DE19953027A1 - Laundry detergent tablets based on surfactant and builder contain disintegration aid granulate of polysaccharide and water-soluble granulation agent - Google Patents

Abstract

Laundry detergent tablets contain: (a) surfactants, (b) builder; and (c) disintegration aid granulate containing polysaccharide and granulation agent with a water solubility of >= 10 g/l at 20 deg C. An Independent claim is also included for the production of the tablets by press agglomeration of the constituents.

Description

Field of the Invention

The invention is in the field of molded detergents and relates to tablets with tensi the, builders and special explosives.

State of the art

Among the solid washing, rinsing and cleaning agents, those in tablet form quickly have a high conquer their market share. What is critical, however, is the speed at which it dissolves eats that the tablets of the market do not go through the induction chambers of the machines, but directly be metered into the wash liquor, for example. Essential components of these tablets are so-called explosives or disintegrants, which are added to them to disintegrate Accelerate contact with water. Overviews can be found e.g. B. in J. Pharm. Sci. 61 (1972) or Römpp Chemilexikon, 9th edition, volume 6, p. 4440. The explosives can be in the form From a macroscopic point of view, bodies are homogeneously distributed, but microscopically they form zones of increased concentration due to manufacturing. Preferred explosives include poly saccharides such as B. natural starch and its derivatives, polyvinylpyrrolidone, Kollidon, alginic acid and their alkali salts, amorphous or also partially crystalline layered silicates (bentonites), polyurethanes, Polyethylene glycols and gas generating systems. Other explosives in the sense of the invention can be present, for example, the publications WO 98/40462 (Rettenmeyer), WO 98/55583 and WO 98/55590 (Unilever) and WO 98/40463, DE 197 09 991 and DE 197 10 254 (Henkel) refer to. The disadvantage, however, is that the explosives of the trade before incorporation into the solid moldings have to be granulated and additionally compacted in order to form the end products to cause a sufficiently rapid disintegration. Since the compression step is time and energy intensive, there is a sustained interest in detergent tablets, which despite high dissolving speed Contain explosives that do not have to be compacted.  

The object of the present invention was accordingly such new detergents to provide tablets.

Description of the invention

The invention relates to detergent tablets containing

• a) surfactants,
• b) Builder and
• c) Disintegrant granules containing polysaccharides and granulating aids, which at 20 ° C a Have water solubility of at least 10 g / l.

Surprisingly, it was found that detergent tablets based on surfactants and builders, which contain the defined explosive granules, a sufficiently high dissolution rate show that the disintegrant granules are not compacted before being introduced into the tablets available.

Surfactants

The primary components of the agents are anionic, nonionic, cationic, amphoteric and / or second rionic surfactants, but are preferably anionic surfactants or combinations of anionic and nonionic surfactants. Typical examples of anionic surfactants are soaps, alkyl benzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α- Methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, Hy Droxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligogluco sidsulfate, protein fatty acid condensates (especially vegetable products based on wheat) and Al kyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow homolog distribution. Preferential alkylbenzene sulfonates, alkyl sulfates, soaps, alkane sulfonates, olefin sulfonates, and methyl esters become wise sulfonates and mixtures thereof.  

Preferred alkylbenzenesulfonates preferably follow the formula (I)

R-Ph-SO ₃ X (I)

in which R is a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph for a phenyl radical and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, Alkanolammonium or Glucammonium stands. Of these, dodecylbenzene is particularly suitable sulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in Form of sodium salts.

Alkyl and / or alkenyl sulfates, which are also often referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary and / or secondary alcohols, which preferably follow the formula (II)

R ² O-SO ₃ Y (II)

in which R ^{2 represents} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and Y represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples of alkyl sulfates that can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, arylselyl alcohol, elaidyl alcohol Gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis. The sulfation products can preferably be used in the form of their alkali salts and in particular their sodium salts. Alkyl sulfates based on C _16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts are particularly preferred. In the case of branched primary alcohols are Oxoalko hole, as z. B. accessible by reaction of carbon monoxide and hydrogen to alpha-olefins by the shop process. Such alcohol mixtures are commercially available under the trade name Dobanol® or Neodol®. Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45®. Another possibility are oxo alcohols, such as those obtained after the classic Enichema or Condea oxo process by adding carbon monoxide and hydrogen to olefins. These alcohol mixtures are a mixture of highly branched alcohols. Such alcohol mixtures are commercially available under the trade name Lial®. Suitable alcohol mixtures are Lial 91®, 111®, 123®, 125®, 145®.

Finally, soaps are to be understood as meaning fatty acid salts of the formula (III)

R ³ CO-OX (III)

in which R ³ CO represents a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and preferably 12 to 18 carbon atoms and X represents alkali metal and / or alkaline earth metal, ammonium, alkylammonium or alkanolammonium. Typical examples are the sodium, potassium, magnesium, ammonium and triethanolammonium salts of caproic acid, caprylic acid, 2-ethylhexanoic acid, calcium prinic acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaoleic acid, petoleic acid, linoleic acid, petoleic acid , Linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Before preferably coconut or palm kernel fatty acid are used in the form of their sodium or potassium salts.

Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polygly colether, fatty acid polyglycol ester, fatty acid amide polyglycol ether, fatty amine polyglycol ether, alkoxylated Triglycerides, mixed ethers or mixed formals, alk (en) yl oligoglycosides, fatty acid N-alkyl glucamides, Pro tein hydrolyzates (especially vegetable products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants polyglycol ether ket ten contained, these can be a conventional, but preferably a narrowed homolog have distribution. Fatty alcohol polyglycol ethers, alkoxylated fatty acids are preferred alkyl ester or alkyl oligoglucoside used.

The preferred fatty alcohol polyglycol ethers follow the formula (IV)

R ⁴ O (CH ₂ CHR ⁵ O) _n H (IV)

in which R ^{4 represents} a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R ^{5 represents} hydrogen or methyl and n represents numbers from 1 to 20. Typical examples are the addition products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide onto capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol Elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, Elaeo stearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures. Addition products of 3, 5 or 7 moles of ethylene oxide onto technical coconut oil alcohols are particularly preferred.

Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (V)

R ⁶ CO- (OCH ₂ CHR ⁷ ) _m OR ⁸ (V)

in which R ⁶ CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{7 is} hydrogen or methyl, R ^{8 is a} linear or branched alkyl radical having 1 to 4 carbon atoms and m is a number from 1 to 20 stands. Typical examples are the formal insert products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, calcium acid , 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and behenic acid and behenic acid and behenic acid. The products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for. B. Calcined hydrotalcite. Reaction products of an average of 5 to 10 moles of ethylene oxide into the ester linkage of technical coconut fatty acid methyl esters are particularly preferred.

Alkyl and alkenyl oligoglycosides, which are also preferred nonionic surfactants, usually follow the formula (VI),

R ⁹ O- [G] _p (VI)

in which R ^{9 represents} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP 0301298 A1 and WO 90/03977. The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (VI) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p must always be an integer in a given compound and especially here can assume the values p = 1 to 6, the value p for a certain alkyl oligo glycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ⁹ can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, capric alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as those obtained in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length C ₈ -C ₁₀ (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C ₈ -C ₁₈ coconut fatty alcohol by distillation and with a proportion of less than 6% by weight of C ₁₂ - Alcohol may be contaminated and alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ⁹ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and the technical mixtures described above, which can be obtained as well as their technical mixtures. Alkyl oligoglucosides based on hardened C _12/14 coconut alcohol with a DP of 1 to 3 are preferred.

Typical examples of cationic surfactants are, in particular, tetraalkylammonium compounds, such as, for example, dimethyldistearylammonium chloride or hydroxyethyl hydroxycetyldimmonium chloride (Dehyquart E) or esterquats. These are, for example, quaternized fatty acid triethanolamine ester salts of the formula (VII),

in which R ¹⁰ CO for an acyl radical with 6 to 22 carbon atoms, R ¹¹ and R ¹² independently of one another for hydrogen or R ¹⁰ CO, R ¹³ for an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _x4 H- Group, x1, x2 and x3 in total for 0 or numbers from 1 to 12, x4 for numbers from 1 to 12 and X for halide, alkyl sulfate or alkyl phosphate. Typical examples of ester quats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, as they occur, for example, in the pressure splitting of natural fats and oils. Technical C _12/18 coconut _fatty acids and in particular partially hardened C _16/18 tallow or palm fatty acids as well as high elaidic acid C _16/18 fatty acid cuts are preferably used. The fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters. With regard to the application properties of the ester quats, an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1, has proven to be particularly advantageous. The preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C _16/18 tallow or palm fatty acid (iodine number 0 to 40 ). From an application point of view, quaternized fatty acid tri ethanolamine ester salts of the formula (VII) have proven to be particularly advantageous in which R ¹⁰ CO is an acyl radical having 16 to 18 carbon atoms, R ^{11 is} R ¹⁰ CO, R ^{12 is} hydrogen, R ^{13 is} a methyl group , (x1 + x2 + x3) is 0 and X is methyl sulfate.

In addition to the quaternized fatty acid triethanolamine ester salts, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (VIII) are also suitable as esterquats,

in which R ¹⁴ CO for an acyl radical with 6 to 22 carbon atoms, R ¹⁵ for hydrogen or R ¹⁴ CO, R ¹⁶ and R ¹⁷ independently of one another for alkyl radicals with 1 to 4 carbon atoms, x5 and x6 in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.

Finally, the quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula (IX) should be mentioned as a further group of suitable ester quats,

in which R ¹⁸ CO for an acyl radical with 6 to 22 carbon atoms, R ¹⁹ for hydrogen or R ¹⁸ CO, R ²⁰ , R ²¹ and R ²² independently of one another for alkyl radicals with 1 to 4 carbon atoms, x7 and x8 in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.

Finally, suitable ester quats are substances in which the ester bond is replaced by an amide bond and which preferably follow the formula (X) based on diethylenetriamine,

in which R ²³ CO represents an acyl radical with 6 to 22 carbon atoms, R ²⁴ for hydrogen or R ²³ CO, R ²⁵ and R ²⁶ independently of one another for alkyl radicals with 1 to 4 carbon atoms and X for halide, alkyl sulfate or alkyl phosphate. Such amide ester quats are available on the market, for example, under the name Incroquat® (Croda).

Examples of suitable amphoteric or zwitterionic surfactants are alkylbetaines, alkylamido betaine, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. Examples of suitable alkylbetaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (XI)

in which R ²⁷ for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R ²⁸ for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ²⁹ for alkyl radicals with 1 to 4 carbon atoms, y1 for numbers from 1 to 6 and Y for a Alkali and / or alkaline earth metal or ammonium. Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, De cyldimethylamin, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C kyldimethylamin _12/14 -Kokosal, Myristyidimethylamin, cetyldimethylamine, stearyldimethylamine, Stearylethylmethyl amine, oleyl dimethyl amine, C _16/18 tallow alkyl dimethyl amine and technical mixtures thereof .

Carboxyalkylation products of amidoamines which follow the formula (XII) are also suitable,

in which R ³⁰ CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, y2 represents numbers from 1 to 3 and R ²⁷ , R ²⁸ , y1 and Y have the meanings given above. Typical examples are atoms reaction products of fatty acids with 6 to 22 carbon, in particular caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, Palmitinsäu acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic and erucic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylamino propylamine, which are condensed with sodium chloroacetate. The use of a condensation product of C _8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate is preferred.

Imidazolinium betaines are also suitable. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines such as aminoethylethanolamine (AEEA) or diethylene triamine. The corresponding carboxyalkylation products are mixtures of different open-chain betaines. Typical examples are condensation products of the above-mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C _12/14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.

Builder

Zeolites, for example, can be used as builders (component b). The fine crystalline, synthetic and bound water-containing zeolite which is frequently used as a detergent builder is preferably zeolite A and / or P. As zeolite P, for example, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P and Y are also suitable. Of particular interest is also a cocrystallized sodium / potassium aluminum silicate made of zeolite A and zeolite X, which as VEGOBOND AX® (commercial product from Condea Augusta SpA) is commercially available. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it can contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 Ethylene oxide groups, C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 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.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates (“layer silicates”) of the general formula NaMSi _x O _{2x + 1} .yH 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 are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP 0164514 A1. Preferred crystalline phyllosilicates of the formula given are those in which M is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the process described in international patent application WO 91/08171. Other suitable layered silicates are known, for example, from patent applications DE 23 34 899 A1, EP 0026529 A1 and DE 35 26 405 A1. Their usability is not limited to a special composition or structural formula. Smectites, in particular bentonites, are preferred here. Suitable layered silicates, which belong to the group of water-swellable smectites, are e.g. B. those of the general formulas

(OH) ₄ Si _8-y Al _y (Mg _x Al _4-x ) O ₂₀ montmorrilonite
(OH) ₄ Si _8-y Al _y (Mg _6-z Li _z ) O ₂₀ hectorite
(OH) ₄ Si _8-y Al _y (Mg _6-z Al _z ) O ₂₀ saponite

with x = 0 to 4, y = 0 to 2, z = 0 to 6. In addition, small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas. Furthermore, due to their ion-exchanging properties, the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na ⁺ and Ca ²⁺ . The amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing. Usable layered silicates are known for example from US 3,966,629, US 4,062,647, EP 0026529 A1 and EP 0028432 A1. Layer silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.

The preferred builder substances also include amorphous sodium silicates with a modulus Na ₂ 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, which are delayed release and have secondary rapid properties. The release delay 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 “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 degrees 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, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE 44 00 024 A1. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray morphous silicates.

It goes without saying that the generally known phosphates are also used as builder substances possible if such use should not be avoided for ecological reasons. Ge the sodium salts of orthophosphates, pyrophosphates and in particular are particularly suitable  the tripolyphosphate. Their content is generally not more than 25% by weight, preferably not more than 20 wt .-%, each based on the finished agent. In some cases it has been shown that in particular tripolyphosphates even in small amounts up to a maximum of 10% by weight, based on the finished agents, in combination with other builder substances for a synergistic improvement of secondary washing power.

The builders are preferably in the detergent tablets in amounts of 10 to 60, in particular 20 up to 40 wt .-% - based on the agent - contain.

Explosives

The disintegrants contained in the sense of the invention (component c) necessarily contain polysaccha ride and granulating agents of a defined water solubility. They are in granular form and are therefore not compact.

Examples of polysaccharides which represent the matrix of the disintegrants are carboxyme starch, starch glycolates in the form of their alkali salts, agar agar, guar gum, pectins etc.), celluloses and to understand their derivatives (carboxymethyl cellulose, microcrystalline cellulose) and the like. The granules preferably contain carboxymethyl celluloses (CMC) and / or carboxymethyl starch ken (CMS), where it has proven to be particularly advantageous if the polysaccharides have a molecule Lar lar in the range of 40,000 to 400,000. The substances are usually in quantities of 50 to 95, in particular 70 to 80 wt .-% - based on the granules - contain.

The granulation aids, which preferably have a water solubility at 20 ° C. of at least 20 g / l and in particular 50 g / l, can be salts of mineral acids or organic carboxylic acids as well as polymers, saccharides and / or surfactants. In a first embodiment of the invention, the salts of inorganic mineral acids come into consideration as granulation aids. Typical examples are the alkali and / or alkaline earth metal salts, aluminum or zinc salts of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid and silicic acid, in particular the alkali metal sulfate, alkali borate and perborate, the various alkali metal silicates ("water glasses") and alkali metal phosphates should be. Magnesium sulfate heptahydrate or borax are preferred. The salts of organic carboxylic acids are also suitable. Typical examples are the alkali and / or alkaline earth metal salts, aluminum or zinc salts of monocarboxylic acids with 1 to 22 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, 2-ethylhexanoic acid. The use of sodium acetate is particularly preferred. Instead of the monocarboxylic acids, corresponding C ₂ -C ₆ -dicarboxylic acids can also be used, so that the appropriate salts of succinic acid, maleic acid, maleic acid, fumaric acid, glutaric acid and adipic acid can be used as suitable granulation aids in the same way as above. Finally, salts of hydroxy-functionalized polyvalent carboxylic acids, such as. B. the above salts of malic acid, tartaric acid and especially citric acid. The use of alkali metal citrates is particularly preferred here.

The third group of suitable granulation aids are the water-soluble polymers which are, for example, protein hydrolyzates, polyamides, polyacrylates and polyurethanes can do. Urea and polyurea are also suitable. Saccharides and Polysaccharides such as e.g. B. sucrose, maltose or starch hydrolysates.

Finally, surface-active compounds are also suitable as granulation aids, which should preferably have good wetting properties. The surfactant granulating aid agents can be anionic, nonionic, cationic and / or amphoteric in nature. Typical case Games for anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alky ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohols holether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglyce ride, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, Fatty acid taurides, N-acylamino acids such as acyl lactylates, acyl tartrates, acyl glutamates and Acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable pro wheat-based products) and alkyl (ether) phosphates. If the anionic surfactants Polygly contain colether chains, these can be a conventional Ho, but preferably a restricted Ho have molog distribution. Typical examples of nonionic surfactants are fatty alcohol polygly colether, alkylphenol polyglycol ether, fatty acid polyglycol ester, fatty acid amide polyglycol ether, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, optionally partially oxi dated alk (en) yl oligoglycosides or glucoronic acid derivatives, fatty acid N-alkyl glucamides, protein hydrolysed sate (especially vegetable products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, can have a conventional, but preferably a narrow homolog distribution sen. Typical examples of cationic surfactants are quaternary ammonium compounds and ester quats, especially quaternized fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imida zolinium betaines and sulfobetaines. The surfactants mentioned are exclusively be known connections. With regard to the structure and manufacture of these substances, see relevant Über visual works, for example J. Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, pp. 54-124 or J. Falbe (ed.), "Catalysts, surfactants and mineral oil additives", Thie me Verlag, Stuttgart, 1978, pp. 123-211. Alkyl oligoglucosides, in particular used in particular with 8 to 10 carbon atoms in the alkyl chain. The granules are preferred  auxiliaries in amounts of 5 to 50 and in particular 20 to 30% by weight, based on the granules contain.

With regard to the desired disintegration times, it has proven to be advantageous if the Granu Care is taken that the granules have a grain size in the range of 0.1 to 5 and in particular which have 0.5 to 3 mm. Because of the high explosive effect, such granules are particularly useful preferably, in which the proportion which is not in the range of 0.1 to 5 mm is less than 25 and above is preferably less than 15% by weight. The adjustment of the grain size can be done by a specialist be adjusted by routine optimization, without this being an inventive step requirement.

For the production of disintegrant granules, a method is preferably used in which polysaccharides in the presence of granulation aids which are water-soluble at 20 ° C of at least 10 g / l, into a lumpy shape. For the preparation of the explosive granules Processes that are already known for the production of detergents are suitable for this purpose. The Granulation can take place in aqueous suspension or dry. Are for this process Components such as paddle mixers from Lödige or in particular spray mixers from Schugi company advantageous, in which the polysaccharides are placed in the mixing chamber and the aq solutions of the granulation aids.

A particularly preferred option is to use disintegrants by fluidized bed granulation ("SKET" granulation). Below this is a granulation with simultaneous drying understand, which is preferably carried out batchwise or continuously. The polysaccharides can be used both in the dried state and as an aqueous preparation. The watery Solutions or melts of the granulation aids are transferred simultaneously or one after the other one or more nozzles are introduced into the fluidized bed. Preferably one is in via a nozzle continuously blow polysaccharide powder into a fluidized bed that is approximately filled with seed material and meter the granulation aids through a second nozzle. This corresponds to a continuous one solid / liquid production, however, requires that appropriately dried polysaccharide powder already exists. The process can also be carried out continuously in liquid / liquid form. In this case however, care must be taken that the aqueous polysaccharide preparation is at such a high temperature is introduced that the droplets are dried immediately after leaving the nozzle without that the polysaccharides decompose. Conversely, the granulation aids, especially the aqueous solutions, are injected at such a low temperature that they are not immediate dry after leaving the nozzle, but can be deposited on the polysaccharide grain nen. The conditions required for this depend in particular on the cross-section of the system and can be found by the person skilled in the art by routine optimization. Preferred used Fluid bed apparatuses have base plates with dimensions of 0.4 to 5 m. Preferably  the granulation was carried out at fluidizing air speeds in the range from 1 to 8 m / s. The discharge the granules from the fluidized bed are preferably classified by size of the granules. The classification can be done, for example, by means of a screening device or by means of an opposing one Air flow (classifier air) take place, which is regulated so that only particles from a certain part size removed from the fluidized bed and smaller particles retained in the fluidized bed become. The inflowing air usually settles out of the heated or unheated classifier air and the heated soil air together. The soil air temperature is between 80 and 400, preferably 90 and 350 ° C. A starting mass is advantageously added at the beginning of the granulation, for example, a polysaccharide granulate from an earlier test approach. If from aqueous polysaccharide preparations, the water in the fluidized bed evaporates, whereby dried to dried germs are formed which are coated with further amounts of polysaccharide, granulated and again dried at the same time. As already explained, the aqueous can Solutions of the granulation aids also together with the polysaccharides or polysaccharide solutions insert gene. In this context, the teaching of German patent applications DE 43 03 211 A1 and DE 43 03 176 A1, the content of which is hereby expressly included. in the For the purposes of the invention it is also possible to use agglomerates which are formed by caking the Granules are formed. The detergent tablets can contain the disintegrant granules in amounts of 0.1 up to 25, preferably 1 to 20 and in particular 5 to 15% by weight, based on the moldings hold.

Auxiliaries and additives

In addition to the ingredients mentioned, the detergents can contain other known additives, for example wise co-builders, optical brighteners, enzymes, enzyme stabilizers, defoamers, co-disintegrants, contain small amounts of neutral filling salts as well as colors and fragrances and the like.

Useful organic builders are, for example, those in the form of their sodium salts settable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, wine acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use ecological reasons are not objectionable, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, wine acid, sugar acids and mixtures of these. The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of acidifying component and thus also serve to set a lower and milder pH value of Detergents or cleaning agents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.  

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000. 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 for the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. 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 2,000 to 30,000 can be used. A preferred dextrin is described in British patent application GB 9419091 A1 . 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 0232202 A1, EP 0427349 A1, EP 0472042 A1 and EP 0542496 A1 as well as from 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 are known. An oxidized oligosaccharide according to German patent application DE 196 00 018 A1 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Other suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably wise ethylenediamine disuccinate. Glyce are also particularly preferred in this context rindisuccinate and glycerol trisuccinate, as described, for example, in the US patent publications US 4,524,009, US 4,639,325, in European patent application EP 0150930 A1 and Japanese patent application JP 93/339896. Suitable amounts are in Zeolite-containing and / or silicate-containing formulations 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 and which have at least 4 Contain carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such cobuilders are described, for example, in international patent application WO 95/20029 wrote.

Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 800 to 150,000 (based on acid and measured against polystyrene sulfonic acid). Suitable copolymeric poly Carboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or Methacrylic acid with maleic acid. Copolymers of acrylic acid have been found to be particularly suitable  Maleic acid proven to contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Their relative molecular weight, based on free acids, is generally from 5,000 to 200,000 preferably 10,000 to 120,000 and in particular 50,000 to 100,000 (each measured against Po lystyrene sulfonic acid). The (co) polymeric polycarboxylates can either be as a powder or as an aqueous Solution are used, with 20 to 55 wt .-% aqueous solutions are preferred. Granules Polymers are usually mixed into one or more basic granules afterwards. In particular Biodegradable polymers made from more than two different mono are also particularly preferred mer units, for example those which according to DE 43 00 772 A1 as monomers salts of acrylic acid re and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE 42 21 381 C2 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives. Other preferred copolymers are those described in German patent applications DE 43 03 320 A1 and DE 44 17 734 A1 are described and as monomers preferably acrolein and acrylic have acid / acrylic acid salts or acrolein and vinyl acetate. Are also preferred as others Builder substances include polymeric aminodicarboxylic acids, their salts or their precursors call. Polyaspartic acids or their salts and derivatives are particularly preferred.

Other suitable builder substances are polyacetals, which are reacted with dialdehydes Polyolcarboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups for example as described in European patent application EP 0280223 A1 can. Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalalde hyd and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid re received.

In addition, the agents can also contain components that make the oil and fat washable made of textiles. The preferred oil and fat dissolving components include for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose a proportion of methoxyl groups from 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and those from the prior art Technology known polymers of phthalic acid and / or terephthalic acid or their deriva ten, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.

Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses, which have no outstanding builder properties, or mixtures of these; In particular, alkali carbonate and / or amorphous alkali silicate, especially sodium silicate with a molar ratio Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used. The content of sodium carbonate in the final preparations is preferably up to 40% by weight, advantageously between 2 and 35% by weight. The content of sodium silicate in the agents (without special builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight.

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 which 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. The bleaching agent content of the agents is preferably from 5 to 35% by weight and in particular up to 30% by weight, advantageously using per borate monohydrate or percarbonate.

As bleach activators, compounds which are aliphatic under perhydrolysis conditions oxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or ge optionally substituted perbenzoic acid result, are used. Substances that are suitable O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl carry groups. Multi-acylated alkylenediamines, in particular tetraacetylethylene, are preferred 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, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyl oxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5- dihydrofuran and those from German patent applications DE 196 16 693 A1 and DE 196 16 767 A1 known enol esters as well as acetylated sorbitol and mannitol or their in the European The patent application EP 0525239 A1 describes mixtures (SORMAN), acylated sugars derivatives, especially pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaa cetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N- acylated lactams, for example N-benzoylcaprolactam, which are known from international patent applications gen WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498 are known. The hydrophilic sub. Known from German patent application DE 196 16 769 A1 substituted acylacetals and those in German patent application DE 196 16 770 and the internatio Nale patent application WO 95/14075 described acyllactams are also preferably used puts. The combinations known from German patent application DE 44 43 177 A1 conventional bleach activators can be used. Such bleach activators are common Quantity range, preferably in amounts from 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total average. In addition to the conventional ones listed above Len bleach activators or in their place can also those from the European patent specifications EP 0446982 B1 and EP 0453 003 B1 known sulfonimines and / or bleach-boosting agents  transition metal salts or transition metal complexes as so-called bleaching catalysts be included. The transition metal compounds in question include in particular those Manganese, iron, cobalt, rutheni known from German patent application DE 195 29 905 A1 um or molybdenum salt complexes and those from German patent application DE 196 20 267 A1 Known N-analog connections, which is known from German patent application DE 195 36 082 A1 manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, which in the German Patent application DE 196 05 688 manganese, iron, cobalt, ruthenium, molybdenum, Titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, derived from the German Patent application DE 196 20 411 A1 known cobalt, iron, copper and ruthenium amine complexes, the manganese, copper and cobalt described in German patent application DE 44 16 438 A1 Complexes described in the European patent application EP 0272030 A1 cobalt Complexes, the manganese complexes known from European patent application EP 0693550 A1, the manganese, iron, cobalt and copper known from European patent EP 0392592 A1 fer complexes and / or those in the European patent EP 0443651 B1 or the European Patent applications EP 0458397 A1, EP 0458398 A1, EP 0549271 A1, EP 0549272 A1, EP 0544490 A1 and EP 0544519 A1 described manganese complexes. Combinations of bleach activators and Transition metal bleaching catalysts are, for example, from the German patent application DE 196 13 103 A1 and the international patent application WO 95/27775 are known. Bleaching enhancer Transition metal complexes, in particular with the central atoms Mn, Fe, Co, Gu, Mo, V, Ti and / or Ru, are in usual amounts, preferably in an amount up to 1 wt .-%, especially of 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the entire mean.

Enzymes in particular come from the class of hydrolases, such as proteases, Estera sen, lipases or lipolytic enzymes, amylases, cellulases or other glyco sylhydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases carry in the Laundry for removing stains, such as stains containing protein, fat or starch, and Graying at. Cellulases and other glycosyl hydrolases can be removed by removing pilling and microfibrils help to maintain color and increase the softness of the textile. To bleach or to inhibit color transfer, oxidoreductases can also be used. Especially from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens enzymatic active ingredients obtained. Preferably who the proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus the, used. There are enzyme mixtures, for example from protease and amylase or Pro tease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipoly enzymes or protease having a table action, lipase or enzymes and cellulase having a lipolytic action, in particular, however, protease- and / or lipase-containing mixtures or mixtures with lipolytic  acting enzymes of particular interest. Examples of such lipolytic enzymes are the well-known cutinases. Peroxidases or oxidases have also been found in some cases proven. Suitable amylases include in particular α-amylases, iso-amylases, pul lulanases and pectinases. Cellobiohydrolases, endoglucanases are preferably used as cellulases and β-glucosidases, which are also called cellobiases, or mixtures thereof. Because the different cellulase types differ in their CMCase and avicelase activities the desired activities can be set by targeted mixtures of the cellulases. The enzymes can be adsorbed on carriers and / or embedded in coating substances around them protect against premature decomposition. The percentage of enzymes, enzyme mixtures or enzyme Granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

In addition to the mono- and polyfunctional alcohols, the agents can contain further enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. In addition to calcium salts, magnesium salts also serve as stabilizers. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous. . Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. For this purpose, what are water-soluble colloids mostly organic are suitable, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Furthermore, soluble starch preparations and other starch products than those mentioned above can be used, e.g. B. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. However, 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, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the Means used.

The agents can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Are suitable for. B. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyle type may be present, e.g. B. 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) diphenyl. Mixtures of the aforementioned brighteners can also be used. Uniform white granules are obtained if the agents, in addition to the usual brighteners, are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, even small amounts , for example 10 ^-6 to 10 ^-3 wt .-%, preferably around 10 ^-5 wt .-%, of a blue dye. A particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).

Dirt-repellant polymers ("should repellants") are those substances which are preferred Contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio Ethylene terephthalate to polyethylene glycol terephthalate can range from 50:50 to 90:10. The molecular weight of the linking polyethylene glycol units is in particular in the range of 750 to 5000, d. that is, the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 up to 100. The polymers have an average molecular weight of about 5,000 to 200,000 and can have a block, but preferably a random structure. Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Next preferred are those polymers which link polyethylene glycol units with one mole molecular weight from 750 to 5000, preferably from 1000 to about 3000 and a molecular weight of Have polymers from about 10,000 to about 50,000. Examples of commercially available polymers are Products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).

Wax-like compounds can be used as defoamers. As "waxy" sol che understood compounds that have a melting point at atmospheric pressure above 25 ° C (room temperature temperature), preferably above 50 ° C and in particular above 70 ° C. The waxy Ent foaming agents are practically insoluble in water, d. H. at 20 ° C in 100 g of water solubility below 0.1% by weight. In principle, all known from the prior art wax-like defoamer substances can be included. Suitable wax-like compounds are in for example bisamides, fatty alcohols, fatty acids, carboxylic acid esters of mono- and polyhydric alcohol len as well as paraffin waxes or mixtures thereof. Alternatively, of course, you can also use them Purpose known silicone compounds are used.

Suitable paraffin waxes are generally a complex mixture of substances without a sharp one Melting point. For characterization, one usually determines its melting range by Differential thermal analysis (DTA) as described in "The Analyst" 87 (1962), 420, and / or his Freezing point. This is the temperature at which the paraffin slowly slows down cooling changes from the liquid to the solid state. Thereby are complete at room temperature liquid paraffins, that is to say those with a solidification point below 25 ° C., are not according to the invention useful. For example, the Paraf known from EP 0309931 A1 can be used finwax mixtures of, for example, 26% by weight to 49% by weight of microcrystalline paraffin wax  a solidification point of 62 ° C to 90 ° C, 20 wt .-% to 49 wt .-% hard paraffin with a solid point of 42 ° C to 56 ° C and 2 wt.% to 25 wt.% soft paraffin with a solidification point from 35 ° C to 40 ° C. Paraffins or paraffin mixtures are preferably used, which in Solidify the range from 30 ° C to 90 ° C. It should be noted that it is solid even at room temperature Apparent paraffin wax mixtures can contain different proportions of liquid paraffin. In the paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible Lich and preferably completely missing. For example, particularly preferred paraffin wax mixtures at 30 ° C a liquid content of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C. Liquid content of less than 30% by weight, preferably from 5% by weight to 25% by weight and in particular from 5% by weight to 15% by weight, at 60 ° C. a liquid fraction of 30% by weight to 60% by weight, in particular from 40% by weight to 55% by weight, at 80 ° C. a liquid fraction from 80% by weight to 100% by weight, and at 90 ° C a liquid content of 100 wt .-%. The temperature at which a liquid content of 100% by weight of the paraffin wax is reached, is still particularly preferred paraffin wax mixtures below 85 ° C, especially at 75 ° C to 82 ° C. The paraffin waxes can be petrolatum, act microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.

Suitable bisamides as defoamers are those which differ from saturated fatty acids with 12 to 22, preferably derived from 14 to 18 carbon atoms and from alkylenediamines with 2 to 7 carbon atoms. Appropriate nete fatty acids are lauric, myristic, stearic, arachic and behenic acid and mixtures thereof, such as it is obtained from natural fats or hardened oils, such as tallow or hydrogenated palm oil are. Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethy lendiamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine. Before pulled diamines are ethylenediamine and hexamethylenediamine. Bisamides are particularly preferred Bismyristoylethylenediamine, bispalmitoylethylenediamine, bisstearoylethylenediamine and mixtures thereof and the corresponding derivatives of hexamethylenediamine.

Suitable carboxylic acid esters as defoamers are derived from carboxylic acids with 12 to 28 carbon atoms. In particular, these are esters of behenic acid, stearic acid, hydroxystearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid. The alcohol portion of the carboxylic acid ester contains a mono- or polyhydric alcohol with 1 to 28 carbon atoms in the hydrocarbon chain. Examples of suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut alcohol, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol, and also ethylene glycol, glycerol, polyvinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol. Preferred esters are those of ethylene glycol, glycerol and sorbitan, the acid part of the ester being selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid. Suitable esters of polyvalent alcohols include xylitol monopalmitate, Pentarythritmonostearat, monostearate of glycerol, ethylene glycol and rat sorbitan, sorbitan Sorbitanmonolau, Sorbitandilaurat, sorbitan, sorbitan dioleate, and sorbitan mixed tallow and diesters. Glycerol esters which can be used are the mono-, di- or triesters of glycerol and the carboxylic acids mentioned, the mono- or diesters being preferred. Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are examples of this. Examples of suitable natural esters as defoamers are beeswax, which mainly consists of the esters CH ₃ (CH ₂ ) ₂₄ COO (CH ₂ ) ₂₇ CH ₃ and CH ₃ (CH ₂ ) ₂₆ COO (CH ₂ ) ₂₅ CH ₃ , and carnauba wax, which is a mixture of carnaubaic acid alkyl esters, often in combination with small amounts of free carnaubaic acid, other long-chain acids, high molecular weight alcohols and hydrocarbons.

Suitable carboxylic acids as a further defoamer compound are in particular behenic acid, stea rinic acid, oleic acid, palmitic acid, myristic acid and lauric acid as well as their mixtures as they are natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil are. Saturated fatty acids with 12 to 22, in particular 18 to 22, carbon atoms are preferred.

Suitable fatty alcohols as a further defoamer compound are the hydrogenated products of be written fatty acids.

Dialkyl ethers may also be present as defoamers. The ethers can be asym be constructed metrically or symmetrically, d. H. two identical or different alkyl chains preferably contain 8 to 18 carbon atoms. Typical examples are di-n-octyl ether, di-i octyl ether and di-n-stearyl ether, particularly suitable are dialkyl ethers which have a melting point above Have 25 ° C, especially above 40 ° C.

Other suitable defoamer compounds are fatty ketones, which are based on the relevant methods of preparative organic chemistry can be obtained. One goes to their manufacture example of carboxylic acid magnesium salts, which at temperatures above 300 ° C below Elimination of carbon dioxide and water are pyrolyzed, for example according to the German Publication DE 25 53 900 OS. Suitable fat ketones are those obtained by pyrolysis of the Ma magnesium salts of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, Elaidic acid, petroselinic acid, arachic acid, gadoleic acid, behenic acid or erucic acid become.

Other suitable defoamers are fatty acid polyethylene glycol esters, preferably by ba sisch homogeneously catalyzed addition of ethylene oxide to fatty acids can be obtained. In particular Ethylene oxide is added to the fatty acids in the presence of alkanolamines as catalyzes sators. The use of alkanolamines, especially triethanolamine, leads to an extremely selective one Ethoxylation of the fatty acids, especially when it comes to low ethoxylated verbin  to manufacture Within the group of fatty acid polyethylene glycol esters, those before moves that have a melting point above 25 ° C, especially above 40 ° C.

Within the group of wax-like defoamers, the paraffin waxes described are particularly preferably used alone as wax-like defoamers or in a mixture with one of the other wax-like defoamers, the proportion of paraffin waxes in the mixture preferably making up more than 50% by weight, based on the wax-like defoamer mixture . The paraffin waxes can be applied to carriers if necessary. All known inorganic and / or organic carrier materials are suitable as carrier materials. Examples of typical inorganic carrier materials are alkali carbonates, aluminosilicates, water-soluble layer silicates, alkali silicates, alkali sulfates, for example sodium sulfate, and alkali phosphates. The alkali silicates are preferably a compound with a molar ratio of alkali oxide to SiO ₂ of 1: 1.5 to 1: 3.5. The use of such silicates results in particularly good grain properties, in particular high abrasion stability and nevertheless high dissolution rate in water. The aluminosilicates referred to as carrier material include in particular the zeolites, for example zeolite NaA and NaX. The compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass. Silicates which are commercially available under the name Aerosil® or Sipernat® can also be used. Examples of suitable organic carrier materials are film-forming polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch. Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof. Particularly suitable mixtures are composed of sodium carboxymethyl cellulose and methyl cellulose, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit. The mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ether in weight ratios of 80:20 to 40:60, in particular 75: 25 to 50:50. Also suitable as a carrier is native starch, which is composed of amylose and amylopectin. Starch is called native starch, as it is available as an extract from natural sources, for example from rice, potatoes, corn and wheat. Native starch is a commercially available product and is therefore easily accessible. Carrier materials which can be used individually or more than one of the abovementioned compounds, in particular selected from the group of alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, water-soluble sheet silicates, alkali metal silicates, polycarboxylates, cellulose ethers, polyacrylate / polymethacrylate and starch. Mixtures of alkali carbonates, in particular sodium carbonate, alkali silicates, in particular sodium silicate, alkali sulfates, in particular sodium sulfate and zeolites are particularly suitable.

Suitable silicones are common organopolysiloxanes, which contain fine-particle silica in turn can also be silanized. Such organopolysiloxanes are, for example described in European patent application EP 0496510 A1. Are particularly preferred Polydiorganosiloxanes, which are known from the prior art. But it can also use siloxane crosslinked compounds are used, such as those known to the person skilled in the art under the name Siliconhar ze are known. As a rule, the polydiorganosiloxanes contain finely divided silica, which is also sila can be kidneyed. Silica-containing dimethylpolysiloxanes are particularly suitable. Advantageously the polydiorganosiloxanes have a Brookfield viscosity at 25 ° C in the range of 5,000 mPa.s up to 30,000 mPa.s, in particular from 15,000 to 25,000 mPa.s. The silicones are preferably on Trä germ materials applied. Suitable carrier materials are already in connection with the Par affine. The carrier materials are generally in amounts of 40 to 90% by weight, preferably in amounts of 45 to 75% by weight, based on defoamers.

The solid preparations can also co-disintegrants, such as polyvinylpyrroli don, Kollidon, alginic acid and their alkali salts, amorphous or partly crystalline layered silicates (Bentonite), polyurethanes, polyethylene glycols and gas-generating systems.

As perfume oils or fragrances, individual fragrance compounds, e.g. B. the synthetic pro Products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used the. 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 benzylsa licylate. The ethers include, for example, benzyl ethyl ether, the aldehydes z. B. the linear Alka nale with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitro nellal, lilial and bourgeonal, to the ketones z. B. the Jonone, α-Isomethylionon and Methylcedrylke clay, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpi neol, the hydrocarbons mainly include terpenes such as limonene and pinene. Before however, mixtures of different odoriferous substances are used, which together address one Generate the appropriate fragrance. Such perfume oils can also contain natural fragrance mixtures, as they are accessible from plant sources, 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 fragrances can be incorporated directly into the agents according to the invention, but they can also be advantageous to apply the fragrances on carriers, which the adhesion of the perfume on the Wä strengthening and slower fragrance release for long-lasting fragrance of textiles For example, cyclodextrins have proven themselves as such carrier materials, the cyclo dextrin-perfume complexes can also be coated with other auxiliaries.  

If desired, the final preparations can also contain inorganic salts as fillers or fillers contain, such as sodium sulfate, which is preferably in amounts of 0 to 10, in particular whose 1 to 5 wt .-% - based on agent - is included.

Manufacture of detergent tablets

Another object of the present invention relates to a method for producing washing medium tablets, in which tensides, builders and disintegrant granules by press agglomeration condensed. The particulate press agglomerates obtained can either be used directly as detergents used or previously treated and / or processed using conventional methods. To the Typical aftertreatments include, for example, powdering with finely divided ingredients Detergents or cleaning agents, which generally further increases the bulk density. A however, preferred post-treatment is also the procedure according to German Pa Tent applications DE 195 24 287 A1 and DE 195 47 457 A1 are dust-like or at least finely divided ingredients (the so-called fines) in the particles produced according to the invention shaped process end products, which serve as the core, are glued and thus ent ent stand, which have these so-called fines as an outer shell. Advantageously happens this in turn by melting agglomeration. For melting agglomeration of the fines expressly to the disclosure in the German patent applications DE 195 24 287 A1 and DE 195 47 457 A1. In the preferred embodiment of the invention, the solid washes medium in tablet form, these tablets in particular from storage and transport technology Reasons preferably have rounded corners and edges. The base of these tablets can be circular or rectangular, for example. Multi-layer tablets, especially tablets with 2 or 3 layers, which can also have different colors, are particularly preferred. Blue white or green-white or cyan-white tablets are particularly preferred. The tablets can also contain pressed and unpressed parts. Shaped body with a particularly advantageous Dissolution rates are obtained if the granular components unite before pressing Proportion of particles that have a diameter outside the range of 0.02 to 6 mm from have less than 20, preferably less than 10 wt .-%. A particle size is preferred distribution in the range from 0.05 to 2.0 and particularly preferably from 0.2 to 1.0 mm.

Examples Manufacturing example H1

A ploughshare mixer from Lödige was charged with up to 50 vol.% Of its filling capacity with carboxymethyl cellulose and the granulation was started, during which a solution of C _8/10 alkyl oligoglucoside (Glucopon® 215 CSUP, Cognis Deutschland GmbH / DE) was sprayed continuously until the glucoside content in the granules - determined by sampling - had reached a weight proportion of 20% by weight. The sieve analysis showed that 90% by weight of the resulting granules had a grain size in the range from 0.2 to 4 mm.

Manufacturing example H2

A fluidized bed was filled with carboxyme with up to 50% by volume of its filling capacity fed with cellulose. Subsequently, at a soil air temperature of 120 ° C (accordingly a temperature of about 60 ° C. in the fluidized bed) continuously add further polysaccharide powder out and sprayed through a nozzle a 50 wt .-% aqueous sucrose solution. The material flows me were determined by regular control of the discharged and classified from the fluidized bed Granules adjusted so that the sucrose content in the end product is about 30% by weight and the amount of water just about 2% by weight. The sieve analysis showed that 90% by weight of the resulting granules had a grain size above 0.8 mm.

Application studies

The two granules H1 and H2 according to the invention as well as two products from the market were combined with other additives at one Compression pressure of 35 kN compressed into tablets (40 g). The tablets were then placed on a Wire rack stored, which stood in water (0 ° d, 25 ° C). The tablets were complete surrounded by water. The decay time from immersion to complete dissolution was measured solution. The composition of the tablets and the disintegration times are summarized in Table 1. Examples 1 and 2 are according to the invention, examples V1 and V2 serve for comparison.  

Table 1

Composition of detergent tablets and disintegration times (quantities as% by weight)

Claims (14)

1. Containing detergent tablets

• a) surfactants,
• b) Builder and
• c) Disintegrant granules, containing polysaccharides and granulating aids, which have a water solubility of at least 10 g / l at 20 ° C.

2. Detergent tablets according to claim 1, characterized in that they as component (a) Contain surfactants that are selected from the group that is formed by alkylbenzenesulfona ten, alkyl sulfates, soaps, alkane sulfonates, olefin sulfonates, methyl ester sulfones, fatty alcohol po lyglycol ethers, alkoxylated fatty acid lower alkyl esters, alkyl and / or alkenyl oligoglycosides, Esterquats and / or betaines. 3. Detergent tablets according to claims 1 and / or 2, characterized in that they are the Surfactants in amounts of 1 to 50 wt .-% - based on the agent - contain. 4. detergent tablets according to at least one of claims 1 to 3, characterized in that they are builders (component b) zeolites, layered silicates, amorphous silicates and / or phosphates contain. 5. detergent tablets according to at least one of claims 1 to 4, characterized in that they contain the builders in amounts of 10 to 60 wt .-% - based on the agent. 6. detergent tablets according to at least one of claims 1 to 5, characterized in that they contain disintegrant granules (component c), which as polysaccharides carboxyme have methyl celluloses (CMC) and / or carboxymethyl starches (CMS). 7. detergent tablets according to at least one of claims 1 to 6, characterized in that that they contain disintegrants, which polysaccharides with a molecular weight in the range have from 40,000 to 400,000. 8. detergent tablets according to at least one of claims 1 to 7, characterized in that that they contain expanding agent granules which contain polysaccharides in amounts of 50 to 95% by weight - based on the granules.   9. detergent tablets according to at least one of claims 1 to 8, characterized in that that they contain disintegrant granules, which act as granulating aids salts of mineral acids or organic carboxylic acids, polymers, saccharides and / or surfactants. 10. detergent tablets according to at least one of claims 1 to 9, characterized in that they contain disintegrant granules, which granulation aids in amounts of 5 to 50% by weight - Based on the granules - have. 11. Detergent tablets according to at least one of claims 1 to 10, characterized in that that they contain disintegrant granules which have a grain size in the range from 0.1 to 5 mm exhibit. 12. Detergent tablets according to at least one of claims 1 to 11, characterized in that that they contain disintegrant granules in which the proportion which is not in the range from 0.1 to 5 mm, is less than 25% by weight. 13. Detergent tablets according to at least one of claims 1 to 12, characterized in that that they contain the disintegrant granules in amounts of 0.1 to 25% by weight, based on the composition, contain. 14. A method for producing detergent tablets according to claim 1, in which the inventory parts compressed by press agglomeration.