EP1306422B1 - Solid washing, rinsing and cleansing agent - Google Patents

Abstract

Surprisingly, it has been found that nonionic surfactants such as geminitensides which completely satisfy the desired complex requirements, can be processed to solids with organic and inorganic carriers at small cost, with the required degree of retarded solution kinetics. <??>Solid washing, rinsing, and cleaning agents, i.e. geminitensides of formula (I): where R<1> and R<2> = linear or branched alkyl and/or 4-22C alkenyl, n = 5-400 are new. An Independent claim is included for preparation of (I) on organic or inorganic carriers.

Description

Field of invention

The invention is in the field of detergents and relates to solid granular washing, rinsing and cleaning agents containing special nonionic surfactants and inorganic ones or organic carriers, processes for their production and the use of solid preparations from the special nonionic surfactants and solid carriers for production the means.

State of the art

Today, machine-washed dishes are subject to high demands. So will crockery that has been completely cleaned of food residues is then rated as faulty if it after the machine dishwashing still whitish, on water hardness or other mineral Salt-based stains, which, due to the lack of wetting agents, consist of dried water droplets come. In order to get glossy and spotless dishes, one uses Rinse aid. The addition of liquid or solid rinse aid, which are added separately can or already in ready-to-use dosage form with the cleaning agent and / or regeneration salt together ("2 in 1", "3 in 1", e.g. in the form of tablets or powders) ensures that the water runs off as completely as possible from the items to be washed, so that the different surfaces are residue-free at the end of the wash program and are shiny.

Common rinse aids are mixtures of e.g. non-ionic surfactants, solubilizers, organic acids and solvents, water and optionally preservatives and fragrances. The task of the surfactants in these compositions is the To influence the interfacial tension of the water so that it is as thin as possible coherent film can run off the items to be washed, so that during the subsequent drying process no water drops, streaks or films remain (so-called wetting effect). That is why surfactants in rinse aids also have to cope with food residues Steam the foam in the dishwasher. As the rinse aid mostly acids for an improvement contain the clear drying effect, the surfactants used must also be used be comparatively insensitive to hydrolysis to acids.

Rinse aids are used both in households and in the commercial sector. In household dishwashers the rinse aid is usually added after the pre-wash and cleaning process about 40 to 65 ° C added. The commercial dishwashers only work with one Cleaning liquor, which can only be obtained by adding the clear rinse solution from the previous Rinsing process is renewed. So there is no complete program during the entire wash program Water exchange takes place. Therefore, the rinse aid must also have a foam-reducing effect, be stable even with a strong temperature gradient from about 85 to about 35 ° C and be prove inert to alkali and active chlorine compounds.

The object of the present invention has now been to use nonionic surfactants in Solid form for the production of solid detergents, dishwashing detergents and cleaning agents, especially of solid dishwashing detergents, in particular the so-called "2 in 1" or "3 in 1" dishwashing detergents, in the form of tablets or powders available, which is thereby are characterized by their excellent rinsing properties, even in the presence of protein soiling have a foam-suppressing effect, even with a sharp temperature gradient are stable, prove to be inert towards alkali and active chlorine compounds Do not gel dissolve and, in particular, have solubility kinetics that allow carryover the highest possible content of the nonionic surfactant in the rinse cycle of the machine process

Description of the invention

The invention relates to solid granular detergents, dishwashing detergents and cleaning agents which are obtained by using gemini surfactants of the formula (I), R ¹ CH (OH) CH ₂ (OCH ₂ CH ₂ ) _n OCH ₂ CH (OH) R ² (I)

in which R ¹ and R ^2, independently of one another, represent linear or branched alkyl and / or alkenyl radicals having 4 to 22 carbon atoms and n represents numbers from 5 to 400, is applied to inorganic or organic supports.

Surprisingly, it has been found that nonionic surfactants of the gemini surfactant type fulfill the desired complex requirement profile to full satisfaction. In particular It should be noted that these surfactants with inorganic or organic carriers Can be processed into solids with little effort that do not gel, but the desired one have delayed solubility kinetics. Let using the granules In particular, powders or tablets with a simultaneous rinse effect can be formulated.

Leave in combination with cleaners or regeneration agents for the ion exchanger so-called "3 in 1" systems can be realized. In addition to its use in the field of mechanical Dishwashing detergents can also be used for conventional cleaning of hard surfaces as well as for the manufacture of detergents. The invention includes the knowledge that the nonionic surfactants are preferably those of the gemini surfactant type with 25 to 40 ethylene oxide units are involved, since these are not only result in particularly good clear drying effects, but also with regard to the Foam absorption, especially in the presence of proteins, the temperature stability and durability deliver the best results against alkalis and active chlorine compounds.

Gemini surfactants

The gemini surfactants according to the invention are usually produced by reacting 1,2-epoxyalkanes with polyethylene glycols. Typical examples are ring opening products of 1,2-hexene epoxide, 2,3-hexene epoxide, 1,2-octene epoxide, 2,3-octene epoxide, 3,4-octene epoxide, 1,2-decene epoxide, 2,3-decene epoxide, 3,4 -Decene epoxide, 4,5-decene epoxide, 1,2-dodecene epoxide, 2,3-dodecene epoxide, 3,4-dodecene epoxide, 4,5-dodecene epoxide, 5,6-dodecene epoxide, 1,2-tetradecene epoxide, 2,3-tetradecene epoxide , 3,4-tetradecene epoxide, 4,5-tetradecene epoxide, 5,6-tetradecene epoxide, 6,7-tetradecene epoxide, 1,2-hexadecene epoxide, 2,3-hexadecene epoxide, 3,4-hexadecene epoxide, 4,5-hexadecene epoxide, 5 , 6-hexadecene epoxide, 6,7-hexadecene epoxide, 7,8-hexadecene epoxide, 1,2-octadecene epoxide, 2,3-octadecene epoxide, 3,4-octadecene epoxide, 4,5-octadecene epoxide, 5,6-octadecene epoxide, 6.7 Octadecene epoxide, 7,8-octadecene epoxide and 8,9-octadecene epoxide and mixtures thereof with polyethylene glycols which have 5 to 400 alkylene oxide units or an average molecular weight in the range from 500 to 300,000, preferably 1,500 to 50,000 and in particular 3,000 to 20,000 daltons. From an application point of view, gemini surfactants which follow the formula (I) and in which R ¹ and R ^{2 are} linear alkyl radicals having 10 to 16 carbon atoms and / or which have 25 to 40 ethylene oxide units have proven particularly advantageous. Due to the manufacturing process, the bisethers can be present as a mixture with monoethers. Usually, however, at least 60 mol%, preferably at least 90 mol% and in particular 95 mol% of all free primary hydroxyl groups are blocked.

Inorganic or organic carriers

As inorganic or organic carriers, for example, zeolites, alkali phosphates, Alkali carbonates, alkali sulfates, alkali hydrogen carbonates, alkali silicates, alkali citrates, polysaccharides and their derivatives or polymers and their mixtures in question.

Zeolites

Among the zeolites, the detergent builders zeolite A and / or P are particularly preferred. ^{Zeolite MAP (R)} (commercial product from Crosfield), for example, is particularly preferred as zeolite P. However, zeolite X and mixtures of A, X and / or P and Y are also suitable. A cocrystallized sodium / potassium aluminum silicate made from zeolite A and zeolite X, which is available as VEGOBOND AX® (commercial product from Condea Augusta), is also of particular interest 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 production. If the zeolite is used as a suspension, it can contain small 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.

Alkali phosphates

In addition to the zeolites, the use of the generally known phosphates as Carrier substances possible. The sodium salts of orthophosphates are particularly suitable, the pyrophosphates and especially the tripolyphosphates.

Alkali silicates

Alkali silicates are to be understood as meaning crystalline, layered alkali and especially sodium 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 sheet silicates are described, for example, in the European patent application EP 0164514 A1 . Preferred crystalline sheet silicates of the formula given are those in which M stands for 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, where B-sodium disilicate can be obtained, for example, by the process described in international patent application WO 91/08171. Further suitable sheet silicates are known, for example, from patent applications DE 2334899 A1, EP 0026529 A1 and DE 3526405 A1 . Their use is not restricted to a specific composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable sheet silicates belonging to the group of the water-swellable smectites are, for example, those of the general formulas (OH) ₄ Si _8-y Al _y (Mg _x Al _4-x ) O ₂₀ montmorillonite (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 sheet silicates according to the above formulas. Furthermore, because of their ion-exchanging properties, the sheet silicates can contain hydrogen, alkali, alkaline earth metal ions, in particular Na ⁺ and Ca ²⁺ . The amount of water of hydration is usually in the range from 8 to 20% by weight and depends on the state of swelling and the type of processing. Usable sheet silicates are known, for example, from US Pat. No. 3,966,629, US Pat. No. 4,062,647, EP 0026529 A1 and EP 0028432 A1 . Layered silicates are preferably used which, due to an alkali treatment, are largely free of calcium ions and strongly coloring iron ions. The preferred inorganic carrier substances also include amorphous sodium silicates with a Na ₂ O: SiO ₂ module 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 washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can have been brought about in various ways, for example by surface treatment, compounding, compaction / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that in X-ray diffraction experiments the silicates do not produce sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-ray radiation that have a width of several degree units of the diffraction angle. However, it can very well even lead to particularly good application properties if the silicate particles give blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted in such a way that the products have microcrystalline areas with a size of 10 to a few hundred nm, with values up to a maximum of 50 nm and in particular up to a maximum of 20 nm being preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared with conventional water glasses, are described, for example, in German patent application DE 4400024 A1 . Densified / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates are particularly preferred.

Other carriers

Examples of polysaccharides are cellulose, carboxymethyl cellulose, or cyclodextrin Starch and its degradation products, especially polyacrylates, are used as polymeric carriers with molecular weights ranging from 1,000 to 50,000.

Solid preparations

In addition to the nonionic surfactants and the carriers, the solid agents can be further used for Detergents, dishwashing detergents and cleaning agents contain typical auxiliaries and additives. In addition to the These include, for example, carriers who can also perform a function as builders Low-foaming, preferably non-ionic co-surfactants, co-builders, oil and fat-dissolving substances, Bleaching agents, bleach activators, graying inhibitors, enzymes, enzyme stabilizers, optical Brighteners, polymers, defoamers, disintegrants, fragrances, inorganic salts and like, as they are explained in more detail below.

Nonionic co-surfactants

Particularly preferred are solid preparations which, in addition to the gemini surfactants, are used as further surfactant component nonionic surfactants, especially addition products of ethylene oxide and / or propylene oxide on fatty or oxo alcohols. Typical examples for nonionic co-surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, Fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, hydroxy mixed ethers, Alk (en) yl oligoglycosides, fatty acid N-alkyl glucamides, protein hydrolysates (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, these can have a conventional, but preferably a narrowed homolog distribution exhibit. Fatty alcohol polyglycol ethers are preferably alkoxylated Fatty acid lower alkyl esters, alkyl oligoglucosides, mixed ethers and, in particular, hydroxy mixed ethers used.

The preferred fatty alcohol polyglycol ethers follow the formula (II), R ⁴ O (CH ₂ CHR ⁵ O) _p1 H (II) 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 p1 represents numbers from 1 to 20. Typical examples are the addition products of an average of 1 to 20 and preferably 5 to 10 mol of ethylene and / or propylene oxide with caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, elaidyl alcohol, stearyl alcohol, isostearyl alcohol , Petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, e-laeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures. Addition products of 3, 5 or 7 mol of ethylene oxide with technical coconut fatty alcohols are particularly preferred.

Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (III) , R ⁶ CO- (OCH ₂ CHR ⁷ ) _p2 OR ⁸ (III)

in which R ⁶ CO stands for a linear or branched, saturated and / or unsaturated acyl radical with 6 to 22 carbon atoms, R ⁷ for hydrogen or methyl, R ⁸ for linear or branched alkyl radicals with 1 to 4 carbon atoms and p2 for numbers from 1 to 20 stands. Typical examples are the formal insertion products of an average of 1 to 20 and preferably 5 to 10 mol of ethylene and / or propylene oxide into the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, caprylic acid, 2 -Ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palm oleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic acid, u-noleic acid, linolenic acid, eleostearic acid, arachucic acid, gadoleic acid and technical mixtures thereof, 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 example, calcined hydrotalcite. Reaction products of an average of 5 to 10 mol of ethylene oxide in the ester bond of technical coconut fatty acid methyl esters are particularly preferred.

Alkyl and alkenyl oligoglycosides, which are also preferred nonionic surfactants, usually follow the formula (IV), R ⁹ O- [G] _q (IV)

in which R ^{9 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and q is numbers from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry. As a representative of the extensive literature, reference is made here to the documents EP 0301298 A1 and WO 90/03977 . The alkyl and / or alkenylol glycosides 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 oligoglycosides. The index number q in the general formula (IV) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While q in a given compound must always be an integer, and above all here can assume the values q = 1 to 6, the value q for a specific alkyl oligoglycoside is an analytically determined mathematical variable that 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, those alkyl and / or alkenyl oligoglycosides are preferred whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ¹³ can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxo synthesis. Preferred are alkyl oligoglucosides of chain length C ₈ -C ₁₀ (DP = 1 to 3), which are obtained as first _{runnings in the distillative separation of technical C 8} -C ₁₈ coconut fatty alcohol and with a proportion of less than 6% by weight C ₁₂ - Alcohol can be contaminated, as can alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ¹³ 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 technical mixtures thereof which can be obtained as described above. Alkyl oligoglucosides based on hardened C _12/14 coconut alcohol with a DP of 1 to 3 are preferred.

Furthermore, mixed ethers which follow, for example, the formula (V) are preferred as nonionic surfactants, R ¹⁰ O (CH ₂ CH ₂ O) _r1 (CH (CH ₃ ) CH ₂ O) _s (CH ₂ CH ₂ O) _r2 R ¹¹ (V) in which R ^{10 stands} for a linear or branched alkyl and / or alkenyl radical with 6 to 22, preferably 12 to 18 carbon atoms, R ¹¹ for an alkyl radical with 1 to 8 carbon atoms or a benzyl radical, r1 and r2 independently of one another for 0 or numbers of 1 to 20 and s stands for 0 or numbers from 0.5 to 5, with the proviso that the sum (r1 + r2 + s) must be different from 0. Typical examples are about coconut fatty alcohol + 10EO-butyl ether, coconut fatty alcohol + 5PO + 4EO-butyl ether or coconut fatty alcohol + 10EO-benzyl ether.

in der R¹² für einen linearen oder verzweigten Alkylrest mit 2 bis 18, vorzugsweise 10 bis 16 Kohlenstoffatomen, R¹³ für Wasserstoff oder einen linearen oder verzweigten Alkylrest mit 2 bis 18 Kohlenstoffatomen, R¹⁴ für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 1 bis 22, vorzugsweise 8 bis 18 Kohlenstoffatomen, n1 und n2 unabhängig voneinander für 0 oder Zahlen von 1 bis 60, vorzugsweise 2 bis 25 und insbesondere 5 bis 15 und m für 0 oder Zahlen von 0,5 bis 5, vorzugsweise 1 bis 2 steht, mit den Maßgaben, dass die Summe der Kohlenstoffatome in den Resten R¹ und R² mindestens 6 und vorzugsweise 12 bis 18 beträgt und die Summe (n1+m+n2) verschieden von 0 ist. Hydroxy mixed ethers (HME) are known nonionic surfactants with an unsymmetrical ether structure and polyalkylene glycol components, which are obtained, for example, by subjecting olefin epoxides to a ring-opening reaction with fatty alcohol polyglycol ethers. Corresponding products and their use in the field of cleaning hard surfaces are, for example, the subject of European patent specification EP 0693049 B1 and international patent application WO 94/22800 (Olin) and the documents cited therein. Typically the following hydroxy mixed ethers of the general formula (VI),

in which R ^{12 is} a linear or branched alkyl radical having 2 to 18, preferably 10 to 16 carbon atoms, R ^{13 is} hydrogen or a linear or branched alkyl radical having 2 to 18 carbon atoms, R ^{14 is} a linear or branched alkyl and / or alkenyl radical with 1 to 22, preferably 8 to 18 carbon atoms, n1 and n2 independently of one another for 0 or numbers from 1 to 60, preferably 2 to 25 and in particular 5 to 15 and m for 0 or numbers from 0.5 to 5, preferably 1 to 2, with the provisos that the sum of the carbon atoms in the radicals R ¹ and R ^{2 is} at least 6 and preferably 12 to 18 and the sum (n1 + m + n2) is different from zero.

R¹² für einen linearen Alkylrest mit 8 bis 10 Kohlenstoffatomen, R¹³ für Wasserstoff, R¹⁴ für einen linearen Alkylrest mit 8 bis 10 Kohlenstoffatomen, n1 für 0, m für Zahlen von 0,5 bis 2 und n2 für Zahlen von 20 bis 40 steht, wie z.B. die Handelsprodukte Dehypon® 3447 und Dehypon® 3557 der Cognis Deutschland GmbH;

R¹² für einen linearen Alkylrest mit 8 bis 10 Kohlenstoffatomen, R¹³ für Wasserstoff, R¹⁴ für einen verzweigten Alkylrest mit 8 bis 10 Kohlenstoffatomen, n1 und m für 0 und n2 für Zahlen von 20 bis 40 steht;

R¹² für einen linearen Alkylrest mit 8 bis 10 Kohlenstoffatomen, R¹³ für Wasserstoff, R¹⁴ für einen linearen Alkylrest mit 8 bis 10 Kohlenstoffatomen, n1 und m für 0 und n2 für Zahlen von 40 bis 60 steht.

As can be seen from the formula, the HME ring opening products can be either internal olefins (R ¹³ not equal to hydrogen) or terminal olefins (R ¹³ equal to hydrogen), the latter being preferred with regard to easier production and more advantageous application properties. Likewise, the polar part of the molecule can be a polyethylene or a polypropylene chain; Mixed chains of PE and PP units, whether in statistical or block distribution, are also suitable. Typical examples are ring opening products of 1,2-hexene epoxide, 2,3-hexene epoxide, 1,2-octene epoxide, 2,3-octene epoxide, 3,4-octene epoxide, 1,2-decene epoxide, 2,3-decene epoxide, 3,4 -Decene epoxide, 4,5-decene epoxide, 1,2-dodecene epoxide, 2,3-dodecene epoxide, 3,4-dodecene epoxide, 4,5-dodecene epoxide, 5,6-dodecene epoxide, 1,2-tetradecene epoxide, 2,3-tetradecene epoxide , 3,4-tetradecene epoxide, 4,5-tetradecene epoxide, 5,6-tetradecene epoxide, 6,7-tetradecene epoxide, 1,2-hexadecene epoxide, 2,3-hexadecene epoxide, 3,4-hexadecene epoxide, 4,5-hexadecene epoxide, 5 , 6-hexadecene epoxide, 6,7-hexadecene epoxide, 7,8-hexadecene epoxide, 1,2-octadecene epoxide, 2,3-octadecene epoxide, 3,4-octadecene epoxide, 4,5-octadecene epoxide, 5,6-octadecene epoxide, 6.7 -Octadecene epoxide, 7,8-octadecene epoxide and 8,9-octadecene epoxide and mixtures thereof with addition products of on average 1 to 50, preferably 2 to 25 and in particular 5 to 15 mol of ethylene oxide and / or 1 to 10, preferably 2 to 8 and in particular 3 up to 5 moles of saturated and / or unsaturated propylene oxide saturated primary alcohols with 6 to 22, preferably 12 to 18 carbon atoms, such as caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, elaidyl alcohol, linroidolyl alcohol, linroidolyl alcohol, linroidyl alcohol, linroidolyl alcohol, linroidolyl alcohol, linroidolyl alcohol, linroidolyl alcohol, Elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures. Hydroxy mixed ethers, which have proven particularly suitable from an application point of view, follow the formula (VI) in FIG

R ¹² for a linear alkyl radical with 8 to 10 carbon atoms, R ¹³ for hydrogen, R ¹⁴ for a linear alkyl radical with 8 to 10 carbon atoms, n1 for 0, m for numbers from 0.5 to 2 and n2 for numbers from 20 to 40 stands, such as the commercial products Dehypon® 3447 and Dehypon® 3557 from Cognis Deutschland GmbH;

R ^{12 stands} for a linear alkyl radical with 8 to 10 carbon atoms, R ¹³ for hydrogen, R ¹⁴ for a branched alkyl radical with 8 to 10 carbon atoms, n1 and m for 0 and n2 for numbers from 20 to 40;

R ^{12 stands} for a linear alkyl radical with 8 to 10 carbon atoms, R ¹³ for hydrogen, R ¹⁴ for a linear alkyl radical with 8 to 10 carbon atoms, n1 and m for 0 and n2 for numbers from 40 to 60.

Co-builder

Organic builders that can be used as co-builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is for ecological reasons is 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, tartaric acid, sugar acids and mixtures of these. The acids themselves can also be used. In addition to their builder effect, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value in detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned in particular. Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed processes. 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 common 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 able to oxidize at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their production are, for example, from the European patent applications EP 0232202 A1, EP 0427349 A1, EP 0472042 A1 and EP 0542496 A1 as well as the 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 19600018 A1 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous. Further suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Glycerol disuccinates and glycerol trisuccinates, as described, for example, in US patents US Pat. No. 4,524,009, US Pat. No. 4,639,325, in European patent application EP 0150930 A1 and Japanese patent application JP 93/339896 , are also particularly preferred. Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15 wt contain two acid groups. Such co-builders are described, for example, in the international patent application WO 95/20029 .

Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid and each measured against polystyrene sulfonic acid). Suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven particularly suitable. Their relative molecular weight, based on free acids, is generally from 5,000 to 200,000, preferably from 10,000 to 120,000 and in particular from 50,000 to 100,000 (each measured against polystyrene sulfonic acid). The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, 20 to 55% strength by weight aqueous solutions being preferred. Granular polymers are usually added to one or more basic granules afterwards. Particularly preferred are also biodegradable polymers composed of more than two different monomer units, for example those which, according to DE 4300772 A1 as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives, or according to DE 4221381 C2 as monomers salts of acrylic acid and containing 2-alkylallylsulfonic acid and sugar derivatives. Further preferred copolymers are those which are described in German patent applications DE 4303320 A1 and DE 4417734 A1 and preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers. Likewise, polymeric A-minodicarboxylic acids, their salts or their precursors are to be mentioned as further preferred builder substances. Polyaspartic acids or their salts and derivatives are particularly preferred.

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyol carboxylic 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 . Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Oil and fat dissolving substances

In addition, the agents can also contain components that make oil and fat washable: from textiles have a positive effect. Among the preferred oil and fat dissolving agents Components include, for example, nonionic cellulose ethers such as methyl cellulose and methylhydroxypropyl cellulose containing from 15 to 30 methoxyl groups Wt .-% and of hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic cellulose ether, as well as the polymers known from the prior art of phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers made from 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.

Bleaching agents and bleach activators

Sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance among the compounds which serve as bleaching agents and produce H ₂ O _{2 in water.} Other bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and _{peracid salts or peracids which provide H 2} O ₂ , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid. The content of bleaching agents in the agents is preferably 5 to 35% by weight and in particular up to 30% by weight, with perborate monohydrate or percarbonate advantageously being used. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Substances which carry O- and / or N-acyl groups with the number of carbon atoms mentioned and / or optionally substituted benzoyl groups are suitable. Polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N- are preferred Acylimides, in particular N-nonanoyl succinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetine, ethylene diacetate 2,5-dihydrofuran and the enol esters known from German patent applications DE 19616693 A1 and DE 19616767 A1, as well as acetylated sorbitol and mannitol or their mixtures (SORMAN) described in European patent application EP 0525239 A1 , acylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetyl fructose , Tetraacetylxylose and Octaacetyllactose and acetylated, optionally N-alkylated tes glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which from the international patent applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95 / 17498 are known. The hydrophilically substituted acyl acetals known from German patent application DE 19616769 A1 and the acyllactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also used with preference. The combinations of conventional bleach activators known from German patent application DE 4443177 A1 can also be used. Such bleach activators are contained in the usual quantity range, preferably in quantities of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent. In addition to the conventional bleach activators listed above or instead of them, the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0446982 B1 and EP 0453 003 B1 can also be contained as so-called bleach catalysts. The transition metal compounds in question include in particular the manganese, iron, cobalt, ruthenium or molybdenum-salen complexes known from German patent application DE 19529905 A1 and their N-analog compounds known from German patent application DE 19620267 A1, which are known from German Patent application DE 19536082 A1 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium described in the German patent application DE 19605688 A1 and copper complexes with nitrogen-containing tripod ligands that from German patent application DE known cobalt 19620411 A1, iron-, copper- and ruthenium-ammine complexes, the manganese, copper described in the German patent application DE 4416438 A1 and cobalt complexes , the cobalt complexes described in European patent application EP 0272030 A1, which are known from the European patent application EP 0693550 A1 manganese Komple xe, the manganese, iron, cobalt and copper complexes known from the European patent specification EP 0392592 A1 and / or those in the European patent specification EP 0443651 B1 or the European patent applications EP 0458397 A1, EP 0458398 A1, EP 0549271 A1, Manganese complexes described in EP 0549272 A1, EP 0544490 A1 and EP 0544519 A1. Combinations of bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 19613103 A1 and international patent application WO 95/27775 . Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular from 0.0025% by weight. % to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, based in each case on the total agent.

Enzymes and enzyme stabilizers

As enzymes come in particular those from the class of hydrolases, such as proteases, Esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned are possible. All these Hydrolases are used in laundry to remove stains such as protein, fat starchy stains, and graying. Cellulases and other glycosyl hydrolases can be done by removing pilling and microfibrils to preserve color and contribute to increasing the softness of the textile. For bleaching or for inhibition Oxidoreductases can also be used for color transfer. Particularly are well suited from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Enzymatic agents obtained from Streptomyces griseus and Humicola insolens. Proteases of the subtilisin type and in particular proteases, obtained from Bacillus lentus are used. Here are enzyme mixtures, for example from protease and amylase or protease and upase or lipolytically acting Enzymes or protease and cellulase or from cellulase and lipase or lipolytic acting enzymes or from protease, amylase and upase or lipolytic acting Enzymes or protease, lipase or lipolytic enzymes and cellulase, in particular, however, mixtures or mixtures containing protease and / or lipase with lipolytic enzymes of particular interest. Examples of such lipolytic acting enzymes are the well-known cutinases. Also peroxidases or oxidases have proven to be suitable in some cases. To the suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and β-glucosidases, the Cellobiases are also called, or mixtures of these are used. Since the differentiate between different cellulase types by their CMCase and Avicelase activities, the desired activities can be set through targeted mixtures of the cellulases will. The enzymes in turn can also be adsorbed on carrier substances and / or embedded in coating substances to prevent premature decomposition protection. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.

In addition to the mono- and polyfunctional alcohols, the agents can contain other enzyme stabilizers. For example, 0.5 to 1% by weight of 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 othoroboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyoboric acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous.

Graying inhibitors

The task of graying inhibitors is to keep the dirt detached from the fiber in to keep the liquor suspended, thus preventing the dirt from reappearing. Water-soluble colloids of mostly organic nature are suitable for this, 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 acid sulfuric acid esters of cellulose or starch. Also water-soluble, Acid group-containing polyamides are suitable for this purpose. Continue to let use soluble starch preparations and other starch products than those mentioned above, E.g. degraded starch, aldehyde starches etc .. Also polyvinylpyrrolidone is useful. However, cellulose ethers, such as carboxymethyl cellulose (Na salt), are preferred Methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, Methylhydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures, and polyvinylpyrrolidone, for example, in amounts of 0.1 to 5% by weight on the funds used.

Optical brighteners

The agents can contain derivatives of diaminostilbene disulfonic acid or alkali metal salts thereof as optical brighteners. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly structured compounds which are used instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyryl type can be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyls, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyls, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls. Mixtures of the abovementioned brighteners can also be used. Uniformly white granules are obtained if, in addition to the usual brighteners, the agents also contain small amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, in addition to the usual brighteners 10 ^-6 to 10 ^-3 % by weight, preferably around 10 ^-5 % by weight, of a blue dye. A particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).

Polymers

Substances that can be used as soil repellants are those that preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, wherein the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate im Can range from 50:50 to 90:10. The molecular weight of the linking In particular, polyethylene glycol units are in the range from 750 to 5000, i.e. the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approx. 15 to 100 be. The polymers are characterized by an average molecular weight from about 5000 to 200,000 and can have a block, but preferably a random structure exhibit. Preferred polymers are those with ethylene terephthalate / polyethylene glycol terephthalate molar ratios from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Also preferred are those polymers which linking polyethylene glycol units with a molecular weight of 750 to 5000, preferably from 1000 to about 3000 and a polymer molecular weight of about 10,000 to about 50,000. Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).

Defoamer

Waxy compounds can be used as defoamers. As "waxy" those compounds are understood which have a melting point at atmospheric pressure above 25 ° C (room temperature), preferably above 50 ° C and in particular above 70 ° C exhibit. The waxy defoamer substances are practically insoluble in water, i.e. at 20 ° C they have a solubility of less than 0.1% by weight in 100 g of water. In principle, all waxy defoamer substances known from the prior art can be used be included. Suitable waxy compounds are, for example, bisamides, Fatty alcohols, fatty acids, carboxylic acid esters of monohydric and polyhydric alcohols as well as paraffin waxes or mixtures thereof. Alternatively you can of course the silicone compounds known for this purpose are used.

Suitable paraffin waxes generally represent a complex mixture of substances without a sharp 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 its freezing point . This is the temperature at which the paraffin changes from the liquid to the solid state through slow cooling. Paraffins which are completely liquid at room temperature, that is to say those with a solidification point below 25 ° C., cannot be used in accordance with the invention. The soft waxes which have a melting point in the range from 35 to 50 ° C. preferably include the group of petrolatum and their hydrogenation products. They are made up of microcrystalline paraffins and up to 70% by weight of oil, have an ointment-like to plastic consistency and are bitumen-free residues from petroleum processing will. They are also preferably bitumen-free, oily to solid hydrocarbons separated by means of solvents from distillation residues of paraffinic and mixed-base crude oils and cylinder oil distillates. They have a semi-solid, quick, sticky to plastic-solid consistency and have melting points between 50 and 70 ° C. These petrolatum represent the most important starting point for the production of micro waxes. The solid hydrocarbons with melting points between 63 and 79 ° C separated from highly viscous, paraffin-containing lubricating oil distillates during dewaxing are also suitable. These petrolatums are mixtures of microcrystalline waxes and high-melting n-paraffins. The paraffin wax mixtures known from EP 0309931 A1 can be used, for example, consisting of, for example, 26% by weight to 49% by weight microcrystalline paraffin wax with a solidification point of 62 ° C. to 90 ° C., 20% by weight to 49% by weight hard paraffin with a congealing point of 42 ° C to 56 ° C and 2% by weight to 25% by weight of soft paraffin with a congealing point of 35 ° C to 40 ° C. Paraffins or paraffin mixtures which solidify in the range from 30.degree. C. to 90.degree. C. are preferably used. It should be noted that paraffin wax mixtures that appear solid at room temperature can contain different proportions of liquid paraffin. In the case of the paraffin waxes which can be used according to the invention, this liquid content is as low as possible and is preferably completely absent. For example, particularly preferred paraffin wax mixtures have a liquid content of less than 10% by weight at 30 ° C., in particular from 2% by weight to 5% by weight, and at 40 ° C. a liquid content of less than 30% by weight, preferably 5 % By weight to 25% by weight and in particular from 5% by weight to 15% by weight, at 60 ° C. a liquid content of 30% by weight to 60% by weight, in particular 40% by weight % to 55% by weight, at 80 ° C. a liquid content of 80% by weight to 100% by weight, and at 90 ° C. a liquid content of 100% by weight. The temperature at which a liquid content of 100% by weight of the paraffin wax is reached is, in particularly preferred paraffin wax mixtures, below 85 ° C, in particular 75 ° C to 82 ° C. The paraffin waxes can be petrolatum, microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.

Suitable bisamides as defoamers are those that differ from saturated fatty acids with 12 to 22, preferably 14 to 18 carbon atoms and alkylenediamines with 2 to 7 carbon atoms derive. Suitable fatty acids are lauric, myristic, stearic, arachic and behenic acids as well as their mixtures, such as those made from natural fats or hardened ones Oils such as tallow or hydrogenated palm oil are available. Suitable diamines are, for example Ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, Hexamethylene diamine, p-phenylene diamine and tolylene diamine. Preferred diamines are ethylenediamine and hexamethylenediamine. Particularly preferred bisamides are bismyristoylethylenediamine, Bispalmitoylethylenediamine, bisstearoylethylenediamine and their Mixtures and the corresponding derivatives of hexamethylene diamine.

Suitable carboxylic acid esters as defoamers are derived from carboxylic acids having 12 to 28 carbon atoms. In particular, they are esters of behenic acid, stearic acid, hydroxystearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid. The alcohol part 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 polyhydric alcohols are, for example, xylitol monopalmitate, pentarythritol monostearate, glycerol monostearate, ethylene glycol monostearate and sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan dilaurate, sorbitan distearate and sorbitan distearate, and sorbitan di-sorbitan di-stearate, sorbitan distearate and sorbitan di-sorbitan, sorbitan, sorbitan, sorbitan, and sorbitan di-ester. 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. Glycerin monostearate, glycerin monooleate, glycerin monopalmitate, glycerin monobehenate and glycerin distearate are examples of these. 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 camauba wax , which is a mixture of carnaubic acid alkyl esters, often in combination with small amounts of free carnaubic acid, other long-chain acids, high molecular weight alcohols and hydrocarbons.

Suitable carboxylic acids as further defoamer compounds are in particular behenic acid, Stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid and their Mixtures such as those made from natural fats or optionally hydrogenated oils such as tallow or hydrogenated palm oil. Preferred are saturated fatty acids with 12 to 22, in particular 18 to 22 carbon atoms. In the same way, the corresponding Fatty alcohols of the same carbon chain length are used.

Dialkyl ethers can also be included as defoamers. The ethers can be asymmetrical or symmetrical, i.e. two identical or different Contain alkyl chains, preferably with 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 25 ° C, in particular above 40 ° C.

Other suitable defoamer compounds are fatty ketones which can be obtained by the relevant methods of preparative organic chemistry. For their preparation one starts, for example, from carboxylic acid magnesium salts, which are pyrolyzed at temperatures above 300 ° C. with elimination of carbon dioxide and water, for example in accordance with the German patent application DE 2553900 OS. Suitable fatty ketones are those which are produced by pyrolysis of the magnesium salts of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselic acid, arachidic acid, gadoleic acid, behenic acid or erucic acid.

Further suitable defoamers are fatty acid polyethylene glycol esters, which are preferably obtained by base homogeneously catalyzed addition of ethylene oxide to fatty acids will. In particular, the addition of ethylene oxide to the fatty acids takes place in the presence of alkanolamines as catalysts. The use of alkanolamines, specifically Triethanolamine, leads to an extremely selective ethoxylation of fatty acids, in particular when it comes to producing low ethoxylated compounds. Within of the group of fatty acid polyethylene glycol esters are preferred which have a Have a melting point above 25 ° C, in particular above 40 ° C.

Within the group of waxy defoamers, the paraffin waxes described are particularly preferably used alone as waxy defoamers or in a mixture with one of the other waxy defoamers, the proportion of paraffin waxes in the mixture preferably being over 50% by weight, based on the waxy defoamer mixture. If necessary, the paraffin waxes can be applied to carriers. All known inorganic and / or organic carrier materials are suitable as carrier material. Examples of typical inorganic carrier materials are alkali carbonates, aluminosilicates, water-soluble sheet 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 combed properties, in particular high abrasion resistance and yet high dissolution rate in water. The aluminosilicates referred to as carrier materials include, in particular, the zeolites, for example zeolite NaA and NaX. The compounds referred to as water-soluble phyllosilicates include, for example, amorphous or crystalline water glass. Furthermore, silicates can be used, which are commercially available under the name Aerosil® or Sipernat®. For example, film-forming polymers, for example polyvinyl alcohols, polyvinylpyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch come into consideration as organic carrier materials. Cellulose ethers which can be used are, in particular, alkali metal carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called mixed cellulose ethers, such as methyl hydroxyethyl cellulose and methylhydroxypropyl 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 a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit. The mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ethers in weight ratios from 80:20 to 40:60, in particular from 75:25 to 50:50. Native starch composed of amylose and amylopectin is also suitable as a carrier. Native starch is the term used for starch that can be obtained as an extract from natural sources, for example from rice, potatoes, corn and wheat. Native starch is a commercially available product and therefore easily accessible. As carrier materials, one or more of the above-mentioned compounds can be used, 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 customary organopolysiloxanes, which can contain finely divided silica, which in turn can also be silanized. Organopolysiloxanes of this type are described, for example, in European patent application EP 0496510 A1 . Polydiorganosiloxanes and in particular polydimethylsiloxanes, which are known from the prior art, are particularly preferred. Suitable polydiorganosiloxanes have an almost linear chain and a degree of oligomerization of 40 to 1500. Examples of suitable substituents are methyl, ethyl, propyl, isobutyl, tert. Butyl and phenyl. Also suitable are amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and / or alkyl-modified silicone compounds, which can be either liquid or resinous at room temperature. Simethicones, which are mixtures of dimethicones with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates, are also suitable. As a rule, the silicones in general and the polydiorganosiloxanes in particular contain finely divided silica, which can also be silanized. Silica-containing dimethylpolysiloxanes are particularly suitable for the purposes of the present invention. The polydiorganosiloxanes advantageously have a Brookfield viscosity at 25 ° C. (spindle 1, 10 rpm) in the range from 5000 mPas to 30,000 mPas, in particular from 15,000 to 25,000 mPas. The silicones are preferably used in the form of their aqueous emulsions. As a rule, the silicone is added to the water initially charged while stirring. If desired, thickeners such as are known from the prior art can be added to increase the viscosity of the aqueous silicone emulsions. These can be of an inorganic and / or organic nature; nonionic cellulose ethers such as methyl cellulose, ethyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methylhydroxypropyl cellulose, methyl hydroxybutyl cellulose and anionic carboxycellulose types such as the carboxymethyl cellulose sodium salt (abbreviation CMC) are particularly preferred. Particularly suitable thickeners are mixtures of CMC to nonionic cellulose ethers in a weight ratio of 80:20 to 40:60, in particular 75:25 to 60:40. As a rule, and especially when the thickener mixtures described are added, use concentrations of about 0.5 to are recommended 10, in particular from 2.0 to 6% by weight - calculated as the thickener mixture and based on aqueous silicone emulsion. The content of silicones of the type described in the aqueous emulsions is advantageously in the range from 5 to 50% by weight, in particular from 20 to 40% by weight, calculated as silicones and based on the aqueous silicone emulsion. According to a further advantageous embodiment, the aqueous silicone solutions contain starch as a thickener which can be obtained from natural sources, for example from rice, potatoes, corn and wheat. The starch is advantageously contained in amounts of 0.1 to 50% by weight, based on silicone emulsion, and in particular in a mixture with the already described thickener mixtures of sodium carboxymethyl cellulose and a nonionic cellulose ether in the amounts already mentioned. To prepare the aqueous silicone emulsions, it is expedient to proceed in such a way that any thickeners which may be present are preswollen in water before the silicones are added. The incorporation of the silicones is expediently carried out with the aid of effective stirring and mixing devices.

Explosives

The solid preparations can also contain disintegrants or disintegrants. This is understood to mean substances that are added to the shaped bodies in order to accelerate their disintegration when they are brought into contact with water. Overviews of this can be found, for example, in J.Pharm.Sci. 61 (1972), Römpp Chemilexikon, 9th edition, volume 6, p. 4440 as well as and Voigt " Textbook of pharmaceutical technology " (6th edition, 1987, p. 182-184). These substances increase their volume when water gets in, whereby on the one hand their own volume increases (swelling) and on the other hand a pressure can be generated through the release of gases, which causes the tablet to disintegrate into smaller particles. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as cross-linked polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives. Cellulose-based disintegrants are used as preferred disintegrants in the context of the present invention. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, viewed formally, represents a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approx. 500 to 5000 glucose units and consequently have average molar masses of 50,000 to 500,000. Cellulose derivatives that can be obtained from cellulose by polymer-analogous reactions can also be used as cellulose-based disintegrants in the context of the present invention. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxyl groups have been replaced by functional groups that 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 amino-celluloses. The cellulose derivatives mentioned are preferably not used alone as cellulose-based disintegrants, but are used in a mixture with cellulose. The cellulose derivative content of these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose, which is free from cellulose derivatives, is particularly preferably used as the cellulose-based disintegrant. Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a constituent of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions that only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. Subsequent deaggregation of the microfine celluloses formed by the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of about 5 μm and can be compacted, for example, to granules with an average particle size of 200 μm. The disintegrants can be homogeneously distributed in the molded body when viewed macroscopically, but when viewed microscopically they form zones of increased concentration due to the production process. Disintegrants that may be present in the context of the invention, such as, for example, Kollidon, alginic acid and its alkali salts, amorphous or also partially crystalline sheet silicates (bentonites), polyacrylates, polyethylene glycols are, for example, the publications WO 98/40462 (Rettenmaier), WO 98/55583 and WO 98/55590 (Unilever) and WO 98/40463, DE 19709991 and DE 19710254 (Henkel) can be found. Express reference is made to the teaching of these scriptures. The moldings can contain the disintegrants in amounts of 0.1 to 25, preferably 1 to 20 and in particular 5 to 15% by weight, based on the moldings.

Fragrances

Individual fragrance compounds, e.g. the synthetic ones, can be used as perfume oils or fragrances Products of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons be used. Fragrance compounds of the ester type are e.g. benzyl acetate, Phenoxyethyl isobutyrate, p-tert-butylcydohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, Phenyl ethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. To the E-them include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8-18 carbon atoms, gtral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. the ionones, α-isomethylionone 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 produce. Such perfume oils can also contain natural fragrance mixtures, as they are accessible from plant sources, e.g. 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 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, it but it can also be advantageous to apply the fragrances to a carrier which ensures the adhesion of the perfume on the laundry and by a slower fragrance release ensure the long-lasting fragrance of the textiles. As such carrier materials have proven For example, cyclodextrins proven, with the cyclodextrin-perfume complexes in addition can still be coated with other auxiliaries.

Inorganic salts

Further suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses, which do not have outstanding builder properties, or mixtures of these; in particular, alkali metal carbonate and / or amorphous alkali metal silicate, especially sodium silicate with a molar ratio Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5, preferably 1: 2 to 1: 3.5, are used. The sodium carbonate content in the final preparations is preferably up to 40% by weight, advantageously between 2 and 35% by weight. The sodium silicate content of the agents (without particular builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight. Sodium sulfate, for example, can also be contained as a filler or adjusting agent in amounts of 0 to 10, in particular 1 to 5% by weight, based on the agent

6 bis 75, vorzugsweise 10 bis 50 Gew.-% Geminitenside und

25 bis 94, vorzugsweise 50 bis 90 Gew.-% anorganische oder organische Träger

bzw.

10 bis 40, vorzugsweise 20 bis 30 Gew.-% Geminitenside und

50 bis 80, vorzugsweise 60 bis 70 Gew.-% anorganische oder organische Träger

mit der Maßgabe enthalten, dass sich die Mengenangaben gegebenenfalls mit Wasser und weiteren Hilfs- und Zusatzstoffen zu 100 Gew.-% ergänzen.The agents according to the invention are basically anhydrous, but due to the manufacturing process they can have a residual moisture content of at most 10, preferably below 8 and in particular below 5% by weight. Such means are preferably used which

6 to 75, preferably 10 to 50 wt .-% gemini surfactants and

25 to 94, preferably 50 to 90% by weight of inorganic or organic carriers

respectively.

10 to 40, preferably 20 to 30% by weight of gemini surfactants and

50 to 80, preferably 60 to 70% by weight of inorganic or organic carriers

with the proviso that the amounts indicated are supplemented, if appropriate, with water and further auxiliaries and additives to make up 100% by weight.

Manufacturing process

The invention also relates to a process for the production of solid granular detergents, dishwashing detergents and cleaning agents, preferably dishwashing detergents, in which gemini surfactants of the formula (I) are applied to inorganic or organic carriers.

The production can take place in such a way that either a mixing of nonionic Surfactants and carriers produced or only the surface of the carrier with the nonionic Surfactants is coated. The means are preferably produced in that the nonionic surfactants and the carriers and, if applicable, the other additives, are mixed together and agglomerated. The solid preparations can, for example by spray drying or spray mixing, in a ploughshare, Lödige or Eirich mixer or by complex granulation processes, for example fluidized bed granulation will. It is particularly preferred that at least the nonionic surfactant component is produced by fluidized bed granulation. Furthermore, it can be particularly preferred when aqueous preparations of the carrier, for example of alkali silicate or alkali carbonate sprayed together with other other components in a drying device granulation can take place at the same time as drying.

Spray drying

The drying device into which the aqueous preparation is sprayed can be any drying apparatus. In a preferred procedure, the drying is carried out as spray drying in a drying tower. The aqueous preparations are exposed in a known manner to a stream of drying gas in finely divided form. An embodiment of spray drying with superheated steam is described in patent publications by Henkel. The working principle disclosed there is hereby also expressly made the subject of the present disclosure of the invention. Reference is made here in particular to the following publications: DE 4030688 A1 and the further publications according to DE 4204035 A1; DE 4204090 A1; DE 4206050 A1; DE 4206521 A1; DE 4206495 A1; DE 4208773 A1; DE 4209432 A1 and DE 4234376 A1. This process has already been presented in connection with the production of the defoamer granule.

Fluidized bed granulation

A particularly preferred way of producing the agents is to use the preliminary products subject to fluidized bed granulation ("SKET" granulation). Below granulation is to be understood with simultaneous drying, which is preferred takes place batchwise or continuously. The primary products can be dried either State as well as an aqueous preparation can be used. Preferred The fluidized bed devices used have base plates with dimensions from 0.4 to The granulation is preferably carried out at fluidizing air velocities in the range of 1 to 8 m / s carried out. The granules are preferably discharged from the fluidized bed via a size classification of the granules. The classification can, for example by means of a sieve device or by a counter-air flow (Classifier air), which is regulated so that only particles above a certain particle size removed from the fluidized bed and retained smaller particles in the fluidized bed will. Usually, the incoming air is composed of the heated air or unheated sifter air and the heated bottom air together. The soil air temperature is between 80 and 400, preferably 90 and 350 and in particular below 70 ° C. A starting mass, for example a granulate from an earlier attempt, submitted.

Press agglomeration

In another, especially if products with high bulk density are to be obtained, In a preferred variant, the mixtures are then subjected to a compaction step subject to further ingredients, the agents only after the compaction step are mixed in. The compaction of the ingredients takes place in a preferred one Embodiment of the invention in a press agglomeration process instead. The press agglomeration process, which the solid premix (dried basic detergent) is subjected, can be realized in various apparatuses. Ever Depending on the type of agglomerator used, different press agglomeration processes are used differentiated. The four most common and under the present Invention preferred press agglomeration processes are extrusion, roller pressing or compacting, hole pressing (pelletizing) and tableting, so that in the context of the present invention preferred press agglomeration processes Extrusion, roller compaction, pelletizing or tableting operations are.

What all processes have in common is that the premix is compressed and plasticized under pressure and the individual particles are pressed together with a reduction in porosity become and cling to each other. For all processes (with some restrictions for tableting) the tools can be heated to higher temperatures or for Cooling away the heat generated by shear forces.

In all processes, one or more binders can be used as an aid for compaction will. However, it should be made clear that the use of several different binders and mixtures of different binders is possible. In a preferred embodiment of the invention, a binder is used used that at temperatures up to a maximum of 130 ° C, preferably up to a maximum 100 ° C and in particular up to 90 ° C is already completely in the form of a melt. That The binder must therefore be selected depending on the process and process conditions or the process conditions, in particular the process temperature, must - if so a specific binder is desired - to be matched to the binder.

The actual compression process is preferably carried out at processing temperatures which at least in the compression step is at least the temperature of the softening point, if not the temperature of the melting point of the binder correspond. In a preferred embodiment of the invention, the process temperature is significantly above the melting point or above the temperature at which the binder is in the form of a melt. In particular, however, it is preferred that the process temperature in the compression step not more than 20 ° C above the melting temperature or the upper limit of the melting range of the binder. True it is technically quite possible to set even higher temperatures; but it has shown that a temperature difference to the melting temperature or to the softening temperature of the binder of 20 ° C is generally quite sufficient and even higher temperatures do not result in any additional advantages. That's why it is - especially for energetic reasons - especially preferred, although above, but as close as possible to the melting point or the upper temperature limit of the Melting range of the binder to work. Has such a temperature control the further advantage that also thermally sensitive raw materials, for example peroxy bleach like perborate and / or percarbonate, but also enzymes, increasingly without serious losses of active substance can be processed. The possibility of the exact Temperature control of the binder, especially in the crucial step of the Compression, i.e. between the mixing / homogenization of the premix and the shape, allows an energetically very favorable and for the temperature sensitive Components of the premix extremely gentle process, as the premix is only exposed to the higher temperatures for a short time. In preferred Press agglomeration processes have the work tools of the press agglomerator (the Screw (s) of the extruder, the roller (s) of the roller compactor and the press roller (s) the pellet press) a maximum temperature of 150 ° C, preferably a maximum of 100 ° C and in particular a maximum of 75 ° C and the process temperature is 30 ° C and in particular a maximum of 20 ° C. above the melting temperature or the upper temperature limit the melting range of the binder. Preferably the duration is Temperature exposure in the compression area of the press agglomerators for a maximum of 2 minutes and in particular lies in a range between 30 seconds and 1 minute.

Preferred binders, which can be used alone or in a mixture with other binders, are polyethylene glycols, 1,2-polypropylene glycols and modified polyethylene glycols and polypropylene glycols. Combinations of polyethylene glycols with nonionic surfactants, especially of the fatty alcohol polyglycol ether type, are particularly preferred. The modified polyalkylene glycols include in particular the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols with a relative molecular weight between 600 and 12,000 and in particular between 1,000 and 4,000. Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which again have relative molecular weights between 600 and 6,000, preferably between 1,000 and 4,000. For a more detailed description of the modified polyalkylene glycol ethers, reference is made to the disclosure of international patent application WO 93/02176 . In the context of this invention, polyethylene glycols include those polymers which, in addition to ethylene glycol, also use C ₃ -C ₅ glycols and glycerol and mixtures thereof as starter molecules. Furthermore, ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included. The polyethylene glycols preferably used can have a linear or branched structure, linear polyethylene glycols being particularly preferred. The particularly preferred polyethylene glycols include those with relative molecular weights between 2,000 and 12,000, advantageously around 4,000, where polyethylene glycols with relative molecular weights below 3,500 and above 5,000 can be used, in particular in combination with polyethylene glycols with a relative molecular weight of around 4,000 Such combinations advantageously contain more than 50% by weight, based on the total amount of the polyethylene glycols, of polyethylene glycols with a relative molecular weight between 3,500 and 5,000. However, polyethylene glycols which are in liquid form at room temperature and a pressure of 1 bar can also be used as binders; This is mainly about polyethylene glycol with a relative molecular weight of 200, 400 and 600. However, these polyethylene glycols, which are liquid per se, should only be used in a mixture with at least one other binder, this mixture again having to meet the requirements according to the invention, i.e. it has to have a melting point or softening point of at least above 45.degree. Also suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives of these with relative molecular weights of up to a maximum of 30,000. Preferred are relative molecular weight ranges between 3,000 and 30,000, for example around 10,000. especially used in combination with polyethylene glycols.

The compacted material preferably has it directly after leaving the production apparatus Temperatures not above 90 ° C, with temperatures between 35 and 85 ° C are particularly preferred. It has been found that outlet temperatures - especially in the extrusion process - from 40 to 80 ° C, for example up to 70 ° C, especially are beneficial.

Extrusion

In a further preferred embodiment, the agent according to the invention is produced by means of an extrusion, as described, for example, in the European patent EP 0486592 B1 or the international patent applications WO 93/02176 and WO 94/09111 or WO 98/12299 . In this case, a solid premix is compressed into a strand under pressure and the strand is cut to the predeterminable granulate dimension by means of a cutting device after exiting the hole shape. The homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to be plastically softened and extrudable under the pressure or under the input of specific work. Preferred plasticizers and / or lubricants are surfactants and / or polymers. For an explanation of the actual extrusion process, reference is hereby expressly made to the above-mentioned patents and patent applications. The premix is preferably fed to a planetary roller extruder or a 2-screw extruder or 2-screw extruder with concurrent or counter-rotating screw guidance, the housing and extruder granulating head of which can be heated to the predetermined extrusion temperature. Under the shear action of the extruder screws, the premix is compressed, plasticized, extruded in the form of fine strands through the perforated nozzle plate in the extruder head and finally under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used the extrudate is reduced to approximately spherical to cylindrical granules by means of a rotating cut-off knife. The hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension. In this way it is possible to produce granules with an essentially uniformly predeterminable particle size, it being possible for the absolute particle sizes to be adapted to the intended use. In general, particle diameters of up to a maximum of 0.8 cm are preferred. Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm. The length / diameter ratio of the cut-off primary granules is preferably in the range from about 1: 1 to about 3: 1. It is also preferred to feed the still plastic primary granules to a further shaping processing step; in the process, edges present on the raw extrudate are rounded so that ultimately spherical to approximately spherical extrudate grains can be obtained. If desired, small amounts of dry powder, for example zeolite powder such as zeolite NaA powder, can also be used in this stage. This shaping can be done in standard rounding devices. It is important to ensure that only small amounts of fine grain are produced in this stage. Drying, which is described as a preferred embodiment in the above-mentioned documents of the prior art, is then possible, but not absolutely necessary. It may just be preferable not to carry out any more drying after the compaction step. Alternatively, extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press (Amandus Kahl) or in the Bepex be-extruder. The temperature control in the transition area of the screw, the predistributor and the nozzle plate is preferably designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least reached, but preferably exceeded. The duration of the temperature action in the compression range of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.

Roller compaction

The solid preparations according to the invention can also be compacted using rollers getting produced. Here, the premix is deliberately between two smooth or with depressions of defined shape provided rollers metered in and between the two rollers under pressure to form a sheet-shaped compact, the so-called Scab, rolled out. The rollers exert a high line pressure on the premix and can be additionally heated or cooled as required. When using smooth rollers produce smooth, unstructured scabbard bands, while the Using structured rollers, correspondingly structured scabs are generated can, in which, for example, certain shapes of the later detergent particles can be specified. The scoop band is then followed by a tee and crushing process broken into smaller pieces and that way too Granules are processed by further known surface treatment processes refined, in particular brought into an approximately spherical shape can be. With the roller compacting, too, the temperature is the same as that of the press Tools, ie the rollers, preferably at a maximum of 150 ° C., preferably at a maximum 100 ° C and especially at a maximum of 75 ° C. Particularly preferred manufacturing processes work in roller compaction with process temperatures of 10 ° C, in particular maximum 5 ° C above the melting temperature or the upper temperature limit the melting range of the binder. It is further preferred here that the duration of the temperature effect in the compression area of the smooth or with depressions of a defined shape provided rollers is a maximum of 2 minutes and in particular is in a range between 30 seconds and 1 minute.

Pelleting

The agent according to the invention can also be produced by means of pelleting. Here, the premix is applied to a perforated surface and pressed through the holes by means of a pressure-giving body with plasticization. In the usual embodiments of pellet presses, the premix is compacted under pressure, plasticized, pressed in the form of fine strands through a perforated surface by means of a rotating roller and finally crushed to granulate grains with a chopping device. The most varied designs of printing roller and perforated die are conceivable here. For example, flat perforated plates are used as well as concave or convex ring matrices through which the material is pressed by means of one or more pressure rollers. The press rollers can also be conically shaped in the case of the plate devices; in the ring-shaped devices, the dies and press roller (s) can rotate in the same direction or in opposite directions. An apparatus suitable for carrying out the method is described, for example, in the German patent application DE 3816842 A1 . The ring die press disclosed in this document consists of a rotating ring die penetrated by press channels and at least one press roller which is operatively connected to its inner surface and which presses the material fed to the die space through the press channels into a material discharge. Here, the ring die and the press roller can be driven in the same direction, so that a reduced shear load and thus a lower temperature increase in the premix can be achieved. Of course, it is also possible to work with heatable or coolable rollers during pelleting in order to set a desired temperature of the premix. During pelleting, too, the temperature of the pressing tools, that is to say the pressure rollers or press rollers, is preferably a maximum of 150.degree. C., preferably a maximum of 100.degree. C. and in particular a maximum of 75.degree. Particularly preferred production processes for roller compaction work at process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.

Tableting

The production as shaped bodies, preferably those in tablet form, is generally carried out by tabletting or press agglomeration. The particulate press agglomerates obtained can either be used directly as detergents, dishwashing detergents or cleaning agents, or they can be aftertreated and / or processed beforehand by customary methods. The usual after-treatments include, for example, powdering with finely divided ingredients of detergents or cleaning agents, which generally further increases the bulk density. A preferred aftertreatment, however, is also the procedure according to German patent applications DE 19524287 A1 and DE 19547457 A1 , whereby powdery or at least finely divided ingredients (the so-called fines) are adhered to the particulate process end products produced according to the invention, which serve as the core, and thus agents are formed which have these so-called fines as an outer shell. This is advantageously done in turn by melt agglomeration. For melt agglomeration of the fines , express reference is made to the disclosure in German patent applications DE 19524287 A1 and DE 19547457 A1 . In the preferred embodiment of the invention, the solid detergents are in tablet form, these tablets preferably having rounded corners and edges, in particular for storage and transport reasons. The base of these tablets can be circular or rectangular, for example. Multi-layer tablets, in particular tablets with 2 or 3 layers, which can also be different in color, are particularly preferred. Blue-white or green-white or blue-green-white tablets are particularly preferred. The tablets can also contain pressed and non-pressed parts. Moldings with a particularly advantageous dissolution rate are obtained if the granular constituents, before pressing, have a proportion of particles which have a diameter outside the range from 0.02 to 6 mm of less than 20, preferably less than 10% by weight. A particle size distribution in the range from 0.05 to 2.0 and particularly preferably from 0.2 to 1.0 mm is preferred.

Commercial applicability

Another object of the invention relates to the use of the solid granular compositions for production detergents, dishwashing detergents and cleaning agents, preferably automatic dishwashing detergents, in which they are used, for example, in amounts of 2 to 100, preferably 7 to 60 and especially 20 to 50 wt .-% - based on the final preparations - can be included.

Examples

Example 1. On 900 g of a mixture consisting of 800 g of sodium tripolyphosphate and 100 g of anhydrous soda, 100 g of PEG-1500-bis (2-hydroxydodecyl ether) at a temperature of 40 ° C. within 1 min added dropwise and mixed for 2 min. A pourable dry granulate was obtained.

Example 2. 200 g of PEG-2000-bis (2-hydroxydodecyl ether) were added dropwise to 800 g of sodium tripolyphosphate at 2000 rpm in a Lödig plowshare mixer at a temperature of 40 ° C. over the course of 1 min and then mixed for 2 min. A pourable dry granulate was obtained.

Example 3. 200 g of a mixture prepared immediately before use and consisting of 90 parts by weight of PEG-1500 bis (2-hydroxydodecyl ether) and 10 parts by weight of water glass were added dropwise at 40 ° C. to 800 g of sodium tripolyphosphate. The addition time was 1 min and the post-mixing time 2 min. A pourable dry granulate was obtained.

Example 4. 200 g of a melt prepared immediately before use and consisting of 90 parts by weight of PEG 1500 bis (2-hydroxydodecyl ether) and 10 parts by weight of PEG 12000 were added dropwise to 800 g of sodium tripolyphosphate in a spray mixer at 20 ° C. The addition time was 2 minutes and the post-mixing time was 4 minutes. Free-flowing dry granules were obtained.

Example 5. 300 g of a mixture prepared immediately before use and consisting of 90 parts by weight of PEG-2000 bis (2-hydroxydodecyl ether) and 10 parts by weight of water glass were added dropwise at 40 ° C. to 700 g of sodium tripolyphosphate. The addition time was 1 min and the post-mixing time 2 min. A pourable dry granulate was obtained.

Examples 6 and 7, comparative example V1. Various dishwashing detergent powders were produced in a mixer. In a dishwasher of the Miele G661 SC type, 25 g of each powder were examined with regard to their clear-dry effect under contamination and rated on a scale from (1) = very good to (5) = inadequate. The results are summarized in Table 1. Preparations 6 and 7 are according to the invention, mixture V1 is used for comparison.

The content of gemini surfactants in Example 6 and Comparative Example C1 was 12 g in each case Example 7, however, only 8 g. It can be seen that when using the granules according to the invention the same clear drying effect is achieved with a lower content of nonionic surfactant, while if the gemini surfactant content is equal in weight, the granules prove to be superior.

Claims (15)

1. Solid granular washing, rinsing and cleansing agents obtainable by applying gemini surfactants of the formula (I), R ¹ CH (OH)CH ₂ (OCH ₂ CH ₂ ) _n OCH ₂ CH (OH) R ²    (I) in which R¹ and R², independently of one another, are linear or branched alkyl and/or alkenyl radicals having 4 to 22 carbon atoms and n is numbers from 5 to 400 onto inorganic or organic carriers.
2. Solid agents according to Claim 1, characterized in that they comprise gemini surfactants of the formula (I), in which R¹ and R² are linear alkyl radicals having 10 to 16 carbon atoms.
3. Solid agents according to Claims 1 and/or 2, characterized in that they comprise gemini surfactants of the formula (I), in which n is numbers from 10 to 50.
4. Solid agents according to at least one of Claims 1 to 3, characterized in that they comprise inorganic or organic carriers chosen from the group formed by zeolites, alkali metal sulphates, alkali metal phosphates, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal silicates, alkali metal citrates, celluloses, carboxymethylcelluloses, cyclodextrins, starches, starch degradation products, polyacrylates, and mixtures thereof.
5. Solid agents according to at least one of Claims 1 to 4, characterized in that they comprise further auxiliaries and additives typical for washing, rinsing and cleansing agents.
6. Solid agents according to at least one of Claims 1 to 5, characterized in that they have a residual moisture of at most 10% by weight.
7. Solid agents according to at least one of Claims 1 to 6, characterized in that they comprise 6 to 75% by weight of gemini surfactants and 25 to 94% by weight of inorganic or organic carriers.
8. Solid agents according to Claim 7, characterized in that they comprise

   10 to 40% by weight of gemini surfactants and

   50 to 80% by weight of inorganic or organic carriers

   with the proviso that the quantitative data, optionally with water and further auxiliaries and additives, add up to 100% by weight.
9. Process for the preparation of granular solid washing, rinsing and cleansing agents, in which gemini surfactants of the formula (I), R ¹ CH (OH) CH ₂ (OCH ₂ CH) _n OCH ₂ CH(OH)R ²    (I) in which R¹ and R², independently of one another, are linear or branched alkyl and/or alkenyl radicals having 4 to 22 carbon atoms and n is numbers from 5 to 400, are applied to inorganic or organic carriers.
10. Process according to Claim 9, characterized in that an intimate mixture of nonionic surfactants and carriers is prepared.
11. Process according to Claims 9 and/or 10, characterized in that the surface of the carriers is coated with the nonionic surfactants.
12. Process according to at least one of Claims 9 to 11, characterized in that the solid agents are prepared by mixing the components in a ploughshare, Lödige or Eirich mixer.
13. Process according to at least one of Claims 9 to 11, characterized in that the solid agents are prepared by spray drying, fluidized-bed granulation, compression agglomeration, extrusion, roll compaction, pelleting, or tableting.
14. Use of the solid agents according to Claim 1 for the preparation of washing, rinsing and cleansing agents.
15. Use according to Claim 14, characterized in that machine dishwashing detergents are prepared.