DE10353986A1 - Surfactant granules with hydrophobic ingredients - Google Patents

Abstract

Surfactant granules containing at least one support material, at least one surfactant and at least hydrophobic solvent which is liquid at 25 ° C., the weight ratio of the solvent (s) to the granule-containing surfactant (s) being> 2: 1, are characterized by a improved cleaning performance on hydrophobic soiling.

Description

The The present invention relates to a surfactant granule, a process for its production and the use of these granules for Improving the cleaning of soiled textiles.

granular Detergents usually contain in addition to the ingredients indispensable for the washing process like surfactants and builders usually other ingredients, which can be summarized by the term washing aids and the different drug classes such as foam regulators, Graying inhibitors, bleaching agents, bleach activators and dye transfer inhibitors include.

in the As washing temperatures fall, washing and cleaning becomes active Surfactant granules and detergent and detergent compositions containing such granules ever higher Requirements regarding the solubility and the primary and secondary washing assets, in particular the Fettauswaschbarkeit, provided. Greasy soils like body fat or collar dirt that used to be already by the higher ones Washing temperatures were converted into easily dispersible forms, have to dispersed at lower temperatures by the detergent and can be removed. In this case, in the prior art, in particular anionic surfactants and alkoxylated anionic surfactants for Proposed surfactant granules with high Fettauswaschvermögen.

Out the European Patent EP-B-0 698 658 (Procter & Gamble) are detergent compositions known, which have improved fat and Ölauswaschvermögen. These compositions contain from 1 to 90% by weight of an anionic Alkylbenzenesulfonate-free surfactant system of at least 30 wt .-% an alkoxylated alkyl sulfate having an average degree of alkoxylation from 0.1 to 10, whereby defined weight ratios of mono-, di-, tri- and higher alkylated fatty alcohol sulfates present. The teaching of EP-B-0 698,659 (Procter & Gamble) extends this surfactant system to use less than 40% by weight of alkylbenzenesulfonate (ABS). Also the ABS-containing Detergent composition has improved wash-off capability for oil and grease stains on.

Of the Use of water-insoluble liquids such as hydrocarbons for improving the dispersibility of a Nonionic surfactant contained in the detergent is disclosed in WO02 / 092748 (Procter & Gamble). The surfactant granules described there contain up to 50% by weight. Nonionic surfactant and up to 40% by weight of liquid hydrocarbon, wherein The relationship which is mutually 5: 1 to 1: 2.

Of the The present invention was based on the object, a surfactant granules to provide that through improved cleaning performance distinguished by hydrophobic contamination. This should be greasy soil especially completely removed even at low washing temperatures become. It has now been found that the called task complex solve by one is hydrophobic, liquid solvent incorporated in certain amounts in surfactant granules.

object The present invention is in a first embodiment a surfactant granules containing at least one carrier material, at least one Surfactant and at least one hydrophobic, liquid at 25 ° C solvent, wherein the weight ratio of the / solvent to which the surfactant (s) contained in the granulate is> 2: 1.

The Inventive surfactant granules contains at least three ingredients: carrier material, surfactant and hydrophobic, at 25 ° C liquid Solvent. According to the invention the latter two ingredients in certain proportions used to each other. Particularly preferred are tenisdgranulated according to the invention, where the weight ratio of the solvent (s) to the surfactant (s) contained in the granules> 3: 1, preferably> 4: 1, more preferably> 5: 1, more preferably> 7.5: 1, more preferably> 10: 1 and in particular> 12: 1 is.

The surfactant granules according to the invention may of course also contain more than one support material, for example a mixture of two or three support materials. Likewise, mixtures of several surfactants and also several different hydrophobic, liquid at 25 ° C solvent may be included. In addition to these ingredients, the granules of the invention may of course contain other ingredients of detergents or cleaners, which, for example, from the groups of laundry detergents such as enzymes, foam regulators, grayness inhibitors, bleaches, bleach activators or color transfer inhibitors, or from the group of dyes, fragrances, polymers, etc.

The surfactant granules according to the invention contain at least one hydrophobic, liquid at 25 ° C solvent. "Liquid at 25 ° C" means in this Context that the relevant solvents at 25 ° C pourable is and preferably a viscosity (Brookfield viscometer, LVT-II at 20 rpm and 25 ° C, spindle 3) below 10,000 mPas. Preference is given to solvents, the viscosities of 500 to 5000 mPas at 25 ° C. using the method mentioned above, preferably 1000 to 4000 mPas and in particular from 1300 to 3000 mPas have.

"Hydrophobic Solvent "means in the context the present invention that the solvent not completely is miscible with water. Preferred tenish granules according to the invention are characterized in that the solvent a LogP value (logarithm of the distribution coefficient of the solvent in water / 1-octanol)> 4 having.

The or the hydrophobic solvents be in preferred surfactant granules according to the invention in certain Quantities used. Here, tenis granules according to the invention are preferred, from 1 to 60% by weight, preferably from 5 to 50% by weight, more preferably 10 to 40% by weight and in particular from 25 to 35% by weight of hydrophobic solvents which are liquid at 25 ° C., contain.

The Solvent, according to the invention in the Surfactant granules may contain different Substance classes come. Preferred hydrophobic solvents are, for example Fatty alcohols, fatty acid esters, Alkanes, alkenes, alkenols, etc. Particularly preferred representatives described below.

Fatty alcohols are obtained from the relevant fatty acids or fatty acid mixtures by high-pressure hydrogenation of the fatty acid methyl esters. The fatty acids, whose methyl esters are high pressure hydrogenated to the fatty alcohols, are technically largely derived from native fats and oils by hydrolysis. While the alkaline saponification already carried out in the past century led directly to the alkali salts (soaps), today only large amounts of water are used for cleavage, which cleaves the fats into glycerol and the free fatty acids. Alternatively, the cleavage can be performed with methanol to directly recover the methyl esters and glycerol. Examples of industrially applied processes are the autoclave cleavage or continuous high pressure cleavage. For example, hexanoic acid (caproic acid), heptanoic acid (capnonic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc. are preferred in the context of the present invention as the basis for the fatty alcohols the use of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotanoic acid (melissic acid) and Unsaturated Sezies 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidinic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 12t octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c octadecatreic acid For reasons of cost, it is preferable not to use the pure species, but technical mixtures of the individual acids, as they are accessible from lipid cleavage. Such mixtures are for example coconut oil (about 6 wt .-% C ₈ , 6 wt .-% C ₁₀ , 48 wt .-% C ₁₂ , 18 wt .-% C ₁₄ , 10 wt .-% C ₁₆ , 2 wt % C ₁₈ , 8% by weight C _{18 '} , 1% by weight C _{18 "} ), palm kernel oil fatty acid (about 4% by weight C ₈ , 5% by weight C ₁₀ , 50% by weight). % C ₁₂ , 15 wt .-% C ₁₄ , 7 wt .-% C ₁₆ , 2 wt .-% C ₁₈ , 15 wt .-% C _{18 '} , 1 wt .-% C _18'' ), tallow fatty acid ( about 3 wt .-% C ₁₄ , 26 wt .-% C ₁₆ , 2 wt .-% C _{16 '} , 2 wt .-% C ₁₇ , 17 wt .-% C ₁₈ , 44 wt .-% C _{18 '} , 3 wt .-% C _18'' , 1 wt .-% C _18''' ), hardened tallow fatty acid (about 2 wt .-% C ₁₄ , 28 wt .-% C ₁₆ , 2 wt .-% C ₁₇ , 63 wt .-% C ₁₈ , 1 wt .-% C _{18 '} ), technical oleic acid (about 1 wt .-% C ₁₂ , 3 wt .-% C ₁₄ , 5 wt .-% C ₁₆ , 6% by weight C _{16 '} , 1% by weight C ₁₇ , 2% by weight C ₁₈ , 70% by weight C _18' , 10% by weight C _{18 "} , 0.5% by weight % C _{18 '''} ), technical palmitic / stearic acid (about 1 wt .-% C ₁₂ , 2 wt .-% C ₁₄ , 45 wt .-% C ₁₆ , 2 wt .-% C ₁₇ , 47 wt. % C ₁₈ , 1% by weight C _{18 '} ) and soybean oil fatty acid (about 2% by weight C ₁₄ , 15 wt .-% C ₁₆ , 5 wt .-% C ₁₈ , 25 wt .-% C _{18 '} , 45 wt .-% C _18'' , 7 wt .-% C _18''' ).

Accordingly, suitable fatty alcohols are hexanol, heptanol, octanol, nonanol, decanol, undecanol, etc. Preferred in the context of the present invention is the use of fatty alcohols such as dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, docosanol, tetracosanol, hexacosanol, triacotanol and the unsaturated Sezies 9c-hexadecenol, 6c-octadecenol, 6t-octadecenol, 9c-octadecenol, 9t-octadecenol, 9c, 12c-octadecadienol, 9t, 12t-octadecadienol, and 9c, 12c, 15c-octadecatreinol. For cost reasons, it is preferred not to use the pure species, but technical mixtures of the individual fatty alcohol get as they are accessible from lipolysis. Such mixtures are, for example, coconut oil (about 6 wt .-% C ₈ , 6 wt .-% C ₁₀ , 48 wt .-% C ₁₂ , 18 wt .-% C ₁₄ , 10 wt .-% C ₁₆ , 2 wt % C ₁₈ , 8% by weight C _{18 '} , 1% by weight C _{18 "} ), palm kernel oil fatty alcohol (about 4% by weight C ₈ , 5% by weight C ₁₀ , 50% by weight). % C ₁₂ , 15 wt .-% C ₁₄ , 7 wt .-% C ₁₆ , 2 wt .-% C ₁₈ , 15 wt .-% C _{18 '} , 1 wt .-% C _18'' ), tallow fatty alcohol ( about 3 wt .-% C ₁₄ , 26 wt .-% C ₁₆ , 2 wt .-% C _{16 '} , 2 wt .-% C ₁₇ , 17 wt .-% C ₁₈ , 44 wt .-% C _{18 '} , 3 wt .-% C _18'' , 1 wt .-% C _18''' ), technical oil alcohols (about 1 wt .-% C ₁₂ , 3 wt .-% C ₁₄ , 5 wt .-% C ₁₆ , 6 wt .-% C _{16 '} , 1 wt .-% C ₁₇ , 2 wt .-% C ₁₈ , 70 wt .-% C _18' , 10 wt .-% C _{18 ''} , 0.5 % By weight C _{18 '"} ), technical palmitic / stearic alcohols (about 1% by weight C ₁₂ , 2% by weight C ₁₄ , 45% by weight C ₁₆ , 2% by weight C ₁₇ , 47 wt .-% C ₁₈ , 1 wt .-% C _{18 '} ) and soybean oil fatty alcohol (about 2 wt .-% C ₁₄ , 15 wt .-% C ₁₆ , 5 wt .-% C ₁₈ , 25 wt. % C _{18 '} , 45% by weight C _18'' , 7% by weight C _18''' ).

alternative to fatty alcohols or in addition can do this the surfactant granules according to the invention as hydrophobic solvents fatty acid ester contain. Among these, the methyl esters are particularly preferred but also suitable are the ethyl esters, n-propyl esters, isopropyl esters and the isomeric butyl esters of fatty acids.

preferred Methyl esters are methyl hexanoate, heptanoic, acid methyl ester, nonanoic acid methyl ester, decanoate, Undecansäuremethylester etc .. In the context of the present invention, the use is preferred of fatty acid methyl esters such as dodecanoate, tetradecanoic, hexadecanoic, octadecanoic, Eicosansäuremethylester, Docosansäuremethylester, tetracosanoate, Hexacosansäuremethylester, Triacotansäuremethylester as well as the unsaturated Sezies 9c-hexadecenoic acid methyl ester, 6c-octadecenoic acid methyl ester, 6t-octadecenoic acid methyl ester, 9c-Octadecensäuremethylester, 9t octadecenoic acid methyl ester, 9c, 12c-octadecadienoic acid methyl ester, 9t, 12t-Octadecadiensäuremethylester and 9c, 12c, 15c octadecate, methyl ester. For cost reasons it is preferable not to use the pure species but to esterify technical mixtures of the individual acids, as they accessible from lipolysis are. Such esterified mixtures are, for example, coconut oil fatty acid methyl ester, Palmkernölfettsäuremethylester, tallow, hardened tallow, technical palmitic / stearic acid methyl ester as well as soybean oil fatty acid methyl ester and rapeseed oil methyl ester.

suitable Ethyl esters are ethylhexylate, heptanoic, octanoate, -nonanoic acid ethyl ester, ethyl decanoate, Undecansäureethylester etc .. In the context of the present invention, the use is preferred of fatty acid ethyl esters such as dodecanoic acid ethyl ester, Tetradecansäureethylester, Hexadecansäureethylester, Octadecansäureethylester, Eicosansäureethylester, Docosansäureethylester, Tetracosansäureethylester, Hexacosansäureethylester, Triacotansäureethylester as well as the unsaturated Sezies 9c-hexadecenoic acid ethyl ester, 6c-Octadecensäureethylester, 6t-octadecenoic acid ethyl ester, 9c-octadecenoic acid ethyl ester, 9t-Octadecensäureethylester, 9c, 12c-Octadecadienoic acid ethyl ester, 9t, 12t-octadecadienoic acid ethyl ester and 9c, 12c, 15c-octadecatreoic acid ethyl ester. For cost reasons it is preferable not to use the pure species but to esterify technical mixtures of the individual acids, as they accessible from lipolysis are. Such esterified mixtures are, for example, coconut oil fatty acid ethyl ester, Palmkernölfettsäureethylester, Talgfettsäureethylester, hardened Talgfettsäureethylester, technical palmitic / stearic acid ethyl ester as well as soybean oil fatty acid ethyl ester and rapeseed oil ethyl ester.

Prefers are also hexanoic acid n-propyl esters, Heptanoic acid n-propyl ester, Octanoic acid n-propyl ester, nonanoic acid n-propyl ester, Decanoic acid-n-propyl ester, Undecanoic n-propyl etc .. In the context of the present invention, the use is preferred of fatty acid n-propyl esters like dodecanoic acid n-propyl ester, Tetradecanoic acid n-propyl ester, Hexadecanoic acid n-propyl ester, Octadecanoic acid n-propyl ester, Eicosanoic acid n-propyl ester, Docosanoic acid n-propyl ester, Tetracosanoic acid n-propyl ester, Hexacosanoic acid n-propyl ester, Triacotanoic n-propyl as well as the unsaturated Sezies 9c-hexadecenoic acid n-propyl ester, 6c-octadecenoic acid n-propyl ester, 6t-octadecenoic acid n-propyl ester, 9c-octadecenoic acid n-propyl ester, 9t-octadecenoic acid n-propyl ester, 9c, 12c-octadecadienoic acid n-propyl ester, 9t, 12t-octadecadienoic acid n-propyl ester and 9c, 12c, 15c octadecatreic acid n-propyl ester. For cost reasons it is preferable not to use the pure species but to esterify technical mixtures of the individual acids, as they accessible from lipolysis are. Such esterified mixtures are, for example, coconut oil fatty acid n-propyl ester, palm kernel oil fatty acid n-propyl ester, Tallow fatty acid n-propyl ester, hardened Tallow fatty acid n-propyl ester, technical Palmitic / stearic acid n-propyl ester as well as soybean oil fatty acid n-propyl ester and rapeseed oil n-propyl ester.

It is also possible to use hexanoic acid isopropyl ester, heptanoic acid isopropylate, isobutyl octanoate, isobutyl nonanoate, isobutylic dexanoate, undecanoic acid isopropyl ester, etc. The use is preferred in the context of the present invention of fatty acid isopropyl esters such as dodecane acid isopropyl ester, iso-propyl tetradecanoate, iso-propyl hexadecanoate, iso-propyl octadecanoate, iso-propyl eicosanoate, iso-propyl docosanoate, iso-propyl tetracosanoate, iso-propyl hexacosanoate, triacotanoic acid Iso-propyl Ester and Unsaturated Sezies 9c-hexadecenoic acid iso-propyl ester, 6c-octadecenoic acid iso-propyl ester, 6t-octadecenoic acid iso-propyl ester, 9c-octadecenoic acid iso-propyl ester, 9t-octadecenoic acid iso-propyl ester, 9c, 12c Octadecadienoic acid iso-propyl ester, 9t, 12t-octadecadienoic acid iso-propyl ester and 9c, 12c, 15c-octadecatreic acid iso-propyl ester. For reasons of cost, it is preferred not to use the pure species, but to esterify technical mixtures of the individual acids, as they are accessible from lipolysis. Such esterified mixtures are for example coconut oil fatty acid iso-propyl ester, palm kernel fatty acid iso-propyl ester, tallow fatty acid iso-propyl ester, hardened tallow fatty acid iso-propyl ester, technical palmitin / stearic acid iso-propyl ester and soybean oil fatty acid iso-propyl ester and rapeseed oil iso-propyl ester ,

Further suitable esters are butyl hexanoate, Heptanoic-butyl Octanoic acid butyl ester, nonanoic acid butyl ester, Decanoic-butyl Undecanoic acid ester etc .. In the context of the present invention, the use is preferred of fatty acid butyl esters such as dodecanoic acid butyl ester, tetradecanoic acid butyl ester, Hexadecanoic-butyl Octadecanoic-butyl Eicosanoic-butyl Docosanoic-butyl This acid-butyl Hexacosanoic acid butyl ester, triacotinic acid butyl ester as well as the unsaturated Sezies 9c-hexadecanoic acid butyl ester, 6c-octadecenoic-butyl 6t-octadecenoic-butyl 9c-octadecenoic-butyl 9t-octadecenoic-butyl 9c, 12c octadecadienoic acid butyl ester, 9t, 12t octadecadienoic acid butyl ester and 9c, 12c, 15c octadecanoic acid butyl ester. For cost reasons it is preferable not to use the pure species but to esterify technical mixtures of the individual acids, as they accessible from lipolysis are. Such esterified mixtures are, for example, coconut oil fatty acid butyl ester, Palm kernel oil fatty acid ester, Tallow fatty acid ester, hardened Tallow fatty acid ester, technical palmitic / stearic acid butyl ester as well as soybean oil fatty acid butyl ester and rapeseed oil butyl ester.

When hydrophobic solvent Preference is also given to hydrocarbons, for example Alkanes and alkenes or mixtures thereof.

Preferred alkanes are, for example, unbranched or branched C _5-24 -alkanes. Unmet these are the unbranched or mono- or di-methyl branched alkanes are preferred. In particular, preferred species are:

zusammenfassend sind erfindungsgemäße Tenisdgranulate bevorzugt, die es als Lösungsmittel C_5–24-Kohlenwasserstoffe, vorzugsweise C_5–24-Alkane, enthalten.But also simply ethyl-substituted, double ethyl-substituted as well as mixed methyl and ethyl-substituted alkanes are preferred:

In summary, tenisd granules according to the invention are preferred which contain, as solvent C _5-24 -hydrocarbons, preferably C _5-24 -alkanes.

It is more preferred when the solvent has a specific flash point. Here are surfactant granules according to the invention preferred in which the flash point of the solvent is 40 to 150 ° C, preferably> 75 ° C and in particular> 95 ° C.

When second ingredient, the surfactant granules of the invention contain one or several surfactants. these can from the groups of anionic, nonionic, cationic or come zwitterionic surfactants.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.

Further Suitable anionic surfactants are sulfated fatty acid glycerol esters. Among fatty acid glycerol esters are to understand the mono-, di- and triesters and their mixtures, such as they are produced by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained. Preferred sulfated fatty acid glycerol esters are included the sulphonated products of saturated fatty acids with 6 to 22 carbon atoms, for example the caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or Behenic acid.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C _7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _12-18 . Fatty alcohols with 1 to 4 EO are suitable. They are used in cleaning agents due to their high foaming behavior only in relatively small amounts, for example in amounts of 1 to 5 wt .-%.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

When other anionic surfactants are especially soaps into consideration. Suitable are saturated fatty acid soaps, like the salts of lauric acid, myristic, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow derived soap mixtures.

The including anionic surfactants the soaps can in the form of their sodium, potassium or ammonium salts and as soluble salts organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.

Suitable are also nonionic surfactants.

As nonionic surfactants are preferably used alkoxylated, preferably ethoxylated, especially primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical is linear or preferably methyl-branched in the 2-position may contain or linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ -alcohols with 3 EO or 4 EO, C _9-11 -alcohol with 7 EO, C _13-15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

In addition to these nonionic surfactants, fatty alcohols containing more than 12 EO can also be used become. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

A another class of preferred nonionic surfactants, the either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half from that.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Further suitable surfactants are polyhydroxy fatty acid amides of the formula

wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1–4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder Propxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having from 1 to 8 carbon atoms, with C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.

[Z] is preferably by reductive amination of a reduced sugar obtained, for example, glucose, fructose, maltose, lactose, galactose, Mannose or xylose. The N-alkoxy or N-aryloxy-substituted compounds can by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxyfatty acid amides are transferred.

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, the granules according to the invention contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. Among the preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Especially preferred are agents according to the invention, which contain a nonionic surfactant that has a melting point above room temperature. As a result, preferred granules are thereby characterized in that they nonionic) surfactants) having a melting point above 20 ° C, preferably above of 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, included.

suitable nonionic surfactants, the melting or softening points in said Temperature range, for example, low-foaming nonionic Surfactants which may be solid or highly viscous at room temperature. Become used at room temperature highly viscous nonionic surfactants, it is preferred that these a viscosity above 20 Pas, preferably above 35 Pas and especially above 40 Pas. Also nonionic surfactants which are waxy at room temperature Consistency are preferred.

Prefers as at room temperature fixed to be used nonionic surfactants derived the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary Alcohols and mixtures of these surfactants with structurally complicated built-up surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants stand out beyond that by good foam control.

In a preferred embodiment The present invention is the nonionic surfactant having a Melting point above room temperature an ethoxylated nonionic surfactant, that from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 moles, in particular at least 20 moles of ethylene oxide per Mol alcohol or alkylphenol emerged.

A particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred granules according to the invention contain ethoxylated nonionic surfactant (s) consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).

The nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25% by weight, especially preferably up to 20 wt .-% and in particular up to 15 wt .-% of total molecular weight of the nonionic surfactant. Especially preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, the additional Having polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules makes preferably more than 30% by weight, particularly preferably more than 50% by weight and more preferably more than 70% by weight of the total molecular weight of such Nonionic surfactants. Preferred granules are characterized that she contain ethoxylated and propoxylated nonionic surfactants in which the Propylene oxide units in the molecule up to 25% by weight, preferably up to 20% by weight and in particular to constitute 15% by weight of the total molecular weight of the nonionic surfactant, contain.

Further particularly preferred nonionic surfactants with melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ^® SLF-18 from Olin Chemicals.

A further preferred granules according to the invention contains nonionic surfactants of the formula (VI) R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ], (VI) in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula may be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is to R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

Summarizing the latter statements, granules according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² in which x is from 1 to 30, preferably from 1 to 20 and especially from 6 to 18, are particularly preferred.

Particularly preferred nonionic surfactants have been found to be weak in the context of the present invention foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here granules according to the invention are preferred which contain as non-ionic (s) surfactants) surfactants of the general formula VII R ^{1 is} -O- (CH ₂ -CH ₂ -O) _w - (CH ₂ -CH (R ² ) -O) _x - (CH ₂ -CH ₂ -O) _y - (CH ₂ -CH (R ³ ) -O) _z -H (VII) in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ ; -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently of one another are integers from 1 to 6.

The preferred nonionic surfactants of formula VII can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in formula X above may vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is usually undisplayed, wherein the linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred. Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, preference is given to granules according to the invention in which R ¹ in formula VII is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² or R ^{3 are} independently selected from -CH ₂ CH ₂ -CH ₃ or CH (CH ₃ ) ₂ are suitable. Preferred granules are characterized in that R ² and R ^{3 are} , independently of one another, values of 3 or 4 and y and z are independently of one another values of 1 or 2 for a radical -CH ₃ , w and x.

In summary, nonionic surfactants which have a C _9-15 -alkyl radical with 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units are particularly preferred for use in the agents according to the invention. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula (VIII) R ¹ O [CH ₂ CH (R ³ ) O] _x R ² (VIII) in which R ^{1 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{2 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably between 1 and have 5 hydroxy groups and are preferably further functionalized with an ether group, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2- Butyl radical, x for values between 1 and 40.

In particularly preferred nonionic surfactants of the above formula (XIII), R ^{3 is} H. In the resulting end-capped poly (oxyalkylated) nonionic surfactants of the formula (IX) R ¹ O (CH ₂ CH ₂ O) _x R ² (IX) In particular those nonionic surfactants are preferred in which R ^{1 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, R ^{2 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably have between 1 and 5 hydroxyl groups and x stands for values between 1 and 40.

In particular, those end-capped poly (oxyalkylated) nonionic surfactants are preferred, which according to the formula (X) R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² (X) in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical with 1 have up to 30 carbon atoms R ² , which is a monohydroxylated intermediate group -CH ₂ CH (OH) - adjacent. In this formula, x stands for values between 1 and 40. Such end-capped poly (oxyalkylated) nonionic surfactants can be prepared, for example, by reacting a terminal epoxide of the formula R ² CH (O) CH ₂ with an ethoxylated alcohol of the formula R ¹ O [CH ₂ CH ₂ O] _x-1 CH ₂ CH ₂ OH.

The specified C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned Nonionic surfactants represent statistical averages that are suitable for a specific Product can be a whole or a fractional number. by virtue of the manufacturing process consist of commercial products of the formulas mentioned mostly not from an individual representative, but from mixtures, which is responsible for both the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation averages and resulting in fractional numbers.

Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG). Usable Alkypolyglycoside meet the general formula RO (G) _z , in which R is a linear or branched, especially in the 2-position methyl branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.

Prefers used are linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl residue is a glucose residue and the alkyl residue is an n-alkyl radical.

At Place of said surfactants or in conjunction with them may also cationic and / or amphoteric surfactants are used.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8–28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.As cationic active substances, the agents according to the invention may contain, for example, cationic compounds of the formulas XIX, XX or XXI:

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

In summary are surfactant granules according to the invention preferably 0.25 to 20% by weight, preferably 0.5 to 15% by weight, particularly preferably 0.75 to 10 wt .-% and in particular 1 to 5 % By weight of surfactant (s), with nonionic surfactants being preferred are.

When third mandatory constituent contain the surfactant granules according to the invention one or more support materials. these can For example, come from the group of builders. Preferred surfactant granules according to the invention are characterized in that they 40 to 99 wt .-%, preferably 50 to 80 wt .-% and in particular 60 to 75% by weight of carrier material (a) contain.

Under the carrier materials Particularly preferred are inorganic support materials, and among these the water-insoluble. A preferred surfactant granules according to the invention is characterized in that the support material based on its weight at least 50 wt .-%, preferably at least 65 wt .-% and in particular at least 75 wt .-% water-insoluble comprises inorganic substances, zeolites being preferred.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula nNa ₂ O · (1 - n) K ₂ O · Al ₂ O ₃ · (2 - 2.5) SiO ₂ · (3.5-5.5) H ₂ O can be described. The zeolite can be used both as a builder in a granular compound, as well as to a kind of "powdering" of the entire mixture to be pressed, wherein usually both ways for incorporating the zeolite are used in the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Further suitable carrier materials are, for example, amorphous or crystalline silicates or phosphates:
Suitable crystalline layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in de M is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of 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 Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that in X-ray diffraction experiments the silicates do not give sharp X-ray reflections typical of crystalline substances, but at best one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a dissolution delay compared with the conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

in the For the purposes of the present invention, preferred washing and cleaning agents are characterized in that these Silicate (s), preferably alkali metal silicates, particularly preferably crystalline or amorphous alkali disilicates, in amounts of from 10 to 60% by weight, preferably from 15 to 50% by weight and especially from 20 to 40% by weight, respectively based on the weight of the washing or cleaning agent.

If the agents according to the invention are used as automatic dishwasher detergents, these compositions preferably contain at least one crystalline layered silicate 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 22, preferably from 1.9 to 4, and y is a number from 0 to 33. The crystalline layer-form silicates of the formula (1) are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS, for example Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyaite), Na -SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ . xH ₂ O, Makatite).

Particularly suitable for the purposes of the present invention are agents which contain crystalline sheet silicates of the formula (I) in which x is 2. Of these, especially Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ , natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3H ₂ O, kanemite), Na-SKS-11 (t-Na ₂ Si ₂ O ₅₎ and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ). An overview of crystalline phyllosilicates can be found, for example, in the article published on pages 805-808 in "Soaps Oils-Fette-Wachse, 116 Volume, No. 20/1990".

In the context of the present application, preferred pitch granules have a weight fraction of the crystalline layered silicate of the formula (I) of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular from 0.4 to 10% by weight .-%, each based on the total weight of these agents on. Particular preference is given to those granules which have a total silicate content of less than 7% by weight, preferably less than 6% by weight, preferably less than 5% by weight, more preferably less than 4% by weight, very preferably less than 3% by weight. % and in particular less than 2.5 wt .-%, wherein it is in this silicate, based on the total weight of the silicate contained, preferably at least 70 wt .-%, preferably at least 80 wt .-% and in particular at least 90 Wt .-% of silicate of the general formula NaMSi _x O _{2x + 1} · yH ₂ O is.

Of course it is also a use of the well-known phosphates as builders possible, if such use is not avoided for environmental reasons should be. Among the variety of commercially available Phosphates have the alkali metal phosphates, with particular preference of Pentasodium or pentakalium triphosphate (sodium or potassium tripolyphosphate) in the washing and cleaning industry the greatest importance.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium phosphate, KDP), KH ₂ PO ₄ , is a white salt of 2.33 gcm ^-3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is light soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^-3 , loss of water at 95 °), 7 moles (density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 moles water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which have a density of 1.62 gcm ^-3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56 gcm ^-3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals. Na ₄ P ₂ O ₇ is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.

Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher mol. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are exact according to the invention such as sodium tripolyphosphate, potassium tripolyphosphate or mixtures can be used from these two; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate used according to the invention.

Further possible support materials are the alkali carriers. As alkali carrier For example, alkali metal hydroxides, alkali metal carbonates, Alkali metal bicarbonates, alkali metal sesquicarbonates, the mentioned alkali metal silicates, alkali metal silicates, and mixtures of aforementioned substances, wherein for the purposes of this invention preferably the Alkali carbonates, especially sodium carbonate, sodium bicarbonate or sodium sesquicarbonate. Especially preferred is a builder system containing a mixture of tripolyphosphate and sodium carbonate. Also particularly preferred is a builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.

One Another preferred carrier material to be used is a spray-dried Tower powder. A particularly preferred spray-dried tower powder contains in addition builders nor surfactant (s), binders, etc. Preferred is a surfactant content of the tower powder from 0.5 to 10% by weight (based on tower powder weight). When Binders can be with particular preference use carboxymethylcellulose. Inventive surfactant granules, characterized in that the carrier material is a spray-dried Tower powder is, are preferred embodiments of the present Invention.

The Preparation of surfactant-containing granules is wide in the art describe, in addition to extensive patent literature also on numerous reviews and monographs used can be. Thus, W. Hermann de Groot, I. Adami, G.F. Moretti "The Manufacture of Modern Detergent Powders ", Hermann de Groot Academic Publisher, Wassenaar, 1995 various spray drying, Mixing and granulating process for the production of detergents and cleaners.

Out energetic reasons it is preferred in the context of the present invention, if the surfactant-containing granules not by spray drying, but over a Granulation is made. In addition to the conventional ones Granulation and agglomeration processes that are used in the most diverse Mixed granulators and Mischagglomeratoren be performed can, For example, are also Preßagglomerationsverfahren used. Process in which the surfactant-containing granules Granulation, agglomeration, press agglomeration or a combination of these methods is therefore produced prefers.

The granulation can be carried out in a variety of apparatuses commonly used in the washing and cleaning industry. Thus, it is possible, for example, to use the usual in pharmacy Verrunder. In such turntable apparatus, the residence time of the granules is usually less than 20 seconds. Conventional mixers and mixed granulators are also suitable for granulation. Both high-intensity mixers ("high-shear mixers") and normal mixers with lower speeds of rotation can be used as mixers. Suitable mixers are, for example Eirich ^® mixer Series R or RV (trademark of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi ^® Flexomix, the Fukae ^® FS-G mixers (trade marks of Fukae Powtech, Kogyo Co., Japan), the Lödige ^® FM, KM and CB mixers (trademarks of Lödige Maschinenbau GmbH, Paderborn) or the Drais ^® series T or KT (trademarks of Drais-Werke GmbH, Mannheim). The residence times of the granules in the mixers are in the range of less than 60 seconds, wherein the residence time also depends on the rotational speed of the mixer. In this case, the residence times are shortened accordingly, the faster the mixer runs. Preferably, the residence times of the granules in the mixer / rounder are less than one minute, preferably less than 15 seconds. In slow-running mixers, eg a Lödige KM, residence times of up to 20 minutes are set, wherein residence times of less than 10 minutes are preferred because of the process economy.

Preferred granulation processes for producing surfactant-containing granules are carried out in mixer granulators in which some mixer parts or the entire mixer are heated to temperatures which are at least 20 ° C. above the temperature which the substances to be granulated have at the beginning of the granulation process. So if solids are granulated, which were stored at 20 ° C and reach this temperature in the mixer, it is preferred that some or all mixer parts have at least a temperature of 40 ° C. Overall, however, a temperature of 120 ° C for the mixer parts or the entire mixer should not be exceeded. Be only parts of the mixer to the above temperature heated, so these are preferably the mixer walls or the mixer tools. The former can be brought to the desired temperature by a heatable jacket, the latter by built-in heating elements.

Further is preferred in the preparation of surfactant-containing granules throughout or partially heated mixers the use of non-aqueous granulation aids, in particular nonionic surfactants having a melting point in the Range from 20 to 50 ° C exhibit. By the described preferred granulation process let yourself the bulk density increase the surfactant granules, at the same time undesirable Wandanbackungen be significantly reduced at the mixer walls. The use of surfactant granules prepared in such a way in tablettable premixes leads to Detergents and cleaning agent shaped bodies, which opposite Blends that are conventional produced granules contain, by a further reduced Distinguish disintegration time.

at the process of press agglomeration is the surfactant-containing granules under pressure and under the action of shear forces compressed and thereby homogenized and then shaping of the apparatus discharged. The most technically significant press agglomeration processes are Extrusion, roll compaction, pelletizing and the Tabletting. In the context of the present invention preferred for the production of the surfactant-containing granules used Preßagglomerationsverfahren are extrusion, roll compaction and pelleting.

In a preferred embodiment The invention is the surfactant-containing granules preferably continuously a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with supplied concurrent or counter-rotating screw guide, the housing and its extruder granulating head to the predetermined extrusion temperature can be heated. Under the shear action of the extruder screws, the premix under pressure, which is preferably at least 25 bar, at extremely high enforcement in dependence of the apparatus used but also may be below, compacted, plasticized, in the form of fine strands through the hole nozzle plate extruded in the extruder head and finally the extrudate by means of a rotating bladed knife preferably about spherical to cylindrical granules reduced. The hole diameter of the hole nozzle plate and the strand cut length become thereby on the selected Granule dimension matched. In this embodiment, the production succeeds of granules of a substantially uniformly predictable particle size, wherein in particular, the absolute particle sizes for the intended use customized could be. Important embodiments see here the production of uniform granules in the millimeter range, for example in the range of 0.8 to 5 mm and in particular in the range from about 1.0 to 3 mm. The length / diameter ratio of severed primary Granules is in an important embodiment in the range of about 1: 1 to about 3: 1. Furthermore, it is preferred that the still plastic primary granules to supply a further shaping processing step; there are rounded edges present on Rohextrudat, so that ultimately spherical close to spherical Extrudatkörner can be obtained. Alternatively you can Extrusions / Pressings also in low pressure extruders, in the Kahl press or be performed in the Bextruder.

In a further preferred embodiment The present invention relates to the production process for the surfactant-containing Granules carried out by means of a Walzenkompaktierung. in this connection is the surfactant-containing granules targeted between two smooth or dosed with wells of defined shape rollers and metered between the two rolls under pressure to form a leaf-shaped compactate, the so-called Schülpe, rolled out. Practice the rollers on the premix a high line pressure and can ever as required in addition heated or cooled become. When using smooth rollers to obtain smooth, unstructured Schülpenbänder while through structured the use of structured rolls accordingly Slugs or individual pellets can be produced in which, for example certain forms of the later Granules or shaped bodies can be specified. The scarf band is subsequently through a tee and crushing process into smaller pieces broken and can be processed in this way to granules, the by further known per se surface treatment method on hardened and tempered, especially in approximate spherical Shape can be brought.

In a further preferred embodiment of the present invention, the preparation of the surfactant-containing granules is carried out by means of pelleting. Here, the surfactant-containing granules are applied to a perforated surface and pressed by a pressure-emitting body through the holes. In conventional embodiments of Pelltpressen the surfactant-containing granules is compacted under pressure, plasticized, pressed by means of a rotating roller in the form of fine strands through a perforated surface and finally crushed with a knock-off device to granules. Here are the most diverse Configurations of pressure roller and perforated die conceivable. For example, flat perforated plates are used as well as concave or convex ring matrices, through which the material is pressed through one or more pressure rollers. The press rollers may also be conically shaped in the plate devices, in the annular devices can matrices and press roll (s) have co-rotating or opposite sense of rotation. An apparatus suitable for carrying out the method according to the invention consists of a rotating annular die interspersed by pressing channels and at least one pressing roller operatively connected to its inner surface, which presses the material supplied to the matrix space through the pressing channels into a material discharge. In this case, ring die and pressing roller are drivable in the same direction, whereby a reduced shear stress and thus lower temperature increase of the premix can be realized. Of course, it is also possible to work with pelletizing with heatable or coolable rollers in order to set a desired temperature of the premix.

One Another object of the present invention is the use of surfactant granules containing at least one surfactant and at least a hydrophobic, at 25 ° C liquid solvent contain, to improve the cleaning of hydrophobic polluted Textiles.

Claims (11)

Surfactant granules containing at least one support material, at least one surfactant and at least one hydrophobic, liquid at 25 ° C solvent, characterized in that the weight ratio of the solvent / s / in the granules contained surfactant (s)> 2: 1. Tenis granulate according to claim 1, characterized in that that this weight ratio of the solvent (s) to the surfactant (s) contained in the granules> 3: 1, preferably> 4: 1, more preferably> 5: 1, more preferably> 7.5: 1, more preferably> 10: 1 and in particular> 12: 1 is. Tenisdgranulat according to any one of claims 1 or 2, characterized in that it 1 to 60 wt .-%, preferably 5 to 50 wt .-%, particularly preferably 10 to 40 wt .-% and in particular 25 to 35 wt .-% hydrophobic, at 25 ° C liquid solvent, contains. Tenisdgranulat according to any one of claims 1 to 3, characterized in that it contains as solvent C _5-24 -hydrocarbons, preferably C _5-24 -alkanes. Tenisdgranulat according to one of claims 1 to 4, characterized in that the solvent a LogP value> 4 having. Surfactant granules according to one of claims 1 to 5, characterized in that the Flash point of the solvent 40 to 150 ° C, preferably> 75 ° C and in particular> 95 ° C. Surfactant granules according to one of claims 1 to 6, characterized in that it 0.25 to 20% by weight, preferably 0.5 to 15% by weight, more preferably 0.75 to 10 wt .-% and in particular 1 to 5 wt .-% surfactant (s), wherein nonionic surfactants are preferred. Surfactant granules according to one of claims 1 to 7, characterized in that it 40 to 99 wt .-%, preferably 50 to 80 wt .-% and in particular 60 to 75% by weight of carrier material (a) contains. Surfactant granules according to one of claims 1 to 8, characterized in that the support material based on its weight at least 50 wt .-%, preferably at least 65 wt .-% and in particular at least 75 wt .-% water-insoluble comprises inorganic substances, zeolites being preferred. Surfactant granules according to one of claims 1 to 9, characterized in that the Carrier material spray-dried Tower powder is. Use of surfactant granules which at least a surfactant and at least one hydrophobic, liquid at 25 ° C solvent contain, to improve the cleaning of hydrophobic polluted Textiles.