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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/83—Mixtures of non-ionic with anionic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0047—Detergents in the form of bars or tablets
  • C11D17/0065—Solid detergents containing builders
  • C11D17/0073—Tablets
  • C11D17/0086—Laundry tablets
• • 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
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/08—Silicates
• • 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
  • C11D3/2075—Carboxylic acids-salts thereof
  • C11D3/2086—Hydroxy carboxylic acids-salts thereof
• • 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
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
  • C11D1/146—Sulfuric acid esters
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
  • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/662—Carbohydrates or derivatives

Definitions

• the present invention is in the field of compressed washing and cleaning agents. It comprises a process for the production of detergent tablets, with advantageous product properties such as hardness, breaking strength and good solubility with process advantages such as low equipment costs, low Pressing forces and low temperatures can be combined.
• Detergent tablets are widely described in the prior art are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents have a number of advantages over powdered detergents: you are easier to dose and handle and because of their compact size Structure advantages in storage and transportation. Also in the patent literature Detergent tablets thus described comprehensively.
• EP-A-0 522 766 discloses shaped bodies made of a compact, particulate Detergent composition, wherein at least part of the particles with a material that is coated both as a binder and as a disintegrant acts when dissolving the moldings in water.
• This document also refers to the general Difficulty, molded body with adequate stability and good solubility to manufacture.
• the particle size in the mixture to be compressed should be above of 200 ⁇ m, the upper and lower limits of the individual particle sizes not should deviate from each other by more than 700 ⁇ m.
• binders in particular polyethylene glycol
• EP-A-0 711 828 Unilever
• binders in particular polyethylene glycol
• EP-A-0 711 828 Unilever
• detergent tablets which are formed by pressing a particulate detergent composition at temperatures between 28 ° C and the melting point of the binding material, always below the melting temperature is pressed. From the examples in this document it can be seen that that the moldings produced according to their teaching higher breaking strengths have when pressing at elevated temperature.
• the object of the present invention was to provide a simplified method of manufacture to provide moldings, the moldings with regard to their breaking strength, Storage stability and their dissolution behavior exceed the known moldings.
• a powdery or granular, free-flowing premix is pressed in suitable forms in the process according to the invention.
• the pressing can take place at any temperature and any pressing pressure. While usually only high compression pressures and / or temperatures lead to sufficiently stable moldings, detergent tablets can be produced by the process according to the invention which, with compression pressures below 15 N / cm 2 , already outperform the conventional moldings in terms of stability. Working at an elevated temperature can also be dispensed with in the method according to the invention, although working at a higher temperature can be useful and does not lead to the loss of the advantages of the method according to the invention. Usually, an increase in temperature at the same pressing pressure leads to a higher breaking strength of the moldings.
• the process according to the invention is preferably carried out with compression pressures below 15 N / cm 2 and at temperatures below 30 ° C., which leads to moldings which, in terms of their stability and dissolving values, outperform conventional detergent tablets.
• the low pressing temperatures are particularly advantageous when the moldings contain temperature-labile ingredients that would tend to decompose at elevated temperatures.
• the particulate detergent and cleaning agent composition which is pressed into the molded article, contains 5 to 20% by weight of an over-dried amorphous silicate, 0.5 to 10% by weight of polyethylene glycol and 1 to 15% by weight of water or aqueous solutions of others Active ingredients and auxiliaries.
• an over-dried amorphous silicate 0.5 to 10% by weight of polyethylene glycol and 1 to 15% by weight of water or aqueous solutions of others Active ingredients and auxiliaries.
• laundry detergent and cleaning product tablets are obtained even at low compression pressures and without the use of elevated temperatures, which combine high stability with excellent dissolving properties.
• the particulate detergent and cleaning agent composition which is pressed into the shaped body, can be produced in any known manner and can in principle have any bulk density. Parts of the composition or even the complete composition can thus be produced by the process of spray drying or roller compaction.
• the particulate detergent and cleaning agent composition is produced with particular advantage by granulating and compressing its ingredients or individual compounds in mixing granulators.
• the granulation can be carried out in both high-intensity and slow-running mixers.
• high-speed mixers are the Lödige® CB 30 recycler (trademark of Lödige Maschinenbau GmbH, Paderborn), the Fukae® FS-G mixer (trademark of Fukae Powtech, Kogyo Co., Japan), the Eirich® mixer type R ( Trademarks of the machine factory Gustav Eirich, Hardheim) or the Drais® K-TTP 80 (trademark of Drais-Werke GmbH, Mannheim),
• examples of slow-speed mixing granulators are the Drais® KT 160 and the Lödige® KM 300. The latter, which is often called Lödige ploughshare mixers is particularly suitable for carrying out this process step.
• the production of mixed granulation is carried out of the premix to be pressed, the over-dried amorphous silicate in the mixer submitted, further optional builder components and auxiliary substances added and with the mixer running, water or aqueous solutions added, followed by the surfactants or surfactant compounds are added.
• the other detergent and cleaning agent components such as bleach, Enzymes, soil repellents and the like are added.
• the one used as component b) Polyethylene glycol can be used together with the surfactant compounds in the first step or else with the remaining ingredients are added in the preparation step. Prefers is the addition in the preparation step.
• the polyethylene glycol can be commercially available Forms are added, the melting points depending on the molecular weight distribution vary.
• PEG 4000 is preferred in amounts between 0.5 to 10% by weight, preferably from 1 to 4 % By weight, based on the weight of the shaped body, is used.
• the molded body can also be used organic polymeric substances which in Combination with the polyethylene glycol contributes to the strength of the molded articles.
• polyvinyl pyrrolidone, polyacrylates and copolymers are made here Maleic acid and acrylic acid called.
• the bulk density of the premix to be compressed can vary within wide limits, depending on the density of the molded bodies that are to be formed. For reasons in the packaging and transport economy, bulk weights of the premix are above Aim for 400 g / l, with higher bulk weights, in particular over 500 g / l and more than 600 g / l are particularly preferred. Such bulk densities lead to molded body densities above 800 g / l, which in turn for reasons of packaging and The aim is to achieve transportation economics.
• the granules or the granulate mixtures are usually compressed at Room temperature or at best slightly elevated temperatures, for example in Temperature range up to about 50 ° C. Preference is given to pressing in the room temperature range, So made in the range of about 18 to 30 ° C.
• the duration of the pressing process is determined by the machine type selected. It is in usually less than 1 minute and is usually in the range of a few seconds or significantly below.
• the portioned compacts can have a predetermined spatial shape and a predetermined size are manufactured.
• the portioned compacts can each be separate individual elements be formed, the predetermined dosage of detergents and / or cleaning agents corresponds.
• For the use of laundry detergents in machines common in Europe Type with horizontally arranged mechanics can be the formation of the portiorated Compacts as tablets, in the shape of a cylinder or cuboid, are expedient, one Diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred.
• Commercial Hydraulic presses, eccentric presses or rotary presses are suitable Devices in particular for the production of such compacts.
• the spatial shape of another embodiment of the shaped body is in its dimensions the induction chamber of commercial household washing machines adapted so that the Shaped bodies can be metered directly into the induction bowl without a metering aid, where they are dissolves during the induction process. It goes without saying that the Detergent tablets easily possible via a dosing aid and within the scope of present invention preferred.
• Another preferred shaped body that can be produced has a plate-like or plate-like structure with alternating thick and short short segments, so that individual segments of this bars at the predetermined breaking points, which represent the short, thin segments, can be broken off and entered into the machine.
• This principle of bar-shaped Shaped body detergent can also be implemented in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the length.
• the layer structure of the moldings can be stacked, a dissolution process of the inner layer (s) at the edges of the molded body already then occurs when the outer layers are not yet completely dissolved, it can but also a complete covering of the inner layer (s) by the further external layer (s) can be reached, which prevents the early Solution of components of the inner layer (s) leads.
• a molded body consists of at least three layers, ie two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleach, while in the case of the stacked shaped body, the two outer layers and in the case of the shell-shaped one Shaped bodies, however, the outermost layers are free of peroxy bleach.
• Multi-layer moldings have the advantage that they do not have only one induction chamber or via a dosing device which is added to the wash liquor, can be used; rather, it is also possible in such cases, the molded body into the machine in direct contact with the textiles without staining would be feared by bleach and the like.
• the bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions, or else they can be coated using the method of melt coating.
• the silicates used according to the invention are over-dried amorphous sodium silicates with a modulus Na 2 O: SiO 2 of 1: 2 to 1: 3.3, preferably of 1: 2 to 1: 2.8 and in particular of 1: 2 to 1: 2, 6, which have water contents below 15% by weight, based on the weight of the silicate.
• Conventional amorphous silicates, so-called glasses of water have residual water contents between 17 and 20 wt .-%, so that the term overdry in the context of this application means that the water content of the silicate used is below 15% by weight.
• Overdried amorphous silicates which are delayed in dissolution and have secondary washing properties are to be used with preference in the process according to the invention.
• amorphous also means “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments.
• the water introduced into the process according to the invention is used in the production of the Premix to be pressed (the particulate detergent and cleaning agent composition) applied to the silicate particles.
• This can either be pure Water are added, or an aqueous solution of active ingredients and auxiliary substances, which are usually used in detergents and cleaning agents.
• the water or the aqueous solutions are used in amounts of 1 to 15% by weight, based on the weight the shaped body, added during granulation, quantities are particularly preferred from 2 to 10, in particular from 3 to 8% by weight, based on the weight of the shaped body. Pure water is preferably added, which contains no solutes.
• anionic, nonionic, cationic and / or amphoteric surfactants can be used in the particulate detergent and cleaning agent composition to be pressed. From an application point of view, mixtures of anionic are preferred and rich ionic surfactants, the proportion of anionic surfactants should be greater than the proportion of nonionic surfactants.
• the total surfactant content of the moldings is at 5 to 60% by weight, based on the weight of the shaped body, with surfactant contents above 15 % By weight are preferred.
• Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
• Preferred surfactants of the sulfonate type are C 9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from C 12-18 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 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
• the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
• Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
• fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol.
• Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated Fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, Capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
• Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
• the alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12-18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10-20 oxo alcohols and those half esters secondary alcohols of this chain length are preferred.
• alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
• C 16-18 alk (en) yl sulfates are particularly preferred for reasons of washing technology. It can also be particularly advantageous and particularly advantageous for machine washing agents to use C 16-18 alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and at relatively low washing temperatures from, for example, room temperature to 40 ° C. show a low tendency to crystallize.
• the agents therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably C 12-18 fatty alkyl sulfates or mixtures of C 12-14 fatty alkyl sulfates or C 12-18 fatty alkyl sulfates with C 16-18 fatty alkyl sulfates and in particular C 12-16 fatty alkyl sulfates with C 16-18 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.
• the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
• Suitable anionic surfactants are also 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 especially ethoxylated fatty alcohols.
• alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
• Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof.
• Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are non-ionic surfactants (description see below).
• alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
• Soaps are particularly suitable as further anionic surfactants.
• saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural Fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
• the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or Triethanolamine.
• the anionic surfactants are preferably in the form their sodium or potassium salts, especially in the form of the sodium salts.
• the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may 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 from coconut, palm, tallow fat 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 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 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 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 is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for 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 either as the sole nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, such as those found in Japanese Patent application JP 58/217598 are described or preferably according to the in the international patent application WO-A-90/13533 will.
• 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 can be suitable.
• the amount of these nonionic surfactants is preferably not more than that of ethoxylated fatty alcohols, especially not more than half of it.
• Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 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) in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated Derivatives of this rest.
• R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
• R 1 represents a linear, branched or cyclic alkyl radical or an aryl
• [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, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
• other builder and cobuilder substances can also be used in the detergent compositions. These include in particular zeolites, citrates and polymeric polycarboxylates.
• the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
• zeolite P zeolite MAP (R) (commercial product from Crosfield) is particularly preferred.
• zeolite X and mixtures of A, X and / or P are also suitable.
• the zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production.
• the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
• Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
• the sodium salts of the orthophosphates are particularly suitable, the pyrophosphates and especially the tripolyphosphates.
• Their salary is generally not more than 25% by weight, preferably not more than 20% by weight, in each case on the finished product.
• tripolyphosphates in particular even in small quantities up to a maximum of 10% by weight, based on the finished product Medium, in combination with other builder substances for a synergistic improvement of secondary washing power.
• Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and Mixtures of these.
• Preferred salts are the salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures from these.
• the acids themselves can also be used.
• the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents.
• Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
• Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
• the hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000.
• DE dextrose equivalent
• Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 can be used.
• a preferred dextrin is described in British patent application 94 19 091.
• the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
• oxidizing agents capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
• Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO- A-92/18542, WO-A-93/08251, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A-95/20608.
• a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
• Suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate.
• ethylenediamine disuccinate preferably ethylenediamine disuccinate.
• glycerol disuccinates and glycerol trisuccinates as described, for example, in US Pat U.S. Patents US 4,524,009, US 4,639,325, in European Patent application EP-A-0 150 930 and Japanese patent application JP 93/339896 to be discribed.
• Suitable amounts are those containing zeolite and / or silicate Formulations at 3 to 15% by weight.
• organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which have at least 4 carbon atoms and at least one hydroxy group as well contain a maximum of two acid groups.
• Such cobuilders are used, for example, in the international patent application WO-A-95/20029.
• Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight from 800 to 150,000 (based on acid).
• Suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or Methacrylic acid with maleic acid. Copolymers of Acrylic acid with maleic acid, 50 to 90 wt .-% acrylic acid and 50 to 10 % By weight of maleic acid.
• Their relative molecular mass, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000, and especially 50000 to 100000.
• the (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution are used, 20 to 55% by weight aqueous solutions being preferred.
• biodegradable polymers composed of more than two different monomer units, for example those which, according to DE-A-43 00 772, are salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
• Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
• Suitable builder substances are oxidation products of carboxyl-containing ones Polyglucosans and / or their water-soluble salts, such as, for example are described in international patent application WO-A-93/08251 or their Manufactured, for example, in international patent application WO-A-93/16110 is described. Oxidized oligosaccharides according to the older ones are also suitable German patent application P 196 00 018.1.
• further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors.
• Polyaspartic acids are particularly preferred or their salts and derivatives, of which in the German patent application P 195 40 086.0 discloses that, in addition to cobuilder properties, it also has a have a bleach-stabilizing effect.
• polyacetals which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups have, for example, as in European patent application EP-A-0 280 223 can be obtained.
• Preferred polyacetals are made from Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
• the detergent tablets can known additives commonly used in detergents, for example Bleaching agents and bleach activators, foam inhibitors, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filling salts as well as colors and fragrances, Contain opacifiers or pearlescent agents.
• bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
• the bleaching agent content of the agents is preferably 1 to 40% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate or percarbonate.
• bleach activators can be incorporated into the preparations.
• Bleach activators can be compounds that are aliphatic under perhydrolysis conditions
• Peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used.
• Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups.
• acylated alkylenediamines especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, in particular Triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from the German patent applications DE 196 16 6
• German patent application DE 196 16 769 known hydrophilically substituted acylacetals and in German patent application DE 196 16 770 and international patent application Acyl lactams described in WO 95/14075 are also preferably used.
• the transition metal compounds in question include in particular known from the German patent application DE 195 29 905 manganese, iron, Cobalt, ruthenium or molybdenum salt complexes and those from the German patent application DE 196 20 267 known N-analog compounds, which from the German Patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or Molybdenum-carbonyl complexes, which are described in German patent application DE 196 05 688 manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and Copper complexes with nitrogenous tripod ligands resulting from the German patent application DE 196 20 411 known cobalt, iron, copper and ruthenium amine complexes, those described in German patent application DE 44 16 438 Manganese, copper and cobalt complexes described in the European patent application Cobalt complexes described in EP 0 272 030, which result from the European patent application EP 0 693 550 known manga
• Combinations of bleach activators and transition metal bleaching catalysts are, for example, from the German patent application DE 196 13 103 and international patent application WO 95/27775 known.
• Bleach-enhancing transition metal complexes, especially with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru are used in conventional amounts, preferably in an amount up to 1% by weight, in particular from 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on all means.
• the agents can also contain components that make oil and fat washable made of textiles. This effect is particularly evident if a textile is soiled, which has previously been repeatedly with an inventive Detergent containing this oil and fat-dissolving component is washed has been.
• the preferred oil and fat dissolving components include, for example non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, as well as the polymers of phthalic acid and / or of the known from the prior art Terephthalic acid or its derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified Derivatives of these. Of these, the sulfonated ones are particularly preferred Derivatives of phthalic acid and terephthalic acid polymers.
• alkali carbonates also by sulfur-free, 2 to 11 carbon atoms and optionally one further carboxyl and / or amino groups and / or amino acids Salts to be replaced.
• Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
• Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
• the foam inhibitors, in particular silicone or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
• the salts of polyphosphonic acids are preferably the neutral sodium salts for example 1-hydroxyethane-1,1-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylene diamine tetramethylene phosphonate in amounts from 0.1 to 1.5% by weight.
• Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question.
• Bacterial strains or are particularly well suited Mushrooms such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents.
• Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used.
• enzyme mixtures for example from protease and amylase or protease and lipase or Protease and cellulase or from cellulase and lipase or from protease, amylase and Lipase or protease, lipase and cellulase, but especially mixtures containing cellulase of special interest.
• Peroxidases or oxidases have also been found in some Cases proved to be suitable.
• the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to prevent them from premature decomposition protect.
• the proportion of enzymes, enzyme mixtures or enzyme granules can, for example about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
• the moldings can be derivatives of diaminostilbenedisulfonic acid as optical brighteners or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed Compounds which instead of the morpholino group a diethanolamino group, a Carry a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, e.g.
• the laundry detergent and cleaning product tablets After pressing, the laundry detergent and cleaning product tablets have an initial stability which increases over time due to post-curing. Post-curing times of several days are usually to be observed, whereby the breaking strength can increase by a factor of 2 to 3.
• Detergent tablets produced by the process according to the invention have high breaking strengths shortly after production, which increases to about 90 percent of their final value in the course of 2 hours. A further increase in the breaking strength during storage is not observed.
• the breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to
• ⁇ stands for diametral fracture stress (DFS) in Pa
• P is the force in N which leads to the pressure exerted on the molded body, which is the Breakage of the shaped body causes
• D is the shaped body diameter in meters
• t is the height of the moldings.
• the dissolving rate or the residue behavior of the shaped bodies can be determined using several test methods.
• a shaped body was added to 3.5 kg of dry laundry in a washing machine (Miele Novotronic W 918) in a conventional metering device. After water had run in, the metering device was weighed with the shaped body. A colored wash program (40 ° C, 11 l water, 16 ° d) was then carried out. After 5 and 10 minutes, the washing program was interrupted and the metering device with the remains of the shaped body was weighed. The residue in% by weight of the initial value is given as the test result.
• an online washing machine (Miele Deluxe W 717) equipped with a conductivity measuring cell was loaded with 4.5 kg of filling laundry and a washing program (40 ° C., 17 l of water, 16 ° d) was started after the addition of a shaped body.
• the time until the conductivity is constant corresponds to the time required for the molded article to dissolve completely.
• the moldings E1 to E5 were obtained, which are characterized by the physical data given in Table 2.
• the comparative examples V1 to V5 in Table 2 are taken from the patent literature.
• the comparative examples S1 and S2 correspond in their composition to example E3 according to the invention, except that in each case the over-dried amorphous silicate was mixed with a water glass normal Water content of 18 wt .-% replaced and the amount of free water added reduced accordingly.
• Sokalan CP5® is an acrylic acid-maleic acid copolymer from BASF physical data of the moldings [units: see table] E1 E2 E3 E4 E5 V1 V2 V3 V4 V5 Molded body height [cm] 2nd 2nd 2.7 2.3 2.4 1 2.5 2.5 2nd 2nd Shaped body ⁇ [cm] 4.4 4.4 5 5 5 4th 4.5 4.5 4.5 4.5 Molded body weight [g] 25th 25th 40 40 40 ng ng ng 50 50 Density [g / cm 3 ] 0.82 0.82 0.75 0.89 0.85 ng 1.24 1.39 1.25 1.40 Pressing force [kN] ⁇ 10 ⁇ 10 0.2 0.2 0.2 0.126 0.9 3.3 1.1 2.8 Pressure [N / cm 2 ] ⁇ 6.6 ⁇ 6.6 10.2 10.2 10.2 1
• over-dried amorphous silicate over-dried water glass
• a not over-dried water glass with a water content of 18% by weight is used with a correspondingly reduced addition of water
• the mixture does not give any tablets at pressing forces of 200 N, which means that when it is ejected from the press it occurs as a result from instability to tablet destruction (S1).
• Stable tablets could only be obtained with compressive forces of 25 kN (S2). These tablets are characterized by poor solubility and high residue formation.

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• 1997
  • 1997-03-07 DE DE19709411A patent/DE19709411A1/de not_active Ceased
• 1998
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