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
  • C11D3/3749—Polyolefins; Halogenated polyolefins; Natural or synthetic rubber; Polyarylolefins or halogenated polyarylolefins
• • 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
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0047—Detergents in the form of bars or tablets
  • C11D17/0065—Solid detergents containing builders
  • C11D17/0073—Tablets
  • C11D17/0091—Dishwashing tablets
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—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 dishwashing detergent tablets which contain a granulate which absorbs water particularly well and forwards it to the interior. In this case, there is an increase in volume, so that this granulate is suitable as a disintegrant for pressed molded articles, in particular from detergent compositions for dishwashers.
• Machine dishwashing generally consists of a pre-rinse cycle, one or more intermediate rinses, a rinse cycle and a drying cycle. This applies in principle to mechanical washing both in households, as well as in the commercial sector.
• the detergents used for machine washing of dishes can be liquid, powdery, pasty or tablet-shaped.
• the use of tablets is becoming increasingly popular because of the ease of handling and metering. There are already described several manufacturing processes are obtained by the tablets with temporally influenced dissolution behavior. Such tablets are often no longer filled into the dosing in the door of the machine, but added directly into the engine room, whereby a certain part of the tablets is already dissolved in the pre-wash, thereby chemically supporting the effect of normally addition-free tap water in this rinse phase.
• the solubility of the individual constituents or constituent mixtures is varied in EP-A-750 662 by adding hydrophobizing agents having different boiling and melting points to them.
• the pulverulent and / or crystalline constituents which contain no free water and no hydrated salts are coated alone or together with other readily soluble pulverulent or optionally granulated inorganic constituents by spraying on a liquid or liquefied hydrophobicizing compound. After addition of other components, the batch is compressed into tablets.
• DE-A-19 502 774 describes fracture-stable, readily soluble tablets which are obtained by the addition of sodium hypophosphate with high phase I content.
• Disintegrating agents for tablets or granules are auxiliaries which prevent the disintegration of tablets or granules in contact with liquids, in particular Positively influence water. In this case, both the disintegration of tablets in coarse parts and subsequently a disintegration into smaller particles is to be effected and accelerated.
• inorganic and organic substances As a disintegrating agent for tablets, a variety of inorganic and organic substances are known, for example, inorganic substances such as bentonites, persalts, acetates, alkali carbonates / bicarbonates and citric acid.
• organic compounds include starch, modified starch and starch degradation products, cellulose, cellulose ethers such as methylcellulose, hydroxypropylcellulose and carboxymethylcellulose, poly (meth) acrylates, polyvinylpyrrolidone and cross-linked polyvinylpyrrolidone, alginates, gelatin and pectins.
• disintegrants are citric acid or citrates, bicarbonates and carbonates, bisulfate and percarbonate, microcrystalline cellulose, sugar, sorbitol or swellable phyllosilicates. called by the type of bentonite or smectite.
• the disintegrants are used in amounts of 1 to 25 wt.% As a single raw material or as a compound.
• tablet disintegrants are incorporated in the tablet and preferably in the outer solid shell of the tablet.
• combinations of soluble acids and alkali carbonates are used.
• Other possible disintegrants can be found in the Handbook of Pharmaceutical Excipients (1986), examples of which are: starch (modified starch sodium starch gluconate), gum (agar, guar and others), cellulose, carboxymethyl cellulose, alginates, silicon dioxide, Clay, polyvinylpyrrolidone, polysaccharides and ion exchange resins.
• EP 1 043 388 describes dishwashing detergent tablets containing disintegrant granules comprising cellulose and polymers / copolymers of (meth) acrylic acid.
• the object of the invention is to provide compressed molded articles of washing and cleaning formulations, in particular for machine dishwashing detergents, which contain a particularly effective disintegrating agent, so that they disintegrate quickly and effectively both in the metering chamber, as well as in the cutlery basket of the Geschirrutzs.
• phosphate-containing or phosphate-free dishwasher cleaning tablets characterized in that in addition to conventional ingredients as a disintegrant a compacted granules is contained, which contains at least one polymer comprising ⁇ -olefins as monomeric units.
• the disintegrant contains a combination of such a polymer with water-swellable cellulose and / or cellulose derivatives or cellulose-containing material.
• the water-swellable cellulose is used in the form of cellulose fibers or microcrystalline cellulose, the supermolecular structural elements may have the form of fibrils in the longitudinal direction of which crystalline and amorphous areas can alternate. Fibrils of native cellulose having a maximum length of 300 ⁇ m have proven particularly suitable. Both microcrystalline and amorphous cellulose (derivatives) and mixtures thereof can be used.
• Cellulosic material should be one in which cellulose is at least predominantly chemically unchanged. As cellulosic material is primarily TMP (Thermo Mechanical Pulp) and CTMP (Chemo Thermo Mechanical Pulp) into consideration. There are two types of so-called wood pulp. In the TMP process wood chips are fiberized under pressure of steam at about 130 ° C in pressure refiner to TMP. When using chemicals in the Holzschnitzelverdämpfung isibt CTMP (see Römpp Chemie-Lexikon 9th Edition (1995), page 3207 keyword “paper”). The cellulose-containing material is preferably used with particle sizes of from 20 to 200 .mu.m, more preferably from 40 to 60 .mu.m (before compaction).
• cellulose is used in purified form (commercial cellulose), this preferably has bulk densities of from 40 g / l to 350 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 can be from 350 g / l to 550 g / l.
• the bulk densities of the cellulose derivatives may be 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 cellulose can be between 30 .mu.m and 400 .mu.m, in the case of granulated types, the average particle size is between 350 .mu.m and 800 .mu.m.
• the particle size of the cellulose derivatives or of the cellulose-containing materials can be between 30 ⁇ m and 3000 ⁇ m.
• the polymer used for the disintegrant may be present as a homopolymer or as a copolymer, which may comprise units of at least one ⁇ -olefin of any type, e.g. Olefins having 2 to 18 carbon atoms, wherein the double bond (s) may be represented at any position.
• a copolymer of an ⁇ -olefin and a cis-bifunctional acid, particularly preferably maleic acid is preferably used for the disintegrating agent according to the invention.
• the salt formation is preferably carried out with cations of alkali, ammonia and amines, or mixtures thereof.
• a particularly preferred disintegrant comprises a maleic-olefin copolymer available in the form of its Na salt under the trade name Sokalan® CP9 from BASF, Germany.
• Sokalan® CP9 has hitherto only been known as a dispersant for organic and inorganic solids in aqueous and aqueous-organic media, in liquid form. The use as granules and the use as a disintegrant is not yet described.
• the particle size of the polymer / copolymer used in the granules should preferably not exceed 800 .mu.m, since the particles can otherwise settle visibly on the dishes.
• the disintegrating agent may consist entirely of said polymer, or it may be a mixture of such a polymer with cellulose (derivatives) or cellulose-containing material.
• the proportion of cellulose (derivatives) or of the cellulose-containing material in the disintegrant granulate can be from 50 to 99% by weight, preferably from 70 to 97% and particularly preferably from 80 to 95% by weight.
• the proportion of the polymer can be from 50 to 1% by weight, preferably from 30 to 3% by weight, particularly preferably from 20 to 5% by weight, of the disintegrant granulate.
• regenerated celluloses such as viscose may also be used.
• cellulose ethers Due to their water-absorbing capacity, water-swellable cellulose derivatives such as cellulose ethers and cellulose esters and mixed modifications thereof are also useful. Suitable cellulose ethers are e.g. Methylcellulose, hydroxypropylcellulose and carboxymethylcellulose, as well as modified carboxymethylcellulose.
• the granules may contain water-swellable cellulose derivatives 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, nonionic modified celluloses and starches such as alkoxylated celluloses and starches such as hydroxypropyl and hydroxyethyl starch or hydroxypropyl and hydroxyethyl cellulose and alkyletherethererte products such as methylcellulose and mixed modified celluloses and starches from the aforementioned modifications, which leads to crosslinking.
• ionically modified celluloses and starches such as carboxymethyl modified cellulose and starch
• nonionic modified celluloses and starches such as alkoxylated celluloses and starches such as hydroxypropyl and hydroxyethyl starch or hydroxypropyl and hydroxyethyl cellulose and alkyletherethererte products
• 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. 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 proven itself.
• 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.%.
• the disintegrant granules may also comprise other types of polymer, such as finely divided and / or aqueous solutions of soluble polymers of (meth) acrylic acid or copolymers of (meth) acrylic acid or salts thereof or mixtures thereof Polymers or copolymers or salts thereof with high water absorption capacity.
• Suitable are linear polymers of (meth) acrylic acid, copolymers of (meth) acrylic acid or salts thereof having weight average molecular weights of 5,000 to 70,000 and crosslinked polymers of (meth) acrylic acid, copolymers of (meth) acrylic acid or salts thereof having weight average molecular weights of 1,000 .000 to 5,000,000 can be viewed.
• the copolymers are preferably copolymers of (meth) acrylic acid and 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, their relative molar mass, 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 may be contained, prepared from (meth) acrylic acid.
• the polymers are preferably used in the preparation of the granules in the form of their aqueous solutions, but can also be used in the form of finely divided powders.
• the polymers / copolymers used according to the invention can be incorporated particularly well into the granules if they are at most 800 ⁇ m in size.
• Suitable co-binders which simultaneously have a surfactant character are so-called polymer surfactants. These are understood to mean reaction products which, in addition to the typical polymer structures of the abovementioned polymers, have additional structural elements which unfold a surfactant effect. Examples of these are graft polymers with alkoxylated fatty alcohol or carboxylate-containing polymers with methoxyalkylene oxide monomer units, furthermore maleic acid / vinyl ethers / longer-chain fatty amine copolymers and also 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.
• the polymer surfactants can also be incorporated alone, ie without a polymeric binder component and without a surfactant component, into the disintegrant granules.
• the polymer surfactants will be present in the disintegrant granules with a proportion of up to 30% by weight, as sole component with 1 to 40% by weight, preferably with 5 to 20% by weight.
• the polymers / copolymers which contain ⁇ -olefins as monomeric units, for example .alpha.-olefins and maleic acid, or salts thereof with cellulose (derivatives) or cellulose-containing material and optionally further modified water-swellable Polysaccharide derivatives in the granules combined, wherein the weight ratio (cellulose (derivative) / cellulosic material: polymer) of 50: 1 to 1: 1 may be, preferably from 20: 1 to 5: 1, most preferably a weight ratio of 12: 1 to 8: 1.
• the polymers / copolymers or salts thereof together with cellulose (derivatives) or the cellulose-containing material are predispersed in water, wet granulated and then dried.
• the wet granulation and the subsequent evaporation gives the granules a porous structure in which the polymer / copolymer or its salt is attached to the surface of the cellulose, of the cellulose derivative or of the cellulose-containing material.
• the granules are preferably dried to a residual water content of 1 to 8% by weight, based on the weight of the granules.
• the porous structure gives a particularly favorable absorption capacity for liquids, in the case of water with rapid volume increase.
• the disintegrant granules to be used according to the invention are initially produced by mixing the granule constituents to be used according to the invention with customary mixing processes. For example, 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 is depending on the compression device used.
• a water content of at least 10% by weight, preferably 20% by weight, is required in order to achieve good compaction. and to guarantee a high liquid absorption in the later dry granulate.
• these precompounds are mechanically compacted.
• the final compaction is essential.
• the compression using pressure can be done in various ways.
• the products can be placed between two pressure surfaces in roller compactors, e.g. smooth or profiled, compacted.
• the output of the Kompaktats takes place as a strand.
• Densification methods in dies with punches or pillow rolls result in copactate forms such as tablets or briquettes.
• Roller compactors, extruders, roller or die presses, but also granulation presses can be used as compacting machines.
• pelleting presses Compaction with pelleting presses has proved particularly suitable, granules being obtained by suitable process control which can be dried without further comminution.
• suitable pelleting presses are e.g. produced by the companies Amandus Kahl and Fitzpatrick.
• conventional dryers such as drum dryers (eg temperatures of 95 to 120 ° C) or fluidized bed dryer (temperatures, for example, from 70 to 100 ° C) suitable.
• 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 are adjusted to a particle size distribution of 0.05 to 3 mm, preferably 0.1 to 1.5 mm.
• the removal of dust particles below 0.1 mm may e.g. be carried out with conventional screening devices.
• any other conventional method may also be used, e.g. the spraying in the spray granulation in a fluidized bed, but for the swelling and water absorption behavior of the disintegrant granules according to the invention, but the wet granulation and subsequent drying has been found to be particularly suitable.
• the polymer used is "frozen” by the granulation and drying process in a particular three-dimensional "cocked” configuration. Upon contact with water, the "frozen” configuration is changed very quickly in favor of another configuration in which the hydrophobic and hydrophilic regions of the polymer align in the water to bring the polymer into an energetically favorable state. The blasting effect is thus based on a configuration change of the polymer used.
• the configuration change has a particularly pronounced effect when the granules used as disintegrants consist entirely of a polymer containing at least one ⁇ -olefin.
• granules are obtained by the wet granulation and the subsequent drying of cellulose / cellulose derivatives predispersed in water together with the polymer / copolymer, or of the cellulose-containing material and / or starch / starch derivatives, which also has a high explosive effect.
• the efficiency is probably achieved by the capillary action of the pores and the resulting rapid penetration of the granules with water.
• Shaped bodies of various compositions of cleaning formulations. containing such granules according to the invention are rapidly and effectively blasted when used in dosing or direct addition in baskets of domestic or commercial dishwashers.
• the disintegrant granules to be used according to the invention have bulk densities of from 80 g / l to 800 g / l, preferably from 100 g / l to 500 g / l, very particularly preferably from 250 g / l to 400 g / l, and are in the layer (s) (s) / area (s) of the molded articles in which they contain are contained in amounts of 1 wt.% To 15 wt.%, Preferably 2 wt.% To 10 wt.% And particularly preferably 3 to 6 wt.%.
• the granules on contact with water this increases rapidly under volume and is therefore suitable as a disintegrant for pressed moldings, so that they rapidly disintegrate in water.
• Such moldings must have sufficient stability and strength to allow handling, packaging and storage, but should disintegrate rapidly on contact with water, so that the ingredients can develop the desired effect.
• the invention relates to compressed molded articles, for example tablets, cubes, cuboids, spheres and the like, in which a compacted, porous granules are contained as disintegrating agents.
• the shaped articles can consist of any type of composition which can be broken up into their individual parts, in particular of detergent compositions.
• Moldings of detergent formulations for dishwashers in tablet, bar or cube form are particularly preferred.
• the detergent tablets can be pressed from only one detergent composition (single-phase tablets), or they can consist of several phases, layers or regions, ie, for example, two- or three-phase tablets (eg "3 in 1").
• individual components of the cleaning agent can be separated from each other, so that they are provided at different times during the cleaning process.
• An example of this is the separation of the cleaning, the salt function and the rinse aid function into individual regions of the molding used.
• the spatial form of the moldings can be adapted in their dimensions of the dispensing compartment of the dishwasher, but all reasonable manageable shapes can be designed. These include e.g. also cylindrical embodiments with an oval or circular cross-section and shaped body with a plate or panel-like structure.
• a preferred shaped body consists of alternately thick long and thin short segments, so that individual segments of such a bar at predetermined breaking points, which are represented by the short thin segments, broken and can be entered into the metering chamber or the cutlery basket of the machine. This principle of the bar-shaped shaped body can also be realized in other geometric polygonal shapes.
• a tablet produced in this way preferably has a weight of from 5 to 120 g, particularly preferably from 10 to 30 g, with diameters of from 20 to 50 mm being preferred.
• Detergent tablets for different purposes, especially for dishwashers are basically known.
• Such detergent formulations formed as shaped articles generally comprise builders, bleaching agents and bleach activators, surfactants, tableting aids, disintegrants and other customary additives and auxiliaries.
• the composition of the cleaning agent which is present as a molded body, not decisive, as long as it is a composition which is suitable as a cleaning agent, especially for use in a dishwasher.
• Any conventional moldable composition suitable for this purpose may be mixed with the disintegrant granules of the present invention and compressed.
• the compositions described below are merely preferred embodiments of the detergent compositions without the granules being usable only in such compositions.
• a preferred embodiment of the invention is a phosphate-containing dishwashing detergent tablet containing: 10 to 75 parts by weight.
• Polyphosphate (s) 60 to 0 parts by weight. other inorganic builders, 20 to 0 parts by weight. organic builders, 7 to 20 parts by weight peroxide bleaching agent, 10 to 1 parts by weight.
• Bleach activator (s) 0 to 16 parts by weight.
• Surfactant (s) 0.1 to 10 parts by weight.
• a phosphate-free dishwashing detergent tablet comprising: 0 to 50 parts by weight. Citrate (s) / citric acid, 36 to 0 parts by weight. Silicate, 32 to 0 parts by weight Na carbonate, 0 to 20 parts by weight. bicarbonate, 10 to 0 parts by weight. polymeric organic builders, 4 to 18 parts by weight peroxide bleaching agent, 8.8 to 1 part by weight. Bleach activator (s), 0.2 to 16 parts by weight. Surfactant (s), 10 to 0.1 parts by weight. Disintegrator granules, 1 to 5 parts by weight other, customary auxiliaries and additives.
• both mono-, as well as double or triple tablets are preferred.
• the disintegrant may be included in all layers / phases of the cleaning tablet, but is preferably contained in only one or two (in the presence of multiple layers / phases) layers / phases. This is preferred to dissolve a first layer / phase containing rapidly acting ingredients in the rinse water in a short time and to provide the ingredients therewith, while another layer / phase containing ingredients will be at a later time the rinsing process to be used, slower dissolves, since it contains no or a "slower" disintegrant.
• Suitable builders in the detergent composition are all customary and known builders, in particular 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, tartaric and malic acid.
• co-builders and dispersants are used as auxiliary builder.
• Such co-builders or dispersants may be, inter alia, polyacrylic acids or copolymers with polyacrylic acid and its sodium salts.
• Typical bleaching agents are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, sodium percarbonate, peroxypyrophosphates, citrate perhydrates, and H 2 O 2 -forming peracidic salts, peracids, such as perbenzoates, peroxyphthalates, diperazelaic acid and diperdodecanedioic acids.
• peracids such as perbenzoates, peroxyphthalates, diperazelaic acid and diperdodecanedioic acids.
• bleaching agents or bleach systems may also be present in the composition.
• suitable peroxygen compounds are in particular hydrogen peroxide and under the washing conditions hydrogen peroxide donating inorganic salts to which alkali metal perborates such.
• Sodium perborate tetrahydrate and sodium perborate monohydrate further include alkali metal carbonate perhydrates such as sodium carbonate perhydrate ("sodium percarbonate”) and persilicates and / or persulfates such as caroate.
• the bleach system of the detergent formulation may contain inorganic or organic peracids, especially percarboxylic acids, e.g. B.
• acids which can be used are peracetic acid, perbenzoic acid, linear or branched octane, nonane, decane or dodecane monoperacids, decane and dodecane diperacids, mono- and diperphthalic acids, isophthalic and terephthalic acids, phthalimidopercaproic acid, terephthaloyldiamidopercaproic acid and e-phthalimido peroxohexanoic acid (PAP).
• peracetic acid perbenzoic acid
• linear or branched octane nonane
• decane or dodecane monoperacids
• decane and dodecane diperacids mono- and diperphthalic acids
• isophthalic and terephthalic acids phthalimidopercaproic acid
• terephthaloyldiamidopercaproic acid e-phthalimido peroxohexanoic acid (PAP).
• percarboxylic acids can be used as free acids or as salts of the acids, preferably alkali or alkaline earth metal salts.
• solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle.
• a particularly preferably used peracid is the peracid available under the trade name Eureco® (Ausimont, Italy).
• Peroxygen compounds are present in amounts of preferably up to 50% by weight, more preferably from 5% to 30% and most preferably from 8% to 25% by weight.
• bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.
• the content of bleaching agents in tablets is preferably 5-60% by weight and especially 7-20% by weight.
• the bleach catalysts used are usually quaternized imines or sulfonimines, as described, for example, in US Pat. No. 5,360,568, US Pat. No. 5,360,569 and EP-A-453,003, as well as manganese complexes, as described, for example, in WO-A 94/21777 are.
• Other useful metal-containing bleach catalysts are described in EP-A-458,397, EP-A-458,398 and EP-A-549,272.
• Bleach catalysts are generally used in amounts of up to 1 wt .-%, in particular 0.01 to 0.5 wt .-%, based on the detergent formulation.
• 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).
• compounds of the substance classes of polyacylated sugar or sugar derivatives with C 1 -C 10 -acyl radicals can be used, preferably with acetyl, propionyl, octanoyl, nonanoyl or benzoyl radicals, in particular acetyl radicals.
• Suitable sugars or sugar derivatives are mono- or disaccharides and their reduced or oxidized derivatives, preferably glucose, mannose, fructose, sucrose, xylose or lactose.
• bleach activators of this class of substances are, for example, pentaacetylglucose, xylose tetraacetate, 1-benzoyl-2,3,4,6-tetraacetylglucose and 1-octanoyl-2,3,4,6-tetraacetylglucose.
• O-Acyloximester such as O-acetylactone oxime, O-benzoylacetone oxime, bis (propylimino) carbonate or bis (cyclohexylimino) carbonate.
• acylated oximes and oxime esters are described, for example, in EP-A-028 432 and EP-A-267 046.
• N-acyl caprolactams such as N-acetyl caprolactam, N-benzoyl caprolactam, N-octanoyl caprolactam, N-octanoyl caprolactam, or carbonyl biscaprolactam.
• bleach activators are 2-alkyl- or 2-aryl- (4H) -3,1-benzoxain-4-ones, as described, for example, in EP-B-332 294 and EP-B-502 013.
• 2-phenyl- (4H) -3,1-benzoxain-4-one and 2-methyl- (4H) -3,1-benzoxain-4-one are useful.
• bleach activators from the classes of N- or O-acyl compounds for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic acid anhydrides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives, such as pentaacetyl-glucose are used.
• polyacylated alkylenediamines in particular tetraacetylethylenediamine
• acylated glycolurils in particular tetra
• a preferred bleach activator is a quaternized glycine nitrile from the group consisting of N-methylmorpholinium acetonitrile methyl sulfate, sulfate and hydrogen sulfate.
• bleaching agents and bleach activators As a bleach system (bleaching agents and bleach activators), it is also possible for all of the bleaching agents and activators mentioned in DE 199 59 589 A1 to be present. In addition, the bleach systems mentioned in European patent application EP 02 028 958.3 can also be used.
• the different constituents of the detergent composition are contained in different phases / layers / regions of the moldings.
• a component to be provided at a late time of the cleaning operation is in a phase / layer / region in which no disintegrant is contained.
• the cleaning agents may also contain one or more surfactants (s) from the group of nonionic, anionic, cationic and / or amphoteric surfactants.
• nonionic surfactants in the detergent composition only in small amounts, preferably below about 16% by weight, more preferably in ranges of from 0 to 8% by weight of the detergent, or in the detergent phase, which preferably contains the disintegrant.
• Detergents come from the groups of surfactants, enzymes, corrosion inhibitors and dyes and fragrances. These substances are described below.
• the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
• EO ethylene oxide
• 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 of these, 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 means which, for a particular product, may be an integer or a fractional number.
• preferred Alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
• fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
• nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
• the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
• nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.
• Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
• the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
• polyhydroxy fatty acid amides of the formula (I) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
• the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
• the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
• R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
• R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
• R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyaryl radical having 1 to 8 carbon atoms, wherein C 1 -C 4 alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.
• [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• the N-alkoxy- or N-aryloxy-substituted compounds can then be converted by reaction with fatty acid methyl esters in Presence of an alkoxide can be converted as a catalyst into the desired polyhydroxy fatty acid amides.
• the automatic dishwashing detergent tablets according to the invention comprise nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols.
• the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
• EO ethylene oxide
• the preferred ethoxylated alcohols include, for example, C 12 -C 14 -alcohols with 3 EO or 4 EO, C 9 -C 11 -alcohol 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 of these, 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 means which, for a particular product, may be an integer or a fractional number.
• Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). additionally Fatty alcohols with more than 12 EO can also be used for these nonionic surfactants. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
• detergent tablets according to the invention which contain a nonionic surfactant which has a melting point above room temperature.
• preferred detergent tablets are characterized in that they contain as ingredient c) nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and in particular between 26, 6 and 43.3 ° C included.
• Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If high-viscosity nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.
• Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
• Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
• the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant resulting from the reaction of a monohydroxyalkanol or alkylphenol having from 6 to 20 carbon atoms, preferably at least 12 Mol, more preferably at least 15 moles, in particular at least 25 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
• a particularly preferred room temperature solid nonionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16 -C 20 alcohol), preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and especially at least 25 moles of ethylene oxide won.
• C 16 -C 20 alcohol straight chain fatty alcohol having 16 to 20 carbon atoms
• C 18 alcohol preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and especially at least 25 moles of ethylene oxide won.
• the so-called “narrow range ethoxylates" are particularly preferred.
• the nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule.
• such PO units make up to 25 wt .-%, particularly preferably 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
• Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
• the alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
• nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
• Nonionic surfactants which may be used with particular preference are available, for example, under the name Poly Tergent® SLF-18 from Olin Chemicals.
• Further preferred detergent tablets according to the invention contain nonionic surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (OH) R 2 ], in which R 1 represents a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15 ,
• nonionic surfactants which may be used are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2 X is butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
• each R 3 in the above formula may be different.
• R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
• R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
• Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
• each R 3 in the above formula may be different if x is 2.
• the alkylene oxide unit in the square bracket can be varied.
• R 3 H
• R 3 propylene oxide
• the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
• R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
• Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
• Suitable enzymes in the detergent tablets according to the invention are, in particular, those from the classes of hydrolases, such as proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of said enzymes. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy stains. For bleaching and oxidoreductases can be used. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Coprinus cinereus and Humicola insolens as well as from their genetically modified variants obtained enzymatic agents.
• hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of said enzymes. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy stains.
• subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
• enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic acting enzymes, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
• lipolytic enzymes are the known cutinases.
• Peroxidases or oxidases have also proved suitable in some cases.
• Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
• the enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation.
• the proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-%.
• preferred detergent tablets are characterized in that they contain protease and / or amylase.
• detergent moldings are preferred in which the enzyme (s) is / are not included in one phase together with the bleach-enhancing drug combination.
• Detergent tablets characterized in that at least one phase contains bleach while at least one other phase contains enzymes are also preferred embodiments of the present invention.
• the detergents according to the invention may contain corrosion inhibitors for protecting the items to be washed or the machine, with silver protectants in particular being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art.
• silver protectants can be selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes. Particularly preferred to use are benzotriazole and / or alkylaminotriazole.
• cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
• chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, zinc compounds can be used to prevent corrosion on the items to be washed.
• organic redox-active compounds such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds.
• zinc compounds can be used to prevent corrosion on the items to be washed.
• detergent tablets contain corrosion inhibitors, they are preferably separated from the bleaching agents. Accordingly, detergent tablets in which at least one phase contains bleach while at least one other phase contains corrosion inhibitors are preferred.
• Preferred anionic surfactants are the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
• Preferred sulfosuccinates contain C8 to C18 fatty alcohol residues or mixtures of these.
• Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty acids, which in themselves constitute nonionic surfactants (see description below).
• alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
• Preferred anionic surfactant mixtures contain combinations of alk (en) ylsulfates, in particular mixtures of saturated and unsaturated fatty alk (en) ylsulfates, and alkylbenzenesulfonates, sulfonated fatty acid glycerol esters and / or ⁇ -sulfofatty acid esters.
• mixtures are preferred here which contain as anionic surfactants alk (en) ylsulfates and alkylbenzenesulfonates, alk (en) ylsulfates and ⁇ -sulfofatty acid methyl esters and / or sulfonated fatty acid glycerol esters.
• anionic surfactants are in particular soaps, preferably in amounts of 0.1 to 5 wt.% Into consideration. Suitable examples are saturated fatty acid soaps, 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. Particularly preferred are those soap mixtures 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 present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
• the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of their sodium salts.
• inorganic salts which react alkaline in water.
• These inorganic alkaline salts include in particular bicarbonates, carbonates or mixtures thereof.
• alkali metal carbonate and especially sodium carbonate are used.
• Examples of other customary additives and auxiliaries are enzymes, magnesium silicates, aluminum aluminates, benzotriazole, glycerol, magnesium stearate, polyalkylene glycols, hexametaphosphate and phosphonates.
• Another component of the detergent composition are substances which have an anti-corrosion effect on glass. Glass corrosion protection is also already achieved through the use of the polymer used for the disintegrant, since such a polymer lays a thin film over the glass which protects the glass from corrosion, but other well-known anti-corrosive agents can also be used. Examples of these are metal oxides, e.g. Oxides of zinc, aluminum, tin, magnesium, calcium, strontium, silicon, titanium, zirconium, manganese and lanthanum, or insoluble inorganic zinc compounds, as described in EP 0383482, or zinc or magnesium salts of organic compounds, such as they are described in DE 101 40 535.
• Oxides of zinc, aluminum, tin, magnesium, calcium, strontium, silicon, titanium, zirconium, manganese and lanthanum or insoluble inorganic zinc compounds, as described in EP 0383482, or zinc or magnesium salts of organic compounds, such as they are described in DE 101 40 535.
• colorants and fragrances may be added to the machine dishwashing detergents according to the invention in tablet form in order to improve the aesthetic impression of the resulting products and to the consumer in addition to the performance to provide a visually and sensory "typical and distinctive" product.
• perfume oils or perfumes individual fragrance compounds, eg.
• ethers, aldehydes, ketones, alcohols and hydrocarbons are used as the synthetic products of the ester type. Fragrance compounds of the ester type are e.g.
• the ethers include, for example, benzyl ethyl ether to the aldehydes z. B.
• the linear alkanals having 8 to 18 carbon atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones z.
• the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and termpineol; the hydrocarbons mainly include the terpenes such as limonene and pinene.
• mixtures of different fragrances are used, which together produce an attractive fragrance.
• perfume oils may also contain natural fragrance mixtures as are available from vegetable sources, e.g.
• Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil are also suitable.
• the fragrances can be incorporated directly into the moldings of the invention, but it may also be advantageous to apply the fragrances on carriers.
• carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
• an incorporation of the fragrances as ingredient d) in the inventive Detergent components is possible and leads to a fragrance impression when opening the machine.
• the agents according to the invention can be dyed with suitable dyes.
• Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and against light and no pronounced substantivity to the substrates to be treated with the agents such as glass, ceramic or plastic dishes, not to stain them.
• the coloring of individual phases for optical differentiation is preferred.
• the tablets mentioned in the examples can be used as mono-, double- and triple-phase tablets.
• the individual constituents can be distributed in different regions / phases of the shaped bodies.
• Table 1 Examples of compositions of phosphate-containing dishwashing tablets (all amounts in parts by weight).
• formulation 1 2 3 4 Component: Na tripolyphosphate 35,00 45,00 18,00 60,00 Na carbonate 30.00 20.00 10.00 - Na-bicarbonate - - 10.00 - silicate 4.00 10.00 5.00 - citrate - 5.00 10.00 - Na-percarbonate or Na-perborate 15.00 8.00 20.00 20.00 20.00 TAED 4.00 5.00 2.00 2.00 2.00 nonionic surfactant 2.00 1.00 5.00 2.00 phosphonate 1.00 0.50 2.00 1.00 Acrylate-maleate copolymer 1.00 - 5.00 3.00 enzymes 2.00 1.00 3.00 2.00 Polyethylene glycol 1,500 - 10,000 2.00 3.00 1.00 2.00 Perfume 0.50 0.05 2.00 1.00 explosives 3.50 1.45 7.00 7.00
• Table 2 Examples of compositions of phosphate-free dishwasher tablets (all amounts in parts by weight).
• formulation 5 6 7 Component: Na carbonate 30.00 15.00 - Na-bicarbonate - - 5.00 silicate 4.00 15.00 30.00 citrate 35,00 50,00 20.00 Na-percarbonate or Na-perborate 15.00 8.00 18,00 TAED 4.00 5.00 2.00 nonionic surfactant 2.00 1.00 5.00 phosphonate 1.00 0.50 2.00 Acrylate-maleate copolymer 1.00 - 5.00 enzymes 2.00 1.00 3.00 Polyethylene glycol 1,500 - 10,000 2.00 3.00 1.00 Perfume 0.50 0.05 2.00 explosives 3.50 1.45 7.00
• Nilyl XL 16 is a commercially available cellulose-based disintegrant available from FMC corporation USA.
• Supercel is the disintegrant described herein according to the invention containing cellulose and an ⁇ -olefin-maleic acid copolymer (Sokalan CP9) in the form of a "mixed granulate"
• a disintegrant comprising a polymer containing at least one alpha-olefin "(Supercel) disintegrates a dishwashing detergent composition compressed into a tablet at a low concentration much faster than previously available disintegrants on the market.
• Basic formulation used for a detergent composition ingredient % w / w sodium tripolyphosphate 50 sodium 30.75 Enzymes (granules) 10 Polyethylene glycol MW 200 1.2 Polyethylene glycol MW 4000 1 perfume oil 0.05 Alkoxylated (EO / PO) fatty alcohol 1 94 ⁇
• a 3-phase tablet is prepared, in which one phase of the detergent composition corresponded, as stated above. This phase represented 20% of the total tablet.
• the total weight of the 3-phase tablet was 20 g.
• the disintegration time of the disintegrant-containing phase after storage was determined. The results are shown in Table 5.
• Table 5 Decay times of the phases containing the disintegrant in seconds
• a disintegrating agent (Supercel) according to the invention not only shows a significantly better explosive effect immediately after pressing the tablet than a commercially available disintegrating agent Cellulosic disintegrants, but still has this better explosive effect even after prolonged storage.
• Example 4 To the detergent composition of Example 4 is added as disintegrant once 6% w / w Supercel, once 6% w / w Supercel + 2% w / w Sokalan CP 9 in granular form ("CP 9 granules"). Three-phase tablets are compressed as in Example 4, one of the phases consisting of these detergent compositions. This phase accounts for 20% of a 20 g tablet. Again, the disintegration time of this phase is determined in water after storage. The results are shown in Table 6.
• Table 6 Disintegration times of the disintegrant-containing phase after storage in seconds
• Table 6 Age of the tablet explosives Supercel Supercel + CP 9 granules 1 day 57 sec 37 sec 4 weeks 56 sec 48 sec 8 weeks 152 sec 94 sec
• detergent compositions were prepared: ingredient Formulation A Formulation B % w / w % w / w sodium tripolyphosphate 74.75 78.25 Enzymes (granules) 11 12 Polyethylene glycol MW 200 1.2 1.2 Polyethylene glycol MW 4000 1.5 1.5 perfume oil 0.05 0.05 Alkoxylated (EO / PO) 1 1 fatty alcohol Phosphonate granules (HEDP) 1 1 Sokalan® CP9 granules 5 5 Nilyn XL 16 4.5 0

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