EP1253193A2 - Solid detergent compositions and the production and use thereof - Google Patents

Abstract

Solid surfactant mixtures (I) with a core containing non-ionic surfactant(s) and a shell containing, as shell substance (II), anionic surfactant(s) or non-ionic surfactant(s) other than those in the core or zwitterionic surfactant(s) or a mixture of at least two of these. Independent claims are also included for the following: (1) Production of (I) by depositing a shell substance (II) from an aqueous solution or a melt onto a solid core of non-ionic surfactant as above, with evaporation of water. (2) Detergents containing (I).

Description

The invention relates to the field of detergents, in particular new coated surfactant compositions for use in detergents, especially in detergent compactates.

State of the art

Detergents and cleaning agents usually contain a mixture of different surfactants there is usually a proportion of nonionic surfactants in such a surfactant mixture. Such non-ionic surfactants are usually in the form of liquids with different viscosities or as solids. With a few exceptions, the latter solid nonionic surfactants usually a sticky surface.

Because of these facts, the incorporation of nonionic surfactants into washing or cleaning was active Preparations have so far had various problems. For the production of common powder As a rule, the nonionic surfactants were used in detergents or cleaning agents Spray drying process sprayed onto the spray tower powder in the spray tower. Alternatively, could the application of nonionic surfactants to a detergent powder also by others, usually for Application of liquid compounds to solids using processes such as spraying in a fluidized bed.

However, this approach is disadvantageous for several reasons. For example, that corresponding nonionic surfactant or a mixture of two or more nonionic surfactants always in liquid form. This is particularly the case with non-ionic surfactants with a higher molecular weight connected with the fact that a corresponding solution of the nonionic surfactant is prepared must be applied to a powder before it is applied in one of the methods described can be. In addition, the handling of nonionic surfactants is rational Manufacture of detergents or cleaning agents cumbersome.

The methods known from the prior art and the products obtainable thereby indicate this further disadvantages.

For example, washing or cleaning agent compactates are often required by the consumer, which are usually said to be in extrudate, granule or tablet form. Become such a compact however, made from the above powders, the nonionic contained therein Surfactants are not permanently integrated in the compact, but tend to migrate. The hike non-ionic surfactants, for example, on the surfaces of the compacts. Such superficially non-ionic Compactates containing surfactants, however, tend to cake. However, this has a particular impact disadvantageously on the decay rate of compactates that migrate contain nonionic surfactants.

In addition, such nonionic surfactants present superficially in the compacts can be used Appropriate packaging material for the compactates penetrate, leading to unsightly stains the packaging material. In addition, such nonionic surfactants are permanent withdrawn from the compact, which reduces the washing or cleaning power.

Various attempts have also been made according to the prior art, surface sticky Detackify surfactant compositions by dusting them with inorganic salts. Problematic However, the effect of such processes is that the abrasion resistance of such pollinated ones Granules left something to be desired, whereby after storage and transportation of such surfactant compositions often forms an undesirable fine dust.

There has therefore been a need for surfactant compositions that meet the above Do not have disadvantages of the surfactant compositions known from the prior art. In particular there was a need for such compositions as a nonionic or a Contain a mixture of two or more nonionic surfactants, such compositions for use in detergents or cleaning agents, especially in detergents or cleaning agents Compacts are suitable and such compacts the above-mentioned, known from the prior art Do not have disadvantages. There was also a need for surfactant compositions the at least one nonionic surfactant or a mixture of two or more nonionic Contain surfactants, such a surfactant composition being used in a wide variety of ways Detergents or cleaning agents are suitable and are in powder form, the powder flowing freely and does not tend to cake even under unfavorable storage conditions.

The present invention is therefore based on the object of such surfactant compositions To make available.

The objects underlying the invention are achieved by a composition and a method solved for their manufacture, as described in the text below.

Description of the invention

The invention therefore relates to surfactant mixtures in solid form which have a core and a shell have, the core at least one nonionic surfactant and the shell as a shell substance at least an anionic surfactant or at least one non-core nonionic surfactant or at least one zwitterionic surfactant or a mixture of two or more of the surfactants mentioned contains.

Nonionic surfactants

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 50, in particular 2 to about 30 or 3 to about 15, moles of ethylene oxide (EO) per mole of alcohol, in which the Alcohol residue may be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched residues in the mixture, such as are usually present in oxo alcohol residues. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-14 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, and mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. 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 coconut alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferred nonionic surfactants, either as the sole nonionic Surfactant or in combination with other non-ionic surfactants as part of the core of Surfactant compositions according to the invention are used, preferably alkoxylated ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, such as those found in the Japanese Patent application JP 58/217598 are described or preferably according to the in the international Patent application WO-A-90/13533 can be prepared.

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkyl polyglycosides which can be used satisfy the general formula RO (G) _z , in which R represents a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G is the Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for 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.

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

The surfactant compositions according to the invention can preferably contain alkyl polyglycosides, where APG surfactant compositions are above 0.2% by weight based on the total Surfactant composition, are preferred. Surfactant compositions suitable according to the invention contain APG in amounts of 0.2 to 10% by weight, preferably in amounts of 0.2 to 5% by weight and especially in amounts of 0.5 to 3% by weight.

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 alkanolamides in the context of the present invention as part of the surfactant compositions according to the invention suitable. The amount of these nonionic surfactants is preferably not more than that Amount of the ethoxylated fatty alcohols contained in a surfactant composition according to the invention, especially not more than half of them.

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.Other suitable nonionic surfactants are polyhydroxy fatty acid amides of the formula (I),

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 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 propoxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, 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 rest.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy substituted Connections can then, for example, according to the teaching of the international application WO-A-95/07331 by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst be converted into the desired polyhydroxy fatty acid amides.

Within the scope of the present invention are the core of the surfactant compositions according to the invention Both liquid and solid nonionic surfactants are suitable. If a surfactant composition according to the invention contains a mixture of two or more nonionic surfactants as the core, so For example, a mixture of such nonionic surfactants can be composed such that it contains both solid and liquid nonionic surfactants, but essentially one overall has a solid physical state. However, it is also provided according to the invention that a surfactant composition according to the invention contains only liquid surfactants in the core. In such Cases it is necessary that the liquid surfactants in the surfactant compositions according to the invention are mounted on a carrier material.

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 sheet silicates, alkali silicates, alkali sulfates, for example sodium sulfate, and alkali phosphates. The alkali silicates are preferably a compound with a molar ratio of alkali oxide to SiO ₂ of 1: 1.5 to 1: 3.5. The use of such silicates results in particularly good grain properties with a 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 can also be used, which are referred to as Aerosil® or Sipemat® are on the market.

Examples of organic carrier materials are polymers such as polyvinyl alcohols, polyvinyl pyrrolidones, Poly (meth) acrylates, polycarboxylates, cellulose derivatives such as cellulose ethers and starch in question. Suitable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, Hydroxyethyl cellulose and so-called mixed cellulose ethers, such as methyl hydroxyethyl cellulose and methylhydroxypropyl cellulose, and mixtures of two or more thereof. Especially suitable mixtures contain, for example, sodium carboxymethyl cellulose and methyl cellulose, wherein the carboxymethyl cellulose usually has a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose a degree of substitution of Has 1.2 to 2 methyl groups per anhydroglucose unit.

The mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ether in weight ratios from 80:20 to 40:60, in particular from 75:25 to 50:50.

Also suitable as a carrier is native starch, which is composed of amylose and amylopectin. As a native Starch is called 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 therefore light accessible. Carrier materials can be one or more of the compounds mentioned above are used, in particular selected from the group of alkali carbonates, alkali sulfates, Alkali phosphates, zeolites, water-soluble sheet silicates, alkali silicates, polycarboxylates, cellulose ethers, Polyacrylate / polymethacrylate and starch. Mixtures of alkali carbonates are particularly suitable, in particular Sodium carbonate, alkali silicates, especially sodium silicate, alkali sulfates, especially Sodium sulfate and zeolites.

If the core of a surfactant composition according to the invention contains a nonionic surfactant, that shows a stability dependent on the pH value, the carrier material should preferably do so be selected that the stability of a corresponding core of an inventive Nonionic compound contained surfactant composition is not affected. So should especially when the core of a surfactant composition according to the invention is non-ionic Surfactant contains a fatty acid alkyl ester, a carrier material can be selected, the stability guaranteed such a connection. Compounds are particularly suitable here as carrier materials, which have an essentially neutral or acidic pH. Especially for such nonionic surfactants, in particular carrier materials suitable for fatty acid methyl ester ethoxylates Examples are zeolites, sodium sulfate, polyacrylates, cellulose, microcrystalline cellulose, carboxymethyl cellulose, Methyl cellulose or starch.

Depending on the physical state of the core of a surfactant composition according to the invention Present surfactant or mixture of two or more surfactants can be the proportion of nonionic Surfactant or nonionic surfactants in the core up to 100 wt .-%. If the core of an invention If the surfactant composition contains a carrier material, the ratio is from Carrier material for nonionic surfactant preferably about 10:90 to about 90:10, for example about 20:80 to about 80:20 or about 30:70 to about 60:40.

Within the scope of a further embodiment of the present invention, an inventive one can Core surfactant composition in addition to a nonionic surfactant or a mixture of two or more nonionic surfactants and optionally a carrier material or one or more further compounds contain. Suitable as a component of the core of the surfactant compositions according to the invention are, for example, anionic surfactants as mentioned in the further text become.

If a surfactant composition according to the invention is essentially an anionic surfactant or a mixture contains two or more anionic surfactants, the ratio of nonionic Surfactants to anionic surfactants preferably about 2:98 to about 50:50 or about 5:95 to about 30:70 if the nonionic surfactant is a liquid product at a maximum of about 30 ° C is. However, the nonionic surfactant has a melting point or melting range of more than about 30 ° C, especially more than about 40 ° C, the ratio of nonionic Surfactants to anionic surfactants preferably about 2:98 to about 90:10 or about 5:95 to about 70:30.

coating substances

A surfactant composition according to the invention has, in addition to a core, as described in the context of existing text has already been described, also an envelope. One in the context of the present Envelope suitable for the invention has one or more envelope substances.

In the context of a preferred embodiment of the present invention are used as coating substances Surfactants selected from the group consisting of olefin sulfonates, ester sulfonates, sulfates based on linear (fatty alcohols and Ziegler alcohols) or branched alcohols (oxo alcohols), Alkane sulfonates, fatty acid monoglyceride sulfates, betaines, alkyl polyglycosides, isethionates, sarcosides, Taurates, fatty alcohol ethoxylates with up to 40 EO units, fatty acid ester ethoxylates with 1 to 5 EO units, polyethylene glycols with a molecular weight of more than about 2000, fatty acid ethylene glycol esters, Acyl lactylates, alkyl oligoglucoside sulfates, protein fatty acid condensates, (in particular herbal products based on soy), alkyl (ether) phosphates and acylated amino acids such as acylglutamate, or mixtures of two or more of them.

The abovementioned compounds which can be used as coating substances can be used within the scope of the present invention Invention individually or as a mixture of two or more substances from one or each several of the substance classes mentioned are used. In a preferred embodiment The present invention uses compounds as coating substances which have a crystalline or amorphous structure. Preferably, the shell contains the invention Surfactant Compositions Surfactants that work at room temperature or in a range up to about 60 ° C or about 50 ° C have a non-sticky surface.

The shell of a surfactant composition according to the invention can also have surfactants which have a pasty or sticky consistency in the temperature range mentioned above. The amount Such surfactants on the entire shell must be such that the shell of the invention Overall, the surfactant composition is not pasty or sticky.

The shell of a surfactant composition according to the invention can consist of one layer or of several Layers. If the shell is built up from a layer, then the shell substances should be chosen such that the above requirements with regard to the stickiness of the outer shell are satisfied. However, if, for example, the shell of a surfactant composition according to the invention has a stickiness which is not the aim in view of the present invention another layer can be applied to such a layer, for example, which regulates the consistency of the casing in such a way that the requirements according to the invention are met are. With regard to the composition of the individual layers of such, from several Layers existing shell, it is only necessary that the composition of the Envelope-forming layers overall meet the above requirements for the ingredients of the envelope enough.

A surfactant composition according to the invention is then used in the context of the present invention referred to as non-sticky when in at a temperature of at least about 20 ° C to about 40 ° C a commercially available big bag remains essentially free-flowing after a storage period of 1 week, this means that the big bag can be emptied without clumping.

In the context of a first embodiment of the present invention, the inventive Surfactant compositions as a coating substance at least one anionic surfactant.

In the context of the present invention, all anionic surfactants are basically anionic Suitable for surfactants. In the context of a preferred embodiment of the present invention at least one anionic surfactant used as a coating substance from the group of the sulfates or Sulfonates.

Suitable surfactants of the sulfonate type are preferably C _8-18 alkylbenzenesulfonates, in particular C _12-18 olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained, for example, from C _8-18 monoolefins with end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of 2-sulfofatty acids (ester sulfonates), for example the 2-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Among fatty acid glycerol esters are to understand the mono-, di- and triesters as well as their mixtures as they are produced by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of triglycerides can be obtained with 0.3 to 2 mol of glycerol. Preferred sulfonated fatty acid glycerol esters are Sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, Caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

The alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₈ -C ₁₈ fatty alcohols, for example C ₁₂ -C ₁₆ fatty alcohols, for example made from 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 this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. In the context of the present invention, the C ₁₂ - C ₁₆ alkyl sulfates and C ₁₂ -C ₁₄ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C _12-18 - Fatty alcohols with 1 to 4 EO are suitable.

Other anionic surfactants suitable in the context of the present invention 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 thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

If the core of a surfactant composition according to the invention contains a nonionic surfactant, that the pH-dependent stability shows, the shell should preferably be designed in such a way that the stability of a corresponding core of a surfactant composition according to the invention contained nonionic compound is not affected. In particular, if the core of a surfactant composition according to the invention is a nonionic surfactant Contains fatty acid alkyl, a shell material can be selected, the stability of such a compound guaranteed. Anionic surfactants which are particularly suitable as coating materials are those which in a form ensuring an essentially neutral or acidic pH. Especially suitable for such nonionic surfactants, in particular for fatty acid methyl ester ethoxylates Wrapping materials are, for example, neutral pastes of anionic surfactants, in particular a neutral one Fatty alcohol sulfate paste. Such a neutral fatty alcohol sulfate paste can be obtained, for example, by that a fatty alcohol sulfate paste present after sulfation with a pH of about 9-10 by stirring in a 50% aqueous solution of citric acid to a pH of about 6 - 7 neutralized.

Within the scope of a further embodiment of the present invention, an inventive one can Surfactant composition as a single coating substance or as part of a mixture of two or more coating substances contain a nonionic surfactant. Nonionic surfactants suitable as coating substances solid non-ionic surfactants with a non-sticky surface. However, it can be in the frame of the present invention, nonionic surfactants are also used as coating substances are liquid or have a sticky surface. In this case, such non-ionic surfactants however, be present in the mixture with at least one second coating substance such that the coating as a whole has a non-sticky surface. Basically, all are non-ionic as a coating substance Suitable surfactants that have already been listed in the context of the present text, provided that they are used alone or ensure a non-sticky surface in a mixture with one or more additional coating substances.

Depending on the desired application of the detergent additives according to the invention the weight ratio of shell to core can vary within a wide range. For example, are suitable Shell to core weight ratios from about 10: 1 to about 1: 100 or about 5: 1 to about 1:50 Within the scope of a preferred embodiment of the present invention, the weight fraction of the Shell on the entire surfactant composition according to the invention about 1 to about 30 wt .-%, for example about 2 to about 20 or about 5 to about 10% by weight. The weight ratio of anionic surfactants in the shell to nonionic surfactants in the core of a surfactant composition according to the invention should be within the scope of a preferred embodiment of the present invention 90:10 to about 10:90 or about 20:80.

The coating substances are preferably water-soluble compounds which further preferably a water solubility at 20 ° C. of at least 0.1 g / l, preferably at least 1 g / l and in particular have at least about 10 g / l

In the context of a further embodiment of the present invention, the envelope of an inventive Surfactant composition in addition to one or more of the above compounds contain yet another coating substance or a mixture of two or more additional coating substances.

These further coating substances are preferably water-soluble compounds, which further preferably has a water solubility at 20 ° C. of at least 1 g / l, preferably at least 5 g / l and in particular at least 10 g / l and advantageously more, for the Use of a surfactant composition according to the invention in washing or cleaning agents useful Have properties, for example the complexation of hardness and heavy metal ions. Alternatively, in principle, meltable compounds also come in instead of the water-soluble ones Question.

The further coating substances are used in particular in the context of a preferred embodiment then used as part of the shell of a detergent additive according to the invention if the The hardness, abrasion resistance or water solubility of the casing can be set to a specific value and this value cannot be achieved with the above-mentioned coating substances.

In a first embodiment of the invention, these substances can be the salts of inorganic Trade mineral acids. Typical examples are the alkali and / or alkaline earth metal salts, aluminum or zinc salts of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid and silica, in particular the alkali sulfate, alkali borates and perborates, the various alkali silicates ("Water glasses") and alkali phosphates to be called. Typical examples are sodium sulfate heptahydrate or borax.

The salts of organic carboxylic acids are also suitable. Typical examples are the alkali and / or Alkaline earth metal salts, aluminum or zinc salts of monocarboxylic acids with 1 to 22 carbon atoms, for example acetic acid, caproic acid, caprylic acid, 2-ethylhexanoic acid or coconut fatty acid or mixtures of two or more of them. The use of sodium acetate is particularly preferred.

Instead of the monocarboxylic acids, corresponding C ₂ -C ₆ dicarboxylic acids can also be used, so that the corresponding salts of succinic acid, maleic acid, fumaric acid, glutaric acid and adipic acid can be used as suitable additional coating substances in the same way as above.

Finally, salts of hydroxy-functionalized polyvalent carboxylic acids can also be used, such as. the above-mentioned salts of malic acid, tartaric acid and especially citric acid. The use of alkali metal citrates is particularly preferred here.

The third group of suitable further coating substances are the water-soluble polymers, at which are, for example, protein hydrolyzates, polyamides, polycarboxylates and polyurethanes can act. Urea and polyurea are also suitable. Saccharides are also suitable and polysaccharides, e.g. Sucrose, maltose or starch hydrolysates. Are particularly preferred here the polycarboxylates, for example copolymers of acrylate / methacrylate, copolymers of Acrylate / maleinate (e.g. Sokalan CP 5, manufacturer: BASF), or polyaspartate.

In the context of a further preferred embodiment of the present invention, the shell has of a detergent additive according to the invention as a further coating substance at least one water-soluble Polymer. Water-soluble polymers are particularly suitable as a component of the Shell of a detergent additive according to the invention if parameters such as hardness, abrasion resistance or water solubility should be affected. The proportion of such a water-soluble polymer is about 0 to about 50% by weight, depending on the desired properties of the casing, based on the entire coating substance, in particular about 1 to about 30 wt .-%, for example about 5 to about 25% by weight.

manufacturing

The surfactant compositions according to the invention can be prepared by processes that already are known for the production of detergents. As part of a first manufacturing process a surfactant core is first produced, which is then mixed with an aqueous solution of the coating substance is brought into contact.

The production of a corresponding surfactant core also runs according to fundamentally known methods Procedure. If it is the core anionic surfactant or mixture from two or more anionic surfactants is a solid, a corresponding one Surfactant core, for example by grinding the surfactant or surfactant mixture to a desired one Size. If it is in the core anionic surfactants or Mixture of two or more anionic surfactants is a liquid, so the production takes place a correspondingly suitable surfactant core, for example by applying the liquid surfactant or surfactant mixture, for example from a suitable solution, to a powder or granule present carrier material with simultaneous drying, e.g. in the fluidized bed process or in a fluidized bed process. Such methods can be used, for example, in conventional mixing apparatus be performed.

A surfactant core produced in this way is then mixed with a solution in a second process step brought into contact with a coating substance or a mixture of two or more coating substances. This is preferably done at higher temperatures, with the coating substance on the surfactant core precipitates and includes it.

A particularly preferred option is to subject the surfactant cores to fluidized bed granulation . This is understood to mean granulation with simultaneous drying, which is preferably carried out batchwise or continuously. The aqueous solutions of the coating materials are introduced simultaneously or in succession through one or more nozzles into a fluidized bed with surfactant cores. Preferably, surfactant cores are blown in continuously via a nozzle and the coating materials are metered in via a second nozzle. This corresponds to a continuous solid / liquid production, but presupposes that appropriate surfactant cores are already available. The SKET process, for example from Glatt and Haase, is particularly suitable. The resulting granulate is divided into size fractions at the same time, in the context of the present invention preferably a good grain fraction in a range from approximately 0.1 to approximately 1.5 mm, in particular approximately 0.2 to approximately 1.2 mm, and a fine fraction (for example <0.1 mm, preferably <0.2 mm) and a coarse fraction (for example> 1.5 mm, preferably> 1.2 mm) is separated off. The coarse fraction is, for example, ground and returned to the SKET process together with the fine fraction.

Fluidized bed apparatuses which are preferably used have base plates with dimensions of 0.4 to 5 m. The granulation is preferably carried out at fluidizing air speeds in the range from 1 to 8 m / s carried out. The granules are preferably discharged from the fluidized bed by means of a size classification the granules. The classification can, for example, by means of a screening device or by an opposite air flow (classifier air), which is regulated so that only particles from a certain particle size removed from the fluidized bed and smaller particles in the fluidized bed be held back. The inflowing air usually settles out of the heated or unheated classifier air and the heated bottom air together. The soil air temperature is there between 80 and 400, preferably between 90 and 350 ° C.

Industrial applicability

Another object of the present invention relates to the use of the invention Surfactant compositions for the production of detergents, preferably in detergents, which in Form of powders, granules, extrudates in or tablets. The present invention relates to hence also detergents which contain a surfactant composition according to the invention.

Further preferred ingredients of such detergents, which are used using the inventive Surfactant compositions are available are inorganic and organic builder substances, whereby as inorganic builder substances mainly zeolites, crystalline layered silicates and amorphous Silicates with image properties and - where permissible - also phosphates, for example tripolyphosphates, are used. The builder substances are preferably those according to the invention Detergents in amounts of about 10 to about 60% by weight, based on the total detergent, contain. If these compounds are water-soluble, they can, for example, also be used as others Envelope substances used in the abovementioned sense in the detergent additives according to the invention become. This applies equally to the silicates, dextrins and polyacrylates described below and the like.

Zeolite A and / or P, which is often used as detergent images and contains no crystalline, synthetic and bound water, 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 which contain two or more zeolites selected from the group consisting of zeolite A, X, P or Y are also suitable. Of particular interest is also a cocrystallized sodium / potassium aluminum silicate from zeolite A and zeolite X, which is commercially available as VEGOBOND AX® (commercial product from Condea Augusta SpA). 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 wt .-%, in particular 20 to 22% by weight of bound water.

(OH)₄Si_8-yAl_y(Mg_xAl_4-x)O₂₀ Montmorrilonit

(OH)₄Si_8-yAl_y(Mg_6-zLi_z)O₂₀ Hectorit

(OH)₄Si_8-yAl_y(Mg_6-zAl_z)O₂₀ Saponit

mit x = 0 bis 4, y = 0 bis 2, z = 0 bis 6. Zusätzlich kann in das Kristallgitter der Schichtsilicate gemäß den vorstehenden Formeln geringe Mengen an Eisen eingebaut sein. Ferner können die Schichtsilicate aufgrund ihrer ionenaustauschenden Eigenschaften Wasserstoff-, Alkali-, Erdalkaliionen, insbesondere Na⁺ und Ca²⁺ enthalten. Die Hydratwassermenge liegt meist im Bereich von 8 bis 20 Gew.-% und ist vom Quellzustand bzw. von der Art der Bearbeitung abhängig. Brauchbare Schichtsilicate sind beispielsweise aus US 3,966,629, US 4,062,647, EP 0026529 A1 und EP 0028432 A1 bekannt. Vorzugsweise werden Schichtsilicate verwendet, die aufgrund einer Alkalibehandlung weitgehend frei von Calciumionen und stark färbenden Eisenionen sind.Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x O2 _{x + 1} * yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP 0164514 A1 . Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ * yH ₂ O are preferred, 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 2334899 A1, EP 0026529 A1 and DE 3526405 A1 . Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable sheet silicates, which belong to the group of water-swellable smectites, are, for example, those of the general formulas

(OH) ₄ Si _8-y Al _y (Mg _x Al _4-x ) O ₂₀ montmorrilonite

(OH) ₄ Si _8-y Al _y (Mg _6-z Li _z ) O ₂₀ hectorite

(OH) ₄ Si _8-y Al _y (Mg _6-z Al _z ) O ₂₀ saponite

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

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

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

Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts , such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. The acids have a builder effect typically also the property of an acidifying component and are therefore also used for adjustment a lower and milder pH value of detergents or cleaning agents. In particular are citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures to name from 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 molar masses in the range from 400 to 500,000. A polysaccharide with a dextrose equivalent ( DE ) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure for the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2,000 to 30,000 can be used. A preferred dextrin is described in British patent application GB 9419091 A1 , The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP 0232202 A1, EP 0427349 A1, EP 0472042 A1 and EP 0542496 A1 as well as from international patent applications WO 92/18542, WO 93/08251, WO 93/16110, WO 94 / 28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known. An oxidized oligosaccharide according to German patent application DE 19600018 A1 is also suitable . A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

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

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

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

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

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

Other suitable ingredients of the detergents according to the invention are water-soluble inorganic Salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses, which are not outstanding Have builder properties, or mixtures of these: especially alkali carbonate and / or amorphous alkali silicate, especially sodium silicate with a molar ratio Na20: SiO2 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5. The content in the invention Detergent on sodium carbonate is preferably up to 40 wt .-%, advantageously between 2 and 35% by weight. The content of sodium silicate in the agent (without special Builder properties) is generally up to 10 wt .-% and preferably between 1 and 8% by weight.

In addition to the ingredients mentioned, the detergents can usually contain other known detergents additives used, for example defoamers, salts of polyphosphonic acids, optical brighteners, Enzymes, enzyme stabilizers, small amounts of neutral filling salts as well as colors and fragrances, Contain opacifiers or pearlescent agents.

The detergents according to the invention preferably contain the defoamers in total amounts of 75 to 99% by weight, preferably from 80 to 95 and in particular from 85 to 90% by weight. With the defoamers can be wax-like compounds and / or silicone compounds. one Embodiments of the present invention are exclusive as defoamers contain waxy defoamer compounds. Such connections are understood to be "waxy" if which have a melting point at atmospheric pressure above 25 ° C (room temperature), preferably have above 50 ° C and in particular above 70 ° C. The wax-like, if any, contained according to the invention Defoamer substances are practically insoluble in water, i.e. at 20 ° C they show 100 g Water has a solubility below 0.1% by weight. In principle, all known from the prior art wax-like defoamer substances can be included. Suitable waxy compounds are, for example, bisamides, fatty alcohols, fatty acids, carboxylic acid esters of mono- and polyvalent ones Alcohols and paraffin waxes or mixtures thereof. Alternatively, you can of course also use the known silicone compounds can be used for this purpose.

Suitable paraffin waxes generally represent a complex mixture of substances without a sharp melting point. For characterization, one usually determines its melting range by differential thermal analysis (DTA), as described in "The Analyst" 87 (1962), 420 , and / or its solidification point , This is the temperature at which the paraffin changes from the liquid to the solid state by slow cooling. Paraffins which are completely liquid at room temperature, that is to say those having a solidification point below 25 ° C., cannot be used according to the invention. For example, the paraffin wax mixtures known from EP 0309931 A1 of, for example, 26% by weight to 49% by weight of microcrystalline paraffin wax with a solidification point of 62 ° C. to 90 ° C., 20% by weight to 49% by weight hard paraffin can be used with a solidification point of 42 ° C to 56 ° C and 2 wt .-% to 25 wt .-% soft paraffin with a solidification point of 35 ° C to 40 ° C. Paraffins or paraffin mixtures which solidify in the range from 30 ° C. to 90 ° C. are preferably used. It should be noted that even paraffin wax mixtures that appear solid at room temperature can contain different proportions of liquid paraffin.

In the paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible and 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.

Bisamides suitable 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. suitable Fatty acids are lauric, myristic, stearic, arachic and behenic acid and mixtures thereof as they are from natural fats or hardened oils, such as tallow or hydrogenated palm oil are. Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, Pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluyiendiamine. preferred Diamines are ethylenediamine and hexamethylenediamine. Particularly preferred bisamides are bismyristoyiethylenediamine, Bispalmitoyiethylenediamine, Bisstearoyiethylenediamine and their mixtures as well the corresponding derivatives of hexamethylenediamine.

Carboxylic acid esters suitable as defoamers are derived from carboxylic acids having 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 part of the carboxylic acid ester contains a mono- or polyhydric alcohol with 1 to 28 carbon atoms in the hydrocarbon chain. Examples of suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut alcohol, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol as well as ethylene glycol, glycerin, 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. Eligible esters of polyhydric alcohols are, for example, xylitol monopalmitate, pentarythritol monostearate, glycerol monostearate, ethylene glycol monostearate and sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan dilaurate, sorbitan dististearate, sorbitan dandghenoate and mixed sorbitan dibehenate, and sorbitan dandebehenate, and sorbitan dandebehenate as well as mixed sorbitan dandebehenate and sorbitan dandebiolate. 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 natural esters suitable 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 carnauba acid alkyl esters, often in combination with small amounts of free carnauba acid, other long-chain acids, high-molecular alcohols and hydrocarbons.

Carboxylic acids which are also suitable as defoamer compounds are, in particular, behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid and mixtures thereof, as can be obtained from natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil. Saturated fatty acids with 12 to 22, in particular 18 to 22, carbon atoms are preferred.

Fatty alcohols which are also suitable as defoamer compounds are the hydrogenated products of the fatty acids described. Dialkyl ethers may also be present as defoamers. The ethers can be constructed asymmetrically or symmetrically, ie contain two identical or different alkyl chains, preferably with 8 to 18 carbon atoms. Typical examples are di-n-octyl ether, di-isooctyl ether and di-n-stearyl ether; dialkyl ethers which have a melting point above 25 ° C., in particular above 40 ° C., are particularly suitable.

Other suitable defoamer compounds are fatty ketones of the formula (III), R 1 -CO-R 2 in which R ¹ and R ² independently of one another represent linear or branched hydrocarbon radicals having 11 to 25 carbon atoms and 0 or 1 double bond. Such ketones are known substances that can be obtained by the relevant methods of preparative organic chemistry. For their preparation, one starts, for example, from carboxylic acid magnesium salts which are pyrolyzed at temperatures above 300 ° C. with the elimination of carbon dioxide and water, for example according to the German laid-open specification DE 2553900 OS . Suitable fat ketones are those which are prepared by pyrolysis of the 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. Hentriacontanon-16; (R ¹ and R ² stands for an alkyl radical with 15 carbon atoms), tritriacontanone-17 (R ¹ and R ² stands for an alkyl radical with 16 carbon atoms), stearone (pentatriacontanone-18; R ¹ and R ² stands for an alkyl radical with 17 Carbon atoms), heptatriacontanone-19 (R ¹ and R ² stands for an alkyl radical with 18 carbon atoms), arachinone (nonatriacontanone-20; R ¹ and R ² stands for an alkyl radical with 19 carbon atoms), hentetracontanone-21 (R ¹ and R ² stands for an alkyl radical with 20 carbon atoms) and / or Behenon (triatetracontanone-22: R ¹ and R ² stands for an alkyl radical with 21 carbon atoms).

Other suitable defoamers are fatty acid polyethylene glycol esters of the formula (IV), R 3 COO (CH 2 CH 2 O) n H in which R ³ CO is a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms and n is a number from 0.5 to 1.5. Such fatty acid polyethylene glycol esters are preferably obtained by base-homogeneously catalyzed addition of ethylene oxide to fatty acids, in particular addition of ethylene oxide to the fatty acids is carried out in the presence of alkanolamines as catalysts. The use of alkanolamines, especially triethanolamine, leads to an extremely selective ethoxylation of the fatty acids, especially when it comes to producing low-ethoxylated compounds. For the purposes of the present invention, preference is given to fatty acid polyethylene glycol esters of the formula (II) in which R ³ CO is a linear acyl radical having 12 to 18 carbon atoms and n is the number 1. Lauric acid ethoxylated with 1 mol of ethylene oxide is particularly suitable. Within the group of fatty acid polyethylene glycol esters, preference is given to those which have a melting point above 25 ° C., in particular above 40 ° C.

According to a further embodiment of the present invention, the detergents according to the invention contain, as defoamers, a mixture of at least one wax-like defoamer, preferably a paraffin wax, and a defoaming silicone compound. For the purposes of the present invention, suitable silicones are conventional organopolysiloxanes which can have a content of finely divided silica, which in turn can also be silanated. Such organopolysiloxanes are described, for example, in European patent application EP 0496510 A1 . Polydiorganosiloxanes which are known from the prior art are particularly preferred. Suitable polydiorganosiloxanes can have an almost linear chain and are characterized according to the following formula (III), where R ^{4 can} independently represent an alkyl or an aryl radical and z can stand for numbers in the range from 40 to 1500. Examples of suitable substituents R ⁴ are methyl, ethyl, propyl, isobutyl, tert-butyl and phenyl. However, compounds crosslinked via siloxane can also be used, as are known to the person skilled in the art under the name silicone resins. As a rule, the polydiorganosiloxanes contain finely divided silica, which can also be silanized. Silica-containing dimethylpolysiloxanes are particularly suitable. The polydiorganosiloxanes advantageously have a Brookfield viscosity at 25 ° C. in the range from 5,000 mPas to 30,000 mPas, in particular from 15,000 to 25,000 mPas. The silicones are preferably applied to carrier materials. Suitable carrier materials have already been described in connection with the paraffins. The carrier materials are generally present in amounts of 40 to 90% by weight, preferably in amounts of 45 to 75% by weight, based on defoamers.

In a further preferred embodiment of the present invention, the Detergent according to the invention as a defoaming compound at least one wax-like compound and a defoaming silicone compound.

(a) mindestens ein Weichwachs mit einem Schmelzpunkt im Bereich von 35 bis 50 °C,

(b) mindestens ein Hartwachs mit einem Schmelzpunkt oberhalb von 50 °C,

(c) gegebenenfalls Silicon und

(d) Trägermaterialien (Soda, Natriumsulfat, Zeolith, Silikat, Stärke, Cellulose etc.).

In a further preferred embodiment of the present invention, the detergents according to the invention contain as a defoaming compound

(a) at least one soft wax with a melting point in the range from 35 to 50 ° C,

(b) at least one hard wax with a melting point above 50 ° C,

(c) optionally silicone and

(d) carrier materials (soda, sodium sulfate, zeolite, silicate, starch, cellulose etc.).

(e) 5 bis 25 Gew.-% mindestens einem Weichwachs mit einem Schmelzpunkt im Bereich von 35 bis 50 °C,

(f) 1 bis 10 Gew.-% mindestens einem Hartwachs mit einem Schmelzpunkt oberhalb von 50 °C,

(g) 1 bis 10 Gew.-% mindestens einem Amidwachs mit einem Schmelzpunkt oberhalb von 100 °C,

(h) 0 bis 10 Gew.-% Siliconen und

(i) ad 100 Gew.-% Trägermaterialien (Soda, Na-sulfat, Zeolith, Silikat, Stärke, Cellulose etc.).

In a further preferred embodiment of the present invention, the detergent additives according to the invention contain as a defoaming compound

(e) 5 to 25% by weight of at least one soft wax with a melting point in the range from 35 to 50 ° C,

(f) 1 to 10% by weight of at least one hard wax with a melting point above 50 ° C,

(g) 1 to 10% by weight of at least one amide wax with a melting point above 100 ° C.,

(h) 0 to 10% by weight of silicones and

(i) ad 100% by weight of carrier materials (soda, sodium sulfate, zeolite, silicate, starch, cellulose etc.).

In a further preferred embodiment of the present invention, the detergents according to the invention contain petrolates or their hydrogenation products as soft wax in the defoamer component. The preferred soft waxes are paraffin mixtures in the C chain range from C ₂₀ to C ₆₀ , with about 80% in the C chain range from C ₂₅ to C ₅₀ . The preferred paraffin mixture contains linear as well as branched paraffins in a ratio of approximately 40:60. The paraffin mixture can also contain hydrogenated paraffins.

In the context of a further preferred embodiment of the present invention, the detergents according to the invention contain microcrystalline waxes as hard wax in the defoamer component which are in the C chain range from C ₂₅ to C ₅₀ and have a softening point of> 50 ° C.

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.

Other suitable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 35% by weight and in particular up to 30% by weight, advantageously using perborate monohydrate or percarbonate.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are polyacylated alkylenediamines, in particular tetraacetylethylene 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, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyloxy, 2,5-diacetyloxy, 2,5-ethylene glycol 2,5-dihydrofuran and the enol esters known from German patent applications DE 19616693 A1 and DE 19616767 A1 as well as acetylated sorbitol and mannitol or their mixtures described in European patent application EP 0525239 A1 (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose , Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkyl ized glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are known from international patent applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95 / 17498 are known.

The hydrophilically substituted acylacetals known from German patent application DE 19616769 A1 and the acyl lactams described in German patent application DE 19616 770 and international patent application WO 95/14075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE 4443177 A1 can also be used. Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent.

In addition to the conventional bleach activators listed above or in their place, the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0446982 B1 and EP 0453 003 B1 can also be present as so-called bleaching catalysts. The transition metal compounds in question include in particular the manganese, iron, cobalt, ruthenium or molybdenum-salt complexes known from German patent application DE 19529905 A1 and their N-analog compounds known from German patent application DE 19620267 A1 , which are known from German Patent application DE 19536082 A1 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium described in German patent application DE 196 05 688 - and copper complexes with nitrogen-containing tripod ligands that from German patent application DE 19620411 A1 known cobalt-, iron-, copper- and ruthenium-ammine complexes, the manganese described in the German patent application DE 4416438 A1, copper and cobalt complexes , in European Patent application EP 0272030 A1 described cobalt complexes known from European patent application EP 0693550 A1 manganese Complexes, the manganese, iron, cobalt and copper complexes known from European patent EP 0392592 A1 and / or those described in European patent EP 0443651 B1 or European patent applications EP 0458397 A1, EP 0458398 A1, EP 0549271 A1, Manganese complexes described in EP 0549272 A1, EP 0544490 A1 and EP 0544519 A1 . Combinations of bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 19613103 A1 and international patent application WO 95/27775 .

Bleach-enhancing transition metal complexes, especially with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru are used in customary amounts, preferably in an amount up to 1% by weight, in particular from 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1 wt .-%, each based on the total agent used.

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

The enzymes can be adsorbed on carriers and / or embedded in coating substances around them protect against premature decomposition. The percentage of enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

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

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

As optical brighteners, the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl-diphenyls, or 4- ( 4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls. Mixtures of the above-mentioned brighteners can also be used. Uniformly white granules are obtained if, apart from the usual brighteners, the agents are used in customary amounts, for example between 0.1 and 0 5% by weight, preferably between 0.1 and 0.3% by weight, also in small amounts, for example 10 ^-6 to 10 ^-3 % by weight, preferably around 10 ^-5 % by weight, of a blue dye A particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).

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

Individual fragrance compounds , for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances . Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexylpropylatepylatepylatepylatepionate, stally. The ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, ulial and bourgeonal, the ketones, for example, the jonones, (α-isomethylionone and methylcedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene, but preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures contain as they are accessible from plant sources, e.g. pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.Muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil are also suitable , 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 it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.

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

manufacturing

The detergents according to the invention obtainable using the additives mentioned can be found in Form of powders, extrudates, granules or tablets can be produced or used. For the production such means, the corresponding methods known from the prior art are suitable. The agents are preferably prepared in that various particulate components, the detergent ingredients are mixed together. The particulate Components by spray drying, simple mixing or complex granulation processes, for example, fluidized bed granulation. It is particularly preferred that at least one surfactant-containing component is produced by fluidized bed granulation. Can continue it may be particularly preferred if aqueous preparations of the alkali silicate and the alkali carbonate are sprayed together with other detergent ingredients in a drying facility, whereby granulation can take place simultaneously with the drying. At the drying facility, in which the aqueous preparation is sprayed on, can be any drying apparatus.

In a preferred process, the drying is carried out as spray drying in a drying tower. The aqueous preparations are exposed to a drying gas stream in finely divided form in a known manner. Patent publications by Henkel describe an embodiment of spray drying with superheated steam. The working principle disclosed there is hereby expressly made the subject of the present disclosure of the invention. Reference is made here in particular to the following publications: DE 4030688 A1 and the further publications according to DE 4204035 A1, DE 4204090 A1, DE 4206050 A1, DE 4206521 A1, DE 4206495 A1, DE 4208773 A1, DE 4209432 A1 and DE 4234376 A1.

In another, especially when high bulk density agents are to be obtained, preferred Variant, the mixtures are then subjected to a compacting step, with further Ingredients are only added to the agents after the compacting step. The compacting of the ingredients takes place in a preferred embodiment of the invention in a press agglomeration process instead of. The press agglomeration process to which the solid premix (dried basic detergent) subject can be realized in various devices. Depending on A distinction is made between the type of agglomerator used and different press agglomeration processes. The four most common press agglomeration processes preferred in the context of the present invention are extrusion, roller pressing or compacting, hole pressing (pelleting) and tableting so that preferred in the present invention Press agglomeration processes Extrusion, roll compacting, pelletizing or tableting processes are. All processes have in common that the premix compresses under pressure and is plasticized and the individual particles are pressed together while reducing the porosity and stick together. With all processes (with tableting with restrictions) the Heat tools to higher temperatures or to dissipate the shear forces Cool heat. In all processes, one or more binders can be used as an aid to compaction be used. However, it should be made clear that the use of several different binders and mixtures of different binders is possible. In a preferred embodiment of the invention, a binder is used that at temperatures up to a maximum of 130 ° C, preferably up to a maximum of 100 ° C and in particular up to 90 ° C already completely is present as a melt. The binder must therefore depend on the process and process conditions be selected or the process conditions, in particular the process temperature, - if a particular binder is desired - must 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 even that Temperature of the melting point of the binder.

In a preferred embodiment of the invention, the process temperature is significantly higher the melting point or above the temperature at which the binder is in the form of a melt. In particular However, it is preferred that the process temperature in the compression step does not exceed 20 ° C above the melting temperature or the upper limit of the melting range of the binder lies. It is technically possible to set even higher temperatures; it has but shown that a temperature difference to the melting temperature or the softening temperature the binder of 20 ° C is generally sufficient and even higher temperatures no additional benefits. Therefore it is - especially for energetic reasons - particularly preferred, above, but as close as possible to the melting point or to the upper one Working temperature limit of the melting range of the binder. Such temperature control has the further advantage that thermally sensitive raw materials, for example peroxy bleach such as perborate and / or percarbonate, but also enzymes, increasingly without serious Active substance losses can be processed. The possibility of precise temperature control of the binder in particular in the crucial step of compaction, i.e. between mixing / homogenization the premix and the shape, allows an energetically very favorable and extremely gentle process control for the temperature-sensitive components of the premix, because the premix is only exposed to the higher temperatures for a short time.

In preferred press agglomeration processes, 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) a temperature of at most 150 ° C, preferably at most 100 ° C and in particular at most 75 ° C and the process temperature is 30 ° C and in particular a maximum of 20 ° C above the melting temperature or the upper temperature limit of the melting range of the binder. The duration of the temperature effect in the compression range is preferably Press agglomerators a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.

Preferred binders which can be used alone or in a mixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and also modified polyethylene glycols and polypropylene glycols. The modified polyalkylene glycols include in particular the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols with a relative molecular weight between 600 and 12,000 and in particular between 1,000 and 4,000. Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which again have relative molecular weights between 600 and 6,000, preferably between 1,000 and 4,000. For a more detailed description of the modified polyalkylene glycol ethers, reference is made to the disclosure of the international patent application WO 93/02176 . In the context of this invention, polyethylene glycols include those polymers which, in addition to ethylene glycol, also use C ₃ -C ₅ glycols and glycerol and mixtures of these as starting molecules. Ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included. The polyethylene glycols preferably used can have a linear or branched structure, linear polyethylene glycols being particularly preferred. The particularly preferred polyethylene glycols include those with relative molecular weights between 2,000 and 12,000, advantageously around 4,000, polyethylene glycols with relative molecular weights below 3,500 and above 5,000, in particular in combination with polyethylene glycols with a relative molecular weight of around 4,000, and can be used Such combinations advantageously have more than 50% by weight, based on the total amount of polyethylene glycols, of polyethylene glycols with a relative molecular weight between 3,500 and 5,000. However, polyethylene glycols can also be used as binders, which are per se in liquid state at room temperature and a pressure of 1 bar; Here we are mainly talking about polyethylene glycol with a relative molecular mass of 200, 400 and 600. However, these per se liquid polyethylene glycols should only be used in a mixture with at least one further binder, this mixture again having to meet the requirements according to the invention, that is to say having a melting point or softening point of at least above 45 ° C. Likewise suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights of up to a maximum of 30,000. Relative molecular weight ranges between 3,000 and 30,000, for example around 10,000 are preferred. Polyvinylpyrrolidones are preferably not used as sole binders but in combination with other used in particular in combination with polyethylene glycols.

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

In a preferred embodiment, the detergent according to the invention is produced by means of an extrusion , as described, for example, in European patent EP 0486592 B1 or international patent applications WO 93/02176 and WO 94/09111 or WO 98/12299 . In this case, a solid premix is pressed in the form of a strand under pressure and the strand is cut to the predeterminable size of the granulate after it has emerged from the hole shape by means of a cutting device. The homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to become plastically softened and extrudable under the pressure or under the entry of specific work. Preferred plasticizers and / or lubricants are surfactants and / or polymers. For an explanation of the actual extrusion process, reference is hereby expressly made to the patents and patent applications mentioned above. Preferably, the premix is preferably fed to a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guidance, the housing and the extruder pelletizing head of which can be heated to the predetermined extrusion temperature. Under the shear action of the extruder screws, the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally, under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating knives. The hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granule size. In this way, granules of an essentially uniformly predeterminable particle size can be produced, the absolute particle sizes in particular being able to be adapted to the intended use. In general, particle diameters up to at most 0.8 cm are preferred.

Important embodiments see the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm in front. The length / diameter ratio of the chipped primary granules is preferably in the range from about 1: 1 to about 3: 1. It is also preferred to use the still plastic primary granulate to carry out a further shaping processing step: the raw extrudate existing edges rounded, so that ultimately spherical to approximately spherical extrudate grains can be obtained. If desired, small amounts of dry powder, for example zeolite powder, such as zeolite NaA powder, can also be used. This shape can be in commercially available rounding machines. Care should be taken to ensure that at this stage only minor Amounts of fine grain content arise. A drying process, which is described in the above-mentioned documents of the The prior art is described as a preferred embodiment, but is subsequently possible not mandatory.

It may just be preferred not to carry out any drying after the compacting step. Alternatively, extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press (Fa. Amandus Kahl) or in the Bepex extruder. Temperature control is preferred designed in the transition area of the screw, the pre-distributor and the nozzle plate, that the melting temperature of the binder or the upper limit of the melting range of the binder at least reached, but is preferably exceeded. The duration of the exposure to temperature lies here in the compression range of the extrusion, preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.

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

Particularly preferred production processes work with roller compaction at process temperatures, the 10 ° C, in particular a maximum of 5 ° C above the melting temperature or the upper one Temperature limit of the melting range of the binder. It is further preferred that the duration of exposure to temperature in the compression area of the smooth or with depressions of roller in a defined form is a maximum of 2 minutes and especially in one area is between 30 seconds and 1 minute.

The detergent according to the invention can also be produced by pelleting . The premix is applied to a perforated surface and pressed through the holes by means of a pressure-producing body with plasticization. In conventional embodiments of pellet presses, the premix is compressed under pressure, plasticized, pressed through a perforated surface by means of a rotating roller in the form of fine strands and finally comminuted into granules using a knock-off device. The most varied configurations of the pressure roller and perforated die are conceivable here. For example, flat perforated plates are used as well as concave or convex ring matrices through which the material is pressed using one or more pressure rollers. The press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation.

An apparatus suitable for carrying out the method is described, for example, in German laid-open specification DE 3816842 A1 . The ring die press disclosed in this document consists of a rotating ring die interspersed with press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge. In this case, the ring die and press roller (s) can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved. Of course, it is also possible to work with heatable or coolable rollers in the pelletizing in order to set a desired temperature of the premix. In pelletizing, too, the temperature of the pressing tools, that is to say the pressure rollers or pressure rollers, is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at most 75 ° C. Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.

Another pressing agglomeration process that can be used to produce the detergents according to the invention is tableting. Due to the size of the tablets produced, it may be useful for tableting to add conventional disintegration aids, e.g. cellulose and its derivatives, in particular in coarser form, or cross-linked PVP in addition to the binder described above, which facilitate the disintegration of the pressed length in the wash liquor. The particulate press agglomerates obtained can either be used directly as detergents or aftertreated and / or prepared beforehand by customary methods. The usual aftertreatments include, for example, powdering with finely divided ingredients from washing or cleaning agents, which generally further increases the bulk density. However, a preferred aftertreatment is also the procedure according to German patent applications DE 19524287 A1 and DE 19547457 A1 , in which dusty or at least finely divided ingredients (the so-called fine fractions) are adhered to the particulate end products of the process, which serve as the core, and thus give rise to agents , which have these so-called fines as an outer shell. In turn, this advantageously takes place by melting agglomeration.

For melt agglomeration of the fine fractions, reference is expressly made to the disclosure in German patent applications DE 19524287 A1 and DE 19547457 A1 . In the preferred embodiment of the invention, the solid detergents are in tablet form, these tablets preferably having rounded corners and edges, in particular for storage and transport reasons. The base of these tablets can be circular or rectangular, for example. Multi-layer tablets, in particular tablets with 2 or 3 layers, which can also have different colors, are particularly preferred. Blue-white or green-white or blue-green-white tablets are particularly preferred. Detergent tablets generally contain a disintegrant, which is said to bring about the rapid dissolution of the tablet or the rapid disintegration of the tablet in the aqueous liquor. In this context, reference is expressly made to the content of the German patent applications DE 19709991 A1 and DE 19710254 A1 , in which preferred cellulose-based disintegrant granules are described.

The invention furthermore relates to the use of surfactant compositions according to the invention for the production of detergents.

The invention also relates to the use of surfactant compositions according to the invention or of surfactant compositions produced by a process according to the invention for the production of detergents in the form of powders, granules, extrudates, agglomerates or Tablets.

The invention is explained in more detail below by examples.

Examples example 1 a) Preparation of the carrier material for the liquid nonionic surfactant

a) 67,4 GT Zeolith NaA (wasserfrei gerechnet),

b) 2,1 GT ethoxylierter Talg-Fettalkohol mit 5 EO als Dispersions-Stabilisator

c) 4,0 GT Acrylsäure-Maleinsäure Copolymer (Na-Salz)

d) 2,5 GT Na-Seife (C12-18-Cocos-Talgseife 1:1)

e) 4,4 GT Natriumsulfat

The following constituents were mixed with the addition of water to form a slurry in a batch container equipped with a stirring device (GT = parts by weight)

a) 67.4 GT zeolite NaA (calculated anhydrous),

b) 2.1 pbw of ethoxylated tallow fatty alcohol with 5 EO as a dispersion stabilizer

c) 4.0 pbw of acrylic acid-maleic acid copolymer (sodium salt)

d) 2.5 GT Na soap (C12-18 coconut tallow soap 1: 1)

e) 4.4 pbw of sodium sulfate

It was used as an aqueous dispersion (filter cake) containing 48% by weight of anhydrous zeolite as well as the other additives mentioned under (a) and 50.2% by weight of water. As a polycarboxylic acid a copolymer of acrylic acid and maleic acid with a molecular weight of 70,000 (Sokalan in Form of the sodium salt used.

The aqueous slurry, which had a temperature of 85 ° C. and a viscosity of 10 200 mPas, was sprayed with a pressure of 40 AT in a tower in which combustion gases at a temperature of 226 ° C. (measured in the ring channel) were directed towards the spray product. The outlet temperature of the dry gas was 63 ° C. The granular adsorbent leaving the spray tower contained 19.6 pbw of water.
The grain spectrum determined by sieve analysis gave the following weight distribution: over 1.6 mm 2% by weight 1.6 to 0.8 mm 39% by weight 0.8 to 0.4 mm 52% by weight 0.2 to 0.1 mm 7% by weight less than 0 1 mm 0% by weight

The bulk weight was 563 g / l.

Talg-Fettalkohol mit 5 EO 2,1 Gew.-%

Zeolith NaA 67,4 Gew.-%

Wasser (gebunden im Zeolith): 19,6 %

Acrylsäure-Maleinsäu re Copolymer (Na-Salz) 4,0 Gew.-%

Na-Seife (C12-18-Cocos-Talgseife 1:1) 2,5 Gew.-%

Natriumsulfat 4,4 Gew.-%

The spray tower powder produced according to a) had the following composition:

Tallow fatty alcohol with 5 EO 2.1% by weight

Zeolite NaA 67.4% by weight

Water (bound in the zeolite): 19.6%

Acrylic acid-maleic acid copolymer (Na salt) 4.0% by weight

Na soap (C12-18 coconut tallow soap 1: 1) 2.5% by weight

Sodium sulfate 4.4% by weight

b) Preparation of the solid nonionic surfactant / zeolite granules

15.0 pbw of a nonionic surfactant (coconut alcohol + 7 EO) heated to 50 ° C. were combined in one rotating mixing devices equipped mixer (spray mixer) to 85.0 GT of the spray-dried Component sprayed on within 1.5 minutes and mixing continued for 2 minutes. The The mixture removed from the mixer and having a temperature of 33 ° C was after cooling free-flowing to room temperature and had a bulk density of 700 g / 1. The grain size distribution was practically unchanged from the starting material.

Cocosalkohol + 7 EO: 15,0 Gew.-%

Talg-Fettalkohol mit 5 EO: 1,8 Gew.-%

Zeolith NaA: 57,1 Gew.-%

Wasser (gebunden im Zeolith): 16,7 %

Acrylsäure-Maleinsäure Copolymer (Na-Salz) 3,4 Gew.-%

Na-Seife (C12-18-Cocos-Talgseife 1:1) 2,2 Gew.-%

Natriumsulfat 3,8 Gew.-%

The granules produced according to b) had the following composition:

Coconut alcohol + 7 EO: 15.0% by weight

Tallow fatty alcohol with 5 EO: 1.8% by weight

Zeolite NaA: 57.1% by weight

Water (bound in the zeolite): 16.7%

Acrylic acid-maleic acid copolymer (Na salt) 3.4% by weight

Na soap (C12-18 coconut tallow soap 1: 1) 2.2% by weight

Sodium sulfate 3.8% by weight

c) Production of the granules according to the invention with a core of solid nonionic surfactant / zeolite granules and a shell made of fatty alcohol sulfate

A1) Fettalkoholsulfat in Form des Natriumsalzes, hergestellt aus einer C 12/14- Fettalkoholmischung

A2) C12/C14-Alkyloligoglucosid mit einem DP von 1,5 (Glucopon 600)

A3) das unter b) hergestellte feste Niotensid / Zeolith-Granulats mit einer Körnung von über 1,6 mm 2 Gew.-% 1,6 bis 0,8 mm 39 Gew.-% 0,8 bis 0,4 mm 52 Gew.-% 0,2 bis,0,1 mm 7 Gew.-% unter 0 1 mm 0 Gew.-% und einem Schüttgewicht von 700 g/l.

Starting Materials:

A1) Fatty alcohol sulfate in the form of the sodium salt, produced from a C 12/14 fatty alcohol mixture

A2) C12 / C14 alkyl oligoglucoside with a DP of 1.5 (Glucopon 600)

A3) the solid nonionic surfactant / zeolite granules with a grain size of over 1.6 mm 2% by weight 1.6 to 0.8 mm 39% by weight 0.8 to 0.4 mm 52% by weight 0.2 to 0.1 mm 7% by weight less than 0 1 mm 0% by weight and a bulk density of 700 g / l.

The surfactant ingredients A1) and A2) are commercial products from Cognis GmbH Germany, Düsseldorf

Production of the granules in the fluidized bed (= SKET process):

The granules were produced in a continuous fluidized bed. In doing so aqueous surfactant pastes A1) and A2) are simultaneously introduced into the fluidized bed via nozzles. Separately Of these, the nonionic surfactant / zeolite granulate A3) was automatically regulated solids metering added. The product streams of aqueous surfactant paste and admixed nonionic surfactant / zeolite granules were controlled so that granules with the desired weight composition revealed. In the fluidized bed, the surfactant paste is sprayed onto the solid non-ionic surfactant / zeolite granulate, it envelops it while drying the water.

The surfactant granules are considered dried if the free water content is below 10 wt .-%, preferably from 0.5 to 5 wt .-%, each based on the finished granules.

A fluidized bed apparatus with a base plate with a diameter of 2.5 m was used.

The granules were discharged via a size classification of the granules. This classification was done by means of an opposite air flow (classifier air), which was regulated so that only particles from a certain particle size removed from the fluidized bed and smaller particles in the fluidized bed be held back.

In the process in the fluidized bed, it is necessary that a starting mass be used at the start of the process is available. 2 t of solid nonionic surfactant / zeolite granules were presented as starting mass, which as initial carrier for the sprayed surfactant pastes.

The surfactant granules obtained from the fluidized bed were then in a separate fluidized bed cooled and classified by means of a sieve into granules with grain sizes between 0.2 and 1.6 mm as good grain fraction, in granules over 1.6 mm as oversize fraction and in granules under 0.2 mm as Undersize fraction. The granules of the undersize fraction are returned to the fluidized bed. The oversize fraction is ground, preferably in grain sizes below 0.5 mm, and also in the fluidized bed returned.

Characteristics of the process:

Vortex air velocities in m / s: 3.0 (under process conditions)

Temperatures in ° C: Soil air 170 Sifter air 20 Air outlet 85

Throughput: surfactant A1) in t / h: 0.5 t

Throughput: surfactant A2) in t / h: 0.5 t

Throughput: Solid non-ionic surfactant / zeolite granules A3) in t / h: 1.5 t

Starting mass (= zero filling) 2.0 t non-ionic surfactant / zeolite granulate

Paste temperature of A1) before injection: 70 ° C

Paste temperature of A2) before injection: 60 ° C

The granules obtained were classified according to the grain size: over 1.6 mm 5% by weight 1.6 to 0.8 mm 65% by weight 0.8 to 0.4 mm 25% by weight 0.2 to 0.1 mm 5% by weight less than 0 1 mm 0% by weight

The bulk density was 610 g / l.

The water content was 0.5% (without taking into account the water bound to zeolite)

C 12/14-Fettalkoholsulfat: 14,5 Gew.-%

C12/C14-Alkyloligoglucosid: 12,2 Gew.-%

Cocosalkohol + 7 EO: 11,0 Gew.-%

Talg-Fettalkohol mit 5 EO 1,3 Gew.-%

Zeolith NaA 41,5 Gew.-%

Wasser (gebunden im Zeolith): 12,1 %

Acrylsäure-Maleinsäure Copolymer (Na-Salz) 2,5 Gew.-%

Na-Seife (C12-18-Cocos-Talgseife 1:1) 1,6 Gew.-%

Natriumsulfat 2,8 Gew.-%

Freies Wasser: 0,5 % Gew.-%

The fluidized bed granules produced according to c) had the following composition:

C 12/14 fatty alcohol sulfate: 14.5% by weight

C12 / C14 alkyl oligoglucoside: 12.2% by weight

Coconut alcohol + 7 EO: 11.0% by weight

Tallow fatty alcohol with 5 EO 1.3% by weight

Zeolite NaA 41.5% by weight

Water (bound in the zeolite): 12.1%

Acrylic acid-maleic acid copolymer (Na salt) 2.5% by weight

Na soap (C12-18 coconut tallow soap 1: 1) 1.6% by weight

Sodium sulfate 2.8% by weight

Free water: 0.5% by weight

d) Production of detergent tablets

Wirbelschichtgranulat: 57,5 Gew.-%

C 12-18 Fettalkoholsulfat (Sulfopon 1218 G): 7,0 Gew.-%

The fluidized bed granules produced according to c) were mixed by blending with bleaching agent, bleach activator and further processing components to form the premix to be pressed, and thus a molded article with the following composition was produced:

Fluidized bed granules: 57.5% by weight

C 12-18 fatty alcohol sulfate (Sulfopon 1218 G): 7.0% by weight

(Sulfopon 1218 G is a commercial product from Cognis GmbH Germany, Düsseldorf)

Sodium percarbonate: 20.0% by weight

TAED: 5.0% by weight

Foam inhibitor: 3.5% by weight

Enzymes: 1.5% by weight

Perfume: 0.5% by weight

Disintegration aid (cellulose): 5.0% by weight

This mixture was then turned into tablets in a Korsch eccentric press (diameter: 44 mm, height: 22 mm, weight: 37.5 g) pressed.

Comparative Example 1

festes Niotensid/Granulat: 42,3 Gew.-%

getrocknetes C 12/14-Fettalkoholsulfat: 8,244,8 Gew.-%

getrocknetes C12/C14-Alkyloligoglucosid: 7,0 Gew.-%

C 12-18 Fettalkoholsulfat (Sulfopon 1218 G): 7,0 Gew.-%

Sulfopon 1218 G ist ein Handelsprodukte der Cognis Deutschland GmbH, Düsseldorf

Natriumpercarbonat: 20,0 Gew.-%

TAED: 5,0 Gew.-%

Schauminhibitor: 3,5 Gew.-%

Enzyme: 1,5 Gew.-%

Parfüm: 0,5 Gew.-%

Desintegrationshilfsmittel (Cellulose): 5,0 Gew.-%

Solid nonionic surfactant / granules were produced as described in Example 1 under a).
In deviation from Example 1, these solid nonionic surfactant / granules were not coated in a fluidized bed with C 12/14 fatty alcohol sulfate in the form of the sodium salt and C 12/14 alkyl oligoglucoside with a DP of 1.5 (Glucopon 600), but rather for the production of Premix to be pressed into detergent tablets was prepared as follows:

solid nonionic surfactant / granules: 42.3% by weight

dried C 12/14 fatty alcohol sulfate: 8,244.8% by weight

dried C12 / C14 alkyl oligoglucoside: 7.0% by weight

C 12-18 fatty alcohol sulfate (Sulfopon 1218 G): 7.0% by weight

Sulfopon 1218 G is a commercial product from Cognis Deutschland GmbH, Düsseldorf

Sodium percarbonate: 20.0% by weight

TAED: 5.0% by weight

Foam inhibitor: 3.5% by weight

Enzymes: 1.5% by weight

Perfume: 0.5% by weight

Disintegration aid (cellulose): 5.0% by weight

This mixture was then turned into tablets in a Korsch eccentric press (diameter: 44 mm, height: 22 mm, weight: 37.5 g) pressed.

Solubility of detergent tablets:

The detergent tablets produced according to Example 1 or Comparative Example 1 were placed in a beaker introduced with 500 ml of water and measured the time until the detergent tablets disintegrate were. "Decay" here means that after this time there are no larger particles in the aqueous Phase.

The detergent tablet produced according to Example 1 disintegrated in 30 seconds, that according to the comparative example 1 tablet produced only disintegrated after 5 minutes.

Claims (12)

Surfactant mixtures in solid form, characterized in that they have a core and a shell, the core at least one nonionic surfactant and the shell as shell substance at least one anionic surfactant or at least one nonionic surfactant not contained in the core or at least one zwitterionic surfactant or a mixture contains two or more of the surfactants mentioned. Surfactant mixtures according to claim 1, characterized in that the core contains at least one alcohol ethoxylate or an ester ethoxylate with 2 to 30 ethylene oxide units or a mixture thereof as the nonionic surfactant. Surfactant mixtures according to claim 1 or 2, characterized in that the core contains a carrier substance. Surfactant mixtures according to one of claims 1 to 3, characterized in that the shell contains a sulfate or sulfonate as the coating substance. Surfactant mixtures according to one of claims 1 to 4, characterized in that they contain at least one fatty alcohol sulfate as the coating substance. Surfactant mixtures according to one of claims 1 to 5, characterized in that the casing has a water solubility of at least 0.1 g / l at 20 ° C. A process for the preparation of solid surfactant mixtures, characterized in that a coating substance according to claim 1 is deposited on a surfactant core in solid form which contains at least one nonionic surfactant from an aqueous solution or melt while the water evaporates. Process according to claim 7, characterized in that the deposition is carried out by intimately mixing the surfactant core, which is in solid form, with an aqueous solution or melt of the coating substance and, if appropriate, removing water in the process. Process according to claim 7, characterized in that the solid surfactant core and an aqueous solution or melt of the coating substance are subjected to simultaneous drying and granulation in the Wibel layer. Detergent, at least containing a surfactant mixture according to one of claims 1 to 6 or a surfactant mixture prepared according to one of claims 7 to 9, Detergent according to claim 10, characterized in that it is in the form of an extrudate, granulate or tablet. Use of surfactant mixtures according to one of claims 1 to 6 for the production of Detergents.