EP2066736A2

EP2066736A2 - Hyper-branched polymers for the provision of hygienic characteristics

Info

Publication number: EP2066736A2
Application number: EP07820539A
Authority: EP
Inventors: Mirko Weide; Steve DÖRING; Roland Breves; Anja SCHLÖSSER; Jörg TILLER; Andreas Fuchs
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2006-09-27
Filing date: 2007-09-25
Publication date: 2009-06-10
Also published as: DE102006046073A1; JP2010505015A; WO2008037698A2; WO2008037698A3; US20090238889A1

Abstract

The invention relates to hyper-branched polymers having a hydrophobic core and an antimicrobial and/or anti-adhesive active shell for providing surfaces with semi-permanent hygienic characteristics.

Description

Hyperbranched polymers for hygienic equipment

description

The present invention relates to hyperbranched polymers having a hydrophobic core and an antimicrobial and / or anti-adhesive shell for semi-permanent hygienic finishing of surfaces.

For hygiene reasons, cleaning agents are often equipped with antimicrobial additives. However, the antimicrobial effect is usually limited to the duration of the cleaning, because the antimicrobial additive is washed off the treated surface together with the detergent again. However, it is desirable to provide a longer lasting antimicrobial effect on the treated surfaces.

A possible approach to solving this problem might be to permanently antimicrobialize the surfaces in question by covalent bonding of antimicrobial substances. However, such permanent equipment is usually very difficult to do, if at all.

The object of the present invention was therefore to provide substances which permit longer-lasting or semi-permanent hygienic finishing of surfaces without having to be covalently fixed to the respective surfaces.

Ideally, these substances should also be able to be incorporated into conventional detergents and cleaners, so that at the same time semi-permanent sanitary equipment can be achieved with the normal cleaning of the surfaces.

Surprisingly, it has now been found that hyperbranched block copolymers which, on the one hand, carry a hydrophobic core and, on the other hand, antimicrobially active groups, in particular quaternary ammonium groups, are outstandingly suitable for achieving this object.

The preparation of hyperbranched block copolymers starting from diisopropenylbenzene and further monomers, for example vinylpyridine, is already known from the prior art (Polymer (2003) 44 (8), 2213-2220; Macromolecular Chemistry and Physics (2001) 202 (9), 1569- 1575, WO04 / 113418). However, none of these publications describes the preparation of antimicrobially active hyperbranched block copolymers. WO 03/024217 describes compositions containing a mixture of quaternary ammonium compounds and dendritic polymers, but no dendritic polymers are described which would themselves comprise quaternary ammonium compounds.

Furthermore, it is already known that dendrimeric polymers can be provided with antimicrobial properties (WO98 / 26662, US6440405, WO01 / 012725).

WO98 / 26662 describes dendrimers which are modified to give antimicrobial properties with oligosaccharides. In US6440405 dendrimers are described with quaternary ammonium groups. However, the dendrimers disclosed in these patents do not have the hydrophobic regions which are advantageous according to the invention and which allow the semi-permanent adhesion according to the invention and thus a longer-lasting antimicrobial effect.

WO01 / 012725 describes curable antimicrobial hyperbranched polymer compositions containing a hyperbranched polymer, an antimicrobially active compound and optionally a polyester resin. A possible antimicrobial compound that can be used is also a quaternary ammonium salt. Again, however, no polymers are described which would have the inventively advantageous structure of hydrophobic areas in combination with antimicrobially effective areas that allow the inventive advantageous semi-permanent adhesion.

A first subject of the present invention are therefore hyperbranched polymers, characterized in that they comprise a hydrophobic core and an antimicrobially and / or anti-adhesively active shell.

According to the invention, "core" means the interior of the hyperbranched polymer The core in this sense comprises, on the one hand, the hyperbranched core in the true sense, ie the region which serves as a nucleus for the formation of the hyperbranched polymer; Core "according to the invention may also include those areas on the branches of the hyperbranched polymer, which immediately adjoin this hyperbranched core, Namem, then, when these areas are hydrophobic areas. The terms "core" and "hyperbranched core" may thus be different according to the invention, wherein the core of the hyperbranched polymer comprises the hyperbranched core in the true sense. The hydrophobic region of the hyperbranched polymer can now be located both in the hyperbranched core alone and also in the immediately adjoining areas of the branches.

In a preferred embodiment, the hydrophobic region is only in the hyperbranched core in the true sense. In this embodiment, the "hydrophobic core" of the hyperbranched polymer is the hyperbranched core as such, so that in this embodiment the meanings of "core" and "hyperbranched core" are identical.

In a further preferred embodiment, the hydrophobic region is located not only in the hyperbranched core, but also in the immediately adjoining regions of the branches. In this embodiment, the meanings of "core" and "hyperbranched core" are correspondingly different.

By "shell" is meant an area that joins the core of the polymer from the inside out, and the shell is appropriately formed by antimicrobial and / or anti-adhesive areas located on the branches of the hyperbranched polymer In one embodiment, the antimicrobially and / or anti-adhesively active shell may directly adjoin the hyperbranched core or else be located further out on the hyperbranched polymer, the latter in particular when hydrophobic regions adjoin the hyperbranched core.

The hydrophobic region is preferably formed by silicone groups or by hydrophobic hydrocarbons, which may optionally also contain heteroatoms. The hydrophobic hydrocarbon may be, for example, an optionally substituted polyacrylate or polymethacrylate. As stated, the hydrophobic region can be confined to the hyperbranched core or, moreover, extend into the branches of the polymer. The hydrophobic region preferably consists of monomers which are lined up in a block-like manner.

In a preferred embodiment of the invention, the hydrophobic core contains aromatic radicals C ₆ -io-aryl, in particular phenyl.

In a particular embodiment, only the hyperbranched core contains aromatic radicals C ₆ . ₁₀ -aryl. In order for the hydrophobicity of the molecule to be sufficient, in this embodiment, the number of hydrophobic aromatic radicals contained in the core should preferably be at least 15 or 20, more preferably at least 30, 40 or 50, especially at least 100, 120 or 150, amount.

In another particular embodiment, the hyperbranched polymer branches are bonded to the hydrophobic core, which itself hydrophobic regions with aromatic residues include C ₆ _i ₀ aryl, which is followed from inside to outside antimicrobial and / or antiadhesive areas. The hydrophobic regions in the branches are preferably polymeric units of at least 10 or 20, preferably at least 30, 40 or 50, particularly preferably at least 70, 100 or 150, in particular from 10 to 5000, 50 to 3000 or 100 to 2000, block-like monomers. The aromatic radicals may optionally also be monosubstituted or polysubstituted, in particular by hydrophobic groups, in particular by C _1-6 -alkyl. As aromatic radicals, phenyl radicals are preferred. The hydrophobic areas of the branches consist in a preferred embodiment of optionally modified polystyrene units of the monomer number given above.

Of course, according to the invention, the hydrophobic core of the hyperbranched polymer can also be formed by different hydrophobic regions. For example, it is possible that the hyperbranched core consists of a silicone, polyacrylate or polymethacrylate, followed by branches, the aromatic radicals C ₆ . Wear _10- aryl.

The antimicrobial and / or microorganism-anti-adhesive effective portion of the hyperbranched polymer preferably constitutes the outer shell of the polymer. This range is preferably hydrophilic, thereby enabling solubility of the polymer in an aqueous medium. The antimicrobially and / or anti-adhesively effective regions are preferably also formed by block-like monomers, so that the hyperbranched polymer is preferably a hyperbranched block copolymer. "Anti-adhesive" in the sense of the present invention means in particular that the polymers prevent the adhesion of microorganisms, preferably of bacteria and / or fungi.

The block-like juxtaposed units, each of which forms a hygienically effective area, that is to say an antimicrobially and / or anti-adhesive area, need not themselves be antimicrobial and / or anti-adhesive. It is sufficient and preferred if not the individual units themselves, but only the block-like polymeric structure is antimicrobial and / or anti-adhesive to microorganisms. Examples of antimicrobially active substances or polymeric regions which can be used according to the invention are described in Tashiro, Macromol. Mater. Closely. (2001) 286, 63-87, especially in Chapter 4. Some of the polymeric units mentioned here unfold only after polymerization of the monomers and optionally subsequent chemical Modification antimicrobial and / or micro-organisms anti-adhesive effect. As a preferred example of this particular pyridine-containing monomers may be mentioned, which form polymeric regions with antimicrobial activity only after polymerization and subsequent quaternization of the nitrogen atom.

Examples of polymers which are antimicrobial and / or anti-adhesive in this sense are in particular polymers which contain biguanide groups or alkylated heteroatom groups, in particular quaternary ammonium groups, quaternary pyridinium groups, quaternary phosphonium groups or tertiary sulfonium groups wear.

Alternatively, however, the antimicrobially active region may of course also contain units which are themselves antibacterial and / or anti-adhesive to microorganisms, these are then preferably also arranged in a block, but this need not be mandatory because the antimicrobial effect in this embodiment also can be given without block-like arrangement.

The antimicrobially and / or anti-adhesively active regions may, for example, also be oligosaccharides, for example as described in WO98 / 26662 or chitin or chitosin derivatives. However, a disadvantage of carbohydrate-modified hyperbranched polymers is that the carbohydrates usually only allow specific interactions with bacteria, and therefore, when using carbohydrates, the spectrum of antibacterial activity may be limited.

If the antimicrobial and / or anti-microbial region of the hyperbranched polymer is a polymeric unit, it is preferably at least 20, 30, 40 or 80, preferably at least 120, 160 or 200, more preferably at least 280, 400 or 600, in particular from 40 to 20,000, 200 to 12,000 or 400 to 8,000, optionally chemically modified block-like monomers. The optionally chemically modified block-like monomers are, according to the above, preferably units comprising a group having an alkylated positively charged heteroatom, wherein the groups having an alkylated positively charged heteroatom are preferably selected from quaternary ammonium, quaternary pyridinium, quaternary Phosphonium ions and ternary sulfonium ions. The quaternizing or terning group is preferably C _1-12 -alkyl, more preferably C _1-6 -alkyl. Thus, the antimicrobial and / or anti-adhesive polymeric units are preferably polycations, in particular heteroatom polycations. In a preferred embodiment, the antimicrobial and / or against microorganisms anti-adhesive effective units by C _1-12 alkyl, in particular by C _1-6 alkyl, preferably by methyl, ethyl, propyl or butyl at least partially quaternized polyvinylpyridines, in particular poly-4-vinylpyridines, or nitrogen-carrying poly (m) ethacrylates.

For the preparation of the nitrogen-bearing poly (m) ethacrylates, in particular monomers of the following general formula may be used:

wherein R ^{3 is} hydrogen, methyl or ethyl, A ^{2 is} O or NH and V ^{2 is} a linear or branched, saturated or unsaturated hydrocarbon radical having 1 to 15 carbon atoms and R ⁴ and R ^{5 are} independently methyl or ethyl ,

In particular, as vinyl monomers of this general formula, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate (DMEMA), dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminoethylacrylamide, dimethylam inoethyl-methacrylamide, dimethylaminopropyl-acrylamide (DMAPA), dimethylaminopropyl-methacrylamide (DMAPMA), dimethylaminobutyl-acrylamide, dimethylam inobutyl-methacrylamide, diethylaminoethylacrylamide or diethylaminoethylmethacrylamide.

The ratio between the number of monomers in the antimicrobially and / or anti-adhesively effective range to the number of monomers in the hydrophobic range is preferably at least 2: 1, particularly preferably at least 3: 1, in particular at least 4: 1 or 5: 1 and particular embodiments at least 6: 1 or 8: 1, wherein the upper limit is preferably 100: 1, more preferably 50: 1, especially 30: 1, in particular 25: 1. In a particularly preferred embodiment, the ratio is between 10: 1 and 30: 1, in particular between 15: 1 and 25: 1.

The hyperbranched polymer preferably comprises at least 3, in particular 3 to 10,000, particularly preferably 3 to 1000, in particular 3 to 100 or 3 to 10, branches. In which hyperbranched polymer may be a dendrimer, but in a preferred embodiment it is a hyperbranched polymer having a lower degree of branching. In a particularly preferred embodiment, only the hyperbranched core is branched, while the branches which attach to the hyperbranched core are linear. The degree of branching of the hyperbranched core is preferably from 0.4 to 0.8, more preferably from 0.4 to 0.5. (For the definition of the degree of branching, see, for example, Hölter et al., (1997) Acta Polymer., 48, 30-35.) The branches which attach to the hyperbranched core are, as already stated, preferably block copolymer units. The molecular weight of the hyperbranched polymer in a preferred embodiment is from 40,000 to 200,000 g / mol.

The hyperbranched polymer according to the invention is furthermore preferably a water-soluble molecule which can be solubilized in a stable manner, especially in the presence of surfactants in an aqueous environment. Surprisingly, this also applies in particular to hyper-branched polymers according to the invention having a cationically charged shell in the presence of anionic surfactants, although polymers having cationic groups generally precipitate in the presence of anionic surfactants.

The hyperbranched polymers according to the invention are furthermore preferably amphoteric molecules, in that at least two different conformational states can be formed: in dissolved form in an aqueous environment, the hydrophobic core is located inside the molecule, while the antimicrobial units are directed outwards aqueous medium are directed. As a result of contact with a hydrophobic surface, the structure reverses, the conformation changes: the hydrophobic core binds to the hydrophobic surface and the antimicrobial effective areas are directed away from the surface and thereby act antimicrobially and / or anti-adhesively against microorganisms.

A further particular advantage of the hyperbranched polymers according to the invention is the fact that the hyperbranched polymers according to the invention can serve as carriers in particular for hydrophobic substances. Examples of such substances include biocides, especially triclosan, dyes and fragrances. The present invention therefore also hyred-branched polymers according to the invention containing non-covalently bound active ingredients, wherein the active ingredients are preferably selected from biocides, dyes and fragrances.

The hyperbranched polymers can be obtained starting from a hyperbranched core with several living centers, in particular by anionic, cationic or radical block copolymerization. The hyperbranched core itself can also be obtained by polymerization become. With regard to corresponding literature on anionic polymerization, reference may be made in particular to the publication by Hadjichristidis et al. in Chem. Rev. (2001) 101, 3747-3792. With regard to literature on radical polymerization, reference may be made, for example, to the publications by Kamigaito et al. in Chem. Rev. (2001) 101, 3689-3745, Hawker et al. in Chem. Rev. (2001) 101, 3661-3688 and Matyjaszewski et al. in Chem. Rev. (2001) 101, 2921-2990, for literature on cationic polymerization, to the publication by Charleux et al. in Advances in Polymer Science (1999) 142, 1-69.

The present invention therefore provides a process for producing an antimicrobially and / or anti-adhesively active hyperbranched polymer according to the invention comprising the following steps: a) preparation of a hyperbranched core with several living centers, b) reaction of the compound according to (a) with monomers which carry quaternary ammonium groups, quaternary phosphonium groups or ternary sulfonium groups.

The present invention therefore also provides a process for preparing an antimicrobially and / or anti-adhesively active hyperbranched polymer according to the invention comprising the following steps: a) preparation of a hyperbranched core with several living centers, b) reaction of the compound according to (a) with monomers, containing organically bound nitrogen, phosphorus or sulfur, wherein the nitrogen-containing group is preferably pyridine, c) reacting the product of (b) with an alkylating reagent, wherein the alkylating reagent is preferably a Alkyl halide, in particular an alkyl chloride, bromide or iodide, particularly preferably a C ^ -alkyl halide, especially a C ^ ₄ - alkyl halide, for converting the heteroatom mentioned in (b) into a quaternary or ternary heteroatom ,

The present invention therefore also provides a process for preparing an antimicrobially and / or anti-adhesively active hyperbranched polymer according to the invention comprising the following steps: a) preparation of a hyperbranched core with several living centers, b) reaction of the compound according to (a) with monomers, carrying the hydrophobic groups, wherein the hydrophobic groups are preferably aromatic groups C ₆ . ₁₀ - aryl and wherein the aromatic groups may optionally be mono- or polysubstituted by hydrophobic radicals, in particular by C ^ -alkyl, c) reaction of the product according to (b) with monomers which carry quaternary ammonium groups, quaternary phosphonium groups or ternary sulfonium groups.

The present invention therefore also provides a process for preparing an antimicrobially and / or anti-adhesively active hyperbranched polymer according to the invention comprising the following steps: a) preparation of a hyperbranched core with several living centers, b) reaction of the compound according to (a) with monomers, carrying the hydrophobic groups, wherein the hydrophobic groups are preferably aromatic groups C _6-K r aryl and wherein the aromatic groups may optionally also be mono- or polysubstituted by hydrophobic radicals, in particular by Ci_ ₆ alkyl, c ) Reacting the product of (b) with monomers containing organically bound nitrogen, phosphorus or sulfur, wherein the nitrogen-containing group is preferably pyridine, d) reacting the product of (c) with an alkylating reagent, wherein the alkylating reagent is preferably an alkyl halide, in particular a Alkyl chloride, bromide or iodide, particularly preferably a C ^ -alkyl halide, especially a C _1-4 alkyl halide, for converting the heteroatom mentioned in (c) into a quaternary or ternary heteroatom.

In a preferred embodiment, the hyperbranched core with several living centers is a polyanion, polycation or polyradical stabilized by mesomeric and / or inductive effects, in particular a resonance-stabilized polyanion, polycation or polyradical, in particular an aromatically stabilized polyanion , Polycation or polyradical.

The present invention also relates to hyperbranched polymers obtainable by the aforementioned processes.

In a particularly preferred embodiment, the hyperbranched polymers are prepared starting from aromatically stabilized polyanions, as described, for example, in Polymer (2003) 44 (8), 2213-2220. The aromatically stabilized anions can be prepared starting from divinylbenzene or 1,3-diisopropenylbenzene, for example, by carrying out a limited anionic polymerization by reaction with an organometallic compound, for example butyllithium, thereby producing a branched polymer core with several living centers. In this way, a hyperbranched core with hydrophobic aromatic radicals is already obtained accordingly. If this core is large enough, it may already be sufficient to allow binding to hydrophobic surfaces. In a particular embodiment of the present invention, a molecule according to the invention can now be obtained already starting from this hydrophobic core by anionic polymerization with monomers carrying antimicrobial groups, which molecule can bind well to hydrophobic surfaces as well as having good antimicrobial properties. The antimicrobial group can be bound to the core both by copolymerization with other monomers and by bulk polymerization. Optionally, other units, in particular by polymerization, may also be inserted between the core and the antimicrobial unit. Furthermore, other units can also join the area with the antimicrobial groups.

In a preferred embodiment, in order to increase the hydrophobicity of the molecule and thus the ability to bind to hydrophobic surfaces, in addition at least one hydrophobic block with aromatic radicals is inserted into the molecule. This is of course also necessary for the preparation of such inventive highly branched macromolecules, which do not already have a corresponding hydrophobic core due to their production.

The incorporation of the hydrophobic block is preferably carried out starting from the anionic polymer core by reacting this polymer core with monomers which have hydrophobic aromatic groups, in particular C ₆ . ₁₀ -Aryl, especially phenyl. The aromatic groups may optionally be substituted by hydrophobic residues, in particular by Ci _-6 -alkyl.

By reacting the resulting polymer core with hydrophobic aromatic branches with monomers bearing antimicrobial groups or groups that can be converted into antimicrobial groups in a subsequent step, a block with antimicrobial activity can now be incorporated. In particular, by reacting first with pyridine-containing monomers and subsequent quaternization of the pyridine residues, a block with antimicrobially active quaternary ammonium ions can be prepared.

Accordingly, the hyperbranched polymer according to the invention is particularly preferably a hyperbranched block copolymer which comprises, on the one hand, hydrophobic blocks and, on the other hand, antimicrobially active blocks.

The preparation of the aromatically stabilized polymeric anion is preferably carried out by reacting Diisopropenylbenzol in an organic solvent, preferably THF (tetrahydrofuran), with an organometallic compound, preferably butyllithium, at a temperature of preferably 20 to 40 ⁰ C, in particular about 30 ⁰ C. To implement the polymeric anion with monomers carrying hydrophobic groups, is preferably carried out first cooling the solution to a temperature from -20 to -40 ⁰ C, in particular about ⁰ -30 C, and subsequent addition of the monomer, wherein the monomers preferably styrene.

The reaction of the so obtained product with monomers which carry pyridine groups is carried out, preferably also at a temperature of -20 to -40 ° C, particularly at about -30 ⁰ C. The pyridine groups supporting monomer is preferably 4-vinyl pyridine.

Before the reaction with the alkylating reagent, it is preferable to terminate the polymerization reaction initially, for example by adding methanol, and to work up the hyperbranched block copolymer thus obtained. The alkylation reaction is preferably carried out at room temperature in an organic solvent, in particular in chloroform.

As an example of the preparation of a hydrophobic hyperbranched core by radical polymerization, the use of vinylbenzyl chloride (VBC) or 2- (2-bromopropionyloxy) ethyl acrylate (BPEA) may be mentioned, with their use hyperbranched cores corresponding to aromatic radicals or polyacrylate radicals Rev. (2001) 101, 2981-2982), which also contain terminal halogen end groups as a starting point for the further radical polymerization (Matyjaszewski et al., Chem. Rev. (2001) 101, 2981-2982). By conversion of this hyperbranched core by means of free-radical polymerization with acrylates containing alkylatable nitrogen groups, such as 2- (diethylamino) ethyl methacrylate, and subsequent conversion of the reaction product with an alkylating reagent, it is likewise possible to obtain hyperbranched polymers according to the invention.

For example, the preparation of a hydrophobic core containing a silicone polymer can be accomplished from a hyperbranched core using hexamethyltrisiloxane by using butyl lithium as a starter. If appropriate, a styrene block can also subsequently be polymerized onto the silicone polymer (compare Zilliox et al. (1975) Macromolecules 8, 573-578). A 4-vinylpyridine block which can be antimicrobially activated by subsequent alkylation can then be polymerized onto the styrene block.

Optionally, a highly branched polymer according to the invention may contain, in addition to the hydrophobic region and the antimicrobially and / or anti-adhesively active region, also further units, in particular blocks, which may be located in particular between hydrophobic core and antimicrobial and / or anti-adhesive shell of the molecule or but can join from the inside to the outside of the antimicrobial and / or anti-adhesive shell. In a However, in a preferred embodiment, the branches of the hyperbranched polymer each consist of only one hydrophobic inner block and one outer antimicrobial and / or anti-adhesive block.

A particular subject of the present invention are therefore hyperbranched block copolymers which comprise at least 3, preferably 3 to 10,000, in particular 3 to 1000, branches which from the inside to the outside each have a hydrophobic area with at least 2, preferably at least 5, in particular at least 25 or at least 40 juxtaposed monomers having aromatic groups C ₆ _i ₀ -aryl and an adjoining thereto outwardly antimicrobially and / or anti-adhesively effective range each having at least 8, preferably at least 20, in particular at least 100 or at least 150 lined up units in which the aromatic groups may optionally also be monosubstituted or polysubstituted by hydrophobic radicals, in particular by C _1-6 -alkyl, and in which the units of the antimicrobially active region are preferably positively charged organic groups, in particular quaternized P yridine groups (pyridinium groups).

A further subject matter of the present invention is the use of the hyperbranched polymers according to the invention, in particular of the hyperbranched block copolymers, for the treatment and / or antimicrobial finishing of surfaces. The surface can be any surface. In particular, hydrophobic surfaces are suitable, but also hydrophilic or positively or negatively charged surfaces or metallic surfaces can be treated and / or finished with hyperbranched polymers according to the invention. As examples of treatable surfaces his particular household surfaces, textiles, in particular of synthetic material, the hair or the tooth surface called. As examples of treatable materials are in particular ceramic and plastic surfaces and wood and metals called.

Accordingly, the hyperbranched polymers according to the invention are preferably present in agents for cleaning surfaces, in particular hard surfaces, in particular in machine or hand dishwashing detergents, in detergents or other cleaning agents, in hair treatment compositions, in particular in shampoos, or in dental treatment agents, in particular toothpastes.

Another object of the present invention is therefore the use of the hyperbranched polymers according to the invention in a cleaning agent, in particular in a means for cleaning hard surfaces, in particular in machine or hand dishwashing detergents, in detergents or other cleaning agents, in hair treatment preparations, in particular in shampoos, or in dental treatment, especially in toothpastes.

The present invention therefore also provides compositions, in particular cleaning and / or finishing agents, in particular means for cleaning and / or finishing hard surfaces, in particular a machine or hand dishwashing detergent, a detergent or another cleaning agent, furthermore hair treatment agent, in particular a shampoo, and dental treatment, in particular a toothpaste, containing hyperbranched polymers according to the invention, in particular hyperbranched block copolymers. The cleaning and / or finishing agent is preferably a liquid, gel or pasty aqueous cleaning agent.

Compositions according to the invention preferably contain the hyperbranched block copolymers of the invention in amounts of up to 20% by weight, in particular in amounts of from 0.01 to 10.0% by weight, more preferably in amounts of from 0.1 to 3.0% by weight. %.

In a preferred embodiment, the composition according to the invention is a hard surface cleanser or a laundry detergent for textiles. These two embodiments are therefore explained in more detail below. Of course, the components mentioned below may also be present in other compositions according to the invention.

The detergents and cleaning agents according to the invention may be any conceivable type of cleaning agent, both concentrates and agents to be used undiluted, for use on a commercial scale, in the washing machine or in hand washing or cleaning. These include, for example, detergents for textiles, carpets, or natural fibers, for which according to the present invention the term laundry detergent is used. These include, for example, dishwashing detergents for dishwashers or manual dishwashing detergents or cleaners for hard surfaces such as metal, glass, porcelain, ceramics, tiles, stone, painted surfaces, plastics, wood or leather; for such according to the present invention, the term cleaning agent is used. In a broader sense sterilizing and disinfecting agents are to be regarded as detergents and cleaners in the sense of the invention.

Embodiments of the present invention include all of the prior art and / or all suitable administration forms of the washing or cleaning agents according to the invention. These include, for example, solid, powdery, liquid, gelatinous or pasty agents, optionally also of several phases, compressed or uncompressed; furthermore belong For example: Extrudates, granules, tablets or pouches, both in large containers and packaged in portions.

In addition to inventive hyperbranched polymers, a washing or cleaning agent according to the invention optionally contains further ingredients such as enzymes, enzyme stabilizers, surfactants, for. As nonionic, anionic and / or amphoteric surfactants, and / or bleaching agents, and / or builder, and optionally other conventional ingredients, which are carried out in the following.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferably branched at 2-position methyl can, or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, Ci ₂ -i ₄ -alcohols with 3 EO or 4 EO, C ₉ . _ir alcohol containing 7 EO, C. ₁₃ ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ - _M -AlkOhOl with 3 EO and C ₁₂ _ ₁₈ -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferred nonionic surfactants 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 having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters ,

Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG). Usable Alkypolyglycoside satisfy the general formula RO (G) _z , in which R is a linear or branched, especially in the 2-position methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of glycosylation z is between 1, 0 and 4.0, preferably between 1, 0 and 2.0 and in particular between 1, 1 and 1, 4. Preference is given to using linear alkyl polyglucosides, that is to say alkyl polyglycosides in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical. Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The proportion of these nonionic surfactants is preferably not higher than that of the ethoxylated fatty alcohols, especially not more than half of them.

Further suitable surfactants are polyhydroxy fatty acid amides of the formula (I)

R ¹

R-CO-N- [Z] (I)

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

The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

R ¹ -OR ²

R-CO-N- [Z] (II)

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein Ci_ ₄ alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives thereof residue.

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

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. As surfactants of the sulfonate type are preferably C ₉ .i ₃ -alkylbenzenesulfonates, olefinsulfonates, that is, mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as they are, for example, from Ci ₂ -i ₈ monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates, the ₂ -i ₈ alkanes are obtained for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization from Ci. Likewise suitable are the esters of .alpha.-sulfo fatty acids (ester sulfonates), for example the .alpha.-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) yl sulfates are the alkali and especially the sodium salts of the Schwefelsäurehalbester C ₂ -C ₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C ₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. From the washing are the C ₂ -C ₆ alkyl sulfates and C _ir Ci ₅ alkyl sulfates and C ₄ -C ₅ alkyl sulfates of preferably. 2,3-alkyl sulfates are also suitable anionic surfactants.

Also, the sulfuric acid monoesters of straight-chain or branched C ₇ ethoxylated with 1 to 6 moles of ethylene oxide. ₂ alcohols, such as 2-methyl-branched C ₉ _n alcohols having on average 3.5 mol of ethylene oxide (EO) or Ci ₂ _i ₈ -fatty alcohols having 1 to 4 EO, are suitable. You will be in cleaning mittein due to their high foaming behavior only in relatively small amounts, for example in amounts up to 5 wt .-%, usually from 1 to 5 wt .-%, used.

Further 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 _i ₈ -Fettalkoholreste or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol radical which is derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (description see above). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

As further anionic surfactants are particularly soaps into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.

The anionic surfactants, including the soaps, may 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 present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

The surfactants may be contained in the detergents or detergents according to the invention overall in an amount of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight, based on the finished composition ,

Detergents or cleaners according to the invention may contain bleaches. Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxopyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as persulfates or persulfuric acid. Also useful is the urea peroxohydrate percarbamide, which can be described by the formula H ₂ N-CO-N H ₂ H ₂ O ₂ . In particular, when using the means for cleaning hard surfaces, for example in automatic dishwashing, they may, if desired, also bleach from the group of organic bleach contain, although their use in principle also in agents for the textile laundry is possible. Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-Phthalimidoperoxycapronsäure (Phthalimidoperoxyhexansäure, PAP), o- Carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonylamidoperoperuccinates, and aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-Terephthaloyl-di (6-aminopercaproic acid) can be used.

The content of bleach detergent or cleaning agent may be from 1 to 40% by weight and in particular from 10 to 20% by weight, with perborate monohydrate or percarbonate being advantageously used.

In order to achieve an improved bleaching effect during washing at temperatures of 60 ^° C. and below, and in particular during the laundry pretreatment, the agents may also contain bleach activators. As bleach activators it is possible, in particular, to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic 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 stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular 1, 3,4,6 Tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), acylated hydroxycarboxylic acids, such as triethyl-O-acetylcitrate (TEOC), Carboxylic acid anhydrides, in particular phthalic anhydride, isoic anhydride and / or succinic anhydride, carboxamides, such as N-methyldiacetamide, glycolide, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, isopropenyl acetate, 2,5-diacetoxy-2,5-dihydrofuran and those from German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol or their in the European patent application E P 0 525 239 described mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetylxylose and Octaacetyllactose and acetylated, optionally N-alkylated glucamine or glucose nolactone, triazole or triazole derivatives and / or particulate caprolactams and / or caprolactam derivatives, preferably N-acylated lactams, for example N-benzoylcaprolactam and N-acetylcaprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used. Likewise, nitrile derivatives such as cyanopyridines, nitrile quats, for example N-alkylammonium acetonitriles, and / or cyanamide derivatives can be used. Preferred bleach activators are sodium 4- (octanoyloxy) benzenesulfonate, n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), undecenoyloxybenzenesulfonate (UDOBS), sodium dodecanoyloxybenzenesulfonate (DOBS), decanoyloxybenzoic acid (DOBA, OBC 10) and / or dodecanoyloxybenzenesulfonate ( OBS 12), as well as N-methylmorpholinum acetonitrile (MMA).

Other bleach activators which can be used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula

in the R ^{1 is} -H, -CH ₃ , a C ₂ - ₂₄ alkyl or alkenyl, a substituted C ₂ . ₂₄ alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, -OH, -NH ₂ , -CN, a

Alkyl or alkenylaryl with a C ^ _24- alkyl group, or a substituted alkyl or

Alkenylaryl radical having a C ^ _24- alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -

CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -

CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6 and X is an anion.

Particularly preferred is a cationic nitrile of the formula

R4

I ₊ R5-N- (CH ₂₎ -cnx ^"

re

in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ - CH ₃ , -CH (CH ₃ ) -CH ₃ , wherein R ⁴ additionally also -H may be and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^", (CH ₃ CH ₂ CH ₂₎ ₃ N ⁽⁺⁾ CH ₂ -CN ^X", (CH ₃ CH (CH ₃₎₎ ₃ N ⁽⁺⁾ CH ₂ - CN X ^' , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{' are} particularly preferred, wherein from the group of these substances, in turn, the cationic nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^' in which X ^{' is} an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is particularly preferred.

The bleach activator is preferably present in the detergents and cleaners according to the invention in an amount of from 0.01 to 20% by weight, preferably in an amount of from 0.1 to 15% by weight, in particular in an amount of from 1 to 10% by weight. -%, especially in an amount of 2 to 5 wt .-%, based on the total composition.

In addition to, or in place of, the conventional bleach activators, so-called bleach catalysts may also be included. These substances are bleach-enhancing transition metal salts or transition metal complexes. Suitable transition metals here are in particular Mn, Fe, Co, Ru, Mo, Ti, V or Cu in different oxidation states. Guanidines (Sundermeyer et al., Journal of Molecular Catalysis A: Chemical (2001) 175, 51-63), aminophenols, amine oxides (WO97 / 48786), salenes (EP0846156, EP0630964), sodimines (EP912690), are particularly suitable as complexing ligands. Rev. (2005) 105, 2329-2363 Heterocycles (Chem. Rev. (2005) 105, 2329-2363), lactams (EP1520910), monocyclic and cross-bridged polycyclic polyazaalkanes (EP0458397, EP977828), terpyridines (WO02 / 088289), dendrimers (EP1148117), tetraamido Ligands (EP918840), bis- and tetrakis (pyridylmethyl) alkylamines (EP783035), other N-containing heterocycles (EP1445305, EP0765381), secondary amines (EP0892846), Polyoxometallate (EP0761809) and other possible ligands described in the literature.

Particular mention may be made of Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes and also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N, containing tripod ligands and Co, Fe, Cu and Ru amine complexes.

It is particularly preferred to use complexes of manganese in the oxidation state II, IM, IV or V, which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the inventive compositions which as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-triazacyclononane (TACN ), 1, 5,9-trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1, 4,7-triazacyclononane (Me / TACN). Suitable manganese complexes are for example, [Mn ^l "2 (μ-O) ₁ (μ-OAc) 2 (TACN) 2] (Clθ4) 2, [Mn ^l " Mn ^lv (μ-O) 2 (μ-OAc) ₁ (TACN) 2 ] (BPh ₄ ) 2, [Mn ^IV ₄ (μ-O) ₆ (TACN) ₄ ] (CIO ₄ ) ₄ , [Mn " ¹ ₂ (μ-O) ₁ (μ-OAc) ₂ (Me-TACN)] ₂ ] (CIO ₄ ) ₂ , [Mn " ¹ Mn ^lv (μ-O) i (μ-O Ac) ₂ (Me-TACN) ₂ ] (CIO ₄ ) ₃ , [Mn ' ^v ₂ (μ-O) ₃ (Me-TACN) _2] (PF ₆₎ ₂ and [Mn ^'v ₂ (μ-O) ₃ (Me / Me-TACN) _2] (PF ₆₎ ₂ (OAc = OC (O) CH _3).

Bleach catalysts may be used in conventional amounts, preferably in an amount up to 5 wt .-%, in particular from 0.0025 wt .-% to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt. %, in each case based on the total weight of the washing or cleaning agent used. In special cases, however, more bleach catalyst can be used.

Detergents or cleaners according to the invention generally comprise one or more builders, in particular zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological reasons against their use, also the phosphates. The latter are particularly preferred builders to be used in automatic dishwashing detergents.

To mention here are crystalline, layered sodium silicates of the general formula

NaMSi _x O _{2x + I} yH ₂ O, where M is sodium or hydrogen, x is a number from 1, 6 to 4, preferably 1, 9 to 4.0 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. Such crystalline layered silicates are described, for example, in European Patent Application EP 164514. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-

Sodium disilicates Na ₂ Si ₂ O ₅ 7H ₂ O preferred. Such compounds are commercially available, for example, under the name ^SKS® (Clariant company). Thus, it is mainly SKS-6 ^® is a δ-sodium having the formula Na ₂ Si ₂ O ₅ ^{^} yH ₂ O, SKS-7 ^® is predominantly a beta-sodium disilicate. By reaction with acids (for example citric acid or carbonic acid) kanemite NaHSi ₂ O ₅ yH ₂ O, commercially available under the name SKS- ^9® or SKS- ^10® (Clariant), is formed from the δ-sodium disilicate. It may also be advantageous to use chemical modifications of these phyllosilicates. For example, the alkalinity of the layered silicates can be suitably influenced. Phyllosilicates doped with phosphate or with carbonate have altered crystal morphologies in comparison with the δ-sodium disilicate, dissolve more rapidly and show an increased calcium binding capacity in comparison with δ-sodium disilicate. Thus, phyllosilicates of the general empirical formula x Na ₂ O • y SiO ₂ • z P ₂ O ₅ , in which the ratio x to y is a number 0.35 to 0.6, the ratio x to z a number from 1, 75 to 1200 and the ratio y to z correspond to a number from 4 to 2800, described in the patent application DE 196 01 063. The solubility of the phyllosilicates can also be increased by using particularly finely divided phyllosilicates become. Also compounds from the crystalline layer silicates with other ingredients can be used. In particular, compounds with cellulose derivatives which have advantages in the disintegrating effect and are used in particular in detergent tablets, and compounds with polycarboxylates, for example citric acid, or polymeric polycarboxylates, for example copolymers of acrylic acid, may be mentioned.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

An optionally usable, finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P. As zeolite P zeolite MAP ^® (commercial product from Crosfield) is particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

n Na ₂ O (1-n) K ₂ O Al ₂ O ₃ (2 - 2.5) SiO ₂ (3.5-5.5) H ₂ O.

can be described. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water. Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of greatest importance in the washing and cleaning agent industry.

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

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1, 91 like ^'3 , melting point 60 °) and monohydrate (density 2.04 like ^{' 3} ). Both salts are white powders which are very slightly soluble in water and which lose the water of crystallization when heated and at 200 ^° C. into the weak acid diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt of density 2.33, like ^'3 , has a melting point of 253 ° C [decomposition to form potassium polyphosphate (KPO ₃ )] J and slightly soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 like ^"3 , water loss at 95 °), 7 moles (density 1, 68 like ^'3 , melting point 48 ° C with loss of 5 H ₂ O) and 12 moles water (Density 1, 52 like ^'3 , melting point 35 ° C with loss of 5 H ₂ O), becomes anhydrous at 100 ⁰ C and on more intense heating in the diphosphate Na ₄ P ₂ O _7. Disodium hydrogen phosphate is by neutralization of phosphoric acid prepared with soda solution using phenolphthalein as an indicator Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals containing as dodecahydrate a density of 1.62 ^"3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ⁰ C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) a density of 2.536 like ^"3 have. Trisodium phosphate is readily soluble in water under alkaline reaction and is obtained by evaporation of a solution of exactly 1 mole Disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56 ^'3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It is produced, for example, by heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 ^'3 , melting point 988 ° C, also indicated 880 ⁰ C) and as decahydrate (density 1, 815-1, 836 like ^{' 3} , Melting point 94 ° C with loss of water). Both substances are colorless crystals which are soluble in water with alkaline reaction. Na ₄ P ₂ O ₇ is formed on heating of disodium phosphate to> 200 ° C or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33% ^'3 , which is soluble in water, the pH being 1% Solution at 25 ° C is 10.4.

Condensation of the NaH ₂ PO ₄ or of the KH ₂ PO ₄ gives rise to relatively high molecular weight sodium and potassium phosphates, in which cyclic representatives, the sodium or potassium metaphosphates and chain-type, the sodium or potassium polyphosphates, can be distinguished. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The industrially important pentasodium triphosphate (Na ₅ P ₃ O ₁₀ ; sodium tripolyphosphate) is an anhydrous or water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _{n which} crystallizes with 6 H ₂ O and which is non-hygroscopic. Na with n = 3. In 100 g of water at room temperature dissolve about 17 g, at 60 ⁰ C about 20 g, at 100 ⁰ C, about 32 g of the salt water-free salt; after two hours of heating the solution to 100 ⁰ C caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with soda solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. Continue to exist Sodium potassium tripolyphosphates, which are also usable in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH -> Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

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

As organic cobuilders, it is possible in particular to use in the detergents and cleaners according to the invention polycarboxylates or polycarboxylic acids, polymeric polycarboxylates, polyaspartic acid, polyacetals, optionally oxidized dextrins, further organic cobuilders (see below) and phosphonates. These classes of substances are described below.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use can not be avoided for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

The acids themselves can also be used. In addition to their builder effect, they also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners, unless the pH resulting from the mixture of the other components is desired. In particular, system and environmentally compatible acids such as citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these are to be mentioned. But also mineral acids, in particular sulfuric acid or bases, in particular ammonium or alkali hydroxides can serve as pH regulators. Such regulators are contained in the agents according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight. Other suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular weight of 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular 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 with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 2,000 to 10,000 g / mol, and particularly preferably from 3,000 to 5,000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2,000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol. The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of the (co) polymeric polycarboxylates may be from 0.5 to 20% by weight, in particular from 1 to 10% by weight.

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

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

Further preferred copolymers are those which have as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate. Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives.

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

Further 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 processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500 000 g / mol. In this case, 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 of the reducing action of a polysaccharide compared to dextrose, which is a DE of 100 has. Both maltodextrins with a DE of between 3 and 20 and dry glucose syrups with a DE of between 20 and 37 and also yellow dextrins and white dextrins with relatively high molecular weights in the range from 2 000 to 30 000 g / mol are useful.

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. Particularly preferred organic builders for agents according to the invention are oxidized starches or their derivatives from the applications EP 472042, WO 97/25399, and EP 755944.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. Ethylenediamine-N, ^{N'-disuccinate} (EDDS) is preferably used in form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are in zeolith-, carbonate and / or silicate-containing formulations between 3 and 15 wt .-%.

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

Another substance class with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

Moreover, all compounds capable of forming complexes with alkaline earth ions can be used as co-builders.

Builder substances may optionally be present in the detergents or cleaners according to the invention in amounts of up to 90% by weight. They are preferably contained in amounts of up to 75% by weight. Detergents according to the invention have builder contents of, in particular, from 5% by weight to 50% by weight. In agents according to the invention for the cleaning of hard surfaces, in particular for the automated cleaning of dishes, the content of builder substances is in particular from 5% by weight to 88% by weight, wherein preferably no water-insoluble builder materials are used in such agents. In a preferred embodiment of the invention means for the particular automatic cleaning of dishes are 20 wt .-% to 40 wt .-% of water-soluble organic builder, in particular alkali, 5 wt .-% to 15 wt .-% alkali carbonate and 20 wt .-% bis 40 wt .-% Alkalidisilikat included.

Solvents that can be used in the liquid to gelatinous compositions of detergents and cleaners, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible in the specified concentration range with water. The solvents 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. dimethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, Methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents.

Solvents may be used in the liquid to gelled detergents and cleaners according to the invention in amounts of between 0.1 and 20% by weight, but preferably below 15% by weight and in particular below 10% by weight.

To adjust the viscosity, one or more thickeners or thickening systems can be added to the composition according to the invention. These high-molecular substances, which are also called swelling agents, usually absorb the liquids and swell up to finally pass into viscous true or colloidal solutions.

Suitable thickeners are inorganic or polymeric organic compounds. The inorganic thickeners include, for example, polysilicic acids, clay minerals such as montmorillonites, zeolites, silicas and bentonites. The organic thickeners are derived from the groups of natural polymers, modified natural polymers and fully synthetic polymers. Such naturally derived polymers include, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar gum, locust bean gum, starch, dextrins, gelatin and casein. Modified natural products, which are used as thickeners, come mainly from the group of modified starches and celluloses. By way of example, carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propylcellulose and core flour ethers may be mentioned here. Fully synthetic thickeners are polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.

The thickeners may be present in an amount of up to 5% by weight, preferably from 0.05 to 2% by weight, and more preferably from 0.1 to 1.5% by weight, based on the finished composition ,

The washing and cleaning agent according to the invention may optionally contain further conventional ingredients sequestering agent, electrolyte and other auxiliaries, such as optical brighteners, grayness inhibitors, silver corrosion inhibitors, dye transfer inhibitors, foam inhibitors, abrasives, dyes and / or fragrances, as well as microbial active ingredients, UV absorbents and / or enzyme stabilizers.

Detergents according to the invention can be used as optical brightener derivatives of Diaminostilbendisulfonsäure or their alkali metal salts. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or similarly constructed compounds which are substituted for the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Further, brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls. Mixtures of the aforementioned optical brightener can be used.

Graying inhibitors have the task of keeping suspended from the textile fiber dirt suspended in the fleet. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, other than the above-mentioned starch derivatives can be used, for example aldehyde starches. Preference is given to using cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions.

To effect silver corrosion protection, silver corrosion inhibitors can be used in dishwashing detergents according to the invention. Such are known in the art, for example benzotriazoles, iron (III) chloride or CoSO ₄ . For example, as known from European Patent EP 0 736 084 B1, particularly suitable silver corrosion inhibitors for use in conjunction with enzymes are manganese, titanium, zirconium, hafnium, vanadium, cobalt or cerium salts and / or complexes where the said metals are present in one of the oxidation states II, IM, IV, V or VI. Examples of such compounds are MnSO ₄ , V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , Co (NO ₃ ) ₂ , Co (NO ₃ ) ₃ , and the like mixtures.

"Soil-release" or "soil repellents" are mostly polymers which impart soil repellency when used in a laundry detergent detergent and / or aid in the soil release performance of the other detergent ingredients. A similar effect can also be observed in their use in hard surface cleaners.

Particularly effective and long-known soil release agents are copolyesters with dicarboxylic acid, alkylene glycol and polyalkylene glycol units. Examples of these are copolymers or copolymers of polyethylene terephthalate and polyoxyethylene glycol (DT 16 17 141, or DT 22 00 911). In German Offenlegungsschrift DT 22 53 063 acidic agents are mentioned which contain, inter alia, a copolymer of a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol. Polymers of ethylene terephthalate and polyethylene oxide terephthalate and their use in detergents are described in German patents DE 28 57 292 and DE 33 24 258 and European patent EP 0 253 567. European patent EP 066 944 relates to compositions containing a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios. European Patent EP 0 185 427 discloses methyl or ethyl group end-capped polyesters having ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and laundry detergents containing such soil release polymer. European patent EP 0 241 984 relates to a polyester which, besides oxyethylene groups and terephthalic acid units, also contains substituted ethylene units and also glycerine units. From the European patent EP 0 241 985 polyesters are known, which in addition to oxyethylene groups and terephthalic acid units, 1, 2-propylene, 1, 2-butylene and / or 3-methoxy-1, 2-propylene groups and glycerol units and with C _R to C ₄ -alkyl groups are endgruppenverschlossen. European Patent Application EP 0 272 033 discloses, at least to some extent, C 1 -C ₄ -alkyl or acyl radicals end-capped polyesters having polypropylene propylene terephthalate and polyoxyethylene terephthalate units. European Patent EP 0 274 907 describes sulfoethyl end-capped terephthalate-containing soil release polyesters. According to European Patent Application EP 0 357 280, sulfonation of unsaturated end groups results in soil-release polyesters with terephthalate, alkylene glycol and poly-C ₂ . ₄ - made glycol units. International Patent Application WO 95/32232 relates to acidic, aromatic soil release polymers. International Patent Application WO 97/31085 discloses non-polymeric soil repellent active ingredients for multi-functional cotton materials: a first entity, which may be cationic, for example, is capable of adsorption to the cotton surface by electrostatic interaction, and a second Unit that is hydrophobic is responsible for the retention of the drug at the water / cotton interface.

The color transfer inhibitors contemplated for use in textile according to the invention include in particular polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole.

When used in automated cleaning processes, it may be advantageous to add foam inhibitors to the agents concerned. As foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable surfactant-type foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bistearylethylenediamide. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes. Preferably, the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are bound to a granular, water-soluble, or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamides are preferred.

In addition, a hard surface cleaning agent according to the invention may contain abrasive constituents, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and glass microspheres and mixtures thereof. Abrasives are preferably present in the detergents according to the invention in an amount of not more than 20% by weight, in particular in an amount of from 5 to 15% by weight.

Dyes and fragrances are added to detergents and cleaners in order to improve the aesthetic appearance of the products and to provide the consumer with a visually and sensory "typical and unmistakable" product in addition to the washing and cleaning performance. As perfume oils or fragrances, individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals having 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones, for example, the ionone, α-isomethyl ionone and Methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons include mainly the terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, for example, pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood. Usually, the content of detergents and cleaners to dyes is less than 0.01 wt .-%, while perfumes can account for up to 2 wt .-% of the total formulation. The fragrances can be incorporated directly into the detergents or cleaners, but it can also be advantageous to apply the fragrances to carriers, which enhance the adhesion of the perfume to the items to be cleaned and provide a slower release of fragrance for long-lasting fragrance, especially of treated textiles. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients. A further preferred carrier for fragrances is the described zeolite X, which can also absorb fragrances instead of or in mixture with surfactants. Preference is therefore given to washing and cleaning agents containing the described zeolite X and fragrances, which are preferably at least partially absorbed on the zeolite.

Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to textile fibers so as not to stain them.

Detergents or cleaners may contain antimicrobial agents to combat microorganisms. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistatics and fungicides, etc. The following are examples of substances from these groups which are benzalkonium chlorides, alkylaryl sulfonates, halophenols and phenol mercuriacetate. The terms antimicrobial action and antimicrobial active ingredient in the context of the teaching according to the invention have the customary meaning, which is described, for example, by KH Wallhäußer in "Praxis der Sterilisation, Desinfektion - Konservierung: Keim Identification - Betriebshygiene" (5th edition - Stuttgart, New York: Thieme, Suitable antimicrobial agents are preferably selected from the groups of alcohols, amines, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes , Urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1, 2-dibromo-2,4-dicyanobutane, iodo-2-propyl butyl carbamate, iodine, iodophores, peroxo compounds, halogen compounds and any mixtures of the foregoing.

The antimicrobial agent may be selected from ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, benzoic acid, salicylic acid, dihydracetic acid, o-phenylphenol, N-methylmorpholine. acetonitrile (MMA), 2-benzyl-4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 4,4'-dichloro-2'-hydroxydiphenyl ether (dichlosan), 2,4 , 4'-trichloro-2'-hydroxydiphenyl ether (trichlosan), chlorhexidine, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) -urea, N, N '- (1, 10-decanediyldi- 1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis (4-chlorophenyl) - 3,12-diimino-2,4,11,13-tetraaza-tetradecandiimidamide, glucoprotamines, antimicrobial quaternary surface active compounds, guanidines including the bi- and polyguanidines such as 1,6-bis (2-ethylhexyl-biguanido-hexane ) dihydrochloride, 1, 6-di- (N _1, N ^ -phenyldiguanido- N _5, N ₅ ') -hexane-tetrahydochlorid, 1, 6-di (Ni, Ni'-phenyl-Ni, N _r methyldiguanido -N ₅ , N ₅ ') -hexanedihydrochloride, 1,6-di- (Ni, Ni'-o-chlorophenyldiguanido- N ₅ , N ₅ ') -hexane dihydrochloride, 1,6-di- (N ₁₁ N ₁ '- 2,6-dichlorophenyldiguanido-N ₅ , N ₅ ') hexane dihydrochloride, 1,6-di- [N ₁ , N ₁ '-beta (p-methoxyphenyl) diguanido-N ₅ , N ₅ ' ] -hexane dihydrochloride, 1,6-di- (N ₁ , N 1 -α-alpha-methyl-beta-phenyldiguanido-N, N ₅ ') - hexane dihydrochloride, 1,6-di- (N ₁ , N, -p-nitrophenyldiguanido-N, N'-hexane-dihydrochloride, omega: omega-di- (N, N'-phenyldiguanido-N, N, N''-di-n-propyl ether dihydrochloride, omega: omega'-di- (N _L N ^ -p-chlorophenyldiguanido-Ns.Ns'J-di-n-propyl ether tetrahydrochloride, 1, 6-D i- (N ₁ , N ₁ '-2,4-dichlorophenyldiguanido-N ₅ , N ₅ ') hexane-tetrahydrochloride, 1,6-di- (N ₁ , N 1 -p-methylphenyl-diguanido- N ₅ , N ₅ ' ) hexane-dihydrochloride, 1,6-di- (N ₁ , N, Λδ-trichlorophenyldiguanido-N, N'-hexane tetrahydrochloride, 1,6-di- [N ₁ , N ₁ '-alpha- (p-chlorophenyl) ethyldiguanido-N ₅ , N ₅ '] hexane dihydrochloride, omega: omega-di- (N ₁ , N ₁ ' -p-chlorophenyldiguanido-N ₅ , N ₅ ') m-xylenedihydrochloride, 1, 12-di- (N -iN-i'-p-chlorophenyldiguanido-Ns.Ns'J dodecane-dihydrochloride, 1, 10-di- (N ₁ , N 1 -phenyl-diguanido- N ₅ , N ₅ ') -decane-tetrahydrochloride, 1, 12-di- (N ₁ , N 1 -phenyl-diguanido- N ₅ , N ₅ ') dodecane-tetrahydrochloride, 1,6-di- (N, N 1 -o-chlorophenyl-diguanido- N ₅ , N ₅ ') -hexane-dihydrochloride , 1, 6-di- (N ₁ , N 1 -o-chlorophenyl-diguanido- N ₅ , N ₅ ') hexane-tetrahydrochloride, ethylene-bis (1-tolyl biguanide), ethylene-bis (p-tolyl biguanide) Ethylene bis (3,5-dimethylphenylbiguanide), ethylene bis (p-tert-amylphenyl biguanide), ethylene bis (nonylphenyl biguanide), ethylene bi s- (phenylbiguanide), ethylene bis (N-butylphenylbiguanide), ethylene bis (2,5-diethoxyphenylbiguanide), ethylene bis (2,4-dimethylphenyl biguanide), ethylene bis (o-diphenylbiguanide), ethylene bis (mixed amyl naphthylbiguanide), N-butyl-ethylene-bis (phenylbiguanide), trimethylene bis (o-tolylbiguanide), N-butyl-trimethyl-bis- (phenyl biguanide) and the corresponding salts such as acetates, gluconates, hydrochlorides, Hydrobromides, citrates, bisulfites, fluorides, polymaleates, N-cocoalkyl sarcosinates, phosphites, hypophosphites, perfluorooctanoates, silicates, sorbates, salicylates, maleates, tartrates, fumarates, ethylenediaminetetraacetates, iminodiacetates, cinnamates, thiocyanates, arginates, pyromellitates, tetracarboxybutyrates, benzoates, glutarates, Monofluorophosphates, perfluoropropionates and any mixtures thereof. Also suitable are halogenated xylene and cresol derivatives, such as p-chlorometacresol or p-chloro-meta-xylene, and natural antimicrobial agents of plant origin (for example, from spices or herbs), animal and microbial origin. Preferably, antimicrobial surface-active quaternary compounds, a natural antimicrobial agent of plant origin and / or a natural antimicrobial agent of animal origin, most preferably at least one natural antimicrobial agent of plant origin from the group comprising caffeine, theobromine and theophylline and essential oils such as eugenol, thymol and geraniol, and / or at least one natural antimicrobial agent of animal origin from the group, comprising enzymes such as protein from milk, lysozyme and lactoperoxidase, and / or at least one antimicrobial surface-active agent quaternary compound having an ammonium, sulfonium, phosphonium, iodonium or arsonium group, peroxo compounds and chlorine compounds are used. Also substances of microbial origin, so-called bacteriocins, can be used.

The suitable as antimicrobial agents quaternary ammonium compounds (QAC) have the general formula (R ¹ ) (R ² ) (R ³ ) (R ⁴ ) N ⁺ X ^" , in which R ¹ to R ⁴ identical or different C ₁ -C ₂₂ - alkyl radicals, C ₇ -C ₂₈ -aralkyl radicals, or heterocyclic radicals, or in the case of an aromatic compound such as pyridine-even three groups together with the nitrogen atom forming the heterocycle, for example a pyridinium or imidazolinium compound, and X ^" Halide ions, sulfate ions, hydroxide ions or similar anions. For optimum antimicrobial activity, preferably at least one of the radicals has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.

QACs can be prepared by reacting tertiary amines with alkylating agents, such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide. The alkylation of tertiary amines with a long alkyl radical and two methyl groups succeeds particularly easily, and the quaternization of tertiary amines with two long radicals and one methyl group can be carried out with the aid of methyl chloride under mild conditions. Amines having three long alkyl radicals or hydroxy-substituted alkyl radicals are less reactive and are preferably quaternized with dimethyl sulfate.

Suitable QACs are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B (m, p-dichlorobenzyl-dimethyl-C 12 -alkylammonium chloride, CAS No. 58390-78-6), benzoxonium chloride (benzyldodecyl-bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide, CAS No. 57-09-0 ), Benzetonium chloride (N, N-dimethyl-N- [2- [p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzylammonium chloride, CAS No. 121-54 Dialkyldimethylammonium chlorides such as di-n-decyldimethylammonium chloride (CAS No. 7173-51-5-5), didecyldi-methylammonium bromide (CAS No. 2390-68-3), dioctyldimethylammoniumchloric, 1-cetylpyridinium chloride (CAS No. 123-03-5) and thiazolinium iodide (CAS No. 15764-48-1) and mixtures thereof. Particularly preferred QACs are the benzalkonium chlorides with C ₈ -C ₁₈ -alkyl radicals, in particular C ₁₂ -C ₁₄ -alkyl-benzyl-dimethyl-ammonium chloride.

Benzalkonium halides and / or substituted benzalkonium halides are for example commercially available as Barquat ^® ex Lonza, Marquat® ^® ex Mason, Variquat ^® ex Witco / Sherex and Hyamine ^® ex Lonza and as Bardac ^® ex Lonza. Other commercially obtainable antimicrobial agents are hexaminium N- (3-chloroallyl) as Dowicide and Dowicil ^® ^® ex Dow, Benzethonium as Hyamine ^® 1622 ex Rohm & Haas, methylbenzethonium as Hyamine ^® 10X ex Rohm & Haas, cetylpyridinium chloride such Cepacol ex Merrell Labs.

The antimicrobial agents are used in amounts of 0.0001 wt .-% to 1 wt .-%, preferably from 0.001 wt .-% to 0.8 wt .-%, particularly preferably from 0.005 wt .-% to 0.3 wt .-% and in particular from 0.01 to 0.2 wt .-% used.

The detergents or cleaners according to the invention may contain UV absorbents (UV absorbers) which are applied to the treated textiles and improve the lightfastness of the fibers and / or the lightfastness of other formulation constituents. Under UV absorber are organic substances (sunscreen) to understand, which are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, for example, to give off heat.

Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, in the 3-position phenyl-substituted acrylates (cinnamic acid derivatives, optionally with cyano groups in the 2-position), salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid. The biphenyl and, above all, stilbene derivatives as described for example in EP 0728749 A are described and commercially available as Tinosorb FD ^® ^® or Tinosorb FR ex Ciba. As UV-B absorbers may be mentioned: 3-Benzylidencampher or 3-Benzylidennorcampher and its derivatives, for example 3- (4-Methylbenzy- liden) camphor, as described in EP 0693471 B1; 4-aminobenzoic acid derivatives, preferably A- (dimethylamino) benzoic acid 2-ethylhexyl ester, 4- (dimethylamino) benzoic acid 2-octyl ester and A- (dimethylamino) benzoic acid amyl ester; Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate; Triazine derivatives such as 2,4,6-trianilino (p-carbo-2'-ethyl-1'-hexyloxy) -1, 3,5-triazine and octyl triazone, as described in EP 0818450 A1 or dioctyl butamido Triazone (Uvasorb® HEB); Propane-1,3-diones such as 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives as described in EP 0694521 B1. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and their alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; Sulfonic acid derivatives of 3-Benzylidencamphers, such as 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.

As a typical UV-A filter in particular derivatives of benzoylmethane come into question, such as 1 - (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1, 3-dione and also enamine compounds, as described in DE 19712033 A1 (BASF). Of course, the UV-A and UV-B filters can also be used in mixtures. In addition to the soluble substances mentioned, insoluble photoprotective pigments, namely finely dispersed, preferably nano-metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are in particular zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. As salts silicates (talc), barium sulfate or zinc stearate can be used. The oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape. The pigments may also be surface-treated, that is to say hydrophilized or hydrophobicized. Typical examples are coated titanium dioxides, such as, for example, titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck; preferred hydrophilic coating agents are silicones and particularly preferably trialkoxyoctylsilanes or simethicones.) Micronized zinc oxide is preferably used see the review by P. Finkel in SÖFW Journal 122 (1996), p. 543.

The UV absorbents are usually used in amounts of from 0.01% by weight to 5% by weight, preferably from 0.03% by weight to 1% by weight.

Agents according to the invention may contain enzymes to increase the washing or cleaning performance, it being possible in principle to use all enzymes established for this purpose in the prior art. These include in particular proteases, amylases, lipases, Hembellulasen, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Based on the natural molecules, improved variants are available for use in detergents and cleaners, which are correspondingly preferred be used. Agents according to the invention preferably contain these further enzymes in total amounts of 1 × 10 ^-6 to 5 percent by weight, based on active protein.

Among the proteases, subtilisin type ones are preferred. Examples thereof are the subtilisin BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense the proteases TW3 and TW7. Subtilisin Carlsberg in a developed form under the trade names Alcalase ^® from Novozymes A / S, Bagsvasrd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. Listed under the name BLAP ^® variants of the protease from Bacillus lentus DSM 5483 (WO 91/02792 A1) to derive, in particular, in WO 92/21760 A1, WO 95/23221 A1, WO 02/088340 A2 and WO 03 / 038082 A2. Further useful proteases from various Bacillus sp. And B. gibsonii strains are found in the patent applications WO 03/054185, WO 03/056017, WO 03/055974, WO 03/054184, DE 102006022216 and DE 102006022224.

Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, under the trade names Purafect ^®, Purafect ^® OxP and Properase.RTM ^® by the company Genencor, that under the trade name Protosol® ^® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ^® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ^® and protease P ^® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, B. amyloliquefaciens or B. stearothermophilus and also their further developments improved for use in detergents and cleaners. The enzyme from B. licheniformis is available from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar® ^® ST. Development products of this α-amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^®. The α- amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ^®, and variants derived from the α-amylase from B. stearothermophilus under the names BSG ^® and Novamyl ^®, likewise from Novozymes. Other usable commercial products are for example, the amylase-LT®, Stainzyme® and Stainzyme Ultra®, the latter also from the company Novozymes.

Furthermore, the α-amylase from Bacillus sp. Disclosed in the application WO 02/10356 A2 for this purpose. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) described in the application WO 02/44350 A2. Furthermore, the amylolytic enzymes which belong to the sequence space of α-amylases, which is defined in the application WO 03/002711 A2, and those which are described in the application WO 03/054177 A2 can be used. Likewise, fusion products of the molecules mentioned can be used, for example those from application DE 10138753 A1.

In addition, the enhancements available under the trade names Fungamyl.RTM ^® by Novozymes of α-amylase from Aspergillus niger and A. oryzae, which are. Another commercial product is, for example, the amylase ^LT® .

Compositions according to the invention may contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ^®, Lipolase Ultra ^®, LipoPrime® ^®, Lipozyme® ^® and Lipex ^®. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusaήum solani pisi and Humicola insolens. Likewise useable lipases are available from Amano under the designations Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacillis sp. ^Lipase® , Lipase ^AP® , Lipase M- ^AP® and Lipase ^{AML® are} available. From the company Genencor, for example, the lipases, or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products are the originally marketed by Gist-Brocades preparations M1 Lipase ^® and Lipomax® ^® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® to mention also the product Lumafast® ^® from Genencor.

Detergents according to the invention, especially if they are intended for the treatment of textiles, may contain cellulases, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously supplement each other in terms of their various performance aspects. These performance aspects include in particular Contributions to the primary washing performance, to the secondary washing performance of the agent (anti-redeposition effect or grayness inhibition) and to avivage (tissue effect), up to the exercise of a "stone washed" effect.

A useful fungal, endoglucanase (EG) -rich cellulase preparation, or its further developments are offered by Novozymes under the trade name Celluzyme ^®. The products Endolase® ^® and Carezyme ^®, likewise available from Novozymes, are based on the 50 kD EG and 43 kD EG from H. insolens DSM 1800. Further commercial products of this company are Cellusoft® ^® and Renozyme ^®. The latter is based on the application WO 96/29397 A1. Performance-enhanced cellulase variants are disclosed, for example, in the application WO 98/12307 A1. Likewise, the cellulases disclosed in the application WO 97/14804 A1 can be used; For example, it revealed 20 kD EG Melanocarpus, available from AB Enzymes, Finland, under the trade names Ecostone® ^® and Biotouch ^®. Further commercial products from AB Enzymes are Econase® ^® and ECOPULP ^®. Other suitable cellulases from Bacillus sp. CBS 670.93 and CBS 669.93 are disclosed in WO 96/34092 A2, wherein those derived from Bacillus sp. CBS 670.93 from the company Genencor under the trade name Puradax ^{® is} available. Further commercial products of the company Genencor are "Genencor detergent cellulase L" and lndiAge ^® Neutra.

Compositions according to the invention may contain, in particular for the removal of certain problem soiling, further enzymes which are combined under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases. Suitable mannanases are available, for example under the name Gamanase ^® and Pektinex AR ^® from Novozymes, under the name Rohapec ^® B1 L from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, USA , A suitable β-glucanase from a B. alcalophilus is disclosed, for example, in the application WO 99/06573 A1. The obtained from B. subtilis beta-glucanase is available under the name Cereflo ^® from Novozymes.

To increase the bleaching effect, detergents and cleaners according to the invention may also contain hydrogen peroxide-producing oxidoreductases. The hydrogen peroxide-producing oxidoreductase is preferably an oxidoreductase which produces hydrogen peroxide by using oxygen as an electron acceptor. In particular, oxidoreductases of EC classes EC 1.1.3 (CH-OH as electron donor), EC 1.2.3 (aldehyde or oxo group as electron donor), EC 1.4.3 (CH-NH ₂ as donor), EC 1.7 are used. 3 (N-containing group as donor) and EC 1.8.3 (S-containing group as donor), enzymes of the EC class EC 1.1.3 are preferred. Preferred enzymes are in particular selected from the group consisting of malate oxidase (EC 1.1.3.3), glucose oxidase (EC 1.1.3.4), hexose oxidase (EC 1.1.3.5), cholesterol oxidase (EC 1.1.3.6), Galactose oxidase (EC 1.1.3.9), pyranose oxidase (EC 1.1.3.10), alcohol oxidase (EC 1.1.3.13), choline oxidase (EC 1.1.3.17, see in particular WO 04/58955), oxidases for long-chain Alcohols (EC 1.1.3.20), glycerol-3-phosphate oxidase (EC 1.1.3.21), cellobiose oxidase (EC 1.1.3.25), nucleoside oxidase (EC 1.1.3.39), D-mannitol oxidase (EC 1.1 3.40), xylitol oxidase (EC 1.1.3.41), aldehyde oxidase (EC 1.2.3.1), pyruvate oxidase (EC 1.2.3.3), oxalate oxidase (EC 1.2.3.4), glyoxylate oxidase (EC 1.2 .3.5), indole-3-acetaldehyde oxidase (EC 1.2.3.7), pyridoxal oxidase (EC 1.2.3.8), aryl aldehyde oxidase (EC 1.2.3.9), retinal oxidase (EC 1.2.3.11), L- Amino acid oxidase (EC 1.4.3.2), amine oxidase (EC 1.4.3.4, EC 1.4.3.6), L-glutamate oxidase (EC 1.4.3.11), L-lysine oxidase (EC 1.4.3.14), L aspartate-Oxi dase (EC 1.4.3.16), tryptophan alpha.beta oxidase (EC 1.4.3.17), glycine oxidase EC 1.4.3.19), urea oxidase (EC 1.7.3.3), thiol oxidase (EC 1.8.3.2) and glutathione oxidase (EC 1.8.3.3). The hydrogen peroxide-producing oxidoreductase, in a preferred embodiment, is one which uses a sugar as an electron donor. The hydrogen peroxide-producing and sugar oxidizing oxidoreductase according to the invention is preferably selected from glucose oxidase (EC 1.1.3.4), hexose oxidase (EC 1.1.3.5), galactose oxidase (EC 1.1.3.9) and pyranose oxidase (EC 1.1.3.10 ). Particularly preferred according to the invention is the glucose oxidase (EC 1.1.3.4). Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.

In addition to the hydrogen peroxide-producing oxidoreductase, it is also possible for further oxidoreductases to be present in the compositions according to the invention, in particular oxidases, oxygenases, laccases (phenol oxidase, polyphenol oxidases) and / or dioxygenases. Suitable commercial products for laccases may be mentioned Denilite® ^® 1 and 2 from Novozymes. In a preferred embodiment, the further oxidoreductase is selected from enzymes which use peroxides as electron acceptors (EC Class 1.11 or 1.11.1), in particular from catalases (EC 1.11.1.6), peroxidases (EC 1.11.1.7), glutathione peroxidases (EC 1.11.1.9), chloride peroxidases (EC 1.11.1.10), manganese peroxidases (EC 1.11.1.13) and / or lignin peroxidases (EC 1.11.1.14), which are generally also summarized under the term peroxidases. Instead of or in addition to these peroxidases, perhydrolases can also be used. Perhydrolases, formerly also called metal-free haloperoxidases, usually contain the catalytic triad Ser-His-Asp in the reaction center and catalyze the reversible formation of peracids starting from carboxylic acids and hydrogen peroxide. With regard to perhydrolases which can be used according to the invention, reference may be made in particular to the applications WO 98/45398, WO 04/58961, WO 05/56782 and US Pat PCT / EP05 / 06178. When using perhydrolases, carboxylic acids, their salts and / or their esters and / or derivatives thereof are accordingly preferably also present in the compositions according to the invention.

The enzymes used in agents according to the invention are either originally derived from microorganisms, such as the genera Bacillus, Streptomyces, Humicola or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, such as transgenic expression hosts of the genera Bacillus or filamentous fungi.

The purification of the relevant enzymes is conveniently carried out by conventional methods, for example by precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.

The agents of the invention may be added to the enzymes in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-containing agents, solutions of the enzymes, advantageously as concentrated as possible, sparing water and / or added with stabilizers. Alternatively, these proteins can be adsorbed and / or encapsulated on a solid support for both the solid and liquid dosage forms.

Encapsulation can be carried out, for example, by spray-drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type in which an enzyme-containing core a water, air and / or chemical impermeable protective layer is coated. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

The encapsulated form lends itself to protecting the enzymes or other ingredients from other ingredients, such as bleaches, or to allow for controlled release. Depending on the size of these capsules, a distinction is made to MiIIi-, micro- and nanocapsules, with microcapsules for enzymes being particularly preferred. Such capsules are disclosed, for example, in patent applications WO 97/24177 and DE 19918267. Another possible encapsulation method is that the proteins are encapsulated in this substance, starting from a mixture of the protein solution with a solution or suspension of starch or a starch derivative. Such an encapsulation process is described in the application WO 01/38471.

In a particular embodiment, granulation of the enzymes can also be carried out as described in the application DE 102006018780. In addition to the enzymes, it is also possible to granulate further sensitive detergent or cleaning agent ingredients, such as, for example, fragrances, optical brighteners or bleach activators, in order to protect them from other components, in particular from bleaching agents which may be present.

In this embodiment, the sensitive detergent or cleaning agent ingredient is granulated together with a chemically inert carrier material and a chemically inert binder. The support material may in this case be selected from inorganic substances, such as, for example, clays, silicates or sulfates, in particular talc, silicic acids, metal oxides, in particular aluminum oxides and / or titanium dioxide, silicates, in particular phyllosilicates, sodium aluminum silicates, bentonites and / or aluminosilicates (zeolites). However, it may also be an organic compound such as polyvinyl alcohol (PVA), in particular at least partially hydrolyzed PVA. It is particularly advantageous if these compounds fulfill an additional benefit, for example a builder function when using the washing or cleaning agent.

By contrast, in this embodiment, a binder is a solid, waxy or liquid material which is solid at room temperature and which is chemically inert to such an extent that it can not be mixed with any of the ingredients of the production, processing and storage conditions of the granules Granules or agent in an affecting the overall efficiency of the granules extent reacts. It is a different material from the substrate. It is or becomes at least so viscous under the conditions of granule production that it virtually sticks the other ingredients together. Of particular importance here is the physico-chemical interaction with the carrier material, which leads to the resulting mass becoming an overall homogeneous phase which can subsequently be converted into individual granulate particles. In this pulp, which is formed predominantly of the carrier material and binder components, the other ingredients and in particular the ingredient to be formulated are included. Suitable binders are inorganic or organic substances which have the properties described, for example non-crosslinked, polymeric compounds selected from the group of polyacrylates, polymethacrylates, methacrylic acid-ethyl acrylate copolymers, polyvinylpyrrolidones, polysaccharides or substituted polysaccharides, in particular Cellulose ethers, and / or polyvinyl alcohols (PVA), preferably partially hydrolyzed polyvinyl alcohols and / or ethoxylated polyvinyl alcohols and their copolymers and mixtures. PVA or its derivatives are suitable both as a carrier material and as a binder component due to their adsorption properties and their co-existing binding effect. They can therefore be used as binders, if they are not already used as a carrier material.

Otherwise, reference is made to DE 102006018780 with regard to this embodiment.

Furthermore, it is possible to assemble two or more enzymes together so that a single granule has several enzyme activities.

A protein contained in an agent according to the invention can be protected especially during storage against damage such as inactivation, denaturation or disintegration, for example by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Preferred agents according to the invention contain stabilizers for this purpose.

One group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used for this purpose, including, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or Esters of the compounds mentioned. Also peptide aldehydes, that is, oligopeptides with reduced C-terminus, in particular those of 2 to 50 monomers are used for this purpose. Among the peptidic reversible protease inhibitors include ovomucoid and leupeptin. Also, specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are suitable.

Other enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Certain organic acids used as builders are additionally capable of stabilizing a contained enzyme.

Lower aliphatic alcohols, but especially polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other frequently used enzyme stabilizers. Di-glycerol phosphate also protects against denaturation due to physical influences. Likewise Calcium and / or magnesium salts used, such as calcium acetate or calcium formate.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations. Polyamine N-oxide containing polymers act simultaneously as enzyme stabilizers and as dye transfer inhibitors. Other polymeric stabilizers are linear C ₈ -C ₈ polyoxyalkylenes. Also, alkylpolyglycosides can stabilize the enzymatic components of the agent according to the invention and are able, preferably, to additionally increase their performance. Crosslinked N-containing compounds preferably perform a dual function as soil release agents and as enzyme stabilizers. Hydrophobic, nonionic polymer stabilizes in particular an optionally contained cellulase.

Reducing agents and antioxidants increase the stability of the enzymes to oxidative degradation; For example, sulfur-containing reducing agents are familiar. Other examples are sodium sulfite and reducing sugars.

Particular preference is given to using combinations of stabilizers, for example of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts. The effect of peptide-aldehyde stabilizers is favorably enhanced by the combination with boric acid and / or boric acid derivatives and polyols, and still further by the additional action of divalent cations, such as calcium ions.

In the case of solid agents, the proteins can be used, for example, in dried, granulated and / or encapsulated form. They may be added separately, ie as a separate phase, or with other ingredients together in the same phase, with or without compaction. If microencapsulated enzymes are to be processed in solid form, the water can be removed by methods known from the prior art from the aqueous solutions resulting from the workup, such as spray drying, centrifuging or by solubilization. The particles obtained in this way usually have a particle size between 50 and 200 microns.

Liquid, gelatinous or pasty agents according to the invention may be concentrated in the proteins on the basis of a protein recovery and preparation carried out according to the prior art aqueous or nonaqueous solution, suspension or emulsion, but also in gel form or encapsulated or as a dried powder. Such detergents or cleaners according to the invention are generally prepared by simple mixing of the ingredients which can be added in bulk or as a solution in an automatic mixer.

The proportion of the enzymes, the enzyme liquid formulation (s) or the enzyme granules in a washing or cleaning agent may, for example, be about 0.01 to 5% by weight, preferably 0.12 to about 2.5% by weight.

A cleaning agent according to the invention, in particular a hard surface cleaner according to the invention, may also contain one or more propellants (INCI propellants), usually in an amount of 1 to 80% by weight, preferably 1 to 5 to 30% by weight, in particular 2 to 10 wt .-%, particularly preferably 2.5 to 8 wt .-%, most preferably 3 to 6 wt .-%, contained.

Propellants are inventively usually propellants, especially liquefied or compressed gases. The choice depends on the product to be sprayed and the field of application. When using compressed gases such as nitrogen, carbon dioxide or nitrous oxide, which are generally insoluble in the liquid detergent, the operating pressure decreases with each valve actuation. Detergent-soluble or even solvent-acting liquefied gases (liquefied gases) as propellants offer the advantage of constant operating pressure and uniform distribution because the propellant vaporizes in the air, taking up more than a hundred times that volume.

According to INCI suitable blowing agents are accordingly: butanes, carbon dioxides, dimethyl carbonates, dimethyl ether, ethanes, Hydrochlorofluorocarbon 22, hydrochlorofluorocarbon 142b, hydrofluorocarbon 152a, hydrofluorocarbon 134a, hydrofluorocarbon 227ea, isobutanes, isopentanes, nitrogen, nitrous oxides, pentanes, propanes. Chlorofluorocarbons (chlorofluorocarbons, CFCs) as blowing agents, however, because of their harmful effect on the - shielding against hard UV radiation - ozone shield of the atmosphere, the so-called ozone layer, preferably largely and in particular completely omitted.

Preferred blowing agents are liquefied gases. Liquefied gases are gases that can be converted from the gaseous to the liquid state at usually already low pressures and 20 ^° C. In particular, liquefied gases, however, are the - in oil refineries as by-products in the distillation and cracking of crude oil and in the natural gas treatment in the gasoline separation hydrocarbons propane, propene, butane, butene, isobutane (2-methylpropane), isobutene (2-methylpropene, isobutylene) and mixtures thereof.

The cleaning agent particularly preferably contains propane, butane and / or isobutane, in particular propane and butane, as one or more propellants, more preferably propane, butane and isobutane.

In a preferred embodiment, the agent with a hyperbranched polymer according to the invention is designed so that it can be used regularly as a care agent, for example by being added to the washing process, applied after washing or applied independently of the washing. The desired effect is to prevent and / or reduce the growth and / or adhesion of microorganisms.

A separate subject of the invention are processes for the automated cleaning of textiles or of hard surfaces, in which at least in one of the process steps a hyperbranched polymer according to the invention is used.

This includes both manual and mechanical processes, with mechanical processes being preferred on account of their more precise controllability, for example with regard to the quantities and reaction times used.

Methods for cleaning textiles are generally distinguished by the fact that various cleaning-active substances are applied to the items to be cleaned in a plurality of process steps and washed off after the action time, or that the items to be cleaned are otherwise treated with a detergent or a solution of this agent. The same applies to processes for cleaning all other materials than textiles, which are summarized by the term hard surfaces. All conceivable washing or cleaning processes can be enriched in at least one of the process steps by hyperbranched polymers according to the invention, and then constitute embodiments of the present invention.

Another object of the present invention is also a product comprising a composition according to the invention or a detergent or cleaning agent according to the invention, in particular a hard surface cleaner according to the invention, and a spray dispenser. The product may be both a single-chamber and a multi-chamber container, in particular a two-chamber container. In this case, the spray dispenser is preferably a manually activated spray dispenser, in particular selected from the group consisting of aerosol spray dispensers (also known as spray can), pressure-building spray dispensers, pump spray dispensers and trigger spray dispensers, in particular pump spray dispensers and Trigger spray dispenser with a transparent polyethylene or polyethylene terephthalate container. Spray dispensers are described in more detail in WO 96/04940 (Procter & Gamble) and the US patents cited therein about spray dispensers, to which reference is made in this regard and the contents of which are hereby incorporated by reference. Triggersprühspender and pump sprayer have over compressed gas tanks the advantage that no propellant must be used. By means of suitable particle-like attachments, nozzles, etc. (so-called "nozzle valves") on the spray dispenser, the enzyme in this embodiment may optionally also be added to the composition in a form immobilized on particles and thus metered as cleaning foam

The following examples further illustrate the invention without being limited thereto.

embodiments

Example 1: Synthesis of hyperbranched block copolymers

To a 1 L Buchi glass reactor, 250 ml of THF (tetrahydrofuran) and 0.92 ml (5,84x10 ³ mol) of 1, 3-diisopropenylbenzene introduced and heated to 30 ⁰ C. With vigorous stirring, an equimolar amount of butyllithium (4.39 ml, 5.84 × 10 ³ mol) is then injected at this temperature. Here, a green color is observed. After a reaction time of 15 min is cooled to -30 ⁰ C. 0.9 ml (8.69 × 10 ^-3 mole) of styrene is injected into these living crosslinked cores after 30 minutes. There is a color change to orange and then to green again. After a reaction time of about 4 h at -30 ° C 9.3 ml (0.08 mol) of 4-vinylpyridine are added. There is a renewed color change from green to yellow to colorless. After a reaction time of 16 h, the reaction is stopped by adding 10 ml of degassed methanol. The workup is carried out by concentration of the polymer solution on a rotary evaporator (to about% of the volume) followed by precipitation in ether. The precipitated polymer can be centrifuged off. In a second step, the hyperbranched block copolymer (1g) prepared is alkylated with 2 ml of methyl iodide in chloroform at room temperature for 8 hours. A work-up of the yellow polymer is carried out by precipitation with diethyl ether and centrifuging.

Analysis of the polymers

According to ¹ H-NMR, the ratio of styrene to 4-vinylpyridine was determined to be 1:10. This result corresponds exactly to the planned approach. The synthesized hyperbranched block copolymer was measured with a DMF-GPC. It could have a molecular weight of M _w = 57000 g / mol as well a nonuniformity of U = 0.71 can be determined. The DMF-GPC was calibrated with a PS calibration standard.

application

In order to coat a surface antimicrobially, a 1% clear colorless aqueous solution is prepared from the alkylated hyperbranched block copolymer. From this solution, a volume of 80 μl was applied to a glass surface of 1 in 2 and distributed. After evaporation of the solvent, a clear homogeneous film could be obtained.

Example 2 Antimicrobial Spray Test with Staphylococcus aureus

To carry out the bacterial tests, S. aureus cells are incubated in a standard nutrient medium from Merck (2.5% by weight) for 6 hours with shaking at 37 ° C. (seeded with 100 μl storage suspension in PBS (1010 cells / ml) in 50 ml nutrient medium ). After centrifuging at 2750 rpm for 10 min, the cells are washed in dist. Water is suspended at a concentration of 10 ⁶ cells per milliliter. This suspension is sprayed onto a coated glass or ceramic slide and overlaid with liquid nutrient agar. After an incubation period of approximately 16 h at 37 ° C., the colonies formed on the non-antimicrobial areas are stained red with a staining solution (5 mg / ml TTC). It was found that no colony formation takes place in the sprayed area of the slides, ie that the growth of Staphylococcus aureus is suppressed.

In Figure 1, the result of an antimicrobial test can be seen as an example from AF 249. Table 1 shows a selection of antimicrobial hyperbranched polymers which had antimicrobial properties as coating.

Tab.:1 Results of the antimicrobial spray test

Tab. 2: Results of the antimicrobial spray test and the solubility

Example 3: Microbiological investigations based on JIS Z 2801: 2000

For the quantitative evaluation of the biostatic or biocidal properties, the so-called film contact method based on the Japanese Industrial Standard JIS Z 2801: 2000 was used. The polymers AF 148 and AF 152 were used. The polymers were dissolved in 10% ethanol and applied to Petri dishes and dried.

Subsequently, a germ suspension of defined germ density is applied to the coated test samples and distributed evenly on this by means of cover glass. The control is an uncoated Petri dish. As a test germ to check the microbiological efficacy of the gram-positive Staphylococcus aureus. After a defined incubation period, in this case 0 and 24 hours, the test specimens are shaken out with the added bacterial suspension and a dilution series is produced to determine the germ count. The biocidal activity is detected by colony-forming units (CFU) compared to the non-equipped control. Tab. 3: Results of microbiological investigations

As can be seen, the survival rate of Staphylococcus aureus by the hyperbranched polymers could be lowered by at least 4 to 5 powers of ten.

Example 4 Experimental Procedure of the Storage Experiments

In order to test the dye absorption capacity, a stock solution of the dye oil red (Fig .: 1) was prepared in acetone. From this solution 10 different defined amounts were removed, pipetted into snap-top lids and the solvent was completely removed. Subsequently, 1 ml of a 1% aqueous polymer solution of AF 249 (3 star with styrene / 4-vinylpyridine ratio of 1: 19.6) was added to each tube.

The 10 snap-cap glasses were sonicated for 24 h. The liquid was then transferred from the snap-cap lids into Eppendorf Microtubes and centrifuged in an ultracentrifuge (2 min, 10000 rpm). This ensures that unincorporated insoluble dye particles interfere with the subsequent UV / VIS measurement. In the subsequent UV / VIS measurements, the absorption at 518 nm was compared and plotted against the initial concentration of the dye. It was found that the dye uptake initially increases linearly and saturation is reached above a certain concentration. To quantify the uptake capacity, the centrifugate from the last two samples was taken up with acetone. From this solution, the residual amount of undissolved dye was determined by absorption. From the difference between initial weight (2,84x10 ⁰⁷ mol) and the determined residual amount of dye (1, 44x10 ^{~ 08} mol) follows the absorbed amount of dye (2,69x10 ^{~ 07} mol). This corresponds to an average of 2.28 molecules of dye per hyperbranched polymer at a molecular weight of 85,000 g / mol. Example 5: Verification of storage stability at 50 ^° C.

The storage stability of the polymer product mixture was carried out at 50 ^° C. over a period of 74 days. Three different approaches were investigated:

• 0% commercial WC cleaner; 1% by weight AF 249 in water

• 10% commercial WC cleaner; 1% by weight AF 249 in water

• 100% commercial WC cleaner; 1% by weight AF 249

The clear yellowish solutions were stored for 74 days at a temperature of 50 ° C. After this storage period, no difference could be detected compared to the initially scheduled samples. Discoloration or clouding could not be observed. To verify that the antimicrobial activity of the solution is still present after this time, 70 μl of the various solutions were removed and a glass slide coated on a 1 in ^{2 area} . The film was subjected to an antimicrobial spray test with Staphylococcus aureus. It is clearly evident that S. aureus is prevented from growing on all three coatings. Thus, the antimicrobial activity is not limited by a long-term storage at 50 ⁰ C.

Example 6: Verification of Storage Stability After Three Thawing Cycles

In another test different polymer product mixtures were frozen three times at -20 ⁰ C for three days and thawed. The three different approaches were as in the tests at 50 ⁰ C around:

• 0% commercial WC cleaner; 1% by weight AF 249 in water

• 10% commercial WC cleaner; 1% by weight AF 249 in water

• 100% commercial WC cleaner; 1% by weight AF 249

After the three cycles no differences to the initially frozen samples could be detected. Turbidity or discoloration could not be observed. The antimicrobial activity was tested as in the case of the long-term storage test at 50 ^° C. with S. aureus. It is clearly evident that no growth of S. aureus takes place on the polymer / product solution coated areas. Thus, the antimicrobial activity is not limited by the freeze-thaw cycles used. pictures

FIG. 1 shows the results of the antimicrobial test of AF 249 on ceramic (left) and on glass (right). The experiment was carried out as described in Example 2. As can be seen, the sprayed areas are free of microorganisms, while on the unsprayed areas bacterial growth is observed.

FIG. 2 shows the results of an antimicrobial test of AF 249 on ceramics (tiles). The attachment of Staphylococcus aureus was investigated. The adhesion values of the untreated tile (0 h) as well as the values 16 h and 24 h after treatment according to the film contact method are shown from left to right. On the far left, for comparison, the adhesion to a) an untreated plastic surface is shown, besides b) the adhesion to an untreated tile. In addition, from left to right are the adhesion to tiles, with c) 100% of a commercial toilet cleaner, d) 100% of a commercial toilet cleaner plus 2 wt .-% AF 249, e) 10% of a commercial toilet Cleaner and d) 10% of a commercial toilet cleaner plus 2 wt .-% AF 249 were treated.

Claims

claims

1. hyperbranched polymer, characterized in that it comprises a hydrophobic core and an antimicrobial and / or anti-adhesive effective shell.

2. Hyperbranched polymer according to claim 1, characterized in that the hydrophobic core comprises silicone groups or a hydrophobic hydrocarbon, which may optionally also contain heteroatoms.

3. Hyperbranched polymer according to claim 2, characterized in that the hydrophobic hydrocarbon contains aromatic radicals C ₆ _i ₀ -aryl.

4. Hyperbranched polymer according to one of claims 1 to 3, characterized in that the hydrophobic core comprises a hyperbranched core, are bound to the branches, each comprising a hydrophobic region to which an antimicrobial and / or anti from inside to outside Adhesive effective areas connects.

5. Hyperbranched polymer according to claim 4, characterized in that the hydrophobic region in the branches is polymeric units of at least 10 block-like arranged monomers.

6. Hyperbranched polymer according to claim 5, characterized in that each monomer comprises an aromatic radical C ₆ _i ₀ aryl.

7. Hyperbranched polymer according to claim 5 or 6, characterized in that the hydrophobic region in the branches is an optionally modified polystyrene.

8. A hyperbranched polymer according to any one of claims 1 to 7, characterized in that it is the antimicrobial and / or anti-adhesive effective range to polymeric units of at least 20 optionally chemically modified block-like arranged monomers.

9. Hyperbranched polymer according to claim 8, characterized in that the optionally chemically modified block-like monomers are units comprising a group with an alkylated positively charged heteroatom.

10. Hyperbranched polymer according to claim 9, characterized in that the groups with an alkylated positively charged heteroatom are selected from quaternary ammonium ions, quaternary pyridinium ions, quaternary phosphonium and ternary sulfonium ions.

11. Hyperbranched polymer according to one of claims 8 to 10, characterized in that it ethacrylate If the antimicrobial and / or antiadhesive area around a through C _1- ₁₂ alkyl, at least partially quaternized polyvinylpyridine or nitrogen group carrying poly (m) is.

12. A hyperbranched polymer according to any one of claims 1 to 11, characterized in that the ratio between the number of monomers in the antimicrobial and / or antiadhesive effective range to the number of monomers in the hydrophobic region is at least 2: 1.

13. A hyperbranched polymer according to any one of claims 1 to 12, characterized in that the ratio between the number of monomers in the antimicrobial and / or antiadhesive effective range to the number of monomers in the hydrophobic range is between 2: 1 and 100: 1.

14. Hyperbranched polymer according to one of claims 1 to 13, characterized in that the polymer comprises 3 to 10,000 branches.

15. Hyperbranched polymer according to any one of claims 1 to 14, characterized in that the hyperbranched core of the hyperbranched polymer has a degree of branching of 0.4 to 0.8.

16. Hyperbranched polymer according to one of claims 1 to 15, characterized in that it is the aromatic radicals C ₆ . ₁₀ -Aryl is phenyl radicals.

17. Hyperbranched polymer according to one of claims 1 to 16, characterized in that it is a water-soluble molecule.

18. Hyperbranched polymer according to one of claims 1 to 17, characterized in that it contains a non-covalently bound active substance.

19. Hyperbranched polymer according to claim 18, characterized in that the active ingredient is selected from biocides, dyes and fragrances.

20. A process for preparing a hyperbranched polymer according to any one of claims 1 to 17, comprising the following steps: a) preparation of a hyperbranched core with several living centers, b) reaction of the compound according to (a) with monomers, the quaternary ammonium groups, quaternary Carry phosphonium groups or ternary sulfonium groups.

21. A process for preparing a hyperbranched polymer according to any one of claims 1 to 17, comprising the following steps: a) preparation of a hyperbranched core with several living centers, b) reacting the compound according to (a) with monomers containing organically bound nitrogen, phosphorus or C) reaction of the product from (b) with an alkylating reagent for converting the heteroatom mentioned in (b) into a quaternary or ternary heteroatom.

22. A process for preparing a hyperbranched polymer according to any one of claims 1 to 17, comprising the following steps: a) preparation of a hyperbranched core with several living centers, b) reaction of the compound according to (a) with monomers which carry hydrophobic groups, c) Reaction of the product according to (b) with monomers which carry quaternary ammonium groups, quaternary phosphonium groups or ternary sulfonium groups.

23. A process for preparing a hyperbranched polymer according to any one of claims 1 to 17, comprising the following steps: a) preparation of a hyperbranched core with several living centers, b) reaction of the compound according to (a) with monomers which carry hydrophobic groups, c) Reaction of the product from (b) with monomers which contain organically bonded nitrogen, phosphorus or sulfur, d) reaction of the product from (c) with an alkylating reagent for converting the heteroatom mentioned in (c) into a quaternary or ternary heteroatom ,

24. Use of hyperbranched polymers according to any one of claims 1 to 19 for the treatment and / or antimicrobial and / or anti-adhesive finishing of surfaces.

25. Use of hyperbranched polymers according to any one of claims 1 to 19 in a cleaning agent, in a hair treatment agent or a dental treatment agent.

26. Use of hyperbranched polymers according to any one of claims 1 to 19 as a carrier for active substances.

27. A composition selected from the group consisting of cleaning agents, hair treatment compositions and dental treatment compositions containing hyperbranched polymers according to any one of claims 1 to 19.

28. A composition according to claim 27, characterized in that the cleaning agent is a hard surface cleaner or a laundry detergent.

29. A composition according to claim 27 or 28, characterized in that the hyperbranched polymers are contained in an amount of up to 20 wt .-% in the composition.

30. The composition according to any one of claims 27 to 29, characterized in that it additionally contains surfactants, in particular selected from anionic, nonionic, amphoteric and zwitterionic surfactants.

31. The composition according to any one of claims 27 to 30, characterized in that it additionally contains acids, in particular selected from citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof.

32. A composition according to any one of claims 27 to 31, characterized in that it additionally contains a builder, in particular selected from zeolites, silicates, carbonates, organic cobuilders and phosphates.

33. A composition according to any one of claims 27 to 32, characterized in that it additionally contains bleach.

34. A composition according to any one of claims 27 to 33, characterized in that it contains at least one further component selected from the group consisting of alkaline substances, hydrotropes, solvents, thickeners, dyes, Perfumes, corrosion inhibitors, sequestering agents, electrolytes, optical brighteners, grayness inhibitors, silver corrosion inhibitors, dye transfer inhibitors, foam inhibitors, abrasives, UV absorbers, solvents, abrasives, antistatic agents, pearlescers, enzymes and skin protection agents.

35. The composition according to any one of claims 27 to 34, characterized in that it is a solid, gelatinous, pasty or liquid composition.

36. A product comprising hyperbranched polymers according to any one of claims 1 to 19 or a composition according to any one of claims 27 to 34 and a spray dispenser for metering the composition as an aerosol and / or as a foam.

37. A method for semi-permanent antimicrobial and / or anti-adhesive finishing of surfaces, characterized in that the surface is treated with a hyperbranched polymer according to any one of claims 1 to 19 or with a composition according to any one of claims 27 to 34.