WO2000022087A1 - Shaped detergent bodies with organic oligocarboxylic acids - Google Patents

Abstract

The invention relates to shaped detergent bodies containing solid organic oligocarboxylic acids. Said shaped bodies have advantageous application technology-related properties. To this end, at least 80 wt. % of the oligocarboxylic acids have particle sizes which are greater than 800 νm.

Description

 'Detergent tablets with organic oligocarboxylic acids'

The present invention is in the field of compact moldings which have washing and cleaning properties. Such detergent tablets comprise, for example, detergent tablets for washing textiles, detergent tablets for machine dishwashing or cleaning hard surfaces, bleach tablets for use in washing machines or dishwashers, water softening tablets or stain remover tablets. In particular, the invention relates to detergent tablets which are used for washing textiles in a household washing machine and are briefly referred to as detergent tablets.

Detergent tablets are widely described in the prior art and are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents and cleaning agents have a number of advantages over powdered ones: They are easier to dose and handle and, thanks to their compact structure, have advantages in terms of storage and transport. Detergent tablets are therefore also comprehensively described in the patent literature. A problem that occurs again and again when using shaped articles which are active in washing and cleaning is the insufficient rate of disintegration and dissolution of the shaped articles under conditions of use. Since sufficiently stable, that is to say shape and break-resistant molded articles can only be produced by relatively high compression pressures, there is a strong compression of the molded article components and consequent delayed disintegration of the molded article in the aqueous liquor and thus to a slow release of the active substances in the Washing or cleaning process. The delayed disintegration of the moldings has the further disadvantage that conventional detergent tablets do not pass through the induction chamber of household items. Have the washing machine rinsed in since the tablets do not disintegrate into secondary particles that are small enough to be washed into the washing drum from the rinsing chamber. In addition, there is the problem of adjusting the formulation in the production of washing and cleaning-active moldings. While in the case of powdery or liquid detergents and cleaning agents, the formulations can be adapted with little effort, for example to changing requirements with regard to washing or cleaning ability or to national circumstances, changing the ingredients or their quantities in premixes to be compressed often leads to that the tabletting properties of the mixture change drastically and result in molded articles which, with the desired hardness, no longer have sufficient disintegration times.

To overcome the dichotomy between hardness, i.e. Transport and handling stability, and easy disintegration of the moldings, many solutions have been developed in the prior art. A particularly well-known approach from the pharmaceutical industry and extended to the field of detergent tablets is the incorporation of certain disintegration aids which facilitate the access of water or which swell or develop gas or other forms upon access of water. Other proposed solutions from the patent literature describe the compression of premixes of certain particle sizes, the separation of individual ingredients from certain other ingredients, and the coating of individual ingredients or of the entire shaped body with binders.

The use of citric acid in detergent tablets is also widely described in the prior art. Citric acid usually serves as a component of a carbon dioxide-producing shower system, the second component of which is a carbonate and / or hydrogen carbonate.

For example, European patent application EP 687 464 (Allphamed Arzneimittel GmbH) describes a process for the preparation of effervescent tablets in which an active ingredient or combination of active ingredients is mixed with the effervescent additives in an air-conditioned room and tabletted with the addition of glycerol or propylene glycol as a binder becomes. This document does not deal with detergents and cleaning agents, and there is also no information whatsoever about the particle size of the citric acid used.

Detergent tablets in the form of effervescent tablets are described in WO87 / 02052 (Ockhuizen et al). The moldings disclosed in this document contain 2 to 6 wt .-% detergent concentrate and 40 to 60 wt .-% sodium hydrogen carbonate and 33 to 53 wt .-% solid organic acid, preferably citric acid. The amounts of detergent-active substance that are disclosed in this document are clearly too small for applications in textile washing, and this document also lacks details of the particle sizes of the solid organic acids used.

A detergent composition which contains anionic surfactant, cationic surfactant and an acid and an alkali source, which together function as an effervescent system, is described in WO97 / 43366 (Procter & Gamble). This document teaches that the acid source (e.g. citric acid) preferably consists entirely of particles with sizes below 710 μm. Detergent tablets are not mentioned in this document.

WO98 / 04672 (Procter & Gamble) discloses a process for the production of compounds for detergent compositions, in which a surfactant and an acid source are mixed and agglomerated (optionally tableted) and subsequently mixed with an alkali source. This document does not teach the production of detergent tablets of high hardness and with good disintegration properties, nor is information given about the particle size.

The present invention was based on the object of providing moldings which are characterized by short disintegration times given a given hardness and can thus also be metered via the dispensing chamber of household washing machines. An incorporation form for organic oligocarboxylic acids was to be found, which enables the production of molded bodies with optimal properties. The invention relates to detergent tablets made of compressed, particulate detergents and cleaning agents which contain solid organic oligocarboxylic acid (s) in amounts of 0.1 to 20% by weight, based on the molded article, with at least 80% by weight. % of the organic oligocarboxylic acid particles have a particle size above 800 μm.

The use of these coarse-particle organic oligocarboxylic acids advantageously influences the physical properties of detergent tablets. While one is inclined to believe that finely divided acid components dissolve much faster because of the significantly larger surface area and consequently contribute to a faster disintegration time, the present invention shows that exactly the opposite is the case. The solid organic oligocarboxylic acids mentioned are commercially available in a wide variety of qualities, and the grain sizes also vary widely.

In the context of the present invention, the term “solid organic oligocarboxylic acid” denotes substances which are in the solid state at room temperature and owe their acidic character to the existence of at least two carboxyl groups. These substances are described in detail below.

The organic (n) oligocarboxylic acid (s) are present in preferred detergent tablets in amounts of 1 to 15% by weight, preferably 2 to 10% by weight and in particular 3 to 7% by weight.

According to the invention, at least 80% by weight of the particles of the organic oligocarboxylic acids) have sizes above 800 μm, higher proportions of particles with sizes above 800 μm and coarser qualities of the organic oligocarboxylic acids being preferred. In particular, detergent tablets are preferred in the context of the present invention in which at least 85% by weight, preferably at least 90% by weight and in particular the total amount of the organic oligocarboxylic acid particles have particle sizes above 800 μm. Washing and washing are particularly preferred Detergent tablets, which are characterized in that at least 20% by weight, preferably at least 25% by weight, particularly preferably at least 30% by weight and in particular at least 35% by weight of the organic oligocarboxylic acid particles have particle sizes in the range from 1000 μm up to 1400 μm.

In order to have an advantageous homogeneous particle size distribution, the organic oligocarboxylic acid (s) used should in particular be free of fine or dust components, ie should not contain any particles smaller than 400 μm in diameter. Particularly preferred detergent tablets contain organic oligocarboxylic acid particles which are substantially free of particles with sizes below 0.2 mm.

In the context of the present invention, “substantially free” means contents below 2% by weight, preferably below 1% by weight and in particular below 0.5% by weight, in each case based on the totality of the particles.

According to the invention, it is also possible to granulate the organic oligocarboxylic acid (s) with other raw materials and to adjust them to the required particle spectrum by grinding and sieving operations. According to the invention, it is therefore also possible to use compounds which consist of at least 60% by weight, based on the compound, of organic oligocarboxylic acid (s), these compounds then having to meet the particle size criteria according to the invention, ie that at least 80% by weight .-% of the compounds have particle sizes above 800 microns. According to the invention, preference is also given to detergent tablets containing organic oligocarboxylic acid-containing compounds which contain at least 60% by weight of organic oligocarboxylic acid, in each case based on the weight of the compound, with at least 80% by weight of the compounds having particle sizes above 800 µm.

The organic oligocarboxylic acid (s) contained in the detergent tablets according to the invention is / are carboxylic acids with two or more carboxyl groups. Starting with the C ₂ dicarboxylic acid (oxalic acid), in addition to the dicarboxylic acids of increasing chain lengths (for example malonic acid, succinic acid, adipic acid) acid) also unsaturated and / or C-chain-substituted dicarboxylic acids can be used. Examples of the compounds mentioned are maleic acid, fumaric acid, malic acid (hydroxysuccinic acid) and tartaric acid (2,3-dihydroxysuccinic acid).

Of course, tri- and higher carboxylic acids can also be used, which can also be saturated or unsaturated, branched or substituted in the C chain. The best-known example from this group is citric acid (2-hydroxy-1,2,3-propanetricarboxylic acid). Mixtures of the acids mentioned can also be used in the context of the present invention. Detergent tablets preferred in the context of the present invention are therefore characterized in that they contain, as organic oligocarboxylic acid (s), one or more acids from the group adipic acid, malic acid, citric acid, fumaric acid, maleic acid, malonic acid, oxalic acid and tartaric acid.

In the context of the present invention, detergent tablets which contain citric acid as the organic oligocarboxylic acid are particularly preferred.

Citric acid, chemically exact 2-hydroxy-1,2,3-propane tricarboxylic acid, is commercially available in the form of colorless rhombuses as an anhydrous substance (density 1.665, melting point 153 ° C) or as a monohydrate (density 1.542, melting point 100 ° C). Citric acid was first isolated from lemon juice by Scheele in 1784, Liebig determined the structure in 1838. Lemon juice is produced by precipitation with lime milk as calcium citrate, which is broken down by sulfuric acid into calcium sulfate and free citric acid. Techn. 90% of citric acid is obtained by fermenting sugar solutions (from waste containing carbohydrates such as molasses, sulfite waste liquor, etc.). The previous surface process with Aspergillus niger cultures has largely given way to the submerged process. More recently, methods of fermenting n-alkanes have also been best. Developed citric acid-forming yeast species (Candida). Chemical production processes, for example from oxaloacetic anhydride and ketene, are irrelevant to fermentative production. Around 400,0001 citric acids are currently produced annually worldwide. In addition to the organic oligocarboxylic acid (s) used according to the invention, the detergent tablets contain customary ingredients of detergents and cleaning agents, in particular from the groups of surfactants and / or builders and / or bleaches. Further ingredients that can be used in the detergent tablets according to the invention are, for example, bleach activators, enzymes, dyes and fragrances, optical brighteners, polymers, foam inhibitors, etc.

To develop the washing performance, the detergent tablets according to the invention can contain surface-active substances from the group of anionic, nonionic, zwitterionic or cationic surfactants, anionic surfactants being clearly preferred for economic reasons and on the basis of their performance spectrum.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C ₉ . ₁₃ - Alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C ₁₂ . _18- Monoolefmen with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Alkanesulfonates which are derived from C ₁₂ are also suitable. ₁₈ -alkanes can be obtained, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfated fatty acid glycerol esters are the sulfate products of saturated fat 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.

Alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half-esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C ₁₀ -C ₂₀ -Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical which is produced on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. From the washing are the C ₁₂ -C ₁₅ alkyl sulfates and C ₁₂ -C ₁₅ - alkyl sulfates and preferred C ₁₄ -C ₁₅ alkyl sulfates. In addition, 2,3-alkyl sulfates, which are produced for example according to US -Patentschriften 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C ₇ ethoxylated with 1 to 6 mol of ethylene oxide. ₂₁ alcohols, such as 2-methyl-branched C ₉ . _π alcohols with an average of 3.5 moles 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.

Other 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. 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 nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. Likewise it is also possible to use 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 are suitable, 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, including the soaps, 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 of their sodium or potassium salts, in particular in the form of the sodium salts.

In the context of the present invention, detergent tablets are preferred which contain 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 10 to 20% by weight of anionic surfactant (s), based in each case on the Molded body weight, included.

When selecting the anionic surfactants that are used in the laundry detergent and cleaning product tablets according to the invention, there are no basic conditions to be observed that prevent freedom of formulation. However, preferred detergent tablets have a soap content which exceeds 0.2% by weight, based on the total weight of the tablet. The preferred anionic surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates, with preferred detergent tablets 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight of fatty alcohol sulfate (s) in each case based on the molded body weight.

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 has a linear or preferably 2-methyl branching can be or linear and can contain methyl-branched radicals in the mixture, as are usually present in oxo alcohol residues. However, 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 . _u 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. _{12th 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). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferably used nonionic surfactants, which are 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 with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkypolyglycosides that can be used satisfy the general formula RO (G) _z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is Is a symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4. Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.

The detergent tablets according to the invention can preferably contain alkylpolyglycosides, with APG contents of over 0.2% by weight, based on the entire tablet, being preferred. Particularly preferred washing and cleaning agent foils contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 to 3% by weight.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

R ^J

R-CO-N- [Z] (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)

R ^ OR ²

R-CO-N- [Z] (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 is an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, where C,. ₄ - Alkyl or phenyl radicals are preferred and [Z] stands for a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.

[Z] is preferably obtained by reductive amination of 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.

In addition to the wash-active substances, builders are the most important ingredients in detergents and cleaning agents. The detergent tablets according to the invention can contain all builders commonly used in detergents, especially zeolites, the silicates, carbonates, organic cobuilders used according to the invention within a certain particle size range and - where there are no ecological prejudices against their use - also the phosphates. The builders mentioned can also be used in surfactant-free molded articles, so that it is possible according to the invention to produce molded articles which can be used for water softening or as bleach tablets. Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} Η ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ß- and δ-sodium disilicate

'yH ₂ O is preferred, it being possible for β-sodium disilicate to be obtained, for example, by the process described in international patent application WO-A-91/08171.

Amorphous sodium silicates with a modulus Na ^ O: SiO ₂ from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term "amoφh" is also understood to mean "roentgenamoφh". 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. This is to be integrated in such a way that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray silicates. The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

nNa, O ^• (ln) K ₂ O ^• Al ₂ O ₃ ^■ (2 - 2.5) SiO ₂ ^• (3.5 - 5.5) H ₂ O

can be described. The zeolite can be used both as a builder in a granular compound, and can also be used for a kind of "powdering" of the entire mixture to be used, usually using both ways of incohering the zeolite into the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry.

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance. Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 like ^"3 , melting point 60 °) and as a monohydrate (density 2.04 like ^{" 3} ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, ^ a ₂ H ₂ V ₂ 0 ₁ ) at 200 ° C, at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 ^"3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) J and is easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ^ PO ^ is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly ^'3 , water loss at 95 °), 7 mol. (Density 1.68 gladly ^"3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 ^"3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ O ₇ when heated more strongly. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals that like a dodecahydrate a density of 1.62 ^"3 and a melting point of 73-76 ° C (decomposition), as a decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C. and, in anhydrous form (corresponding to 39-40% P ₂ O ₅ ), a density of 2.536 ^{″ 3} . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 ^"3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction He- heating of Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 like ^{" 3} , melting point 94 ° with loss of water) . Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P, O ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 ^"3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] which crystallizes with 6 H ₂ O. " -Na with n = 3. Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is sprayed off. watered. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH - »Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

According to the invention, these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.

Organic cobuilders which can be used in the detergent tablets according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adi pinic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. In addition to their builder effect, the acids typically also have the property of an acid long-range component and thus also serve to set a lower and milder pH of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid, 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve water solubility, the polymers can also contain AUylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.

Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers .

Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are made from dialde hyden such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

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, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 owns. 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 g / mol can be used.

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. 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 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediaminisisuccinate, are further suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol are also preferred in this context. cerintrisuccinate. Suitable amounts are 3 to 15% by weight in formulations containing zeolite and / or silicate.

Further usable organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups. Such cobuilders are described, for example, in international patent application WO 95/20029.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, l-hydroxyethane-l, l-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds that are able to form complexes with alkaline earth ions can be used as cobuilders.

The amount of builder is usually between 10 and 70% by weight, preferably between 15 and 60% by weight and in particular between 20 and 50% by weight. Again, the amount of builders used depends on the intended use, so that bleach tablets can have higher amounts of builders (for example between 20 and 70% by weight, preferably between 25 and 65% by weight and in particular between 30 and 55% by weight), for example detergent tablets (usually 10 to 50% by weight, preferably 12.5 to 45% by weight) .-% and in particular between 7.5 and 37.5% by weight).

In order to facilitate the disintegration of highly compressed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, in order to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology '^''(6th edition, 1987, pp. 182-184), tablet disintegrants or disintegration accelerators are understood as auxiliary substances which are suitable for the rapid disintegration of tablets in water or gastric juice and release of the pharmaceuticals in an absorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling) and on the other hand a pressure can be generated by the release of gases, which breaks the tablet into smaller particles disintegrates. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives.

Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case based on the molded article weight.

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets form such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight contain. Pure cellulose has the formal gross composition (C ₆ H _{] 0} O ₅ ) _n and, formally speaking, represents a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the disintegrant based on cellulose.

The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be treated. Detergent tablets which contain disintegrants in granular or optionally granulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application PCT / EP 98/1203 (Henkel ) described. These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm. The above and in the documents cited in more detail above coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30 HG from Rettenmaier available in the present invention.

Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, to granules with an average particle size of 200 μm.

Preferred detergent tablets also contain a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular of 4 to 6 wt .-%, each based on the molded body weight.

It is also technically possible to coat the molded body with a coating that covers the entire molded body. Coated detergent tablets of this type can be produced by spraying a melt or solution of the coating material onto the molded article or by immersing the molded article in the melt or solution. In preferred embodiments of the present invention, however, the detergent tablets are not coated with a coating that covers the entire tablet.

Supported by the use of the auxiliaries according to the invention in the particle size range mentioned and optionally by the use of disintegration aids (see below), detergent tablets can be produced according to the invention, which disintegrate extremely quickly into their constituents when water hardness is high. Particularly preferred in the context of the present invention are detergent tablets which disintegrate completely in water at 30 ° C. in less than 60 seconds into their seconds articles which are so small that they can be washed in via the washing-in chamber of a household washing machine.

The production of washable and cleaning-active molded articles takes place by applying pressure to a mixture to be veφressing, which is located in the cavity of a press. In the simplest case of molded body production, which is hereinafter simply called tableting, the mixture to be tabletted is made directly, i.e. without previous granulation. The advantages of this so-called direct tableting are its simple and inexpensive application, since no further process steps and consequently no further plants are required. However, these advantages are offset by disadvantages. For example, a powder mixture that is to be tabletted directly must have sufficient plastic deformability and have good flow properties; furthermore, it must not show any tendency to segregate during storage, transport and filling of the die. These three requirements are extremely difficult to master with many substance mixtures, so that direct tableting is not often used, particularly in the manufacture of detergent tablets. The usual way of producing detergent tablets is therefore based on powdery components (“primary particles”) which are agglomerated or granulated by suitable processes to form secondary particles with a larger particle diameter. These granules or mixtures of different granules are then mixed with individual powdery additives and fed to the tableting.

The present invention therefore also relates to a process for the production of detergent tablets by shaping molding a particulate premix which contains solid organic oligocarboxylic acid (s) in amounts of 0.1 to 20% by weight, based on the premix , wherein at least 80 wt .-% of the organic oligocarboxylic acid particles have particle sizes above 800 microns. In the process according to the invention, too, the use of the organic oligocarboxylic acid (s) mentioned is preferred in a particle size distribution in which significantly more than 80% by weight of the organic oligocarboxylic acid particles have particle sizes above 800 μm. Processes preferred according to the invention are characterized in that the premix contains organic oligocarboxylic acid (s) in amounts of 1 to 15% by weight, preferably 2 to 10% by weight and in particular 3 to 7% by weight, and at least 85% by weight %, preferably at least 90% by weight and in particular the total amount of the organic oligocarboxylic acid particles have particle sizes above 800 μm, preferably at least 20% by weight, preferably at least 25% by weight, particularly preferably at least 30% by weight. % and in particular at least 35% by weight of the organic (n) oligocarboxylic acid particles have particle sizes in the range from 1000 μm to 1400 μm.

Of course, it is also possible to granulate the organic oligocarboxylic acid (s) with other raw materials and adjust them to the required particle spectrum by grinding and sieving operations. Accordingly, it is also possible to use compounds in the process according to the invention which comprise at least 60% by weight, based on the compound, of organic oligocarboxylic acid (s), these compounds then having the abovementioned. Particle size criteria must meet, i.e. that at least 80% by weight of the compounds have particle sizes above 800 μm.

In the method according to the invention, the above-mentioned. Oligocarboxylic acids can preferably be used, i.e. In preferred processes, one or more acids from the group of adipic acid, malic acid, citric acid, fumaric acid, maleic acid, malonic acid, oxalic acid and tartaric acid, preferably citric acid, are / are used as the organic oligocarboxylic acid.

Preferred detergent tablets within the scope of the present invention are formed by pressing a particulate premix consisting of at least one surfactant-containing granulate and at least one subsequently admixed powder Component received. The granules containing surfactant can be produced by customary industrial granulation processes such as compacting, extraction, mixer granulation, pelleting or fluidized bed granulation. It is advantageous for the later detergent tablets if the premix to be veφresses has a bulk density that comes close to the usual compact detergent. In particular, it is preferred that the premix to be veφress has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1.

In preferred process variants, the surfactant-containing granules also meet certain particle size criteria. Methods according to the invention are preferred in which the surfactant-containing granules have particle sizes between 100 and 2000 μm, preferably between 200 and 1800 μm, particularly preferably between 400 and 1600 μm and in particular between 600 and 1400 μm.

In addition to the active substances (anionic and / or nonionic and / or cationic and / or amphoteric surfactants), the surfactant granules preferably also contain carriers which particularly preferably come from the group of builders. Particularly advantageous processes are characterized in that the surfactant-containing granulate contains anionic and / or nonionic surfactants and builders and has total surfactant contents of at least 10% by weight, preferably at least 20% by weight and in particular at least 25% by weight .

Before the particulate premix is pressed into detergent tablets, the premix can be "powdered" with finely divided surface treatment agents. This can be of advantage for the quality and physical properties of both the premix (storage, molding) as well as the finished detergent tablets. Finely divided powdering agents are well known in the art, mostly zeolites, silicates or other inorganic salts being used. However, the premix is preferably “powdered” with finely divided zeolite, zeolites of the faujasite type being preferred. In the context of the present invention, the term "zeolite of the faujasite type" denotes all three zeolites that form the faujasite sub-section of the zeolite structure section 4 (compare Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 92). In addition to the zeolite X, zeolite Y and faujasite and mixtures of these compounds can also be used, the pure zeolite X being preferred. Mixtures or cocrystallizates of faujasite-type zeolites with other zeolites, which do not necessarily have to belong to the zeolite structure group 4, can also be used as powdering agents, it being advantageous if at least 50% by weight of the exhaust is means consist of a zeolite of the faujasite type.

In the context of the present invention, detergent tablets are preferred which consist of a particulate premix which contains granular components and subsequently admixed powdery substances, the or one of the subsequently admixed powdery components being a zeolite of the faujasite type with particle sizes below 100 μm, is preferably below 10 μm and in particular below 5 μm and is at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1% by weight of the premix to be treated.

In addition to the constituents mentioned, surfactant, builder and disintegration aid, or in their place in the process according to the invention, the particulate premixes to be treated can additionally contain one or more substances from the group of bleaching agents, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, Foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, regardless of which other ingredients are contained in the molded articles. If cleaning tablets or bleach tablets for machine dishwashing are manufactured, bleaching agents from the category of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monophthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidopercapid [Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1, 9-diperoxyacelysacidacidacidacid, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or bromine-releasing substances can also be used as bleaching agents in molded articles for automatic dishwashing. Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid,

Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium are considered. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

In order to achieve an improved bleaching effect when washing or cleaning at temperatures of 60 ° C. and below, bleach activators can be incorporated as the sole component or as an ingredient of component b). Bleach activators which can be used are compounds which, under perhydrolysis conditions, aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or given if substituted perbenzoic acid result, are used. Suitable substances are those which carry O- and / or N-acyl groups of the stated number of carbon atoms and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate, ethylene glycol, Diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the moldings. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest. Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules in the inventive Molded bodies can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

In addition, the detergent tablets can also contain components that positively influence the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

The shaped bodies can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-moφholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure, which instead of the Moφholino Grappe a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2- sulfostyryl) diphenyls. Mixtures of the aforementioned brighteners can also be used.

Dyes and fragrances are added to the detergent tablets according to the invention in order to improve the aesthetic impression of the products and, in addition to the performance, give the consumer a visually and sensorially "typical and unmistakable" To provide product. Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexyl benzylatepylpropionate, and The ethers include, for example, benzylethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the jonones, cc -Isomethylionon and methyl-cedrylketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include tephenols such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citras, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The dye content of the plasticizers according to the invention is usually below 0.01% by weight, while fragrances can make up up to 2% by weight of the total formulation.

The fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles by slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries. In order to improve the aesthetic impression of the agents according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to textile fibers, in order not to dye them.

The molded articles according to the invention are first produced by dry mixing the constituents, which can be wholly or partially pregranulated, and then providing information, in particular feeding them into tablets, whereby conventional methods can be used. To produce the shaped bodies according to the invention, the premix is compacted in a so-called die between two punches to form a solid compact. This process, which is briefly referred to as tableting in the following, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.

First, the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molded body being formed being determined by the position of the lower punch and the shape of the pressing tool. The constant dosing, even at high mold throughputs, is preferably achieved by volumetric dosing of the premix. As the tableting continues, the upper punch touches the premix and lowers further in the direction of the lower punch. During this compression, the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix), the plastic deformation begins, in which the particles flow together and the molded body is formed. Depending on the physical properties of the premix, some of the premix particles are also crushed and sintering of the premix occurs at even higher pressures. With increasing pressing speed, that is to say high throughput quantities, the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities. In the last step of tableting the Finished molded articles are pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point in time, only the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.).

Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down. For small production quantities, eccentric tablet presses are preferably used, in which the punch or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine. The pressing can take place with one upper and one lower punch, but several punches can also be attached to one eccentric disk, the number of die holes being increased accordingly. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table. The number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available. Each die on the die table is assigned an upper and lower punch, whereby the press-back can in turn be built up only by the upper or lower punch, but also by both stamps. The die table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compaction, plastic deformation and ejection by means of rail-like cam tracks during the rotation. At locations where a particularly serious lifting or lowering of the punches is required (filling, compacting, ejecting), these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks. The filling The matrix is developed via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix. The pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure build-up being achieved by rolling the punch shaft heads past adjustable pressure rollers.

Rotary presses can also be provided with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet. For the production of two-layer and multi-layer molded bodies, several filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before further filling. Through suitable process management, jacket and dot tablets can also be produced in this way, which have an onion-shell-like structure, the top side of the core or the core layers not being covered in the case of the dot tablets and thus remaining visible. Rotary tablet presses can also be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing. The throughputs of modern rotary tablet presses are over one million molded articles per hour.

When tableting with concentricity presses, it has proven to be advantageous to carry out the tabletting with the smallest possible fluctuations in the weight of the tablet. The fluctuations in hardness of the tablet can also be reduced in this way. Small fluctuations in weight can be achieved in the following ways:

- Use of plastic inserts with small thickness tolerances

- Low number of revolutions of the rotor

- Big filling shoes

- Matching the filler paddle speed to the speed of the rotor

- Filling shoe with constant powder height

- Decoupling of filling shoe and powder feed All non-stick coatings known from the art are suitable for reducing stamp caking. Plastic coatings, plastic inserts or plastic stamps are particularly advantageous. Rotating punches have also proven to be advantageous, with the upper and lower punches being designed to be rotatable if possible. In the case of rotating stamps, a plastic insert can generally be dispensed with. The stamp surfaces should be electropolished here.

It was also shown that long pressing times are advantageous. These can be set with pressure rails, several drawer rollers or low rotor speeds. Since the fluctuations in the hardness of the tablet are caused by the fluctuations in the pressing forces, systems should be used which limit the pressing force. Here elastic stamps, pneumatic compensators or resilient elements can be used in the force path. The dracking roller can also be designed to be resilient.

Tableting machines suitable in the context of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Hörn & Noack Pharmatechnik GmbH, Worms, IMA Veφackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms. Other providers include Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Mediopharm Kamnik (SI). For example, the hydraulic double-pressure press HPF 630 from LAEIS is particularly suitable. D. Tableting tools are, for example, from Adams Tablettierwerkzeuge, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil , Hörn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Other providers are e.g. Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).

The molded body can be manufactured in a predetermined spatial shape and a predetermined size. Practically all sensibly manageable designs come as a room shape tions into consideration, for example, the design as a board, the shape of bars or bars, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.

The portioned compacts can each be designed as separate individual elements that correspond to the predetermined dosage of the detergents and / or cleaning agents. However, it is also possible to form compacts which combine a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined breaking points. For the use of laundry detergents in machines of the type customary in Europe with horizontally arranged mechanics, the portioned compacts as tablets, in cylinder or cuboid form can be expedient, with a diameter / height ratio in the range from 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 pressed articles.

The spatial shape of another embodiment of the molded body is adapted in its dimensions to the detergent dispenser of commercially available household washing machines, so that the molded body can be metered directly into the dispenser without metering aid, where it dissolves during the dispensing process. However, it is of course also possible to use the detergent tablets without problems using a metering aid and is preferred in the context of the present invention.

Another preferred molded body that can be manufactured has a plate-like or panel-like structure with alternately thick long and thin short segments, so that individual segments of this "bolt" at the predetermined breaking points, which represent the short thin segments, are broken off and into the Machine can be entered. This principle of the "bar-shaped" shaped body detergent can also be used in other geometric Shapes, for example vertically standing triangles, which are connected to one another only on one of their sides, are realized.

However, it is also possible that the various components are not pressed into a uniform tablet, but that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous application properties of the molded body. If, for example, components are contained in the moldings that mutually influence one another negatively, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the first component has already reacted. when the second goes into solution. The layer structure of the molded body can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the molded body when the outer layers have not yet been completely removed, but it is also possible for the inner layer (s) to be completely encased ) can be achieved by the layer (s) lying further outwards, which leads to the premature dissolution of components of the inner layer (s).

In a further preferred embodiment of the invention, a molded body consists of at least three layers, that is to say two outer and at least one inner layer, at least one peroxy bleaching agent being contained in one of the inner layers, while in the case of the stacked molded body the two outer layers and in the case of the shell-shaped molded body the outermost layers, however, are free of peroxy bleach. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes that may be present in a molded body. Such multilayer molded bodies have the advantage that they can be used not only via a dispensing chamber or via a metering device which is added to the washing liquor; rather, in such cases it is also possible to put the molded body into direct contact with the textiles in the machine without the risk of bleaching from bleaching agents and the like. Similar effects can also be achieved by coating individual constituents of the detergent and cleaning agent composition to be treated or the entire molded article. For this purpose, the bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions, or else they can be coated using the melt coating method.

In addition to the layer structure, multi-phase shaped bodies can also be produced in the form of toroidal core tablets, core jacket tablets or so-called "bulleye" tablets. An overview of such embodiments of multi-phase tablets is described in EP 055 100 (Jeyes Group). This document discloses toilet detergent blocks which comprise a molded body made of a slowly soluble detergent composition in which a bleach tablet is embedded. At the same time, this document discloses the most varied forms of configuration of multi-phase shaped bodies, from simple multi-phase tablets to complicated multi-layer systems with inlays.

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be determined by means of the measured quantity of the diametrical field response. This can be determined according to

2P πDt

Here σ stands for diametrical fracture stress (DFS) in Pa, P is the force in N, which leads to the pressure exerted on the molded body, which causes the molded body to break, D is the molded body diameter in meters and t the height of the molded body. Examples:

For the production of detergent tablets which contain organic oligocarboxylic acid, a surfactant granulate was mixed with other processing components and pressed into tablets on an eccentric tablet press. The citric acid added via the processing components as an example of an organic oligocarboxylic acid to be used preferably had different particle size distributions depending on the molded article series. The composition of the surfactant granules is given in Table 1 below, the composition of the premixes to be treated (and thus the composition of the shaped bodies) can be found in Table 2. Table 3 shows the particle size distributions of the citric acid types used in the different shaped bodies.

Table 1: Composition of the granules [% by weight]

Table 2: Composition of the preparation [% by weight]

compacted cellulose (particle size: 90% by weight> 400 μm)

Table 3: Number of sieves of citric acid types in% [mm]

The tablettable premixes were pressed in a Korsch eccentric press into tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g). The pressure was set so that two series of moldings were obtained (El, ET, E2, E2 \ E3, E3 \ VI, VI ^' and V2, V2 ^' ), which differ in their hardness. The hardness of the tablets was measured by deforming the tablet until it broke, the force acting on the side surfaces of the tablet and the maximum force that the tablet withstood being determined.

To determine the tablet disintegration, the tablet was placed in a beaker with water (600 ml of water, temperature 30 ° C.) and the time until the tablet disintegrated completely. Tables 4 and 5 show the experimental data for the individual tablet series:

Table 4: Detergent tablets [physical data]

Table 5: Detergent tablets [physical data]

Claims

Claims:

1. washing and cleaning agent shaped body made of compressed, particulate washing and cleaning agent, characterized in that they contain solid organic oligocarboxylic acid (s) in amounts of 0.1 to 20 wt .-%, based on the shaped body, wherein at least 80% by weight of the organic oligocarboxylic acid particles have a particle size above 800 μm.

2. Detergent form according to spoke 1, characterized in that they contain organic oligocarboxylic acid (s) in amounts of 1 to 15% by weight, preferably 2 to 10% by weight and in particular 3 to 7% by weight. , contain.

3. Detergent form according to one of claims 1 or 2, characterized in that at least 85 wt .-%, preferably at least 90 wt .-% and in particular the total amount of organic oligocarboxylic acid particles have particle sizes above 800 microns.

4. Detergent and molded article according to one of claims 1 to 3, characterized in that at least 20% by weight, preferably at least 25% by weight>, particularly preferably at least 30% by weight> and in particular at least 35% by weight % of the organic oligocarboxylic acid particles have particle sizes in the range from 1000 μm to 1400 μm.

5. washing and cleaning agent shaped body according to one of claims 1 to 4, characterized in that the organic oligocarboxylic acid particles are substantially free of particles with sizes below 0.2 mm.

6. Detergent form according to one of claims 1 to 5, characterized in that they contain organic oligocarboxylic acid-containing compounds which contain at least 60% by weight> organic oligocarboxylic acid, in each case based on the weight of the compound, at least 80 % By weight of the compounds have particle sizes above 800 μm.

7. Detergent form according to one of claims 1 to 6, characterized in that they contain as organic oligocarboxylic acid (s) one or more grappa acids adipic acid, malic acid, citric acid, fumaric acid, maleic acid, malonic acid, oxalic acid and tartaric acid.

8. washing and cleaning agent shaped body according to one of claims 1 to 7, characterized in that they contain citric acid as the organic oligocarboxylic acid.

9. Detergent form according to one of claims 1 to 8, characterized in that it additionally contains a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight. -%, preferably from 3 to 7 wt .-%> and in particular from 4 to 6 wt .-%, each based on the molded body weight.

10. Detergent and molded article according to one of claims 1 to 9, characterized in that they are not coated with a coating which covers the entire molded article.

11. Detergent and molded article according to one of claims 1 to 10, characterized in that they completely disintegrate into their secondary articles in water at 30 ° C in less than 60 seconds.

12. A process for the preparation of washing and cleaning agent shaped bodies by shaping a particulate premix, characterized in that the premix contains solid organic oligocarboxylic acid (s) in amounts of 0.1 to 20% by weight, based on the premix, where at least 80% by weight of the organic oligocarboxylic acid particles have particle sizes above 800 μm.

13. The method according spoke 12, characterized in that the premix organic oligocarboxylic acid (s) in amounts of 1 to 15 wt .-%, preferably from 2 to 10 Wt .-% and in particular from 3 to 7 wt .-% and have at least 85 wt .-%, preferably at least 90 wt .-% and in particular the total amount of the organic oligocarboxylic acid particle sizes above 800 microns, preferably at least 20 wt %, preferably at least 25% by weight, particularly preferably at least 30% by weight and in particular at least 35% by weight of the organic (n) oligocarboxylic acid particles have particle sizes in the range from 1000 μm to 1400 μm.

14. The method according to any one of claims 12 or 13, characterized in that one or more acids from the group adipic acid, malic acid, citric acid, fumaric acid, maleic acid, malonic acid, oxalic acid and tartaric acid, preferably citric acid, are used as the organic oligocarboxylic acid.

15. The method according to any one of claims 12 to 14, characterized in that the particulate premix additionally contains surfactant-containing granules (s) and a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1.

16. The method according spoke 15, characterized in that the surfactant-containing granules have particle sizes between 100 and 2000 microns, preferably between 200 and 1800 microns, particularly preferably between 400 and 1600 microns and in particular between 600 and 1400 microns.

17. The method according to any one of claims 12 to 16, characterized in that the particulate premix additionally one or more substances from the grape group of bleaching agents, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils , Anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.