DE19952383A1 - Detergents and cleaning agents - Google Patents

Abstract

The invention relates to detergents or cleaning agents that contain tensides and optionally other conventional ingredients as well as particles with a particle size of from 5 to 500 nm. The inventive detergents or cleaning agents impart to the surface to be cleaned temporary dirt-repellent properties.

Description

The present invention relates to a detergent and cleaning agent, the tenside and also contains other common ingredients, a means for cleaning hard surfaces chen, a rinse aid for use in the automatic cleaning of dishes and a Laundry detergent.

Cleaning substrates, i. H. both hard surfaces and textiles of great importance both in the household and in the commercial sector. On the one hand the washing and cleaning processes have hygienic reasons, in many cases they are also theoretical reasons. The aesthetic reasons are especially for translucent or smooth surfaces of importance. So lose "dusty" glasses including Window panes and surfaces made of porcelain at least partially shine.

Observations in nature have shown that surfaces of plants have dirt-repellent properties because dirt particles can be found on these surfaces cannot deposit sustainably. Such surfaces are able to get through Clean rain or moving water. This effect is reflected on the Surface wax layers and especially on their surface structure returned.

European patent EP 0772 514 describes a self-cleaning replica of plants Surface of objects reveals an artificial surface structure Has elevations and depressions and is characterized in that the distance between the surveys in the range of 5 to 200 µm and the height of the surveys in the Range from 5 to 100 µm and at least the elevations are made of hydrophobic Polymers and durable hydrophilic materials exist and the surveys do not Water or detachable by water with detergents.

The surfaces disclosed in the prior art have a permanent presence Surface with a defined structure. These surfaces are in the area of washing and detergents unsuitable because of the large number of surfaces to be cleaned  a permanent change already in the manufacturing process of these substrates should be taken into account.

The present invention was based on the object of a washing and cleaning agent To make available that is suitable for temporarily cleaning the substrate to be cleaned in this way change that the surface of the substrate to be cleaned temporarily dirt-repellent Properties are conferred.

Surprisingly, it was found that a surface is temporarily dirt-repellent Properties can be imparted if an agent that is in addition to surfactants optionally contains other conventional ingredients, particles with a particle size of 5 up to 500 nm can be added.

Temporary change of the surface in the sense of the present invention means that the effect after a few, especially up to 4 washing and cleaning cycles can be maintained.

The present invention accordingly relates to a washing and cleaning agent, containing surfactants and optionally other usual ingredients, thereby characterized in that it contains particles with a particle size of 5 to 500 nm.

The particles used according to the invention are preferably water-insoluble or only slightly water-soluble particles which temporarily remain on the substrate to be cleaned after the washing or cleaning process. According to the invention, these particles have a particle size of 5 to 500 nm, preferably 5 to 250 nm. Because of the particle size, these particles are also referred to as nanoscale particles. Any insoluble solids which are present in the size distribution mentioned can be used as particles. Examples of suitable particles are any precipitated silica, aerogels, xerogels, Mg (OH) ₂ , boehmite (Al (O) OH, ZrO ₂ , ZnO, CeO ₂ , Fe ₂ O ₃ , Fe ₃ O ₄ , TiN, hydroxylapatite, bentonites, Hectorite, SiO _2. CeO ₂ , SnO ₂ , In ₂ O _3. SnO ₂ , NgAl ₂ O ₄ , HfO ₂ , sols, such as SiO ₂ sols, Al ₂ O ₃ sols or TiO ₂ sols, as well as any mixtures the previous one.

The content of these nanoscale particles in the agents according to the invention should be so be dimensioned so that the surface of the substrate to be cleaned is sufficiently covered. The agents preferably contain 0.01 to 35% by weight, particularly preferably 0.01 to 20  % By weight and in particular 0.5 to 10% by weight of the nanoscale particles, based on the finished funds.

By using the nanoscale particles it is possible to increase the wettability of the cleaning substrates significantly. There are often contact angles of 5 ° to reach 20 °, which means that a drop of water or oil almost completely on the Surface spreads.

This is particularly advantageous because it ensures that the Liquid from the wetted substrate is guaranteed and residues do not accumulate in the Can accumulate drops and form visible stains after drying.

A further improvement can be achieved if the surface of the nanoscale particles is modified. This can be done, for example, through conventional Complexing agents take place, which prevents the precipitation of Ca or Mg salts can. These compounds can be applied in such an amount that they are in the finished agents in amounts of 1 to 8 wt .-%, preferably from 3.0 to 6.0 wt .-% and in particular 4.0 to 5.0 wt .-%, based on the finished agent, are included. They are usually on the surface of the particles.

A preferred class of complexing agents are the phosphonates. Among these preferred Compounds include in particular organophosphonates such as 1-hydroxyethane 1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylene triamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2,4- tricarboxylic acid (PBS-AM), mostly in the form of their ammonium or alkali metal salts be set. The phosphonates are applied in such an amount to the surface of the Applied particles that they in the finished agent in amounts of 0.01 to 2.0 wt .-%, preferably 0.05 to 1.5 wt .-% and in particular from 0.1 to 1.0 wt .-% are included.

Substances that complex heavy metals can also be used as complexing agents Ren. Suitable heavy metal complexing agents are, for example, ethylenediaminetetraacetic acid acid (EDTA) or nitrilotriacetic acid (NTA) in the form of the free acids or as an alkali metal salts and derivatives of the foregoing and alkali metal salts of anionic polyelectro lytes such as polymaleates and polysulfonates.  

Other suitable complexing agents are low molecular weight hydroxycarboxylic acids such as Citro Nenoic acid, tartaric acid, malic acid, lactic acid or gluconic acid or salts thereof, where Citric acid or sodium citrate are particularly preferred.

The surface of the particles can be modified, for example, simply by stirring a suspension of the particles with the complexing agent takes place during the Stir on the surface of the particles.

It will be apparent to those skilled in the art that not all of the complexing agent into which agents are to be incorporated onto which nanoscale particles are applied got to. It is also possible to incorporate all or part of these connections directly.

A further increase in wettability can also be achieved by adding hydrophilizing agents. Examples of such hydrophilizing agents are mono- or polyvalent alcohols, alkanolamines or glycol ethers, provided that they are miscible with water. Before hydrophilizing agents are preferably selected from ethanol, n- or i-propanol, butanols, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propylene glycol, dipropylene ether -, or -ethyl ether, di-isopropylene glycol monomethyl or -ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether alcohols, especially C ₁ -C ₄ -alkanols, glycols, polyethylene glycols, preferably with a molecular weight between 100 and 100,000, in particular between 200 and 10,000, and polyols, such as sorbitol and mannitol, and polyethylene glycol which is liquid at room temperature, carboxylic acid esters, polyvinyl alcohols, ethylene oxide-propylene oxide block copolymers and also any mixtures of the above.

The agents according to the invention can be in liquid to gel form or also in solid form available.

If the agents are in liquid to gel form, they are usually aqueous preparations, which may also contain other water-miscible organic solutions agents and thickeners. To the organic miscible with water agents count z. B. the compounds mentioned above hydrophilizing. The Her The provision of liquid to gel preparations can be carried out continuously or in batches by simply mixing the components, if necessary at an elevated temperature.  

A liquid composition according to the invention can be used to adjust the viscosity one or more or thickening systems are added. The viscosity of the invented Compositions according to the invention can be prepared using customary standard methods (for example Brookfield viscometer RVD-VII can be measured at 20 rpm and 20 ° C, spindle 3) and is preferably in the range from 100 to 5000 mPas. Preferred compositions have viscosities of 200 to 4000 mPas, values between 400 and 2000 mPas are particularly preferred.

Suitable thickeners are usually polymeric compounds. These too Swelling agents, mostly organic high molecular substances, the liquids soak up, swell and finally into viscous real or colloidal solutions pass over, come from the groups of natural polymers, the modified natural Chen polymers and the fully synthetic polymers.

Natural polymers that are used as thickeners are included in for example agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, Guar flour, locust bean gum, starch, dextrins, xanthan gum, gelatin and casein. Modified natural products mainly come from the group of modified starches and Celluloses, examples include carboxymethyl cellulose and other cellulose ethers, Hy called droxyethyl and propyl cellulose as well as core meal ether.

In addition, surfactant thickeners can also be used, e.g. B. alkyl polyglycosides such as C _8-10 alkyl polyglucoside (APG® 220, manufacturer: Henkel KGaA); C _12-14 - alkyl polyglucoside (APG® 600, manufacturer: Henkel KGaA).

The means in solid form include e.g. B. powders, compacts, such as granules and Shaped body (tablets) The individual forms can be according to the prior art known processes, such as spray drying, granulation and pressing sen.

The surfactants contained according to the invention are preferably selected from nonionic, anionic, amphoteric and cationic surfactants and any mixtures thereof.

The surfactants are preferably in an amount of 0.1 to 50% by weight, preferably of 0.1 to 35 wt .-% and in particular from 0.1 to 15 wt .-%, based on the combination setting, before.  

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 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 may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and preferred by average 2 to 8 EO per mole of alcohol. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO to 7 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 7 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. Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention. Here block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not distributed in blocks but statistically. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

Particularly preferred examples of non-ionic surfactants which have good run-off behavior The fatty alcohol polyethylene glycol ethers, Fettal, cause water on hard surfaces alcohol polyethylene / polypropylene glycol ether and mixed ether. the possibly closed end group could be.

Examples of fatty alcohol polyethylene glycol ethers are those with the formula (I)

R ¹ O- (CH ₂ CH ₂ O) _n1 H (I)

in which R ^{1 is} a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and n1 is a number from 1 to 5.

The substances mentioned are known commercial products. Typical examples are investment products of an average of 2 or 4 moles of ethylene oxide with technical C _12/14 coconut oil alcohol (Dehydol® LS-2 or LS-4, from Henkel KGaA) or addition products from by an average of 4 moles of ethylene oxide on C _14/15 oxo alcohols (Dobanol®45-4, Shell). The products can have a conventional or narrowed homolog distribution.

Fatty alcohol polyethylene / polypropylene glycol ethers are to be understood as meaning nonionic surfactants of the formula (II)

in which R ^{2 is} a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, n2 for numbers from 1 to 0 and m2 for numbers from 1 to 4.

These substances are also known commercial products. Typical examples are addition products of an average of 5 moles of ethylene oxide and 4 moles of propylene oxide with technical C _12/14 coconut fatty alcohol (Dehydol® LS-54, from Henkel KGaA), or 6.4 moles of ethylene oxide and 1.2 mol of propylene oxide over technical C _10/14 coconut fatty alcohol (Dehydol®LS-980, from Henkel KGaA).

Mixed ethers are to be understood as end group-locked fatty alcohol polyglycol ethers with the formula (III)

in R ³ for a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, n3 for numbers from 1 to 10, m2 for 0 or numbers from 1 to 4 and R ⁴ for an alkyl radical has 1 to 4 carbon atoms or a benzyl radical.

Typical examples are mixed ethers of the formula (III) in which R ^{3 stands} for a technical C _12/14 cocoalkyl radical, n3 for 5 or 10, m3 for 0 and R ⁴ for a butyl group (Dehypon®LS-54 or LS -104, Henkel KGaA). The use of mixed ethers containing butyl or benzyl groups is particularly preferred for technical reasons.

Hydroxyalkyl polyethylene glycol ethers are compounds with the general formula (IV)

in which R ^{5 represents} hydrogen or a straight-chain alkyl radical having 1 to 16 carbon atoms,
R ^{6 is} a straight-chain or branched alkyl radical having 4 to 8 carbon atoms,
R ^{7 represents} hydrogen or an alkyl radical having 1 to 16 carbon atoms and
n4 for a number from 7 to 30
with the proviso that the total number of carbon atoms contained in R5 and R7 is 6 to 16.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, 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, carbon 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 an arbitrary number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of nonionic surfactants that are used especially in solid agents are, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fat acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dime thylamine 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 them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula V,

in the R ⁸ CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ⁹ 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.

The group of polyhydroxy fatty acid amides also includes compounds of the formula VI

in which R ¹⁰ for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ¹¹ for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ¹² for a linear, branched or cyclic alkyl radical or represents an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives of this residue.

[Z] is preferably obtained by reductive amination of a 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 the inter national application WO-A-95/07331 by reaction with fatty acid methyl esters in Ge presence of an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides leads.

Anionic surfactants 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 disulfates such as are obtained, for example, from C _12-18 monoolefins with a terminal or internal double bond by sulfonation 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 sulf oxidation with subsequent hydrolysis or neutralization. Likewise, the esters of a-sulfo fatty acids (ester sulfonates), e.g. B. the a-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

As alk (en) yl sulfates, the alkali and especially the sodium salts of sulfuric acid are half-esters of C ₁₂ -C ₁₈ 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, straight-chain alkyl radical produced on a petrochemical basis. 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 Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under fatty acid glyce The mono-, di- and triesters as well as their mixtures are to be understood as Rinestern, as in 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 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, My ristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 moles 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 radicals 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.

Other suitable anionic surfactants include soaps, in particular can be used in powdery form and at higher pH values. Suitable are ge saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, Pal mitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, e.g. B. coconut, palm kernel, olive oil 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 tri ethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.

So-called gemini surfactants can be considered as further surfactants. Below are in generally understood such compounds that two hydrophilic groups and two hydro possess phobic groups per molecule. These groups are usually separated by a so-called called "spacers" separated from each other. This spacer is usually a carbon chain, which should be long enough that the hydrophilic groups have a sufficient distance so that they can act independently of one another. Such surfactants are characterized in generally due to an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases however under the term gemini surfactants not only dimeric but also trimeric surfactants Roger that.

Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers of dimer alcohol. bis- and trimer alcohol tris sulfates and ether sulfates. End group capped dimers and trimeric mixed ethers are particularly characterized by their bi- and multifunctionality. So the end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes. Gemini can also be used. Polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides.

Examples of the cationic surfactants which can be used in the agents according to the invention are especially quaternary ammonium compounds. Ammonium halides such as Alkyltrimethylammoniumchloride, Dialkyldimethylammoniumchloride and Trialkylmethyl  ammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, Distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzyl ammonium chloride and tricetylmethylammonium chloride. Further used according to the invention Quaternized protein hydrolyzates are bare cationic surfactants.

Also suitable according to the invention are cationic silicone oils such as those in the Commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino modified Silicon, which is also called Amodimethicone), SM-2059 (Manufacturer: General Elec tric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Gold schmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

Alkylamidoamines, especially fatty acid amidoamines such as that under the name Tego Amid®S 18 available stearylamidopropyldimethylamine, can also be used and are characterized by their good biodegradability.

Quaternary ester compounds are also very readily biodegradable "Esterquats", such as the methylhydroxyalkyl sold under the trademark Stepantex® dialkoyloxyalkylammonium methosulfates.

This is an example of a quaternary sugar derivative that can be used as a cationic surfactant Commercial product Glucoquat®100, according to CTFA nomenclature a "Lauryl Methyl Gluceth- 10 Hydroxypropyl Dimonium Chloride ".

In the laundry detergent and cleaning product tablets according to the invention all can be more common builders used in detergents and cleaning agents, in particular other zeolites, silicates, carbonates, organic cobuilders and - where no ecological precedent parts exist against their use - including the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} . H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 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 are Na ₂ Si ₂ O ₅ . yH ₂ O 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 have been brought about in various ways, for example by surface treatment, compounding, compaction / compression or by overdrying. In the context of this invention, the term “amorphous” also means “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide any harmful X-ray reflections as are typical for crystalline substances, but at most one or more maxima of the scattered X-ray radiation 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.

The fine crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product of Crosfield) is particularly preferred. However, zeolite X and mix are also suitable genes from A, X and / or P.

Zeolites from Fau are further preferred and particularly suitable zeolites to call jasit type. The mineral faujasite belongs to the zeolites X and Y. the faujasite types within the zeolite structure group 4, which are characterized by the double Subunit D6R is marked (compare Donald W. Breck: "Zeolite Molecular Sieves ", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 92). To Zeo lith structure group 4 includes the minerals Cha in addition to the faujasite types mentioned bazit and gmelinit as well as the synthetic zeolites R (Chabazit-type), S (Gmelinit-type), L and ZK-5. The latter two synthetic zeolites have no mineral analogues.

Zeolites of the faujasite type are composed of β-cages which are linked tetrahedrally via D6R subunits, the β-cages being arranged in a manner similar to the carbon atoms in the diamond. The three-dimensional network of the faujasite-type zeolites used in the process according to the invention has pores of 2.2 and 7.4 Å, the unit cell also contains 8 cavities with a diameter of approximately 13 Å and can be calculated using the formula Na ₈₆ [ (AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ]. Describe 264H ₂ O. The network of zeolite X contains a void volume of approximately 50%, based on the dehydrated crystal, which represents the largest empty space of all known zeolites (zeolite Y: approx. 48% void volume, faujasite: approx. 47% void volume). (All data from: Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, pages 145, 176, 177).

In the context of the present invention, the term “zeolite of the faujasite type” denotes all three zeolites that form the faujasite subgroup of zeolite structure group 4. Next According to the invention, zeolite X also includes zeolite Y and faujasite and mixtures of these compounds can be used according to the invention, the pure zeolite X being preferred. Mixtures or cocrystallizates of faujasite-type zeolites with other zeolites then, which do not necessarily have to belong to the zeolite structure group 4, are inventive can be used according to, the advantages of the method according to the invention being particularly clear Lich emerge when at least 50 wt .-% of the zeolites of the faujasite type are.

The aluminum silicates that are used in the process according to the invention are com commercially available, and the methods for their representation are in standard monographs wrote.

Examples of commercially available X-type zeolites can be described by the following formulas:

Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ]. xH ₂ O,

K ₈₆ [AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ]. xH ₂ O,

Ca ₄₀ Na ₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ]. xH ₂ O,

Sr ₂₁ Ba ₂₂ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ]. xH ₂ O,

in which x can take values between 0 and 276 and the pore sizes from 8.0 to 8.4 A have.

A co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X), which is available from CONDEA Augusta S. p. A. is sold under the brand name VEGOBOND AX® and through 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. The zeolite can be used both as a builder in a granular Compound used, as well as a kind of "powdering" of the whole to be pressed Mixture are used, usually both ways of incorporating the zeolite be used in the premix. Suitable zeolites have an average particle size of less than 10 µm (volume distribution; measurement method: Coulter Counter) on and included preferably 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 buildersub punching possible, provided that such use is not avoided for ecological reasons should be. Among the multitude of commercially available phosphates are the alkali metal phosphates with particular preference for pentasodium or pentapotassium tri phosphate (sodium or potassium tripolyphosphate) in the detergent and cleaning agent ind struck 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 that lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ) at 200 ° C, at higher temperatures 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 pH 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 and} has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] easily 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 5H ₂ O) and 12 mol. Water (density 1.52 gcm ^-3 , melting point 35 ° with loss of 5H ₂ O), becomes anhydrous at 100 ° and changes to 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 that have a density of 1.62 gcm ^{-3 as} a dode cahydrate and a melting point of 73-76 ° C (decomposition), as a 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 prepared 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 e.g. B. when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more 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. Na ₄ P ₂ O ₇ is formed when dodium triumphosphate is heated to <200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating 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 the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. For the latter in particular, a large number of terms are used: 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 6H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n - Na with n = 3. In 100 g of water about 17 g of the crystal water-free salt dissolve at room temperature, about 20 g at 60 ° and about 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 + 2KOH → 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 umtripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

Detergents and cleaning agents according to the invention can be used as organic cobuilders molded articles, in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, Aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and Phosphonates are used. These classes of substances are described below.

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such polycarboxylic acids ver standing that have more than one acid function. For example, these are lemons acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fu Martic acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such a  ger use for ecological reasons is not objectionable, as well as mixtures of the sen. 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 their buil the effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or rice cleaning agents. In particular, citric acid, succinic acid, glutaric acid, adi pinic acid, gluconic acid and any mixtures of these.

Polymeric polycarboxylates are also suitable as builders, for example the Alka limetal salts of 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 respective acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. These figures deviate significantly from the molecular weight data for which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrene sulfonic acids are generally significantly higher than the molar masses specified in this publication.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, this can Group in turn the short-chain polyacrylates, the molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may be preferred.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As particularly ge copolymers of acrylic acid with maleic acid which have 50 to 90% by weight have proven suitable % Acrylic acid and 50 to 10 wt .-% maleic acid. Your molecular weight, be pulled on free acids, is generally 2000 to 70,000 g / mol, preferably 20,000 up to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.  

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

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

Biodegradable polymers of more than two ver. Are also particularly preferred different monomer units, for example those that act as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as a mono contain more salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.

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

Likewise, other preferred builder substances are polymeric aminodicarboxylic acids, de ren salts or their precursors. Polyaspa are particularly preferred Ragic acids or their salts and derivatives.

Other suitable builder substances are polyacetals, which are produced by the implementation of Dial dehydrogenated with polyol carboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups have pen, can be obtained. Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcar receive bonic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches that can. The hydrolysis can be carried out according to customary methods, for example acid or enzyme catalysis based procedures. They are 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, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a Polysac charids compared to dextrose, which has a DE of 100. Both are usable 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 a higher molar mass range from 2000 to 30000 g / mol.  

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. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine di succinate, are other suitable cobuilders. This is ethylenediamine-N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Continue to be In this connection, glycerol disuccinates and glycerol trisuccinates are also preferred. Suitable amounts are in formulations containing zeolite and / or silicate at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acid ren or their salts, which may optionally also be in lactone form and wel che at least 4 carbon atoms and at least one hydroxyl group and maximum contain two acid groups.

Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Among the Hydroxyalkanephosphonaten is the 1-hydroxyethane-1,1-diphosphonate (HEDP) from special of importance as a cobuilder. It is preferably used as the sodium salt, the Disodium salt neutral and the tetrasodium salt reacts alkaline (pH 9). As an aminoalkane phosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), Diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in Question. They are preferably in the form of the neutral sodium salts, e.g. B. as Hexasodium salt of EDTMP or as hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The Aminoalkanephosphonates also have a strong ability to bind heavy metals. Accordingly, it may be preferred, especially if the compositions also contain bleach be to use aminoalkanephosphonates, in particular DTPMP, or mixtures of to use the phosphonates mentioned.

In addition, all compounds that are capable of complexing with alkaline earth ions train as cobuilders.

Furthermore, the agents according to the invention can all usually be found in washing and cleaning agents Containing agents contained substances, such as enzymes, bleach, bleach activato  ren, graying inhibitors, foam inhibitors, inorganic salts, solvents, pH Adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes, silicone oils, Soil-release connections, optical brighteners, graying inhibitors, run-in preventers, Anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fun gicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, repellents and Im Impregnating agents, swelling and sliding resistant agents, UV absorbers or their mixtures.

Enzymes that can be used in the compositions come from the class of oxidases, Pro teases, lipases, cutinases, amylases, pullulanases, cellulases, hemicellulases, xylanases and peroxidases and mixtures thereof, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Alcalase®, Esperase® and / or Savinase®, Amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Purafect® OxAm, Lipases like Lipolase®, Lipomax®, Lumafast® and / or Lipozym®, cellulases like Cellu zyme® and or Carezame®. Are particularly suitable from fungi or bacteria, such as Ba cillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia active ingredients. The optionally used enzymes can, as for example in European patent EP 0 564 476 or in international patent applications WO 94/23005 described, adsorbed on carrier substances and / or incorporated in coating substances be bedded to protect them against premature inactivation. You are in the fiction moderate surfactant mixtures, preferably in amounts of up to 10% by weight, in particular of 0.2 wt .-% to 2 wt .-%, contain, with particular preference against oxidative degradation stabilized enzymes.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate are of particular importance. Other useful bleaching agents are, for example, persulfates and mixed salts with persulfates, such as the salts available under the trade name CAROAT®, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -supplying acid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, diperdodecthalenoponic acid or phthaloic acid, phthaloic acid such as phthaloic 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.

To be used when washing at temperatures of 60 ° C and below, and especially when washing pretreatment can achieve an improved bleaching effect, bleach activators in the detergent tablets are incorporated. As bleach activators can  NEN compounds containing aliphatic peroxocarboxylic acids under perhydrolysis conditions preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally result in substituted perbenzoic acid can be used. Suitable substances are those that and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted Wear benzoyl groups. Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4- dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially 1,3,4,6-tetraace tylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulionates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso- NOBS), acylated hydroxycarboxylic acids such as triethyl-O-acetyl citrate (TEOC), carboxylic acid hydrides, especially phthalic anhydride, isatoic anhydride and / or succinic acid hydride, carboxamides, such as N-methyldiacetamide, glycolide, acylated polyvalent alcohols hole, especially triacetin, ethylene glycol diacetate, isopropenylacetate, 2,5-diacetoxy-2,5- dihydrofuran and those from German patent applications DE 196 16 693 and DE 196 16 767 known enol esters as well as acetylated sorbitol and mannitol as their mixtures described in European patent application EP 0 525 239 (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyllactose and acetylated, optionally N-alky gelled glucamine or gluconolactone, triazole or triazole derivatives and / or particulate Caprolactams and / or caprolactam derivatives, preferably N-acylated lactams, for example N-benzoylcaprolactam and N-acetylcaprolactam, which are derived 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 are known. The from the German patent application DE-A- 196 16 769 known hydrophilically substituted acylacetals and those in the German patent Application DE-A-196 16 770 and international patent application WO-A-95/14075 Acyllactams described are also preferably used. Even the one from Germany 's patent application DE-A-44 43 177 known combinations of conventional bleach activators can be used. Similarly, nitrile derivatives such as cyanopyridines, Ni trilquats, e.g. B. N-Alkyammoniumacetonitrile, and / or cyanamide derivatives can be used. Preferred bleach activators are sodium 4- (octanoyloxy) benzene sulfonate, n-nonanoyl or Isononanoyloxybenzenesulfonate (n- or iso-NOBS), undecenoyloxybenzenesulfonate (UDOBS), Sodium dodecanoyloxybenzenesulfonate (DOBS), decanoyloxybenzoic acid (DOBA, OBC 10) and / or dodecanoyloxybenzenesulfonate (OBS 12), and N-methylmorpholinum acetonitrile (MMA). Such bleach activators are in the usual quantity range of 0.01 to 20% by weight, preferably in amounts of 0.1 to 15% by weight, in particular 1% by weight to 10% by weight, based on the total composition.  

In addition to the conventional bleach activators or in their place, too so-called bleach catalysts can be included. These substances are bleach-enhancing transition metal salts or transition metal complexes such as for example Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes are suitable as bleaching catalysts Compounds are preferably used, which are described in DE 197 09 284 A1.

The washing and cleaning agents according to the invention are suitable both for cleaning hard surfaces including dishes and for washing textiles.

Another object of the present invention is accordingly a means for cleaning of hard surfaces containing surfactants and particles with a particle size of 5 to 500 nm.

Cleaning hard surfaces in the sense of the present invention includes cleaning all surfaces in the household and in the commercial sector including feet floors, wall and cabinet surfaces as well as windows. Likewise, the cleaning of Ge dishes included. The cleaning process also includes pre-treatment and post-treatment steps like a flushing process.

In a preferred embodiment, a cleaning agent according to the invention contains of hard surfaces 0.1 to 20% by weight of particles with a particle size of 5 to 500 nm, 3 to 45% by weight of surfactants, up to 10% by weight of organic solvent (hydrophilization medium), possibly complexing agent and water.

In a particularly preferred embodiment, contains a means for cleaning hard Surfaces, especially for cleaning glass, 0.1 to 20 wt .-% particles with a Particle size from 5 to 500 nm, up to 20% by weight of water-soluble organic solvents, preferably ethanol or propanol, up to 10% by weight of organic solvents, preferably glycol ether, 0.1 to 3% by weight of nonionic surfactants, 0.1 to 3% by weight anionic surfactants, up to 2% by weight of alkalizing agent, preferably ammonia or Amines, possibly fragrances and water.

Another object of the present invention is accordingly a textile detergent containing surfactants and particles with a particle size of 5 to 500 nm.  

Depending on their special recipe, the textile detergents can be used for laundry treatment, washing and post-treatment, d. H. used as a fabric softener, etc. become.

In a preferred embodiment, a textile detergent according to the invention contains the is in solid form, 0.1 to 35% by weight of particles with a particle size of 5 to 500 nm, 2.5 wt% to 20 wt% anionic surfactant, 1 wt% to 20 wt% nonionic Surfactant, 30% by weight to 55% by weight of water-insoluble inorganic builder, up to 25% by weight %, in particular 1% by weight to 15% by weight of bleach, up to 8% by weight, in particular 0.5 % By weight to 6% by weight of bleach activator and up to 20% by weight, in particular 0.1% by weight to 15% by weight of inorganic salts, in particular alkali carbonate, sulfate and / or silicate, and up to 2% by weight, in particular 0.4% by weight to 1.2% by weight, of enzyme.

In a preferred embodiment, a textile detergent according to the invention contains the is in liquid form, 0.1 to 32% by weight of particles with a particle size of 5 to 500 nm, up to 15% by weight, in particular 3% by weight to 10% by weight of anionic surfactants, up to 15 % By weight, in particular 3% by weight to 10% by weight, of nonionic surfactants, up to 18% by weight, in particular 4% by weight to 16% by weight of soap, 0.5% by weight, up to 20% by weight of water-soluble organic builders, up to 20% by weight, in particular 0.1% by weight to 5% by weight, of water soluble inorganic builder, and up to 60% by weight, in particular 10% by weight to 50 % By weight of water and / or water-miscible solvent, enzyme and up to 10% by weight, in particular 0.01 wt .-% to 7.5 wt .-% enzyme stabilizer system.  

Examples example 1 Glass cleaner

• A) Glass cleaner formulations with the components shown in Table 1 were produced by mixing the individual components.

Testing A. Treatment of the glass pane

The formulations were rubbed onto a glass sheet and with dirty water (Dispersion of water and a standard carpet dirt) sprayed. The test was in Comparison with an untreated glass pane and a formulation without nanoparticles carried out.

Result

The surface treated with nanoparticles shows an evenly running dirt water film. Large drops form on the untreated surface, on the one with the Glass cleaner polished surface also remain drops. After drying, who which the three panes of glass compared again. On the surface treated with nanoparticles There are no impurities, while one clearly shows on the other surfaces recognizes dirt residues as teardrop-shaped stains.

B. Methylene blue test

Process water was stained with methylene blue and on glass panes prepared as in A. applied. The results are shown in Table 2.  

C. Antifogging test

A glass surface treated with the formulation according to the invention as in A and one untreated glass surfaces were kept above water vapor. The results are in Table 2 reproduced.

Table 2

Evaluation criteria Methylene blue test and long-term test

• 1. 1 = closed water film without edge alignment
• 2. 2 = closed water film with slight edge alignment
• 3. 3 = no hydrophilicity effect

Antifogging test

• 1. 1 = no fogging of the windows
• 2. 6 = fogging of the windows

The test results show that the methylene blue test relates to the invention treated glass panes formed a closed film of water on the surface, while in comparison samples (Examples 1 and 2) in addition to a pronounced edge alignment there was also a drop pattern. The antifogging test was compared to the untreated glass plate, no fogging of the glass pane.

Overall, the formulations of the invention show the particles with a Particle size from 5 to 500 nm contain better wetting properties than that Formulations without such particles.

Claims (12)

1. detergents and cleaning agents containing surfactants and optionally other conventional ingredients, characterized in that it contains particles with a particle size of 5 to 500 nm. 2. Detergent and cleaning agent according to claim 1, characterized in that the Particles have a particle size of 5 to 250 nm. 3. Washing and cleaning agent according to one of claims 1 or 2, characterized in that the particles are selected from any precipitated silicas, aerogels, xerogels, Mg (OH) ₂ , boehmite (Al (O) OH, ZrO ₂ , ZnO, CeO ₂ , Fe ₂ O ₃ , Fe ₃ O ₄ , TiO ₂ , TiN, hydroxyapatite, bentonite, hectorite, SiO _2. CeO ₂ , SnO ₂ , In ₂ O _3. SnO ₂ , NgAl ₂ O ₄ , HfO ₂ , sols , such as SiO ₂ sols, Al ₂ O ₃ sols or TiO ₂ sols, and mixtures of the above. 4. washing and cleaning agent according to one of claims 1 to 3, characterized records that the agent 0.1 to 35 wt .-% of the particles, based on the finished Means included. 5. Detergent and cleaning agent according to one of claims 1 to 4, characterized records that the surfaces of the particles are modified with complexing agents selected from the phosphonates, such as 1-hydroxyethane-1,1-diphosphonic acid, Ami notri (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) so such as 2-phosphonobutane-1,2,4-tricarboxylic acid (PBS-AM), mostly in the form of their Ammonium or alkali metal salts are present, heavy metal complexing agents, such as Ethylenediaminetetraacetic acid or nitrilotriacetic acid in the form of the free acids or as alkali metal salts, their derivatives, alkali metal salts of anionic polyelectrics trolytes such as polymaleates and polysulfonates, as well as low molecular weight hydroxycar bonic acids, such as citric acid, tartaric acid, malic acid, lactic acid or gluconic acid or their salts. 6. washing and cleaning agent according to one of claims 1 to 5, characterized in that it contains hydrophilizing agents selected from the group consisting of ethanol, n- or i-propanol, butanols, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, Diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol , 3-Me thyl-3-methoxybutanol, propylene glycol t-butyl ether alcohols, in particular C ₁ -C ₄ alkanols, glycols and polyols and at room temperature liquid polyethylene glycol, carboxylic acid esters and any mixtures of the above contains. 7. washing and cleaning agent according to one of claims 1 to 6, characterized records that they are in liquid to gel or in solid form, especially as Powder or compact, such as tablets, are present. 8. washing and cleaning agent according to one of claims 1 to 7, characterized records that the surfactants are selected from the nonionic, anionic, am thermal and cationic surfactants and their mixtures. 9. washing and cleaning agent according to one of claims 1 to 8, characterized records that builders selected from the group of zeolites, silicates, carbo nate, organic builders and cobuilders and phosphates are included. 10. washing and cleaning agent according to one of claims 1 to 9, characterized records that enzymes, bleaching agents, bleach activators, graying inhibitors, Foam inhibitors, inorganic salts, solvents, pH adjusting agents, fragrances, Perfume carriers, fluorescent agents, dyes, hydrotopes, silicone oils, soil release ver bindings, optical brighteners, graying inhibitors, run-in preventers, creases protective agents, color transfer inhibitors, antimicrobial agents, germicides, fun gicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, phobing and Impregnating agents, swelling and anti-slip agents, UV absorbers or their mixtures are included. 11. Means for cleaning hard surfaces containing surfactants and particles with a Particle size from 5 to 500 nm. 12. Textile detergent containing surfactants and particles with a particle size of 5 to 500 nm.