EP1043389A1 - Sprengmittelgranulat enthaltende Waschmitteltabletten - Google Patents
Sprengmittelgranulat enthaltende Waschmitteltabletten Download PDFInfo
- Publication number
- EP1043389A1 EP1043389A1 EP99106369A EP99106369A EP1043389A1 EP 1043389 A1 EP1043389 A1 EP 1043389A1 EP 99106369 A EP99106369 A EP 99106369A EP 99106369 A EP99106369 A EP 99106369A EP 1043389 A1 EP1043389 A1 EP 1043389A1
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- EP
- European Patent Office
- Prior art keywords
- weight
- water
- granules
- washing
- acid
- 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.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
- C11D17/0078—Multilayered tablets
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
- C11D17/0086—Laundry tablets
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
Definitions
- the invention is directed to pressed molded articles of washing and or Detergent compositions which, due to the contained explosive granules, which absorbs water particularly well while increasing the volume and passes on to the inside, quickly disintegrate on contact with water.
- Disintegrants for tablets or granules are auxiliary substances that disintegrate tablets or granules in contact with liquids, in particular Influence water positively.
- the decay of Tablets in large parts and then a disintegration into smaller ones Particles are caused and accelerated.
- inorganic and organic disintegrants for tablets are Substances known, for example inorganic substances such as bentonites, also persalts, acetates, alkali carbonates / hydrogen carbonates and citric acid.
- organic compounds include starch, modified Starch and starch degradation products, cellulose, cellulose ethers, such as Methyl cellulose hydroxypropyl cellulose and carboxymethyl cellulose, poly (meth) acrylates, Polyvinyl pyrrolidone and cross-linked polyvinyl pyrrolidone, Alginates, gelatin and pectins.
- an explosive granulate and its use in washing or cleaning-active moldings such as tablets, known a high adsorption capacity for water and a grain size distribution in which at least 90% by weight has a particle size of at least 0.2 mm and a maximum of 3 mm.
- the granules preferably contain 25-100% by weight of disintegrants, such as starch, starch derivatives, cellulose, cellulose derivatives, e.g. microcrystalline cellulose, CMC, MC, alginic acid, carboxylmethylamylopectin, Polyacrylic acid, polyvinyl pyrrolidone and polyvinyl polypyrrolidone.
- the granules are made by conventional means, such as spray drying, hot steam drying of aqueous preparations or by granulation, pelleting, extrusion or roller compaction powder components.
- the dust-free nature of the explosive granules and the other constituents to be pressed into shaped bodies is shown in this document expressly emphasized.
- the pressed moldings are said to Laboratory test in contact with water without mechanical action quickly disintegrate.
- Citric acid is used as a disintegrant or citrates, bicarbonates and carbonates, bisulfate and percarbonate, microcrystalline Cellulose, sugar, sorbitol or swellable layered silicates called the type of bentonite or smectite.
- the explosives are used in quantities of 1 to 25% by weight as a single raw material or as a compound.
- DE-A-44 04 279 describes the following disintegrants for washing or cleaning tablets: starch, starch derivatives, cellulose, cellulose derivatives, microcrystalline cellulose, salts of polymeric polyacrylates or polymethacrylates, methyl celluloses, hydroxypropyl celluloses or methyl hydroxypropyl celluloses. Acetates or percarbonates are also mentioned as disintegrants.
- the application amounts are up to 15% by weight. Since water-soluble silicates are used as builders, a combination of poly (meth) acrylates and nonionic cellulose ethers can lead to very good results even in quantities of 1% by weight.
- tablet disintegrants are incorporated into the tablet and preferably into the outer hard shell of the tablet.
- Combinations of soluble acids and alkali carbonates are preferably used. Further possible disintegrants can be found in the Handbook of Pharmaceutical Excipients (1986). Examples include: starch (modified starch, sodium starch gluconate), rubber (agar, guar, and others), cellulose, carboxymethyl cellulose, alginates, silicon dioxide, clay, polyvinylpyrrolidone, polysaccharides and ion exchange resins.
- Detergent tablets containing disintegrants are known from EP-A-522 766. that work according to four different mechanisms: swelling, Porosity / capillary action, deformation and chemical reaction. Described starch, starch derivatives, carboxymethyl starch, sodium starch glycolates, Cellulose and cellulose derivatives, carboxymethyl cellulose, cross-linked modified cellulose, microcrystalline cellulose and various organic polymers such as polyethylene glycol, and cross-linked polyvinypyrrolidones and inorganic swelling agents such as bentonites. As well Combinations of organic acids and alkali bicarbonates are mentioned and alkali carbonates.
- EP-A-628 627 describes a water-soluble, water-softening builder in the form of a tablet. Combinations of explosives are used Citric acid and / or partially neutralized polymers and carbonate and / or bicarbonate or an insoluble polyvinylpyrrolidone.
- EP-A-799 886 describes detergent tablets which are used as disintegrants Starch derivatives, cellulose compounds, polyvinylpyrrolidone compounds, Polyvinyl polypyrrolidone compounds, bentonite compounds, alginates May contain gelatin and pectins.
- a polyfunctional organic carboxylic acid such as maleic acid, malic acid, citric acid or tartaric acid together with Carbonates or bicarbonates recommended.
- DE-A-197 09 991 describes a disintegrant for pressed molded articles powder or granular ingredients, this disintegrant compacted, finely divided cellulose material, possibly in combination with Contains surfactants.
- the volume of the disintegrant with a particle size from 0.2 to 6 mm increases on contact with water and thereby unfolds in compressed moldings explosive effect, which leads to the faster disintegration of the Shaped body contributes.
- WO 95/21908 shows an approach in which amorphous, partially crystalline and / or crystalline layered silicates in the tablets are incorporated, and the tablets water up to a maximum Contain an amount that the ingredients can bind as crystal water.
- a treatment of the is also described in WO 98/40463 already mentioned above remaining ingredients of the formulation before mixing with the Disintegrant granules described, with a preferably anhydrous Treatment is pointed out.
- This special type of treatment requires in this case that dust particles below 0.2 mm before mixing with the Disintegrant granules should be separated as completely as possible since it otherwise deterioration of the disintegration properties of the tablets is coming.
- the object of the invention is to produce pressed molded articles of washing and cleaning formulations to provide that no special treatments require before pressing and included when used in dosing chambers domestic or commercial washing machines disintegrate quickly and effectively.
- This object is achieved by washing and / or cleaning compositions in the form of pressed bodies, containing in relatively fine form, as granules and / or cogranulate customary washing and / or cleaning substances, Builders, auxiliaries and additives and 3 to 15% by weight, based on Total weight of the compositions, compacted disintegrant granules from water-soluble, water-swellable cellulose and optionally further modified water-swellable polysaccharide derivatives and one or more polymers / copolymers of (meth) acrylic acid or salts the same, the disintegrant granules having a moisture content of 2 up to 8% by weight and has a specific porosity of 600 to 1000 ml / kg.
- the disintegrant granulate preferably also contains one or more liquid, surfactants that gel or thicken with water.
- the water-swellable cellulose is shaped in the disintegrant granulate of cellulose fibers or microcrystalline cellulose, where the super-molecular structural elements have the form of fibrils, in whose longitudinal direction can alternate between crystalline and amorphous areas. Fibrils of native cellulose have also been particularly suitable proven a maximum length of 300 microns. It can be both microcrystalline as well as amorphous cellulose and mixtures thereof.
- the cellulose preferably has bulk densities of 40 g / l to 300 g / l, very particularly preferably from 65 g / l to 170 g / l. Are already granulated Types used, their bulk density is higher and can vary from 350 g / l to 550 g / l.
- the bulk weights of the cellulose derivatives can range from 50 g / l to 1000 g / l, preferably in the range from 100 g / l and 800 g / l.
- the particle size of the cellulose can be between 30 ⁇ m and 400 ⁇ m, in the case of granulated types, the average particle size is between 350 ⁇ m and 800 ⁇ m.
- the particle size of the cellulose derivatives can be between 30 ⁇ m and 3000 ⁇ m.
- the proportion of cellulose in the disintegrant granulate is between 60 to 99 % By weight, preferably between 60 to 95% by weight.
- the explosive granules are also regenerated celluloses, such as viscose.
- cellulose derivatives that are swellable in water such as cellulose ethers and cellulose esters and mixed modifications the same can also be used.
- Suitable cellulose ethers are e.g. Methyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose, as well modified carboxymethyl cellulose.
- the granules in Water-swellable cellulose derivatives and starch or starch derivatives as well contain 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 alkyl etherified products such as methyl cellulose as well mixed modified celluloses and starches from the above modifications, that leads to networking. Suitable strengths are also cold swelling starches, which are caused by mechanical or degrading reactions Starch grain are formed.
- 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 hydroxy
- this includes swelling starches from extruder and drum drying processes as well as enzymatic, oxidizing or acid-degrading modified products. Contain chemically derivatized starches preferably substituents, which by ester and ether groups in sufficient number are attached to the polysaccharide chains.
- Starches containing ionic substituents such as carboxylate, hydroxyalkyl or modified phosphate groups have proven to be particularly advantageous proven. The has also improved the swelling behavior Proven use of slightly cross-linked starches. Also treated with alkaline Starches can be used because of their good cold water swellability become.
- the combination of cellulose with cellulose derivatives and / or starch and / or starch derivatives proven.
- the quantitative ratios can vary within a wide range the proportion of cellulose derivatives and / or on the combination Starch and / or starch derivatives preferably 0.1 to 85% by weight, particularly preferably 5 to 50% by weight.
- Pure cellulose and cellulose derivatives can also be used together with others modified water-swellable polysaccharide derivatives such as e.g. Strength and / or starch derivatives present in the granules to be used according to the invention his.
- modified water-swellable polysaccharide derivatives such as e.g. Strength and / or starch derivatives present in the granules to be used according to the invention his.
- water-swellable polysaccharide derivatives are polymers of (Meth) acrylic acid or copolymers of (meth) acrylic acid or salts thereof or mixtures of such polymers or copolymers or salts the same with high water absorption capacity in the granules.
- the Polymers can be used as finely divided polymers and / or as soluble polymers be used in aqueous solution.
- Maleic acid or maleic anhydride for example 40 to 90% by weight (Meth) acrylic acid and 60 to 10% by weight of maleic acid or maleic anhydride contain, whose relative molar mass, based on free acids, between 3,000 and 100,000, preferably 3,000 to 70,000 and very particularly preferred Is 5,000 to 50,000.
- Ter- and quattropolymeric polycarboxylates have also proven to be very suitable proven, made from (meth) acrylic acid, maleic acid and vinyl alcohol or vinyl alcohol derivatives, or those of (meth) acrylic acid, ethylenically unsaturated sulfonic acids and sugar derivatives, or such (Meth) acrylic acid, maleic acid, vinyl alcohol derivatives and sulfonic acid groups Monomers Examples of suitable polymers can be found in DE 43 00 772, DE 42 21 371 and WO 95/17444.
- Salt formation is preferably carried out with cations of alkali or ammonia and amines, or their mixtures.
- the polymeric binders are preferred in the manufacture of the granules used in the form of their aqueous solutions, but can also in the form finely divided powder can be used.
- the finely divided polymers / copolymers of (meth) acrylic acid or salts preferably have the same of the cross-linked derivatives described above an average particle size of 45 ⁇ m to 150 ⁇ m. Most notably particle sizes from 45 ⁇ m to 90 ⁇ m are preferred.
- Particles with average particle sizes over 150 ⁇ m show a good one Explosive effects, but are too large after swelling, become when washing filtered off and are visually as particles on the textile after washing visible.
- the proportion of polymers / copolymers in the disintegrant is between 1 and 40% by weight, preferably between 1 and 20% by weight, particularly preferably between 5 and 15% by weight.
- Suitable co-binders that are also surfactant-type are also so-called polymer surfactants. These are reaction products understood, in addition to the typical polymer structures of the aforementioned Binder polymers additional structural elements that develop a surfactant effect exhibit. Examples of these are graft polymers with alkoxylated Fatty alcohol or carboxylate-containing polymers with methoxyalkylene oxide monomer units, also maleic acid / vinyl ether / longer chain fatty amine copolymers as well as half-amides of maleic acid copolymers and copolymers of acrylic acid with long chain acrylates. In a preferred embodiment contain the polymeric surfactants alkylene oxide units.
- the polymer surfactants can also be used alone, i.e.
- the polymer surfactants are used in a proportion of up to 30% by weight contained in the disintegrant granulate as a single component with 1 to 40% by weight, preferably with 5 to 20% by weight.
- the cellulose and optionally other modified water-swellable Polysaccharide derivatives are made with polymers / copolymers from (Meth) acrylic acid or salts thereof combined in the granulate, the weight ratio can be from 50: 1 to 2: 1, preferably from 20: 1 to 5: 1, a weight ratio of 10: 1 is very particularly preferred.
- the cellulose and optionally other modified water-swellable Polysaccharide derivatives are used together with the polymers / copolymers from (Meth) acrylic acid or salts thereof predispersed in water, wet compacted and granulated and then dried. Through the wet granulation and then evaporating the water on you Residual water content of 2 to 8 wt.% Based on the weight of the granules this has a specific porous structure in which the polymer / copolymer of (meth) acrylic acid or its salt on the surface of the Cellulose and optionally other modified water-swellable polysaccharide derivatives is deposited with encrustation of the surface.
- the porous structure results in a particularly favorable absorption behavior for Liquids, in the case of water with rapid volume increase.
- the specific porosity of the The explosive granulate to be used according to the invention is 600 up to 1000 ml / kg, preferably 700 to 900 ml / kg, particularly preferably 850 ml / kg granules.
- the preparation of the disintegrant granules to be used according to the invention is carried out first by mixing the granulate components according to the invention with usual mixing methods.
- mixers from the company Vomm, Lödige, Schugi, Eirich, Henschel or Fukae can be used.
- This first step of mixing and granulating becomes pre-compounds produced by agglomeration processes.
- These pre-compounds form one pourable goods that have a water content between 10 and 80% by weight.
- the required water content in the premix depends on the one used Compression device.
- a water content of at least 10% by weight, preferably 20% by weight is required in order to achieve good compaction. and a high fluid intake in the later dry granulate to guarantee.
- these pre-compounds are mechanically compressed.
- the final compaction is essential for granules.
- the condensing using pressure can be done in several ways.
- the Products can be placed between two pressure surfaces in roller compressors, e.g. smooth or profiled.
- the compactate is ejected as a strand.
- Compaction methods in dies with punches or cushion rollers result in forms of copactate such as tablets or briquettes.
- compaction machines can compactors, extruders, roller or cube presses, but also pelletizing presses are used.
- the water content of 2 to 8% by weight is preferred 2.5 to 7% by weight and particularly preferably 3 to 5% by weight.
- common dryers such as Roller dryer (temperatures e.g. from 95 to 120 ° C) or fluid bed dryer (temperatures e.g. from 70 to 100 ° C).
- the coarse, compacted particles are crushed, e.g. Mills, Carvers or roller mills are suitable.
- the crushing can be done before or after drying.
- the granules to a particle size distribution of 0.05 to 3 mm, preferably 0.1 to 1.5 mm set.
- the removal of dust particles below 0.1 mm can e.g. be carried out with conventional screening devices.
- a disintegrant for pressed molded articles of washing and / or cleaning compositions have grain fractions with average Grain size 0.5 to 3 mm, preferably 1 to 2 mm as special proven suitable. These fractions can be sieved or using a cyclone sifter are obtained, taking care that the proportion of Oversize and fines (undersize) is as low as possible. The shares 5% by weight of oversize or undersize should be used for process engineering reasons based on the weight of the grain fraction. Granules with Larger grain sizes are fed to breaking again, more formed Fine dust is returned to the wet mix and again together with a following wet approach compacted.
- Disintegrant granules have become wet compacting and subsequent Drying proved essential.
- the granulate can contain one or more liquid Water-forming or thickening surfactants selected from the group contain the nonionic, anionic or amphoteric surfactants, wherein nonionic surfactants are particularly preferred.
- liquid surfactants When using liquid surfactants to produce the granulate can also the cellulose and optionally other modified water-swellable Polysaccharide derivatives with the liquid surfactant / surfactant mixture mixed and then the polymer / copolymer of (meth) acrylic acid or its Salt can be mixed in. Then granulate with water usual facilities, the adjustment of a moisture content of 2 to 8% by weight has proven to be particularly favorable, and after known working methods with subsequent compacting by means of rolling mills. The desired grain fractions are made in the same way as for wet granulation described, received. Undersize and oversize are in the granulation stage or crushing stage.
- the structure of the granules obtained in this way is that of wet granulation available similar, but the specific porosity is somewhat lower than with the wet granulation described.
- the water absorption and swelling behavior is very good, however, because water absorption and Volume increases very quickly.
- the nonionic surfactants can be selected from 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, e.g. Sucrose palmitate, pentaerythritol partial ester, which is also ethoxylated can be, as well as alkylphenol polyethylene glycol ethers and phenol polyethylene glycol ethers (if these can be used in the respective country)
- Suitable anionic surfactants are, for example, alkyl sulfates, linear and branched alkylbenzenesulfonates, alkylglycerol ethers, fatty alcohol polyethylene glycol ether sulfates, Paraffin sulfonates, alpha olefin sulfonates, sulfosuccinates, Phosphoric acid esters and fatty alcohol ether carboxylates.
- amphoteric surfactants are selected from coconut fatty acid amidopropyl betaine, modified imidazolines and fatty acid amide derivatives with betaine structure.
- the quantitative ratio of cellulose and any other modified water-swellable polysaccharide derivatives and / or polymers / copolymers of (meth) acrylic acid or salts thereof: surfactant can from 100: 1 to 10: 1. Quantities of 100: 1 are preferred up to 100: 5.
- the disintegrant granules to be used according to the invention have bulk densities from 100 g / l to 500 g / l, preferably 150 g / l to 450 g / l, whole particularly preferably 250 g / l to 400 g / l and are in the moldings in Contain amounts of 3 wt.% To 15 wt.%, Preferably 5 wt.% To 10 % By weight and particularly preferably with 7% by weight.
- the solid is mixed with dibutyl phthalate (or 2-propanol) completely soaked and then the one absorbed in the pores Liquid after a defined time under defined conditions removed by centrifugation.
- the amount of dibutyl phthalate absorbed (or 2-propanol) is a measure of the porosity of the solid.
- the specific porosity of the explosive granules determined using this method is 600 to 1000 ml / kg, preferably 700 to 900 ml / kg, whole particularly preferably 850 ml / kg.
- the specific water absorption capacity of the explosive granules can be determined gravimetrically as follows: A defined amount of granules (eg 2.00 g) is sealed in a thin paper bag, such as a tea bag, and immersed in a vessel with an excess of water. After 3 minutes of immersion, the bag is removed from the water and hung for 10 minutes to drain. The bag is weighed and the water absorption is determined from the weight difference of a wet bag with and without granules. Distilled water or water with a defined hardness can be used for the determination.
- a defined amount of granules eg 2.00 g
- a thin paper bag such as a tea bag
- the water absorption which can be determined in this way is preferably 500 until 2000 %.
- the compacted granulate is characterized by special swelling kinetics off, the expansion does not change linearly depending on the time and should reach a certain level as soon as possible. Especially the swelling behavior in the first 10 seconds is of interest after contact with water if the granules are used as disintegrants for molded articles should be used.
- the granules When in contact with water, the granules rapidly take up volume and is therefore suitable as a so-called explosive for pressed moldings so that they quickly disintegrate in water.
- Such moldings must have sufficient stability and strength to enable handling, packaging and storage however, quickly disintegrate on contact with water, so that the components can have the desired effect.
- Tablets can be used with the disintegrant granules to be used according to the invention with a strength not known from the prior art of more than 50 N and effectively blown up.
- the invention is directed to pressed molded articles of washing and / or Cleaning compositions, especially tablets.
- the moldings can but also cubes, cuboids, balls and the like, in which the Granules are included as a disintegrant.
- the spatial shape of the molded body can in its dimensions of the induction chamber be adapted to the washing machine, but all reasonable manageable Design shapes. These include e.g. also cylindrical configurations with oval or circular cross-section and molded body with a plate-like structure.
- a preferred molded body consists of alternately thick long and thin short segments, so that individual segments of such a bolt at predetermined breaking points through the short thin segments are shown, broken off and into the Detergent dispenser of the machine can be entered. This principle of bar-shaped body can also be in other geometric polygonal shapes be realized.
- a tablet produced in this way preferably has a weight of 10 to 120 g, particularly preferably from 20 to 100 g, the diameter the tablet is usually less than 100 mm.
- Preferred detergent tablets have a maximum diameter of 80 mm, in particular between 30 and 80 mm.
- the tablets preferably have a weight from 10 to 40 g, with diameters from 20 to 50 mm being preferred.
- Such detergent and / or cleaning agent compositions designed as shaped articles usually contain builders, bleach and Bleach activators, surfactants, tabletting aids, disintegrants and others usual additives and auxiliary substances.
- a preferred embodiment of the invention is a phosphate-containing detergent tablet, based on total weight: 53 to 20% by weight Sodium tripolyphosphate, 0 to 5% by weight other organic builders, 12 to 20% by weight Peroxide bleach, 2 to 6% by weight Bleach activator (s), 8 to 20% by weight Surfactant (s), 15 to 5% by weight Na carbonate / Na bicarbonate, 3 to 15% by weight compacted explosive granules and 7 to 9% by weight usual auxiliaries and additives.
- the shaped body is a phosphate-free detergent tablet, containing, based on the total weight: 45 to 20% by weight Zeolite and / or amorphous and / or crystalline disilicates, 2 to 6% by weight other organic builders, 12 to 20% by weight Peroxide bleach, 2 to 6% by weight Bleach activator (s), 8 to 20% by weight Surfactant (s), 15 to 4% by weight Na carbonate / Na bicarbonate, 3 to 15% by weight compacted explosive granules and 13 to 9% by weight usual auxiliaries and additives.
- the shaped body is a water softening tablet, based on total weight: 10 to 30% by weight Zeolite, 20 to 5% by weight Disilicate 5 to 15% by weight polymeric organic builders, 10 to 35% by weight Na bicarbonate, 30 to 0% by weight Citric acid / Na citrate dihydrate, 3 to 12% by weight compacted explosive granules and 22 to 3% by weight other usual auxiliaries and additives.
- the shaped body is a bleach tablet, containing, based on the total weight: 65 to 20% by weight Na carbonate / disilicates, 15 to 30% by weight Peroxide bleach, 4 to 9% by weight Bleach activator (s), 5 to 10% by weight Surfactant (s), 3 to 15% by weight compacted explosive granules and 8 to 16% by weight other usual auxiliaries and additives
- both mono-, as well as double or triple tablets prefers.
- Inorganic substances such as polyphosphates, pyrophosphates, Metaphosphates or phosphonates, layered silicates, amorphous silicates, amorphous disilicates and zeolite.
- the builders system can fillers such as alkali carbonates, bicarbonates e.g. Sodium carbonate or sodium hydrogen carbonate, sesquiocarbonate, sodium sulfate, Magnesium sulfate, or citrate, citric acid, succinic acid, Be tartaric acid and malic acid.
- Co-builders and dispersants also used.
- Such cobuilders or dispersants can be polyacrylic acids and their sodium salts.
- organic builders are copolymers of (meth) acrylic acid and Maleic acid, terpolymers and quattropolymers from (meth) acrylic acid, maleic acid, Vinyl alcohol and vinyl compounds containing sulfo groups.
- the used fine crystalline, synthetic and bound water containing Zeolite is preferably zeolite NaA in detergent quality.
- zeolite NaX zeolite NaX
- zeolite P and mixtures of A, X and P.
- the zeolite can either be spray-dried powder or granular compound, for example up to about 50% by weight of other components such as nonionic surfactants, cellulose ethers and / or polymers Contains polycarboxylates.
- Suitable powdered zeolites have an average particle size of less than 10 ⁇ m (volume distribution; Measurement method: Coulter counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
- Polycarboxylates and / or polymers are used as organic builder substances Polycarboxylates, as well as their acids used.
- Polycarboxylic acids and the polycarboxylates in particular include those in the form of their sodium salts polycarboxylic acids such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids and mixtures of these.
- Suitable polymeric polycarboxylates are, for example, the sodium salts polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 800 to 150,000 (sourced from acid).
- Suitable copolymeric polycarboxylates are, in particular, those of Acrylic acid with methacrylic acid and acrylic acid and methacrylic acid with Maleic acid.
- the copolymers of acrylic acid have proven particularly suitable proven with maleic acid, the 50 to 90 wt.% Acrylic acid and 50 to Contain 10% by weight of maleic acid.
- Their relative molecular mass, based on Acids are generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
- Ter- and quattropolymeric polycarboxylates are also particularly preferred, made from (meth) acrylic acid, maleic acid and vinyl alcohol or Vinyl alcohol derivatives (as described in DE-C-43 00 772) or those from (meth) acrylic acid, 2-alkylallylsulfonic acid and sugar derivatives (as described in DE-C-42 21 381) or those made from (meth) acrylic acid, Maleic acid, vinyl alcohol derivatives and monomers with sulfonic acid groups (described in DE-A-19 516 957).
- the (co) polymeric polycarboxylates are preferably used either as a powder or used as granular compounds. Suitable as granular compounds For example, such as in the international patent application WO-A 92/13937 are described.
- Suitable builder systems are oxidation products of carboxyl-containing ones Polyglucosans and / or their water-soluble salts, as for example in the international patent application WO 93/08251 are described or their manufacture, for example, in the international patent application WO 93/16110.
- polyacetals which can be obtained by reacting dialdehydes with polycarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, as described, for example, in European patent application EP-A-280 223.
- Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
- Polyethylene glycol and / or polypropylene glycol with a molecular weight of 900 to 30,000 are also suitable, as are carboxylated polysaccharides, polyaspartates and polyglutamate.
- Customary peroxide bleaching agents are sodium perborate tetrahydrate and sodium perborate monohydrate, sodium percarbonate, peroxypyrophosphates, citrate perhydrates, as well as H 2 O 2 delivering peracidic salts, peracids such as perbenzoates, peroxyphthalates, diperazelaic acid and diperdodecanedioic acids.
- activators can be incorporated.
- Suitable bleach activators are the N-acyl and O-acyl compounds forming with H 2 O 2 organic peracids, preferably N, N'-tetraacylated diamines, carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. Acetylated mixtures of sorbitol and mannitol can also be used.
- bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,2,5-triazine (DADHT) and acetylated sorbitol mannitol Mixtures (SORMAN).
- TAED N, N, N ', N'-tetraacetylethylene diamine
- DADHT 1,5-diacetyl-2,4-dioxo-hexahydro-1,2,5-triazine
- SORMAN acetylated sorbitol mannitol Mixtures
- Bleaching detergent tablets contain peroxy bleach in quantities from 12 to 20% by weight. Tablets in addition to detergent formulations used as bleach tablets, however, contain peroxy bleach preferably in amounts of 15 to 30% by weight.
- a can Percarbonate content in amounts of 10 to 20% by weight is particularly advantageous if, in particular, at low percarbonate contents below 20 % By weight, further peroxy bleaching agents can be used.
- Bleaching tablets are preferably characterized in that they are 20 to 65% by weight, preferably 30 to 40% by weight, of amorphous, partially crystalline and / or crystalline layered sodium silicates and 15 to 30 % By weight of peroxy bleach, but no zeolite.
- Anionic, nonionic or amphoteric surfactants are used as surfactants Commitment. These can either be in the explosive granules as described above be incorporated, or added to the detergent formulation.
- surfactants are either available for purchase Granules can be used, or they can be in liquid form on individual components the formulation are applied, preferably to the builders.
- the liquid surfactants are preferably incorporated into the formulation Spraying introduced on the solids, spraying either on individual components, e.g. on soda, cellulose, silicate, zeolite, Phosphates can be made, or after mixing the solids of the formulation on the solid mixture.
- cationic surfactants can also be present in detergent formulations, for example quaternary ammonium compounds with C 8 -C 16 N-alkyl or N-alkenyl groups and N-substituents such as methyl, hydroxyethyl or hydroxypropyl groups.
- suitable surfactants of the sulfonate type are preferably C 9 to C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained, for example, from C 12 -C 18 monoolefins with end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
- alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
- esters of sulfo fatty acids e.g. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or Tallow fatty acids.
- Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
- fatty acid glycerol esters are the mono-, di- and triesters as well as their Mixtures to understand how they are made by esterification can be obtained by a monoglycerol with 1 to 3 moles of glycerol.
- Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example the Caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, Stearic acid or behenic acid. Assuming fat and Oils, i.e.
- feed products before sulfonation to become saturated with hydrogen to a large extent, i.e. on Harden iodine numbers less than 5, advantageously less than 2.
- suitable feedstocks are palm oil, palm kernel oil, palm stearin, Olive oil, rape oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, Linseed oil, lard oil or lard. Because of their high natural Proportion of saturated fatty acids, however, it has proven to be particularly advantageous proven to start from coconut oil, palm kernel oil or beef tallow.
- the Sulfation of saturated fatty acids with 6 to 22 carbon atoms or the mixtures from fatty acid glycerol esters with iodine numbers less than 5, the fatty acids containing 6 to 22 carbon atoms, is preferably carried out by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases, as described in international patent application WO-A 91/09009 is specified.
- Preferred alk (en) yl sulfates are the sulfuric acid half esters of the C 12 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half esters of secondary alcohols of this chain length. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
- the compositions contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C12-C14 fatty alkyl sulfates or C 12 -C 18 fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates and in particular C 12 -C 16 fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates .
- not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C 16 to C 22 are used.
- saturated sulfated fatty alcohols predominantly consisting of C 16 and unsaturated sulfated fatty alcohols predominantly consisting of C 18 are particularly preferred, for example those. which are derived from solid or liquid fatty alcohol mixtures of the HD-Ocenol (R) type. Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred.
- the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol ethylene oxide such as 2-methyl branched C 9 -C 11 alcohols with an average of 3.5 mol ethylene oxide (EO) or C12-C18 fatty alcohols with 2 to 4 EO are suitable. Because of their high foaming behavior, they are only used in relatively small amounts in detergents, for example in amounts of 1 to 5%.
- Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, also known as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid Alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols represent.
- Preferred sulfosuccinates contain C8 to C18 Fatty alcohol residues or mixtures thereof.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue that differs from ethoxylated Derives fatty acids, which are non-ionic surfactants (See description below).
- sulfosuccinates whose fatty alcohol residues differ from ethoxylated fatty alcohols with restricted Deriving homolog distribution is particularly preferred. It is the same possible alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the Use alk (en) yl chain or its salts.
- Preferred anionic surfactant mixtures contain combinations of Alk (en) yl sulfates, especially mixtures of saturated and unsaturated Fatty alk (en) yl sulfates, and alkylbenzenesulfonates, sulfated fatty acid glycerol esters and / or a-sulfofatty acid esters.
- Alk (en) yl sulfates especially mixtures of saturated and unsaturated Fatty alk (en) yl sulfates, and alkylbenzenesulfonates, sulfated fatty acid glycerol esters and / or a-sulfofatty acid esters.
- alk (en) yl sulfates especially mixtures of saturated and unsaturated Fatty alk (en) yl sulfates, and alkylbenzenesulfonates, sulfated fatty acid glycerol esters and / or a-
- Suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.1 to 5% by weight.
- saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. Soap mixtures are particularly preferred which are composed of 50 to 100% by weight of saturated C 12 -C 24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
- the anionic surfactants and soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, Di- or triethanolamine are present.
- the anionic are preferably located Surfactants in the form of their sodium or potassium salts, especially in the form their sodium salts.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be methyl or linearly branched in the 2-position , or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
- EO ethylene oxide
- alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example coconut oil, palm oil, tallow oil or oleyl alcohol and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
- the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 Eo, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 5 EO.
- the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- fatty alcohols with more than 12 EO for example those with up to about 80 EO, can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 C atoms and G represents a symbol for a glycose unit with 5 or 6 carbon atoms, preferably glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
- nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may be suitable.
- the amount of these nonionic surfactants is preferably no more than that of ethoxylated fatty alcohols, particularly preferably not more than half of these.
- Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), R 2 -CO-NR 3 - [Z] in the R 2 -CO for an aliphatic acyl radical with 6 to 22 C atoms, R 3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 C atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 C. -Atoms and 3 to 10 hydroxyl groups.
- the detergent formulations contain the nonionic surfactants in amounts of up to 20% by weight.
- alkaline in water inorganic salts preferably up to 15% by weight in the tablets are included.
- inorganic alkaline salts belong in particular to bicarbonates, carbonates or mixtures thereof.
- Alkali carbonate and especially sodium carbonate are preferably used.
- auxiliaries and additives in the compositions according to the invention are: Inorganic salts which react neutral in water, preferably sulfates and chlorides, in particular in the form of their sodium and / or calcium salts; their content in the finished detergent formulation is preferably up to about 20% by weight. Tableting aids, for example polyalkylene glycols and magnesium stearates.
- Enzymes magnesium silicates, aluminum aluminates, benzotriazole, glycerol, magnesium stearate, polyalkylene glycols, hexametaphosphate, phosphonates, bentonites, soil release and soil repellant compounds, carboxymethyl celluloses, solubility improvers, graying inhibitors, foam inhibitors and color softeners, optical brighteners, optical brighteners, optical brighteners, optical brighteners, optical brighteners, optical brighteners, optical brighteners, optical brighteners, optical brighteners, optical brighteners, optical brighteners, optical brighteners, and optical brighteners, optical brighteners, optical brighteners, optical brighteners, optical brighteners, optical brighteners, optical brighteners, optical brighteners, and optical brighteners, as well as optical brighteners, optical brighteners, and optical brighteners, as well as optical brighteners, optical brighteners, and optical brighteners.
- Their content preferably does not exceed 10% by weight.
- compositions may also contain components that include the oil and Grease washability from textiles has a positive effect ("Soil Release Compounds ").
- oil and fat dissolving components include e.g. nonionic cellulose ethers such as methyl hydroxypropyl cellulose with a Proportion of methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and the polymers known from the prior art Phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates.
- the detergent formulations may also contain ingredients which improve the solubility of individual formulation components and thus increasing the dissolution rates of the tablets.
- About these ingredients belong to the described fatty alcohols with 10 to 80 Moles of ethylene oxide per mole of fatty alcohol, in particular polyethylene glycols relative molar masses between 200 and 6000.
- Suitable foam inhibitors are, for example, natural or soaps synthetic origin, which have a high proportion of C18-C24 fatty acids.
- Suitable non-surfactant foam inhibitors are e.g. Organopolysiloxanes and their mixtures with microfine, possibly silanized silica as well as paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silica or bistearylethylenediamide. Mixtures too various foam inhibitors can be used, e.g. such out Silicones, paraffins or waxes.
- the foam inhibitors, in particular paraffin and silicone-containing foam inhibitors a granular, water-soluble or dispersible carrier substance bound. Mixtures of paraffins and bistearylethylenediamine are particularly preferred.
- Enzymes come from the class of proteases, lipases, amylases and cellulases or mixtures thereof. Particularly suitable are enzymes derived from battery strains or fungi, e.g. Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus can be obtained. Proteases of the subtilisin type and in particular proteases are preferred, which are obtained from Bacillus lentus.
- enzyme mixtures for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from Protease, amylase and lipase or protease, lipase and cellulase, in particular however, cellulase-containing mixtures of particular interest.
- Peroxidases or oxidases are also found to be suitable in some cases.
- the enzymes can also be attached to and / or in vehicles Envelopes must be embedded to protect them against premature decomposition.
- the proportion of enzymes, enzyme mixtures or enzyme granules can e.g. about 0.1 to 5% by weight, preferably 0.1 to 2% by weight.
- the stabilizers come in particular for per-compounds and enzymes Salts of polyphosphonic acids, especially 1-hydroxyethane-1,1-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or ethylenediaminetetramethylenephosphonic acid.
- HEDP 1-hydroxyethane-1,1-diphosphonic acid
- DETPMP diethylenetriaminepentamethylenephosphonic acid
- ethylenediaminetetramethylenephosphonic acid especially 1-hydroxyethane-1,1-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or ethylenediaminetetramethylenephosphonic acid.
- Graying inhibitors serve to replace those of the laundry fiber To keep dirt in the wash liquor in suspension and so the graying to prevent laundry.
- Water-soluble colloids are usually more organic for this Suitable in nature, for example the water-soluble polymeric salts Carboxylic acids, glue, gelatin, salts of ether carboxylic acids or Ether sulfonic acids of starch or cellulose or salts of acidic Sulfuric acid esters of cellulose or starch.
- water-soluble, acidic Group-containing polyamides are suitable for this purpose.
- soluble starch preparations and other than those mentioned above Use starch products, e.g. degraded starch, aldehyde starches, etc. Polyvinyl pyrrolidone can also be used.
- cellulose ethers are preferred, such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroypropylcellulose, Methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone in amounts of, for example, 0.1 to 5 % Used.
- the formulations can be derivatives of diaminostilbenedisulfonic acid as optical brighteners or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar connections, which instead of the morpholino group is a diethanolamino group, a Methalamino group, an anilino group or a 2-methoxyethylamino group wear.
- brighteners of the substituted diphenylstyryl type be included, e.g.
- Water softening tablets usually consist of builders such as Layered silicates, amorphous silicates, amorphous disilicates and zeolites, as well as fillers such as sodium carbonate, sodium sulfate, magnesium sulfate, Sodium bicarbonate, citrate and citric acid. Often called Auxiliary builders cobuilders and dispersants also used. Such cobuilders or dispersants can the above-mentioned polyacrylic acids or Copolymers with polyacrylic acid and its sodium salts.
- Low-foaming non-ionic surfactants of the polyalkylene glycol and alkyl polyglucoside type are also used.
- Examples 1 to 5 Examples of compositions of phosphate-free detergent tablets (all amounts in% by weight).
- the nonionic surfactants are in liquid form in the detergent formulation by spraying onto the disilicate or the zeolite, as well as some of the anionic surfactants. More anionic Surfactants are used as granules.
- compositions of phosphate-containing detergent tablets (all amounts in% by weight).
- the nonionic surfactants are in liquid form in the detergent formulation by spraying on the tripolyphosphate, the soda or the Carboxymethyl cellulose introduced.
- Examples 11 to 14 Pressed Shaped Bodies with the Purpose as a) Water Softener of the Following Composition: Use in% example 11 12th 13 14
- Raw material Zeolite A 16.0 16.0 16.0 16.0 Acrylic acid-maleic acid copolymer, 14.5 14.5 14.5 14.5 Na salt
- Example 15 Determination of the strength and disintegration time of a phosphate-containing one Detergent tablet with explosive granules used according to the invention.
- the tablet breaking strength tester is used to determine the tablet strength type TB30 / TBH30MD from Erweka. Doing so the breaking strength by means of a strain gauge with a load cell certainly. The measuring accuracy is +/- 1N. After corresponding Programming, the tablet is placed in the measuring device and the Measuring process started. The device shows the value of the breaking strength.
- the tablet disintegration time is determined as follows:
- the detergent formulation given in Table 4 is pressed into tablets with the disintegrant granules M1 to M7 according to Table 5. The strength and disintegration time of these tablets are determined.
- raw material Quantity in% by weight Na tripolyphosphate 35 Na percarbonate 19th TAED 4th Alkyl benzene sulfonate 4th Fatty alcohol sulfate 14 soda 8th Defoamer, optical brightener, CMC , Phosphonate 6 Microcrystalline cellulose (200 ⁇ m) 2nd Enzymes 1 Fatty alcohol ethoxylate (C12 / C14, E0 4.7) 2nd Explosive preparation M1-M7 or V1 5 Explosives M1 M2 M3 M4 M5 M6 M7 Cellulose 50 50 45 50 47 40 50 Linear PAA 12.5 12.5 10th 10th 12.5 10th - Networked PAA - - - 2nd - - - Carboxymethyl cellulose - - 15 5 10th 20th - Ni
- a roller-compacted cellulose from Degussa serves as comparison V1 AG with the trade name Elcema G 250 (5% moisture, bulk density 400 g / l).
- Table 6 shows that both the composition and - at the same Composition - the moisture content of the disintegrant granules clearly Influence the tablet disintegration time. Explosives with the preferred content of 3 to 5% by weight of moisture shows the best tablet disintegration times.
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Abstract
Description
In EP-A-846 756 werden Tablettensprengmittel in die Tablette und bevorzugt in die äußere feste Hülle der Tablette eingearbeitet. Bevorzugt werden Kombinationen aus löslichen Säuren und Alkalicarbonaten verwendet. Weitere mögliche Sprengmittel können dem ,,Handbook of Pharmaceutical Excipients (1986) entnommen werden. Als Beispiele werden genannt: Stärke (modifizierte Stärke Natrium-Stärke-Gluconate), Gummi (Agar, Guar, und andere), Cellulose, Carboxymethylcellulose, Alginate, Siliziumdioxid, Ton, Polyvinylpyrrolidon, Polysaccharide und Ionenaustauscherharze.
Eine definierte Granulatmenge (z.B. 2.00 g) wird in einen dünnen Papierbeutel, wie einem Teebeutel eingeschweißt und in ein Gefäß mit einem Überschuß an Wasser getaucht. Nach 3 Minuten Eintauchzeit wird der Beutel aus dem Wasser herausgenommen und 10 Minuten zum Abtropfen aufgehängt. Der Beutel wird gewogen und aus der Gewichtsdifferenz eines nassen Beutels mit und ohne Granulat die Wasseraufnahme bestimmt. Für die Bestimmung kann destilliertes Wasser oder Wasser mit definierter Härte verwendet werden.
53 bis 20 Gew.% | Natriumtripolyphosphat, |
0 bis 5 Gew.% | andere organische Gerüststoffe, |
12 bis 20 Gew.% | Peroxidbleichmittel, |
2 bis 6 Gew.% | Bleichaktivator(en), |
8 bis 20 Gew.% | Tensid(e), |
15 bis 5 Gew.% | Na-Carbonat/Na-Hydrogencarbonat, |
3 bis 15 Gew.% | verdichtetes Sprengmittelgranulat und |
7 bis 9 Gew.% | übliche Hilfs- und Zusatzstoffe. |
45 bis 20 Gew.% | Zeolith und/oder amorphe und/oder kristalline Disilikate, |
2 bis 6 Gew.% | andere organische Gerüststoffe, |
12 bis 20 Gew.% | Peroxidbleichmittel, |
2 bis 6 Gew.% | Bleichaktivator(en), |
8 bis 20 Gew.% | Tensid(e), |
15 bis 4 Gew.% | Na-Carbonat/Na-Hydrogencarbonat, |
3 bis 15 Gew.% | verdichtetes Sprengmittelgranulat und |
13 bis 9 Gew.% | übliche Hilfs- und Zusatzstoffe. |
10 bis 30 Gew.% | Zeolith, |
20 bis 5 Gew.% | Disilikat |
5 bis 15 Gew.% | polymeren organischen Gerüststoff, |
10 bis 35 Gew.% | Na-Hydrogencarbonat, |
30 bis 0 Gew.% | Zitronensäure/ Na-Citrat-Dihydrat, |
3 bis 12 Gew.% | verdichtetes Sprengmittelgranulat und |
22 bis 3 Gew.% | sonstige, übliche Hilfs- und Zusatzstoffe. |
65 bis 20 Gew.% | Na-Carbonat/Disilikate, |
15 bis 30 Gew.% | Peroxidbleichmittel, |
4 bis 9 Gew.% | Bleichaktivator(en), |
5 bis 10 Gew.% | Tensid(e), |
3 bis 15 Gew.% | verdichtetes Sprengmittelgranulat und |
8 bis 16 Gew.% | sonstige, übliche Hilfs- und Zusatzstoffe |
Des weiteren sind Polyethylengkykol und/oder Polypropylenglykol mit einem Molekulargewicht von 900 bis 30.000 geeignet, sowie carboxylierte Polysaccharide, Polyaspartate und Polyglutamat.
Die Waschmittel formulierungen enthalten die nichtionischen Tenside in einer bevorzugten Ausführungsform in Mengen bis zu 20 Gew.%.
In Wasser neutral reagierende anorganische Salze, vorzugsweise Sulfate und Chloride, insbesondere in Form ihrer Natrium- und/oder Calciumsalze; ihr Gehalt in der fertigen Waschmittelformulierung beträgt vorzugsweise bis zu etwa 20 Gew.%.
Tablettierhilfsmittel, z.B. Polyalkylenglykole und Magnesiumstearate. Enzyme, Magnesiumsilikate, Aluminiumaluminate, Benzotriazol, Glycerin, Magnesiumstearat, Polyalkylenglykole, Hexametaphosphat, Phosphonate, Bentonite, Soil Release- und Soil Repellent-Verbindungen, Carboxymethylcellulosen, Löslichkeitsverbesserer, Vergrauungsinhibitoren, Schauminhibitoren, optische Aufheller, textilweichmachende Stoffe, sowie Farb- und Duftstoffe. Ihr Gehalt geht bevorzugt nicht über 10 Gew.% hinaus.
Beispiele für Zusammensetzungen phosphatfreier Waschmitteltabletten (alle Mengen in Gew.%). | |||||
Beispiel | 1 | 2 | 3 | 4 | 5 |
Bestandteil: | |||||
Zeolith | 2,0 | 1,0 | 1,0 | 26,0 | 31,0 |
Disilikat | 35,0 | 35,0 | 30,0 | 2,0 | 2,0 |
Soda | 4,2 | 9,3 | 10,2 | 8,6 | 10,8 |
Na-Citrat-Dihydrat | - | - | 5,0 | 5,0 | - |
Copolymer Na-Salz | 3,5 | 3,0 | 3,0 | 2,3 | 3,5 |
Na-Percarbonat | 19,0 | 16,0 | 17,0 | 19,0 | 17,0 |
TAED | 5,0 | 4,0 | 4,0 | 5,0 | 4,5 |
Alkylbenzolsulfonat | 2,5 | - | 2,5 | 7,0 | 6,8 |
Fettalkoholsulfat | 10,5 | 12,0 | 10,0 | 8,0 | 7,0 |
Fettalkoholethoxylat | 5,0 | 4,0 | 4,5 | 3,5 | 4,4 |
Entschäumer | 1,5 | 1,4 | 1,5 | 1,5 | 1,4 |
Phosphonat | 0,7 | 0,7 | 0,7 | 1,0 | 0,7 |
Enzyme | 1,5 | 1,0 | 1,0 | 1,5 | 1,3 |
Soil-Release-Polymer | 1,0 | - | 1,0 | 1,0 | 1,0 |
Carboxymethylcellulose | 1,0 | 1,0 | 1,0 | 1,0 | 1,0 |
Sprengmittelgranulat | 7,0 | 7,0 | 7,0 | 7,0 | 7,0 |
optische Aufheller | 0,3 | 0,3 | 0,3 | 0,3 | 0,3 |
Parfum | 0,3 | 0,3 | 0,3 | 0,3 | 0,3 |
Beispiele für Zusammensetzungen phosphathaltiger Waschmitteltabletten (alle Mengen in Gew.%). | |||||
Beispiel | 6 | 7 | 8 | 9 | 10 |
Bestandteil: | |||||
Na-tripolyphosphat | 35,0 | 35,0 | 32,0 | 37,0 | 33,0 |
Zeolith A | 3,0 | 2,0 | 2,0 | 2,0 | 1,5 |
Silikat | - | 3,0 | 2,0 | 1,5 | - |
Soda | 18,0 | 10,5 | 12,0 | 18,9 | 10,5 |
Na-Citrat-Dihydrat | - | - | 5,0 | - | 7,0 |
Na-Percarbonat | 15,0 | 17,0 | 16,0 | 14,0 | 18,0 |
TAED | 3,0 | 4,0 | 4,0 | 2,0 | 4,0 |
Alkylbenzolsulfonat | 5,0 | 3,0 | 4,0 | 2,4 | - |
Fettalkoholsulfat | 8,0 | 11,0 | 9,0 | 11,0 | 14,0 |
Fettalkoholethoxylat | 2,0 | 2,0 | 2,0 | 1,0 | 2,0 |
Entschäumer | 1,4 | 1,5 | 1,4 | 1,3 | 1,5 |
Phosphonat 2016 D | 1,0 | 1,0 | 1,0 | 0,5 | - |
Soil-Release-Polymer | - | 1,0 | 0,6 | - | - |
Carboxymethylcellulose | 1,0 | 1,4 | 1,4 | 1,0 | 1,0 |
Sprengmittelgranulat | 7,0 | 8,0 | 6,0 | 7,0 | 7,0 |
optische Aufheller | 0,3 | 0,3 | 0,3 | 0,2 | 0,3 |
Parfum | 0,3 | 0,3 | 0,3 | 0,2 | 0,2 |
Beispiel | 11 | 12 | 13 | 14 |
Rohstoff: | ||||
Zeolith A | 16,0 | 16,0 | 16,0 | 16,0 |
Acrylsäure-Maleinsäure-Copolymerisat, | 14,5 | 14,5 | 14,5 | 14,5 |
Na-Salz | ||||
Schichtsilikat SKS-6 | 7,0 | 7,0 | 7,0 | 7,0 |
Soda | - | - | 27,5 | 28,0 |
Natriumhydrogencarbonat | 33,0 | 34,0 | - | - |
Natriumcitrat-Dihydrat | - | - | 24,5 | 25,0 |
Zitronensäure | 19,0 | 19,0 | - | - |
Polyethylenglycol 4000 bis 6000 | 2,5 | 2,5 | 2,5 | 2,5 |
Paraffinöl | 1,0 | - | 1,0 | - |
Sprengmittelgranulat | 7,0 | 7,0 | 7,0 | 7,0 |
Rohstoff | Menge in Gew.% |
Na-tripolyphosphat | 35 |
Na-Percarbonat | 19 |
TAED | 4 |
Alkylbenzolsulfonat | 4 |
Fettalkoholsulfat | 14 |
Soda | 8 |
Entschäumer, optischer Aufheller, CMC, Phosphonat | 6 |
Mikrokristalline Cellulose (200 µm) | 2 |
Enzyme | 1 |
Fettalkoholethoxilat (C12/C14, E0=4,7) | 2 |
Sprengmittelzubereitung M1-M7, bzw V1 | 5 |
Sprengmittel | M1 | M2 | M3 | M4 | M5 | M6 | M7 |
Cellulose | 50 | 50 | 45 | 50 | 47 | 40 | 50 |
Lineares PAA | 12,5 | 12,5 | 10 | 10 | 12,5 | 10 | - |
Vernetztes PAA | - | - | - | 2 | - | - | - |
Carboxymethylcellulose | - | - | 15 | 5 | 10 | 20 | - |
Nio-Tensid | 0,5 | 0,5 | 0,5 | 0,5 | - | 0,5 | - |
Polymertensid | - | - | - | - | - | - | 12,5 |
Wasser zur Kompakt. (Gew.%) | 37 | 37 | 29,5 | 29,5 | 30,5 | 29,5 | 37,5 |
Schüttdichte (g/l) | 335 | 335 | 335 | 335 | 335 | 335 | 335 |
Feuchte (Gew.%) | 6 | 4 | 3 | 3 | 4 | 5 | 3 |
Staubanteil (Gew.%) | 7 | 8 | 6 | 5 | 5 | 5 | 7 |
Sprengmittel | Feuchte [Gew.%] | Festigkeit [N] | Zerfallszeit [s] |
V1 | 5 | 58 | 52 |
M1 | 6 | 62 | 12 |
M2 | 4 | 65 | 9 |
M3 | 3 | 57 | 8 |
M4 | 3 | 63 | 10 |
M5 | 4 | 58 | 9 |
M6 | 5 | 59 | 7 |
M7 | 3 | 58 | 9 |
Claims (8)
- Wasch- und/oder Reinigungszusammensetzungen in Form gepreßter Körper, enthaltend in relativ feiner Form, als Granulat und/oder Cogranulat übliche wasch- und/oder reinigungsaktive Stoffe, Gerüststoffe, Hilfs- und Zusatzstoffe und 3 bis 15 Gew.%, bezogen auf Gesamtgewicht der Zusammensetzungen, verdichtetes Sprengmittelgranulat aus nichtwasserlöslicher, in Wasser quellbarer Cellulose und gegebenenfalls weiteren modifizierten wasserquellbaren Polysaccharidderivaten und ein oder mehrere Polymere/Copolymere von (Meth)acrylsäure oder Salzen derselben, wobei das Sprengmittelgranulat einen Feuchtigkeitsgehalt von 2 bis 8 Gew.% und eine spezifische Porosität von 600 bis 1000 ml/kg aufweist.
- Wasch- und/oder Reinigungszusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß das Sprengmittelgranulat noch ein oder mehrere flüssige, mit Wasser gelbildende oder verdickende Tenside enthält.
- Wasch- und/oder Reinigungszusammensetzung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß im Sprengmittelgranulat die in Wasser quellbare Cellulose und gegebenenfalls weitere modifizierte wasserquellbare Polysaccharidderivate und Polymere/Copolymere von (Meth)acrylsäure in einem Gewichtsverhältnis von 50:1 bis 2:1, vorzugsweise von 20:1 bis 5:1, ganz besonders bevorzugt in einem Gewichtsverhältnis von 10:1 vorhanden sind.
- Wasch- und/oder Reinigungszusammensetzung nach Anspruch 2 oder 3, dadurch gekennzeichnet, daß das Gewichtsverhältnis der kombinierten in Wasser quellbaren Cellulose und gegebenenfalls weitere modifizierte wasserquellbare Polysaccharidderivate und Polymere/Copolymere von (Meth)acrylsäure : flüssigen Tensid(en) von 100:1 bis 10:1 beträgt.
- Wasch- und/oder Reinigungszusammensetzung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß sie eine ein- bis dreiphasige phosphathaltige Waschmitteltablette ist, enthaltend bezogen auf Gesamtgewicht:
53 bis 20 Gew.% Natriumtripolyphosphat, 0 bis 5 Gew.% andere organische Gerüststoffe, 12 bis 20 Gew.% Peroxidbleichmittel, 2 bis 6 Gew.% Bleichaktivator(en), 8 bis 20 Gew.% Tensid(e), 15 bis 5 Gew.% Na-Carbonat/Na-Hydrogencarbonat, 3 bis 15 Gew.% verdichtetes Sprengmittelgranulat und 7 bis 9 Gew.% übliche Hilfs- und Zusatzstoffe. - Wasch- und/oder Reinigungszusammensetzung nach einem der vorstehenden Ansprüche 1 bis 4, dadurch gekennzeichnet, daß sie eine einbis dreiphasige phosphatfreie Waschmitteltablette ist, enthaltend bezogen auf Gesamtgewicht:
45 bis 20 Gew.% Zeolith und/oder amorphe und/oder kristalline 2 bis 6 Gew.% Disilikate, andere organische Gerüststoffe, 12 bis 20 Gew.% Peroxidbleichmittel, 2 bis 6 Gew.% Bleichaktivator(en), 8 bis 20 Gew.% Tensid(e), 15 bis 4 Gew.% Na-Carbonat/Na-Hydrogencarbonat, 3 bis 15 Gew.% verdichtetes Sprengmittelgranulat und 13 bis 9 Gew.% übliche Hilfs- und Zusatzstoffe. - Wasch- und/oder Reinigungszusammensetzung nach einem der vorstehenden Ansprüche 1 bis 4, dadurch gekennzeichnet, daß sie eine einbis dreiphasige Wasserenthärtungstablette ist, enthaltend bezogen auf Gesamtgewicht:
10 bis 30 Gew.% Zeolith, 20 bis 5 Gew.% Disilikat 5 bis 15 Gew.% polymeren organischen Gerüststoff, 10 bis 35 Gew.% Na-Hydrogencarbonat, 30 bis 0 Gew.% Zitronensäure/ Na-Citrat-Dihydrat, 3 bis 12 Gew.% verdichtetes Sprengmittelgranulat und 22 bis 3 Gew.% sonstige, übliche Hilfs- und Zusatzstoffe. - Wasch- und/oder Reinigungszusammensetzung nach einem der vorstehenden Ansprüche 1 bis 4, dadurch gekennzeichnet, daß sie eine einbis dreiphasige Bleichmitteltablette ist, enthaltend bezogen auf Gesamtgewicht:
65 bis 20 Gew.% Na-Carbonat/Disilikate, 15 bis 30 Gew.% Peroxidbleichmittel, 4 bis 9 Gew.% Bleichaktivator(en), 5 bis 10 Gew.% Tensid(e), 3 bis 15 Gew.% verdichtetes Sprengmittelgranulat und 8 bis 16 Gew.% sonstige, übliche Hilfs- und Zusatzstoffe.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DK99106369T DK1043389T3 (da) | 1999-03-29 | 1999-03-29 | Desintegreringsgranulatholdige vaskemiddeltabletter |
AT99106369T ATE201714T1 (de) | 1999-03-29 | 1999-03-29 | Sprengmittelgranulat enthaltende waschmitteltabletten |
ES99106369T ES2159442T3 (es) | 1999-03-29 | 1999-03-29 | Tabletas de detergentes que contienen un desintegrante granular. |
EP99106369A EP1043389B1 (de) | 1999-03-29 | 1999-03-29 | Sprengmittelgranulat enthaltende Waschmitteltabletten |
DE59900108T DE59900108D1 (de) | 1999-03-29 | 1999-03-29 | Sprengmittelgranulat enthaltende Waschmitteltabletten |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99106369A EP1043389B1 (de) | 1999-03-29 | 1999-03-29 | Sprengmittelgranulat enthaltende Waschmitteltabletten |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1043389A1 true EP1043389A1 (de) | 2000-10-11 |
EP1043389B1 EP1043389B1 (de) | 2001-05-30 |
Family
ID=8237873
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99106369A Revoked EP1043389B1 (de) | 1999-03-29 | 1999-03-29 | Sprengmittelgranulat enthaltende Waschmitteltabletten |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1043389B1 (de) |
AT (1) | ATE201714T1 (de) |
DE (1) | DE59900108D1 (de) |
DK (1) | DK1043389T3 (de) |
ES (1) | ES2159442T3 (de) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002042404A1 (en) * | 2000-11-24 | 2002-05-30 | Unilever N.V. | Cleaning tablets |
WO2002044315A1 (en) * | 2000-11-24 | 2002-06-06 | Unilever N.V. | Cleaning compositions |
WO2002062933A1 (en) * | 2001-02-05 | 2002-08-15 | INEOS SILICAS LIMITED (formerly known as CROSFIELD LTD.) | Disintegrants and a process for their manufacture |
EP1314776A1 (de) * | 2001-11-23 | 2003-05-28 | Rohm And Haas Company | Optimierte teilchenförmige Zusammensetzungen |
DE10242222A1 (de) * | 2002-09-12 | 2004-03-25 | Henkel Kgaa | Unter Druck kompaktiertes Wasch- oder Reinigungsmittel |
WO2010063689A1 (de) * | 2008-12-05 | 2010-06-10 | Henkel Ag & Co. Kgaa | Maschinelle geschirrspülmitteltablette |
WO2014075845A1 (en) * | 2012-11-16 | 2014-05-22 | Unilever N.V. | Surface cleaning composition |
US9988526B2 (en) | 2011-11-04 | 2018-06-05 | Akzo Nobel Chemicals International B.V. | Hybrid dendrite copolymers, compositions thereof and methods for producing the same |
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US7550156B2 (en) | 2001-11-23 | 2009-06-23 | Rohm And Haas Company | Optimised pellet formulations |
US9321873B2 (en) | 2005-07-21 | 2016-04-26 | Akzo Nobel N.V. | Hybrid copolymer compositions for personal care applications |
US8674021B2 (en) | 2006-07-21 | 2014-03-18 | Akzo Nobel N.V. | Sulfonated graft copolymers |
US8841246B2 (en) | 2011-08-05 | 2014-09-23 | Ecolab Usa Inc. | Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage |
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 |
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 |
US8853144B2 (en) | 2011-08-05 | 2014-10-07 | Ecolab Usa Inc. | Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage |
BR112014009040A2 (pt) | 2011-11-04 | 2017-05-09 | Akzo Nobel Chemicals Int Bv | copolímero obtenível através da polimerização de pelo menos um primeiro monômero etilenicamente não saturado e pelo menos um segundo monômero etilenicamente não saturado; composição de copolímero; e processo para preparação do copolímero de dendrito |
US8945314B2 (en) | 2012-07-30 | 2015-02-03 | Ecolab Usa Inc. | Biodegradable stability binding agent for a solid detergent |
US9365805B2 (en) | 2014-05-15 | 2016-06-14 | Ecolab Usa Inc. | Bio-based pot and pan pre-soak |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996006156A1 (de) * | 1994-08-19 | 1996-02-29 | Henkel Kommanditgesellschaft Auf Aktien | Verfahren zur herstellung von wasch- oder reinigungsmitteltabletten |
EP0846756A1 (de) * | 1996-12-06 | 1998-06-10 | The Procter & Gamble Company | Beschichtetes Reinigungsmittel in Tablettenform |
WO1998040463A1 (de) * | 1997-03-13 | 1998-09-17 | Henkel Kommanditgesellschaft Auf Aktien | Wasch- oder reinigungsaktive formkörper für den gebrauch im haushalt |
DE19709991A1 (de) * | 1997-03-11 | 1998-09-17 | Herzog Stefan | In Flüssigkeit zerfallender Preßling |
DE19723028A1 (de) * | 1997-06-03 | 1998-12-10 | Henkel Kgaa | Hilfsmittelgranulat für wasch- und reinigungsaktive Formkörper |
WO1998055590A1 (en) * | 1997-06-06 | 1998-12-10 | Unilever Plc | Detergent compositions |
DE19739384A1 (de) * | 1997-09-09 | 1999-03-11 | Henkel Kgaa | Wasch- und Reinigungsmittelformkörper mit verbesserter Löslichkeit |
-
1999
- 1999-03-29 EP EP99106369A patent/EP1043389B1/de not_active Revoked
- 1999-03-29 ES ES99106369T patent/ES2159442T3/es not_active Expired - Lifetime
- 1999-03-29 DK DK99106369T patent/DK1043389T3/da active
- 1999-03-29 AT AT99106369T patent/ATE201714T1/de not_active IP Right Cessation
- 1999-03-29 DE DE59900108T patent/DE59900108D1/de not_active Revoked
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996006156A1 (de) * | 1994-08-19 | 1996-02-29 | Henkel Kommanditgesellschaft Auf Aktien | Verfahren zur herstellung von wasch- oder reinigungsmitteltabletten |
EP0846756A1 (de) * | 1996-12-06 | 1998-06-10 | The Procter & Gamble Company | Beschichtetes Reinigungsmittel in Tablettenform |
DE19709991A1 (de) * | 1997-03-11 | 1998-09-17 | Herzog Stefan | In Flüssigkeit zerfallender Preßling |
WO1998040463A1 (de) * | 1997-03-13 | 1998-09-17 | Henkel Kommanditgesellschaft Auf Aktien | Wasch- oder reinigungsaktive formkörper für den gebrauch im haushalt |
DE19723028A1 (de) * | 1997-06-03 | 1998-12-10 | Henkel Kgaa | Hilfsmittelgranulat für wasch- und reinigungsaktive Formkörper |
WO1998055590A1 (en) * | 1997-06-06 | 1998-12-10 | Unilever Plc | Detergent compositions |
DE19739384A1 (de) * | 1997-09-09 | 1999-03-11 | Henkel Kgaa | Wasch- und Reinigungsmittelformkörper mit verbesserter Löslichkeit |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002042404A1 (en) * | 2000-11-24 | 2002-05-30 | Unilever N.V. | Cleaning tablets |
WO2002044315A1 (en) * | 2000-11-24 | 2002-06-06 | Unilever N.V. | Cleaning compositions |
WO2002062933A1 (en) * | 2001-02-05 | 2002-08-15 | INEOS SILICAS LIMITED (formerly known as CROSFIELD LTD.) | Disintegrants and a process for their manufacture |
EP1314776A1 (de) * | 2001-11-23 | 2003-05-28 | Rohm And Haas Company | Optimierte teilchenförmige Zusammensetzungen |
DE10242222A1 (de) * | 2002-09-12 | 2004-03-25 | Henkel Kgaa | Unter Druck kompaktiertes Wasch- oder Reinigungsmittel |
WO2010063689A1 (de) * | 2008-12-05 | 2010-06-10 | Henkel Ag & Co. Kgaa | Maschinelle geschirrspülmitteltablette |
EP2358855B1 (de) | 2008-12-05 | 2015-08-19 | Henkel AG & Co. KGaA | Maschinelle geschirrspülmitteltablette |
US9988526B2 (en) | 2011-11-04 | 2018-06-05 | Akzo Nobel Chemicals International B.V. | Hybrid dendrite copolymers, compositions thereof and methods for producing the same |
WO2014075845A1 (en) * | 2012-11-16 | 2014-05-22 | Unilever N.V. | Surface cleaning composition |
CN104822819A (zh) * | 2012-11-16 | 2015-08-05 | 荷兰联合利华有限公司 | 表面清洁组合物 |
EA027538B1 (ru) * | 2012-11-16 | 2017-08-31 | Юнилевер Н.В. | Композиция для очистки поверхностей |
Also Published As
Publication number | Publication date |
---|---|
EP1043389B1 (de) | 2001-05-30 |
DE59900108D1 (de) | 2001-07-05 |
ATE201714T1 (de) | 2001-06-15 |
DK1043389T3 (da) | 2001-09-03 |
ES2159442T3 (es) | 2001-10-01 |
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