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
  • 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
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

• the invention is directed to dishwasher tablets, which contain a compacted porous granulate that is particularly good at water picks up and forwards inside. There is an increase in volume, so that this granulate as a disintegrant for pressed moldings, in particular from detergent compositions for dishwashers suitable is.
• Machine dishwashing generally consists of a pre-wash cycle one or more intermediate rinse cycles, a rinse cycle and one Drying cycle. In principle, this applies to machine washing both in Households, as well as in the commercial sector.
• the means used for the automatic cleaning of dishes can be liquid, powder, paste or tablet.
• the application of tablets is because of the easy handling and dosing More and more popular.
• Several manufacturing processes have already been described, through the tablets with dissolving behavior that can be influenced over time be preserved. Such tablets are often no longer in the dosing boxes filled in the door of the machine, but directly into the machine room given, whereby a certain part of the tablets already in the Pre-rinse is loosened and thereby the effect of the normally additive-free Tap water chemically supported in this rinsing phase.
• DE-A-35 41 145 discloses uniformly composed alkaline cleaning tablets Known for dishwashing, which has a broad solubility profile exhibit. These contain a mixture of sodium metasilicate nonahydrate and anhydrous metasilicate and anhydrous pentasodium triphosphate and other components.
• DE-A-41 21 307 discloses stable, bifunctional, phosphate and metasilicate-free low alkaline detergent tablets for mechanical Dishwashing known, the framework substances in part in anhydrous Form used and sprayed with water during manufacture what the desired solubility profile and very good compressibility.
• solubility of the individual components or component mixtures is varied in EP-A-750 662 by the fact that it has hydrophobicizing agents with different boiling and melting points can be added.
• the powdery and / or crystalline components that are not free water and no high-hydrate salts contain alone or together with other readily soluble powder or, if necessary granulated inorganic components by spraying a liquid or liquefied hydrophobizing compound coated. After expand other components, the batch is pressed into tablets.
• Disintegrants for tablets or granules are auxiliary substances that disintegrate tablets or granules in contact with liquids, in particular Influence water positively.
• the decay of Tablets in large parts and then a disintegration into smaller ones Particles are caused and accelerated.
• inorganic and organic disintegrants for tablets are Substances known, for example inorganic substances such as bentonites, also persalts, acetates, alkali carbonates / hydrogen carbonates and citric acid.
• organic compounds include starch, modified Starch and starch degradation products, cellulose, cellulose ethers, such as Methyl cellulose hydroxypropyl cellulose and carboxymethyl cellulose, poly (meth) acrylates, Polyvinyl pyrrolidone and cross-linked polyvinyl pyrrolidone, Alginates, gelatin and pectins.
• 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.
• EP-A-846 756 tablet disintegrants are preferred in the tablet and incorporated into the outer hard shell of the tablet.
• Combinations of soluble acids and alkali carbonates are used.
• Other possible explosives 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.
• the object of the invention is to produce pressed molded articles of washing and cleaning formulations, to provide especially for machine dishwashers, which contain a particularly effective disintegrant, so that both in the dosing chamber and in the cutlery basket of the dishwashing machine disintegrate quickly and effectively.
• phosphate-containing or phosphate-free dishwasher cleaning tablets characterized in that in addition compacted, porous granules from common components water-swellable cellulose and optionally other modified water swellable polysaccharide derivatives and polymers / copolymers of (Meth) acrylic acid or salts thereof as disintegrants in amounts of 0.5 up to 10 parts by weight is included.
• the water-swellable cellulose is in the form of cellulose fibers or microcrystalline cellulose used, the super-molecular structural elements have the shape of fibrils in the longitudinal direction can alternate crystalline and amorphous areas. As particularly suitable have fibrils of native cellulose with a maximum length of 300 ⁇ m proved. Both microcrystalline and amorphous cellulose can be used and mixtures thereof can be used.
• 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, non-ionically 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
• non-ionically modified celluloses and starches such as alkoxylated celluloses and starches such as hydroxypropyl and hydroxye
• 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 finely divided and / or aqueous Solutions of soluble polymers of (meth) acrylic acid or copolymers of (Meth) acrylic acid or salts thereof or mixtures of such polymers or copolymers or salts thereof with high water absorption contained in the granulate.
• Linear ones have proven to be particularly suitable Polymers of (meth) acrylic acid, copolymers of (meth) acrylic acid or salts the same with weight average molecular weights of 5,000 to 70,000 and cross-linked polymers of (meth) acrylic acid, copolymers of (Meth) acrylic acid or salts thereof with weight average molecular weights proven from 1,000,000 to 5,000,000.
• the copolymers are concerned it is preferably a copolymer of (meth) acrylic acid and maleic acid or maleic anhydride, for example 40 to 90% by weight (Meth) acrylic acid and 60 to 10% by weight of maleic acid or maleic anhydride contain, whose relative molar mass, based on free acids, between 3,000 and 100,000, preferably 3,000 to 70,000 and very particularly preferred Is 5,000 to 50,000.
• Ter- and quattropolymeric polycarboxylates have also proven to be very suitable proven, made from (meth) acrylic acid, maleic acid and vinyl alcohol or vinyl alcohol derivatives, or those of (meth) acrylic acid, ethylenically unsaturated sulfonic acids and sugar derivatives, or such (Meth) acrylic acid, maleic acid, vinyl alcohol derivatives and sulfonic acid groups Monomers.
• suitable polymers 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.
• 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 / cellulose derivatives are together with the polymers / copolymers predispersed of (meth) acrylic acid or salts thereof in water, wet compacted and granulated and then dried. Through the wet granulation and the subsequent evaporation of the Water to a residual water content of 2 to 8 wt.% Based on weight of the granules, this receives a specific porous structure in which the Polymer / copolymer of (meth) acrylic acid or its salt on the surface the cellulose / cellulose derivative with encrustation of the surface is attached.
• 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.
• 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. Especially nonionic surfactants are 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 3 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 are selected from alkyl polyglucosides, fatty acid alkylolamides, Fatty acid polyethylene glycol esters, fatty amine oxethylates, Fatty alcohol ethoxylates with 3-15 mol ethylene oxide or propylene oxide, Fatty acid glycerides, sorbitan esters, sucrose esters, e.g.
• Pentaerythritol partial esters which can also be ethoxylated, as well as alkylphenol polyethylene glycol ethers and phenol polyethylene glycol ethers (if these can be used in the respective country)
• the anionic surfactants are selected from alkyl sulfates, linear and branched alkylbenzenesulfonates, alkylglycerol ethers, fatty alcohol polyethylene glycol ether sulfates, Paraffin sulfonates, alpha olefin sulfonates, Sulfosuccinates, phosphoric acid esters and fatty alcohol ether carboxylates.
• amphoteric surfactants are selected from coconut fatty acid amidopropyl betaine, modified imidazolines and fatty acid amide derivatives with betaine structure.
• the quantitative ratio of cellulose 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 specific porosity of the explosive granules is determined using a known standard method for determining the dimension the porosity of solids:
• 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 granulate (e.g. 2.00 g) is placed in a thin paper bag, sealed like a teabag and in a jar with one Excess water submerged. After 3 minutes of immersion, the bag removed from the water and hung for 10 minutes to drain. The bag is weighed and from the weight difference of a wet bag determines the water absorption with and without granules. For the determination can use distilled water or water of defined hardness become.
• 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.
• 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.
• the invention relates to pressed molded articles, for example tablets, Cubes, cuboids, spheres and the like, in which a compacted porous granules are contained as disintegrants.
• Shaped bodies of detergent formulations are particularly preferred for dishwashers in tablet, bar or cube form.
• the spatial shape of the molded body can in its dimensions of the induction chamber be adapted to the dishwasher, however, all sensible design manageable shapes. These include e.g. also cylindrical Designs with oval or circular cross-section and molded body with a plate-like or plate-like structure.
• a preferred one Shaped body consists of alternately thick long and thin short segments, so that individual segments of such a bolt at predetermined breaking points, which are represented by the short thin segments and entered into the dosing chamber or the cutlery basket of the machine can be. This principle of the bar-shaped body can can also be realized in other geometric polygonal shapes.
• a tablet produced in this way preferably has a weight of 5 to 120 g, particularly preferably from 10 to 30 g, with a diameter of 20 to 50 mm are preferred.
• Contain such detergent formulations in the form of shaped articles usually builders, bleaches and bleach activators, Surfactants, tableting aids, disintegrants and other usual additives and auxiliaries.
• a preferred embodiment of the invention is a phosphate-containing dishwasher cleaning tablet, comprising: 10 to 60 parts by weight Polyphosphate (s), 60 to 0 parts by weight other inorganic builders, 10 to 0 parts by weight organic builders, 7 to 20 parts by weight Peroxide bleach, 10 to 1 part by weight Bleach activator (s), 0.2 to 5 parts by weight Surfactant (s), 0.8 to 8 parts by weight Explosive granules, 2 to 6 parts by weight other usual auxiliaries and additives.
• Another preferred embodiment of the invention is a phosphate-free dishwasher cleaning 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 Hydrogen carbonate, 10 to 0 parts by weight polymeric organic builders, 4 to 18 parts by weight Peroxide bleach, 8.8 to 1 part by weight Bleach activator (s), 0.2 to 5 parts by weight Surfactant (s), 8 to 1 part by weight Explosive granules, 1 to 5 parts by weight other usual auxiliaries and additives.
• both mono-, as well as double or triple tablets prefers.
• Customary bleaching agents are sodium perborate tetrahydrate and sodium perborate monohydrate, sodium percarbonate, peroxypyrophosphates, citrate perhydrates, as well as H 2 O 2 -producing peracidic salts, peracids such as perbenzoates, peroxyphthalates, diperazelaic acid and diperdodecanedioic acids.
• the bleach content in tablets is preferably 10-60% by weight. and in particular 15-30% by weight.
• Suitable bleach activators are the N-acyl and O-acyl compounds forming with H 2 O 2 organic peracids, preferably N, N'-tetraacylated diamines, carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. Acetylated mixtures of sorbitol and mannitol can also be used.
• Particularly suitable bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,2,5-triazine (DADHT) and acetylated sorbitol mannitol Mixtures (SORMAN).
• 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 E0, 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.
• Low-foaming non-ionic surfactants of the polyalkylene glycol and alkyl polyglucoside type are also used.
• 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.
• suitable surfactants of the sulfonate type are preferably C 9 to C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and also disulfonates, such as those obtained from C 12 -C 18 monoolefins with a terminal or internal double bond by sulfonating 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 ⁇ -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 ⁇ -sulfofatty acid esters.
• 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.
• alkaline in water inorganic salts are alkaline in water inorganic salts.
• inorganic alkaline salts belong in particular to bicarbonates, carbonates or mixtures thereof.
• Alkali carbonate and especially sodium carbonate are preferably used.
• Examples of other common additives and auxiliaries are enzymes, magnesium silicates, Aluminum aluminates, benzotriazole, glycerin, magnesium stearate, Polyalkylene glycols, hexametaphosphate and phosphonates.
• the tablets mentioned in the examples are mono, double and Triple-phase tablets can be used.
• the individual components are distributed evenly over the individual phases.
• Table 1 Examples of compositions of phosphate-containing dishwasher tablets (all amounts in parts by weight).
• Table 2 Examples of compositions of phosphate-free dishwasher tablets (all amounts in parts by weight).
• example 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

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