DE19958398A1 - Use of partial glyceride polyglycol ethers - Google Patents

Abstract

The use of ethoxylation products of partial glycerides for the production of detergents, dishwashing detergents and cleaning agents is proposed, which are characterized in that they consist of mixtures of partial glyceride ethoxylates and glycerol ethoxylates in a weight ratio of 3.3: 1 to 6: 1.

Description

Field of the Invention

The invention is in the field of surface-active preparations and relates to the Ver use of selected mixtures of ethoxylated partial glycerides and glycerol ethoxylates for the production of washing, rinsing and cleaning agents.

State of the art

Nonionic surfactants are of particular importance for the production of washing, rinsing and Detergents, as they have a special cleaning ability against grease stains have. Their properties complement those of anionic surfactants which they are usually used together have the advantage over them inverse solubility, d. H. nonionic surfactants dissolve at low temperatures while they in the heat by breaking polar hydrogen bonds and are therefore suitable especially for the production of liquid detergents.

Usually, ethoxylated fatty alcohols are used for the production of detergents, each but with a number of particularly stubborn stains, such as B. Make up or lipstick Have weaknesses. Incorporation into solid detergents, especially detergent tablets is associated with problems because the fatty alcohol ethoxylates have a tendency to bleed out, d. H. separate from the homogeneous preparation, which is a whole series of undesirable additions effects: the washing power is reduced, the cardboard is softened and not infrequently Partially deactivated defoamer used.

In this context, reference is made to the European patent EP-B1 0586323 (Kao), from the mixtures, the ethoxylated partial glycerides with defined mono / di / triester distribution and Contain glycerol ethoxylates in a weight ratio of 1: 3 to 3: 1, and their use as Detergent is known.  

Accordingly, the complex object of the present invention has been to create new nonionic Surfactants for the manufacture of solid or liquid washing, rinsing and cleaning agents, preferably two se to provide such in tablet form, which reliably the above disadvantages avoid.

Description of the invention

The invention relates to the use of ethoxylation products of partial glycerides Production of detergents, dishwashing detergents and cleaning agents, which are characterized in that they are made of Mixtures of partial glyceride ethoxylates and glycerol ethoxylates in a weight ratio of 3.3: 1 to 6: 1 and preferably 3.5: 1 to 4.5: 1.

It has been found that the ethoxylation products are particularly critical Soiling such as make-up or lipstick even at low temperatures have a particularly high cleaning ability. This was not to be expected since the Prior art teaches that mixtures of ethoxylated partial glycerides and glycerol ethoxylates have sufficient washing power only up to a weight ratio of 3: 1 maximum. The invention also includes the finding that the mixtures are stable in solid formulations conditions, especially in detergent tablets, d. H. there is no bleeding nor the defoamer is deactivated.

Ethoxylation products of partial glycerides

The ethoxylation products of partial glycerides are known substances, such as those described for example in BE 866868 (Ashland Oil, cited from Derwent Abstract 82097A / 46) and the German patent DE-C320 24 051 (Henkel). Partial alglycerides of the formula (I) are usually used,

in which R ¹ CO represents a linear or branched, saturated or unsaturated acyl radical having 6 to 22, preferably 12 to 18 carbon atoms and R ² and R ³ independently of one another are R ¹ CO or hydrogen, with the proviso that either R ² or R ³ means hydrogen. It is therefore technical mono- and diglyceride mixtures, which are usually obtained by alkali-catalyzed transesterification of corresponding triglycerides with glycerol and optionally subsequent purification by molecular distillation. Such products are commercially available, for example, under the Monomuls® brand (Cognis Deutschland GmbH / DE). The monoglyceride content in these starting materials is usually in the range from 65 to 90% by weight, the difference consists essentially of diglyceride; In addition, small amounts of the starting triglyceride may also be present due to the manufacturing process. The partial glycerides are then subjected to ethoxylation, which can be carried out in a manner known per se. To this end, the starting materials are usually placed in a pressure reactor, the alkaline catalyst, for example sodium methylate or calcined hydro talcite, is added, and the desired amount of ethylene oxide is pressed on. As a rule, an average of 1 to 50 and preferably 5 to 20 moles of ethylene oxide are added per mole of partial glyceride. The temperature is usually in the range of 110 to 180 ° C, the autogenous pressure can rise up to 5 bar gene. After the required amount of ethylene oxide has been given up and the pressure has reached a constant value, it is left for about 30 minutes after-react before the autoclave is cooled, relaxed and the alkaline catalyst is neutralized or filtered, for example by adding lactic acid.

The addition of catalyst can be dispensed with in the ethoxylation if a sufficient amount of alkali is still present from the previous transesterification. At the same time it is clear that considerable changes in the mono / di / triglyceride ratio can occur in the course of the ethoxylation, since the addition of the ethylene oxide runs parallel to a further transesterification. Accordingly, it makes no sense to specify a preferred distribution within the partial glyceride before ethoxylation. The distribution of

46 to 90 wt% monoester
9 to 30% by weight of diesters and
1 to 15% by weight of trieste

with the proviso that the quantities add up to 100% by weight - rather refers to the mixture obtained after the ethoxylation. In which way the ethylene oxide groups affect the Distributing a molecule is difficult to prove analytically. However, it can be assumed that it when using homogeneous alkaline catalysts essentially an addition to the free hydroxyl groups and is only subordinate to an insertion into the carbonyl ester bond. Furthermore, in the case of ethoxylation, the addition to primary versus secondary hydroxyl groups may be preferred. Are heterogeneous catalysts, such as. B. calcined or with fatty acids Hydrophobicized hydrotalcite used, it can also form significant amounts of In sertion products come. As already explained above, another takes place during the ethoxylation Transesterification instead, in the course of which free glycerol is also formed. This stands with the partial glyce ride in the addition of ethylene oxide in competition, with the greater number of free, before naturally preferred primary hydroxyl groups even a preference for the formation of glycerol  ethoxylates exist. Corresponding products are, for example, under the Cetiol® brand HE (Cognis Deutschland GmbH) in the trade.

In an alternative process, the mixtures can also be prepared by first Step triglycerides with ethylene oxide - that is, an insertion into the ester group - and the Transesterification with fatty acids or fatty acid alkyl esters in the second step. A description Such a procedure can be found, for example, by Ropuszynski in IV International Conference on interfacially active substances, Berlin, 1974, essays by the Academy of Sciences the GDR, born in 1976, No. 1N, Akademieverlag Berlin, 1977, pp. 119-121.

Industrial applicability

As already explained, the ethoxylation products can be used for the production of both liquid and solid preparations are used and are usually used in amounts of 1 to 30, preferably 2 up to 15 and in particular 5 to 10% by weight, based on the composition. The preparations can NEN also contain a variety of other common auxiliaries and additives.

Surfactants

Primary components of solid, such as liquid washing, rinsing, cleaning and finishing agents, which are listed below Use of the ethoxylated partial glycerides can be prepared are anionic, non-ionic cal, cationic, amphoteric and / or zwitterionic surfactants, but are preferably anionic Surfactants or combinations of anionic and nonionic surfactants present. Typical case games for anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, Al kyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty al alcohol ether sulfates, glycated ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fat acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfo triglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosi nates, fatty acid taurides, N-acylamino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable Wheat-based products) and alkyl (ether) phosphates. If the anionic surfactants Polygly contain colether chains, these can be a conventional Ho, but preferably a restricted Ho have molog distribution. Alkylbenzenesulfonates, alkylsulfates, soaps and alkanes are preferred sulfonates, olefin sulfonates, methyl ester sulfonates and mixtures thereof.  

Preferred alkylbenzenesulfonates preferably follow the formula (I)

R ⁴ -Ph-SO ₃ X ¹ (II)

in which R ^{4 is} a branched but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X ^{1 is} an alkali metal and / or alkaline earth metal, ammonium, alkyl ammonium, alkanolammonium or glucammonium. Of these, dode cylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts are particularly suitable.

Alkyl and / or alkenyl sulfates, which are also frequently 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 (III)

R ⁵ O-SO ₃ X ² (III)

in which R ^{5 is} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X ^{2 is} an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples of alkyl sulfates that can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, arylselyl alcohol, elaidyl alcohol Gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis. The sulfation products can preferably be used in the form of their alkali salts and in particular their sodium salts. Alkyl sulfates based on C _16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts are particularly preferred. In the case of branched primary alcohols it is 0xoalko hole, as z. B. accessible by reaction of carbon monoxide and hydrogen to alpha-olefins by the shop process. Such alcohol mixtures are commercially available under the trade name Dobanol® or Neodol®. Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45®. Another possibility are oxo alcohols, such as those obtained after the classic Enichema or Condea oxo process by adding carbon monoxide and hydrogen to olefins. These alcohol mixtures are a mixture of highly branched alcohols. Such alcohol mixtures are commercially available under the trade name Lial®. Suitable alcohol mixtures are Lial 91®, 111®, 123®, 125®, 145®.

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

R ⁶ CO-OX ³ (IV)

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

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

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

R ⁷ O (CH ₂ CHR ⁸ O) _n1 H (V)

in which R ^{7 represents} a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R ^{8 represents} hydrogen or methyl and n1 represents numbers from 1 to 20. Typical examples are the addition products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide onto capro alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostyl alcohol , Elaidyl 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 (VI)

R ⁹ CO- (OCH ₂ CHR ¹⁰ ) _n2 OR ¹¹ (VI)

in which R ⁹ CO is a linear or branched, saturated and / or unsaturated acyl radical with 6 to 22 carbon atoms, R ¹⁰ for hydrogen or methyl, R ¹¹ for linear or branched alkyl radicals with 1 to 4 carbon atoms and n2 for numbers from 1 to 20 stands. Typical examples are the formal insert products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, calcium acid , 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and behenic acid and behenic acid and behenic acid. The products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for. B. Calcined hydrotalcite. Reaction products of an average of 5 to 10 moles of ethylene oxide into the ester linkage of technical coconut fatty acid methyl esters are particularly preferred.

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

R ¹² O- [G] _p (VII)

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

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

in which R ¹³ CO represents an acyl radical with 6 to 22 carbon atoms, R ¹⁴ and R ¹⁵ independently of one another for hydrogen or R ¹³ CO, R ^{16 represents} an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _m4 H- Group, m1, m2 and m3 in total for 0 or numbers from 1 to 12, m4 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, as they occur, for example, in the pressure splitting of natural fats and oils. Technical C _12/18 coconut _fatty acids and in particular partially hardened C _16/18 tallow or palm fatty acids as well as high elaidic acid C _16/18 fatty acid cuts are preferably used. The fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters. With regard to the application properties of the ester quats, an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1, has proven to be particularly advantageous. The preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C _16/18 tallow or palm fatty acid (iodine number 0 to 40 ). From an application point of view, quaternized fatty acid triethanolamine ester salts of the formula (VIII) have proven to be particularly advantageous in which R ¹³ CO is an acyl radical having 16 to 18 carbon atoms, R ^{14 is} R ¹³ CO, R ^{15 is} hydrogen, R ^{16 is} a methyl group , m1, m2 and m3 for 0 and Y for methyl sulfate.

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

in which R ¹⁷ CO for an acyl radical with 6 to 22 carbon atoms, R ¹⁸ for hydrogen or R ¹⁷ CO, R ¹⁹ and R ²⁰ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m1 and m2 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 (X) should be mentioned as a further group of suitable ester quats,

in the R ²¹ CO for an acyl radical with 6 to 22 carbon atoms, R ²² for hydrogen or R ²¹ CO, R ²³ , R ²⁴ and R ²⁵ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m1 and m2 in sum 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 (XI) based on diethylenetriamine,

in which R ²⁶ CO stands for an acyl radical with 6 to 22 carbon atoms, R ²⁷ for hydrogen or R ²⁶ CO, R ²⁸ and R ²⁹ 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).

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

in which R ³⁰ for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R ³¹ for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ³² for alkyl radicals with 1 to 4 carbon atoms, q1 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, De cyldimethylamin, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C kyldimethylamin _12/14 -Kokosal, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, Stearylethylmethyl amine, oleyl dimethyl amine, C _16/18 tallow alkyl dimethyl amine and technical mixtures thereof .

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

in the R ³³ CO for an aliphatic acyl radical with 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R ³⁴ for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ³⁵ for alkyl radicals with 1 to 4 carbon atoms, q2 for numbers from 1 to 3, q3 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, palm oleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gadoleic acid, arachachic acid Behenic acid and erucic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylamino propylamine, which are condensed with sodium chloroacetate. The use of a condensation product of C _8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate is preferred.

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

Builder

The washing, rinsing, cleaning and finishing agents according to the invention can furthermore additionally che contain inorganic and organic builder substances, being inorganic builder sub punch mainly zeolites crystalline layered silicates, amorphous silicates and - if permitted - also Phosphates, e.g. B. tripolyphosphate are used. The amount of co-builder is based on that allowance for preferred amounts of phosphates.

The fine crystalline, synthetic and bound water-containing zeolite frequently used as a detergent builder is preferably zeolite A and / or P. As zeolite P, for example, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P and Y are also suitable. Of particular interest is also a cocrystallized sodium / potassium aluminum silicate composed 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 Is 0 to 20 and preferred values 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 is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171. Further suitable layered silicates are known, for example, from patent applications DE 23 34 899 A1, EP 0026529 A1 and DE 35 26 405 A1. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable layered silicates, which belong to the group of water-swellable smectites, are e.g. B. those of the general formulas

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

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

The preferred builder substances also include amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties. The release delay compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays which have a width of several degrees units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE 44 00 024 A1. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray morphous silicates.

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

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

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure for the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30,000 can be used. A preferred dextrin is described in British patent application GB 9419091 A1. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP 0232202 A1, EP 0427349 A1, EP 0472042 A1 and EP 0542496 A1 as well as from international patent applications WO 92/18542, WO 93/08251, WO 93/16110, WO 94 / 28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known. An oxidized oligosaccharide according to German patent application DE 196 00 018 A1 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Other suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably wise ethylenediamine disuccinate. Glyce are also particularly preferred in this context rindisuccinate and glycerol trisuccinate, as described, for example, in the US patent publications US 4,524,009, US 4,639,325, in European patent application EP 0150930 A1 and Japanese patent application JP 93/339896. Suitable amounts are in Zeolite-containing and / or silicate-containing formulations at 3 to 15% by weight.

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

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

Other preferred copolymers are those described in German patent applications DE 43 03 320 A1 and DE 44 17 734 A1 and preferably monomers acrolein and acrylic have acid / acrylic acid salts or acrolein and vinyl acetate. Are also preferred as others Builder substances include polymeric aminodicarboxylic acids, their salts or their precursors call. Polyaspartic acids or their salts and derivatives are particularly preferred.

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

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

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

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

Bleach

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

As bleach activators, compounds which are aliphatic under perhydrolysis conditions oxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or ge optionally substituted perbenzoic acid result, are used. Substances that are suitable O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl carry groups. Multi-acylated alkylenediamines, in particular tetraacetylethylene, are preferred diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyl oxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5- dihydrofuran and those from German patent applications DE 196 16 693 A1 and DE 196 16 767 A1 known enol esters as well as acetylated sorbitol and mannitol or their in the European The patent application EP 0525239 A1 describes mixtures (SORMAN), acylated sugars derivatives, especially pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaa cetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N- acylated lactams, for example N-benzoylcaprolactam, which are known from international patent applications gen WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498 are known. The hydrophilic sub. Known from German patent application DE 196 16 769 A1 substituted acylacetals and those in German patent application DE 196 16 770 and the internatio Nale patent application WO 95/14075 described acyllactams are also preferably used puts. The combinations known from German patent application DE 44 43 177 A1 conventional bleach activators can be used. Such bleach activators are common Quantity range, preferably in amounts from 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total average. In addition to the conventional ones listed above Len bleach activators or in their place can also those from the European patent specifications EP 0446982 B1 and EP 0453 003 B1 known sulfonimines and / or bleach-boosting agents transition metal salts or transition metal complexes as so-called bleaching catalysts be included. The transition metal compounds in question include in particular those  Manganese, iron, cobalt, rutheni known from German patent application DE 195 29 905 A1 um or molybdenum salt complexes and those from German patent application DE 196 20 267 A1 Known N-analog connections, which is known from German patent application DE 195 36 082 A1 manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, which in the German Patent application DE 196 05 688 manganese, iron, cobalt, ruthenium, molybdenum, Titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, derived from the German Patent application DE 196 20 411 A1 known cobalt, iron, copper and ruthenium amine complexes, the manganese, copper and cobalt described in German patent application DE 44 16 438 A1 Complexes described in the European patent application EP 0272030 A1 cobalt Complexes, the manganese complexes known from European patent application EP 0693550 A1, the manganese, iron, cobalt and copper known from European patent EP 0392592 A1 fer complexes and / or those in the European patent EP 0443651 B1 or the European Patent applications EP 0458397 A1, EP 0458398 A1, EP 0549271 A1, EP 0549272 A1, EP 0544490 A1 and EP 0544519 A1 described manganese complexes. Combinations of bleach activators and Transition metal bleaching catalysts are, for example, from the German patent application DE 196 13 103 A1 and the international patent application WO 95/27775 are known. Bleaching enhancer Transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are in usual amounts, preferably in an amount up to 1 wt .-%, especially of 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the entire mean.

Enzymes

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

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

Graying inhibitors

Graying inhibitors have the task of susceptible to the dirt detached from the fiber in the fleet keep swinging and prevent the dirt from re-opening. Here are what Suitable water-soluble colloids mostly organic in nature, for example the water-soluble salts poly merer carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch ke 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. Next Soluble starch preparations and starch products other than those mentioned above can be used the, e.g. B. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. Prefers However, cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarb oxymethyl cellulose and mixtures thereof, and polyvinyl pyrrolidone, for example in amounts of 0.1 up to 5 wt .-%, based on the agent used.  

Optical brighteners

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

Polymers

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

Defoamer

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

Suitable paraffin waxes are generally a complex mixture of substances without a sharp one Melting point. For characterization, one usually determines its melting range by Differential thermal analysis (DTA) as described in "The Analyst" 87 (1962), 420, and / or his Freezing point. This is the temperature at which the paraffin slowly slows down cooling changes from the liquid to the solid state. Thereby are complete at room temperature liquid paraffins, that is to say those with a solidification point below 25 ° C., are not according to the invention useful. To the soft waxes, which have a melting point in the range from 35 to 50 ° C, preferably belong to the group of petrolates and their hydrogenation products. They are made up of micro crystalline paraffins and up to 70 wt .-% oil together have an ointment-like to plastic firm consistency and represent bitumen-free residues from petroleum processing. Especially be distillation residues (petrolatum stocks) of certain paraffin-based and mixed bases are preferred shear crude oils that are processed into petroleum jelly. It is preferably also a question of from distillation residues of paraffin and mixed base crude oils and cylinder oil distillates Bitumen-free, oily to solid hydrocarbons separated by solvents. They are from half-length very fast, sticky to plastic-solid consistency and have melting points between 50 and 70 ° C. These petrolates are the most important basis for the production of micro waxes. Also suitable are those made from highly viscous, paraffin-containing lubricating oil distillates at the dewax Separation of separated solid hydrocarbons with melting points between 63 and 79 ° C. At These petrolates are mixtures of microcrystalline waxes and high-melting ones n-paraffins. For example, the Paraf known from EP 0309931 A1 can be used finwax mixtures of, for example, 26% by weight to 49% by weight of microcrystalline paraffin wax a solidification point of 62 ° C to 90 ° C, 20 wt .-% to 49 wt .-% hard paraffin with a solid point of 42 ° C to 56 ° C and 2 wt .-% to 25 wt .-% soft paraffin with a solidification point from 35 ° C to 40 ° C. Paraffins or paraffin mixtures are preferably used, which in Solidify the range from 30 ° C to 90 ° C. It should be noted that it is solid even at room temperature Apparent paraffin wax mixtures can contain different proportions of liquid paraffin. In the paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible Lich and preferably completely missing. For example, particularly preferred paraffin wax mixtures at 30 ° C a liquid content of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C. Liquid content of less than 30% by weight, preferably from 5% by weight to 25% by weight and in particular from 5% by weight to 15% by weight, at 60 ° C. a liquid fraction of 30% by weight to 60% by weight, in particular  from 40% by weight to 55% by weight, at 80 ° C. a liquid fraction from 80% by weight to 100% by weight, and at 90 ° C a liquid content of 100 wt .-%. The temperature at which a liquid content of 100% by weight of the paraffin wax is reached, is still particularly preferred paraffin wax mixtures below 85 ° C, especially at 75 ° C to 82 ° C. The paraffin waxes can be petrolatum, act microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.

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

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

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

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

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

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

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

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

Suitable silicones are common organopolysiloxanes, which contain fine-particle silica in turn can also be silanized. Such organopolysiloxanes are, for example described in European patent application EP 0496510 A1. Are particularly preferred Polydiorganosiloxanes and in particular polydimethylsiloxanes, which are known from the prior art are. Suitable polydiorganosiloxanes have an almost linear chain and an oligo Degree of merization from 40 to 1500. Examples of suitable substituents are methyl, ethyl, propyl, Isobutyl, tert. Butyl and phenyl. Also suitable are amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl modified silicone compounds that are both liquid at room temperature as well as resinous. Simethicones, which are Mi mixtures of dimethicones with an average chain length of 200 to 300 dimethylsiloxane  Units and hydrogenated silicates. As a rule, the silicones in general contain and Polydiorganosiloxanes in particular fine-particle silica, which can also be silanized. In particular Suitable for the purposes of the present invention are siliceous dimethylpolysuoxanes. Advantage The polydiorganosiloxanes 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. Before the silicones are preferably used in the form of their aqueous emulsions. As a rule, you give the silicone to the water provided with stirring. If desired, one can increase the viscosity ity of the aqueous silicone emulsions thickeners, as known from the prior art are admit. These can be inorganic and / or organic in nature, particularly preferred are nonionic cellulose ethers such as methyl cellulose, ethyl cellulose and mixed ethers such as methyl hy doxyethylcellulose, methylhydroxypropylcellulose, methylhydroxybutylcellulose and anionic car boxycellulose types such as the carboxymethylcellulose sodium salt (abbreviation CMC). Especially ge suitable thickeners are mixtures of CMC to nonionic cellulose ethers in a weight ratio 80: 20 to 40: 60, in particular 75: 25 to 60: 40. As a rule and especially when adding the be written thickener mixtures are recommended use concentrations of about 0.5 to 10, in particular Special from 2.0 to 6 wt .-% - calculated as a thickener mixture and based on aqueous silicones emulsion. The content of silicones of the type described in the aqueous emulsions is advantageous in the range from 5 to 50% by weight, in particular from 20 to 40% by weight - calculated as Sili cone and based on aqueous silicone emulsion. According to a further advantageous embodiment, he keep the aqueous silicone solutions as thickeners starch, which is accessible from natural sources, for example from rice, potatoes, corn and wheat. The starch is advantageously in amounts of 0.1 to 50 wt .-% - based on silicone emulsion - contain and especially in a mixture with the already described thickener mixtures of sodium carboxymethyl cellulose and a nich tional cellulose ether in the amounts already mentioned. For the production of the aqueous silicone mul sions one expediently proceeds in such a way that the thickening which may be present pre-swell medium in water before adding the silicones. Incorporation of the silicones expediently takes place with the aid of effective stirring and mixing devices.

Explosives

If the solid preparations are, for example, detergent tablets or granules can also contain explosives. This includes substances that shape bodies are added to accelerate their decay when brought into contact with water. Overviews can be found e.g. B. in J. Pharm. Sci. 61 (1972) or Römpp Chemilexikon, 9th edition, Volume 6, p. 4440. The disintegrants can be macroscopically distributed homogeneously in the molded body microscopically, however, they form zones of increased concentration due to the manufacturing process. The preferred disintegrants include polysaccharides, such as. B. natural starch and its deri  vate (carboxymethyl starch, starch glycolates in the form of their alkali salts, agar agar, guar gum, pectins etc.), celluloses and their derivatives (carboxymethyl cellulose, microcrystalline cellulose), polyvinyl pyr rolidone, Kollidon, alginic acid and their alkali salts, amorphous or also partially crystalline layered silica cate (bentonite), polyurethanes, polyethylene glycols and gas generating systems. More explosives means that can be present in the sense of the invention are, for example, the publications WO 98/40462 (Rettenmeyer), WO 98/55583 and WO 98/55590 (Unilever) and WO 98/40463, DE 197 09 991 and DE 197 10 254 (Henkel). Reference is expressly made to the teaching of these writings taken. The moldings can contain the disintegrants in amounts of 0.1 to 25, preferably 1 to 20 and in particular 5 to 15 wt .-% - based on the moldings.

Perfume oils and fragrances

As perfume oils or fragrances, individual fragrance compounds, e.g. B. the synthetic pro Products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used the. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert.- Butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, Benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzylsa licylate. The ethers include, for example, benzyl ethyl ether, the aldehydes z. B. the linear Alka nale with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitro nellal, lilial and bourgeonal, to the ketones z. B. the Jonone, α-Isomethylionon and Methylcedrylke clay, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpi neol, the hydrocarbons mainly include terpenes such as limonene and pinene. Before however, mixtures of different odoriferous substances are used, which together address one Generate the appropriate fragrance. Such perfume oils can also contain natural fragrance mixtures, as they are accessible from plant sources, e.g. B. pine, citrus, jasmine, patchouly, rose or Ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, Cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the agents according to the invention, but they can also be advantageous to apply the fragrances on carriers, which the adhesion of the perfume on the Wä strengthening and slower fragrance release for long-lasting fragrance of textiles For example, cyclodextrins have proven themselves as such carrier materials, the cyclo dextrin-perfume complexes can also be coated with other auxiliaries.  

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

Production of detergents

The detergents obtainable using the additives according to the invention can - if it is are solid preparations - in the form of powders, extrudates, granules or agglomerates are manufactured or used. It can be universal as well as fine or co trade laundry detergent, optionally in the form of compact or super compact. To Her Position of such means are the corresponding methods known from the prior art, ge is suitable. The agents are preferably produced in that different particulate compo components containing detergent ingredients are mixed together. The particulate Components can be spray dried, easily mixed or complex granulated ren, for example fluidized bed granulation. It is particularly preferred that at least one surfactant-containing component is produced by fluidized bed granulation. Further it may be particularly preferred if aqueous preparations of the alkali silicate and the alkali carbonates sprayed together with other detergent ingredients in a drying facility be, whereby granulation can take place simultaneously with the drying.

The drying device into which the aqueous preparation is sprayed can be any Act drying equipment. In a preferred procedure, drying is sprayed drying carried out in a drying tower. The aqueous preparations are in be Known way exposed to a drying gas stream in finely divided form. In patent publications The Henkel company developed an embodiment of spray drying with superheated steam described. The principle of work disclosed there is hereby expressly also the subject of present invention disclosure made. Reference is made here in particular to the following the relevant publications: DE 40 30 688 A1 and the further publications according to DE 42 04 035 A1; DE 42 04 090 A1; DE 42 06 050 A1; DE 42 06 521 A1; DE 42 06 495 A1; DE 42 08 773 A1; DE 42 09 432 A1 and DE 42 34 376 A1. This procedure has already been used in connection with the manufacturer of the defoamer grain presented.

A particularly preferred way of producing the agents is to prepare the precursors To subject fluidized bed granulation ("SKET" granulation). Below is a granulation with simultaneous drying to understand, which is preferably carried out batchwise or continuously. The preliminary products can be used both in the dried state and as an aqueous preparation be set. Fluidized bed apparatuses which are preferably used have base plates with dimensions  gene from 0.4 to 5 m. The granulation is preferably in the range at fluidizing air speeds from 1 to 8 m / s. The granules are preferably discharged from the fluidized bed about a size classification of the granules. The classification can be done using a sieve, for example direction or by an opposite air flow (classifier air), which is regulated so that only particles from a certain particle size are removed from the fluidized bed and smaller particles retained in the fluidized bed. The inflowing air usually settles out of the heated or unheated classifier air and the heated soil air together. The soil air temperature temperature is between 80 and 400, preferably 90 and 350 ° C. Advantageously, at the beginning a starting mass of the granulation, for example a granulate from an earlier test batch, submitted.

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 the ingredients take place in a preferred embodiment of the invention in a press agglomerate process. The press agglomeration process to which the solid premix (dried base detergent) can be realized in various devices. Depending on The type of agglomerator used different press agglomeration divorced. The four most common press agglomes preferred in the context of the present invention ration processes are extrusion, roller pressing or compacting, hole pressing (Pelletizing) and tabletting, so that preferred pressag within the scope of the present invention Glomeration processes Extrusion, roll compacting, pelleting 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 out embodiment of the invention, a binder is used that at temperatures up to 130 ° C, preferably up to a maximum of 100 ° C and in particular up to 90 ° C already completely as a melt lies. The binder must therefore be selected depending on the process and process conditions or the process conditions, especially the process temperature, - if a be correct binder is desired - 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 so even correspond to the temperature of the melting point of the binder. In a preferred out In the embodiment of the invention, the process temperature is significantly above the melting point or above the temperature at which the binder is in the form of a melt. In particular, it is be prefers that the process temperature in the compression step is not more than 20 ° C above the melt 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 to the melting temperature or the softening temperature of the binder of 20 ° C is generally quite sufficient and even higher temperatures are no additional advantages effect parts. 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 white ter advantage that thermally sensitive raw materials, such as peroxy bleach such as Perbo Rat and / or percarbonate, but also enzymes, increasingly without serious loss of active ingredient ver can be worked. 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 temperatu sensitive components of the premix extremely gentle process management, because the pre mixture is only exposed to the higher temperatures for a short time. In preferred press agglomerati 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 ren 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 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 1000 and 4000. Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which in turn have relative molecular weights between 600 and 6000, preferably between 1000 and 4000. For a more precise 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 2000 and 12,000, advantageously around 4000, polyethylene glycols with relative molecular weights below 3500 and above 5000, in particular in combination with polyethylene glycols with a relative molecular weight of around 4000, can be used and such combinations advantageously more than 50 wt .-%, based on the total amount of polyethylene glycols, polyethylene glycols with a relative molecular weight between 3500 and 5000 sen. 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 weight 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 3000 and 30,000, for example around 10,000 are preferred. Polyvinylpyrrolidones are preferably not used as the sole binder, but in combination with others, especially in combination with polyethylene glycols.

The compacted material preferably has temperature immediately after it leaves the production apparatus temperatures do not exceed 90 ° C, with temperatures between 35 and 85 ° C especially before are moving. 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 extruded produced, as for example in the European patent EP 0486592 B1 or interna tional patent applications WO 93/02176 and WO 94/09111 and WO 98/12299 who described the. Here, a solid premix is extruded under pressure and the extrudate after exiting drawn from the hole shape by means of a cutting device to the predeterminable granule dimension cut. The homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to become plastic under the pressure or under the entry of specific work softens and becomes extrudable. Preferred plasticizers and / or lubricants are surfactants and / or Po polymers. To explain the actual extrusion process, we hereby expressly refer to the above referenced patents and patent applications. The premix is preferably used preferably a planetary roller extruder or a 2-shaft extruder or 2-screw extruder fed with co-rotating or counter-rotating screw guide, its housing and  Extruder pelletizing head can be heated to the predetermined extrusion temperature. Under the The premixing is sheared by the extruder screws under pressure, which is preferably at least is at least 25 bar, with extremely high throughputs depending on the device used but can also lie below, compressed, plasticized, in the form of fine strands through the perforated nozzles plate extruded in the extruder head and finally the extrudate by means of a rotating tee knife preferably reduced to approximately spherical to cylindrical granules. The hole The diameter of the perforated nozzle plate and the length of the strand cut are based on the selected granulate dimension matched. In this way, the production of granules is essentially uniform Predeterminable particle size, with the absolute particle sizes being specific may be adapted to the intended purpose. In general, particle diameters are up to maximum at least 0.8 cm preferred. Important embodiments see the production of uniform gra nulates in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from about 0.8 to 3 mm. The length / diameter ratio of the chipped primary granule latex is preferably in the range from about 1: 1 to about 3: 1. It is further preferred that to supply still plastic primary granulate to a further shaping processing step; there edges present on the crude extrudate are rounded off, so that ultimately spherical to approximately spherical extrudate grains can be obtained. At this stage, if desired, small Amounts of dry powder, for example zeolite powder such as zeolite NaA powder, can also be used. This shape can be done in standard rounding machines. It is important to ensure that in only small amounts of fine grain are produced at this stage. A drying, which in the above called prior art documents is described as a preferred embodiment subsequently possible, but not mandatory. It may just be preferred after Compaction step no longer drying. Alternatively, extrusio NEN / pressing also in low pressure extruders, in the Kahl press (from Amandus Kahl) or in Bepex extruder can be carried out. Temperature control in the transition zone is preferred richly designed the screw, the pre-distributor and the nozzle plate so that the melting temperature of the binder or the upper limit of the melting range of the binder is at least reached, but is preferably exceeded. The duration of the temperature influence is in the compressor onsection of the extrusion preferably less than 2 minutes and in particular in one area between 30 seconds and 1 minute.

The detergents according to the invention can also be produced by means of roller compaction become. Here, the premix is deliberately defined between two smooth or with wells Formed rollers metered in and between the two rollers under pressure to form a sheet gene compactate, the so-called Schülpe, rolled out. The rollers practice on the premix high line pressure and can be additionally heated or cooled as required. In the Use of smooth rollers gives you smooth, unstructured sash bands, while through that Using structured rollers correspondingly structured slugs can be generated in  which, for example, certain forms of the later detergent particles can be specified nen. The cuff band is subsequently cut into small pieces by a knock-off and crushing process broken pieces and can be processed in this way to granules, which by white Tere known surface treatment processes refined, especially in approximately spherical can be shaped. The temperature of the roller compaction is also pressing tools, i.e. the rollers, preferably at a maximum of 150 ° C., preferably at a maximum 100 ° C and especially at a maximum of 75 ° C. Particularly preferred manufacturing processes work in roller compacting with process temperatures that 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 bandage by lying. It is further preferred that the duration of the temperature exposure in the compressor area of the smooth rollers or with recesses of a defined shape maximum 2 mi grooves 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. Here the premix is applied to a perforated surface and by means of a pressure-giving body pressed through the holes with plasticization. In conventional embodiments of pellet presses the premix is compressed under pressure, plasticized, using a rotating roller in the form of finer Strands pressed through a perforated surface and finally with a knock-off device to Gra crushed granules. Here are the most varied configurations of pressure roller and perforated die conceivable. For example, flat perforated plates are used as well concave or convex ring matrices through which the material by means of one or more pressure rollers is pressed through. The press rollers can also be conical in the plate devices, in the annular devices can die and press roller (s) in the same or opposite direction have. An apparatus suitable for carrying out the method is described, for example, in German described in DE 38 16 842 A1. The ring matrices disclosed in this document The press consists of a rotating ring die with penetrating press channels and at least one with the inner surface of the press roller, which supplies the die space Presses material through the press channels into a material discharge. Here are ring die and press roll can be driven in the same direction, resulting in reduced shear stress and thus lower temperatures increase of the premix is feasible. Of course, it can also be used for pelleting heatable or coolable rollers are worked to a desired temperature of the premix adjust. The pelleting temperature is also the temperature of the pressing tools Pressure rollers or press rolls, preferably at a maximum of 150 ° C, preferably at a maximum of 100 ° C and especially at a maximum of 75 ° C. Particularly preferred manufacturing processes work with the whale zenkompaktierung with process temperatures that are 10 ° C, in particular a maximum of 5 ° C above Melting temperature or the upper temperature limit of the melting range of the binder.  

Shaped bodies, preferably tablets, are generally produced by Tableting or press agglomeration. The particulate press agglomerates obtained can either used directly as a detergent or previously treated by customary methods and / or processed. The usual post-treatments include powdering gene with fine-particle ingredients of detergents or cleaning agents, whereby the bulk density in general is further increased. However, the process is also a preferred aftertreatment as according to German patent applications DE 195 24 287 A1 and DE 195 47 457 A1, wherein dusty or at least finely divided ingredients (the so-called fines) to the invention according to manufactured particulate process end products, which serve as the core, who glued the and thus means arise which have these so-called fines as an outer shell. Before in part this happens in turn by melting agglomeration. To the melting agglomeration The fine fraction is expressly based on the disclosure in the German patent applications DE 195 24 287 A1 and DE 195 47 457 A1 referenced. In the preferred embodiment of the invention are the solid detergents in tablet form, these tablets in particular from storage and preferably have rounded corners and edges for transport reasons. The base surface of these tablets can be circular or rectangular, for example. Multilayer tablets, in particular tablets with 2 or 3 layers, which can also have different colors, are available all preferred. Blue-white or green-white or blue-green-white tablets are special prefers. The tablets can also contain pressed and unpressed parts. Molded body with a particularly advantageous dissolution rate are obtained when the granular components before pressing, a proportion of particles that have a diameter outside the range of Possess 0.02 to 6 mm, 01606 00070 552 001000280000000200012000285910149500040 0002019958398 00004 01487 of less than 20, preferably less than 10% by weight. Before there is a particle size distribution in the range from 0.05 to 2.0 and particularly preferably from 0.2 up to 1.0 mm.  

Examples

A technical mixture of ethoxylated partial glyceride and glycerol ethoxylate (Coco Monoglyceri de + 7.3 EO, Cetiol® HE, Cognis Deutschland GmbH) was used up to a final content of 41% by weight Glycerin ethoxylate enriched and the washing power of different products in one powder formulation (weight ratio of nonionic surfactant / zeolite A = 1: 4) to different soiling determined on polyester / cotton (refined) fabric. The investigations were carried out in Launder-o- meter (temperature: 40 ° C, dosage: 6 g / l, water hardness 20 ° dH, load: 2 kg). The Washability was determined photometrically against a white standard (barium sulfate); the information the measured values (average of three determinations) are in% remission. The composition of the Ge Mix and the results of the washing tests are summarized in Table 1. Example 1 is according to the invention, example V1 corresponds to the blank value without the addition of surfactant, examples V2 to V4 with different levels of glycerol ethoxylates are used for comparison.

Table 1

Composition of ethoxylated partial glycerides and washing performance (quantities as% by weight)

Claims (5)

1. Use of ethoxylation products of partial glycerides for the production of washing, rinsing and cleaning agents, characterized in that they consist of mixtures of partial glycerol ethoxylates and glycerol ethoxylates in a weight ratio of 3.3: 1 to 6: 1. 2. Use according to claim 1, characterized in that partial glycerides of the formula (I) are used,
in which R ¹ CO is a linear or branched, saturated or unsaturated acyl radical having 6 to 22 carbon atoms and R ² and R ³ independently of one another are R ₁ CO or hydrogen, with the proviso that either R ² or R ^{3 is} hydrogen. 3. Use according to claims 1 and / or 2, characterized in that plant tion products of an average of 1 to 50 mol ethylene oxide of partial glycerides. 4. Use according to at least one of claims 1 to 3, characterized in that partial glyceride ethoxylates are used which
46 to 90 wt% monoester
9 to 30% by weight of diesters and
1 to 15% by weight of trieste
with the proviso that the quantities add up to 100% by weight. 5. Use according to at least one of claims 1 to 4, characterized in that one the ethoxylation products in amounts of 1 to 30 wt .-% - based on the agent - used.