DE10134310A1 - Multi-phase compressed detergents have one or more phases interrupted or separated by disintegration agent-containing phases to give more rapid disintegration and solubility - Google Patents

Abstract

Multi-phase compressed detergents containing a builder and surfactant as well as other ingredients have one or more phases interrupted or separated by disintegration agent-containing phases.

Description

The present invention is in the field of compressed washing and Cleaning agents, such as those obtained by tableting or extrusion and for dosing washing and cleaning-active substances. The invention relates to stable washing and cleaning agent compresses such as Washing of textiles in a household washing machine, for automatic dishwashing or cleaning hard surfaces, as bleach tablets for use in washing and Dishwashers or used as water softening tablets.

Detergent tablets are delightful because of their easy handling popularity with the consumer. Such shaped bodies, such as those can be produced by tableting or extrusion, are easier to dose and to be stored as powder detergents and offer due to their compact structure also advantages in transportation. A problem that occurs when using washing and however, cleaning-active compresses occur again and again inadequate rate of disintegration and dissolution. Because of the manufacture of the Compressed used relatively high pressures that lead to a strong Compaction of the active washing and cleaning components and the compressed ones impart hardness and stability necessary for transport and use this often due to a delayed disintegration in the aqueous liquor and a too slow release of the active substances in the washing or cleaning process. The Delayed disintegration of the tablet has the disadvantage, among other things, that it is common Detergent tablets do not pass through the induction chamber of Allow household washing machines to wash in, as the tablets are not going to be quick enough Time disintegrates into secondary particles that are small enough to enter the induction chamber Washing drum to be washed in.

To increase the rate of disintegration and dissolution of compressed products are in the prior art Many solutions have been developed. One way the decay and Increasing the dissolving speed of compressed products is therefore easy soluble salts such as acetates or phosphonates.

International patent application WO 99/31215 describes a detergent tablet a granular component (e.g. organophosphonate) with a particle size of 250 to 1200 µm and a water solubility of 10 g / l. the granular component dissolves faster on than the rest of the tablet. This creates holes or channels in the tablet, which increase the dissolution speed of the tablet by increasing the surface area.

A well known in particular from pharmacy and in the field of washing and Detergent tablet broad approach is the incorporation of certain, also as Disintegration aids called 'disintegrants', which facilitate the access of water or swell upon entry of water or gas evolving or in another form act disintegrating.

Single or multi-phase detergent tablets containing different ones Concentrations of a swelling disintegration aid are the subject of international patent applications WO 98/55590 and WO 00/44870. The different Disintegrant concentrations cause different decay rates of the Tablets phases.

The combination of swelling disintegration aids with shower systems in a washing machine and detergent tablet is eventually used in the international patent application WO 98/54283 (Henkel), while the international patent application WO 98/54284 (Procter and Gamble) the combination of easily soluble salts (e.g. acetate, urea) with Shower systems as decay accelerators in detergent and cleaning tablets for Has subject. Both variants deliver stable tablets with a high rate of disintegration.

All of the above publications disclose single or multi-phase washing and Detergent tablets containing one or more disintegration aids Accelerated tablet breakdown or individual phases of these tablets included. According to the teachings of these documents, the rate of decay of the washing and Detergent tablets in direct relation to the amount of the used Disintegration aid. As a result, the tablet can only accelerate can be achieved by using larger amounts of disintegration aid (s). There these disintegration aids generally have no washing and cleaning activity However, it is desirable to have their share in the total weight of the corresponding Keep tablets as low as possible.

Accordingly, the object of the invention was to compressed washing and Providing detergent formulations that, despite a low level of Disintegration aids, have short disintegration times.

It has now been found that such compressed washing and cleaning agents are short Have disintegration times in which the disintegration aid (s) used do not are completely homogeneously distributed over the entire volume of the compressed material, but rather partially or fully in the manner of certain areas of the Compressed be concentrated that not only the in aqueous solution disintegrant-containing areas decay, but this decay occurs simultaneously Breaking apart of the entire molded body into several fragments, for example the different phases of the compressed. As a fragment in this Context refers to a spatial body that preferably has at least 5% by volume at least 10% by volume and in particular at least 20% by volume of the volume of the original compressed. The previously described disintegration of the compressed product into two or more fragments increases the size of the solvent Solid surface and in this way favors the decay and dissolution process.

The subject of the present application is therefore two-phase or multi-phase compressed Detergent and cleaning agent formulations containing builders, surfactants and others Components of washing and cleaning agents, characterized in that the phase (s) of the compressed product by (a) disintegrant-containing phase (s) at least in part interrupted (is) or separated.

Compresses according to the invention can for example by tableting or Coextrusion / assembly but also by extrusion and subsequent Calendering / packaging, but also provided by roller compaction become. In the context of the present invention, it is preferred that the compressed by Tableting or extrusion is generated.

These compressions preferably have a density above 900 g / l, particularly preferably above 1000 g / l and in particular above 1100 g / l and are characterized by a weight between 5 g and 80 g, preferably between 10 g and 50 g and in particular between 20 g and 40 g.

According to the present invention, two or more are in such a compressed Phases completely separated by another phase containing disintegrant, so it is for the effect according to the invention, namely the fragmentation of the compressed material, is irrelevant whether the first mentioned phases have the same composition or differ in their Differ composition and a compressed according to the invention can both Phases of the same composition as well as phases of different compositions exhibit.

For easy access of the solvent to the disintegrant Enable phase (s) and bring about a rapid disintegration of the compressed material, is / are these phase (s) advantageously with at least one of their phase boundaries part of the Surface of the compressed detergent and cleaning agent. However, there is also one complete or partial coating of the compressed material, for example by a additional coating, possible. In such a case, the resolution behavior of the Coating layer to a determining factor for the total decay time of the compressed Detergents and cleaning agents.

Although to achieve the effect according to the invention, namely the decay of the original compressed into two or more fragments, disintegrant containing Phases of the most varied spatial form (s) can be used, it has proven to be advantageous that the two-phase or multiphase compressed washing and Detergent formulation, one / more layer (s) containing disintegrant exhibit that is / are not planar, or in the case of planarity the phase (s) containing the integration agent, but this is not completely parallel to the surface of the compressed product runs / run.

In the context of the present invention, it is possible that the disintegrant-containing Phase (s) completely separate the neighboring phases of the compressed product. To the According to the invention, however, the use of disintegration aids is minimized preferably two or multi-phase compressed washing and To provide detergent formulations, the disintegrant-containing phase (s) of which does not completely separate neighboring phases of the compressed product, the disintegrant-containing phase (s) the neighboring phases of the compressed product preferably to 10 to 90%, preferably to 20 to 80% and in particular to 30 to 70% separates the common phase interface (s) from one another.

According to the invention, it is preferred if the disintegrant-containing phase (s) of the two-phase or multi-phase compressed detergent and cleaning agent formulation Disintegration aid in amounts above 5% by weight, preferably in amounts above 10% by weight, particularly preferably in amounts above 20 and in particular in amounts contains / contain above 30% by weight, based on the weight of the phase.

Furthermore, it can be advantageous for the course of the washing and cleaning cycle if the disintegrant-containing phase (s) of the two-phase or multiphase compressed phase Washing and cleaning formulation additionally at least one washing and / or contains / contain cleaning active substance. In this way, the targeted temporal Release of certain ingredients realizable. In this context, it is conceivable early release of enzymes or water softeners but also of alkali or acid carriers for setting a desired pH value, for example the pH value controlled release of further ingredients from the resulting fragments of original compressed.

Is such an early release of an active substance undesirable or necessary, or if the amounts of the corresponding active substance are small, so it is preferred according to the invention that the two-phase or multiphase compressed washing and Detergent formulation one / more phase (s) containing disintegrant with one Thickness below 3 mm, preferably below 2 mm and in particular below 1 mm has / have, in this way the effect of fragmentation of the compressed is reinforced.

In addition to one or more disintegration aids, the inventive Compress other common constituents of washing and cleaning agents, in particular one or more active substances from the group of bleaching agents, bleach activators, Builders, surfactants, enzymes, electrolytes, pH adjusting agents, fragrances, perfume carriers, Fluorescent agents, dyes, hydrotopes, foam inhibitors, silicone oils, Anti-redeposition agents, optical brighteners, graying inhibitors, enema preventers, Anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, Fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, repellents and Impregnating agent, swelling and anti-slip agent as well as UV absorber. These active substances are described in more detail below.

In addition to other constituents, bleaching agents and bleach activators can be contained in the compressed products according to the invention as important constituents of washing and cleaning agents. Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and produce H ₂ O ₂ in water. Further bleaching agents which can be used are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Detergent tablets for automatic dishwashing can also contain bleaches from the group of organic bleaches. Typical organic bleaching agents are the diacyl peroxides, such as. B. 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) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxyiminoperacid acid (ε-phthalimidoperoxy-capoic acid), )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipinic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxydiacid-diperoxybutyldiacyldiperbutyldiacyldiperoxybutyldiacyldiperoxybutyldiacyldiperoxybutyldiacid, diperoxybutyldiacyldiperoxybutyldiacyldiperoxybutyldiacyldiperoxybutyldiacyldiperoxybutyldiacid, diperoxybutyldiacyldiperoxybutyldiacid, diperoxybutyldiacyldiperoxybutyldiacid, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine can also be used as a bleaching agent in the tablets for machine dishwashing or bromine-releasing substances are used. Among the appropriate chlorine or bromine releasing materials come, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromo isocyanuric acid, dibromo isocyanuric acid and / or Dichloroisocyanuric acid (DICA) and / or its salts with cations such as potassium and sodium in Consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

To improve the bleaching effect when cleaning at temperatures of 60 ° C and below to achieve the compressed detergents and cleaning agents according to the invention Bleach activators included. As bleach activators, compounds that are under Perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 C- Atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted Perbenzoic acid result are used. Suitable substances are O- and / or N- Acyl groups of the number of carbon atoms mentioned and / or optionally substituted Wear benzoyl groups. Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4- dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5- dihydrofuran.

In addition to the conventional bleach activators or in their place, too so-called bleaching catalysts are incorporated into the compressed products. With these fabrics are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also 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 be used as bleaching catalysts.

In addition to the ingredients mentioned, bleach and bleach activator are builders and Surfactants important ingredients of detergents and cleaning agents. In the invention Compressed detergents and cleaning agents can usually all be in Builders used for cleaning agents, in particular zeolites, Silicates, carbonates, organic cobuilders and - where no ecological prejudices against their use persists - including the phosphates. The builders mentioned can can of course also be used in surfactant-free compressed products.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H 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. 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 β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 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 / compaction or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “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 provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning 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 also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite which can be 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 ₂ O. (1-n) K ₂ O.Al ₂ O _3. (2-2.5) SiO _2. (3.5-5.5) H ₂ O

can be described. 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 goes without saying that the generally known phosphates are also used as Builder substances possible, provided that such use is not for ecological reasons should be avoided. The sodium salts of the orthophosphates are particularly suitable, the pyrophosphates and especially the tripolyphosphates.

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 fabrics and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders that are very easily soluble in water, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₄ ) at 200 ° C, and at higher temperatures in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; it arises 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 gcm ^-3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is light soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^-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 which, as dodecahydrate, have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-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 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises e.g. B. when heating 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 gcm ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , Both substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering 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 gcm ^-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] _n that crystallizes with 6 H ₂ O. -Na with n = 3. In 100 g of water about 17 g of the salt of water free of crystal water dissolve at room temperature, about 20 g at 60 ° and about 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 dewatered by spraying. 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 are exactly like sodium tripolyphosphate, potassium tripolyphosphate or Mixtures of these two can be used; also 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 be used according to the invention.

Usable organic builders are, for example, those in the form of their alkali and in particular sodium salts of polycarboxylic acids, such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided that such use is not permitted for ecological reasons is objectionable, 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 of these.

Alkali carriers can be present as further constituents. Are considered to be alkali carriers Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, Alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the aforementioned substances, in the sense of this invention, the alkali carbonates are preferred, in particular Sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate can be used.

If the compressed material according to the invention is used for automatic dishwashing, then Water-soluble builders are preferred because they work on dishes and hard surfaces Usually less tend to form insoluble residues. Common builders are those low molecular weight polycarboxylic acids and their salts, the homopolymers and copolymers Polycarboxylic acids and their salts, the carbonates, phosphates and silicates. To be favoured for the production of tablets for machine dishwashing trisodium citrate and / or Pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of the disilicates and / or Metasilicates used. A builder system containing a mixture is particularly preferred from tripolyphosphate and sodium carbonate. A is also particularly preferred Buildersystem, which is a mixture of tripolyphosphate and sodium carbonate Contains sodium disilicate.

The compressed detergents and cleaning agents according to the invention can, in addition to the above described builders also contain the above-mentioned detergent substances.

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, 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. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), e.g. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures, as in the preparation by esterification of a monoglycerol with 1 to 3 moles Obtained fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfonated 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.

As 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 fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the α-equivalent compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred for reasons of washing technology. 2,3-Alkyl sulfates, which are commercially available from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

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.

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, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. 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. Are suitable 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. B. 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 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, especially in the form of the sodium salts.

Another group of washing-active substances are the non-ionic surfactants. 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 residue 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. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol 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). In addition to these nonionic surfactants, 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.

Another class of preferred nonionic surfactants, either as the sole nonionic surfactant or used in combination with other nonionic surfactants 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.

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, carbon atoms and G is the Is 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.

Also 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 the ethoxylated fatty alcohols, especially not more than half of it.

Other 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 remainder.

[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 be reacted with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.

In the case of detergents and cleaning agents for machine dishwashing, all surfactants can in principle be used as surfactants. However, the nonionic surfactants described above, and above all the low-foaming nonionic surfactants, are preferred for this purpose. The alkoxylated alcohols are particularly preferred, especially the ethoxylated and / or propoxylated alcohols. The person skilled in the art generally understands alkoxylated alcohols to mean the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the context of the present invention the longer-chain alcohols (C ₁₀ to C ₁₈ , preferably between C ₁₂ and C ₁₆ , such as C ₁₁ -, C ₁₂ -, C ₁₃ -, C ₁₄ -, C ₁₅ -, C ₁₆ -, C ₁₇ - and C ₁₈ -alcohols). As a rule, a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. A further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. If desired, final etherification with short-chain alkyl groups, such as preferably the butyl group, can also give the class of "closed" alcohol ethoxylates, which can also be used for the purposes of the invention. For the purposes of the present invention, very particularly preferred are highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates.

Polymers are another important part of detergents and cleaning agents, though among polymers in the present application in particular substances with builder or Cobuilder properties are to be understood. As organic cobuilders can in the Washing and cleaning agents according to the invention in particular Polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, others organic cobuilders (see below) and phosphonates are used. These substance classes are described below.

Usable organic builders are, for example, the sodium salts of hereinafter referred to as part of the shower system polycarboxylic acids. For example these are the sodium salts of citric acid, adipic acid, succinic acid, glutaric acid, Malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided that such use is not permitted for ecological reasons is objectionable, 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 of these.

Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a 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 to the polymers investigated. 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 Have 2000 to 20,000 g / mol. Because of their superior solubility, this can Group in turn the short-chain polyacrylates, the molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may be preferred.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As special copolymers of acrylic acid with maleic acid have proven suitable, the 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative Molecular mass, based on free acids, is generally from 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

To improve water solubility, the polymers can also allylsulfonic acids, such as for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

Biodegradable polymers of more than two are also particularly preferred various monomer units, for example those which are salts of the monomers Acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives contain.

Further preferred copolymers are those which preferably contain acrolein and Have acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, other preferred builder substances are polymeric aminodicarboxylic acids, their To name salts or their precursors. Are particularly preferred Polyaspartic acids or their salts and derivatives, in addition to cobuilder properties have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups can be obtained. Preferred polyacetals are made from Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from Obtained 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 obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme-catalyzed processes are carried out. It is preferably Hydrolysis products with average molecular weights in the range of 400 to 500000 g / mol. There is one Polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Useful are 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 higher molar masses in the range from 2000 to 30000 g / mol.

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. An oxidized oligosaccharide is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

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

Other useful organic cobuilders are, for example, acetylated Hydroxycarboxylic acids or their salts, which may also be in lactone form can and which have at least 4 carbon atoms and at least one hydroxy group as well as a maximum of two acid groups.

Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Among the Hydroxyalkanephosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) from of particular importance as a cobuilder. It is preferably used as the sodium salt, where the disodium salt is neutral and the tetrasodium salt is alkaline (pH 9). As Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher Homologues in question. They are preferably in the form of neutral sodium salts, z. B. as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP, used. HEDP is preferred as the builder from the phosphonate class used. The aminoalkanephosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the means too Contain bleach, be preferred aminoalkane phosphonates, in particular DTPMP, to use, or to use mixtures of the phosphonates mentioned.

In addition, all compounds that are able to complex with To train alkaline earth ions are used as cobuilders.

Detergents that are used as automatic dishwashing detergents can be used for Protect the wash ware or the machine contain corrosion inhibitors, especially Silver protection agents in the field of automatic dishwashing are of particular importance to have. The known substances of the prior art can be used. Generally can especially silver preservatives selected from the group of triazoles, the benzotriazoles, the Bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. Benzotriazole are particularly preferred and / or alkylaminotriazole. You will also often find it in detergent formulations agents containing active chlorine, which significantly reduce the corrosion of the silver surface can. Chlorine-free cleaners contain oxygen and nitrogen in particular organic redox-active compounds, such as di- and trihydric phenols, e.g. B. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic Compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often found Use. The transition metal salts which are selected from the Group of manganese and / or cobalt salts and / or complexes, particularly preferably the Cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. You can also Zinc compounds are used to prevent corrosion on the wash ware.

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 proteases obtained from Bacillus lentus are used. Are there 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 cellulase-containing mixtures of of special interest. Peroxidases or oxidases have also been found in some cases proven suitable. The enzymes can be adsorbed on carriers and / or in Envelope substances must be embedded to protect them against premature decomposition.

Fragrances are added to the agents according to the invention to give the aesthetic impression to improve the products and give the consumer a sensory "typical and to provide distinctive "product.

Individual perfume oils or fragrances can be used in the context of the present invention Fragrance compounds, e.g. B. the synthetic products of the ester, ether, Aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. Count among the ethers for example benzyl ethyl ether, to the aldehydes z. B. the linear alkanals with 8-18 C- Atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, α- Isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, belong to the hydrocarbons mainly the terpenes like limes and pinene. However, mixtures are preferred different fragrances are used, which together create an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures such as those from plant sources are accessible, e.g. B. pine, citrus, 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 general description of the perfumes that can be used (see above) is generally the different substance classes of fragrances. In order to be perceptible, a Fragrance to be volatile, being in addition to the nature of the functional groups and structure The molecular weight of the chemical compound also plays an important role. So they own Most fragrances have molecular weights of up to about 200 daltons, while molecular weights of 300 daltons and more of an exception. Due to the different volatility of Odoriferous substances change the smell of a compound composed of several odoriferous substances Perfume or fragrance during evaporation, whereby the odor impressions in "Top note", "heart or middle note" (middle note or body) and "base note" (end note or dry out) divided. Because the smell to a large extent, too is based on the intensity of the smell, the top note of a perfume or fragrance does not exist solely from volatile compounds, while the base note largely consists of less volatile, d. H. non-stick fragrances. When composing perfumes For example, more volatile fragrances can be bound to certain fixatives, which prevents it from evaporating too quickly. In the following classification of Fragrance in "more volatile" or "sticky" fragrance is so over Odor impression and whether the corresponding fragrance as a top or heart note is perceived, nothing is said.

Through a suitable selection of the fragrances or perfume oils mentioned, they can be used Way for textile detergent or machine dishwashing detergent both the product smell, in the case of machine dishwashing detergents, the smell when opening the Dishwasher are affected. For the latter impression of smell is the Use of more adhesive fragrances is advantageous, while also for product scenting volatile fragrances can be used. Adhesive odoriferous substances that are used in the The present invention can be used, for example, the essential oils such as Angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, bergamot oil, Champaca flower oil, noble fir oil, noble fir cone oil, elemi oil, eucalyptus oil, fennel oil, Spruce oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, gurjun balsam oil, Helichrysum oil, ho oil, ginger oil, iris oil, kajeput oil, calamus oil, chamomile oil, camphor oil, Kanaga oil, cardamom oil, cassia oil, pine needle oil, Kopalvabalsamöl, coriander oil, Spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, mandarin oil, Melissa oil, musk grain oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, Orange oil, origanum oil, palmarosa oil, patchouli oil, Peru balsam oil, petitgrain oil, pepper oil, Peppermint oil, allspice oil, pine oil, rose oil, rosemary oil, sandalwood oil, celery oil, spik oil, Star anise oil, turpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil, Wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, lemon oil, Lemon oil and cypress oil. But also the higher-boiling or solid fragrances natural or synthetic origin can in the context of the present invention as Adhesive fragrances or fragrance mixtures, i.e. fragrances, are used. To this Compounds count the compounds mentioned below and mixtures these: ambrettolide, α-amyl cinnamaldehyde, anethole, anisaldehyde, anis alcohol, anisole, Anthranilic acid methyl ester, acetophenone, benzylacetone, benzaldehyde, Ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, Benzyl formate, benzyl valerianate, borneol, bomylacetate, α-bromostyrene, n-decylaldehyde, n- Dodecylaldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, Fenchylacetate, geranyl acetate, geranyl formate, heliotropin, heptincarboxylic acid methyl ester, Heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, Iron, isoeugenol, isoeugenol methyl ether, isosafrol, jasmon, camphor, karvakrol, karvon, p- Cresol methyl ether, cumann, p-methoxyacetophenone, methyl-n-amyl ketone, Methylanthranilic acid methyl ester, p-methylacetophenone, methylchavicol, p-methylquinoline, Methyl-β-naphthyl ketone, methyl-n-nonylacetaldehyde, methyl-n-nonyl ketone, muscon, β- Naphthol ethyl ether, β-naphthol methyl ether, nerol, nitrobenzene, n-nonylaldehyde, Nony alcohol, n-octylaldehyde, p-oxy-acetophenone, pentadecanolide, β-phenylethyl alcohol, Phenylacetaldehyde dimethyacetal, phenylacetic acid, pulegon, safrol, Salicylic acid isoamyl ester, salicylic acid methyl ester, salicylic acid hexyl ester, Cyclohexyl salicylic acid, Santalol, Skatol, Terpineol, Thymen, Thymol, γ-undelactone, Vanilin, veratrum aldehyde, cinnamaldehyde, cimate alcohol, cinnamic acid, ethyl cinnamate, Zimtsäurebenzylester. The more volatile fragrances include, in particular lower boiling odoriferous substances of natural or synthetic origin, the αllein or in Mixtures can be used. Examples of more volatile fragrances are Alkyisothiocyanate (alkyl mustard oils), butanedione, limonene, linalool, linaylacetate and Propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, Terpinylacetate, citral, citronellal.

In order to facilitate the disintegration of the highly compressed compressions according to the invention Shortening disintegration times are within the scope of the present invention, Disintegration aids, so-called tablet disintegrants, are used. Under Tablet disintegrants or disintegrants are according to Römpp (9th edition, Vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, p. 182-184) Excipients understood 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 known as "explosives" due to their effectiveness, increase their volume when water enters, and on the one hand increases their own volume (Swelling), on the other hand a pressure can also be generated via the release of gases, which breaks the tablet into smaller particles. Well-known disintegration aids are for example carbonate / citric acid systems, with other organic acids can be used. Swelling disintegration aids are, for example synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein Derivatives. All of the disintegration aids mentioned can be used according to the invention.

In the context of the present invention, disintegration aids are preferred Cellulose-based disintegration aids are used and it is preferred that the Disintegrant-containing phase (s) of the two-phase or multi-phase according to the invention compressed detergent and cleaning agent formulation, as a disintegration aid Disintegration aid based on cellulose, preferably in granular, cogranulated or compact form, contains.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally speaking, is 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 hydroxy 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 disintegrants used on cellulose basis, but used in a mixture with cellulose. The salary these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the disintegrant Cellulose. Pure cellulose-based disintegrant is particularly preferred Cellulose used, which is free of cellulose derivatives. As another means of disintegration on cellulose basis or as a component of this component can be microcrystalline cellulose be used. This microcrystalline cellulose is obtained by partial hydrolysis of Celluloses obtained under such conditions that only the amorphous areas (approx. 30% of the Attack total cellulose mass) of the celluloses and completely dissolve the crystalline ones Leave areas (approx. 70%) undamaged. A subsequent disaggregation by the Hydrolysis resulting microfine celluloses provides the microcrystalline celluloses Have primary particle sizes of approx. 5 µm and, for example, granules with a average particle size of 200 microns are compactible.

In addition to the ingredients mentioned above, the washing and Detergent tablets a gas-releasing system from organic acids and Contain carbonates / bicarbonates.

As organic acids from the carbonates / hydrogen carbonates in aqueous solution Releasing carbon dioxide are, for example, the solid mono-, oligo- and polycarboxylic acids used. From this group citric acid, tartaric acid, Succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid as well Polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid can also be used. Commercially available and as an acidifying agent in the context of the present invention Sokalan® DCS (trademark of BASF), a mixture of Succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight).

The acids mentioned do not have to be stoichiometric to those contained in the compressed products Carbonates or bicarbonates are used.

A preferred washing and in the context of the present invention Compressed detergent additionally contains a shower system.

The gas-developing shower system consists of the compressed washing and cleaning agents in addition to the above-mentioned organic acids from carbonates and / or Bicarbonates. The representatives of this class of substances are the ones for cost reasons Alkali metal salts clearly preferred. In the case of the alkali metal carbonates or -Hydrogen carbonates are the sodium and potassium salts for reasons of cost clearly preferred over the other salts. Of course they don't have to pure alkali metal carbonates or bicarbonates in question are used; rather, mixtures of different carbonates and hydrogen carbonates can be preferred his.

Sodium carbonate forms a white powder with a density of 2.532 gcm ^-3 , whereby a distinction is made between lightly calcined soda with a bulk density of 0.5-0.55 kg / l and heavily calcined soda with 1.0-1.1 kg / l. Sodium carbonate forms three hydrates with water: sodium carbonate decahydrate (crystal soda), Na ₂ CO ₃ .10H ₂ O, colorless, monoclinic, ice-like looking crystals with a density of 1.44 gcm ^-3 , melting point 32-34 °; Sodium carbonate heptahydrate, Na ₂ CO ₃ .7H ₂ O, rhombic crystals of density 1.51 gcm ^-3 , melting point 32-35 °; Sodium carbonate monohydrate, Na ₂ CO ₃ .H ₂ O, rhombic crystals with a density of 2.25 gcm ^-3 , melting point 100 °.

Sodium bicarbonate is a white, alkaline-tasting, odorless, dry air-resistant powder (monoclinic crystals) with a density of 2.159 gcm ^-3 , which decomposes into CO ₂ , H ₂ O and sodium carbonate when heated to over 65 °.

Potassium carbonate (potash) is a white, non-toxic, hygroscopic, granular with a density of 2.428 gcm ^-3 that forms various hydrates. If one leads in conc. Potassium carbonate solution a lot of carbon dioxide, so the less soluble potassium bicarbonate precipitates. In addition, potassium carbonate shows great similarities in its properties to the closely related soda. Potassium carbonate-1,5-water ("potash hydrate") is the stable phase of the potassium carbonate in contact with the saturated solution in the range from 0 ° C to approx. 110 ° C and can be obtained by crystallization from supersaturated potassium carbonate solutions. It crystallizes in shiny, practically dust-free crystals, has a density of 2.155 gcm ^-3 and completely loses its crystal water at temperatures of 130 to 160 ° C. Most large-scale manufacturing processes for potassium carbonate initially lead to potassium carbonate-1,5-water, which is calcined in rotary kilns at 200 to 350 ° C to 98 to 100% potassium carbonate. If this calcination is omitted, the crystallized potassium carbonate 1,5 hydrate is dried at 110 to 120 ° C. and sold as a potash hydrate. Technically common manufacturing processes for the products mentioned are, for example, the process with continuous crystallization (starting materials: KOH and CO ₂ ), the fluidized bed process (starting materials: KOH and CO ₂ ), the amine process (KOH / CO ₂ in the presence of isopropylamine: Mines de Potasse d'Alsace or KOH / CO ₂ in the presence of triethylamine: Kali-Chemie AG) or the nepheline digestion process (mainly former USSR). The ion exchanger process (starting materials: KCl and (NH ₄ ) ₂ CO ₃ ), the magnesia process (Engel-Precht process, Neustaßfurt process; starting materials: KCl, MgCO ₃ .3 H ₂ O and CO ₂ ), the formate potash process (raw materials: potassium sulfate, calcium hydroxide and carbon monoxide), the Piesteritz process (raw materials: potassium sulfate and calcium cyanamide) and the Le Blanc process (raw materials: potassium sulfate, calcium carbonate and carbon).

Trona, a mixed salt of sodium carbonate and sodium bicarbonate, which is also referred to as sodium sesquicarbonate or sodium carbonate sesquihydrate, can also be used as the second component of the shower system. Sodium carbonate sesquihydrate is found in nature as a mineral (Trona) and is described by the formula Na ₂ CO ₃ .NaHCO ₃ .2 H ₂ O. Large Trona deposits are found, for example, in the USA (Green River / Wyoming), Kenya (Lake Magadi) and the Republic of Sudan (Dongola). While the deposits in Africa can be exploited in the open-cast mine, the Trona is mined in the USA. Trona has a density of 2.17 gcm ^-3 and a Mohs hardness of 2.5. Trona is usually used for the production of pure soda, but pure Na ₂ CO ₃ .NaHCO ₃ .2 -H ₂ O can also be produced by the sodium sesquicarbonate process, which is sold. Pure sodium sesquicarbonate is also formed from sodium bicarbonate by standing in humid air with the release of carbon dioxide or by introducing carbon dioxide into a sodium carbonate solution.

In the context of the present invention, it is further preferred that one or more further Phases of the compressed of the two-phase or multi-phase compressed according to the invention Detergent formulations a disintegration aid in amounts of 0.1 to 10% by weight, preferably from 0.5 to 7.5% by weight and in particular from 1.0 to Contain 5 wt .-%, the amounts given to the weight of the respective phase relate and it has proven to be advantageous that this disintegration aid in the Phases a shower system and / or a water-soluble salt with a solubility above 10 g / l and / or urea.

In addition to the components described in detail so far, the Detergent and cleaning agent compresses according to the invention contain further ingredients, the the technical and / or aesthetic properties of the laundry detergent continue to improve. Preferred tablets contain within the scope of the present invention one or more substances from the group of electrolytes, pH adjusting agents, fluorescent agents, Dyes, hydrotopes, foam inhibitors, silicone oils, anti-redeposition agents, optical Brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, Color transfer inhibitors, antimicrobial agents, germicides, fungicides, Antioxidants, antistatic agents, ironing aids, phobing and impregnating agents, swelling and Anti-slip agent and UV absorber.

A wide number of different salts can be used as electrolytes from the group of inorganic salts. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl ₂ in the agents according to the invention is preferred.

In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjusting agents may be indicated. All known ones can be used here Acids or alkalis, provided that their use does not result from application technology or for ecological reasons or for reasons of consumer protection. Usually The amount of these adjusting agents does not exceed 1% by weight of the total formulation.

In order to improve the aesthetic impression of the agent according to the invention, you can use suitable dyes are colored. Preferred dyes, the selection of which Expert has no difficulty, have a high storage stability and Insensitivity to the other ingredients of the agent and to light as well no pronounced substantivity towards textile fibers in order not to dye them.

As foam inhibitors which are used in the compressed products according to the invention can, for example, soaps, paraffins or silicone oils are considered can optionally be applied to carrier materials. suitable Antiredeposition agents, which are also referred to as soil repellents, are for example nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose a proportion of methoxy groups from 15 to 30 wt .-% and of hydroxypropyl groups 1 to 15 wt .-%, each based on the nonionic cellulose ether and the αus from Polymers of phthalic acid and / or terephthalic acid or of known from the prior art their 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 derivatives are particularly preferred Phthalic and terephthalic polymers.

Optical brighteners (so-called "whiteners") can be used in the agents according to the invention can be added to cause graying and yellowing of the treated textiles remove. These substances absorb on the fiber and cause a lightening and feigning bleaching effect by turning invisible ultraviolet radiation into visible convert longer wave light, whereby the ultraviolet absorbed from sunlight Light is emitted as a weak bluish fluorescence and with the yellow tone of the grayed or yellowed laundry results in pure white. Suitable compounds originate, for example from the substance classes of 4,4'-diamino-2,2'-stilbene disulfonic acids (flavonic acids), 4,4'- Distyryl-biphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3- Diarylpyrazolines, naphthalic imides, benzoxazole, benzisoxazole and benzimidazole Systems and the pyrene derivatives substituted by heterocycles.

Graying inhibitors have the task of removing the dirt detached from the fiber in the Keep the liquor suspended and thus prevent the dirt from re-opening. For this are water-soluble colloids mostly organic in nature, for example water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids the starch or cellulose or salts of acidic sulfuric acid esters of cellulose or of strength. Water-soluble polyamides containing acidic groups are also suitable for this purpose suitable. Soluble starch preparations and others other than those mentioned above can also be used Use starch products, e.g. B. degraded starch, aldehyde starches, etc. Also Polyvinyl pyrrolidone is useful. Can still be used as graying inhibitors Cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, Hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof.

Because textile fabrics, especially from rayon, rayon, cotton and their Mixtures that can be creased because the individual fibers prevent bending, kinking. Pressing and squeezing across the grain are sensitive Tablets according to the invention contain synthetic anti-crease agents. Which includes for example synthetic products based on fatty acids, fatty acid esters, Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, mostly with ethylene oxide implemented, or products based on lecithin or modified Organophosphate.

The compressed products according to the invention can be used to control microorganisms contain antimicrobial agents. A distinction is made here depending on the antimicrobial Spectrum and mechanism of action between bacteriostatics and bactericides, Fungistatics and fungicides etc. Important substances from these groups are for example Benzalkoniumchloride, Alkylarlylsulfonate, Halogenphenole and Phenolmercuriacetat, whereby these compounds are also completely dispensed with in the agents according to the invention can.

To unwanted, caused by oxygen and other oxidative processes Changes to the compressed washing and cleaning agents and / or the To prevent treated textiles, the agents can contain antioxidants. To this Compound classes include, for example, substituted phenols, hydroquinones, Pyrocatechnols and aromatic amines as well as organic sulfides, polysulfides, Dithiocarbamates, phosphites and phosphonates.

An increased wearing comfort can result from the additional use of antstatics, which are additionally added to the compressed products according to the invention. antistatic agents increase the surface conductivity and thus enable an improved drainage formed charges. External antistatic agents are usually substances with at least one hydrophilic molecular ligands and give a more or less on the surfaces hygroscopic film. These mostly surface-active antistatic agents can be nitrogenous (amines, amides, quaternary ammonium compounds), phosphorus (Phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents divide. Lauryl (or stearyl) dimethylbenzylammonium chlorides are also suitable as antistatic agents for textiles or as an additive to detergents, with an additional one Finishing effect is achieved.

To improve the water absorption capacity, the rewettability of the treated textiles and to facilitate ironing of the treated textiles can in the derivatives according to the invention, for example silicone derivatives are used. This additionally improve the rinsing behavior of the agents according to the invention through their foam-inhibiting properties. Preferred silicone derivatives are, for example Polydialkyl- or alkylarylsiloxanes, in which the alkyl groups have one to five carbon atoms have and are fully or partially fluorinated. Preferred silicones are Polydimethylsiloxanes, which can optionally be derivatized and then are amino-functional or quaternized or Si-OH, Si-H and / or Si-Cl bonds exhibit.

Finally, the compressions according to the invention can also contain UV absorbers which are based on pull up the treated textiles and improve the lightfastness of the fibers. Compounds which have these desired properties are, for example, those by radiation-free deactivation effective compounds and derivatives of benzophenone with Substituents in the 2- and / or 4-position. Substituted benzotriazoles in 3- Position phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.

The spatial shapes of the compresses according to the invention are in their dimensions Detergent dispenser of commercial household washing machines adapted so that they are direct can be metered into the corresponding compartments of the induction chamber where they are located dissolves during the wash-in process. Alternatively, according to the invention Compressed but of course also be dosed directly into the washing drum, whereby if necessary, dosing aids can be used.

In the context of the present invention, compressed bodies are used as compressed in practical referred to all sensibly manageable configurations, for example the training of shaped bodies as a board, in the form of bars or bars, cubes, cuboids and the like Room element with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section. This last embodiment covers the Presentation form from the actual tablet to compact cylinder pieces with one Ratio of height to diameter above 1. The phase containing disintegrant can all technically feasible within the previously described spatial forms Taking forms, preferred configurations have already been explained above.

Preferred compressions have a circular or oval two-phase or multi-phase Cross-section, whose phase (s) through a further explosive-containing phase with a likewise circular or oval base area is interrupted, the Base of the explosive phase preferably up to the edge of the two or multiphase cross-section of the compressed material is sufficient. In other embodiments the cross section of the compressed product and / or the explosive-containing phase is triangular, have square or any other polygonal bases.

Another preferred molded body that can be used according to the invention has one slab-like or plate-like structure with alternating thick long and thin short Segments, so that individual segments of this "bolt" at the predetermined breaking points, which the represent short thin segments, can be canceled and entered into the machine can. This principle of the "bar-shaped" shaped detergent can also be used in others geometric shapes, for example vertically standing triangles, which only on one their sides are connected alongside each other, can be realized.

Claims (12)

1. Two-phase or multi-phase compressed detergent and cleaning agent formulation containing builders, surfactants and other constituents of detergents and cleaning agents, characterized in that the phase (s) of the compressed product is (at least partially) interrupted by (a) disintegrant-containing phase (s) ) or are separated from each other. 2. Two or multi-phase compressed detergent and cleaning agent formulation, according to claim 1, characterized in that the disintegrant (s) Layer (s) is / are not planar. 3. Two-phase or multi-phase compressed detergent and cleaning agent formulation, according to one of claims 1 or 2, characterized in that the disintegrant-containing phase (s) is / are planar, but not complete runs parallel to the surface of the compressed product. 4. Two or multi-phase compressed detergent and cleaning agent formulation according to one of claims 1 to 3, characterized in that the disintegrant-containing phase (s) the neighboring phases of the compressed material does not completely separate. 5. Two or multi-phase compressed detergent and cleaning agent formulation according to claim 4, characterized in that the disintegrant (s) Phase (s) the adjacent phases of the compressed to 10 to 90%, preferably on 20 to 80% and in particular 30 to 70% of the common phase interface (s) separates from each other. 6. Two or multi-phase compressed detergent and cleaning agent formulation according to one of claims 1 to 5, characterized in that the phase (s) containing disintegrant the disintegrant in quantities above 10% by weight, preferably in amounts above 15% by weight, particularly preferably in amounts above 20 and in particular in amounts above 30% by weight contains / contain based on the weight of the phase. 7. Two- or multi-phase compressed washing and cleaning formulation after one of claims 1 to 6, characterized in that the disintegrant-containing phase (s) additionally at least one washing and / or contains / contain cleaning active substance. 8. Two or multi-phase compressed detergent and cleaning agent formulation according to one of claims 1 to 7, characterized in that the phase (s) containing disintegrant a thickness below 3 mm, preferred has / have below 2 mm and in particular below 1 mm. 9. Two- or multi-phase compressed detergent and cleaning agent formulation according to one of claims 1 to 8, characterized in that the phase (s) containing disintegrant as disintegration aid Disintegration aids based on cellulose, preferably in granular form, cogranulated or compacted form. 10. Two or multi-phase compressed detergent and cleaning agent formulation according to one of claims 1 to 9, characterized in that one / more others Phases of the compressed a disintegration aid in amounts from 0.1 to 10% by weight, preferably from 0.5 to 7.5% by weight and in particular from 1.0 to 5% by weight included, where the quantities are based on the weight of the respective phase Respectively. 11. Two- or multi-phase compressed detergent and cleaning agent formulation according to claim 10, characterized in that the disintegration aid in the Live an effervescent system and / or a water-soluble salt with a solubility is above 10 g / l and / or urea. 12. Two- or multi-phase compressed detergent and cleaning agent formulation according to one of claims 1 to 11, characterized in that the compressed is produced by tableting or extrusion.