EP1090978A1 - Solid washing, rinsing and cleaning agent containing defoaming granules - Google Patents

Abstract

Solid washing, rinsing and detergent agent comprises contains anionic, cationic, amphoteric and/or nonionic surfactants and defoamer granulate comprising silicones and carriers to prevent excess foam production.

Description

Field of the Invention

The invention is in the field of solid washing, rinsing and cleaning agents and relates to Preparations with special defoamers.

State of the art

Detergents for household and industrial laundry, but also detergents and cleaning agents, generally contain organic surfactants, builders and numerous organic and inorganic Additives. The surfactants used for the laundry tend to tend during use for foam development, which has a negative effect on the cleaning result. Therefore there is a practical need to control the development of foam during use. As special Suitable defoamers have proven to be silicones, which are usually based on carrier materials applied and optionally coated with other organic defoaming substances be used in solid washing, rinsing and cleaning agents. Usual defoamers of the However, the market proves to be particularly so when the preparations are particularly foaming contain anionic surfactants or hardly defoamable nonionic surfactants than not sufficient.

It was therefore an object of the present invention to use new defoamers with the use of suitable defoamers to provide solid detergents, dishwashing detergents and cleaning agents, which are characterized in particular by are distinguished by the fact that they also contain strong foaming anionic surfactants or Hardly defoamable nonionic surfactants over the entire duration of the cleaning process develop only such an amount of foam that the foaming, for example of washing or Dishwasher is reliably prevented.

Description of the invention

(a) anionische Tenside, nichtionische, kationische und/oder amphotere Tenside und

(b) Entschäumergranulate, enthaltend Silicone und Trägermaterialien.

The invention relates to solid washing, rinsing and cleaning agents containing

(a) anionic surfactants, nonionic, cationic and / or amphoteric surfactants and

(b) defoamer granules containing silicones and carrier materials.

Surprisingly, it was found that by using the new defoamer granules now Solid detergents, dishwashing detergents and cleaning agents are available which have the desired property profile full satisfaction.

Anionic surfactants

Typical examples of anionic surfactants are soaps, alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxymixed ether sulfates, mono (sulfide) sulfate, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate fatty acids, monoglyl sulfate sulfate, monoglyl sulfate fatty acids and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino acids such as, for example, acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartate, alkyl sulfate, vegetable based (alkyl oligate protein phosphate) products (alkyl oligate protein phosphate) products (alkyl oligate protein phosphate products), in particular alkyl olate condensate phosphate products (alkyl oligate protein phosphate products). If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Alkyl benzene sulfonates, alkyl sulfates, soaps, alkane sulfonates, olefin sulfonates, methyl ester sulfonates and mixtures thereof are preferably used. Preferred alkylbenzenesulfonates preferably follow the formula (I) R-Ph-SO ₃ X (I) in which R stands for a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph for a phenyl radical and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Of these, dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts are particularly suitable. Alkyl and / or alkenyl sulfates , which are also often referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary and / or secondary alcohols, which preferably follow the formula (II) R ² O-SO ₃ Y (II) in which R ^{2 represents} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and Y represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples of alkyl sulfates which can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, petroselachcohol, elaidyl alcohol, Behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained from high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis. The sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts. Alkyl sulfates based on C _16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts are particularly preferred. In the case of branched primary alcohols, these are oxo alcohols, as are obtainable, for example, by converting carbon monoxide and hydrogen to alpha-olefins using the shop method. Such alcohol mixtures are commercially available under the trade names Dobanol® or Neodol®. Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45®. Another possibility are oxo alcohols, such as those obtained after the classic Enichema or Condea oxo process by adding carbon monoxide and hydrogen to olefins. These alcohol mixtures are a mixture of strongly branched alcohols. Such alcohol mixtures are commercially available under the trade name Lial®. Suitable alcohol mixtures are Lial 91®, 111®, 123®, 125®, 145®. Finally, soaps are to be understood as meaning fatty acid salts of the formula (III) R ³ CO-OX (III) in which R ³ CO represents a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and preferably 12 to 18 carbon atoms and X represents alkali and / or alkaline earth metal, ammonium, alkylammonium or alkanolammonium. Typical examples are the sodium, potassium, magnesium, ammonium and triethanolammonium salts of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaoleic acid, petoleic acid, linoleic acid, petoleic acid, linoleic acid, petol acid Linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Coconut or palm kernel fatty acid is preferably used in the form of its sodium or potassium salts.

Nonionic surfactants

Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid, fatty acid amide, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers and mixed formals, alk (en) yl oligoglycosides, fatty acid N-alkylglucamides, protein hydrolysates (in particular vegetable products based on wheat), polyol, Zuckerester, sorbitan esters , Polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these can have a conventional, but preferably a narrow, homolog distribution. Fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters or alkyl oligoglucosides are preferably used. The preferred fatty alcohol polyglycol ethers follow the formula (IV) R ⁴ O (CH ₂ CHR ⁵ O) _n H (IV) in which R ^{4 represents} a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R ^{5 represents} hydrogen or methyl and n represents numbers from 1 to 20. Typical examples are the addition products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide with capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, isostyl alcohol , Petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures. Addition products of 3, 5 or 7 moles of ethylene oxide onto technical coconut oil alcohols are particularly preferred. Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (V) R ⁶ CO- (OCH ₂ CHR ⁷ ) _m OR ⁸ (V) in which R ⁶ CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{7 is} hydrogen or methyl, R ^{8 is a} linear or branched alkyl radical having 1 to 4 carbon atoms and m is a number from 1 to 20 stands. Typical examples are the formal insert products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, caprylic acid, 2 -Ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid, and technical grade mixtures and erucas. 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. Conversion products of an average of 5 to 10 moles of ethylene oxide into the ester linkage of technical coconut fatty acid methyl esters are particularly preferred. Alkyl and alkenyl oligoglycosides , which are also preferred nonionic surfactants, usually follow the formula (VI) , R ⁹ O- [G] _p (VI) in which R ^{9 represents} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP-A1 0 301 298 and WO 90/03977 . The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligo glucosides . The index number p in the general formula (VI) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer and especially here can assume the values p = 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ⁹ can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, 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 oxosynthesis. Alkyl oligoglucosides of chain length C ₈ -C ₁₀ (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C ₈ -C ₁₈ coconut fatty alcohol by distillation and with a proportion of less than 6% by weight of C ₁₂ - Alcohol can be contaminated and alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ⁹ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, 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.

Cationic surfactants

in der R¹⁰CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹¹ und R¹² unabhängig voneinander für Wasserstoff oder R¹⁰CO, R¹³ für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder eine (CH₂CH₂O)_x4H-Gruppe, x1, x2 und x3 in Summe für 0 oder Zahlen von 1 bis 12, x4 für Zahlen von 1 bis 12 und Y für Halogenid, Alkylsulfat oder Alkylphosphat steht. Typische Beispiele für Esterquats, die im Sinne der Erfindung Verwendung finden können, sind Produkte auf Basis von Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Isostearinsäure, Stearinsäure, Ölsäure, Elaidinsäure, Arachinsäure, Behensäure und Erucasäure sowie deren technische Mischungen, wie sie beispielsweise bei der Druckspaltung natürlicher Fette und Öle anfallen. Vorzugsweise werden technische C_12/18-Kokosfettsäuren und insbesondere teilgehärtete C_16/18-Talg- bzw. Palmfettsäuren sowie elaidinsäurereiche C_16/18-Fettsäureschnitte eingesetzt. Zur Herstellung der quatemierten Ester können die Fettsäuren und das Triethanolamin im molaren Verhältnis von 1,1 : 1 bis 3 : 1 eingesetzt werden. Im Hinblick auf die anwendungstechnischen Eigenschaften der Esterquats hat sich ein Einsatzverhältnis von 1,2 : 1 bis 2,2 : 1, vorzugsweise 1,5 : 1 bis 1,9 : 1 als besonders vorteilhaft erwiesen. Die bevorzugten Esterquats stellen technische Mischungen von Mono-, Di- und Triestern mit einem durchschnittlichen Veresterungsgrad von 1,5 bis 1,9 dar und leiten sich von technischer C_16/18- Talg- bzw. Palmfettsäure (lodzahl 0 bis 40) ab. Aus anwendungstechnischer Sicht haben sich quaternierte Fettsäuretriethanolaminestersalze der Formel (VII) als besonders vorteilhaft erwiesen, in der R¹⁰CO für einen Acylrest mit 16 bis 18 Kohlenstoffatomen, R¹¹ für R¹⁰CO, R¹² für Wasserstoff, R¹³ für eine Methylgruppe, x1, x2und x3 für 0 und Y für Methylsulfat steht. Neben den quaternierten Fettsäuretriethanolaminestersalzen kommen als Esterquats ferner auch quaternierte Estersalze von Fettsäuren mit Diethanolalkylaminen der Formel (VIII) in Betracht,

in der R¹⁴CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹⁵ für Wasserstoff oder R¹⁴CO, R¹⁶ und R¹⁷ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, x1 und x2 in Summe für 0 oder Zahlen von 1 bis 12 und Y für Halogenid, Alkylsulfat oder Alkylphosphat steht. Als weitere Gruppe geeigneter Esterquats sind schließlich die quaternierten Estersalze von Fettsäuren mit 1,2-Dihydroxypropyldialkylaminen der Formel (IX) zu nennen,

in der R¹⁸CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹⁹ für Wasserstoff oder R¹⁸CO, R²⁰, R²¹ und R²² unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, x1 und x2 in Summe für 0 oder Zahlen von 1 bis 12 und Y für Halogenid, Alkylsulfat oder Alkylphosphat steht. Schließlich kommen als Esterquats noch Stoffe in Frage, bei denen die Ester- durch eine Amidbindung ersetzt ist und die vorzugsweise basierend auf Diethylentriamin der Formel (X) folgen,

in der R²³CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R²⁴ für Wasserstoff oder R²³CO, R²⁵ und R²⁶ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen und Y für Halogenid, Alkylsulfat oder Alkylphosphat steht. Derartige Amidesterquats sind beispielsweise unter der Bezeichnung Incroquat® (Croda) im Markt erhältlich.Typical examples of cationic surfactants are, in particular, tetraalkylammonium compounds, such as, for example, dimethyldistearylammonium chloride or hydroxyethyl hydroxycetyldimmonium chloride (Dehyquart E) or esterquats . These are, for example, quaternized fatty acid triethanolamine ester salts of the formula (VII) ,

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

in which R ¹⁴ CO for an acyl radical with 6 to 22 carbon atoms, R ¹⁵ for hydrogen or R ¹⁴ CO, R ¹⁶ and R ¹⁷ independently of one another for alkyl radicals with 1 to 4 carbon atoms, x1 and x2 in total for 0 or numbers from 1 to 12 and Y represents halide, alkyl sulfate or alkyl phosphate. Finally, the quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula (IX) should be mentioned as a further group of suitable ester quats,

in which R ¹⁸ CO for an acyl radical with 6 to 22 carbon atoms, R ¹⁹ for hydrogen or R ¹⁸ CO, R ²⁰ , R ²¹ and R ²² independently of one another for alkyl radicals with 1 to 4 carbon atoms, x1 and x2 in total for 0 or numbers from 1 to 12 and Y represents halide, alkyl sulfate or alkyl phosphate. Finally, suitable ester quats are substances in which the ester bond is replaced by an amide bond and which preferably follow the formula (X) based on diethylenetriamine,

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

Amphoteric surfactants

in der R²⁷ für Alkyl- und/oder Alkenylreste mit 6 bis 22 Kohlenstoffatomen, R²⁸ für Wasserstoff oder Alkylreste mit 1 bis 4 Kohlenstoffatomen, R²⁹ für Alkylreste mit 1 bis 4 Kohlenstoffatomen, y1 für Zahlen von 1 bis 6 und Z für ein Alkali- und/oder Erdalkalimetall oder Ammonium steht. Typische Beispiele sind die Carboxymethylierungsprodukte von Hexylmethylamin, Hexyldimethylamin, Octyldimethylamin, Decyldimethylamin, Dodecylmethylamin, Dodecyldimethylamin, Dodecylethylmethylamin, C_12/14-Kokosalkyldimethylamin, Myristyldimethylamin, Cetyldimethylamin, Stearyldimethylamin, Stearylethylmethylamin, Oleyldimethylamin, C_16/18-Talgalkyldimethylamin sowie deren technische Gemische. Weiterhin kommen auch Carboxyalkylierungsprodukte von Amidoaminen in Betracht, die der Formel (XII) folgen,

in der R³⁰CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen und 0 oder 1 bis 3 Doppelbindungen, R³¹ für Wasserstoff oder Alkylreste mit 1 bis 4 Kohlenstoffatomen, R³² für Alkylreste mit 1 bis 4 Kohlenstoffatomen, y2 und y3 unabhängig von einander für Zahlen von 1 bis 6 und Z für ein Alkali- und/oder Erdalkalimetall oder Ammonium steht. Typische Beispiele sind Umsetzungsprodukte von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, namentlich Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Gemische, mit N,N-Dimethylaminoethylamin, N,N-Dimethylaminopropylamin, N,N-Diethylaminoethylamin und N,N-Diethyl-aminopropylamin, die mit Natriumchloracetat kondensiert werden. Bevorzugt ist der Einsatz eines Kondensationsproduktes von C_8/18-Kokosfettsäure-N,N-dime-thylaminopropylamid mit Natriumchloracetat.The preparations can contain alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and / or sulfobetaines as amphoteric or zwitterionic surfactants . Examples of suitable alkyl betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (XI)

in which R ²⁷ for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R ²⁸ for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ²⁹ for alkyl radicals with 1 to 4 carbon atoms, y1 for numbers from 1 to 6 and Z for a Alkali and / or alkaline earth metal or ammonium. Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C _12/14 -Kokosalkyldimethylamin, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearyl, oleyl, C _16/18 tallow alkyl dimethyl amine and technical mixtures thereof. Carboxyalkylation products of amidoamines which follow the formula (XII) are also suitable ,

in which R ³⁰ CO for an aliphatic acyl radical with 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R ³¹ for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ³² for alkyl radicals with 1 to 4 carbon atoms, y2 and y3 independently of one another represents numbers from 1 to 6 and Z represents an alkali and / or alkaline earth metal or ammonium. Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gadoleic acid and arachic acid, arachic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylamino propylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of C _8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate.

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

The preparations according to the invention usually contain the anionic, nonionic, cationic and / or amphoteric surfactants in amounts of 1 to 50, preferably 5 to 35 and in particular 15 to 25% by weight.

Defoamer granules

The defoamer granules which are mandatory as component (b) are the subject of a further patent application the applicant. Silicones are produced in the form of aqueous emulsions for their production on an admixed intermediate product from carrier materials and optionally wax-like defoamers on. The intermediate products are then dried and granulated simultaneously in the fluidized bed. For technical reasons, it is advantageous if at least 85, preferably at least 90 and in particular at least 95% by weight of the particles have an average diameter below 1.5, preferably below 1.3 mm and in particular between 0.1 and 1.5 mm exhibit.

Silicones

For the purposes of the present invention, suitable silicones are conventional organopolysiloxanes which have a content of finely divided silica, which in turn can also be silanized. Such organopolysiloxanes are described for example in the already cited European patent application EP 0496510 A1 . Polydiorganosiloxanes which are known from the prior art are particularly preferred. Suitable polydiorganosiloxanes have an almost linear chain and have a degree of oligomerization of 40 to 1500. Examples of suitable substituents are methyl, ethyl, propyl, isobutyl, tert. Butyl and phenyl. As a rule, the polydiorganosiloxanes contain finely divided silica, which can also be silanized. Silicic acid-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. An essential criterion of the present invention is that the silicones are sprayed in the form of their aqueous emulsions. As a rule, the silicone is added to the water initially introduced with stirring. If desired, so-called thickeners, as are known from the prior art, can be added to increase the viscosity of the aqueous silicone emulsions. The thickeners can be inorganic and / or organic in nature; nonionic cellulose ethers such as methyl cellulose, ethyl cellulose and mixed ethers such as methylhydoxyethyl cellulose, methyl hydroxypropyl cellulose, methyl hydroxybutyl cellulose and anionic carboxy cellulose types such as 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. In general and especially when adding the described thickener mixtures, use concentrations of approximately 0.5 to 10 are recommended. in particular from 2.0 to 6 wt .-% - calculated as a 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, as thickeners, are given starch which is accessible from natural sources, for example from rice, potatoes, corn and wheat. The starch is advantageously present in amounts of 0.1 to 50% by weight, based on the 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, the procedure is expediently such that the thickeners which may be present are allowed to swell in water before the silicones are added. The silicones are expediently incorporated with the aid of effective stirring and mixing devices.

Carrier materials

0 bis 2 Gew.-% Celluloseether

0 bis 75 Gew.-% native Stärke

0 bis 30 Gew.-% Alkalisilicat

0 bis 75 Gew.-% Alkalisulfat

0 bis 95 Gew.-% Alkalicarbonat

0 bis 95 Gew.-% Zeolithe

0 bis 5 Gew.-% Polycarboxylate, wobei sich die Summe zu 100 Gew.-% addieren muß.

All known inorganic and / or organic carrier materials can be used as carrier materials in the sense of the invention. Examples of typical inorganic carrier materials alkali carbonates, aluminosilicates, water-soluble layer silicates, alkali silicates, alkali sulfates, for example sodium sulfate and alkali phosphates. The alkali silicates are preferably a compound with a molar ratio of alkali oxide to SiO ₂ of 1: 1.5 to 1: 3.5. The use of such silicates results in particularly good grain properties, in particular high abrasion stability and nevertheless high dissolution rate in water. The aluminosilicates referred to as carrier material include in particular the zeolites, for example zeolite NaA and NaX. The compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass. Examples of suitable organic carrier materials are film-forming polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch. Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof. Particularly suitable mixtures are composed of sodium carboxymethyl cellulose and methyl cellulose, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit. The mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ethers in weight ratios from 80:20 to 40:60, in particular from 75:25 to 50:50. Such cellulose ether mixtures can be used in solid form or as aqueous solutions, which can be pre-swollen in the usual way. For the purposes of the invention, the native starch which is composed of amylose and amylopectin is particularly preferred as the carrier. Starch is referred to as native starch, as it is available as an extract from natural sources, for example from rice, potatoes, corn and wheat. Native starch is a commercially available product and is therefore easily accessible. Carrier materials which can be used are one or more of the abovementioned compounds, in particular selected from the group of alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, water-soluble sheet silicates, alkali metal silicates, polycarboxylates, carboxymethyl cellulose, polyacrylate / polymethacrylate and starch. Mixtures of alkali carbonates, in particular sodium carbonate, alkali silicates, in particular sodium silicate, alkali sulfates, in particular sodium sulfate, zeolites, polycarboxylates, in particular poly (meth) acrylate, and cellulose ether and native starch are particularly suitable. The carrier materials can be composed as follows:

0 to 2% by weight cellulose ether

0 to 75% by weight native starch

0 to 30% by weight alkali silicate

0 to 75% by weight alkali sulfate

0 to 95 wt% alkali carbonate

0 to 95% by weight zeolites

0 to 5% by weight of polycarboxylates, the sum having to add up to 100% by weight.

Waxy defoamers

For the purposes of the present invention, waxy, water-insoluble defoamer compounds can also be used in addition to the silicones. Compounds which have a melting point at atmospheric pressure above 25 ° C. (room temperature), preferably above 50 ° C. and in particular above 70 ° C., are understood to be “waxy”. The wax-like defoamer substances which may be present according to the invention are practically insoluble in water, ie at 20 ° C. they have a solubility of less than 0.1% by weight in 100 g of water. In principle, all wax-like defoamer substances known from the prior art can additionally be contained. Suitable waxy compounds are, for example, bisamides, fatty alcohols, fatty acids, carboxylic acid esters of mono- and polyhydric alcohols, and paraffin waxes or mixtures thereof. Bisamides are suitable which are derived from saturated fatty acids with 12 to 22, preferably 14 to 18 C atoms and from alkylenediamines with 2 to 7 C atoms. Suitable fatty acids are lauric acid, myristic acid, stearic acid, arachic acid and behenic acid and mixtures thereof, as can be obtained from natural fats or hydrogenated oils, such as tallow or hydrogenated palm oil. Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine. Preferred diamines are ethylenediamine and hexamethylenediamine. Particularly preferred bisamides are bis-myristoyl-ethylenediamine, bis-palmitoyl-ethylenediamine, bis-stearoylethylenediamine and mixtures thereof, and the corresponding derivatives of hexamethylenediamine. Suitable carboxylic acid esters are derived from carboxylic acids with 12 to 28 carbon atoms. In particular, these are esters of behenic acid, stearic 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 as well as ethylene glycol, glycerin, methanol, ethanol, isopropanol, vinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol. Preferred esters are those of methanol, 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. Eligible 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 dististearate, sorbitan dandghenoate and mixed sorbitan dibehenate, and sorbitan dandebehenate, and sorbitan dandebehenate, as well as sorbitan dandebehenate and mixed sorbitan dibehenate. Usable glycerol esters are the mono-, di- or triesters of glycerol and the carboxylic acids mentioned, the mono- or diesters being preferred. Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are examples of this. Examples of suitable natural esters are bees and carnauba wax, the latter being a mixture of carnauba acid alkyl esters, often in combination with small proportions of free carnauba acid, other long-chain acids, high molecular weight alcohols and hydrocarbons. Suitable carboxylic acids as a further defoamer compound are, in particular, behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid and mixtures thereof, as can be obtained from natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil. Saturated fatty acids with 12 to 22, in particular 14 to 18, carbon atoms are preferred. Suitable fatty alcohols as a further defoamer compound are the hydrogenated products of the fatty acids described. The paraffin wax preferred as a further defoamer compound in the sense of the invention generally represents a complex mixture of substances without a sharp melting point. For characterization, its melting range is usually determined by differential thermal analysis (DTA), as in "The Analyst" 87 (1962), 420 , described, and / or its freezing point. This is the temperature at which the paraffin changes from the liquid to the solid state by slow cooling. Paraffins which are completely liquid at room temperature, that is to say those having a solidification point below 25 ° C., cannot be used according to the invention. For example, the paraffin wax mixtures known from EP 0309931 A1 of, for example, 26% by weight to 49% by weight of microcrystalline paraffin wax with a solidification point of 62 ° C. to 90 ° C., 20% by weight to 49% by weight hard paraffin can be used with a solidification point of 42 ° C to 56 ° C and 2 wt .-% to 25 wt .-% soft paraffin with a solidification point of 35 ° C to 40 ° C. Paraffins or paraffin mixtures which solidify in the range from 30 ° C. to 90 ° C. are preferably used. It should be noted that even paraffin wax mixtures that appear solid at room temperature can contain different proportions of liquid paraffin. In the paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible and is preferably absent entirely. Particularly preferred paraffin wax mixtures at 30 ° C have a liquid fraction of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C a liquid fraction of less than 30% by weight, preferably of 5 % By weight to 25% by weight and in particular from 5% by weight to 15% by weight, at 60 ° C. a liquid fraction of 30% by weight to 60% by weight, in particular 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 still below 85 ° C. in particularly preferred paraffin wax mixtures, in particular at 75 ° C. to 82 ° C. For the purposes of the invention, paraffin waxes of the type described are used in particular.

Production of defoamer granules

To produce the defoamer granules that form component (b), a preliminary product is first used from the carrier materials and any wax-like defoamer substances contained manufactured. If the preliminary product also contains wax-like defoamer substances, the proportion by weight of carrier materials is preferably 20 to 98% by weight, in particular 35 to 95 wt .-%, and that of the wax-like defoamer substances preferably 2 to 80 wt .-%, in particular 5 to 65% by weight - calculated on preliminary product. The carrier material can in the usual way Spray drying an aqueous slurry. If additional wax-like defoamer substances can be used, for example, by applying the melted wax-like defoamer substances on the spray-dried, granular carrier material, for example by successive mixing, in particular in the form of a spray. The carrier material is preferably moved by mixing elements or by fluidization held to ensure a uniform loading of the carrier material. The used for it Spray mixers can be operated continuously or discontinuously.

The production of preliminary products containing additional wax-like defoamer substances takes place in a further preferred embodiment according to the invention such that the carrier material dissolves or slurries in water, the waxy defoamer substances in it dispersed and then spray-dried this slurry. The dispersion can be a water-soluble, non-surfactant dispersion stabilizer added in the form of a water-swellable polymer become. Examples of these are the cellulose ethers mentioned, homo- and copolymers of unsaturated Carboxylic acids, such as acrylic acid, maleic acid and copolymerizable vinyl compounds, such as vinyl ether, Acrylamide and ethylene. The addition of such compounds acting as dispersion stabilizers in the aqueous slurry is preferably not more than 5% by weight, especially 1 wt .-% to 3 wt .-%, based on the resulting product. The water content of the slurries can be 30% by weight to 60% by weight, depending on the type or solubility of the support materials. The spray drying of the dispersion can be carried out in a manner known in principle in the manner provided for it Plants, so-called spray towers, using hot, guided in cocurrent or countercurrent Drying gases take place. The drying is carried out in cocurrent with the spray material Drying gases are preferred, as this is particularly important for paraffin-containing precursors Hot air volatility of some constituents of the paraffin is attributed to a loss of activity Minimum can be lowered.

In the context of the present invention, the spraying of the aqueous silicone emulsions onto the preliminary product is preferably carried out continuously onto the solid preliminary product with simultaneous drying and granulation in a fluidized bed, in particular in a continuously operating fluidized bed according to the so-called SKET process. The aqueous silicone emulsions are introduced into the fluidized bed via one or more nozzles. In the sense of the method according to the invention, the preliminary product of carrier material and wax-like defoamer substances are mixed in simultaneously with the aqueous silicone emulsions, but separately from them, preferably by means of an automatically controlled solids metering. The product streams of aqueous silicone emulsion and admixed preliminary product are controlled in such a way that defoamer granules result, which are preferably 2.0 to 25% by weight, in particular 5.0 to 20% by weight, of silicone, calculated as silicone and based on Defoamer granules - included. The remaining 100% by weight of the defoamer granulate is the preliminary product already described. In the fluidized bed, the aqueous silicone emulsion meets the mixed preliminary products with simultaneous evaporation of the water, whereby dried to dried germs are formed, which are coated with further introduced aqueous silicone emulsions or with the mixed preliminary products, granulated and again dried at the same time. The simultaneous drying and granulation takes place in the fluidized bed above a circular inflow floor provided with through-openings for the drying air, the product to be dried remaining stationary above the inflow floor during this drying phase, so that a build-up granulation takes place. More information on the so-called SKET process can be found in European patent EP 0603207 B1 . A particular advantage of the process is that the defoamer granules that are produced are classified or classified by the incoming drying air with regard to their particle size and thus also with regard to their weight, so that those granules which have reached the desired particle size or weight fall out of the fluidized bed the fluidized bed in a discharge lock.

Fluidized bed apparatuses which are preferably used also have circular base plates (inflow base) a diameter between 0.4 and 5 m, for example 1.2 m or 2.5 m. Can as a base plate Perforated floor panels, a Contidurplatte (commercial product from Hein & Lehmann, Federal Republic Germany) or perforated base plates are used, the holes (through openings) of one Grid with mesh sizes smaller than 600 microns are covered. The grid can be within or be arranged above the passage openings. However, the grid preferably lies immediately below the through openings of the inflow floor. This is advantageously implemented in such a way that a metal gauze with the appropriate mesh size is sintered on. Preferably there is the metal gauze made of the same material as the inflow floor, especially stainless steel. The mesh size of said grid is preferably between 200 and 400 μm.

For the purposes of the invention, the method is preferred at swirl air speeds between 1 and 8 m / s and in particular between 1.5 and 5.5 m / s. The granules are advantageously discharged about a size classification of the granules. This classification is preferably carried out using an opposite flow of drying air (classifier air), which is regulated so that only particles come off a certain particle size removed from the fluidized bed and smaller particles in the fluidized bed be held back. In a preferred embodiment, the inflowing air settles from the heated or unheated classifier air and the heated soil air. The soil air temperature is preferably between 80 and 400 ° C. The vortex air cools due to heat loss and by the heat of vaporization and is preferably about 5 cm above that Base plate 60 to 120 ° C, preferably 65 to 90 and in particular 70 to 85 ° C. The air outlet temperature is preferably between 60 and 120 ° C, especially below 80 ° C.

The residence time for the product to be dried, which remains stationary above the inflow floor, is preferably in the range of 5 to 60 minutes. For the purposes of the present invention, the Defoamer granules are considered to be dried, provided that the free water content is below 10% by weight, preferably from 0.1 to 2% by weight, based in each case on the finished granules. In the preferred Process carried out in the fluidized bed, it is necessary that at the beginning of the process a starting mass is present which serves as the initial carrier for the sprayed-in aqueous silicone emulsion serves. The admixed preliminary products or in particular the defoamer granules are suitable as starting mass themselves, which have already been obtained in a previous process. In particular, defoamer granules with a grain size in the range above 0.2 and below 0.9 mm used as the starting mass and preferably fed in via a roller mill. To be favoured the defoamer granules obtained from the fluidized bed are subsequently separated Fluidized bed cooled and classified into granules with grain sizes between 0.9 and 5 mm as good grain fraction, in granules over 5 mm as oversize fraction and in granules under 0.9 mm as subcomfraction. The granules of the undersize fraction are returned to the fluidized bed. The oversize fraction is ground, preferably in grain sizes below 0.9 mm, and likewise returned to the fluidized bed. The agents according to the invention can contain the defoamer granules in Amounts of 1 to 25, preferably 2 to 15 and in particular 3 to 10 wt .-% - based on the Medium - included.

Auxiliaries and additives

The solid washing, rinsing and cleaning agents according to the invention can furthermore additionally contain inorganic and organic builder substances, whereby as inorganic builder substances mainly zeolites, crystalline layered silicates, amorphous silicates and - where permitted - also phosphates, such as. Tripolyphosphate are used.

The fine crystalline, synthetic and bound water-containing zeolite which is frequently used as a detergent builder is preferably zeolite A and / or P. As zeolite P, for example, zeolite MAP ^(R) (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P and Y are also suitable. Of particular interest is also a cocrystallized sodium / potassium aluminum silicate made of zeolite A and zeolite X, which as VEGOBOND AX ^® (commercial product from Condea Augusta SpA) is commercially available. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates 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 Is 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP 0164514 A1 . Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, it being possible, for example, to obtain β-sodium disilicate by the process described in international patent application WO 91/08171 . Further suitable layered silicates are known, for example, from patent applications DE 2334899 A1, EP 0026529 A1 and DE 3526405 A1 . Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable sheet silicates, which belong to the group of 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 montmorrilonite (OH) ₄ Si _8-y Al _y (Mg _6-z Li _z ) O ₂₀ hectorite (OH) ₄ Si _8-y Al _y (Mg _6-z Al _z ) O ₂₀ saponite with x = 0 to 4, y = 0 to 2, z = 0 to 6. In addition, small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas. Furthermore, due to their ion-exchanging properties, the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na + and Ca ²⁺ . The amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing. Useful layer silicates are known, for example, from US 3,966,629, US 4,062,647, EP 0026529 A1 and EP 0028432 A1 . Layer silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.

The preferred builder substances also include amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE 4400024 A1 . Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

Of course, it is also possible to use the generally known phosphates as builders, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable. Their content is generally not more than 25% by weight, preferably not more than 20% by weight, in each case based on the finished composition. In some cases, it has been shown that tripolyphosphates in particular, even in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances lead to a synergistic improvement in the secondary washing ability.

Usable organic 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), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, 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 action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

Other suitable organic builder substances are dextrins , for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure for the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2,000 to 30,000 can be used. A preferred dextrin is described in British patent application GB 9419091 A1 . The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP 0232202 A1, EP 0427349 A1, EP 0472042 A1 and EP 0542496 A1 as well as from international patent applications WO 92/18542, WO 93/08251, WO 93/16110, WO 94 / 28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known. An oxidized oligosaccharide according to German patent application DE 19600018 A1 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Other suitable cobuilders are oxydisuccinates and other derivatives of disuccinates , preferably ethylenediamine disuccinate . Also particularly preferred in this context are glycerol disuccinates and glycerol trisuccinates , as described, for example, in US Pat. Nos . 4,524,009, 4,639,325 , in European patent application EP 0150930 A1 and in Japanese patent application JP 93/339896 . Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.

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

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 measured in each case against polystyrene sulfonic acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000 (measured in each case against polystyrene sulfonic acid). The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, with 20 to 55% by weight aqueous solutions being preferred. Granular polymers are usually subsequently mixed into one or more basic granules. Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which, according to DE 4300772 A1, as salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or as DE 4221381 C2 as monomer salts of acrylic acid and the 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 which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers. Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and derivatives are particularly preferred.

Other suitable builder substances are polyacetals , which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0280223 A1 . Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

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

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

In addition to the ingredients mentioned, the agents can include other known additives, for example Salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, small amounts of contain neutral filling salts as well as colors and fragrances and the like.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 35% by weight and in particular up to 30% by weight, advantageously using perborate monohydrate or percarbonate.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyloxy, 2,5-acetiacetyl, ethylene glycol 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 described in European patent application EP 0525239 A1 (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG) , Pentaacetylfruktose, Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alky gelled glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are known from 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 acylacetals known from German patent application DE 19616769 A1 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE 4443177 A1 can also be used. Bleach activators of this type are present in the customary quantitative range, preferably in amounts 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 in their place, 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 present as so-called bleaching catalysts. The transition metal compounds in question include in particular the manganese, iron, cobalt, ruthenium or molybdenum-salt 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 German patent application DE 196 05 688 - and copper complexes with nitrogen-containing tripod ligands known from the German patent application DE 19620411 A1 cobalt, iron, copper and ruthenium-ammine complexes, the manganese described in the German patent application DE 4416438 A1, copper 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 Complexes, the manganese, iron, cobalt and copper complexes known from European patent EP 0392592 A1 and / or those described in European patent EP 0443651 B1 or 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 0.0025% by weight. % to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total agent.

Particularly suitable enzymes are those from the class of hydrolases, such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling and microfibrils, cellulases and other glycosyl hydrolases can help maintain color and increase the softness of the textile. Oxidoreductases can also be used for bleaching or for inhibiting color transfer. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

In addition to the mono- and polyfunctional alcohols, the agents can contain further enzyme stabilizers . For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. In addition to calcium salts, magnesium salts also serve as stabilizers. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. 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 acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the detergent, are preferred used.

As optical brighteners, the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. Uniformly white granules are obtained if, in addition to the usual brighteners, the agents are present in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, and also in small amounts, for example ^Contain 10 ^-6 to 10 ^-3 wt .-%, preferably by 10 ^-5 wt .-%, of a blue dye. A particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).

As soil release polymers ( _"soil repellants") are those which are suitable are, preferably ethylene terephthalate and / or polyethylene glycol terephthalate contained, the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate in the range of 50: 50 to 90: may be 10 degrees. The molecular weight of the linking polyethylene glycol units is in particular in the range from 750 to 5000, ie the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 to 100. The polymers are characterized by an average molecular weight of about 5000 to 200,000 and can have a block, but preferably a random structure. Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Also preferred are those polymers which have linking polyethylene glycol units with a molecular weight of 750 to 5000, preferably of 1000 to about 3000 and a molecular weight of the polymer from about 10,000 to about 50,000. Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).

Individual fragrance compounds , for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances . Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexylpropylatepylatepylatepylatepionate, stally. The ethers include, for example, benzyl ethyl ether, the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones include, for example, the jonones, α-isomethylionone and methylcedryl ketone the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the agents according to the invention, but they can also be advantageous to apply the fragrances on carriers, which the perfume adheres to the laundry intensify and ensure a long-lasting fragrance of the textiles through a slower fragrance release. Cyclodextrins, for example, have proven successful as such carrier materials, the cyclodextrin-perfume complexes can also be coated with other auxiliaries.

If desired, the final preparations can also contain inorganic salts as fillers or fillers, such as sodium sulfate, which is preferably present in amounts of 0 to 10, in particular 1 to 5% by weight, based on the composition.

Production of funds

The agents available using the new defoamer granules can be in the form of powders, Extrudates, granules or agglomerates are produced or used. It can happen both for universal and fine or color detergents, if necessary in the form of compact or act super compact. To produce such agents are the corresponding, from the Methods known in the art are suitable. The agents are preferably produced by that different particulate components containing detergent ingredients together be mixed. The particulate components can be spray dried, simply mixed or complex granulation processes, for example fluidized bed granulation. It is particularly preferred that at least one surfactant-containing component by fluidized bed granulation will be produced. Furthermore, it can be particularly preferred if aqueous preparations the alkali silicate and the alkali carbonate together with other detergent ingredients be sprayed in a drying device, with a granulation simultaneously with the drying can take place.

The drying device into which the aqueous preparation is sprayed can be any drying apparatus. In a preferred process, the drying is carried out as spray drying in a drying tower. The aqueous preparations are exposed to a drying gas stream in finely divided form in a known manner. Patent publications by Henkel describe an embodiment of spray drying with superheated steam. The working principle disclosed there is hereby 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 manufacture of the defoamer.

In another, especially when high bulk density agents are to be obtained, preferred Variant, the mixtures are then subjected to a compacting step, with further Ingredients are only added to the agents after the compacting step. The compacting of the ingredients takes place in a preferred embodiment of the invention in a press agglomeration process instead of. The press agglomeration process to which the solid premix (dried basic detergent) subject can be realized in various devices. Depending on A distinction is made between the type of agglomerator used and different press agglomeration processes. The four most common press agglomeration processes preferred in the context of the present invention are extrusion, roll pressing or compacting, hole pressing (Pelletizing) and tabletting, so that preferred press agglomeration processes within the scope of the present invention Extrusion, roll compacting, pelletizing or tableting processes are.

All processes have in common that the premix is compressed and plasticized under pressure and the individual particles are pressed together and the porosity is reduced be liable. The tools can be used in all processes (with tableting with restrictions) heat up to higher temperatures or dissipate the shear forces Cool heat.

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

The actual compression process is preferably carried out at processing temperatures that at least in the compression step at least the temperature of the softening point, if not correspond to the temperature of the melting point of the binder. In a preferred embodiment 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 is not more than 20 ° C above the melting temperature or the upper limit of the melting range of the binder. It is technical quite possible to set even higher temperatures; but it has been shown that a Temperature difference from the melting temperature or softening temperature of the binder of 20 ° C is generally sufficient and even higher temperatures no additional advantages cause. Therefore - especially for energy reasons - it is particularly preferred above, but as close as possible to the melting point or the upper temperature limit of the melting range of the binder. Such a temperature control has the other Advantage that also thermally sensitive raw materials, for example peroxy bleaching agents such as perborate and / or percarbonate, but also enzymes, increasingly processed without serious loss of active substance can be. The possibility of precise temperature control of the binder in particular in the decisive step of 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 management, because the premix is only exposed to the higher temperatures for a short time. In preferred press agglomeration processes show the working tools of the press agglomerator (the screw (s) of the extruder, the roller (s) of the roller compactor and the press roller (s) of the pellet press) have a temperature of a maximum 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 of the melting range of the binder. The duration is preferably the temperature effect in the compression area of the press agglomerators a maximum of 2 minutes and is particularly 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 also modified polyethylene glycols and polypropylene glycols. 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 the 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 of these as starting molecules. Ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included. The polyethylene glycols which are preferably used can have a linear or branched structure, linear polyethylene glycols in particular being preferred. The particularly preferred polyethylene glycols include those with relative molecular weights between 2,000 and 12,000, advantageously around 4,000, polyethylene glycols with relative molecular weights below 3,500 and above 5,000, in particular in combination with polyethylene glycols with a relative molecular weight of around 4,000, and can be used Such combinations advantageously have more than 50% by weight, based on the total amount of polyethylene glycols, of polyethylene glycols with a relative molecular weight between 3,500 and 5,000. However, polyethylene glycols can also be used as binders, which are per se in liquid state at room temperature and a pressure of 1 bar; Here we are mainly talking about polyethylene glycol with a relative molecular mass of 200, 400 and 600. However, these per se liquid polyethylene glycols should only be used in a mixture with at least one further binder, this mixture again having to meet the requirements according to the invention, that is to say having a melting point or softening point of at least above 45 ° C. Likewise suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights of up to a maximum of 30,000. Relative molecular mass ranges between 3,000 and 30,000, for example around 10,000, are preferred. Polyvinylpyrrolidones are preferably not used as the sole binder, but in combination with others, in particular in combination with polyethylene glycols.

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

In a preferred embodiment, the detergent according to the invention is produced by means of an extrusion , as described, for example, in European patent EP 0486592 B1 or international patent applications WO 93/02176 and WO 94/09111 or WO 98/12299 . In this case, a solid premix is pressed in the form of a strand under pressure and the strand is cut to the predeterminable size of the granulate after it has emerged from the hole shape by means of a cutting device. The homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to become plastically softened and extrudable under the pressure or under the entry of specific work. Preferred plasticizers and / or lubricants are surfactants and / or polymers. To explain the actual extrusion process, reference is hereby expressly made to the patents and patent applications mentioned above. The premix is preferably fed to a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guidance, the housing and the extruder pelletizing 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 die 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 preferably reduced to approximately spherical to cylindrical granules by means of a rotating knives. The hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension. In this way, the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use. In general, particle diameters up to at most 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 chopped-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; edges present on the crude extrudate are rounded off 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 step. This shape can be done in standard rounding machines. Care should be taken to ensure that only small amounts of fine grain are produced in this stage. Drying, which is described as a preferred embodiment in the abovementioned prior art documents, is subsequently possible, but not absolutely necessary. It may just be preferable not to carry out any drying after the compacting step. Alternatively, extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press (from Amandus Kahl) or in the Bepex extruder. The temperature control in the transition region of the screw, the pre-distributor 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 influence 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.

The detergents according to the invention can also be produced by means of roller compaction . Here, the premix is metered in between two smooth rollers or with recesses of a defined shape and rolled out under pressure between the two rollers to form a sheet-like compact, the so-called Schülpe. The rollers exert a high line pressure on the premix and can be additionally heated or cooled as required. When using smooth rollers, smooth, unstructured sliver belts are obtained, while by using structured rollers, correspondingly structured slugs can be produced in which, for example, certain shapes of the later detergent particles can be specified. The sliver belt is subsequently broken up into smaller pieces by a knocking-off and crushing process and can be processed into granules in this way, which can be refined by further known surface treatment processes, in particular in an approximately spherical shape. In the case of roller compaction, too, the temperature of the pressing tools, that is to say of the rollers, is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at a maximum of 75 ° C. Particularly preferred production processes work in roller compacting with 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. It is further preferred that the duration of the temperature effect in the compression area of the smooth rollers or with depressions of a defined shape is a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.

The detergent according to the invention can also be produced by pelleting . The premix is applied to a perforated surface and pressed through the holes by means of a pressure-producing body with plasticization. In conventional embodiments of pellet presses, the premix is compressed under pressure, plasticized, pressed through a perforated surface by means of a rotating roller in the form of fine strands and finally comminuted into granules using a knock-off device. The most varied configurations of the pressure 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 using one or more pressure rollers. The press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation. An apparatus suitable for carrying out the method is described, for example, in German laid-open specification DE 3816842 A1 . The ring die press disclosed in this document consists of a rotating ring die interspersed with press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied 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, which means that a reduced shear stress 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 in the pelletizing in order to set a desired temperature of the premix. In pelleting too, the temperature of the pressing tools, that is to say the pressure rollers or pressure rollers, is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at a maximum of 75 ° C. Particularly preferred production processes work in roller compacting with 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.

Examples Production of a wax-like pre-product containing defoamer

Example 1. 10,000 kg of an aqueous slurry consisting of 0.5% by weight cellulose ether, 5.0% by weight sodium silicate, 20.7% by weight sodium sulfate, 15.8% by weight sodium carbonate, 2.0% Polyacrylic / methacrylate, 50% by weight of water and 6% by weight of a paraffin wax mixture consisting of 30% by weight of paraffin with a solidification point from 62 ° C. to 90 ° C., 30% by weight of hard paraffin with a solidification point of 42 ° C to 56 ° C and 30 wt .-% soft paraffin with a solidification point of 35 ° C to 40 ° C was atomized with constant homogenization under a pressure of 40 bar in a spray tower and by means of hot, countercurrent combustion gases (temperature in the ring channel 250 ° C, dried in the tower outlet 98 ° C).

Example 2. 10,000 kg of an aqueous slurry consisting of 0.5% by weight cellulose ether, 2.0% by weight sodium silicate, 13% by weight sodium sulfate, 23.5% by weight zeolite, 2.0% by weight % Polyacrylic / methacrylate, 50% by weight of water, 7% by weight of paraffin with a solidification point of 62 ° C. to 90 ° C. and 2% by weight of bis-stearylethylenediamide was homogenized under constant pressure under a pressure of 40 bar Spray tower atomized and dried using hot, countercurrent combustion gases (temperature in the ring channel 250 ° C, in the tower outlet 98 ° C).

Preparation of the aqueous silicone emulsions

Example 3. 2000 kg of an aqueous solution containing 3.7% by weight of a thickener mixture of sodium carboxymethyl cellulose and methyl cellulose in a weight ratio of 70:30 were left to swell at 25 ° C. for 4 hours. 20% by weight of a polysiloxane defoamer (polydimethylsiloxane with microfine silanized silica) were added to this solution. A stable aqueous emulsion was obtained.

Example 4. 2000 kg of an aqueous solution containing 3.7% by weight of a thickener mixture of sodium carboxymethyl cellulose and methyl cellulose in a weight ratio of 70:30 were left to swell at 25 ° C. for 4 hours. 30% by weight of corn starch and 20% by weight of a polysiloxane defoamer (polydimethylsiloxane with microfine silanized silica) were added to this solution. A stable aqueous emulsion was obtained.

Granulation in the fluidized bed

Example 5. In a fluidized bed apparatus (SKET plant) with a circular fluidized bed, through which drying air flowed with approx. 20,000 m ^{3 of} air / h at a temperature of 140 ° C., 650 kg of the powdery precursor produced according to Example 1 were continuously added per hour fed via a solids metering and continuously sprayed 350 kg per hour of the aqueous silicone emulsion prepared according to Example 3 onto this powdery precursor. The temperature in the fluidized bed above the fluidized bed was 85 ° C, the exhaust air 79 ° C. Granules having the following composition were obtained: 7% by weight of silicone, 2.2% by weight of cellulose ether, 9.2% by weight of sodium silicate, 38.0% by weight of sodium sulfate, 29.1% by weight of sodium carbonate , 3.7 wt .-% polyacrylic / methacrylate and 11.0 wt .-% of a paraffin wax mixture consisting of 30% paraffin with a solidification point from 62 ° C to 90 ° C, 30 wt .-% hard paraffin with a solidification point of 42 ° C to 56 ° C and 30% by weight of soft paraffin with a solidification point of 35 ° C to 40 ° C with a bulk density of 810 g / l and a particle size distribution in which 95% by weight of the particles have an average diameter below 1, 5 mm. The product showed very good flow properties and had practically no dust content.

Example 6. According to Example 5, 650 kg per hour of the powdery precursor produced according to Example 2 were continuously fed into the fluidized bed apparatus (SKET plant) at a drying air flow rate of approx. 20,000 m ³ air / h at a temperature of 100 ° C. Solid feed metered in and continuously sprayed 350 kg per hour of the aqueous silicone emulsion prepared according to Example 4 onto this powdery precursor. The temperature in the fluidized bed above the fluidized bed was 65 ° C, the exhaust air 60 ° C. Granules having the following composition were obtained: 7% by weight of silicone, 10.3% by weight of starch, 2.1% by weight of cellulose ether, 3.2% by weight of sodium silicate, 21.2% by weight of sodium sulfate , 38.1% by weight zeolite, 3.3% by weight polyacrylic / methacrylate, 11.5% by weight paraffin and 3.3% by weight bis-stearylethylenediamide with a bulk density of 780 g / l and one Grain distribution at which 95% by weight of the particles had an average diameter below 1.5 mm. The product showed very good flow properties and had no dust content.

Table 1 contains some recipe examples.

Claims (10)

Solid detergents, dishwashing detergents and cleaning agents containing (a) anionic surfactants, nonionic, cationic and / or amphoteric surfactants and (b) defoamer granules containing silicones and carrier materials. Compositions according to Claim 1, characterized in that they contain, as component (a), anionic surfactants which are selected from the group formed by alkylbenzenesulfonates, alkylsulfates, soaps, alkanesulfonates, olefin sulfonates and methyl ester sulfonates. Agents according to claims 1 and / or 2, characterized in that they contain, as component (a), nonionic surfactants which are selected from the group formed by fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters and alkyl oligoglucosides. Agents according to at least one of Claims 1 to 3, characterized in that they contain, as component (a), cationic and / or amphoteric surfactants which are selected from the group formed by esterquats, alkyl betaines and alkyl amido betaines. Agents according to at least one of Claims 1 to 4, characterized in that they contain the surfactants in amounts of 1 to 50% by weight, based on the agents. Agent according to at least one of Claims 1 to 5, characterized in that it is used as a component (b) contain defoamer granules which have polydisiloxanes as silicones. Agents according to at least one of Claims 1 to 6, characterized in that they contain, as component (b), defoamer granules which have silicones together with further wax-like defoamer substances. Agents according to at least one of Claims 1 to 7, characterized in that they contain, as component (b), defoamer granules which have carrier materials which are selected from the group formed by alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, alkali metal silicates, cellulose ethers, Polycarboxylates and starches. Compositions according to at least one of Claims 1 to 8, characterized in that they contain, as component (b), defoamer granules which have waxy defoamer compounds which are selected from the group formed by bisamides, fatty acids, fatty alcohols, carboxylic acid esters or paraffin waxes. Agent according to at least one of claims 1 to 9, characterized in that it contains the defoamer granules in amounts of 1 to 25 wt .-% - based on the agent - included.