol ethers, fatty alcohol polyethylene glycol ether sulfates, paraffin sulfonates, alpha-olefin sulfonates, sulfosuccinates, phosphoric acid esters or fatty alcohol ether carboxylates.
- amphoteric surfactants may, for example, be cocofatty acid amidopropyl betaine, modified imidazolines or fatty acid amide derivatives having betaine structure.
- mixtures of surfactants are used; in a further preferred embodiment, only nonionic surfactants are used.
- the compacted granules according to the invention are characterized by a special swelling kinetics, the extent does not change linearly as a function of time but reaches a very high level after a very short time.
- the swelling behavior in the first 10 seconds after contact with water In the range of the water content of 2 to 8 wt.%
- This combination of properties has a positive influence on the tablets produced with the disintegrating agents and leads there to short tablet disintegration times and a very good dispensing behavior in the dosing chambers of the washing machines.
- the superior effect of the agents according to the invention is shown by the fact that almost all tablets disintegrate and are washed away.
- the specific water absorption capacity of the granules according to the invention is very high and can be determined gravimetrically.
- the water absorption determined in this way is preferably 500 to 2000%
- the liquid uptake (also referred to as specific porosity) of the disintegrants according to the invention is markedly increased in comparison with products of the prior art and is in a range of more than 750 ml / kg, preferably in the range of 800 to 1000 ml / kg.
- This high fluid intake has a significant influence on the swelling effect and water transport in the disintegrant.
- Products of the prior art have an average liquid intake of about 600 ml / kg.
- the preparation of the disintegrant granules according to the invention is carried out first by mixing the granule components according to the invention with conventional mixing methods.
- mixers from Vomm, Lödige, Schugi, Eirich, Henschel or Fukae can be used.
- precompounds are produced by agglomeration processes. These precompounds form a free-flowing product which has a water content of between 10 and 80% by weight.
- the required water content in the premix depends on the compressor used.
- a water content of at least 10%, preferably 20% is required to achieve a good compaction and to guarantee a high liquid absorption in the subsequent dry granules.
- these precompounds are mechanically compacted.
- the compression using pressure can be done in various ways.
- the products can between two pressure surfaces in roller compactors, z. B. smooth or profiled, be compacted.
- the output of the Kompaktates takes place as a strand.
- Compacting methods in dies with punches or cushion rolls result in compact forms such as tablets or briquettes.
- Roller compactors, extruders, roller or die presses, but also granulation presses can be used as compacting machines.
- Suitable pelleting presses are manufactured, for example, by the companies Amandus Kahl and Fitzpatrick.
- the compaction preferably produces a disintegrant granulate having a bulk density of from 100 g / l to 500 g / l, particularly preferably from 150 g / l to 450 g / l and very particularly preferably from 250 g / l to 400 g / l.
- the compliance with a preferred limit of the bulk density of a maximum of 400 g / l has proved to be favorable because of the particularly good swelling properties. Surprisingly, it was found that the granules also have a very good abrasion stability at these bulk densities.
- the coarse, compacted particles are comminuted, e.g. Mills, shredders or roller mills are suitable.
- the comminution can be carried out before or after drying.
- the granules according to the invention are preferably adjusted to a particle size distribution of 0.05 to 3 mm, more preferably 0.1 to 1.5 mm.
- Removal of dust levels below 0.1 mm may be achieved e.g. be carried out with conventional screening devices. Since dust fractions of up to 10 wt. In the application of the granules of the invention does not interfere predominantly, their separation can often be omitted.
- the water content according to the invention of 2 to 8% by weight, preferably 2.5 to 7% by weight and more preferably 3 to 5% by weight is set.
- conventional dryers such as drum dryers (temperatures of, for example, 95-120 ° C.) or fluidized-bed dryers (temperatures of, for example, 70-100 ° C.) are suitable.
- the invention includes the use of the compacted granules as disintegrating agents for molded articles, for example tablets, cubes, spheres and the like. Particularly preferred is the use as a disintegrant for detergent formulations, detergent formulations, stain salts, water softeners in tablet or cube form.
- the disintegrant granules according to the invention are present in the shaped bodies in amounts of 0.5% by weight to 15% by weight, preferably 3% by weight to 8% by weight and more preferably 4% by weight to 7% by weight.
- the moldings of the invention have sufficient stability and strength, and allow safe handling, packaging and storage. On contact with water, however, they should disintegrate rapidly, so that the components can develop the desired effect. A sufficient stability against mechanical effects is given for moldings from a breaking strength of 50 N.
- the granules according to the invention impart to these high-density moldings a decomposition and dissolution characteristic which is otherwise only given in the case of moldings of low strength.
- the tablets for laundry detergent formulations generally contain builders, bleaches and bleach activators, surfactants, tableting aids, disintegrants and other customary additives and auxiliaries.
- Suitable builders are polyphosphates, pyrophosphates, metaphosphates or phosphonates, sheet silicates, amorphous silicates, amorphous disilicates and zeolite.
- Other constituents of the builder system may include fillers such as alkali carbonates, bicarbonates z. For example, sodium carbonate or sodium bicarbonate, sesquiocarbonates, sodium sulfate, magnesium sulfate, or citrate, citric acid, succinic acid, tartaric acid and malic acid. Frequently used as Hilfsgerüststoff co-builders and dispersants.
- Such co-builders or dispersants may 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-containing vinyl compounds can also be used.
- Particular preference is also ter- and quattropolymere polycarboxylates prepared from (meth) acrylic acid, maleic acid and vinyl alcohol or vinyl alcohol derivatives (as described in DE 43 00 772 C2) or those of (meth) acrylic acid, 2-alkylallylsulfonic and sugar derivatives (as described in DE 42 21 381 C1) or those of (meth) acrylic acid, maleic acid, vinyl alcohol derivatives and monomers with sulfonic acid groups (described in DE 195 16 957 A).
- constituents used are polyethylene glycol and / or polypropylene glycol having a molecular weight of from 900 to 30,000, and carboxylated polysaccharides, polyaspartates and polyglutamate. Also mixtures with various organic builders such as e.g. Citric acid is possible.
- Typical bleaching agents to be used 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 of bleaching agents in tablets is preferably 10-60% by weight and in particular 15-50% by weight. In order to achieve a good bleaching effect when washing below 60 ° C and below, activators can be incorporated.
- Suitable bleach activators are the H 2 O 2 organic peracids forming N-acyl and O-acyl compounds, preferably N, N'-tetraacylated diamines, carboxylic anhydrides and esters of polyols such as glucose pentaacetate. Further, acetylated mixtures of sorbitol and mannitol may be used. Particularly suitable as bleach activators are N, N, N ', N'-tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,2,5-triazine (DADHT) and acetylated sorbitol-mannitol. Mixtures (SORMAN).
- cationic surfactants may also be present in detergent formulations, for example quaternary ammonium compounds having C 8 -C 16 N-alkyl or N-alkenyl groups and N-substituents such as methyl, hydroxyethyl or hydroxypropyl groups.
- Tableting aids are also used if appropriate, for example polyalkylene glycols and magnesium stearates.
- Examples of further customary detergent additives and auxiliaries are enzymes, magnesium silicates, aluminum aluminates, benzotriazole, glycerol, magnesium stearate, polyalkylene glycols, hexametaphosphate, phosphonates, bentonites, soil release polymers, carboxymethylcelluloses.
- Dishwashing tablets as an embodiment of detergent formulations generally contain as builders polyphosphates, pyrophosphates, metaphosphates or phosphonates, sheet silicates, amorphous silicates, amorphous disilicates and zeolites, and fillers such as sodium carbonate, sodium sulfate, magnesium sulfate, sodium bicarbonate, citrate and citric acid, succinic acid, tartaric acid and malic acid , Frequently co-builders and dispersants are used as auxiliary builder.
- co-builders or dispersants may be polyacrylic acids or copolymers with polyacrylic acid and its sodium salts.
- Typical bleaching agents are sodium perborate tetrahydrate and sodium perborate monohydrate, sodium percarbonate, peroxypyrophosphates, citrate perhydrates, as well as H 2 O 2 -forming peracidic salts, peracids, such as perbenzoates, peroxyphthalates, diperazelaic acid and diperdodecanedioic acids.
- the content in the tablets is preferably 10-60% by weight, and more preferably 15-50% by weight.
- Low-foaming nonionic surfactants of the type polyalkylene glycol and alkyl polyglucosides are also used.
- Examples of other customary detergent additives and auxiliaries are also here enzymes, magnesium silicates, aluminum aluminates, benzotriazole, glycerol, magnesium stearate, polyalkylene glycols, hexametaphosphate and phosphonates.
- Water softening tablets generally consist of builders such as phyllosilicates, amorphous silicates, amorphous disilicates and zeolites, as well as fillers such as sodium carbonate, sodium sulfate, magnesium sulfate, sodium bicarbonate, citrate and citric acid.
- builders such as phyllosilicates, amorphous silicates, amorphous disilicates and zeolites
- fillers such as sodium carbonate, sodium sulfate, magnesium sulfate, sodium bicarbonate, citrate and citric acid.
- co-builders and dispersants are used as auxiliary builder.
- Such co-builders or dispersants may be polyacrylic acids or copolymers with polyacrylic acid and its sodium salts.
- Low-foaming nonionic surfactants of the type polyalkylene glycol and alkyl polyglucosides are also used.
- Examples of further customary detergent additives and auxiliaries are magnesium silicates, polyalkylene glycols and phosphonates.
- disintegrant granules according to the invention it is possible with the disintegrant granules according to the invention to produce detergent tablets having disintegration times of up to 15 seconds with a tablet breaking strength of up to 80 N.
- 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 dipped 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 drip. The bag is weighed and determined from the difference in weight of a wet bag with and without granules, the water absorption. Distilled water is used for the determination.
- the specific porosity of the disintegrant granules is determined by means of a known standard method for determining the degree of porosity of solids. Principle of the method:
- the solid is completely impregnated with di-n-butyl phthalate (DBP) and then the liquid absorbed in the pores is removed after a defined time under defined conditions by centrifuging.
- the amount of absorbed DBP is considered to be the measure of the porosity of the solid.
- Execution: 3 g of the sample are weighed into a commercially available tared glass filter crucible G3 and mixed with 10 ml of DBP. These crucibles are placed in a beaker, the bottom of which is laid out with filter paper. After exactly 5 minutes, the glass filter crucibles are weighed, then placed in Teflon inserts and centrifuged for 5 minutes at 1800 rev / min.
- a washing and cleaning tablet containing 5% disintegrant is used for the test.
- 500 ml of soft water at a temperature of 23 ° C are added.
- a metal sieve with a mesh size of 4 mm is applied.
- a magnetic stir bar is set in motion at about 200 rpm and a tablet is placed on top of the sieve from above.
- the time from the beginning of the tablet addition to the disintegration of the tablet is measured with a stopwatch. Disintegration is achieved when all tablet parts have fallen through the sieve.
- the washing machine are set 3 tablets in succession.
- the washing machine is connected to a pressure line with 5 bar city water and started in the 60 ° C normal program.
- the flushing time is while 30 sec, the machine takes only once water.
- the experiment is carried out a total of four times, so that 12 tablets are used. After each flush, the remaining tablets are counted. The total amount of non-flushed tablets is given.
- the TB30 / TBH30MD tablet breakage resistance tester from Erweka is used for the determination of the tablet breakage strength.
- the breaking strength is determined by means of a strain gauge with a load cell. The measuring accuracy is +/- 1N. After appropriate programming, the tablet is inserted into the measuring device and started the measuring process. The device displays the value of the breaking strength.
- the disintegrants used in the examples were prepared by wet compaction on a pelleting press made by Amandus Kahl. The degree of compaction was set to 1: 3. The water content of the mixtures before compression is shown in Table 1. After compaction, the granules were dried on a drum dryer from Babcok to the specified moisture contents.
- the comparative example V5 was produced on a roll press WP 150 of the Alexanderwerke without additional water. The pressing pressure was set to 1.1 t / cm. The granules were crushed on a Reibschnitzler. The drying also took place on a belt dryer. The granules have particle sizes between 0.3 and 2 mm, the dust content below 0.1 mm is given in the table.
- Table 1 Formulations for preparing disintegrants in% by weight and properties of the granules explosives V1 V3 V4 V5 M1 M2 M3 M4 M5 M6 M7 cellulose * 50 50 50 80 50 50 45 50 47 40 50 Linear PAA ** 12.5 12.5 12.5 20 12.5 12.5 10 10 12.5 10 - Core PAA *** 2 - CMC ### 15 5 10 20 - Nio surfactant ## 0.5 0.5 0.5 0 0.5 0.5 0.5 0.5 0 0.5 - Polymeric surfactant # 12.5 Water to the compact.
- Example M2 of the invention When comparing Example M2 of the invention with Example V2, there were significant differences in the liquid absorption, which are due to compacting and the moisture content during compaction.
- M2 moisture content of the compacting and drying
- V2 dry-compacted pattern
- Table 3 shows the strength and results of the rinse test of the individual detergent tablets using the different disintegrants: Table 3: Explosive means according to example Humidity (%) Rinse test (do not rupture tabl.) Strength [N] Decay time [sec] V1 18 10 61 50 V2 5 10 58 52 V3 10 6 60 40 M1 6 1 62 12 M2 4 0 65 9 V4 1 3 58 25 M3 3 0 57 8th M4 3 1 63 10 M5 4 1 58 9 M6 5 0 59 7 M7 3 0 58 9
- Table 3 shows that both the composition and the same composition of the moisture content of the disintegrant granules have a significant influence on the tablet disintegration time.
- Disintegrants with the preferred level of 3-5 wt% water as in M2 also show the best disintegration times of the tablets. If, in addition, suitable swellable substances are incorporated as disintegrant component, the disintegration properties can be further increased.
- Table 4 shows the influence of storage time (4 weeks at 40 ° C / 60% relative humidity in a closed container) on the flushing behavior of tablets with disintegrants.
- Table 4 Phosphate-containing detergent tablet according to Table 2 example Moisture of the explosive [%] Rinse test (tablet) Swelling kinetics after 3 sec [mm] immediately n. 4 weeks V4 1 3 3 0.85 M1 6 1 1 0.90 M2 4 0 1 0.97 V3 10 6 7 0.80 V1 18 10 11 0.45 V2 6 10 11 0.47 M3 3 0 - 2.0 M4 3 1 - 1.7 M5 4 1 - 1.6 M6 5 0 - 2.2
- Table 4 shows that the moisture content of the disintegration granules according to the invention leads to superior properties of the tablets produced therewith in the important rinsing test or that the swellability with values of 0.9 and higher is superior to the comparison products.
- Tablets with inventive disintegrant show good storage stability.
- Tablets with In addition to cellulose, M3-M6 also contains cellulose derivatives and thus has a further improved swelling kinetics.
- the tablet disintegration time of highly compressed tablets with inventive disintegrant is superior to the comparison products.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Medicinal Preparation (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Glanulating (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Sewing Machines And Sewing (AREA)
Abstract
Description
Gegenstand der Erfindung ist ein Hilfsmittelgranulat, aufgebaut aus Cellulose und gegebenenfalls Cellulose-/Stärkederivaten, polymeren Bindemitteln und gelbildenden Tensiden, das als Sprengmittel für Tabletten in u.a. Wasch-und Reinigungsmittelformkörper geeignet ist. Weiterhin wird ein Verfahren zur Herstellung der Granulate und deren Verwendung beschrieben.The invention relates to auxiliaries granules, composed of cellulose and optionally cellulose / starch derivatives, polymeric binders and gel-forming surfactants, which are used as disintegrating agents for tablets in u.a. Detergent and cleaning product is suitable. Furthermore, a method for producing the granules and their use is described.
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 bis hin zur Auflösung /Dispergierung aller Waschmittelbestandteile bewirkt und beschleunigt werden.Disintegrating agents for tablets or granules are auxiliaries which positively influence the disintegration of tablets or of the granules on contact with liquids, in particular water. In this case, both the disintegration of tablets into coarse parts as well as subsequently a disintegration into smaller particles up to the dissolution / dispersion of all detergent components should be effected and accelerated.
Tabletten werden durch Pressen eines Ausgangsgranulats mit bestimmten Drücken hergestellt, wobei die Schüttdichte, die z.B. bei Kompaktwaschmitteln ca. 900g/l beträgt, nach dem Tablettieren auf 1200 g/l steigt. Solche Tabletten mit höheren Dichten als das Ausgangsgranulat sind naturgemäß schlechter löslich /zerteilbar als das Ausgangsgranulat. Da sie sich bei der Anwendung in der Waschmaschine jedoch schnell auflösen sollen bzw. zerfallen und auflösen sollen, ist der Zusatz von den Zerfall fördernden Sprengmitteln angebracht.Tablets are made by pressing a starting granulate with certain pressures, the bulk density being e.g. for compact detergents is about 900g / l, after tableting to 1200 g / l increases. Such tablets with higher densities than the starting granules are naturally less soluble / divisible than the starting granules. However, since they should quickly dissolve or disintegrate and dissolve in the application in the washing machine, the addition of decay-promoting explosives is appropriate.
Je nach Wasch- und Reinigungsmittelzusammensetzung sind unterschiedliche Preßdrücke zur Tablettierung erforderlich. So können sich durch die Art des Builders, zum Beispiel Phosphat, Zeolith, Disilikat oder Schichtsilikat, unterschiedliche erforderliche Pressdrücke ergeben und damit unterschiedlich harte oder kompakte Tabletten entstehen. Um die Tabletten sicher gegen äußere mechanische Einwirkungen, etwa beim Transport oder beim Runterfallen gegen Zerbrechen zu schützen, sollten sie jedoch eine Festigkeit von 50 N oder höher aufweisen.Depending on the detergent composition, different compression pressures are required for tabletting. Thus, by the nature of the builder, for example phosphate, zeolite, disilicate or phyllosilicate, different required molding pressures can result and thus different hard or compact tablets. However, in order to protect the tablets safely against external mechanical effects, such as transport or fall-down, they should have a strength of 50 N or higher.
Für die praktischen Anwendung ergeben sich üblicherweise zwei Möglichkeiten der Zugabe der Tablette in die Waschmaschine, einerseits in die Einspülkammer und andererseits in die Waschtrommel. Die Anforderungen an den Tablettenzerfall sind je nach Zugabeort unterschiedlich.For practical application, there are usually two ways of adding the tablet into the washing machine, on the one hand into the dispensing chamber and on the other hand into the washing drum. The requirements for tablet disintegration vary depending on the place of addition.
Die Zugabe in die Einspülkammer ist für den Anwender am bequemsten und für die Qualität des Waschvorganges am sichersten. Jedoch werden sehr hohe Anforderungen an die Zerfallsgeschwindigkeit der Tablette gestellt. Besonders der erste Schritt des Zerfalls der Tablette in grobe Teile muß sehr schnell vonstatten gehen, weil sonst Reste der Tablette in der Einspülkammer verbleiben und nicht zum Waschen genutzt werden. Üblicherweise steht bei modernen Waschmaschinen eine Zeit von ca. 30 sec für die Einspülung der Tabletten über die Einspülkammer zur Verfügung. Die Tabletten müssen sowohl bei heißem als auch bei kaltem Einspülwasser ihre Funktion erfüllen. In der Waschtrommel liegen für den Zerfall der Tablette andere Bedingungen vor, da sowohl mechanische Reibung als auch steigende Wassertemperaturen den Auflöseprozeß der Tablette beeinflussen.Addition to the dispenser is most convenient to the user and safest for the quality of the wash. However, very high Requirements placed on the rate of disintegration of the tablet. In particular, the first step of the disintegration of the tablet in coarse parts must go very quickly, otherwise residues of the tablet remain in the dispenser and are not used for washing. Usually, in modern washing machines, a time of approximately 30 seconds is available for flushing in the tablets via the dispensing chamber. The tablets have to fulfill their function both in hot and cold rinsing water. In the washing drum are different conditions for the disintegration of the tablet, since both mechanical friction and increasing water temperatures affect the dissolution process of the tablet.
Das Problem der langen Zerfallszeiten von hochverdichteten Formkörpern ist schon aus der Pharmazie bekannt. Eine große Anzahl von Verbindungen und Mischungen sind als Tablettensprengmittel in der pharmazeutischen Praxis bekannt. Nach ihrem Wirkungsmechanismus werden für Tablettensprengmittel mehrere Modelle diskutiert, etwa die Entwicklung von Gasblasen (Brausepulver), die gegenseitigen Teilchenabstoßung, der Wassertransport (Dochtwirkung) und die Quellung / Ausdehnung durch Wasseraufnahme.The problem of long disintegration times of highly compressed moldings is already known from pharmacy. A large number of compounds and mixtures are known as tablet disintegrants in pharmaceutical practice. According to their mechanism of action, several models are discussed for tablet disintegrants, such as the development of gas bubbles (effervescent powder), the mutual particle repulsion, the water transport (wicking) and the swelling / expansion by water absorption.
Aus der Literatur sind viele Verbindungen bekannt, die stark quellen. Oftmals ist jedoch die Quellgeschwindigkeit zu gering. Neben der Quellgeschwindigkeit und dem Quellvolumen ist besonders der Quelldruck für die Anwendung wichtig.From the literature many compounds are known that swell strongly. Often, however, the swelling rate is too low. In addition to the source speed and the source volume, the source pressure is especially important for the application.
Um diese Eigenschaften zu messen, sind verschiedene Methoden bekannt. Man kann die Ausdehung ohne Gegendruck oder auch den Quelldruck ohne Ausdehnung messen. Kombinierte Meßmethoden, wobei sowohl der Quelldruck als auch die Ausdehnung erfaßt werden, sind besonders geeignet, Voraussagen zur Eignung von Sprengmitteln in Tabletten zu treffen. Eine solche Methode ist die Messung der Quellkinetik. Hier wird die zeitliche Abhängigkeit der Ausdehnung unter Belastung eines Sprengmittels bestimmt. Es gehen also sowohl der Quelldruck als auch die Ausdehnung in das Ergebnis ein. Es ist bekannt, daß als Sprengmittel geeignete Produkte sich beim Quellvorgang linear oder auch nichtlinear ausdehnen können. Die nichtlinear quellenden Sprengmittel sind wegen der schnelleren Wirkung deutlich besser geeignet als linear quellende Produkte.To measure these properties, various methods are known. You can measure the expansion without back pressure or the swelling pressure without expansion. Combined measuring methods, whereby both the swelling pressure and the expansion are detected, are particularly suitable for making predictions on the suitability of disintegrants in tablets. One such method is the measurement of the swelling kinetics. Here, the time dependence of the expansion under load of a disintegrant is determined. Thus, both the swelling pressure and the expansion enter into the result. It is known that products suitable as disintegrating agents can expand linearly or nonlinearly during the swelling process. The nonlinear swelling disintegrants are due to the faster effect much better suited than linear swelling products.
Den Ausführungen der WO 98/ 55575 zum Stand der Technik ist zu entnehmen, daß auf dem Gebiet der Wasch- und Reinigungsmittel auch die Sprengmittel eingesetzt werden können, die bei der Herstellung von Arzneimitteltabletten bekannt sind.The statements of WO 98/55575 to the prior art can be seen that in the field of detergents and cleaning agents and the disintegrating agents can be used, which are known in the manufacture of medicament tablets.
In der DE-OS 2 251 249 werden z.B. rasch zerfallende Arzneimitteltabletten beschrieben, die durch Verpressen von Arzneimittelgranulat und Sprengmittelgranulat hergestellt werden. Die Verwendung granularen Ausgangsmaterialien führt zu einer porösen Tablettenstruktur. Beispielhaft wird ein Sprengmittelgranulat auf Basis von Stärke mit einer Teilchengröße von 2,0 bis 0,3 mm verwendet.In DE-OS 2,251,249 e.g. rapidly disintegrating drug tablets prepared by compressing drug granules and disintegrant granules. The use of granular starting materials results in a porous tablet structure. By way of example, disintegrant granules based on starch with a particle size of 2.0 to 0.3 mm are used.
Aus der DE-OS 2 355 204 sind Arzneitabletten bekannt, die aus granularen Bestandteilen gepreßt werden, wobei die Granulate aus Gründen der Tablettenstabilität vor dem Verpressen auf einen Feuchtigkeitsgehalt von unter 2% eingestellt werden.Drug tablets are known from DE-OS 2 355 204, which are pressed from granular components, the granules are set for reasons of tablet stability prior to compression to a moisture content of less than 2%.
Die US 3,629,393 beansprucht Arzneimitteltabletten mit verzögerter Abgabe des Wirkstoffes, die aus granularen Bestanteilen gepreßt werden, wobei Sprengmittel aus hochmolekularen, wasserquellbaren Verbindungen, wie etwa Cellulosederivate in Form von Granulaten eingesetzt werden. Die Granulatdimensionen bewegen sich in den Beispielen um 0,84 mm.
Die US 4,072,535 beschreibt die Verwendung von Sprengmitteln aus vorkompaktierter Stärke für Pharmaka und Waschmittel. Die Korngröße des Kompaktates beträgt 0,05 mm bis 0,42 mm, der Feuchtegehalt wird mit 9-16%, bevorzugt 11-13% angegeben. Die Desintegrationszeiten der Beispielstabletten liegen bei mehreren Minuten.US 3,629,393 claims sustained-release drug tablets which are pressed from granular ingredients using disintegrants of high molecular weight, water-swellable compounds such as cellulose derivatives in the form of granules. The granule dimensions move in the examples by 0.84 mm.
US 4,072,535 describes the use of pre-compacted starch disintegrators for pharmaceuticals and detergents. The grain size of Kompaktates is 0.05 mm to 0.42 mm, the moisture content is 9-16%, preferably 11-13%. The disintegration times of the example tablets are several minutes.
Aus der DE-OS 2 321 693 sind Waschmitteltabletten bekannt, die 1 bis 25 Gew.% faserförmiger Cellulose als Sprengmittel enthalten. In den Beispielen werden Tabletten mit einer Festigkeit von 15 bis 19 N hergestellt, wobei kompaktierte Cellulosegranulate verwendet werden.Detergent tablets are known from DE-OS 2 321 693, containing 1 to 25 wt.% Fibrous cellulose as disintegrant. In the examples, tablets having a strength of 15 to 19 N are prepared using compacted cellulose granules.
In der EP 0 170 791 werden tablettenförmige Waschzusätze beschrieben, die aus granulatförmigen Bestandteilen gepreßt werden, wobei auch 1 bis 5 Gew.% granulatförmige Tablettensprengmittel auf Basis von vernetztem
Polyvinylpyrrolidon und/oder Celluloseethern zum Einsatz kommen. Die Granulate sollen frei von Staubanteilen sein. Die Tabletten weisen Bruchfestigkeiten von 50 bis 120 N auf und weisen lange Lösezeiten von mehreren Minuten auf.In EP 0170791 tablet-shaped washing additives are described which are pressed from granular components, wherein also 1 to 5 wt.% Granular tablet disintegrants based on crosslinked
Polyvinylpyrrolidone and / or cellulose ethers are used. The granules should be free of dust particles. The tablets have breaking strengths of 50 to 120 N and have long dissolution times of several minutes.
Aus WO98/40463 sind wasch- oder reinigungsaktive Formkörper bekannt, die unter Verwendung eines Sprengmittelgranulates hergestellt werden, das ein hohes Adsorptionsvermögen für Wasser und eine Korngrößenverteilung aufweist, bei der mindestens 90 Gew.% eine Partikelgröße von mindestens 0,2 mm und maximal 3 mm haben. Der Staubanteil < 0.1 mm liegt unter 1%. Das Sprengmittelgranulat enthält mindestens 20 Gew.% Sprengmittel, wie etwa Stärke, Stärkederivate, Cellulose, Cellulosederivate. 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 Granulierung, Pelletierung, Extrusion oder Walzenkompaktierung pulverförmiger Bestandteile. Detaillierte Verfahrensangaben zum Granulationsprozeß bzw. zu weiteren Verfahrensschritten nach der Granulierung der Sprengmittelgranulate werden nicht gemacht. Die beispielhaft hergestellte Waschmitteltablette enthält ein Sprengmittel auf Basis kompaktierter Cellulose aus thermochanisch behandelten Holzstoffen und weist eine Tablettenhärte von 45 N auf. Tabletten mit höherer Festigkeit, d.h. über 50 N werden nicht beschrieben.From WO98 / 40463 washing or cleaning active moldings are known, which are prepared using a disintegrant granules having a high water adsorption capacity and a particle size distribution, wherein at least 90 wt.% A particle size of at least 0.2 mm and a maximum of 3 mm to have. The dust content <0.1 mm is less than 1%. The disintegrant granules contain at least 20% by weight of disintegrants, such as starch, starch derivatives, cellulose, cellulose derivatives. According to the teaching of this patent, the presence of anionic or nonionic surfactants adversely affects tablet disintegration time. The granules are prepared by conventional means, such as spray drying, hot steam drying of aqueous preparations, or by granulation, pelleting, extrusion or roll compaction of powdered ingredients. Detailed process information on the granulation process or on further process steps after the granulation of the disintegrant granules are not made. The detergent tablet prepared by way of example contains a disintegrant based on compacted cellulose from thermochanically treated wood pulp and has a tablet hardness of 45 N. Higher strength tablets, i. over 50 N are not described.
WO 98/ 55575 beschreibt ein Hilfsmittelgranulat für wasch- und reinigungsmittelaktive Formkörper. Die beanspruchten Hilfsmittelgranulate enthalten 10 bis 95 Gew% Cellulose mit Teilchengrößen unter 0,1 mm sowie 5 bis 90 Gew% mikrokristalline Cellulose. Gemäß der Beispiele werden in den Hilfsmittelgranulaten die Cellulosen teilweise mit Carboxymethylcellulose, TAED und Citronensäure/Bicarbonat kombiniert. Die Korngrößen des Kompaktates betragen mehr als 90 Gew% von 0,3 bis 2,0 mm, weniger als 5 Gew% kleiner 0,2 mm und weisen keinen Staubanteil auf. Für die Herstellung ist die Walzenkompaktierung des trockenen Vorgemisches bevorzugt. Detaillierte Verfahrensangaben zur Granulatherstellung werden nicht gemacht. Die unter Verwendung der Hilfsmittelgranulate beispielhaft hergestellten Waschmitteltabletten weisen niedrige Festigkeiten von 35 N oder weniger auf. Stabilere, stärker kompaktiertere Tabletten mit höherer Festigkeit ab 50 N werden nicht beschrieben.WO 98/55575 describes an auxiliary granulate for washing and cleaning agent-active moldings. The claimed auxiliary granules contain 10 to 95% by weight of cellulose having particle sizes below 0.1 mm and 5 to 90% by weight of microcrystalline cellulose. According to the examples, in the auxiliary granules the celluloses are partially combined with carboxymethyl cellulose, TAED and citric acid / bicarbonate. The particle sizes of Kompaktates be more than 90% by weight of 0.3 to 2.0 mm, less than 5% by weight less than 0.2 mm and have no dust content. For the preparation, roll compaction of the dry premix is preferred. Detailed process information for granule production are not made. The detergent tablets exemplified using the excipient granules have low strengths of 35 N or less. More stable, more compact tablets with higher strength from 50 N are not described.
In den nach veröffentlichten europäischen Patentanmeldungen EP 1 004 656 A1 und EP 1 004 661 A1 werden Cellulose/Cellulosederivate bzw. Stärke/Stärkederivate zusammen mit verdickenden Tensiden und feinteiligen Polymerisaten der (Meth)acrylsäure in verdichteter, granulierter Form als Sprengmittelgranulat für Wasch- und Reinigungsmittel, Wasserenthärter und Fleckensalze in Tablettenform beansprucht. Die Granulate weisen eine nichtlineare Quellkinetik auf, wobei in Bezug auf den gesamten Quellvorgang in der Anfangsphase des Quellprozesses eine sehr starke Volumenvergrößerung auftritt. Über das Auflöseverhalten der Tabletten in der Einspülkammer einer Waschmaschine werden keine Angaben gemacht.In published European patent applications EP 1 004 656 A1 and EP 1 004 661 A1, cellulose / cellulose derivatives or starch / starch derivatives are combined with thickening surfactants and finely divided polymers of (meth) acrylic acid in compacted granulated form as disintegrant granules for detergents and cleaners , Water softeners and stain salts in tablet form claimed. The granules have a non-linear source kinetics, wherein in relation to the entire swelling process in the initial phase of the swelling process, a very large increase in volume occurs. About the dissolution behavior of the tablets in the dispenser of a washing machine no information is given.
Die Patentanmeldung WO 98/ 40462 beschreibt einen Preßling aus pulver- und/oder granulatförmigen Inhaltsstoffen, insbesondere Waschmittelinhaltsstoffen, der als Sprengmittel wirkende Partikel aus cellulosehaltigem Material enthält, das auch in kompaktierter Form vorliegen kann. Besonders bevorzugt als Cellulosekomponente werden thermomechanisch (TMP) und chemischthermomechanisch (CTMP) behandelte Holzstoffe. Die Teilchengröße des kompaktierten Sprengmittels kann bei 0,2 bis 6 mm liegen. Über die Cellulosekomponente können dem Preßling auch tensidische Rohstoffe zugeführt werden, wobei 0,5 - 5 % Tensid / Preßling erwähnt werden. Das entspricht einem Tensidgehalt von ca 14 - 45 Gew% im Cellulose-Sprengmittel, wenn man die erwähnten Einsatzkonzentrationen an kompaktiertem Granulat von 3 bis 6 % /Preßling zugrunde legt. Detaillierte verfahrenstechnische Angaben zur Herstellung des Sprengmittelgranulates bzw. dessen Wirkung im Preßling in Form von Ausführungsbeispielen werden nicht gemacht.The patent application WO 98/40462 describes a compact of powdered and / or granular ingredients, in particular detergent ingredients, which contains particles of cellulose-containing material which act as disintegrating agents and which can also be present in compacted form. Especially preferred as the cellulose component are thermomechanical (TMP) and chemical thermomechanical (CTMP) treated wood pulps. The particle size of the compacted disintegrant may be 0.2 to 6 mm. Surfactant raw materials can also be fed to the compact via the cellulose component, with 0.5-5% surfactant / compact being mentioned. This corresponds to a surfactant content of about 14 to 45% by weight in the cellulose disintegrating agent, if the mentioned use concentrations of compacted granules of 3 to 6% / compact are taken as a basis. Detailed procedural information on the preparation of the disintegrant granules or its effect in the compact in the form of embodiments are not made.
Nach der EP 0 750 662 B1 ist es möglich Reinigungstabletten mit hoher Bruch- und Lagerstabilität herzustellen, wenn man bei der Herstellung wasserfrei arbeitet und die Mischungsbestandteile vorab hydrophobiert. Die Tabletten enthalten keine Sprengmittelgranulate und weisen Bruchfestigkeiten von >150 N auf, das Auflöseverhalten ist stark verzögert.According to EP 0 750 662 B1, it is possible to produce cleaning tablets having a high resistance to breakage and storage if anhydrous preparation is used in the preparation and the mixture constituents are hydrophobic in advance. The tablets contain no disintegrant granules and have breaking strengths of> 150 N, the dissolution behavior is greatly delayed.
Zum Stand der Technik gehören auch Verkaufsprodukte der Firma Degussa AG mit der Bezeichnung Elcema G250 und Elcema G 400, welche aus kompaktierter reiner Cellulose bestehen und seit 1971 als Tablettensprengmittel eingesetzt werden. Diese Produkte werden durch Trockengranulation hergestellt und haben eine Teilchengröße von 0,03 bis zu 0,40 mm. Der Feuchtegehalt liegt bei <6 % .The prior art also includes sales products of the company Degussa AG with the name Elcema G250 and Elcema G 400, which consist of compacted pure cellulose and have been used since 1971 as a tablet disintegrant. These products are made by dry granulation and have a particle size of 0.03 to 0.40 mm. The moisture content is <6%.
Aufgabe der Erfindung ist es deshalb, ein gegenüber dem Stand der Technik verbessertes Sprengmittelgranulat für Tabletten bereitzustellen. Es soll insbesondere derart schnell und stark quellen, daß damit gefertigte Tabletten in der Einspülkammer von Waschmaschinen während der kurzen Wassereinspülzeit weitgehend aufgelöst werden. Ferner soll das Sprengmittelgranulat eine hohe Abrasionsstabilität aufweisen und in seiner Wirkung nicht durch im Zuge seines Herstellungsprozesses zwangsläufig anfallende Fein- und insbesondere Staubanteile eingeschränkt werden. Weiterhin sollen die Sprengmittel in Tabletten mit hohen Festigkeiten über 50 N eine Kombination aus guter Sprengwirkung und guter Löslichkeit gewährleisten und durch Lagerung der Tabletten über mehrere Wochen nur geringe Alterungserscheinungen in Form einer Abschwächung der Eigenschaften erfahren.The object of the invention is therefore to provide a comparison with the prior art improved disintegrant granules for tablets. In particular, it should swell so rapidly and strongly that tablets made using it are largely dissolved in the dispensing chamber of washing machines during the brief water scavenging time. Furthermore, the disintegrant granules should have a high Have abrasion resistance and are not limited in its effect by inevitably incurred in the course of its manufacturing process fine and dust in particular parts. Furthermore, the disintegrants in tablets with high strengths above 50 N should ensure a combination of good explosive action and good solubility and experience only minor signs of aging in the form of a weakening of the properties by storage of the tablets over several weeks.
Darüber hinaus umfaßt die Aufgabe auch die Bereitstellung eines Verfahrens zur Herstellung der Sprengmittelgranulate sowie deren Verwendung in Tabletten für Wasch- und Reinigungsverfahren.In addition, the object also includes the provision of a method for producing the disintegrant granules and their use in tablets for washing and cleaning processes.
Diese Aufgabe wird gelöst durch ein verdichtetes Sprengmittelgranulat für Tabletten, aufgebaut aus
- A) 60 - 99 Gew.% nichtwasserlöslicher, in Wasser quellbarer Cellulose und gegebenenfalls weitere, modifizierte wasserquellbare Polysaccharidderivate,
- B) 1 - 40 Gew.% mindestens eines polymeren Bindemittels in Form eines Polymerisates bzw. Copolymerisates der (Meth)acrylsäure und /oder deren Salze,
- C) 0 - 7 Gew.% mindestens eines flüssigen, mit Wasser gelbildenden Tensides,
dadurch gekennzeichnet, daß das Sprengmittelgranulat einen Feuchtigkeitsgehalt von 2 bis 8 Gew. % aufweist.This object is achieved by a compressed disintegrant granules for tablets, composed of
- A) 60-99% by weight of non-water-soluble, water-swellable cellulose and optionally further, modified water-swellable polysaccharide derivatives,
- B) 1 to 40% by weight of at least one polymeric binder in the form of a polymer or copolymer of (meth) acrylic acid and / or salts thereof,
- C) 0 to 7% by weight of at least one liquid, water-gelling surfactant,
characterized in that the disintegrant granules have a moisture content of 2 to 8 wt.%.
Überraschender Weise wurde gefunden, daß die Sprengmittelkompaktate wirksamer sind, wenn sie einen bestimmten Wassergehalt aufweisen. Gemäß der Lehre des Standes der Technik und der praktischen Erfahrung war zu erwarten, daß ein möglichst niedriger Wassergehalt im Fertiggranulat zur besten Quellwirkung führen würde.Surprisingly, it has been found that the explosive compacts are more effective if they have a certain water content. According to the teaching of the prior art and the practical experience, it was expected that the lowest possible water content in the final granules would lead to the best swelling effect.
Hier wird in Wasser nicht lösliche, quellbare Cellulose verwendet. Als besonders geeignet haben sich Fibrillen nativer Cellulose mit einer maximalen Länge von 0,30 mm erwiesen. Es können sowohl mikrokristalline als auch amorphe feinteilige Cellulose und Mischungen derselben verwendet werden.Here, water-insoluble, swellable cellulose is used. Particularly suitable fibrils native cellulose with a maximum length of 0.30 mm proved. Both microcrystalline and amorphous particulate cellulose 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 in einer vorteilhaften Ausführung 350 g/l bis 550 g/l betragen. Die Schüttgewichte der Cellulosederivate liegen typisch im Bereich von 50 g/l bis 1000 g/l, bevorzugt im Bereich von 100 g/l und 800 g/l.The finely divided cellulose preferably has apparent densities of from 40 g / l to 300 g / l, very particularly preferably from 65 g / l to 170 g / l. If already granulated types are used, their bulk density is higher and, in an advantageous embodiment, can be from 350 g / l to 550 g / l. The bulk densities of the cellulose derivatives are typically in the range of 50 g / l to 1000 g / l, preferably in the range of 100 g / l and 800 g / l.
Die Teilchengröße der feinteiligen Cellulose liegt bevorzugt zwischen 0,030 mm und 0,20 mm, im Falle von aufgranulierten Typen ist die bevorzugte mittlere Teilchengröße zwischen 0,350 mm und 0,800 mm. Die Teilchengröße der feinteiligen Cellulosederivate beträgt bevorzugt 0,030 mm bis 3,0 mm.The particle size of the finely divided cellulose is preferably between 0.030 mm and 0.20 mm, in the case of granulated types, the preferred average particle size is between 0.350 mm and 0.800 mm. The particle size of the finely divided cellulose derivatives is preferably 0.030 mm to 3.0 mm.
Der Anteil der Cellulose im Sprengmittelgranulat liegt zwischen 60 bis 99 Gew%, bevorzugt zwischen 60 bis 95 Gew%.The proportion of cellulose in disintegrant granules is between 60 to 99% by weight, preferably between 60 to 95% by weight.
In einer besonderen Ausführungsform der Erfindung werden auch regenerierte Cellulosen wie Viskose verwendet. Besonders regenerierte Cellulosen in Pulverform zeichnen sich durch eine sehr gute Wasseraufname aus. Das Viskosepulver kann dabei aus geschnittenen Viskosefaser oder durch Fällung der gelösten Viskose hergestellt werden. Auch durch Elektronenstrahl abgebaute niedermolekulare Cellulose ist beispielsweise zur Herstellung des Sprengmittelgranulates geeignet. In einer vorteilhaften Ausführungsform werden weichgemachte Regeneratfasern verwendet. Als ein typischer Weichmacher für derartige Produkte sei hier beispielsweise Glycerin erwähnt.In a particular embodiment of the invention, regenerated celluloses such as viscose are also used. Especially regenerated celluloses in powder form are characterized by a very good water absorption. The viscose powder can be produced from cut viscose fiber or by precipitation of the dissolved viscose. Low molecular weight cellulose degraded by electron beam is also suitable, for example, for producing the disintegrant granulate. In an advantageous embodiment, plasticized regenerated fibers are used. As a typical plasticizer for such products may be mentioned here, for example, glycerol.
Weiterhin können die erfindungsgemäßen Granulate in einer vorteilhaften Ausführungsform in Wasser quellbare Cellulosederivate, wie Celluloseether und Celluloseester und Stärke oder Stärkederivate sowie andere quellbare Polysaccharide und Polygalaktomannane enthalten, beispielsweise ionisch modifizierte Cellulosen und Stärken wie carboxymethylmodifizierte Cellulose und Stärke, nichtionisch modifizerte Cellulosen und Stärken wie alkoxylierte Cellulosen und Stärken, wie etwa Hydroxpropyl- und Hydroxyethylstärke bzw. Hydroxpropyl- und Hydroxyethylcellulose und alkylveretherte Produkte wie etwa Methylcellulose sowie gemischt modifizerte Cellulosen und Stärken aus den vorgenannten Modifizierungen, gegebenenfalls kombiniert mit einer Modifizierung die zur Vernetzung führt. Geeignete Stärken sind auch kaltquellende Stärken, die durch mechanische oder abbauende Reaktionen am Stärkekorn gebildet werden. Hierzu zählen vor allem Quellstärken aus Extruder- und Walzentrocknerprozessen sowie enzymatisch, oxidierend oder säureabbauend modifizierte Produkte. Chemisch derivatisierte Stärken enthalten vorzugsweise Substituenten, die durch Ester- und Ethergruppen in ausreichender Zahl an die Polysaccharidketten angeknüpft sindFurthermore, in an advantageous embodiment, the granules according to the invention may comprise water-swellable cellulose derivatives such as cellulose ethers and cellulose esters and starch or starch derivatives and other swellable polysaccharides and polygalactomannans, for example ionically modified celluloses and starches such as carboxymethyl-modified cellulose and starch, nonionically modified celluloses and starches such as alkoxylated celluloses and starches such as hydroxypropyl and hydroxyethyl starch or hydroxypropyl and hydroxyethyl cellulose and alkyletherified products such as methylcellulose, as well as mixed modified celluloses and starches from the aforementioned modifications, optionally combined with a modification to Networking leads. Suitable starches are also cold-swelling starches which are formed by mechanical or degrading reactions on the starch grain. These include, above all, swelling powders from extruder and drum dryer processes as well as enzymatically, oxidatively or acid-degrading modified products. Chemically derivatized starches preferably contain substituents attached to the polysaccharide chains in sufficient numbers by ester and ether groups
Stärken, die mit ionischen Substituenten wie etwa Carboxylat- , Hydroxyalkyl- oder Phosphatgruppen modifiziert sind , haben sich als besonders vorteilhaft erwiesen und sind deshalb bevorzugt. Zur Verbesserung des Quellverhaltens hat sich auch die Verwendung von leicht anvernetzten Stärken bewährt. Auch alkalisch behandelte Stärken können wegen ihrer guten Kaltwasserquellbarkeit verwendet werden.Starches modified with ionic substituents such as carboxylate, hydroxyalkyl or phosphate groups have been found to be particularly advantageous and are therefore preferred. To improve the swelling behavior, the use of easily cross-linked starches has proven itself. Also alkaline treated starches can be used because of their good cold water swellability.
In einer vorteilhaften Ausführungsform hat sich die Kombination von Cellulose mit Cellulosederivate und/oder Stärke und/oder Stärkederivate bewährt. Die Mengenverhältnisse können in weiten Grenzen schwanken, bezogen auf die Kombination beträgt der Anteil der Cellulosederivate und/oder Stärke und/oder Stärkederivate bevorzugt 0,1 bis 85 Gew.%, besonders bevorzugt 5 bis 50 Gew.%.In an advantageous embodiment, the combination of cellulose with cellulose derivatives and / or starch and / or starch derivatives has been proven. The proportions can vary within wide limits, based on the combination, the proportion of cellulose derivatives and / or starch and / or starch derivatives preferably 0.1 to 85 wt.%, Particularly preferably 5 to 50 wt.%.
Als Bindemittel werden Polymere bzw. Copolymere von (Meth)acrylsäure oder Mischungen von derartigen Polymeren oder Copolymeren im Granulat verwendet. Die Polymerisate sind ausgewählt aus der Gruppe Homopolymeren der (Meth)acrylsäure, aus der Gruppe der Copolymeren mit folgenden Monomerkomponenten ethylenisch ungesättigten Dicarbonsäuren und/oder deren Anhydriden und/oder ethylenisch ungesättigten Sulfonsäuren und/oder Acrylestern und/oder Vinylestern und/oder Vinylethern bzw. deren Verseifungsprodukten und/oder Vernetzern und/oder Pfropfgrundlagen auf Basis von Polyhydroxverbindungen.Binders used are polymers or copolymers of (meth) acrylic acid or mixtures of such polymers or copolymers in the granules. The polymers are selected from the group of homopolymers of (meth) acrylic acid, from the group of copolymers with the following monomer components of ethylenically unsaturated dicarboxylic acids and / or their anhydrides and / or ethylenically unsaturated sulfonic acids and / or acrylic esters and / or vinyl esters and / or vinyl ethers or their saponification products and / or crosslinkers and / or graft bases based on polyhydroxy compounds.
Als besonders geeignet haben sich unvernetzte Polymere bzw. Copolymere von (Meth)acrylsäure, mit gewichtsmittleren Molekulargewichten von 5.000 bis 70.000 erwiesen. Bei den Copolymeren handelt es sich vorzugsweise um Copolymere von (Meth)acrylsäure und ethylenisch ungesättigten Dicarbonsäuren bzw. deren Anhydriden, wie etwa 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. Als gut geeignete Bindemittel haben sich auch ter- und quattropolymere Polycarboxylate erwiesen, aufgebaut aus (Meth)acrylsäure, Maleinsäure und gegebenenfalls voll oder teilweise verseiften Vinylalkoholderivaten, oder solche aus (Meth)acrylsäure, ethylenisch ungesättigen Sulfonsäuren und Polyhydroxyeinheiten, wie etwa Zuckerderivaten, oder solche aus (Meth)acrylsäure, Maleinsäure, Vinylalkoholderivaten und sulfonsäuregruppenhaltigen Monomeren. Beispiele für geeignete Polymerisate befinden sich in den Patentschriften DE 43 00 772, DE 42 21 371 und WO 95/17444.Non-crosslinked polymers or copolymers of (meth) acrylic acid having weight-average molecular weights of 5,000 to 70,000 have proved to be particularly suitable. The copolymers are preferably copolymers of (meth) acrylic acid and ethylenically unsaturated dicarboxylic acids or their anhydrides, such as maleic acid or maleic anhydride, which contain, for example, 40 to 90% by weight of (meth) acrylic acid and 60 to 10% by weight of maleic acid or Maleic anhydride whose relative molecular weight, based on free Acids, between 3,000 and 100,000, preferably 3,000 to 70,000 and most preferably 5,000 to 50,000. Also suitable as suitable binders are ter- and quattropolymere polycarboxylates, composed of (meth) acrylic acid, maleic acid and optionally fully or partially saponified vinyl alcohol derivatives, or those of (meth) acrylic acid, ethylenically unsaturated sulfonic acids and polyhydroxy units, such as sugar derivatives, or such from (meth) acrylic acid, maleic acid, vinyl alcohol derivatives and monomers containing sulfonic acid groups. Examples of suitable polymers can be found in the patents DE 43 00 772, DE 42 21 371 and WO 95/17444.
Die polymeren Bindemittel werden bei der Herstellung bevorzugt in Form ihrer wäßrigen Lösungen eingesetzt, können aber auch in Form feinteiliger Pulver angewendet werden. Die Bindemittelpolymerisate liegen vorzugsweise in teil bzw. vollneutralisierter Form vor, wobei die Salzbildung vorzugsweise mit Kationen von Alkalimetallen, Ammoniak und Aminen, bzw. deren Mischungen erfolgt.The polymeric binders are preferably used in the preparation in the form of their aqueous solutions, but can also be used in the form of finely divided powders. The binder polymers are preferably in part or fully neutralized form, the salt formation is preferably carried out with cations of alkali metals, ammonia and amines, or mixtures thereof.
Der Anteil der Polymeren/Copolymeren im Sprengmittel liegt zwischen 1 und 40 Gew%, bevorzugt zwischen 1 und 20 Gew%, besonders bevorzugt zwischen 5 und 15 Gew%. Polymergehalte oberhalb 15% im Sprengmittel führen zu härteren Sprengmittelgranulaten, während Polymergehalte unter 1% zur Bildung weicher Granulate neigen, die weniger abriebbeständig sind.The proportion of polymers / copolymers in the disintegrant is between 1 and 40% by weight, preferably between 1 and 20% by weight, more preferably between 5 and 15% by weight. Polymer contents above 15% in the disintegrant result in harder disintegrant granules, while polymer contents below 1% tend to form soft granules that are less resistant to abrasion.
Geignete Polymerbindemittel sind auch vernetzte Polymere aus (Meth)acrylsäure. Sie werden bevorzugt als feinteilige Pulver angewendet und weisen bevorzugt mittlere Teilchengrößen von 0,045 mm bis 0,150 mm auf und werden bevorzugt mit 0,1 bis 10 Gew.% eingesetzt. Teilchen mit mittleren Teilchengrößen über 0,150 mm ergeben zwar auch gute Sprengmittelgranulate, führen aber nach dem Auflösen der mit den Granulaten hergestellten Tabletten zu visuell als Teilchen sichtbaren Quellkörpern, die sich beispielsweise im Falle von Textilwäschen deutlich sichtbar auf dem Textilgut in störender Weise ablagern.Suitable polymer binders are also crosslinked polymers of (meth) acrylic acid. They are preferably used as finely divided powders and preferably have average particle sizes of 0.045 mm to 0.150 mm and are preferably used with 0.1 to 10 wt.%. Although particles having an average particle size of more than 0.150 mm also give good disintegrant granules, but after dissolution of the pellets produced with the granules visually visible as particles swelling bodies, which are clearly visible, for example, in the case of textile washes deposited on the textile material in a disturbing manner.
Eine besondere Ausführungsform der Erfindung stellt die Kombination von löslichen Poly(meth)acrylat Homo- und Copolymeren und den zuvor genannten feinteiligen vernetzten Polymerteilchen dar.A particular embodiment of the invention is the combination of soluble poly (meth) acrylate homo- and copolymers and the aforementioned finely divided crosslinked polymer particles.
Geeignete Co-Bindemittel, die gleichzeitig einen Tensidcharakter haben, sind auch sogenannte Polymertenside. Hierunter werden Reaktionsprodukte verstanden, die neben den typischen Polymerstrukturen der zuvor genannten Bindemittelpolymere zusätzliche, eine Tensidwirkung entfaltende Strukturelemente aufweisen. Ausgewählt sind hier Pfropfpolymere mit alkoxyliertem Fettalkohol oder carboxylathaltige Polymere mit methoxyalkylenoxid-Monomereinheiten zu erwähnen, ferner MaleinsäureNinylether/längerkettige Fettamin-Copolymere sowie Halbamide von Maleinsäurecopolymeren und Copolymere von Acrylsäure mit langkettigen Acrylaten. In einer bevorzugten Ausführungsform enthalten die Polymertenside Alkylenoxideinheiten. Polymertenside können mit bis zu 30 Gew.% im Sprengmittelgranulat vorhanden sein.
Es hat sich gezeigt, daß zur Herstellung der erfindungsgemäßen Sprengmittelgranulate die vorgenannten Polymertenside in Alleinanwendung ohne Anwesenheit von polymerer Bindemittelkomponente und ohne Tensidkomponente geeignet sind. Die erforderlichen Mengen an Polymertensid im Sprengmittelgranulat liegen im Bereich von 1 bis 40 Gew.%, bevorzugt bei 5 bis 20 Gew. %.
Demzufolge erfolgt eine weitere Lösung der gestellten Aufgabe durch ein verdichtetes Sprengmittelgranulat für Tabletten, aufgebaut aus
- A) 60 - 99 Gew.% nichtwasserlöslicher, in Wasser quellbarer Cellulose und gegebenenfalls weitere, modifizierte wasserquellbare Polysaccharidderivate,
- D) 1 - 40 Gew.% mindestens eines polymeren Bindemittels
dadurch gekennzeichnet, daß das Sprengmittelgranulat einen Feuchtigkeitsgehalt von 2 bis 8 Gew. % aufweist und das polymere Bindemittel D) ein Polymertensid gemäß Anspruch 7 ist.Suitable co-binders which simultaneously have a surfactant character are also so-called polymer surfactants. These are understood as reaction products which in addition to the typical polymer structures of the aforementioned binder polymers have additional, a surfactant effect unfolding structural elements. Selected are graft polymers with alkoxylated fatty alcohol or carboxylate-containing polymers with methoxyalkylene oxide monomer units, also maleic acid vinyl ethers / longer-chain fatty amine copolymers and hemiamides of maleic acid copolymers and copolymers of acrylic acid with long-chain acrylates. In a preferred embodiment, the polymeric surfactants contain alkylene oxide units. Polymer surfactants can be present in the disintegrant granules with up to 30% by weight.
It has been found that for the preparation of the disintegrant granules according to the invention, the abovementioned polymer surfactants are suitable for use alone without the presence of a polymeric binder component and without a surfactant component. The required amounts of polymer surfactant in disintegrant granules are in the range of 1 to 40 wt.%, Preferably 5 to 20 wt.%.
Accordingly, a further solution of the problem by a compressed disintegrant granules for tablets, constructed from
- A) 60-99% by weight of non-water-soluble, water-swellable cellulose and optionally further, modified water-swellable polysaccharide derivatives,
- D) 1 - 40% by weight of at least one polymeric binder
characterized in that the disintegrant granules have a moisture content of 2 to 8 wt.% And the polymeric binder D) is a polymer surfactant according to claim 7.
Als weiteren Bestandteil enthält das Sprengmittelgranulat ein oder mehrere flüssige, mit Wasser gelbildende Tenside, ausgewählt aus der Gruppe der nichtionischen, anionischen oder amphoteren Tenside, die in Mengen bis zu 7 Gew.%, vorzugsweise bis zu 3,5 Gew. % vorhanden sind. Wenn der Tensidgehalt im Sprengmittel zu hoch ist, resultieren neben einer erhöhten Abrasion der damit gefertigten Tabletten auch schlechtere Quelleigenschaften.As a further constituent, the disintegrant granules contain one or more liquid, water-gelling surfactants selected from the group of nonionic, anionic or amphoteric surfactants which are present in amounts of up to 7% by weight, preferably up to 3.5% by weight. If the surfactant content in the disintegrant is too high, in addition to an increased abrasion of the tablets produced therewith, also worse swelling properties result.
Die nichtionischen Tenside können beispielsweise Alkylpolyglucoside, Fettsäure-Alkylolamide, Fettsäure-Polyethylenglykolester, Fettaminoxethylate, Fettalkoholethoxylate mit 3-15 Mol Ethylenoxid oder Propylenoxid, Fettsäureglyceride, Sorbitanester, Saccharoseester, z.B. Saccharosepalmitat, Pentaaerythrit-Partialester, die auch ethoxyliert sein können, sowie Alkylphenol-Polyethylenglykolether oder Phenolpoly -ethylenglykolether sein.The nonionic surfactants may include, for example, alkyl polyglucosides, fatty acid alkylolamides, fatty acid polyethylene glycol esters, fatty amine oxethylates, Fatty alcohol ethoxylates with 3-15 moles of ethylene oxide or propylene oxide, fatty acid glycerides, sorbitan esters, sucrose esters, for example sucrose palmitate, pentaerythritol partial esters, which may also be ethoxylated, and alkylphenol-polyethylene glycol ethers or phenol-poly-ethylene glycol ethers.
Die anionische Tenside können beispielsweise Alkylsulfate, lineare und verzweigte Alkybenzolsulfonate, Alkylglycerolether, Fettalkoholpolyethylenglycolethersulfate, Paraffinsulfonate, Alpha-Olefinsulfonate, Sulfosuccinate, Phosphorsäureester oder Fettalkoholethercarboxylate sein.The anionic surfactants may be, for example, alkyl sulfates, linear and branched alkyl benzene sulfonates, alkyl glycerol ethers, fatty alcohol polyethylene glycol ether sulfates, paraffin sulfonates, alpha-olefin sulfonates, sulfosuccinates, phosphoric acid esters or fatty alcohol ether carboxylates.
Die amphoteren Tenside können beispielsweise Cocosfettsäureamidopropylbetain, modifizierte Imidazoline oder Fettsäureamidderivate mit Betainstruktur sein.The amphoteric surfactants may, for example, be cocofatty acid amidopropyl betaine, modified imidazolines or fatty acid amide derivatives having betaine structure.
In einer bevorzugten Ausführungsform der Erfindung werden Gemische von Tensiden eingesetzt, in einer weiteren bevorzugten Ausführungsform werden nur nichtionische Tenside eingesetzt.In a preferred embodiment of the invention, mixtures of surfactants are used; in a further preferred embodiment, only nonionic surfactants are used.
Das erfindungsgemäße verdichtete Granulat zeichnet sich durch eine besondere Quellkinetik aus, die Ausdehnung ändert sich in Abhängigkeit von der Zeit nicht linear sondern erreicht nach sehr kurzer Zeit bereits ein sehr hohes Niveau. Von besonderem Interesse ist dabei das Quellverhalten in den ersten 10 Sekunden nach Berührung mit Wasser. Im Bereich des erfindungsgemäßen Wassergehaltes von 2 bis 8 Gew.% kommt es zu einer unerwartet hohen Volumenausdehnung, einer hohen Geschwindigkeit der Ausdehnung und einem hohen Quelldruck. Diese Eigenschaftskombination hat einen positiven Einfluß auf die mit den Sprengmitteln hergestellten Tabletten und führt dort zu kurzen Tablettenzerfallszeiten und einem sehr guten Einspülverhalten in den Dosierkammern der Waschmaschinen. Bei den Einspültests zeigt sich die überlegene Wirkung der erfindungsgemäßen Mittel dadurch, daß fast sämtliche Tabletten zerfallen und weggespült werden.The compacted granules according to the invention are characterized by a special swelling kinetics, the extent does not change linearly as a function of time but reaches a very high level after a very short time. Of particular interest is the swelling behavior in the first 10 seconds after contact with water. In the range of the water content of 2 to 8 wt.% According to the invention there is an unexpectedly high volume expansion, a high speed of expansion and a high swelling pressure. This combination of properties has a positive influence on the tablets produced with the disintegrating agents and leads there to short tablet disintegration times and a very good dispensing behavior in the dosing chambers of the washing machines. In the rinsing tests, the superior effect of the agents according to the invention is shown by the fact that almost all tablets disintegrate and are washed away.
Das spezifische Wasseraufnahmevermögen des erfindungsgemäßen Granulats ist sehr hoch und kann gravimetrisch bestimmt werden. Die auf diese Weise bestimmbare Wasseraufnahme beträgt vorzugsweise 500 bis 2000 %The specific water absorption capacity of the granules according to the invention is very high and can be determined gravimetrically. The water absorption determined in this way is preferably 500 to 2000%
Überraschenderweise hat sich weiterhin herausgestellt, daß ein gewisser Staubanteil, der nach der Lehre des Standes der Technik in Granulaten für Wasch- und Reinigungsmitteltabletten nicht vorhanden sein soll, im erfinderischen Sprengmittelkompaktat nicht stört und darüber hinaus zu einer guten Lagerstabilität der damit hergestellten Tabletten beiträgt. Anteile eines Feinstaubanteils von kleiner 0,1 mm bis zu 10 Gew.%, vorzugsweise bis zu 8 Gew.% können in den erfindungsgemäßen Sprengmittelgranulaten vorhanden sein.Surprisingly, it has further been found that a certain proportion of dust, which according to the teaching of the prior art should not be present in granules for detergent tablets, does not interfere with the inventive disintegrant composition and, moreover, gives a good result Storage stability of the tablets produced therewith contributes. Parts of a fine dust content of less than 0.1 mm up to 10% by weight, preferably up to 8% by weight, may be present in the disintegrant granules according to the invention.
Die Flüssigkeitsaufnahme ( auch als spezifische Porosität bezeichnet) der erfindungsgemäßen Sprengmittel ist im Vergleich zu Produkten des Standes der Technik deutlich erhöht und liegt in einem Bereich von über 750 ml/kg, vorzugsweise im Bereich 800 bis 1000 ml/kg. Diese hohe Flüssigkeitsaufnahme hat einen signifikanten Einfluß auf die Quellwirkung und den Wassertransport im Sprengmittel. Produkte nach dem Stand der Technik haben durchschnittlich Flüssigkeitsaufnahmewerte von ca. 600 ml/kg.The liquid uptake (also referred to as specific porosity) of the disintegrants according to the invention is markedly increased in comparison with products of the prior art and is in a range of more than 750 ml / kg, preferably in the range of 800 to 1000 ml / kg. This high fluid intake has a significant influence on the swelling effect and water transport in the disintegrant. Products of the prior art have an average liquid intake of about 600 ml / kg.
Die Herstellung der erfindungsgemäßen Sprengmittelgranulate erfolgt zunächst durch Mischen der erfindungsgemäßen Granulatbestandteile mit üblichen MischVerfahren. Beispielsweise können Mischer der Firmen Vomm, Lödige, Schugi, Eirich, Henschel oder Fukae eingesetzt werden. Bei diesem ersten Schritt des Mischens und Granulierens werden Vorcompounds durch Agglomerationsverfahren hergestellt. Diese Vorcompounds bilden eine rieselfähige Ware, die einen Wassergehalt zwischen 10 und 80 Gew% hat. Der erforderliche Wassergehalt im Vorgemisch ist abhängig von der verwendeten Verdichtungseinrichtung. Ein Wassergehalt von mindestens 10%, bevorzugt 20% ist erforderlich, um eine gute Verdichtung zu erzielen und eine hohe Flüssigkeitsaufnahme im späteren Trockengranulat zu garantieren. Bei Wassergehalten zwischen 60 und 80 Gew.% ist darauf zu achten, daß es bei bestimmten Verdichtungsapparaten, wie etwa der Ringmatrizenpresse während während des Preßvorganges dazu kommen kann, daß das Wasser aus der Mischung gedrückt werden kann, wohingegen in Extruder keine derartigen Phänomene zu beobachten sind. D.h. die Verdichtungstechnik muß letztlich dem Wassergehalt der Vormischung angepaßt werden. Für Ringmatrizenpresse und Pelletierpressen hat sich ein Wassergehalt von 20 bis 60 Gew.%, bevorzugt von 20 bis 40 Gew.% bewährt. Darüber hinaus sollte auch aus wirtschaftlichen Gründen der Wassergehalt des Vorcompounds nicht höher als erforderlich sein, weil dieses Wasser im späteren Trockenprozeß unter Aufwendung von Energie entfernt werden muß.The preparation of the disintegrant granules according to the invention is carried out first by mixing the granule components according to the invention with conventional mixing methods. For example, mixers from Vomm, Lödige, Schugi, Eirich, Henschel or Fukae can be used. In this first step of mixing and granulating, precompounds are produced by agglomeration processes. These precompounds form a free-flowing product which has a water content of between 10 and 80% by weight. The required water content in the premix depends on the compressor used. A water content of at least 10%, preferably 20% is required to achieve a good compaction and to guarantee a high liquid absorption in the subsequent dry granules. At water contents of between 60 and 80% by weight, care must be taken that in certain compacting apparatus, such as the ring die press, during the pressing operation, the water may be forced out of the mixture, whereas in extruders no such phenomena are observed are. That the compaction technique must ultimately be adapted to the water content of the premix. For Ringmatrizenpresse and pelleting presses, a water content of 20 to 60 wt.%, Preferably from 20 to 40 wt.% Has proven. In addition, for economic reasons, the water content of the precompound should not be higher than necessary because this water must be removed in the subsequent drying process with the expenditure of energy.
Im nächsten Schritt werden diese Vorcompounds mechanisch verdichtet. Für das Quell- und Wasseraufnahmeverhalten des erfindungsgemäßen Granulats ist die abschließende Verdichtung wesentlich. Das Verdichten unter Anwendung von Druck kann auf verschiedene Weise erfolgen. Die Produkte können zwischen zwei Druckflächen in Walzenverdichtern, z. B. glatt oder profiliert, verdichtet werden. 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.In the next step, these precompounds are mechanically compacted. For the swelling and water absorption behavior of the granules according to the invention is the final consolidation essential. The compression using pressure can be done in various ways. The products can between two pressure surfaces in roller compactors, z. B. smooth or profiled, be compacted. The output of the Kompaktates takes place as a strand. Compacting methods in dies with punches or cushion rolls result in compact forms such as tablets or briquettes. Roller compactors, extruders, roller or die presses, but also granulation presses can be used as compacting machines.
Als besonders geeignet hat sich die Verdichtung mit Pelletierpressen erwiesen,
wobei durch eine geeignete Prozeßführung Granulate erhalten werden, die ohne weitere Zerkleinerung getrocknet werden können. Geeignete Pelletierpressen werden z.B. von den Firmen Amandus Kahl und Fitzpatrick hergestellt.Compaction with pelleting presses has proven particularly suitable
wherein granules are obtained by a suitable process control, which can be dried without further comminution. Suitable pelleting presses are manufactured, for example, by the companies Amandus Kahl and Fitzpatrick.
Durch die Verdichtung wird vorzugsweise ein Sprengmittelgranulat mit einer Schüttdichte von 100 g/l bis 500 g/l, besonders bevorzugt von 150 g/l bis 450 g/l und ganz besonders bevorzugt von 250 g/l bis 400 g/l erzeugt. Die Einhaltung einer bevorzugten Grenze der Schüttdichte von maximal 400 g/l hat sich wegen der besonders guten Quelleigenschaften als günstig erwiesen. Überraschenderweise wurde gefunden, daß die Granulate auch bei diesen Schüttdichten eine sehr gute Abriebstabilität aufweisen.The compaction preferably produces a disintegrant granulate having a bulk density of from 100 g / l to 500 g / l, particularly preferably from 150 g / l to 450 g / l and very particularly preferably from 250 g / l to 400 g / l. The compliance with a preferred limit of the bulk density of a maximum of 400 g / l has proved to be favorable because of the particularly good swelling properties. Surprisingly, it was found that the granules also have a very good abrasion stability at these bulk densities.
Die groben, verdichteten Teilchen werden zerkleinert, wobei z.B. Mühlen, Schnitzler oder Walzenstühle geeignet sind. Die Zerkleinerung kann vor oder nach der Trocknung durchgeführt werden. Dabei werden die erfindungsgemäßen Granulate bevorzugt auf eine Teilchengrößenverteilung von 0,05 bis 3 mm, besonders bevorzugt 0,1 bis 1,5 mm, eingestellt.The coarse, compacted particles are comminuted, e.g. Mills, shredders or roller mills are suitable. The comminution can be carried out before or after drying. The granules according to the invention are preferably adjusted to a particle size distribution of 0.05 to 3 mm, more preferably 0.1 to 1.5 mm.
Eine Entfernung von Staubanteilen unter 0,1 mm kann z.B. mit üblichen Siebeinrichtungen durchgeführt werden. Da Staubanteile bis zu 10 Gew. in der Anwendung der erfindungsgemäßen Granulate überwiegend nicht stört, kann deren Abtrennung oftmals unterbleiben.Removal of dust levels below 0.1 mm may be achieved e.g. be carried out with conventional screening devices. Since dust fractions of up to 10 wt. In the application of the granules of the invention does not interfere predominantly, their separation can often be omitted.
Im Trocknungsvorgang wird der erfindungsgemäße Wassergehalt von 2 - 8 Gew%, bevorzugt 2,5 - 7 Gew.% und besonders bevorzugt 3 - 5 Gew.% eingestellt. Hierfür sind übliche Trockner wie z.B. Walzentrockner ( Temperaturen z.B. von 95 - 120°C) oder Fließbett-Trockner (Temperaturen z.B. von 70 - 100°C) geeignet.In the drying process, the water content according to the invention of 2 to 8% by weight, preferably 2.5 to 7% by weight and more preferably 3 to 5% by weight is set. For this purpose, conventional dryers such as drum dryers (temperatures of, for example, 95-120 ° C.) or fluidized-bed dryers (temperatures of, for example, 70-100 ° C.) are suitable.
Die Erfindung schließt die Verwendung der verdichteten Granulate als Sprengmittel für gepreßte Formkörper, beispielsweise Tabletten, Würfel, Kugeln und dergleichen ein. Besonders bevorzugt ist die Verwendung als Sprengmittel für Reinigungsmittelformulierungen, Waschmittelformulierungen, Fleckensalze, Wasserenthärter in Tabletten- oder Würfelform.The invention includes the use of the compacted granules as disintegrating agents for molded articles, for example tablets, cubes, spheres and the like. Particularly preferred is the use as a disintegrant for detergent formulations, detergent formulations, stain salts, water softeners in tablet or cube form.
Die erfindungsgemäßen Sprengmittelgranulate sind in den Formkörpern in Mengen von 0,5 Gew.% bis 15 Gew.% vorzugsweise 3 Gew.% bis 8 Gew.% und besonders bevorzugt 4 Gew.% bis 7 Gew.% enthalten.The disintegrant granules according to the invention are present in the shaped bodies in amounts of 0.5% by weight to 15% by weight, preferably 3% by weight to 8% by weight and more preferably 4% by weight to 7% by weight.
Die erfindungsgemäßen Formkörper weisen eine ausreichende Stabilität und Festigkeit auf, und ermöglichen eine sichere Handhabung, Verpackung und Lagerung. Bei Kontakt mit Wasser sollen sie jedoch rasch zerfallen, so daß die Bestandteile die gewünschte Wirkung entfalten können. Eine ausreichende Stabilität gegen mechanische Einwirkungen ist für Formkörper ab einer Bruchfestigkeit von 50 N gegeben. Die erfindungsgemäßen Granulate verleihen diesen hochverdichteten Formkörpern eine Zerfalls- und Auflösecharakteristik wie sie sonst nur bei Formkörpern niedriger Festigkeit gegeben ist.The moldings of the invention have sufficient stability and strength, and allow safe handling, packaging and storage. On contact with water, however, they should disintegrate rapidly, so that the components can develop the desired effect. A sufficient stability against mechanical effects is given for moldings from a breaking strength of 50 N. The granules according to the invention impart to these high-density moldings a decomposition and dissolution characteristic which is otherwise only given in the case of moldings of low strength.
Die Formkörper für Waschmittelformulierungen enthalten in der Regel Gerüststoffe, Bleichmittel und Bleichaktivatoren, Tenside, Tablettierhilfsmittel, Sprengmittel und weitere übliche Zusätze und Hilfsstoffe.The tablets for laundry detergent formulations generally contain builders, bleaches and bleach activators, surfactants, tableting aids, disintegrants and other customary 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.Suitable builders are polyphosphates, pyrophosphates, metaphosphates or phosphonates, sheet silicates, amorphous silicates, amorphous disilicates and zeolite. Other constituents of the builder system may include fillers such as alkali carbonates, bicarbonates z. For example, sodium carbonate or sodium bicarbonate, sesquiocarbonates, sodium sulfate, magnesium sulfate, or citrate, citric acid, succinic acid, tartaric acid and malic acid. Frequently used as Hilfsgerüststoff co-builders and dispersants. Such co-builders or dispersants may 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. 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 195 16 957 A).Copolymers of (meth) acrylic acid and maleic acid, terpolymers and quattropolymers of (meth) acrylic acid, maleic acid, vinyl alcohol and sulfo-containing vinyl compounds can also be used. Particular preference is also ter- and quattropolymere polycarboxylates prepared from (meth) acrylic acid, maleic acid and vinyl alcohol or vinyl alcohol derivatives (as described in DE 43 00 772 C2) or those of (meth) acrylic acid, 2-alkylallylsulfonic and sugar derivatives (as described in DE 42 21 381 C1) or those of (meth) acrylic acid, maleic acid, vinyl alcohol derivatives and monomers with sulfonic acid groups (described in DE 195 16 957 A).
Als weiteren Bestandteile werden Polyethylengkykol und/oder Polypropylenglykol mit einem Molekulargewicht von 900 bis 30.000 verwendet, sowie carboxylierte Polysaccharide, Polyaspartate und Polyglutamat. Auch Mischungen mit verschiedenen organischen Buildern wie z.B. Zitronensäure sind möglich.Other constituents used are polyethylene glycol and / or polypropylene glycol having a molecular weight of from 900 to 30,000, and carboxylated polysaccharides, polyaspartates and polyglutamate. Also mixtures with various organic builders such as e.g. Citric acid is possible.
Übliche zu verwendende 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.% . 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).Typical bleaching agents to be used 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 of bleaching agents in tablets is preferably 10-60% by weight and in particular 15-50% by weight. In order to achieve a good bleaching effect when washing below 60 ° C and below, activators can be incorporated. Suitable bleach activators are the H 2 O 2 organic peracids forming N-acyl and O-acyl compounds, preferably N, N'-tetraacylated diamines, carboxylic anhydrides and esters of polyols such as glucose pentaacetate. Further, acetylated mixtures of sorbitol and mannitol may be used. Particularly suitable as bleach activators are N, N, N ', N'-tetraacetylethylenediamine (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 may also be present in detergent formulations, for example quaternary ammonium compounds having C 8 -C 16 N-alkyl or N-alkenyl groups and N-substituents such as methyl, hydroxyethyl or hydroxypropyl groups.
Auch Tablettierhilfsmittel werden gegebnenfalls eingesetzt, beispielsweise Polyalkylenglykole und Magnesiumstearate.Tableting aids are also used if appropriate, for example polyalkylene glycols and magnesium stearates.
Beispiele für weitere übliche Waschmittelzusätze und Hilfsstoffe sind Enzyme, Magnesiumsilikate, Aluminiumaluminate, Benzotriazol, Glycerin, Magnesiumstearat, Polyalkylenglykole, Hexametaphosphat, Phosphonate, Bentonite, Soil Release Polymere, Carboxymethylcellulosen.Examples of further customary detergent additives and auxiliaries are enzymes, magnesium silicates, aluminum aluminates, benzotriazole, glycerol, magnesium stearate, polyalkylene glycols, hexametaphosphate, phosphonates, bentonites, soil release polymers, carboxymethylcelluloses.
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 embodiment of detergent formulations generally contain as builders polyphosphates, pyrophosphates, metaphosphates or phosphonates, sheet silicates, amorphous silicates, amorphous disilicates and zeolites, and fillers such as sodium carbonate, sodium sulfate, magnesium sulfate, sodium bicarbonate, citrate and citric acid, succinic acid, tartaric acid and malic acid , Frequently co-builders and dispersants are used as auxiliary builder. Such co-builders or dispersants may 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.%.Typical bleaching agents are sodium perborate tetrahydrate and sodium perborate monohydrate, sodium percarbonate, peroxypyrophosphates, citrate perhydrates, as well as H 2 O 2 -forming peracidic salts, peracids, such as perbenzoates, peroxyphthalates, diperazelaic acid and diperdodecanedioic acids. The content in the tablets is preferably 10-60% by weight, and more preferably 15-50% by weight.
Schaumarme nichtionische Tenside vom Typ Polyalkylenglykol und Alkylpolyglucoside werden ebenfalls eingesetzt.Low-foaming nonionic surfactants of the type polyalkylene glycol and alkyl polyglucosides are also used.
Beispiele für weitere übliche Reinigungsmittelzusätze und Hilfsstoffe sind auch hier Enzyme, Magnesiumsilikate, Aluminiumaluminate, Benzotriazol, Glycerin, Magnesiumstearat, Polyalkylenglykole, Hexametaphosphat sowie Phosphonate.Examples of other customary detergent additives and auxiliaries are also here enzymes, magnesium silicates, aluminum aluminates, benzotriazole, glycerol, magnesium stearate, polyalkylene glycols, hexametaphosphate and 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 generally consist of builders such as phyllosilicates, amorphous silicates, amorphous disilicates and zeolites, as well as fillers such as sodium carbonate, sodium sulfate, magnesium sulfate, sodium bicarbonate, citrate and citric acid. Frequently co-builders and dispersants are used as auxiliary builder. Such co-builders or dispersants may be polyacrylic acids or copolymers with polyacrylic acid and its sodium salts.
Schaumarme nichtionische Tenside vom Typ Polyalkylenglykol und Alkylpolyglucoside werden ebenfalls eingesetzt.Low-foaming nonionic surfactants of the type polyalkylene glycol and alkyl polyglucosides are also used.
Beispiele für weitere übliche Waschmittelzusätze und Hilfsstoffe sind Magnesiumsilikate, Polyalkylenglykole und Phosphonate.Examples of further customary detergent additives and auxiliaries are magnesium silicates, polyalkylene glycols and phosphonates.
In einer bevorzugten Ausführungsforme ist es mit den erfindungsgemäßen Sprengmittelgranulaten möglich, Waschmitteltabletten mit Zerfallszeiten von bis zu 15 sec bei einer Tablettenbruchfestigkeit von bis zu 80 N herzustellen.In a preferred embodiment, it is possible with the disintegrant granules according to the invention to produce detergent tablets having disintegration times of up to 15 seconds with a tablet breaking strength of up to 80 N.
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 will be explained in more detail with reference to embodiments. All data are by weight unless otherwise indicated in individual cases.
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 wird destilliertes Wasser verwendet.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 dipped 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 drip. The bag is weighed and determined from the difference in weight of a wet bag with and without granules, the water absorption. Distilled water is used for the determination.
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 70 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 rate and the swelling height under load, 3.00 g of granules are placed in a cylindrical plastic vessel with an inner diameter of 60 mm and covered with a water-permeable nonwoven. The layer thickness of the granules is depending on the bulk density 1- 3 mm. A movable bored punch weighing 58 grams is placed on the web and connected to a path measuring instrument which records the travel of the punch as a function of time. By adding 70 ml of water, the granules are brought to swell and thereby determined displacement of the punch (path length) is determined as a function of time and graphically evaluated.
Die Bestimmung der spezifischen Porosität des Sprengmittelgranulates erfolgt mittels einer bekannten Standardmethode zur Bestimmung des Maßes der Porosität von Feststoffen. Prinzip der Methode:The specific porosity of the disintegrant granules is determined by means of a known standard method for determining the degree of porosity of solids. Principle of the method:
Der Feststoff wird mit Di-n-butylphthalat (DBP) vollständig getränkt und anschließend die in den Poren aufgenommene Flüssigkeit nach einer definierten Zeit unter definierten Bedingungen durch Zentrifugieren entfernt. Die Menge an absorbiertem DBP gilt als maß für die Porosität des Feststoffes.
Durchführung:
3 g der Probe werden in einen handelsüblichen tarierten Glasfiltertiegel G3 eingewogen und mit 10 ml DBP versetzt. Diese Tiegel stellt man in ein Becherglas, dessen Boden mit Filterpapier ausgelegt ist. Nach genau 5 Minuten werden die Glasfiltertiegel gewogen , anschließend in Tefloneinsätze gestellt und 5 Minuten bei 1800 U/min zentrifugiert. Nach dem Zentrifugieren werden die Tiegel den Tefloneinsätzen entnommen und wiederum gewogen.
Die Porosität wird nach folgender Formel berechnet:
P = Absorptionsvermögen in ml DBP je kg Feststoff (Porosität)
M2 = Gewicht des Tiegels mit feuchter Probe nach Zentrifugieren in g
M1 = Gewicht des Tiegels mit trockener Probe mit Lösungsmittel in g
Dichte = 1,050 g/ml DBP
E = eingewogene Probenmenge in gThe solid is completely impregnated with di-n-butyl phthalate (DBP) and then the liquid absorbed in the pores is removed after a defined time under defined conditions by centrifuging. The amount of absorbed DBP is considered to be the measure of the porosity of the solid.
Execution:
3 g of the sample are weighed into a commercially available tared glass filter crucible G3 and mixed with 10 ml of DBP. These crucibles are placed in a beaker, the bottom of which is laid out with filter paper. After exactly 5 minutes, the glass filter crucibles are weighed, then placed in Teflon inserts and centrifuged for 5 minutes at 1800 rev / min. After centrifuging, the crucibles are removed from the Teflon inserts and weighed again.
The porosity is calculated according to the following formula:
P = Absorptive capacity in ml DBP per kg solid (porosity)
M2 = weight of crucible with moist sample after centrifugation in g
M1 = weight of the crucible with dry sample with solvent in g
Density = 1.050 g / ml DBP
E = weighed sample quantity in g
Eine Wasch-und Reinigungstablette mit einem Gehalt von 5% Sprengmittel wird für den Test eingesetzt. In ein Becherglas werden 500 ml Weichwasser mit einer Temperatur von 23°C gegeben. In 10 cm Höhe wird ein Metallsieb mit einer Maschenweite von 4 mm angebracht. In dem Becherglas wird ein Magnetrührstab mit ca. 200 U/min in Bewegung versetzt und von oben eine Tablette auf das Sieb aufgelegt. Die Zeit vom Beginn der Tablettenzugabe bis zum Zerfall der Tablette wird mit einer Stoppuhr gemessen. Der Zerfall ist erreicht, wenn alle Tablettenteile durch das Sieb gefallen sind.A washing and cleaning tablet containing 5% disintegrant is used for the test. In a beaker 500 ml of soft water at a temperature of 23 ° C are added. At a height of 10 cm, a metal sieve with a mesh size of 4 mm is applied. In the beaker, a magnetic stir bar is set in motion at about 200 rpm and a tablet is placed on top of the sieve from above. The time from the beginning of the tablet addition to the disintegration of the tablet is measured with a stopwatch. Disintegration is achieved when all tablet parts have fallen through the sieve.
In die Einspülschublade der Waschmaschine werden 3 Tabletten hintereinander eingestellt. Die Waschmaschine wird an eine Druckleitung mit 5 bar Stadtwasser angeschlossen und im 60°C-Normalprogramm gestartet. Die Einspülzeit beträgt dabei 30 sec, wobei die Maschine nur einmal Wasser nimmt. Der Versuch wird insgesamt viermal durchgeführt, wobei also 12 Tabletten eingesetzt werden. Nach jedem Einspülvorgang werden die zurückgebliebenen Tabletten gezählt. Die Gesamtmenge an nicht eingespülten Tabletten wird angegeben.In the Einspülschublade the washing machine are set 3 tablets in succession. The washing machine is connected to a pressure line with 5 bar city water and started in the 60 ° C normal program. The flushing time is while 30 sec, the machine takes only once water. The experiment is carried out a total of four times, so that 12 tablets are used. After each flush, the remaining tablets are counted. The total amount of non-flushed tablets is given.
Für die Bestimmung der Tablettenbruchfestigkeit wird der Tablettenbruchfestigkeitstester vom Typ TB30/TBH30MD von der Firma Erweka verwendet. Dabei wird die Bruchfestigkeit mittels eines Dehnungsmeßstreifens mit einer Kraftmeßdose bestimmt. Die Meßgenauigkeit beträgt +/- 1N.
Nach entsprechender Programmierung wird die Tablette in die Meßeinrichtung eingelegt und der Meßvorgang gestartet. Das Gerät zeigt den Wert der Bruchfestigkeit an.For the determination of the tablet breakage strength, the TB30 / TBH30MD tablet breakage resistance tester from Erweka is used. The breaking strength is determined by means of a strain gauge with a load cell. The measuring accuracy is +/- 1N.
After appropriate programming, the tablet is inserted into the measuring device and started the measuring process. The device displays the value of the breaking strength.
In ein 500-ml-Becherglas werden 100g getrocknetes Sprengmittelgranulat mit einer Teilchengröße > 1 mm gegeben. In das Granulat taucht eine Metalldissolver - scheibe mit 3,5 cm Durchmesser ein, die mit einem Rührmotor verbunden ist.
Der Rührmotor wird auf 800 U/min eingestellt und eine Minute gerührt.
Dabei erfährt das Granulat einen mehr oder weniger deutlichen Abrieb.
Nach Ablauf der Zeit wird mittels Siebanalyse der Anteil der Kornfraktion mit < 1 mm bestimmt. Der Anteil < 1 mm wird in Prozent der Gesamtmenge angegeben.Into a 500 ml beaker is added 100 g of dried disintegrant granules having a particle size> 1 mm. The granulate is immersed in a 3.5 cm diameter metal dissolver disc, which is connected to a stirring motor.
The stirring motor is set at 800 rpm and stirred for one minute.
In this case, the granules undergoes a more or less significant abrasion.
After expiry of the time, the fraction of the grain fraction <1 mm is determined by sieve analysis. The fraction <1 mm is given as a percentage of the total quantity.
Die in den Beispielen verwendeten Sprengmittel wurden durch Naßkompaktierung auf einer Pelletierpresse der Firma Amandus Kahl hergestellt. Der Verdichtungsgrad wurde auf 1:3 eingestellt. Der Wassergehalt der Gemische vor der Verdichtung ist der Tabelle 1 zu entnehmen. Nach der Kompaktierung wurden die Granulate auf einem Walzentrockner der Firma Babcok auf die angegebenen Feuchtegehalte getrocknet. Das Vergleichbeispiel V5 wurden auf einer Walzenpresse WP 150 der Alexanderwerke ohne zusätzliches Wasser produziert. Der Preßdruck wurde auf 1,1 t/cm eingestellt. Die Granulate wurden auf einem Reibschnitzler zerkleinert. Die Trocknung erfolgte ebenfalls auf einem Bandtrockner.
Die Granulate weisen Teilchengrößen zwischen 0,3 und 2 mm auf, der Staubanteil unter 0,1 mm ist in der Tabelle angegeben.
The granules have particle sizes between 0.3 and 2 mm, the dust content below 0.1 mm is given in the table.
Als Vergleichsbeispiel V2 wurde eine walzenkompaktierte Cellulose der Firma Degussa AG mit der Handels-Bezeichnung Elcema G 250 verwendet. ( 5% Feuchte, Schüttdichte 400 g/lAs Comparative Example C2, a roll-compacted cellulose from Degussa AG with the trade name Elcema G 250 was used. (5% moisture, bulk density 400 g / l
Beim Vergleich des erfindungsgemäßen Beispiels M2 mit dem Beispiel V2 ergaben sich deutliche Unterschiede in der Flüssigkeitsaufnahme, die durch Kompaktierverfahren und den Feuchtegehalt beim Kompaktieren begründet sind. Mit dem erfindungsgemäßen Feuchtegehalt beim Kompaktieren und Trocknen (M2) ergeben sich 950 ml/kg Aufnahme an DBP, das trockenkompaktierte und damit in der Kapillarstruktur zusammengedrückte Muster (V2) ergab eine Aufnahme von nur 600 ml/kg DBP.When comparing Example M2 of the invention with Example V2, there were significant differences in the liquid absorption, which are due to compacting and the moisture content during compaction. With the moisture content of the compacting and drying (M2) according to the invention, 950 ml / kg uptake of DBP results, the dry-compacted pattern (V2) thus compressed in the capillary structure gave uptake of only 600 ml / kg DBP.
Damit zeigt sich, daß die Aufnahmefähigkeit der erfindungsgemäßen Sprengmittelgranulate gegenüber dem Vergleichsprodukt deutlich erhöht ist.This shows that the absorption capacity of the disintegrant granules according to the invention is significantly increased compared to the comparative product.
Phosphathaltige Waschmitteltablette: Festigkeit der Tablette und Einspültests unter Verwendung der Granulate der vorgenannten Beispiele:
Tabelle 3 zeigt die Festigkeit und die Ergebnisse des Einspültests der einzelnen Waschmitteltabletten bei Verwendung der verschiedenen Sprengmittel:
Tabelle 3 zeigt, daß sowohl die Zusammensetzung als auch bei gleicher Zusammensetzung der Feuchtegehalt des Sprengmittelgranulates einen deutlichen Einfluß auf die Tablettenzerfallszeit haben. Sprengmittel mit dem bevorzugten Gehalt von 3-5 Gew% Wasser wie bei M2 zeigen auch die besten Zerfallszeiten der Tabletten. Werden zusätzlich noch geeignete quellbare Substanzen als Sprengmittelkomponente eingebaut, können die Zerfalleigenschaften noch weiter gesteigert werden.Table 3 shows that both the composition and the same composition of the moisture content of the disintegrant granules have a significant influence on the tablet disintegration time. Disintegrants with the preferred level of 3-5 wt% water as in M2 also show the best disintegration times of the tablets. If, in addition, suitable swellable substances are incorporated as disintegrant component, the disintegration properties can be further increased.
Tabelle 4 zeigt den Einfluß der Lagerzeit ( 4 Wochen bei 40°C/ 60% rel. Luftfeuchte im geschlossenen Behälter) auf das Einspülverhalten von Tabletten mit Sprengmitteln.
Tabelle 4 zeigt, daß der erfindungsgemäße Feuchtigkeitsgehalt im Sprengmittelgranulat zu überlegenen Eigenschaften der damit hergestellten Tabletten im wichtigen Einspültest führt bzw daß die Quellbarkeit mit Werten von 0,9 und höher den Vergleichsprodukten überlegen ist. Tabletten mit erfindungsgemäßem Sprengmittel zeigen eine gute Lagerstabilität. Tabletten mit M3-M6 enthalten neben der Cellulose auch noch Cellulosederivate und weisen dadurch eine nochmals verbesserte Quellkinetik auf.Table 4 shows that the moisture content of the disintegration granules according to the invention leads to superior properties of the tablets produced therewith in the important rinsing test or that the swellability with values of 0.9 and higher is superior to the comparison products. Tablets with inventive disintegrant show good storage stability. Tablets with In addition to cellulose, M3-M6 also contains cellulose derivatives and thus has a further improved swelling kinetics.
Phosphatfreie Waschmitteltablette: Festigkeit der Tablette und Einspültest unter Verwendung eines der Granulate der vorgenannten Beispiele:
Auch hier zeigen die Vergleichsgranulate V1 und V2 deutlich geringere Wirkung als das erfindungsgemäße Produkt aus Beispiel M6/M7. Handelsübliche Tabletten zeigen unterschiedliches Löseverhalten. Tabletten niedriger Festigkeit lösen sich schneller als solche mit hoher Festigkeit.
Das Granulat aus Beispiel M3 führte zu sehr guten Zerfallszeiten von Disilikat-Tabletten.The granules from example M3 led to very good disintegration times of disilicate tablets.
Gepreßte Formkörper mit dem Verwendungszweck als Fleckensalz der folgenden Zusammensetzung:
Wasserenthärter der folgenden Zusammensetzung:
Maschinen-Geschirr-Reiniger der folgenden Zusammensetzung:
Ergebnisse zur Festigkeit und Zerfallszeit der Reinigungstabletten
Die Tablettenzerfallszeit hochverdichteter Tabletten mit erfindungsgemäßem Sprengmittel ist den Vergleichsprodukten überlegen.The tablet disintegration time of highly compressed tablets with inventive disintegrant is superior to the comparison products.
Einfluß eines hohen Tensidgehaltes auf die Eigenschaften des SprengmittelgranulatesInfluence of a high surfactant content on the properties of the disintegrant granules
Ein erfindungsgemäßes Granulat (M2) mit einem Gehalt an nichtionischem Tensid von 0,5 Gew % wird mit einem Granulat der gleichen Rezeptur und
Herstellungstechnologie verglichen, dessen Nio-Tensidgehalt auf 12 Gew% erhöht wurde (V7).
Die folgende Tabelle 11 zeigt die Quellkinetik dieser beiden Granulate nach 3, 5 und 10 Sekunden Quellzeit.
As compared to the preparation technology, the Nio-surfactant content was increased to 12% by weight (V7).
Table 11 below shows the swelling kinetics of these two granules after 3, 5 and 10 seconds of swelling time.
In einem weiteren Test wurde der Abrieb der beiden Muster M2 und V7 verglichen.
Die Ergebnisse machen deutlich, daß Sprengmittelgranulate mit einem Tensidgehalt außerhalb der erfindungsgemäßen Ausführung sowohl im Quellverhalten als auch in der Abriebfestigkeit deutlich schlechtere Eigenschaftswerte aufweisen.The results make it clear that disintegrant granules having a surfactant content outside the inventive embodiment have significantly poorer property values both in the swelling behavior and in the abrasion resistance.
Claims (25)
- Compacted disintegrant granular material for tablets, consisting of:A) 60 to 99 % by weight of a water-insoluble cellulose which is swellable in water and optionally other modified water-swellable polysaccharide derivatives,B) 1 to 40 % by weight of at least one polymeric binder in the form of a polymer or a copolymer of (meth)acrylic acid and/or salts thereof,C) 0 to 7 % by weight of at least one liquid surfactant which forms a gel with water,wherein the sum of A), B) and C) amounts to 100 % by weight, characterised in that the disintegrant granular material has a moisture content of from 2 to 8 % by weight.
- Disintegrant granular material according to claim 1, characterised in that it contains from 1 to 15 % by weight of polymeric binder and from 0.1 to 3.5 % by weight of surfactant.
- Disintegrant granular material according to either claim 1 or claim 2, characterised in that the surfactants are non-ionic and/or anionic and/or amphoteric surfactants.
- Disintegrant granular material according to any one of claims 1 to 3, characterised in that the surfactants are selected from fatty alcohol ethoxylates preferably having from 3 to 15 mol of ethylene oxide, fatty alcohol sulphates, linear alkylbenzenesulphonates, alkyl ether sulphates, alkylpolyglycosides, and mixtures thereof.
- Disintegrant granular material according to any one of claims 1 to 4, characterised in that it contains up to 10 % by weight of crosslinked, finely-divided copolymers of (meth)acrylic acid.
- Disintegrant granular material according to any one of claims 1 to 5, characterised in that it contains from 0 to 30 % by weight of at least one polymer surfactant.
- Compacted disintegrant granular material for tablets, consisting ofA) 60 to 99 % by weight of water-insoluble cellulose which is swellable in water and optionally other modified water-swellable polysaccharide derivatives,D) 1 to 40 % by weight of at least one polymeric binderwherein the sum of A) and D) amounts to 100 % by weight, characterised in that the disintegrant granular material has a moisture content of from 2 to 8 % by weight and the polymeric binder D) is a polymer surfactant selected from graft polymers with alkoxylated fatty alcohol or carboxylate-containing polymers with methoxyalkyleneoxide monomer units, maleic acid/vinylether/longer-chain fatty amine-copolymers, semi-amides of maleic acid copolymers and copolymers of acetyl acid with long-chain acrylates.
- Disintegrant granular material according to any one of claims 1 to 7, characterised in that it has a moisture content of from 2.5 to 7 % by weight, preferably from 3 to 5 % by weight.
- Disintegrant granular material according to any one of claims 1 to 8, characterised in that from 0.1 to 85 % by weight, preferably from 5 to 50 % by weight of water-swellable polysaccharide derivatives are present, based on the cellulose.
- Disintegrant granular material according to any one of claims 1 to 9, characterised in that the water-swellable polysaccharide derivatives are modified anionically and/or non-ionically and/or physically and/or in a crosslinked manner and are derived from cellulose, starch and polygalactomannan.
- Disintegrant granular material according to any one of claims 1 to 10, characterised in that carboxymethylcellulose, carboxymethylstarch, hydroxyalkylcellulose, hydroxyalkylstarch, alkylcellulose, guar meal or locust bean seed is used.
- Disintegrant granular material according to any one of claims 1 to 11, characterised in that at least one regenerated cellulose is used.
- Disintegrant granular material according to any one of claims 1 to 12, characterised in that prior to compacting, the celluloses and polysaccharide derivatives are present in the form of finely-divided particles having particle sizes of between 0.03 and 3 mm.
- Disintegrant granular material according to any one of claims 1 to 13, characterised in that the polymers or copolymers of (meth)acrylic acid are selected from the group of homopolymers of (meth)acrylic acid, from the group of copolymers with the following monomer components: ethylenically unsaturated dicarboxylic acids and/or the anhydrides thereof and/or ethylenically unsaturated sulphonic acids and/or acrylic esters and/or vinyl esters and/or vinyl ethers or saponification products of vinyl ethers and/or crosslinkers and/or graft base materials based on polyhydroxy compounds.
- Disintegrant granular material according to any one of claims 1 to 14, characterised in that the particle size is from 0.05 to 3.0 mm, preferably from 0.1 to 1.5 mm.
- Disintegrant granular material according to any one of claims 1 to 15, characterised in that said granular material has a porosity of from 800 to 1000 ml/kg.
- Disintegrant granular material according to any one of claims 1 to 16, characterised in that it contains up to 10 % by weight, preferably up to 8 % by weight of a fine dust content of less than 0.1 mm.
- Disintegrant granular material according to any one of claims 1 to 17, characterised in that it has a bulk density of from 100 g/l to 500 g/l, preferably from 150 g/l to 450 g/l and most preferably from 250 g/l to 400 g/l.
- Disintegrant granular material according to any one of claims 6 to 18, characterised in that the polymer surfactants contain akyleneoxide units in the polymer skeleton.
- Process for producing the disintegrant granular materials according to any one of claims 1 to 19 by mixing the components to be granular materials to form a premix and subsequently compacting the premix, characterised in that a moisture content of from 10 to 80 % by weight is adjusted in the premix and after compacting, the premix is dried to a moisture content of from 2 to 8 % by weight and optionally the desired grain size distribution is adjusted by milling and screening.
- Process according to claim 20, characterised in that compacting is carried out using rollers under friction, roller or cube presses, extruders or by ring matrix presses or pelletising presses.
- Process according to either claim 20 or claim 21, characterised in that compacting is carried out at a moisture content of from 20 to 40 % by weight using ring matrix or pelletising presses.
- Process according to any one of claims 20 to 22, characterised in that the moisture content after drying is adjusted to 2.5 to 7 % by weight, preferably to 3 to 5 % by weight.
- Use of a disintegrant granular material according to any one of claims 1 to 19 as a disintegrant for tablets, in particular for washing tablets, cleaning tablets, water softening tablets and stain removal salt tablets.
- Use of a disintegrant granular material according to any one of claims 1 to 19 as a disintegrant in detergent tablets having a breaking strength of up to 80 N and a tablet disintegration time of at most of 15 seconds.
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES99106370T ES2270547T3 (en) | 1999-03-29 | 1999-03-29 | COMPACTED DISGREGANT GRANULATE FOR COMPRESSED MOLDING BODIES; ITS MANUFACTURE AND USE. |
PT99106370T PT1043391E (en) | 1999-03-29 | 1999-03-29 | High density disintegrating granulate for tablets; method for making it and its use |
DE59913705T DE59913705D1 (en) | 1999-03-29 | 1999-03-29 | Compacted disintegrant granules for pressed moldings; its production and use |
EP99106370A EP1043391B1 (en) | 1999-03-29 | 1999-03-29 | High density disintegrating granulate for tablets; method for making it and its use |
AT99106370T ATE334187T1 (en) | 1999-03-29 | 1999-03-29 | COMPACTED EXPLOSIVE GRANULES FOR PRESSED MOLDINGS; ITS PRODUCTION AND USE |
US09/534,455 US6303560B1 (en) | 1999-03-29 | 2000-03-27 | Compacted disintegrant granulate for compression-molded articles, its production and its use |
PL339271A PL196418B1 (en) | 1999-03-29 | 2000-03-28 | Granulated concentrate of a bursting substances for compacted formpieces, method of obtaining such concentrate and application thereof |
CZ20001116A CZ293387B6 (en) | 1999-03-29 | 2000-03-28 | Compacted disintegrant granulate for tablets, process for its preparation and use |
HU0001329A HU228596B1 (en) | 1999-03-29 | 2000-03-29 | Densifyed granulate of substance enchancing disintegration for tablets, method for its producing and use |
TR2000/00832A TR200000832A3 (en) | 1999-03-29 | 2000-03-29 | Condensed explosive grains for compressed mold bodies. |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99106370A EP1043391B1 (en) | 1999-03-29 | 1999-03-29 | High density disintegrating granulate for tablets; method for making it and its use |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1043391A1 EP1043391A1 (en) | 2000-10-11 |
EP1043391B1 true EP1043391B1 (en) | 2006-07-26 |
Family
ID=8237874
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99106370A Expired - Lifetime EP1043391B1 (en) | 1999-03-29 | 1999-03-29 | High density disintegrating granulate for tablets; method for making it and its use |
Country Status (10)
Country | Link |
---|---|
US (1) | US6303560B1 (en) |
EP (1) | EP1043391B1 (en) |
AT (1) | ATE334187T1 (en) |
CZ (1) | CZ293387B6 (en) |
DE (1) | DE59913705D1 (en) |
ES (1) | ES2270547T3 (en) |
HU (1) | HU228596B1 (en) |
PL (1) | PL196418B1 (en) |
PT (1) | PT1043391E (en) |
TR (1) | TR200000832A3 (en) |
Families Citing this family (44)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19709991C2 (en) * | 1997-03-11 | 1999-12-23 | Rettenmaier & Soehne Gmbh & Co | Detergent compact and process for its manufacture |
DE19710254A1 (en) * | 1997-03-13 | 1998-09-17 | Henkel Kgaa | Shaped or active cleaning moldings for household use |
DE19936235A1 (en) * | 1999-08-05 | 2001-02-15 | Benckiser Nv | Manufacturing process for molded parts and mold for use therein |
DE19953792A1 (en) * | 1999-11-09 | 2001-05-17 | Cognis Deutschland Gmbh | Detergent tablets |
DE19953793A1 (en) * | 1999-11-09 | 2001-05-17 | Cognis Deutschland Gmbh | Surfactant granules with an improved dissolution rate |
DE10005576A1 (en) * | 2000-02-09 | 2001-08-23 | Reckitt Benckiser Nv | Detergent tablet for use as, e.g. dishwasher detergent, experiences buoyancy upon contact with water reservoir that it at least remains suspended in the water |
EP1167433A1 (en) * | 2000-06-19 | 2002-01-02 | Mifa Ag Frenkendorf | Product based on polysaccharides coprocessed with an insoluble disintegrant, process for its preparation and the use |
AU2002223575A1 (en) * | 2000-10-18 | 2002-04-29 | Unilever Plc | Cleaning compositions |
WO2002033037A1 (en) * | 2000-10-18 | 2002-04-25 | The Procter & Gamble Company | Detergent tablet |
ATE312902T1 (en) * | 2000-10-31 | 2005-12-15 | Procter & Gamble | LAUNDRY DETERGENT |
EP1201743A1 (en) * | 2000-10-31 | 2002-05-02 | The Procter & Gamble Company | Detergent compositions |
WO2002042404A1 (en) * | 2000-11-24 | 2002-05-30 | Unilever N.V. | Cleaning tablets |
DE60137258D1 (en) * | 2000-12-21 | 2009-02-12 | Unilever Nv | CLEANING COMPOSITIONS |
DE10105801B4 (en) | 2001-02-07 | 2004-07-08 | Henkel Kgaa | Detergents and cleaning agents comprising fine microparticles with detergent components |
DE50304955D1 (en) † | 2003-06-28 | 2006-10-19 | Dalli Werke Gmbh & Co Kg | Alpha olefin and alpha olefin cellulose granules as disintegrants |
US7425595B2 (en) * | 2003-12-15 | 2008-09-16 | Absorbent Technologies, Inc. | Superabsorbent polymer products including a beneficial additive and methods of making and application |
US7423090B2 (en) * | 2003-12-15 | 2008-09-09 | Absorbent Technologies, Inc. | Methods of making and using a superabsorbent polymer product including a bioactive, growth-promoting additive |
US20050215463A1 (en) * | 2004-03-29 | 2005-09-29 | Nippon Shokubai Co., Ltd. | Detergent and fabric care additive containing carboxylic acid polymer |
EP1781709A4 (en) * | 2004-08-27 | 2011-07-06 | Absorbent Technologies Inc | Superabsorbent polymers in agricultural applications |
US20070167330A1 (en) * | 2006-01-17 | 2007-07-19 | Savich Milan H | Superabsorbent polymer applicator |
US7607259B2 (en) * | 2006-01-17 | 2009-10-27 | Absorbent Technologies, Inc. | Superabsorbent polymer root dip |
US20070163172A1 (en) * | 2006-01-17 | 2007-07-19 | Savich Milan H | Biodegradable mat containing superabsorbent polymers |
CN104817704B (en) * | 2006-05-12 | 2018-05-22 | 住友精化株式会社 | The manufacturing method and granulated carboxyl group-containing polymer particle of granulated carboxyl group-containing polymer particle |
US8674021B2 (en) | 2006-07-21 | 2014-03-18 | Akzo Nobel N.V. | Sulfonated graft copolymers |
US8703204B2 (en) | 2007-05-03 | 2014-04-22 | Bend Research, Inc. | Nanoparticles comprising a cholesteryl ester transfer protein inhibitor and anon-ionizable polymer |
US8309129B2 (en) | 2007-05-03 | 2012-11-13 | Bend Research, Inc. | Nanoparticles comprising a drug, ethylcellulose, and a bile salt |
US9545384B2 (en) | 2007-06-04 | 2017-01-17 | Bend Research, Inc. | Nanoparticles comprising drug, a non-ionizable cellulosic polymer and tocopheryl polyethylene glocol succinate |
EP2162120B1 (en) | 2007-06-04 | 2016-05-04 | Bend Research, Inc | Nanoparticles comprising a non-ionizable cellulosic polymer and an amphiphilic non-ionizable block copolymer |
EP2231169B1 (en) | 2007-12-06 | 2016-05-04 | Bend Research, Inc. | Pharmaceutical compositions comprising nanoparticles and a resuspending material |
EP2240162A4 (en) | 2007-12-06 | 2013-10-09 | Bend Res Inc | Nanoparticles comprising a non-ionizable polymer and an amine-functionalized methacrylate copolymer |
EP2108676B1 (en) | 2008-04-03 | 2017-12-27 | OrganoClick AB | Crosslinked paper based material |
BR112012001604B1 (en) | 2009-07-31 | 2019-12-17 | Akzo Nobel Nv | personal care composition |
EP2380960A1 (en) * | 2010-04-19 | 2011-10-26 | The Procter & Gamble Company | Detergent composition |
EP2441825A1 (en) * | 2010-10-14 | 2012-04-18 | Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House | Process for preparing laundry detergent particles |
US9596801B2 (en) | 2010-10-25 | 2017-03-21 | Vjs Investments Limited | Superabsorbent polymer seed coatings and associated methods |
US8636918B2 (en) | 2011-08-05 | 2014-01-28 | Ecolab Usa Inc. | Cleaning composition containing a polysaccharide hybrid polymer composition and methods of controlling hard water scale |
US8853144B2 (en) | 2011-08-05 | 2014-10-07 | Ecolab Usa Inc. | Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage |
US8841246B2 (en) | 2011-08-05 | 2014-09-23 | Ecolab Usa Inc. | Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage |
US8679366B2 (en) | 2011-08-05 | 2014-03-25 | Ecolab Usa Inc. | Cleaning composition containing a polysaccharide graft polymer composition and methods of controlling hard water scale |
MX2014005089A (en) | 2011-11-04 | 2014-08-08 | Akzo Nobel Chemicals Int Bv | Graft dendrite copolymers, and methods for producing the same. |
BR112014008874A2 (en) | 2011-11-04 | 2017-04-25 | Akzo Nobel Chemicals Int Bv | dendrite hybrid copolymer composition |
US8945314B2 (en) | 2012-07-30 | 2015-02-03 | Ecolab Usa Inc. | Biodegradable stability binding agent for a solid detergent |
DE102013225169A1 (en) * | 2013-12-06 | 2015-06-11 | Henkel Ag & Co. Kgaa | Blondiermitteltabletten |
US9365805B2 (en) | 2014-05-15 | 2016-06-14 | Ecolab Usa Inc. | Bio-based pot and pan pre-soak |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4404279A1 (en) * | 1994-02-10 | 1995-08-17 | Henkel Kgaa | Tablet with builder substances |
DE19709991C2 (en) * | 1997-03-11 | 1999-12-23 | Rettenmaier & Soehne Gmbh & Co | Detergent compact and process for its manufacture |
DE19710254A1 (en) * | 1997-03-13 | 1998-09-17 | Henkel Kgaa | Shaped or active cleaning moldings for household use |
DE19722832A1 (en) * | 1997-05-30 | 1998-12-03 | Henkel Kgaa | Detergent tablets with improved dissolving properties |
DE29724283U1 (en) * | 1997-06-03 | 2000-10-05 | Henkel KGaA, 40589 Düsseldorf | Aid granules for washing and cleaning active moldings |
GB9711831D0 (en) * | 1997-06-06 | 1997-08-06 | Unilever Plc | Cleaning compositions |
DE19739384A1 (en) * | 1997-09-09 | 1999-03-11 | Henkel Kgaa | Detergent tablets with improved solubility |
-
1999
- 1999-03-29 AT AT99106370T patent/ATE334187T1/en active
- 1999-03-29 EP EP99106370A patent/EP1043391B1/en not_active Expired - Lifetime
- 1999-03-29 ES ES99106370T patent/ES2270547T3/en not_active Expired - Lifetime
- 1999-03-29 PT PT99106370T patent/PT1043391E/en unknown
- 1999-03-29 DE DE59913705T patent/DE59913705D1/en not_active Expired - Lifetime
-
2000
- 2000-03-27 US US09/534,455 patent/US6303560B1/en not_active Expired - Lifetime
- 2000-03-28 CZ CZ20001116A patent/CZ293387B6/en not_active IP Right Cessation
- 2000-03-28 PL PL339271A patent/PL196418B1/en unknown
- 2000-03-29 TR TR2000/00832A patent/TR200000832A3/en unknown
- 2000-03-29 HU HU0001329A patent/HU228596B1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
TR200000832A2 (en) | 2000-10-23 |
HU228596B1 (en) | 2013-04-29 |
PL339271A1 (en) | 2000-10-09 |
PL196418B1 (en) | 2007-12-31 |
DE59913705D1 (en) | 2006-09-07 |
ES2270547T3 (en) | 2007-04-01 |
ATE334187T1 (en) | 2006-08-15 |
CZ293387B6 (en) | 2004-04-14 |
EP1043391A1 (en) | 2000-10-11 |
CZ20001116A3 (en) | 2003-03-12 |
HUP0001329A3 (en) | 2002-07-29 |
HUP0001329A2 (en) | 2001-02-28 |
PT1043391E (en) | 2006-12-29 |
TR200000832A3 (en) | 2000-10-23 |
US6303560B1 (en) | 2001-10-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1043391B1 (en) | High density disintegrating granulate for tablets; method for making it and its use | |
EP1004656B1 (en) | Densified granulate, its manufacturing process and its use as disintegrant for compacted mouldings | |
EP1004661A1 (en) | High density granule, method for production thereof, and its use as disintegrant in tablets | |
EP0966518B1 (en) | Household detergent or cleaning action shaped bodies | |
DE69819542T2 (en) | CLEANING SUPPLIES | |
DE69109192T2 (en) | Detergent compositions. | |
EP1036839A2 (en) | Tablets and particulate detergents comprising cross-linked polyvinylpyrrolidone and its use | |
EP1043389B1 (en) | Detergent tablets containing a granular disintegrant | |
EP1007616B1 (en) | Additive granules for moulded bodies having a detergent and cleaning action | |
EP1263814B1 (en) | Used of cross-linked polyvinylpyrrolidone as a disintegrant in compact, particulate detergents and cleaning agents | |
EP1043388B1 (en) | Machine dishwashing tablets containing a granular disintegrant | |
EP1083216A2 (en) | Cogranulates comprising layered alkali metal silicates and disintegrants | |
DE69803832T3 (en) | DETERGENT COMPOSITIONS | |
DE69914172T2 (en) | Coated detergent in tablet form | |
DE69829044T2 (en) | Detergent tablet with high mechanical and solvent properties | |
DE60105842T2 (en) | CLEANING COMPOSITIONS | |
WO2000031231A1 (en) | Additive granule for moulded bodies having a detergent and cleaning action | |
DE29723656U1 (en) | Shaped or active cleaning moldings for household use | |
DE60224007T2 (en) | CLEANING COMPOSITIONS | |
DE60110251T2 (en) | CLEANING TABLETS | |
DE69901873T3 (en) | Production process for detergent tablet | |
WO2000042161A1 (en) | Additive granules for moulded bodies having detergent and cleaning action | |
DE29723655U1 (en) | Shaped or active cleaning moldings for household use | |
DE29723652U1 (en) | Shaped or active cleaning moldings for household use | |
DE29723653U1 (en) | Shaped or active cleaning moldings for household use |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20000121 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
AKX | Designation fees paid |
Free format text: AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
AXX | Extension fees paid |
Free format text: AL PAYMENT 20010411;LT PAYMENT 20010411;LV PAYMENT 20010411;MK PAYMENT 20010411;RO PAYMENT 20010411;SI PAYMENT 20010411 |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: DALLI-WERKEWAESCHE-UND KOERPERPFLEGE GMBH & CO.K |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: DALLI-WERKE GMBH & CO. KG |
|
17Q | First examination report despatched |
Effective date: 20050506 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK RO SI |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20060726 Ref country code: IE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060726 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060726 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REF | Corresponds to: |
Ref document number: 59913705 Country of ref document: DE Date of ref document: 20060907 Kind code of ref document: P |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061026 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061026 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20061027 |
|
REG | Reference to a national code |
Ref country code: GR Ref legal event code: EP Ref document number: 20060403602 Country of ref document: GR |
|
REG | Reference to a national code |
Ref country code: PT Ref legal event code: SC4A Free format text: AVAILABILITY OF NATIONAL TRANSLATION Effective date: 20061024 |
|
LTIE | Lt: invalidation of european patent or patent extension |
Effective date: 20060726 |
|
ET | Fr: translation filed | ||
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2270547 Country of ref document: ES Kind code of ref document: T3 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20070427 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070331 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070331 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070331 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070329 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060726 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 59913705 Country of ref document: DE Representative=s name: FLEISCHER, ENGELS & PARTNER MBB, PATENTANWAELT, DE |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 18 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GR Payment date: 20170314 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PT Payment date: 20170323 Year of fee payment: 19 Ref country code: AT Payment date: 20170322 Year of fee payment: 19 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20180321 Year of fee payment: 20 Ref country code: DE Payment date: 20180302 Year of fee payment: 20 Ref country code: NL Payment date: 20180321 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20180321 Year of fee payment: 20 Ref country code: FR Payment date: 20180323 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20180427 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20180327 Year of fee payment: 20 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 334187 Country of ref document: AT Kind code of ref document: T Effective date: 20180329 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20181003 Ref country code: PT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20181001 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180329 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R071 Ref document number: 59913705 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MK Effective date: 20190328 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 Expiry date: 20190328 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20190328 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MK Effective date: 20190329 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20190408 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20201204 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20190330 |