EP0897976A2 - High density detergent granulate with high solubility and with improved greasy soil removal - Google Patents

Abstract

Production of detergents and cleansing agents containing silicate builders is effected in a conventional mixing/granulating device by (i) introducing a silicate builder which is treated with a nonionic surfactant so as to have a bulk density ≥ 800g/l but which has prior to the surfactant treatment no particles of diameter ≥ 2.0mm; and (ii) mixing and granulating with conventional ingredients to give a product with bulk density ≥ 750g/l.

Description

The present invention relates to silicate-containing detergent compositions containing a high bulk density, very good solubility and very good primary and secondary washing power, in particular have a high fat washability. Specifically affects The invention detergent compositions with high bulk density, both in the induction channel of commercially available washing machines and, for example, in the hand wash basin dissolve quickly and residue-free and without clumping or gelling form a wash liquor in no time, which is characterized by an outstanding cleaning effect distinguished.

Detergent compositions are known from European patent EP-B-0 698 658 (Procter & Gamble), which have an improved fat and oil wash-out capacity. These compositions contain 1 to 90% by weight of an anionic alkylbenzenesulfonate-free surfactant system comprising at least 30% by weight of an alkoxylated alkyl sulfate with an average degree of alkoxylation of 0.1 to 10, with defined weight ratios of mono-, di-, tri- and higher alkylated Fatty alcohol sulfates are present. The teaching of EP-B-0 698 659 (Procter & Gamble) extends this surfactant system to be used to the use of less than 40% by weight alkylbenzenesulfonate (ABS). The ABS-containing detergent composition also has an improved wash-out capacity for oil and grease stains.

International patent WO96 / 06908 (Procter & Gamble) discloses detergent compositions which contain more than 10% by weight of ethylenediamine disuccinate as a builder component, in particular in combination with water-soluble cationic surfactants, glucamides and oleyl sarconisate. These agents also have an improved fat washability.

The exposure of silicates to nonionic surfactants is known, for example, from WO96 / 20269 (Henkel). Neither these nor other documents which deal with the exposure of silicates to nonionic surfactants impose restrictions on the particle size distribution or the bulk density of the silicate used.

None of the above documents discloses the use of a special silicate Builder component in high bulk density detergent compositions for improvement of primary and secondary washing power.

It has now been found that the use of silicates to which nonionic surfactants have been added Particle sizes below 2.0 mm in the granulation step in the manufacture of detergents with bulk weights above 750 g / l leads to formulations that are characterized by an outstanding Cold water solubility, flushability and cleaning effect, especially for Mark grease soiling.

a) eine silikatische Builderkomponente in das Verfahren eingebracht wird, die sich dadurch auszeichnet, daß das Silikat mit Niotensiden beaufschlagt ist, die silikatische Builderkomponente ein Schüttgewicht von mehr als 800 g/l aufweist und die Korngrößenverteilung des zu beaufschlagenden Silikats vor der Beaufschlagung mit Niotensid keine Teilchen oberhalb eines Durchmessers von 2,0 mm aufweist sowie

b) mit weiteren üblichen Inhaltsstoffen von Wasch- und Reinigungsmitteln vermischt oder granuliert wird, wobei ein Schüttgewicht von mindestens 750 g/l eingestellt wird.

The invention relates to a method for producing detergents and cleaning agents which contain a silicate builder component in conventional mixing / granulating devices, wherein

a) a silicate builder component is introduced into the process, which is characterized in that the silicate is acted on by nonionic surfactants, the silicate builder component has a bulk density of more than 800 g / l and the particle size distribution of the silicate to be acted upon before the exposure to nonionic surfactant Has particles above a diameter of 2.0 mm and

b) is mixed or granulated with other usual ingredients of washing and cleaning agents, a bulk density of at least 750 g / l being set.

In the process according to the invention, silicate builder components are preferred which have at least 40% of the particles sizes between 0.4 and 0.8 mm.

Lödige Pflugscharmischer" bezeichnet wird, ist zur Durchführung dieser Verfahrensstufe besonders geeignet.The process according to the invention can be carried out in both high-intensity and slow-running mixers. Examples of high-speed mixers are the Lödige® CB 30 recycler, the Schugi® granulator, the Eirich® mixer type R or the Drais® K-TTP 80, examples of slow-speed mixer granulators are the Drais® KT 160 and the Lödige® KM 300. The latter, which is often called

Lödige ploughshare mixer "is particularly suitable for carrying out this process step.

The silicates used according to the invention can be both crystalline and amorphous, amorphous silicates are preferred.

Suitable amorphous sodium silicates are those with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably of 1: 2 to 1: 2.8 and in particular of 1: 2 to 1: 2.6 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 / compaction or by overdrying (for example water content of the silicate below 18% by weight). 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 provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 . Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

It is also possible to use crystalline, layered sodium silicates which have the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and is preferred Values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. 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-A-91/08171 .

Silicate compounds, which may contain other constituents, can also be used in the invention Procedures are used insofar as they relate to the general conditions Particle size and bulk density are sufficient. Preferred are, for example Silicate carbonate compounds.

The silicates used according to the invention and to be loaded with nonionic surfactant have before exposure to a particle diameter of less than 2.0 mm, with silicates with a particle size below 0.8 mm are preferred. Silicates are particularly preferred, in which at least 40% of the silicate particles of the silicate used have sizes between 0.4 and 0.8 mm. A bulk density of the used is absolutely necessary Silicates above 800 g / l.

It is preferred to apply less than 10% by weight of the silicate particles, in particular between 2 and 5% by weight of nonionic surfactant (s), based on the detergent and cleaning agent.

Non-ionic surfactants suitable for acting on the silica particles are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical is linear or preferably in 2 Position can be methyl-branched or can contain linear and 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 _12-14 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 thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical 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 tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

A C _12-18 alcohol ethoxylated with 5 to 8 ethylene oxide units is preferably suitable for the application of the silicate particles.

In addition, alkyl glycosides of the general formula RO (G) _x , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C., can also be used as further nonionic surfactants to act on the silicate particles -Atoms means and G is the symbol which stands for a glycose unit with 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 addition, the washing and Detergents contain other nonionic surfactants that do not have the impacted silicate particles were brought into the procedure, but at a different time than pure substances or as compounds and granules can be added. In addition to the So-called nonionic surfactants, which can also be added, can be used in this way other nonionic surfactants are incorporated into the detergents and cleaning agents become.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, such as them are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533 .

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 can be suitable. The amount of these nonionic surfactants is preferably not more than that of ethoxylated fatty alcohols, especially not more than half of it.

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 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_1-4Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder Propxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (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 oxy-alkyl 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 propylated, 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 compounds can then, for example according to the teaching of international application WO-A-95/ 07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

The nonionic surfactant introduced into the process according to the invention becomes at least partially given up on the silicate.

Without wishing to be limited by theory, the applicant assumes that the use of the nonionic surfactant in the form of the nonionic surfactant-silicate compound the amount of nonionic surfactant in the wash liquor, which is necessary for a certain cleaning success lower total nonionic surfactant concentrations in the agents is achievable. Will that If nonionic surfactant is added as a granulating liquid, the components will stick together and the bulk density of the agents obtained in this way is less than 750 g / l. Through the Exposure to the silicate with the nonionic surfactant, the nonionic surfactant at least partially adheres to the outer surface of the silicate particles, on the one hand the bulk density of the finished Detergent composition increases because of the granular bulk density and the bulk density of the nonionic surfactant-silicate compound are high, on the other hand the nonionic surfactant fully dispensed to the wash liquor faster, which means that compared to adding the Nonionic surfactant as a granulating liquid reduces the total proportion of agents in nonionic surfactant can or the agents deliver better results with the same nonionic surfactant content. Of the The proportion of finished detergent and cleaning agent compositions is nonionic surfactant preferably below 10% by weight, in particular from 2 to 5% by weight, based on the composition, the total surfactant content of the agents may well be significantly higher, and preferably is above 20% by weight. The percentage of nonionic surfactant that is applied to the silicate is preferably above 50% by weight of the total nonionic surfactant content.

In addition to the silicates used according to the invention, other builder and cobuilder substances can also be used be used in the detergent compositions. Which includes in particular zeolites, citrates and polymeric polycarboxylates.

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

It goes without saying that the generally known phosphates are also used as builder substances possible if such use is not avoided for ecological reasons should be. The sodium salts of orthophosphates, pyrophosphates, are particularly suitable and especially the tripolyphosphates. Their salary is generally not more than 25% by weight, preferably not more than 20% by weight, in each case based on the finished agent. 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 to a synergistic improvement of the Secondary washing power.

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if provided such use is not objectionable for ecological reasons, as well as mixtures from 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 this.

The acids themselves can also be used. The acids have a builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, methods. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure for is the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 can be used. A preferred dextrin is described in British patent application 94 19 091 . 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 production are sufficiently known from the prior art. 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. Are particularly preferred in this context, glycerin and glycerol, for example as American US in patents US 4,524,009, US 4,639,325, disclosed in European Patent Application EP-A 0 150 930 and Japanese Patent Application No. 93/339896 will. 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-A-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 from 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid have been found to be particularly suitable Maleic acid proved to be 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 5000 to 200000, preferably 10000 to 120000 and in particular 50000 to 100000.

The (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution are used, 20 to 55% by weight aqueous solutions being preferred.

Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which, according to DE-A-43 00 772, are monomers salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.

Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Other suitable builder substances are oxidation products of carboxyl group-containing polyglucosans and / or their water-soluble salts, as are described, for example, in international patent application WO-A-93/08251 or whose preparation is described, for example, in international patent application WO-A-93/16110 . Oxidized oligosaccharides according to the older German patent application P 196 00 018.1 are also suitable.

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids or their salts and derivatives, of which German Patent Application P 195 40 086.0 discloses that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.

Further 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-A-0 280 223 . 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 to the ingredients mentioned, the agents can be known, usually in detergents additives used, for example bleaching agents and bleach activators, Foam inhibitors, salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filling salts as well as colors and fragrances, opacifiers or pearlescent agents.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 1 to 40% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate or percarbonate.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the preparations. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetyloxy, 2,5-acetiacetyl, ethylene glycol 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 mixtures described in European patent application EP 0 525 239 (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG ), Pentaacetylfruktose, Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkylated tes glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. The hydrophilically substituted acylacetals known from German patent application DE 196 16 769 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE 44 43 177 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 0 446 982 and EP 0 453 003 may 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 195 29 905 and their N-analog compounds known from German patent application DE 196 20 267 , which consist of the German patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium described in German patent application DE 196 05 688 -, Vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium amine complexes known from German patent application DE 196 20 411 , the manganese described in German patent application DE 44 16 438 , Copper and cobalt complexes, the cobalt complexes described in European patent application EP 0 272 030 , the manganese complexes known from European patent application EP 0 693 550 , the manganese, iron, cobalt and copper complexes known from European patent EP 0 392 59 2 and / or further manganese complexes known from the prior art. Combinations of bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 196 13 103 and international patent application WO 95/27775 . Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total agent.

As further surfactant components which are introduced into the process according to the invention can come anionic and optionally amphoteric and / or cationic as well if appropriate, further nonionic surfactants into consideration, at least a part of the nonionic surfactants in the form of a silicate nonionic compound in the Procedures must be introduced.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are 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 sulfonating 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 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. Among fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they are the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. Preferred sulfated fatty acid glycerol esters are the 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.

As alk (en) yl sulfates are the alkali and especially 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, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar 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 especially 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. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. In particular, those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C _12-24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.

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 of their Sodium or potassium salts, especially in the form of the sodium salts.

In addition, the agents can also contain components that make oil and fat washable made of textiles. This effect is particularly evident if a textile is soiled, which has previously been repeatedly with an inventive Detergent containing this oil and fat-dissolving component is washed has been. 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 15 to 30% by weight of methoxyl groups and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, as well as the polymers of phthalic acid and / or of the known from the prior art Terephthalic acid or its derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified Derivatives of these. Of these, the sulfonated ones are particularly preferred Derivatives of phthalic acid and terephthalic acid polymers.

Examples Example:

A finely divided silicate carrier composed of 5% by weight of sodium carbonate, 76% by weight of water glass and 19% by weight of water was produced by spray drying. The particle size distribution was ≤ 2.0 mm with 86% of the particles between 0.8 and 0. 4 mm was brought. This carrier was loaded with nonionic surfactant and had a bulk density of 824 g / l. The remaining surfactants, builders and additives were added to a Lödige mixer and the silicate charged with nonionic surfactant was added while the mixer was running. In this way, the agent E1 according to the invention was obtained with a bulk density of 760 g / l and the composition [% by weight]: Soap 0.76 C ₁₃ alkylbenzenesulfonate Na 7.49 C ₈ -C ₁₈ fatty alcohol sulfate 11.48 Water glass 11.29 sodium 1.01 Zeolite A 19.09 C _13-15 oxo alcohol 3 to 7 EO 2.39 C ₁₂ -C ₁₈ fatty alcohol 7 EO 1.04 Sokalan CP5® 3.58 Tylose 0.24 opt. Brightener 0.21 Phosphonate 0.51 aqueous NaOH, 50% 0.18 Sodium percarbonate 18.40 TAED 7.00 Salts 1.59 enzyme 1.56 Perfume 0.36 Foam inhibitor 3.64 Repelotex® 0.50 water rest Sokalan CP5 ® is an acrylic acid-maleic acid copolymer from BASF
Repelotex ® is a terephthalic acid-ethylene glycol-polyethylene glycol ester from Rhône-Poulenc.

For induction tests in standard induction troughs and for detachment attempts in the hand wash test (in particular at temperatures up to 30 ° C.) this was demonstrated by the process according to the invention Manufactured agents have comparable to better results than commercially available universal detergents with the same amounts of nonionic surfactant. On greasy and / or oily stains the cleaning performance of the agents according to the invention was consistently better than that of the comparative examples.

The application test was carried out under practical conditions in one Household washing machine (Miele W 717). For this, the machine was cleaned with 3 kg Filling laundry and 0.5 kg test fabric soiled with natural grease (cotton / linen) loaded. Washing conditions: tap water of 16 ° dH (equivalent to 160 mg CaO / l), amount of detergent used per detergent: 76 g, washing temperature 60 ° C, Washing time 60 min, liquor ratio (kg of laundry to liter of washing water in Main wash cycle) 1 to 5.7, rinse three times with tap water, spin off and Dry.

The agent E1 produced by the method according to the invention was tested against two commercially available universal detergents V1 and V2, the test fabrics being examined after drying in accordance with DIN 6174 (colorimetric determination of color differences in body colors) using a Minolta CR 300 (3-point measurement). The results of the color distance measurements are summarized in Table 1: Color distance values medium E1 V1 V2 dE (w) (initial value - wash value) 43.3 31.2 30.7

Claims (8)

Process for the production of detergents and cleaning agents which contain a silicate builder component in conventional mixing / granulating devices, characterized in that a) a silicate builder component is introduced into the process, which is characterized in that the silicate is acted on by nonionic surfactants, the silicate builder component has a bulk density of more than 800 g / l and the particle size distribution of the silicate to be acted upon before the exposure to nonionic surfactant Has particles above a diameter of 2.0 mm and b) is mixed or granulated with other usual ingredients of washing and cleaning agents, a bulk density of at least 750 g / l being set. A method according to claim 1, characterized in that at least 40% of the silicate particles Have sizes between 0.4 and 0.8 mm. Method according to one of claims 1 or 2, characterized in that the silicate with less than 10% by weight nonionic surfactant (s), in particular with 2 to 5% by weight nonionic surfactant (s), based on the detergent and cleaning agent. Process according to one of claims 1 to 3, characterized in that a C _12-18 alcohol ethoxylated with 5 to 8 ethylene oxide units is used to apply the silicate. Method according to one of claims 1 to 4, characterized in that for the application of the silicate alkyl polyglycosides are used. Method according to one of claims 1 to 5, characterized in that the further Detergent and cleaning agent ingredients are selected from anionic, cationic and / or amphoteric surfactants, builders, cobuilders, bleaches and their precursors, bleach activators, enzymes, optical brighteners, complexing agents, soil repellents and perfume. Washing and cleaning agent, produced according to one or more of claims 1 to 6, characterized in that the content of nonionic surfactants in the agent is below 10 % By weight, based on the weight of the composition. Washing and cleaning agent, produced according to one or more of claims 1 to 6, characterized in that the total content of the surfactant above 20 wt .-%, based on the weight of the agent.