EP1113067A2 - Preparation containing surfactants - Google Patents

Abstract

Alkoxylated carboxylic acid ester surfactants for use in detergents are stabilized by addition of a carrier. A composition suitable for use in detergents comprises: (A) an alkoxylated carboxylic acid ester surfactant of formula (I); and (B) a carrier. R<1>CO(OR<3>)nOR<2> (I) R<1>CO = aliphatic acyl; R<2> = aliphatic alkyl; R<3> = aliphatic alkylene; and n = 3-15.

Description

The present invention relates to surfactants for incorporation in detergents suitable particulate preparations, a process for their preparation of these preparations as well as a washing and Cleaning supplies.

Alkoxylated carboxylic acid esters are known nonionic surfactants that are in particular due to its favorable ecological properties and low foam award. In powdered formulations, they have little stability on. Especially in the presence of alkaline compounds and in the presence of The alkoxylated carboxylic acid esters can become water or moisture decompose rapidly into the acid and the corresponding alcohol.

The object of the present invention was to provide a preparation to put in which alkoxylated carboxylic acid esters are stabilized so that the alkoxylated carboxylic acid esters also incorporated in detergents and cleaning agents and can be stored over a longer period of time.

Surprisingly, it was found that the alkoxylated carboxylic acid esters can be stabilized by being on a carrier material, preferably a neutral carrier material can be applied. As part of solid washing and Detergents can be stored for several weeks without changing the content on alkoxylated carboxylic acid esters significantly reduced.

a) mindestens ein Tensid mit der Formel (I) R¹CO(OR³)_nOR²    worin

R¹CO

für einen aliphatischen Acylrest

R²

für einen aliphatischen Alkylrest

R³

für einen aliphatischen Alkylenrest und

n

für ein Zahl zwischen 3 und 15 steht, sowie

b) mindestens ein Trägermaterial.

The present invention accordingly relates to a preparation which is suitable for incorporation into detergents and cleaning agents and contains

a) at least one surfactant with the formula (I) R ¹ CO (OR ³ ) _n OR ² wherein

R ¹ CO

for an aliphatic acyl radical

R ²

for an aliphatic alkyl radical

R ³

for an aliphatic alkylene radical and

n

stands for a number between 3 and 15, and

b) at least one carrier material.

The alkoxylated carboxylic acid esters used according to the invention are compounds known from the prior art, which can be obtained, for example, by esterification of the alkoxylated carboxylic acids with alcohols. The compounds are preferably prepared by reacting carboxylic acid esters with alkylene oxides using suitable catalysts, for example calcined hydrotalcite, with which carboxylic acid esters can be alkoxylated both with monohydric and with polyhydric alcohols. Particularly suitable compounds with the formula I are those in which the radical R ¹ CO is an acyl radical having 12 to 22 carbon atoms, R ^{2 is} a C _1-4 alkyl radical and R ^{3 is} an ethylene or propylene radical. n is preferably a number between 5 and 11, which number represents an average value. Particularly preferred nonionic surfactants with formula I are alkoxylated methyl laurate, methyl coconut fatty acid and methyl tallow fatty acid with an average of 5, 6, 9 or 11 alkoxy units per molecule.

According to the invention, the nonionic surfactant with the formula I is applied to a carrier material upset. The carrier materials are all solid at room temperature Substances in question. A particularly good stability is obtained if that Carrier material is neutral on its surface and particularly preferably one the smallest possible proportion of water, chemically bound or as crystal water. Suitable carrier materials are e.g. inorganic salts or builder materials, which can optionally be coated. Those in the field of washing and Substances known as builder materials become special preferred because they are used in a possible use of the surfactant-containing preparation Develop an additional effect in the cleaning cycle.

Examples of builder materials that also act as carriers for the nonionic surfactants can be used with the formula I are, in particular, the amorphous and crystalline zeolites, bentonites, silicates, carbonates, organic cobuilders and - if there are no ecological concerns about their use - including the phosphates. The The builders mentioned below are all used as carrier materials for the Preparations according to the invention are suitable. These materials can not only be used as Carriers for the nonionic surfactants are used with the formula I, but also as separate preparations in the manufacture of detergents and cleaning agents, which contain the preparations according to the invention are used as ingredients.

For example, crystalline, layered sodium silicates with the general formula NaMSi _x O _{2x + 1} H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, and preferred values are suitable for x are 2, 3 or 4. 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 disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving 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. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

Fine-crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula n Na ₂ O (1-n) K ₂ O Al ₂ O ₃ (2 - 2.5) SiO ₂ (3.5 - 5.5) H ₂ O can be described. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It goes without saying that the generally known phosphates are also used as Builder substances possible, provided that such use is not from ecological Reasons should be avoided. Among the variety of commercially available Phosphates have the alkali metal phosphates with particular preference for Pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) in the Detergent and cleaning agent industry the greatest importance.

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

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

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to the diphosphate Na ₄ P ₂ O ₇ when heated to a greater extent. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

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

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) . Substances are colorless crystals that are soluble in water with an alkaline reaction. Na4P207 is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.
Condensation of NaH ₂ PO ₄ or KH2PO4 results in higher mol. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

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

According to the invention, these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also mixtures of Sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of Potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of Sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

As organic cobuilders in the machine according to the invention Dishwashing detergents, in particular polycarboxylates / polycarboxylic acids, polymers Polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances will described below.

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as polycarboxylic acids Carboxylic acids are understood that carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, Malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided that such use is not for ecological reasons objectionable, 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 besides theirs Builder effect typically also the property of an acidifying component and thus also serve to set a lower and milder pH value of Detergents or cleaning agents. In particular, citric acid, Succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of to call this.

Other carrier materials, which can also be builders at the same time, are polymers Suitable polycarboxylates, these are, for example, the alkali metal salts Polyacrylic acid or polymethacrylic acid, for example those with a relative Molecular mass from 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight have from 2000 to 20,000 g / mol. Because of their superior solubility, can this group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.

Also suitable are copolymeric polycarboxylates, especially those of Acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid have proven particularly suitable proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain. Their relative molecular weight, based on free acids, is in general 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 up to 40,000 g / mol.

The (co) polymeric polycarboxylates can be either as a powder or as an aqueous one Solution are used. The content of the agents in (co) polymeric polycarboxylates is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve water solubility, the polymers can also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer contain.

Biodegradable polymers of more than two are also particularly preferred various monomer units, for example those which are salts of the monomers Acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or the as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives contain.

Further preferred copolymers are those which preferably contain acrolein as monomers and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Are particularly preferred Polyaspartic acids or their salts and derivatives.

Other builder substances suitable as carrier materials are polyacetals, which by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and have at least 3 hydroxyl groups, can be obtained. Preferred Polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde and terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or Obtain glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example Oligomers or polymers of carbohydrates by partial hydrolysis of starches can be obtained. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme-catalyzed processes are carried out. It is preferably Hydrolysis products with average molecular weights in the range of 400 to 500000 g / mol. there is a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, particularly preferred from 2 to 30, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which a DE out of 100. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called Yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol.

The oxidized derivatives of such dextrins are theirs Reaction products with oxidizing agents that are capable of at least one To oxidize the alcohol function of the saccharide ring to the carboxylic acid function. Likewise an oxidized oligosaccharide is suitable, an oxidized at C6 of the saccharide ring Product can be particularly beneficial.

Oxydisuccinates and other derivatives of disuccinates are also preferred Ethylene diamine disuccinate are other suitable cobuilders. This is ethylenediamine-N, N'-disuccinate (EDDS) preferred in the form of its sodium or magnesium salts used. Also preferred in this context Glycerol disuccinates and glycerol trisuccinates. Suitable amounts are in Zeolite-containing and / or silicate-containing formulations at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated Hydroxycarboxylic acids or their salts, which may also be in lactone form and which have at least 4 carbon atoms and at least one Contain hydroxy group and a maximum of two acid groups.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a cobuilder. It is preferably used as the sodium salt used, the disodium salt neutral and the tetrasodium salt alkaline (pH 9) responds. Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral reacting sodium salts, e.g. B. as the hexasodium salt of EDTMP or as Hepta and Octa sodium salt of DTPMP, used. As a builder, the Class of phosphonates preferably uses HEDP. The aminoalkane phosphonates also have a strong ability to bind heavy metals. Accordingly, it is preferred, especially if the agents also contain bleach, Aminoalkanephosphonate, especially DTPMP to use, or mixtures of the to use the named phosphonates.

In addition, all compounds that are able to complex with To train alkaline earth ions are used as cobuilders.

In a preferred embodiment of the present invention, the Carriers have a neutral surface, which is particularly preferred if it is on no water, e.g. B. as crystal water or bound water, contain. Anhydrous compounds are preferably used, e.g. so-called over-dried substances such as over-dried zeolites and silicates.

It is also possible to cover the carrier materials with a neutral substance, which provides stability of the nonionic surfactants with the formula I is not affected. The Coating is preferably applied when zeolites are used as carriers be used. Suitable coating materials are preferably such Substances that act as active substances in detergents and cleaning agents are suitable. Examples of such substances are, for example, the so-called Known nonionic surfactants, cellulose and cellulose derivatives known as sugar surfactants salts of polycarboxylic acids already described above.

As sugar surfactants, in particular the alkyl and alkenyl oligoglycosides and To name polyhydroxy fatty acid amides.

The alkyl and alkenyl oligoglycosides have the general formula R ¹ O (G) _x in which R ^{1 is} a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched alkyl or alkenyl radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 carbon atoms , preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

in der R²CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R³ 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.Polyhydroxy fatty acid amides which can be used are those having the formula (II).

in the R ² CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ³ 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 stands.

The polyhydroxy fatty acid amides are known substances that usually 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 can be obtained can. With regard to the processes for their production, reference is made to the US patents US-A-1,985,424, US-A-2,016,962 and US-A-2,703,798 and the International Patent application WO-A-92/06984 referenced. Preferably the derive Polyhydroxy fatty acid amides of reducing sugars with 5 or 6 carbon atoms, especially on the glucose.

The sugar surfactants can be in the form of aqueous solutions as they are made from the Manufacturing processes are obtained for application to the carrier material used, the product obtained being dried simultaneously or later.

Cellulose and cellulose derivatives are cellulose, carboxycelluloses, cellulose esters, Cellulose ether etc. can be used. Examples of suitable derivatives are hydroxypropyl methyl cellulose (HPMC), ethyl (hydroxyethyl) cellulose (EHEC), hydroxypropyl cellulose (HPC), methyl cellulose (MC), ethyl cellulose (EC), carboxymethyl cellulose (CMC), Carboxymethylmethyl cellulose (CMMC), hydroxybutyl cellulose (HBC), Hydroxybutylmethylcellulose (HBMC), Hydrdoxyethylcellulose (HEC), Hydroxyethylcarboxymethylcellulose (HECMC), Hydroxyethylethylcellulose (HEEC), Hydroxypropyl cellulose (HPC), hydroxypropyl carboxymethyl cellulose (HPCMC), Hydroxyethylmethylcellulose (HEMC), Methylhydroxyethylcellulose (MHEC), Methyl hydroxyethyl propyl cellulose (MHEPC), methyl cellulose (MC) and propyl cellulose (PC) and mixtures thereof, being carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose and methylhydroxyproplcellulose and the alkali salts of CMC and the slightly ethoxylated MC or mixtures of the foregoing.

A preparation according to the invention preferably contains from 10 to 50% by weight Surfactants with the formula I and from 50 to 90 wt .-% carrier material. In Embodiments in which the carrier material is first coated become this Coating preferably in an amount of 0.1% to 10% by weight, especially preferably from 1 to 5% by weight, based on the amount of support material, applied.

Another object of the present invention relates to a method for Production of the preparation according to the invention, in which the carrier material in itself is known to act with the surfactant of formula I. The loading the carrier material with the surfactant is carried out in a manner known per se, for example by impregnating the carrier material with the nonionic surfactant with the formula I. as by spraying the liquid components onto the solid support or by Mixing the solid and liquid components.

If the carrier material is first coated with a neutral substance, it can this coating can be done, for example, by first slurrying the Carrier material made with an aqueous solution of the coating material and this is then spray dried.

The preparation produced according to the invention is particularly advantageously suitable for Incorporation in detergents and cleaning agents.

Another object of the present invention is accordingly a washing and Detergent, the preparation described above and any other Contains surfactants and common ingredients.

Furthermore, the agents according to the invention can all usually be used in detergents and cleaning agents substances contained, such as other surfactants, in particular anionic surfactants, and other builder substances, inorganic salts, bleaching agents, Bleach activators, enzymes, enzyme stabilizers, graying inhibitors, Foam inhibitors, silicone oils, soil release compounds, color transfer inhibitors, Salts of polyphosphonic acids, optical brighteners, fluorescent agents, fragrances, Dyes, antistatic agents, ironing aids, phobing and impregnating agents, swelling and Anti-slip agents, UV absorbers or their mixtures.

In addition to those according to the invention, the agents can be in the form of those described above Preparations and other surfactants selected from the nonionic, anionic, contain cationic and amphoteric surfactants.

Examples of nonionic surfactants are non-esterified alkoxylated fatty alcohols, the sugar surfactants already described as coating materials, in particular Dialkyl and alkenyl oligoglycosides and polyhydroxy fatty acid amides, and amine oxides in Consideration.

Preferred nonionic surfactants are those which are usually present in liquid alkoxylated fatty alcohols. Alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear are particularly suitable and may contain methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. 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 -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ alcohols with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C12-C14 alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 7EO. 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 of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

The sugar surfactants already described can also be considered as further surfactants. They can be in the form of aqueous solutions as they come from the manufacturing process be obtained, used. Other forms of use are granules, their Manufacturing process in which W097 / 03165 is described, or steam-dried Products obtained according to the procedure described in WO95 / 14519 can be.

Anionic surfactants that can be used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _12-18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-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. Under Fatty acid glycerol esters are the mono-, di- and triesters as well as their mixtures understand how they are produced by esterification of a monoglycerin with 1 up to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerin be preserved. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example the Caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, Stearic acid or behenic acid.

Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil 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, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 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. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are 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.

Soaps are particularly suitable as further anionic surfactants. Are suitable saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural Fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

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

The detergents and cleaning agents according to the invention can be used as further ingredients Builders included. Examples of these substances have already been mentioned above Suitable carrier materials for the surfactants with the formula I have already been described. she can be used as carrier substances for other ingredients or as individual substances be added to the agents according to the invention.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further usable 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, diperdodecanedioic acid or phthaloiminoperacids such as phthaliminopercaproic acid. Organic peracids, alkali perborates and / or alkali percarbonates are preferably used in amounts of 0.1 to 40% by weight, preferably 3 to 30% by weight, in particular 5 to 25% by weight.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular 1,3,4,6, are preferred -Tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, more particularly n-nonanoyl or isononanoyloxybenzenesulfonate (n - or iso-NOBS), carboxylic anhydrides, more particularly phthalic anhydride, isatoic anhydride and / or succinic anhydride, glycolide , acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and the enol esters known from German patent applications DE 196 16 693 and DE 196 16 767 as well as acetylated sorbitol and mannitol or their European patent application EP 0 525 239 mixtures described (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetyl xylose and octaacetyl lactose as well as acetylated, optionally N-alkylated glucamine or gluconolactone, triazole or triazole derivatives and / or particulate caprolactams and / or caprolactam derivatives, preferably N-acylated lactams, for example N-benzoylcaprolactam, which are known from international patent applications WO-A-94 / 27970, WO-A-94/28102, WO-A-94/28103, WO-A-95/00626, WO-A-95/14759 and WO-A-95/17498. The hydrophilically substituted acylacetals known from German patent application DE-A-196 16 769 and the acyl lactams described in German patent application DE-A-19616 770 and international patent application WO-A-95/14075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE-A-44 43 177 can also be used. Nitrile derivatives such as cyanopyridines, nitrile quats and / or cyanamide derivatives can also be used. Preferred bleach activators are sodium 4- (octanoyloxy) benzenesulfonate, undecenoyloxybenzenesulfonate (UDOBS), sodium dodecanoyloxybenzenesulfonate (DOBS), decanoyloxybenzoic acid (DOBA, OBC 10) and / or N-methylmorpholinum acetonitrile (M). Bleach activators of this type are present in the customary quantitative range from 0.01 to 20% by weight, preferably in amounts from 0.1 to 15% by weight, in particular 1% by weight to 10% by weight, based on the total agent .

The bleach activator can be coated with coating substances in a known manner or if necessary, using auxiliaries, in particular methyl celluloses and / or Carboxymethyl celluloses, granulated or extruded / pelleted and if desired, contain further additives, for example dye, the Dye has no coloring effect on the textiles to be washed. Preferably contains such granules over 70% by weight, in particular from 90 to 99% by weight Bleach activator. A bleach activator is preferably used, the under Washing conditions forms peracetic acid.

In addition to the conventional bleach activators listed above or other You can also use those from European patent specifications EP-A-0 446 982 and EP-A-0 453 003 known sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes as so-called bleaching catalysts be included. The transition metal compounds in question include in particular those known from German patent application DE-A-195 29 905 Manganese, iron, cobalt, ruthenium or molybdenum salt complexes and their N-analogue compounds, that from German patent application DE-A-195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the in the German patent application DE-A-196 05688 manganese, iron, Cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, which are known from German patent application DE-A-196 20 411 known cobalt, iron, copper and ruthenium amine complexes, which in the German patent application DE 44 16 438 manganese, copper and Cobalt complexes described in European patent application EP-A-0 272 030 described cobalt complexes, which are from the European patent application EP-A-0 693 550 known manganese complexes, which are known from the European patent EP-A-0 392 592 known manganese, iron, cobalt and copper complexes and / or those in the European patent EP-A-0 443 651 or the European patent applications EP-A-0 458 397, EP-A-0 458 398, EP-A-0 549 271, EP-A-0 549 272, EP-A-0 544 490 and EP-A-0 544 519 described manganese complexes. Combinations of Bleach activators and transition metal bleach catalysts are for example from the German patent application DE-A-196 13 103 and the international patent application WO-A-95/27775 known. Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are in usual Amounts, preferably in an amount up to 1% by weight, in particular 0.0025% by weight up to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the entire mean.

Enzymes in particular come from the hydrolase class, such as Proteases, esterases, lipases or lipolytically active enzymes, amylases, Cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned in Question. All of these hydrolases contribute to stain removal in laundry, such as stains containing protein, fat or starch, and graying. Cellulases and other glycosyl hydrolases can be removed by pilling and Microfibrils help to maintain color and increase the softness of the textile. Oxidoreductases can also be used for bleaching or for inhibiting color transfer be used.

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 lipase 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 to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5% by weight, preferably 0.1 to about 3% by weight.

Examples

A slurry of 70.6% by weight zeolite P (Crosfield), 3.0% by weight carboxymethyl cellulose, 2.6% by weight APG600 (alkylpolyglycoside, manufacturer Cognis GmbH, Düsseldorf) and 23 , 7 wt .-% water. This slurry was spray dried. The material obtained was then impregnated with Stantex S6030 (Cognis GmbH), so that the support material contained 27% by weight of the ethoxylated fatty acid methyl ester (FMEO). The key figures of the product obtained are shown in Table 1 below. Key figures example Bulk density (g / l) 435 Sieve numbers (%) 1.6 mm 1 0.8 mm 6 0.4 mm 27 0.2 mm 49 0.1 mm 17th D0.1 mm 1 Solubility in% 2.5 Package test (grade) 4th Water (%) 13.3

The FMEO content was analyzed analytically and the samples were stored at 50 ° C. and a humidity of 80%. The content of surfactants with the formula I was determined at the beginning, after 7, 14, 34 and 42 days. The results are shown in Table 2 below: FMEO content (%) 0 7 14 34 42 to Days Days Days Days Days example 27 25th 25th 25th 24th

Claims (10)

Preparation suitable for incorporation in detergents and cleaning agents, containing a) at least one surfactant with the formula (I) R ¹ CO (OR ³ ) _n OR ² wherein

R ¹ CO

for an aliphatic acyl radical

R ²

for an aliphatic alkyl radical

R ³

for an aliphatic alkylene radical and

n

stands for a number between 3 and 15, and

b) at least one carrier material. Preparation according to claim 1, characterized in that in formula (I) R ¹ CO is an acyl radical having 12 to 22 carbon atoms, R ^{2 is} a C _1-4 alkyl radical and R ^{3 is} an ethylene or propylene radical. Preparation according to claim 1 or 2, characterized in that the carrier material is neutral on the surface. Preparation according to one of claims 1 or 2, characterized in that the carrier material is selected from amorphous and crystalline zeolites, silicates, carbonates, organic cobuilders and phosphates, which can optionally be coated. Preparation according to claim 3, characterized in that the carrier material is coated with nonionic surfactant selected from the sugar surfactants, cellulose or a cellulose derivative, or polycarboxylate. Preparation according to claim 5, characterized in that the sugar surfactants are selected from the alkyl and alkenyl oligoglycosides having the formula (II) R ⁴ O (G) _x in which R ⁴ denotes a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched alkyl or alkenyl radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms , preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
and polyhydroxy fatty acid amides with the formula (III)

in which R ⁵ CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ⁶ 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 stands. Preparation according to one of Claims 1 to 6, characterized in that it contains from 10 to 50% by weight of surfactants with the formula (I) and from 50 to 90% by weight of carrier. Process for the preparation of a preparation comprising a) at least one surfactant with the formula (I) R ¹ CO (OR ³ ) _n OR ² wherein

R ¹ CO

for an aliphatic acyl radical

R ²

for an aliphatic alkyl radical

R ³

for an aliphatic alkylene radical and

n

stands for a number between 3 and 15, and

b) at least one carrier material, wherein the carrier material is acted upon in a manner known per se with the surfactant of the formula (I). Detergents and cleaning agents containing a preparation according to one of the Claims 1 to 7 and surfactants and other usual ingredients. Agent according to claim 9, characterized in that there are further builder substances, inorganic salts, bleaching agents, bleach activators, enzymes, enzyme stabilizers, graying inhibitors, foam inhibitors, silicone oils, soil release compounds, color transfer inhibitors, salts of polyphosphonic acids, optical brighteners, fluorescent agents, antifoulants, colorants Contains ironing aids, phobing and impregnating agents, swelling and anti-slip agents, UV absorbers or mixtures thereof.