EP2021453A2 - Amadoriases in washing and cleaning products - Google Patents

Abstract

The invention relates to body care products, hair care products, shampoos, oral care, dental care and dental prosthesis care products, dental brace care products, cosmetics, therapeutics, washing agents, cleaning agents, brightening products, bleaching products, disinfectants, rinsing agents, hand washing products, dishwashing agents, machine dishwashing agents and agents for the bleaching and disinfecting treatment of filter media, textiles, furs, paper, skins or leather, the products containing amadoriases. The invention also relates to the use of amadoriases.

Description

 "Amadoriases in detergents and cleaners"

The present invention relates to personal care products, hair care products, shampoos, oral, dental and dental prosthesis care products, braces, cosmetics, therapeutics, detergents, cleaning agents, brightening agents, bleaching agents, disinfectants, rinse aids, hand washing, hand dishwashing, machine dishwashing and bleaching or disinfecting treatment of filter media , Textiles, furs, paper, hides or leather containing amadoriases and uses of amadoriases.

Stains of biological origin, especially those derived from foods, are particularly stubborn when heated. Here are complex reactions take place, which are summarized under the term "Maillard reaction" or "non-enzymatic browning". The reducing sugars contained in foods react with an amino group of proteins, peptides or amino acids. The result is the derivative of an N-glycosylamine, from which the Amadori rearrangement forms the derivative of a 1-amino-deoxy-2-ketose "aminoketose." Subsequently, a large number of further reactions take place, for example, to melanoidines (browning). , various flavors and cross-linked proteins.

These Amadori products or products of the Maillard reaction are either already contained in the soil on the textile or tableware or arise only during cleaning and thus possibly enhance the discoloration. An effective and gentle means of removing such discoloration is not known in the art.

There is therefore a not insignificant need for agents that counteract the undesirable discoloration caused by these Amadori products.

Accordingly, the present invention is a laundry detergent, detergent, rinse aid, hand wash, hand dishwashing or machine dishwashing detergent containing at least one amadoriase.

In the context of the present invention, an amadoriase is defined as an enzyme capable of degrading the Amadori rearrangement products.

The amadoriase present in the composition of the invention decomposes the products of the Amadori rearrangement described above and thereby advantageously prevents the typical stubborn stains that have arisen due to Maillard reactions.

The effect of the amadoriase is synergistically enhanced by the use of at least one protease, which increases the availability of a substrate of amadoriase, the peptides. The action of the protease is in turn enhanced by the degradation of the Amadori products, as these are reversible inhibitors of the protease. The reversible inhibition also leads to a stabilization of the enzyme in the agent according to the invention, which is canceled by the consumption of the substrate by the Amadoriase.

The stains caused by the Maillard reaction are partly formed in the washing machine or in the dishwasher. By using the amadoriase in the composition according to the invention, this formation is prevented or reduced.

In addition, the use of the amadoriase in a particularly preferred embodiment of the composition according to the invention realizes an advantageous bleaching effect if the agent contains at least one surfactant and at least one perhydrolase. Also particularly preferred is an agent which contains at least one bleach activator and / or at least one bleach catalyst. The stain and possibly also substances contained in the WascIWReingungsmittel is or are then oxidized by the Amadoriase and thereby produces hydrogen peroxide. This responds by the also used Perhydrolase to a peracid and leads to the desired bleaching. This enzymatic production of hydrogen peroxide has over the usual in the prior art direct addition to the product, inter alia, the advantage that the substance is produced only immediately in the application, storage instability is avoided, loss of hydrogen peroxide during storage by degradation is avoided, and that no Hydrogen peroxide must be declared as a recipe ingredient. Another advantage is the continuous re-production of hydrogen peroxide while it is deprived of equilibrium by its activity.

This bleaching action can also be used in other than the above-mentioned inventive compositions, as long as they contain at least one surfactant and at least one perhydrolase.

Other objects of the present invention are thus personal care products, hair care products, shampoos, oral, dental and denture care products, braces, cosmetics, therapeutics, brightening agents, bleaching agents, disinfectants and agents for bleaching or disinfecting treatment of filter media, textiles, furs, paper, skins or Leather containing at least one Amadoriase.

Preferred according to the invention is an amadoriase which can be obtained from fungi or bacteria. Particularly preferred are amadoriases from the species Aspergillus and Bacillus.

Particularly preferred are amadoriases obtainable from organisms selected from Agrobacterium tumefaciens, Agrobacterium tumefaciens, Arthrobacter sp., Aspergillus clavatus, Aspergillus fumigatus, Aspergillus nidulans, Aspergillus oryzae, Aspergillus terreus, Bacillus halodurans, Candida boidinii, Coniochaeta sp. Corynebacterium sp., Cryptococcus neoformans, Debaryomyces hansenii, Eupenicillium terrenum, Filobasidiella neoformans, Gibberella zeae, Neosartorya fischeri, Ulocladium sp., Fusarium oxysporum, Acremonium, Bacillus cereus, Bacillus clausii; Brevibacterium linens, Thermobifidafusca; Bacillus anthracis, Bacillus thuringiensis, Eobacillus kaustophilus, Bacillus subtilis, Oceanobacillus ^• \ ^{,! ("} " Iheyensjs, Geobacillus kaustophilus, Penicillium spp., Penicillium janthinellum, Pichia sp., Bacillus licheniformis, and Schizosaccharomyces pombe.

Very particular preference is given to amadoriases whose amino acid sequences comprise a sequence or consist of a sequence which, with the amino acid sequences given in SEQ ID NO: 1 to 26, is at least 80, 85 or 90%, preferably at least 91, 92 or 93%, in particular at least 94, 95 or 96%, more preferably at least 97, 98 or 99% and most preferably 100% match. Such amadoriases are obtainable, for example, by one or multiple conservative amino acid substitutions from an amadoriase according to one of the sequences 1 to 26, or by derivatization, fragmentation, deletion mutation or insertion mutation of an amadoriase according to one of the sequences 1 to 26.

For the purposes of the present application, a protein is to be understood as meaning a polymer composed of the natural amino acids and having a largely linear structure and assuming a function which is generally three-dimensional in order to perform its function. In the present application, the 19 proteinogenic, naturally occurring L-amino acids and glycine are designated by the internationally used 1- and 3-letter codes.

For the purposes of the present application, an enzyme is to be understood as meaning a protein which has a specific biocatalytic function.

For the purposes of the present application, nucleic acids are understood to mean the molecules which are naturally constructed from nucleotides and serve as information carriers, which code for the linear amino acid sequence in proteins or enzymes. They can be present as a single strand, as a single strand that is complementary to this single strand, or as a double strand. As the naturally more durable information carrier, the nucleic acid DNA is preferred for molecular biology work. In contrast, for the realization of the invention in a natural environment, such as in an expressing cell, an RNA formed, which is why essential to the invention RNA molecules are also embodiments of the present invention.

For DNA, consider the sequences of both complementary strands in all three possible reading frames. Further, it should be noted that different codon triplets can encode the same amino acids so that a particular amino acid sequence can be derived from a plurality of different and possibly low identity nucleotide sequences (degeneracy of the genetic code). In addition, various organisms have differences in the use of these codons. For these reasons, both amino acid sequences and nucleotide sequences must be included in the scope consideration, and specified nucleotide sequences are to be considered as exemplifying only a particular amino acid sequence.

The information unit corresponding to a protein is also referred to as gene within the meaning of the present application.

The present invention involves the production of recombinant proteins. These are to be understood according to the invention as meaning all genetic engineering or microbiological processes which are based on the genes for the proteins of interest being introduced into a host organism suitable for production and being transcribed and translated by the latter. Suitably, the introduction of the relevant genes via vectors, in particular expression vectors; but also those that cause the gene of interest in the host organism can be inserted into an already existing genetic element such as the chromosome or other vectors. The functional unit of gene and promoter and any other counterparts is referred to as expression cassette according to the invention. However, it does not necessarily have to exist as a physical entity.

One of ordinary skill in the art will appreciate methods that are well known today, such as chemical synthesis or polymerase chain reaction (PCR) in using standard molecular biological and / or proteinchemical methods, it is possible to prepare the corresponding nucleic acids, including complete genes, using known DNA and / or amino acid sequences. Such methods are known, for example, from Sambrook, J., Fritsch, EF and Maniatis, T. 2001. Molecular cloning: a laboratory manual, 3rd edition CoId Spring Laboratory Press.

Changes in the nucleotide sequence, as can be brought about, for example, by molecular biological methods known per se, are referred to as mutations. Depending on the nature of the change, for example, deletion, insertion or substitution mutations or those in which different genes or parts of genes are fused or recombined with one another are known; these are gene mutations. The associated organisms are called mutants. The proteins derived from mutant nucleic acids are called variants. Thus, for example, deletion, insertion substitution mutations or fusions lead to deletion, insertion-substitution-mutated or fusion genes and, at the protein level, to corresponding deletion, insertion or substitution variants or fusion proteins.

Fragments are understood to mean all proteins or peptides which are smaller than natural proteins or those which correspond to fully translated genes and, for example, can be obtained synthetically. Due to their amino acid sequences, they can be assigned to the relevant complete proteins. For example, they may adopt the same structures or perform catalytic or partial activities, such as the complexation of a substrate. Fragments and deletion variants of starting proteins are in principle similar; while fragments tend to be smaller fragments, the deletion mutants tend to lack only short regions, and thus only individual subfunctions.

The fragments correspond at the nucleic acid level to the partial sequences. Within the meaning of the present application, chimeras or hybrid proteins are to be understood as meaning proteins which are encoded by nucleic acid chains which naturally originate from different or from the same organism. This procedure is also called recombination mutagenesis. For example, the purpose of such recombination may be to induce or modify a particular enzymatic function using the fused protein portion. For the purposes of the present invention, it is irrelevant whether such a chimeric protein consists of a single polypeptide chain or several subunits to which different functions can be distributed.

Proteins obtained by insertion mutation are to be understood as meaning those variants which have been obtained by methods known per se by inserting a nucleic acid or protein fragment into the starting sequences. They are due to their principle similarity to the chimeric proteins. They differ from those only in the size ratio of the unchanged protein part to the size of the entire protein. In such insertionsmutierten proteins, the proportion of foreign protein is lower than in chimeric proteins.

Inversion mutagenesis, ie a partial sequence reversal, can be regarded as a special form of both the deletion and the insertion. The same applies to a new grouping of different parts of the molecule which deviates from the original amino acid sequence. It can be regarded as a deletion variant, as an insertion variant, as well as a shuffling variant of the original protein.

For the purposes of the present application, derivatives are understood as meaning those proteins whose pure amino acid chain has been chemically modified. Such derivatizations can be carried out, for example, biologically in connection with protein biosynthesis by the host organism. For this molecular biological methods can be used. However, they can also be carried out chemically, for example by the chemical transformation of a side chain of an amino acid or by covalent binding of another compound to the protein. For example, such a compound may also be other proteins act, which are bound, for example via bifunctional chemical compounds to proteins of the invention. Such modifications may, for example, affect the substrate specificity or binding strength to the substrate or cause a temporary blockage of the enzymatic activity when the coupled substance is an inhibitor. This can be useful, for example, for the period of storage. Similarly, derivatization is the covalent attachment to a macromolecular carrier.

Proteins can also be grouped into groups of immunologically related proteins by reaction with an antiserum or antibody. The members of a group are characterized by having the same antigenic determinant recognized by an antibody.

For the purposes of the present invention, all enzymes, proteins, fragments and derivatives, unless they need to be explicitly addressed as such, are summarized under the generic term proteins.

For the purposes of the present invention, vectors are understood as consisting of nucleic acids which contain a gene of interest as a characteristic nucleic acid region. They can establish this in a species or cell line over several generations or cell divisions as a stable genetic element. Vectors, especially when used in bacteria, are special plasmids, ie circular genetic elements. One differentiates in the genetic engineering on the one hand between those vectors which serve the storage and thus to a certain extent also the genetic engineering, the so-called cloning vectors, and on the other hand those which fulfill the function of realizing the gene of interest in the host cell, that is, the expression of the protein. These vectors are referred to as expression vectors.

By comparison with known enzymes, which are deposited for example in generally accessible databases, can be from the amino acid or Nucleotide sequence to conclude the enzymatic activity of a considered enzyme. This can be qualitatively or quantitatively modified by other regions of the protein that are not involved in the actual reaction. This could, for example, relate to enzyme stability, activity, reaction conditions or substrate specificity.

Such a comparison is accomplished by associating similar sequences in the nucleotide or amino acid sequences of the proteins of interest. This is called homologization. A tabular assignment of the respective positions is referred to as alignment. In the analysis of nucleotide sequences, in turn, both complementary strands and all three possible reading frames are to be taken into account; as well as the degeneracy of the genetic code and the organism-specific codon usage. Meanwhile, alignments are created using computer programs, such as the algorithms FASTA or BLAST; this procedure is described, for example, by D.J. Lipman and W.R. Pearson (1985) in Science, Vol. 227, pp. 1435-1441.

A summary of all matching positions in the compared sequences is called a consensus sequence.

Such a comparison also allows a statement about the similarity or homology of the compared sequences to each other. This is expressed in percent identity, that is, the proportion of identical nucleotides or amino acid residues at the same positions. A broader concept of homology includes the conserved amino acid substitutions in this value. It then speaks of percent similarity. Such statements can be made about whole proteins or genes or only over individual areas.

Creating an alignment is the first step in defining a sequence space. This hypothetical space includes all sequences to be derived by permutation in individual positions, taking into account all the variations occurring in the relevant individual positions of the alignment. Every hypothetical protein molecule makes a point in this i; , ^{"" ■} Se ^'quenzteum. For example, two amino acid sequences different in only two in the substantial identity bodies each having two different amino acids, thus a sequence space of four different amino acid sequences. A very large sequence space is obtained when to individual sequences of a space in each case further Homologous sequences can be found, and very low homologous sequences can be recognized as belonging to a sequence space via such high homologies in pairs.

Homologous regions of different proteins are defined by matches in amino acid sequence. These can also be identified by identical function. It goes as far as complete identities in the smallest areas, so-called boxes, which contain only a few amino acids and usually perform essential functions for the overall activity. The functions of the homologous regions are to be understood as the smallest partial functions of the function carried out by the entire protein, such as, for example, the formation of individual hydrogen bonds for the complexation of a substrate or transition complex.

In the context of the present invention, the nucleic acid is suitably cloned into a vector. The molecular-biological dimension of the invention thus consists in vectors with the genes for the corresponding proteins. These may include, for example, those derived from bacterial plasmids, viruses or bacteriophages, or predominantly synthetic vectors or plasmids with elements of various origins. With the other genetic elements in each case, vectors are able to establish themselves as stable units in the respective host cells over several generations. For the purposes of the invention, it is irrelevant whether they establish themselves as extrachomosomal units or integrate them into a chromosome. Which of the numerous systems known from the prior art is chosen depends on the individual case. Decisive factors may be, for example, the achievable copy number, the selection systems available, in particular antibiotic resistances, or the cultivability of the host cells capable of accepting the vectors. The vectors form suitable starting points for molecular biological and biochemical investigations of the relevant gene or protein and for further developments according to the invention and ultimately for the amplification and production of proteins according to the invention. They represent embodiments of the present invention insofar as the sequences of the nucleic acid regions which can be used according to the invention are each within the homology regions specified above.

Cloning vectors are suitable in addition to the storage, the biological amplification or the selection of the gene of interest for the characterization of the gene in question, such as the creation of a restriction map or sequencing.

Expression vectors are chemically similar to the cloning vectors, but differ in those partial sequences that enable them to replicate in the host organisms optimized for the production of proteins and to express the contained gene there. The expression is influenced, for example, by promoters which regulate the transcription of the gene. Thus, the expression can be carried out by the natural, originally located in front of this gene promoter, but also after genetic engineering, both by a promoter provided on the expression vector of the host cell and by a modified or a completely different promoter of another organism.

Preferred are expression vectors which are regulatable via changes in the culture conditions or addition of certain compounds, such as cell density or specific factors. Expression vectors allow the associated protein to be produced heterologously, that is, in an organism other than that from which it can naturally be obtained. Also, homologous protein recovery from a gene naturally expressing host organism via an appropriate vector is within the scope of the present invention. This may have the advantage of being natural, associated with translation ^• },

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Mbdifikationsreaktionen on the resulting protein to be performed exactly as they would run naturally.

Can also be used according to the invention cell-free expression systems in which the protein biosynthesis is understood in vitro. Such expression systems are also established in the art.

The in vivo synthesis of an enzyme, that is, by living cells, requires the transfer of the associated gene into a host cell, their so-called transformation. As host cells are in principle all organisms, that is prokaryotes or eukaryotes. Preference is given to those host cells which can be genetically well handled, for example, the transformation with the expression vector and its stable establishment, for example, unicellular fungi or bacteria. In addition, preferred host cells are characterized by good microbiological and biotechnological handling. This concerns, for example, easy culturing, high growth rates, low demands on fermentation media and good production and secretion rates for foreign proteins. Frequently, the optimal expression systems for the individual case must be determined experimentally from the abundance of different systems available according to the prior art. Each protein of the invention can be obtained in this way from a variety of host organisms.

Preference is given to those host cells which are regulatable in their activity due to genetic regulatory elements which are provided, for example, on the expression vector, but may also be present in these cells from the outset. For example, by controlled addition of chemical compounds that serve as activators, by changing the culture conditions or when reaching a specific cell density, these can be excited for expression. This allows a very economical production of the proteins of interest.

Preferred host cells are prokaryotic or bacterial cells. As a rule, bacteria are distinguished from eukaryotes by shorter generation times and lower demands on culturing conditions. Thereby can inexpensive methods for obtaining the proteins of interest can be established. In Gram-negative bacteria, such as Escherichia coli (E. coli), a large number of proteins are secreted into the periplasmic space, ie into the compartment between the two membranes enclosing the cells. This can be advantageous for special applications. Gram-positive bacteria, such as Bacilli or Actinomycetes or other representatives of Actinomycetales, on the other hand, have no outer membrane, so that secreted proteins are readily released into the nutrient medium surrounding the cells, from which, according to another preferred embodiment, the expressed proteins usable according to the invention can be directly purified ,

A variant of this production principle is expression systems in which additional genes, for example those provided on other vectors, influence the production of proteins of interest. These may be modifying gene products or those that are to be co-purified with the protein of interest, such as to affect its enzymatic function. These may be, for example, other proteins or enzymes, inhibitors or elements that influence the interaction with various substrates.

Due to the extensive experience that one has, for example, with regard to the molecular biological methods and the cultivability with coliform bacteria, they are preferred for obtaining enzymes which can be used according to the invention. Particularly preferred are those of the genera Escherichia coli, in particular non-pathogenic, suitable for biotechnological production strains.

Representative members of these genera are the K12 derivatives and B strains of Escherichia coli. Strains that can be derived from them by genetic and / or microbiological methods known per se, and thus can be regarded as derivatives thereof, have the greatest importance for genetic and microbiological work and are preferably used for the development of inventive methods. Such derivatives may, for example, via deletion or insertion mutagenesis with respect to their requirements of the culture conditions be altered, have other or additional selection markers or express other or additional proteins. In particular, these may be derivatives which, in addition to the protein produced according to the invention, express further economically interesting proteins.

It is well known to those skilled in the art that the heterologous expression of genes is particularly successful when the chosen host cell is particularly closely related to the organism from which the source gene is derived. Therefore, expression systems within the Actinomyceten are preferred systems for expression, particularly Streptomyceten, including Streptomyces coelicolor, Streptomyces avermitilis, Streptomyces lividans and, in principle, especially those Streptomyceten strains that are particularly suitable for a technical production of enzymes by appropriate selection or genetic manipulation ,

Also, such microorganisms are preferred, which are characterized in that they have been obtained after transformation with one of the vectors described above. These may, for example, be cloning vectors which have been introduced into any bacterial strain for storage and / or modification. Such steps are common in the storage and further development of related genetic elements. Since the relevant genetic elements can be directly transferred from these microorganisms into Gram-negative bacteria suitable for expression, the above-mentioned transformation products are also realizations of the subject matter of the invention.

Eukaryotic cells may also be useful in the production of proteins of interest. Examples thereof are fungi such as Actinomycetes or yeasts such as Saccharomyces or Kluyveromyces. This may be particularly advantageous, for example, if the proteins are to undergo specific modifications in the context of their synthesis that enable such systems. These include, for example, the binding of low molecular weight compounds such as membrane anchors or Oligosaccaride. The host cells are cultured and fermented in a manner known per se, for example in discontinuous or continuous systems. In the first case, a suitable nutrient medium is inoculated with the organisms and the product is harvested from the medium after an experimentally determined period. Continuous fermentations are characterized by achieving a flow equilibrium in which over a relatively long period of time cells partly die off but also regrow and at the same time product can be removed from the medium.

Fermentation processes are well known in the art and represent the actual large-scale production step; followed by a suitable purification method. All fermentation processes which are based on one of the above-described processes for the preparation of the recombinant proteins represent correspondingly preferred embodiments of this subject matter of the invention.

In this case, the optimum conditions for the production processes used, for the host cells and / or the proteins to be produced must be experimentally determined on the basis of the previously optimized culture conditions of the relevant strains according to the knowledge of the person skilled in the art, for example regarding fermentation volume, media composition, oxygen supply or stirrer speed.

Fermentation processes, characterized in that the fermentation is carried out via a feed strategy, are also contemplated. Here, the media components consumed by the ongoing cultivation are fed; One also speaks of a feeding strategy. As a result, considerable increases in both the cell density and in the dry biomass and / or especially the activity of the protein of interest can be achieved.

Similarly, the fermentation can also be designed so that unwanted metabolic products are filtered out or neutralized by the addition of buffer or matching counterions.

The produced protein can be harvested subsequently from the fermentation medium. This fermentation process is preferred over dry matter product processing, but requires the provision of suitable secretion markers and transport systems.

Without secretion u.U. the purification of the protein from the cell mass is required, and also various Verfahrer are known, such as precipitation z.B. by ammonium sulfate or ethanol, or the chromatographic purification, if necessary, to homogeneity. However, the majority of the described technical methods should manage with an enriched, stabilized preparation.

All of the elements already outlined above can be combined into methods to produce proteins of interest. It is conceivable for each protein of interest a variety of possible combinations of process steps. The optimal method must be determined experimentally for each specific case.

By expression or cloning, the Amadoriasen of interest can be provided in the amount required for technical use.

The amadoriases which can be used according to the invention have a pH optimum, preferably in the weakly acidic to alkaline range, of about pH 4 to 12, in particular pH 6 to 11, preferably pH 7 to 10, and more preferably about pH 7 to 8 and about pH 9 -10 on.

The activity of such enzymes is usually expressed in terms of U, the unit corresponding to that amount of enzyme which generates 1 μmol of hydrogen peroxide (H ₂ O ₂ ) at a fixed pH and temperature in 1 minute.

The temperature optimum of the invention can be used according amadoriases is approximately in the range of 20 to 60 ⁰ C, in particular in the range from 30 to 6O ⁰ C and most preferably from about 30 to 40 ⁰ C for liquid products, and from about 40 to 60 ° C for powder products , Another object of the present invention is the use of an amadoriase for the enzymatic degradation of Amadori products. A preferred embodiment of the use according to the invention is the use in detergents, dishwashing detergents and cleaners.

Another object of the present invention is the use of an amadoriase for the enzymatic generation of hydrogen peroxide in situ. A preferred embodiment of the use according to the invention is the use for bleaching, for color transfer inhibition and for disinfection.

The amadoriases which can be used according to the invention can advantageously be used in personal care products, hair care preparations, shampoos; Oral, dental and dental prosthetic care preparations, orthodontic appliances, cosmetics, therapeutics, detergents, cleansing preparations, brightening preparations, bleaching preparations, disinfectants, rinse-off preparations, hand washing preparations, hand dishwashing detergents, machine dishwashing detergents and bleaching or disinfecting treatment preparations for filter media, textiles, furs, paper, hides or leather are introduced.

The washing, rinsing, cleaning or bleaching agent according to the invention preferably has an amadoriase activity of 0.1 to 18 U / ml wash liquor, cleaning solution or user solution in the process; it is preferably present as a free-flowing powder having a bulk density of 300 g / l to 1200 g / l, in particular 500 g / l to 900 g / l before. Alternatively, it may also be in the form of a pasty or liquid detergent, in particular in the form of a non-aqueous liquid detergent or a non-aqueous paste or in the form of an aqueous liquid detergent or a water-containing paste.

The washing, rinsing, cleaning or bleaching agent according to the invention may be packaged in an air-impermeable container, from which it is released shortly before use or during the washing process, in particular, the Amadoriase with a room temperature or in the absence of water for the enzyme and / or whose substrate impermeable substance be wrapped, which under

Application conditions of the agent becomes permeable to the enzyme and / or its substrate.

The washing, rinsing or cleaning agent according to the invention preferably contains in addition to Amadoriase

5% by weight to 70% by weight, in particular 10% by weight to 50% by weight of surfactant,

10% by weight to 65% by weight, in particular 12% by weight to 60% by weight of water-soluble, water-dispersible inorganic builder material,

From 1% by weight to 10% by weight, in particular from 2% by weight to 8% by weight, of water-soluble organic builders,

Not more than 15% by weight of solid inorganic and / or organic acids or acid salts,

Not more than 5% by weight complexing agent for heavy metals,

Not more than 5% by weight of grayness inhibitor,

• not more than 5% by weight of color transfer inhibitor and

• not more than 5% by weight foam inhibitor.

Due to their great technical importance, the various aspects and other ingredients according to the invention will now be described in detail, in addition to the particularly preferred embodiments presented so far. described washing detergents and cleaners characterized by the Amadoriasen described above.

Here, a distinction is made according to the laundry between textiles and solid surfaces. The conditions to be selected for this, in particular via the other ingredients, such as temperature, pH, ionic strength, redox ratios or mechanical influences, should be optimized for the respective cleaning problem. So usual temperatures for detergents and cleaners in the range of 10 ⁰ C with manual means over 40 ° C and 60 ⁰ C up to 95 ° for mechanical means or in technical applications. Since the temperature is usually infinitely adjustable in modern washing machines and dishwashers, all intermediate stages of the temperature are included. Preferably the ingredients of the products concerned are coordinated. Synergies in terms of cleaning performance are preferred.

An amadoriase which can be used according to the invention can be used both in products for large consumers or technical users and in products for the private consumer, with all types of detergents established in the prior art also representing embodiments of the present invention. These include, for example, concentrates and undiluted agents; 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.

Embodiments of the present invention include all established and / or all appropriate dosage forms. These include, for example, solid, powdery, liquid, gelatinous or pasty agents, optionally also of several phases, compressed or uncompressed; further include, for example: extrudates, granules, tablets or pouches, packed both in large containers and in portions.

The inventively employable Amadoriasen be combined in inventive compositions, for example, with one or more of the following ingredients: nonionic, anionic and / or cationic surfactants, (optionally further) bleaching agents, bleach activators, bleach catalysts, builders and / or cobuilders, solvents, thickeners, sequestering agents, electrolytes , optical brighteners, grayness inhibitors, corrosion inhibitors, especially silver protectants, soil release agents, color transfer (or transfer) inhibitors, foam inhibitors, abrasives, dyes, perfumes, antimicrobial ,. 1) 1. ,,; *

Active ingredients, UV protectants, enzymes such as proteases, amylases, lipases, cellulases, hemicellulases or oxidases, stabilizers, especially enzyme stabilizers, and other components known in the art.

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 can be linear or preferably methyl-branched in the 2-position , 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 for example, C _2- i ₄ alcohols containing 3 EO or 4 EO, n-alcohol with 7 EO, C _13-15 include alcohols containing 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 Ci _2-14 -alcohol 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 meet the general formula RO (G) ₂ , in which R is a linear or branched, in particular 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 represents a glycose unit having 5 or 6 C-atoms, preferably glucose, stands. 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-tallow alkyl-N, N-dihydroxyethyl amine 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.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. As surfactants of the sulfonate type are preferably C _9-13 - alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those from C ₁₂ -1 ₈ - monoolefins with terminal or internal double bond by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates, which are obtained from C ₂ i ₈ alkanes, for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. 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 containing 6 to 22 carbon atoms, while spelleds of 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 Cio-C ₂ o-oxoalcohols 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. Of washing technology interest, the Ci ₂ -Ci ₆ alkyl sulfates and Ci ₂ -Ci ₅ alkyl sulfates and Ci ₄ -Ci ₅ alkyl sulfates are preferred. 2,3-alkyl sulfates are also suitable anionic surfactants.

Also, the Schwefelsäuremonoester the ethoxylated with 1 to 6 moles of ethylene oxide chain or branched C7 _-2 1-alcohols such as 2-methyl-branched Cg _-H alcohols containing on average 3.5 mol ethylene oxide (EO) or C _{2- 8} i - Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of up to 5% by weight, usually from 1 to 5% by weight.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain Cβ-iβ fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). 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 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 ,

Compositions according to the invention may contain further bleaching agents. Among the compounds which serve as bleaches and deliver H ₂ O ₂ in water, the sodium percarbonate, the sodium perborate tetrahydrate and the

Sodium perborate monohydrate 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 contain bleaching agents from the group of organic bleaches, although their use is also possible in principle for laundry detergents. 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 peroxybenzoic acid i;

and their 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-phthalimidoperoxycaproic acid (phthalimidoperoxyhexanoic acid, PAP), o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonylamido-persuccinates, and aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxy-brassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-Terephthalyl-di (6-aminopercaproic acid) can be used.

The content of bleaching agent content 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 a good bleaching effect when 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 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 alkylene diamines, 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, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), acylated hydroxycarboxylic acids, such as triethyl-O-acetyl citrate (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 the German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol or their mixtures described in the European patent application EP 0 525 239 (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine or gluconolactone, triazole or triazole derivatives and / or particulate caprolactams and / or caprolactam derivatives, preferably N-acylated lactams, for example N-benzoyl-caprolactam and N-acetyl-caprolactam. 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 dodecanoyloxybenzene sulfonate (OBS 12), as well as N-methylmorpholinum acetonitrile (MMA).

Such bleach activators can in the usual amount range of 0.01 to

20 wt .-%, preferably in amounts of 0.1 to 15 wt .-%, in particular 1 wt .-% to 10 wt .-%, based on the total composition, be contained.

Further bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula

in which R ¹ is -H, -CH _3, a C _2- 24 alkyl or alkenyl group, a substituted C _2-24 - alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, OH , -NH ₂ , -CN, an alkyl or Alkenylarylrest with a Ci-24-alkyl group, or for <. ; , ^■ ; ^{■■ ■■}

egg ierte alkyl or alkenylaryl radical having a Ci _-2 4-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 _3r -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₎ -CN

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, and, to the cationic selected from the group of these substances Nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" in which X ^{" represents} an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is particularly preferred.

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 such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru amine complexes are also suitable as bleach catalysts. It is particularly preferred to use complexes of manganese in the oxidation state II, III, IV or IV, 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 compositions of the invention, 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 ^πl 2 (μ-O) i (μ-OAc) ₂ (TACN) ₂ ] (CIO ₄ ) 2, [Mn ^lll 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 ^III 2 (μ-O) ₁ (μ-OAc) 2 (Me-TACN ) ₂ ] (Clθ4) 2, [Mn ^MI Mn ^lv (μ-O) i (μ-OAc) ₂ (Me-TACN) ₂ ] (CIO ₄ ) S, [Mn ¹ ^ -O) ₃ (Me-TACN ) _2] (PFe) ₂ and [Mn ^'v ₂ (μ-O) ₃ (Me / Me TACN) _2] (PFe) 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 bleach activator-containing agents. In special cases, however, more bleach catalyst can be used.

According to WO 99/63038 also acetonitrile derivatives and according to WO 99/63041 bleach-activating transition metal complex compounds in combination with amylases can develop a bleach-activating effect.

Enzymes which catalyze a perhydrolysis reaction of a substrate with hydrogen peroxide, so that peracids are formed, can also be used as the bleach activator. Such enzymes can be derived from lipases or cutinases, or from esterases or proteases, if there takes place wholly or partly a perhydrolysis reaction instead of hydrolysis. Such perhydrolases are described, for example, in WO2005 / 056782 (based on an esterase) or WO2004 / 058961 (on the basis of a modified subtilisin Carlsberg). The use of the bleaching system according to the invention under

• to ^'h' i \ lfen tah 'me of Perhydrolases is also part of the present invention. Agents according to the invention can thus contain lipases or cutinases, on the one hand because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases which were originally obtainable from Humicola lanuginosa {Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are for example marketed 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 Fusarium 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, the preparations originally sold by Gist-Brocades 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, furthermore, the product Lumafast ^® from Genencor.

As a rule, compositions according to the invention contain 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 name here are crystalline, layered sodium silicates of the general formula

NaMSi _x O _Σx + i'yHaO, 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 0 164 514. Preferred crystalline Phyllosilicates of the formula given are those in which M is sodium and x takes the values 2 or 3. In particular, both β- and δ-

Sodium disilicates Na ₂ Si ₂ O ₅ -yH ₂ O preferred. Such compounds are commercially available, for example, under the name ^SKS® (from Clariant). Thus, SKS- ^{6® is} predominantly a δ-sodium disilicate of the formula

Na ₂ Si ₂ OS yH ₂ O, in SKS-7 ^® mainly to the ß-sodium disilicate. Reaction with acids (for example citric acid or carbonic acid) results from the δ-

Sodium disilicate Kanemit NaHSi ₂ O _S yH ₂ O, commercially available under the names SKS-9 ^® or SKS-10 ^® (Clariant). 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 carbonate have, compared to the δ-sodium disilicate, altered crystal morphologies, dissolve more rapidly and show an increased calcium binding capacity in comparison to 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 layered silicates can also be increased by using particularly finely divided layered silicates. 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 to conventional amorphous sodium silicates can be achieved in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying be caused. 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. Particular preference is given to 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

nNa 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 variety of commercially available Phosphates have the alkali metal phosphates with particular preference of pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate) in the detergent and cleaning industry the greatest importance.

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 dihydrate (density 1.91 like ^"3 , melting point 60 °) and as monohydrate (density 2.04 like ^{" 3} ). Both salts are white powders which are very soluble in water and which lose the water of crystallization when heated and at 200 ^cC 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 (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt of density 2.33, like ^'3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPOa) _x ], and is readily 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 , loss of water at 95 °), 7 moles (density 1, 68 like ^"3 , melting point 48 ° with loss of 5 H ₂ O) and 12 moles water ( Density 1, 52 like ^"3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° C and goes on stronger heating in the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or :. , , , ^■ 32

! T ^• 1! I ir

1

; ,. '_ »• 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 prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 ^"3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction When heating Thomas slag with coal and potassium sulfate, despite the higher price, the more soluble, hence 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 °, also indicated 880 °) and as decahydrate (density 1, 815-1, 836 like ^{' 3} , melting point 94 ° with loss of water). Both substances are colorless crystals which are soluble in water with an 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 ° 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ gives rise to higher molecular weight sodium and potassium phosphates containing cyclic representatives, the sodium or potassium metaphosphates and chain-like types Sodium or Kaliumpolyphosphate, may differ. 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 technically important pentasodium triphosphate, Na ₅ P ₃ Oi _O (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° 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. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:

(NaPOs) ₃ + 2 KOH -> Na ₃ K ₂ P ₃ Oi ₀ + 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. f, J s -

Ate- organic cobuilders can be used in the washing and cleaning agents according to the invention in particular polycarboxylates or polycarboxylic acids, polymeric polycarboxylates, polyaspartic acid, polyacetals, optionally oxidized dextrins, other 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, environmentally friendly 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 here. But also mineral acids, especially 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. i - ^r i! ii,! ⁿ »

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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. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molecular weights in the range of 2,000 to 30,000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Particularly preferred organic builders for agents according to the invention are oxidized starches or their derivatives from applications EP 472 042, WO 97/25399, and EP 755 944.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are in zeolithhaltigen 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, the 1-hydroxyethane-1, 1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably used in the form of the neutrally reacting sodium salts, for example as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP. As a builder is from the class of phosphonates preferred to use HEDP. 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 compositions 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 ethyl ether, propylene glycol methyl, -ethyl or -propyl ether, dipropylene glycol monomethyl -, or -ethyl ether, di-isopropylene glycol monomethyl, or -ethyl ether, methoxy, ethoxy or Butoxytriglykol, 1-butoxyethoxy-2-propanol, 3-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, compositions according to the invention may be admixed with one or more thickeners or thickening systems. 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 are, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour,

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. Examples which may be mentioned here carboxymethylcellulose and other cellulose ethers, hydroxyethyl and - propylcellulose and core flour ethers. 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 ,

If appropriate, the washing or cleaning agent according to the invention may contain sequestering agents, electrolytes and other auxiliaries as further customary ingredients. > 4

Detergents according to the invention may contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid 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 replace 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). 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-SaIz), 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 from the prior 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, III, 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. as well as their 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 thereof are copolymers or copolymers of polyethylene terephthalate and polyoxyethylene glycol (DT 16 17 141, or DT 22 OO 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 185427 discloses methyl or ethyl 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 Cr to C ₄ alkyl groups are endgruppenverschlossen. From the European patent application EP 0 272 033 are at least partially by C- _M alkyl or acyl radicals end-capped polyesters with poly-propylene terephthalate and Pόlyoxyβthylenterephthalat units known. European Patent EP 0 274 907 describes sulfoethyl end-capped terephthalate-containing soil release polyesters. According to the European patent application EP 0 357 280, sulfonation of unsaturated end groups produces soil-release polyesters with terephthalate, alkylene glycol and poly-C 1-6 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.

Particularly suitable for use in textile detergents according to the invention in question color transfer inhibitors 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 compositions. As foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of Ci ₈ -C ₂₄ fatty acids. Suitable non-surfactant 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. Abrasive substances are preferably not more than 20% by weight, in particular from 5% by weight to 15% by weight, in the cleaning agents according to the invention.

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-lsomethylionon 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. I,

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The fragrances can be incorporated directly into the detergents and 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 fragrance release for long-lasting fragrance, in particular 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. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate. The terms antimicrobial action and antimicrobial active substance have the usual meaning in the context of the teaching according to the invention, which is described, for example, by KH Wallhäußer ln "Practice of Sterilization, Disinfection - Preservation: Germ Identification - Company Hygiene" (5th edition - Stuttgart, New York: Thieme, 1995 Suitable antimicrobial agents are preferably selected from the groups of alcohols, amines, aldehydes, antimicrobial acids or their salts, carboxylic esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, Urea derivatives, oxygen, nitrogen acetals and formal, 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 preceding.

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-chloro-chloro-O-S, -diimino-AH.is-tetra-aza-tetradecandiimidamide, glucoprotamines, antimicrobial quaternary surface active compounds , Guanidines including the bi- and polyguanidines, such as, for example, 1,6-bis (2-ethylhexyl-biguanido-hexane) -dihydrochloride, 1,6-di- (Ni, Ni'-phenyldiguanido-N ₅ , N ₅ ' ) hexane-tetrahydrochloride, 1,6-di- (Ni, NV-phenyl-Ni, methyldiguanido-N ₅ , N ₅ ' ) -hexane dihydrochloride, 1,6-di- (Ni, Ni'-chlorophenyldiguanido- N ₅ , N ₅ ') -hexane dihydrochloride, 1,6-di- (Ni, Ni'-2,6-) dichlorophenyldiguanido-N ₅ , N ₅ ') hexane dihydrochloride, 1,6-di- [Ni, Ni'-beta- (p-methoxyphenyl) diguanido-N ₅ , N ₅ '] -hexane dihydrochloride, 1, 6- di- (Ni, Ni'-alpha-methyl-.beta.--phenyldiguanido-N _5, N ₅ ') -hexane dihydrochloride, 1, 6-di (Ni, Ni'-p-nitrophenyldiguanido-N _5, N ₅ ') hexane-dihydrochloride, omega: omega-di (Ni.N / -phenyldiguanido-N ₅ , N ₅ ') -di-n-propyl ether dihydrochloride, omega: omega'-di- (Ni, Ni ') p-chlorophenyldiguanido-N ₅ , N ₅ ') -di-n-propyl ether tetrahydrochloride, 1,6-di- (Ni, Ni'-2,4-) methylphenyldiguanido- N ₅ , N ₅ ') hexane dihydrochloride, 1,6-di- (Ni, Ni'-2,4,5-trichlorophenyldiguanido-N ₅ , N ₅ ') hexane-tetrahydrochloride, 1,6-di- [N ₁ , Ni'-alpha- (p -chlorophenyl) ethyldiguanido-N ₅ , N ₅ '] hexane dihydrochloride, omega: omega-di- (Ni, Ni'-p-chlorophenyldiguanido-N ₅ , N ₅ ') m-xylene dihydrochloride, 1, 12-di- (N _1, Ni'-p-chlorophenyldiguanido-Ns.Ns'J dodecane dihydrochloride, 1, 10-di- (Ni ₁ N ₁ '- phenyldiguanido- N _5, N ₅ ') -decane-tetrahydrochloride, 1, 12-di- (N ₁ , N-i'-phenyldiguanido- ^■

n-tetrahydrochloride, 1,6-di- (N ₁ , Ni'-o-chlorophenyldiguanido- N ₅₁ N ₅ ') hexane dihydrochloride, 1,6-di- (N ₁ , Ni'-o-chlorophenyldiguanido- N ₅₁ N ₅ ') hexane tetrahydrochloride, ethylene bis (1-tolyl biguanide), ethylene bis (p-tolyl biguanide), ethylene bis (3,5-dimethylphenylbiguanide), ethylene bis (p-tert -amylphenylbiguanide), ethylene-bis- (nonylphenylbiguanide), ethylene-bis- (phenylbiguanide), ethylene-bis- (N-butylphenylbiguanide), ethylene-bis (2,5-diethoxyphenylbiguanide), ethylene-bis (2,4-dimethylphenyl biguanide), ethylene bis (o-diphenylbiguanide), ethylene bis (mixed amyl naphthyl biguanide), N-butyl ethylene bis (phenyl biguanide), trimethylene bis (o-tolyl biguanide), 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, imine odiacetates, cinnamates, thiocyanates, arginates, pyromellitate, tetracarboxybutyrates, benzoates, glutarates, monofluorophosphates, perfluoropropionates and any mixtures thereof. Also suitable are halogenated xylene and cresol derivatives, such as p-chloromethacresol or p-chloro-metaxylyl, and natural antimicrobial agents of plant origin (for example, from spices or herbs), of 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 quaternary compound with an ammonium, sulfonium, phosphonium, iodonium - or Arsoniumgruppe, 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 (QAV) 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 4 -alkyl radicals, C ₇ -C ₂₈ -aralkyl radicals or heterocyclic radicals, where two or, in the case of an aromatic inclusion as in pyridine, even three radicals together with the nitrogen atom form the heterocycle, for example a pyridinium or imidazolinium compound, and X ^{~ are} 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 is particularly easy, 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-dimethylbenzyl-ammonium chloride, CAS No. 8001-54-5), benzalkone B (mp-dichlorobenzyl-dimethyl-C 12 -alkylammonium chloride, CAS No. 58390-78 6), benzoxonium chloride (benzyl-dodecyl-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- [2- [p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzylammonium chloride, CAS No. 121-54-0), dialkyldimethylammonium chlorides such as di-π-decyl-dimethyl-ammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyl-dimethyl-ammonium chloride, 1-cetylpyridinium chloride (CAS No 123-03-5) and thiazoline iodide (CAS No. 15764-48-1) and mixtures thereof. Particularly preferred QUATS are the benzalkonium chlorides containing C ₈ -C ₁₈ alkyl, in particular Ci _Σ -C -Aklyl-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. '/ vi'. '

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Other commercially obtainable antimicrobial agents are N- (3-chloroallyl) - hexaminiumchlorid as Dowicide and Dowicil ^{® ®} ex Dow, benzethonium chloride such as Hyamine ^® 1622 ex Rohm & Haas, methylbenzethonium as Hyamine ^® 10X ex Rohm & Haas, cetylpyridinium chloride such as 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 of

0.005 wt .-% to 0.3 wt .-% and in particular from 0.01 to 0.2 wt .-% used.

The agents may contain UV absorbers (UV absorbers), which are applied to the treated textiles and improve the light resistance of the fibers and / or the light resistance of other formulation ingredients. 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 described, for example in EP 0728749 A and are available as Tinosorb FD ^{® ®} or Tinosorb FR ex Ciba commercially. 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 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl A- (dimethylamino) benzoate and A- (dimethylamino) benzoic acid;

(Dimethylamino) benzoesäureamylester; Esters of cinnamic acid, preferably 2-ethylhexyl A-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (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 its alkali metal, alkaline earth metal, 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-bionylidenemethyl) 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. You may have a spherical shape, but it can also be such particles for Use ic, which have an ellipsoidal or otherwise deviating from the spherical shape shape. The pigments can also be surface-treated, ie hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck; preferred hydrophilic coating agents are silicones and particularly preferably trialkoxyoctylsilanes or simethicones the review by P. Finkel in SÖFW Journal, Volume 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.

Compositions according to the invention may contain, in addition to the enzymes which can be used according to the invention, further enzymes in order 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, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Agents according to the invention preferably contain enzymes in total amounts of 1 × 10 ^-6 to 5 percent by weight, based on active protein. The protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method (AG Gornall, CS Bardawill and MM David, J. Biol. Chem., XT7_ (1948), pp. 751-766).

Among the proteases, those of the subtilisin type are preferable. Examples thereof are the subtilisins 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 Proteases TW3 and TW7. Subtilisin Carlsberg is in developed form under the trade names Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. Of the protease from Bacillus lentus DSM 5483 (WO 91/02792 A1) the listed under the name BLAP ^® variants, particularly in WO 92/21760 A1, WO 95/23221 A1, WO 02/088340 A2 and WO 03 derive, / 038082 A2. Other useful proteases from various Bacillus sp. and B. gibsonü are apparent from the patent applications WO 03/054185 A1, WO 03/056017 A2, WO 03/055974 A2 and WO 03/054184 A1.

Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, the ^® under the trade names Purafect ^®, Purafect Prime, Purafect ^® OxP and Properase.RTM ^® from 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 ^® from 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, from B. amyloliquefaciens or from β. stearothermophilus and their improved for use in detergents and cleaners further developments. 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 of B. amyloliquefaciens is sold by Novozymes under the name BAN ^®, and variants derived from the α-amylase from B.. stearothermophilus under the names BSG ^® and

Nova ^{'myl ® 1,} also from 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. Similarly, fusion products of the molecules mentioned can be used, for example those from application DE 10138753 A1 or point mutations thereof. In addition, the enhancements available under the trade names Fungamyl.RTM ^® by Novozymes of α-amylase from Aspergillus niger and A. oryzae. Further commercial products are for example the Amylase-LT ^® and Stainzyme® ^® and Stainzyme® ^® Ultra, also the latter from 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 8. 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. Another commercial product is, for example, the amylase ^LT® .

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 graying inhibition) and softening (fabric 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 ^® available also from Novozymes based on the 50 kD EG and 43 kD EG applicable 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 from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, United States. A suitable β-glucanase from a S. alcalophilus is disclosed, for example, in the application WO 99/06573 A1. The from ß. subtilis .beta.-glucanase obtained is available under the name Cereflo ^® from Novozymes.

To increase the bleaching effect, detergents and cleaners according to the invention may be oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases, laccases (phenol oxidases, polyphenol oxidases). and perhydrolase, bleach activator or bleach catalyst. Suitable commercial products Denilite® ^® 1 and 2 from Novozymes should be mentioned. 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.

The enzymes additionally 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 Escherichia coli, Bacillus , Streptomyces 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.

Agents according to the invention can be added to the enzymes - the amadoriases as well as the optionally additionally used enzymes - in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers. Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those 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 is coated with a water, air and / or chemical impermeable protective layer. 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.

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

The protein concentration to be attributed to the enzymes contained, in particular to the amadoriases contained, can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method (AG Gornall, CS Bardawill and MM David, J. Biol. Chem. R. P. (1948), pp. 751-766).

A protein and / or enzyme contained in an agent according to the invention can be protected against damage, for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage, in particular during storage. 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 are frequently used for this purpose orEsteV used, including in particular derivatives with aromatic groups, such as ortho, meta or para-substituted phenylboronic, in particular 4-formylphenyl-boronic acid, or the salts or esters of said compounds. 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 Cl ₂ , 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 capable, as disclosed in WO 97/18287, of additionally 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 are 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 Ce-C ₁₈ polyoxyalkylenes. Also, alkylpolyglycosides can stabilize the enzymatic components of the agent according to the invention and, preferably, are capable of additionally increasing their performance. Crosslinked compounds containing N preferably fulfill 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 sulphite and reducing sugars, but also catalase in suitably low concentration.

Particular preference is given to using combinatons 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.

Agents according to the invention are characterized in a preferred embodiment in that they consist of more than one phase, for example in order to release the active substances contained in time or in space. These may be phases in different, but in particular phases in the same physical states.

The compositions according to the invention are preferably in the form of single-phase or multiphase, in particular two-phase, liquid and sprayable compositions which are used in particular in a bottle with a spray system. When spraying the agent is particularly well saturated with oxygen, which is why one can speak of a particular advantage for an enzyme bleach or disinfection.

The multiphase liquid and sprayable agents (sprays) are either applied via a multichamber bottle with spray system or they are shaken several times before use to produce a temporary emulsion. ' 1.

Organic solvents which are capable of effecting the two-phase nature of the agents are, for example, hydrocarbons and alkyl ethers. As hydrocarbons in particular, those are preferred which have a boiling point above 150 ⁰ C and preferably above 180 ⁰ C. As alkyl ethers are particularly dialkyl, especially C ₆ -C ₈ alkyl ethers with particular preference of C ₈ -C ₂ alkyl ether, for example dioctyl, into consideration.

Other organic solvents which also have excellent cleaning properties include butoxypropoxypropanols (BPP), which are commercially available as a mixture of several isomers. Since BPPs are not completely miscible with water, they are particularly suitable for use in multi-phase agents. However, if BPPs are to be used in single-phase aqueous-based compositions, it is necessary to additionally use emulsifiers. For examples of possible emulsifiers, reference is made to the disclosure of WO 96/30580.

The compositions according to the invention may contain surfactants, namely anionic, nonionic, cationic, zwitterionic, amphoteric surfactants or any desired mixtures thereof. The content of surfactants may vary within a wide range. Even smaller amounts, but still show a dirt-dispersing and thus cleaning-enhancing effect may be included; The content of the surfactant surfactants is, for example, in a range from 0.2 to 10% by weight, with contents of from 0.5 to 10% by weight and in particular from 1 to 8% by weight of anionic and / or nonionic Surfactants is particularly preferred. Amphoteric surfactants and / or cationic surfactants are also preferred for use in the present invention and may additionally act as fabric softeners.

In addition, the compositions may contain fragrances, deodorants, preservatives, antibacterial agents, insect repellents (mothproofing agents) and / or colorants, as well as one or more finishing agents, lubricants, fungicides, etc., as long as these additives do not interfere with the distribution of the agent. Also pH Regulatory substances such as organic acids, especially citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof, may be included. The amounts of these additives, when present, generally comprise from about 0.2% to 5% by weight of the total composition.

The liquid and sprayable agents are preferably used in a bottle with a spray system. Flasks with a spray system are known to those skilled in the art. Particularly suitable are bottles with a pump or trigger spray container, which allow to apply a fine and concentrated spray targeted to the textile. The bottles can be made from any material known for such purposes; Typically, these are plastic and plastic bottles, with polyethylene and polypropylene materials being preferred. However, the person skilled in the art also knows other materials which are equally suitable. To protect the spray device, the bottle may have a plug cap. Again, the prior art embodiments are known in the art. Also suitable are pumps which produce foams when used. Such foam generation device is known as "F2 Finger Pump Foamer" manufactured by Airspray ^® in the market. Furthermore, a manually activated spray dispenser, in particular selected from the group comprising aerosol spray dispensers, self-pressurizing spray dispensers, pump spray dispensers and trigger spray dispensers, in particular pump spray dispensers and trigger spray dispensers with a container made of polyethylene or polyethylene terephthalate is particularly suitable. Such trigger bottles are offered for example by the company Afa-Polytec. The spray head is preferably equipped with a foam nozzle. Also known to those skilled in the art are single lever or single arm dispensers comprising and enveloping a fluid container and a foam producing device. An improved embodiment of such a foam dispenser is described in the German patent application 199 51 011.3.

Compositions according to the invention, which are composed of more than one solid component, can be prepared in a simple manner in that Components, in particular powder, granules or extrudates with different ingredients and / or different release behavior in total loose form are mixed together. The preparation of solid agents according to the invention from one or more phases can be carried out in a known manner, for example by spray drying or granulation, the enzymes and any other thermally sensitive ingredients such as, for example, bleaching agents optionally being added separately later. For the preparation of compositions according to the invention having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, preference is given to a process known from the European patent specification EP 0 486 592 which has an extrusion step. Another preferred preparation by means of a granulation process is described in the European patent EP 0642 576.

Proteins can be used for solid agents, for example in dried, granulated, encapsulated or encapsulated and additionally dried 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.

The encapsulated form lends itself, as discussed above, also to protecting the enzymes 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, with the patent applications WO 97/24177 and DE 199 18 267. Another possible encapsulation method is that the enzymes suitable for use in detergents or cleaners, encapsulated in starch, or the starch derivative, starting from a mixture of the enzyme solution with a solution or suspension of starch or a starch derivative become. Such an encapsulation process is described in the German application DE 199 56 382.

There may also be at least two solid phases connected to each other. Thus, there is a possibility to provide a solid means according to the invention in which compression or compacting into tablets. Such tablets may be monophase or polyphase. Thus, this dosage form also offers the possibility to present a solid agent according to the invention with two solid phases. For the production of compositions according to the invention in tablet form, which may be single-phase or multiphase, monochromatic or multicolored and / or consist of a plurality of layers, preferably all constituents - optionally one layer at a time - are mixed together in a mixer and the mixture is mixed by means of conventional tablet presses, For example, eccentric or rotary presses, pressed with compressive forces in the range of about 50 to 100 kN / cm ² , preferably at 60 to 70 kN / cm ² . Particularly in the case of multilayer tablets, it may be advantageous if at least one layer is pre-compressed. This is preferably carried out at pressing forces between 5 and 20 kN / cm ² , in particular at 10 to 15 kN / cm ² . Preferably, a tablet produced in this way has a weight of from 10 g to 50 g, in particular from 15 g to 40 g. The spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible.

It is particularly advantageous if in multiphase means at least one of the phases contains an amylase-sensitive material, in particular starch, or is at least partially surrounded or coated by it. In this way, this phase is mechanically stabilized and / or protected against external influences and simultaneously attacked by an effective in the wash liquor amylase, so that the release of the ingredients is facilitated.

Likewise preferred agents according to the invention are characterized in that they are in total liquid, gelatinous or pasty. The proteins contained, preferably a protein according to the invention, are preferred for such agents on the basis of a protein recovery carried out according to the prior art V ^■■ !,: ^■

'/ ΪJ r'

- ^ ii '?. i; (5 ^! ', ¹ M ¹ ' ii,, [\ '' uncfPräßaration in concentrated aqueous or nonaqueous solution, for example in liquid form, for example as a solution, suspension or emulsion, but also in gel form or encapsulated or added as a dried powder Washing or cleaning agents in the form of solutions in common solvents are usually prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.

One embodiment of the present invention is those liquid, gelatinous or pasty compositions to which a protein essential to the invention and / or one of the other proteins contained and / or one of the other ingredients contained has been encapsulated, preferably added in the form of microcapsules. Particularly preferred are those with capsules of amylase sensitive material. Such co-use of amylase-sensitive materials and an amylolytic enzyme in a detergent may exhibit synergistic effects, such as the starch-cleaving enzyme assisting cleavage of the microcapsules, thus controlling the release process of the encapsulated ingredients so that their release will not occur during the period Storage and / or not at the beginning of the cleaning process, but only at a certain time takes place. On this mechanism, complex detergent and cleaner systems can be based on a wide variety of ingredients and various capsule types, which are particularly preferred embodiments of the present invention.

A comparable effect is given when the ingredients of the detergent or cleaner are distributed over at least two different phases, for example two or more solid, interconnected phases of a tablet detergent or detergent, or different granules within the same powdered agent. Two or more phase cleaners are state of the art for use in both automatic dishwashers and detergents. The activity of an amylolytic enzyme in a previously activated phase is a prerequisite for the activation of a later phase, if it is surrounded by an amylase-sensitive shell or coating, or the

Afnyläsβ-sensitive material is an integral part of the solid phase, in the partial or complete hydrolysis of the phase in question disintegrates.

The ingredients of detergents and cleaners are suitably able to assist one another in their performance. Thus, it is also known from the application WO 98/45396 that polymers which can be used simultaneously as co-builders, such as, for example, alkyl-poly-glycosides, can stabilize and increase the activity and the stability of enzymes contained. Thus, it is preferred if a polyol oxidase according to the invention modified by one of the other ingredients listed above, in particular stabilized and / or increased in its contribution to the washing or cleaning performance of the agent.

A further subject of the invention are processes for the cleaning of textiles or of hard surfaces, which are characterized in that in at least one of the process steps an amadoriase according to the invention described above becomes active.

Because in this embodiment, the invention is realized in that the inventive improved enzymatic properties are exploited in terms of improvement in principle every cleaning process. Each purification process is enriched for the activity in question if it is added in at least one process step. Such methods are realized, for example, with machines such as common household dishwashers or household washing machines. Preferred methods are preferred according to the information given above. Further preferred are such processes, which are characterized in that the Amadoriase is used via an agent described above.

Another object of the invention is a hair-washing and / or hair care compositions containing inventively usable amadohases.

Hair-washing and / or hair-care preparations and bubble baths, shower baths, creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, Emulsions, wax / fat compounds, stick preparations, powders or ointments which comprise amadoriases which can be used according to the invention can be used as auxiliaries and additives for mild surfactants, oil bodies, emulsifiers, superfatting agents, pearlescing waxes, consistency regulators, thickeners, polymers, silicone compounds, fats, waxes, stabilizers , biogenic agents, deodorants, antiperspirants, antidandruff agents, film formers, swelling agents, UV protection factors, antioxidants, hydrotropes, preservatives, insect repellents, self-tanning agents, solubilizers, perfume oils, dyes and the like.

Typical examples of suitable mild, i. particularly skin-compatible surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkylsulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, D-olefinsulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines and / or protein fatty acid condensates, the latter preferably based on wheat proteins.

Examples of oil bodies are Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C ₆ -C ₂₂ fatty acids with linear C ₆ -C ₂ 2 fatty alcohols, esters of branched C ₆ -C 1 ₃ carboxylic acids with linear such as myristyl myristate, myristyl palmitate, myristyl stearate, Myristylisostearat, myristyl, Myristylbehenat, Myristylerucat, cetyl myristate, cetyl palmitate, cetyl stearate, Cetylisostearat, cetyl oleate, cetyl behenate, Cetylerucat, Stearylmyristat, stearyl palmitate, stearyl stearate, Stearylisostearat, stearyl oleate, stearyl behenate, Stearylerucat, isostearyl, isostearyl palmitate, Isostearylstearat, isostearyl isostearate, Isostearyloleat, isostearyl behenate, Isostearyloleat, oleyl, oleyl palmitate, oleyl stearate, oleyl isostearate, oleate, Oleylbehenat, oleyl, behenyl myristate, behenyl, behenyl, Behenylisostearat, behenyl oleate, behenyl, erucyl, erucyl, erucyl, erucyl, erucyl, erucyl, erucyl behenate and erucyl. Also suitable are esters of linear C ₆ -C ₂₂ -fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C ₆ -C ₂₂ fatty alcohols, i -1

, ii in particular dioctyl malates, esters of linear and / or branched fatty acids with polyhydric alcohols (such as propylene glycol, dimerdiol or trimer triol) and / or Guerbet alcohols, triglycerides based on C ₆ -Cio fatty acids, liquid mono- / di- / Triglyceridmischungen on fetch based on C ₆ -C ₁₈ fatty acids, esters of Ce-C ^ -Fettalko- and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C ₂ -C ₂ dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C ₆ -C ₂₂ fatty alcoholates, Guerbet carbonates, esters of benzoic acid with linear and / or branched (For example, Finsolv® TN), linear or branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, ring-opening products of epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenic hydrocarbons, such as squalane, squalene or dialkylcyclohexanes into consideration ,

Examples of suitable emulsifiers are nonionic surfactants from at least one of the following groups:

(1) addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms, to alkylphenols having 8 to 15 carbon atoms in the Alkyl group and alkylamines having 8 to 22 carbon atoms in the alkyl radical;

(2) Ci _2/18 fatty acid _mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol;

(3) glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products;

(4) alkyl and / or alkenyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alk (en) yl radical and their ethoxylated analogs;

(5) addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;

(6) polyol and especially polyglycerol esters; (7) addition products of 2 to 15 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;

(8) partial esters based on linear, branched, unsaturated or saturated _C6 / ₂₂ - fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (for example sorbitol), alkyl glucosides (for example methyl glucoside, butyl glucoside, lauryl glucoside) as well as polyglucosides (eg cellulose);

(9) mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts;

(10) wool wax alcohols;

(11) polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;

(12) mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE 1165574 PS and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol,

(13) Polyalkylene glycols as well

(14) Glycerol carbonate.

The addition products of ethylene oxide and / or of propylene oxide to fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or castor oil are known, commercially available products. These are homolog mixtures whose mean Alkoxyl- lierungsgrad the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate, with which the addition reaction is carried out corresponds. C _12/18-fatty acid mono- and diesters of addition products of ethylene oxide onto glycerol are known from DE 2024051 as refatting agents for cosmetic preparations.

Alkyl and / or alkenyl mono- and oligoglycosides, their preparation and their use are known in the art. They are prepared in particular by reacting glucose or oligosaccharides with primary alcohols having 8 to 18 carbon atoms. With respect to the glycoside, it holds that both monoglycosides in which a cyclic sugar residue is glycosidically linked to the fatty alcohol, as : ^' i ^{■ •} ; ^V'67

'; τ ^'■:; oligomeric glycosides having a degree of oligomerization of preferably about 8 are suitable. The degree of oligomerization is a statistical mean, which is based on a homolog distribution typical for such technical products.

Typical examples of suitable polyglycerol esters are polyglyceryl-2 dipolyhydroxystearates (Dehymuls® PGPH), polyglycerol-3-diisostearates (Lameform® TGI), polyglyceryl-4 isostearates (Isolan® Gl 34), polyglyceryl-3 oleates, diisostearoyl polyglyceryl-3 diisostearates (Isolan ® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010 / 90), Polyglyceryl-3 Cetyl Ether (Chimexane® NL), Polyglyceryl -3 distearates (Cremophor® GS 32) and polyglyceryl polyricinoleates (Admul® WOL 1403) polyglyceryl dimerate isostearates and mixtures thereof.

Furthermore, zwitterionic surfactants can be used as emulsifiers. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3 - Hydroxyethylimidazoline having in each case 8 to 18 carbon atoms in the alkyl or acyl group and Kokosacylaminoethylhydroxyethylcarboxymethylglycinat. Particularly preferred is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine. Also suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a _{C8 /} ie-alkyl or -acyl group in the molecule at least one free amino group and at least one -COOH or _-SO3H group and are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C Atoms in the alkyl group. Particularly preferred ampholytic Surfactants are the N-cocoalkylaminopropionate, the Kokosacylaminoethylamino- propionate and the In addition to the ampholytic, quaternary emulsifiers are also suitable, with those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.

Superfatting agents may be substances such as lanolin and lecithin, as well as polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the latter also serving as foam stabilizers.

Suitable pearlescing waxes are, for example: alkylene glycol esters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polybasic, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances, such as fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides having 12 to 22 carbon atoms with fatty alcohols having 12 to 22 carbon atoms and / or polyols having 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.

As consistency factors are primarily fatty alcohols or hydroxy fatty alcohols having 12 to 22 and preferably 16 to 18 carbon atoms and in addition partial glycerides, fatty acids or hydroxy fatty acids into consideration. Preference is given to a combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates.

Suitable thickening agents are, for example, Aerosil types (hydrophilic silicic acids), polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose; Polyethylene glycol mono- and diesters of fatty acids, polyacrylates,

(e.g., Carbopol® from Goodrich or Synthalene® from Sigma), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, narrow alcohol homoxylates with narrow homolog distribution or alkyl oligoglucosides, and electrolytes such as saline and ammonium chloride.

Suitable cationic polymers are, for example, cationic cellulose derivatives, e.g. a quaternized hydroxyethylcellulose available under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers, e.g. Luviquat® (BASF), condensation products of polyglycols and amines, quaternized collagen polypeptides, such as lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat® L / Grünau), quaternized wheat polypeptides, polyethylenimine, cationic silicone polymers, e.g. Amidomethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretine® / Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat® 550 / Chemviron), polyamino-polyamides, such as e.g. described in FR 2252840 A and their crosslinked water-soluble polymers, cationic chitin derivatives such as quaternized chitosan, optionally microcrystalline distributed, condensation products of dihaloalkylene, such as. Dibromobutane with bis-dialkylamines, e.g. Bis-dimethylamino-1,3-propane, cationic guar gum, e.g. Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese, quaternized ammonium salt polymers, e.g. Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 from Miranol.

Suitable anionic, zwitterionic, amphoteric and nonionic polymers are, for example, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and their esters, unvarnished and polyols crosslinked polyacrylic acids, acrylamidopro- pyltrimethylammonium chloride / acrylate copolymers, octylacrylamide / methyl methacrylate / tert.butylaminoethylmethacrylamide-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, vinylpyrrolidone / dimethylaminoethyl methacrylate / inylcaprolactam terpolymers and optionally derivatized cellulose ethers and silicones.

Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl-modified silicone compounds which may be both liquid and resin-form at room temperature. Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units and hydrogenated silicates. A detailed overview of suitable volatile silicones can also be found in Todd et al. in Cosm.Toil. 91 _. , 27 (1976).

Typical examples of fats are glycerides, as waxes u.a. natural waxes, e.g. Candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugarcane wax, ouricury wax, montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax), crepe fat, ceresin, ozokerite (ground wax), petrolatum, paraffin waxes, microwaxes; chemically modified waxes (hard waxes), e.g. Montan ester waxes, sasol waxes, hydrogenated jojoba waxes and synthetic waxes, such as e.g. Polyalkylene waxes and polyethylene glycol waxes in question.

As stabilizers, metal salts of fatty acids, e.g. Magnesium, aluminum and / or zinc stearate or ricinoleate can be used.

Biogenic active ingredients are, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes.

Kosrnetisfche deodorants (deodorants) counteract body odors, cover or eliminate them. Body odors are caused by the action of skin bacteria on apocrine sweat, forming unpleasant-smelling degradation products. Accordingly, deodorants contain active ingredients which act as anti-sprouting agents, enzyme inhibitors, odor absorbers or odor maskers.

As germ-inhibiting agents, which may optionally be added to the cosmetics of the invention, in principle all substances effective against gram-positive bacteria are suitable, such as. B. 4-hydroxybenzoic acid and its salts and esters, N- (4-chlorophenyl) -N ^'- (3,4 dichlorophenyl) urea, ^{2,4,4'-trichloro-2'-hydroxydiphenyl} ether (triclosan), 4-chloro -3,5-dimethylphenol, 2,2 ^{'-methylene-bis} (6-bromo-4-chlorophenol), 3-methyl-4- (1-methylethyl) phenol, 2-benzyl-4-chlorophenol, 3- (4 - chlorophenoxy) -1, 2-propanediol, 3-iodo-2-propynyl butylcarbamate, chlorhexidine, 3,4,4 ^'- trichlorocarbanilide (TTC), antibacterial fragrances, menthol, mint oil, phenoxyethanol, glycerol monolaurate (GML), diglycerol monocaprate (DMC) , Salicylic acid N-alkylamides such. Salicylic acid n-octylamide or salicylic acid n-decylamide.

Enzyme inhibitors can also be added to the cosmetics of the invention. For example, esterase inhibitors may be suitable enzyme inhibitors. These are preferably trialkyl citrates such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, trihydrate citrate and especially triethyl citrate (Hydagen® CAT, Henkel KGaA, Dusseldorf / FRG). The substances inhibit the enzyme activity and thereby reduce odors. Further substances which are suitable as esterase inhibitors are sterol sulfates or phosphates, such as, for example, lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and their esters, for example glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, Adipic acid monoethyl ester, diethyl adipate, malonic acid and diethyl malonate, hydroxycarboxylic acids and their esters such as citric acid, malic acid, tartaric acid or diethyl tartrate, and zinc glycinate. Suitable odor absorbers are substances that absorb and largely retain odor-forming compounds. They reduce the partial pressure of the individual components and thus also reduce their propagation speed. It is important that perfumes must remain unimpaired. Odor absorbers have no activity against bacteria. They contain, for example, as a main component of a complex zinc salt of ricinoleic acid or special, largely odorless fragrances, which are known in the art as "fixatives", such. B. Extracts of Labdanum or Styrax or certain Abietinsäurederivate. Odor maskers are fragrances or perfume oils which, in addition to their function as odor maskers, give the deodorants their respective scent. Examples of perfume oils are mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers, stems and leaves, fruits, fruit peel, roots, woods, herbs and grasses, needles and twigs, as well as resins and balsams. Furthermore, animal raw materials come into question, such as civet and Castoreum. Typical synthetic fragrance compounds are ester type products, ethers, aldehydes, ketones, alcohols and hydrocarbons.

Antiperspirants (antiperspirants) reduce the formation of sweat by influencing the activity of eccrine sweat glands and thus counteract underarm wetness and body odor. Aqueous or anhydrous formulations of antiperspirants typically contain the following ingredients:

(a) astringent agents,

(b) oil components,

(c) nonionic emulsifiers,

(d) coemulsifiers,

(e) bodybuilder,

(f) adjuvants such as. B. thickener or complexing agent and / or

(g) non-aqueous solvents such as. As ethanol, propylene glycol and / or glycerol.

Salts of aluminum, zirconium or zinc are especially suitable as astringent antiperspirant active ingredients. Such suitable antiperspirant active \ ^] '' ^■ "<V ',><■

Drugs are e.g. Aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate and their complex compounds e.g. With propylene glycol-1, 2. Aluminiumhydroxyallantoinat, aluminum chloride tartrate, aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pen tachlorohydrat and their complex compounds z. With amino acids such as glycine.

In addition, antiperspirants may contain customary oil-soluble and water-soluble adjuvants in smaller amounts. Such oil-soluble adjuvants may be e.g. be:

• anti-inflammatory, skin-protecting or fragrant essential oils,

• synthetic skin-protecting agents and / or

• oil-soluble perfume oils.

Usual water-soluble additives are e.g. Preservatives, water-soluble fragrances, pH adjusters, e.g. Buffer mixtures, water-soluble thickeners, e.g. water-soluble natural or synthetic polymers such as e.g. Xanthan gum, hydroxyethyl cellulose, polyvinyl pyrrolidone or high molecular weight polyethylene oxides.

Climbazole, octopirox and zinc pyrethion can be used as anti-dandruff agents.

Typical film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid and salts thereof and similar compounds.

Suitable swelling agents for aqueous phases are montmorillonites, clay minerals, pemulen and alkyl-modified carbopol types (Goodrich). Further suitable polymers or swelling agents can be reviewed by R. Lochhead in Cosm.Toil. 108, 95 (1993). Under UV sun protection factors are, for example, at room temperature, liquid or crystalline organic substances present (sunscreen) to understand, which are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, eg heat again. UVB filters can be oil-soluble or water-soluble. Examples of oil-soluble substances are:

3-benzylidene camphor or 3-benzylidene norcamphor and its derivatives, e.g. 3- (4-methylbenzylidene) camphor as described in EP 0693471 B1;

4-aminobenzoic acid derivatives, preferably 4-dimethylamino) benzoic acid 2-ethylhexyl ester, 4- (dimethylamino) benzoic acid 2-octyl ester and 4- (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 ^I -hexyloxy) -1,3,5-triazine and Octyl Triazone as described in EP 0818450 A1 or Dioctyl Butamido Triazone (Uvasorb® HEB);

Propane-1,3-diones, e.g. 1- (4-tert-butylphenyl) -3-4'-methoxyphenyl) propane-1,3-dione;

Ketotricyclo (5.2.1.0) decane derivatives as described in EP 0694521 B1.

Suitable water-soluble substances are:

2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts;

Sulphonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid and its salts;

Sulfonic acid derivatives of the 3-benzylidene camphor, e.g. 4- (2-oxo-3-bornylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) -sulfonic acid and its salts.

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 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 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 can also be surface-treated, ie hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones. In sunscreens, so-called micro- or nanopigments are preferably used. Preferably, micronized zinc oxide is used. Further suitable UV photoprotective agents can be found in the review by P.Finkel in SÖFW-Journal 122, 543 (1996). In addition to the two aforementioned groups of primary light stabilizers, it is also possible to use secondary light stabilizers of the antioxidant type which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates into the skin. Typical examples are amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine) , Carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives (eg dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (eg thioredoxin, glutathione, cysteine, cystine, Cystamine and its glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-oleoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate , Distearyl thiodipropionate, thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (eg buthionine sulfoximines, homocysteinsulfoximine, butynesulfones, penta, hexa, heptathionine sulfoximine) in very small amounts compatible dosages (eg pmol to μmol / kg), furthermore (metal) chelators (eg α-hydroxyfatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, Biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (eg γ-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (eg ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate ), Tocopherols and derivatives (eg, vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and benzylic resin coniferyl benzoate, rutinic acid and derivatives thereof, α-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordihydroguaiacetic acid , Nordihydroguajaretsäure, Trihydroxybutyrophenon, uric acid and its derivatives, mannose and its derivatives, superoxide dismutase, zinc and de derivatives (eg ZnO, ZnSO ₄ ) selenium and its derivatives (eg selenium methionine), stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide) and the derivatives suitable for this purpose (salts, esters, ethers, sugars, nucleotides, nucleosides, Peptides and lipids) of these drugs. In order to improve the flow behavior, it is also possible to use hydrotropes, such as, for example, ethanol, isopropyl alcohol, or polyols. Polyols contemplated herein preferably have from 2 to 15 carbon atoms and at least two hydroxyl groups. The polyols may contain other functional groups, in particular amino groups, or be modified with nitrogen. Typical examples are

• glycerin;

Alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and polyethylene glycols having an average molecular weight of 100 to 1,000 daltons;

Technical Oligoglyceringemische with an intrinsic degree of condensation of 1, 5 to 10 such as technical Diglyceringemische with a diglycerol content of 40 to 50 wt .-%;

Methyolverbindungen, in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;

Lower alkyl glucosides, especially those having 1 to 8 carbons in the alkyl radical, such as, for example, methyl and butyl glucoside;

Sugar alcohols having 5 to 12 carbon atoms, such as sorbitol or mannitol,

• sugars having 5 to 12 carbon atoms, such as glucose or sucrose;

• amino sugars, such as glucamine;

• Dialcoholamines, such as diethanolamine or 2-amino-1,3-propanediol.

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and the other classes of substances listed in Appendix 6, Part A and B of the Cosmetics Regulation. As insect repellents are N, N-diethyl-m-toluamide, 1, 2-pentanediol or ethyl Butylacetylaminopropionate in question, suitable as a self-tanner dihydroxyacetone.

As perfume oils are called mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers (lily, lavender, roses, Jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel (bergamot, lemon, oranges), roots (macis, angelica, celery, cardamom, Costus, Iris, Calmus), woods (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), needles and twigs (spruce, fir, pine, pines), Resins and balms (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Furthermore, animal raw materials come into question, such as civet and Castoreum. Typical synthetic fragrance compounds are ester type products, ethers, aldehydes, ketones, alcohols and hydrocarbons.

As dyes, the substances suitable and suitable for cosmetic purposes can be used, as compiled, for example, in the publication "Cosmetic Colorants" of the Dye Commission of the Deutsche Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pp. 81-106. These dyes are usually used in concentrations of 0.001 to 0.1 wt .-%, based on the total mixture.

The total amount of auxiliaries and additives may be 1 to 50, preferably 5 to 40 wt .-% - based on the means - amount. The preparation of the agent can be carried out by conventional cold or hot processes; It is preferable to work according to the phase inversion temperature method.

Another object of the invention is an oxidation dye for dyeing keratin fibers containing Amadoriasen used in the invention and in particular Amadoriasen invention. As keratin fibers are wool, feathers, furs and especially human hair to understand.

To prepare the oxidizing agents according to the invention, the oxidation dye precursors and the amadoriases are incorporated in a suitable aqueous carrier with the exclusion of atmospheric oxygen. Such carriers are z. As thickened aqueous solutions, creams (emulsions), gels or surfactant-containing foaming preparations, eg. As shampoos or foam aerosols or other preparations that are suitable for use on the hair.

In principle, anhydrous powders are also suitable as carriers; in this case, the oxidation colorants are dissolved or dispersed in water immediately before use. As carrier components are preferred

Wetting and emulsifying agent

thickener

Reducing agents (antioxidants) Hair care additives

Fragrances and

Solvents such. For example, water, glycols or lower alcohols.

As wetting and emulsifying z. As anionic, zwitterionic, ampholytic and nonionic surfactants. Also cationic surfactants can be used to achieve certain effects.

Suitable thickeners are the water-soluble high molecular weight polysaccharide derivatives or Polypep-tide, z. As cellulose or starch ethers, gelatin, plant gums, biopolymers (xanthan gum) or water-soluble synthetic polymers such. As polyvinylpyrrolidone, polyvinyl alcohol, polyethylene oxides, polyacrylamides, polyurethanes, polyacrylates and others.

Furthermore, surfactant-containing preparations can also be thickened by solubilization or emulsification of polar lipids. Such lipids are for. B. fatty alcohols having 12-18 C-atoms, (free) fatty acids having 12-18 C-atoms, fatty acid partial glycerides, sorbitan fatty acid esters, fatty acid alkanolamides, low ethoxylated fatty acids or fatty alcohols, lecithins, sterols. Finally, one can gel-based carrier based on aqueous soap gels, z. As of ammonium oleate, produce.

Reducing agents (antioxidants) added to the carrier to prevent premature oxidative development of the dye before application to the hair are e.g. For example, sodium sulfite or sodium ascorbate. Hair care additives may include, for example, fats, oils or waxes in emulsified form, structuring additives such. As glucose or pyridoxine, avivierende components such. As water-soluble proteins, protein degradation products, amino acids, water-soluble cationic polymers, silicones, vitamins, panthenol or plant extracts.

Finally, fragrances and solvents such as. As glycols such as 1, 2-propylene glycols, glycerol, glycol ethers such as. As butyl glycol, ethyl diglycol or lower monohydric alcohols such as ethanol or isopropanol.

In addition, other adjuvants may be included which improve the stability and performance characteristics of the oxydation dyes, e.g. As complexing agents such as EDTA, NTA or organophosphonates, swelling and penetration agents such. As urea, guanidine, bicarbonates, buffer salts such. As ammonium chloride, ammonium citrate, ammonium sulfate or alkanolammonium salts and optionally propellants.

Another object of the invention is an agent for oral, dental or denture care, in particular prosthesis cleaner containing Amadoriasen invention for bleaching or disinfection.

In the case of partial dentures or dentures, both the administration as denture cleansing tablets, as well as mouthwash or mouthwash or toothpaste is suitable.

The oral, dental and / or dental prosthesis care products according to the invention can be present, for example, as a mouthwash, gel, liquid toothbrush lotion, stiff toothpaste, denture cleaner or denture adhesive cream.

For this purpose, it is necessary to incorporate the Amadoriasen used in the invention in a suitable carrier. ,

As a carrier, e.g. also pulverulent preparations or aqueous-alcoholic solutions serve as mouthwash 0 to 15 wt .-% ethanol, 1 to 1.5 wt .-% flavor oils and 0.01 to 0.5 wt .-% sweeteners or as mouthwash concentrates 15 to 60 wt .-% ethanol, 0.05 to 5 wt .-% aroma oils, 0.1 to 3 wt .-% sweeteners and optionally other excipients may be included and diluted with water before use. The concentration of the components must be so high that, after dilution, the specified lower concentration limits are not undershot during use.

However, gels and more or less flowable pastes, which are expressed from flexible plastic containers or tubes and applied to the teeth with the aid of a toothbrush, can also serve as the carrier. Such products contain higher levels of humectants and binders or consistency regulators and polishing components. In addition, aromatic oils, sweeteners and water are also contained in these preparations.

As humectants, e.g. Glycerol, sorbitol, xylitol, propylene glycols, Polyethenylenglycole or mixtures of these polyols, in particular those Polyethenylenglycole be used with molecular weights of 200 to 800 (from 400 to 2000). Preferably, sorbitol is contained as humectant in an amount of 25-40 wt .-%.

As anticalculus agents and as demineralization inhibitors, condensed phosphates may be present in the form of their alkali salts, preferably in the form of their sodium or potassium salts. The aqueous solutions of these phosphates react alkaline due to hydrolytic effects. By addition of acid, the pH of the oral, dental and / or dental prosthesis care agents according to the invention is adjusted to the preferred values of 7.5-9.

It is also possible to use mixtures of different condensed phosphates or else hydrated salts of the condensed phosphates. The specified amounts of 2-12% by weight, however, refer to the anhydrous salts. Preferably, the condensed phosphate is a sodium or potassium tripolyphosphate in an amount of 5-10% by weight of the composition. A preferred active ingredient is a caries-inhibiting fluorine compound, preferably from the group of fluorides or monofluorophosphates in an amount of 0.1 to 0.5 wt .-% fluorine. Suitable fluorine compounds are, for example, sodium monofluorophosphate (Na ₂ PO ₃ F), potassium monofluorophosphate, sodium or potassium fluoride, tin fluoride or the fluoride of an organic amino compound.

Suitable binders and consistency regulators are, for example, natural and synthetic water-soluble polymers such as carrageenan, tragacanth, guar, starch and their non-ionic derivatives such as hydroxypropyl guar, hydroxyethyl starch, cellulose ethers such as hydroxyethyl cellulose or methylhydroxypropyl cellulose. Also, agar-agar, xanthan gum, pectins, water-soluble carboxyvinyl polymers (for example Carbopol ^® types), polyvinyl alcohol, polyvinyl pyrrolidone, high molecular weight polyethylene glycols (molecular weight 10 ³ to 10 ⁶ D). Further substances which are suitable for viscosity control are phyllosilicates such as montmorillonite clays, colloidal thickening silicas, eg airgel silica or fumed silicas.

As polishing components may all heretofore known polishing agent, but preferably precipitated and gel silicas, aluminum hydroxide, aluminum silicate, alumina, alumina trihydrate, insoluble sodium metaphosphate, calcium pyrophosphate, calcium hydrogen phosphate, dicalcium phosphate, chalk, hydroxyapatite, hydrotalcites, talc, magnesium aluminum silicate (Veegum ^®), calcium sulfate, magnesium carbonate, Magnesium oxide, sodium aluminum silicates, such as zeolite A or organic polymers, such as polymethacrylate, are used. The polishing agents are preferably used in smaller amounts of eg 1-10% by weight.

The dental and / or oral care products according to the invention can be improved in their organoleptic properties by adding aroma oils and sweeteners. Aromatic oils are all natural and synthetic flavors which are customary for oral, dental and / or dental care products. Natural flavors can be used both in the form of the essential oils isolated from the drugs and those isolated from individual components become. At least one aromatic oil from the group of peppermint oil, spearmint oil, aniseed oil, caraway oil, eucalyptus oil, fennel oil, cinnamon oil, geranium oil, sage oil, thyme oil, marjoram oil, basil oil, citrus oil, Gaultheria oil or one or more synthetically produced components of these oils isolated therefrom should preferably be present. The most important components of the oils mentioned are, for example, menthol, carvone, anethole, cineole, eugenol, cinnamaldehyde, geraniol, citronellol, linalool, salvos, thymol, terpinene, terpinol, methylchavicol and methyl salicylate. Further suitable flavors are, for example, menthyl acetate, vanillin, ionone, linalyl acetate, rhodinol and piperitone. Suitable sweeteners are either natural sugars such as sucrose, maltose, lactose and fructose or synthetic sweeteners such as saccharin sodium salt, sodium cyclamate or aspartame.

In particular, alkyl and / or alkenyl (oligo) glycosides can be used as surfactants. Their preparation and use as surfactants are described, for example, in US Pat. No. 3,839,318, US Pat. No. 3,707,535, US Pat. No. 3,547,828 DE-A-1943689, DE-A-20 36472 and DE-A- 30 01 064 and EP-A-77 167 known. With regard to the glycoside radical, monoglycosides (x = 1) in which a pentose or hexose radical is glycosidically bound to a primary alcohol having 4 to 16 carbon atoms, as well as oligomeric glycosides having a degree of oligomerization x to 10, are suitable. The degree of oligomerization is a statistical mean, which is based on a homolog distribution typical for such technical products.

As alkyl and / or alkenyl (oligo) glycoside, an alkyl and / or alkenyl (oligo) glucoside of the formula RO (C ₆ Hi _O O) _x -H, in which R is an alkyl radical and is preferably suitable / or alkenyl group having 8 to 14 carbon atoms and x has an average of 1 to 4. Particular preference is given to alkyl oligoglucosides based on hydrogenated C 12/14 coconut alcohol having a DP of from 1 to 3. The alkyl and / or alkenyl glycoside surfactant can be used very sparingly, amounts of from 0.005 to 1% by weight being sufficient are.

In addition to the alkyl glucoside surfactants mentioned, other nonionic, ampholytic and cationic surfactants may also be present, as there are, for example: Fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, monoglyceride ether sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, ether carboxylic acids, fatty acid glucamides, alkylamido betaines and / or protein fatty acid condensates, the latter preferably based on wheat proteins. In particular, to solubilize the usually water-insoluble aroma oils, a non-ionic solubilizer from the group of surface-active compounds may be required. Particularly suitable for this purpose are, for example, ethoxylated fatty acid glycerides, ethoxylated fatty acid sorbitan partial esters or fatty acid partial esters of glycerol or sorbitan ethoxylates. Solubilizers from the group of ethoxylated Fettsäureglyceride include especially addition products of 20 to 60 moles of ethylene oxide with mono- and diglycerides of linear fatty acids having 12 to 18 carbon atoms or triglycerides of hydroxy fatty acids such as oxystearic acid or ricinoleic acid. Further suitable solubilizers are ethoxylated fatty acid sorbitan partial esters; these are preferably addition products of 20 to 60 moles of ethylene oxide with sorbitan monoesters and sorbitan diesters of fatty acids with 12 to 18 carbon atoms. Also suitable solubilizers are fatty acid partial esters of glycerol or sorbitan ethoxylates; These are preferably mono- and diesters of Ci ₂ -Ci ₈ fatty acids and adducts of 20 to 60 moles of ethylene oxide with 1 mole of glycerol or 1 mole of sorbitol.

The oral, dental and / or dental prosthesis care agents according to the invention preferably contain as solubilizer for optionally contained aroma oils addition products of 20 to 60 moles of ethylene oxide to hardened or uncured castor oil (ie to Oxystearinsäure- or ricinoleic acid triglyceride), to glycerol mono- and / or distearate or sorbitan mono- and / or distearate.

Other common additives for oral, dental and / or denture care medium are e.g.

Pigments, e.g. Titanium dioxide, and / or dyes, pH adjusters and buffering agents, e.g. Sodium bicarbonate, sodium citrate,

Sodium benzoate, citric acid, phosphoric acid or acid salts, eg NaH ₂ PO ₄ Wound-healing and anti-inflammatory substances such as allantoin, urea, panthenol, azulen or camomile extract further against tartar effective substances such as organophosphonates, eg Hydroxyethandiphosphonate or Azacycloheptandiphosphonat preservatives such as sorbic acid salts, p-hydroxybenzoic acid esters. Plaque inhibitors such as hexachlorophene, chlorhexidine, hexetidine, triclosan, bromochlorophene, phenylsalicylic acid ester.

In a particular embodiment, the composition is a mouthwash, a mouthwash, a denture cleanser or a denture adhesive.

In addition to the already mentioned ingredients for oral, dental and / or dental prosthesis care, per-compounds such as, for example, peroxoborate, peroxomonosulfate or percarbonate are additionally suitable for prosthesis cleaners according to the invention, in particular prosthesis cleansing tablets and powders. They have the advantage that, in addition to the bleaching effect, they simultaneously have a deodorizing and / or disinfecting effect. The use of such per-compounds in prosthesis cleaners is between 0.01 and 10 wt .-%, in particular between 0.5 and 5 wt .-%.

As further ingredients are also enzymes, e.g. Proteases and carbohydrase, suitable for the breakdown of proteins and carbohydrates. The pH can be between pH 4 and pH 12, in particular between pH 5 and pH 11.

For the prosthesis cleansing tablets, additional auxiliaries are additionally necessary, such as, for example, agents which give off a bubbling effect, for example CO ₂ releasing substances such as sodium bicarbonate, fillers, for example sodium sulfate or dextrose, lubricants, for example magnesium stearate, flow regulators, for example colloidal silica and granulating agents, such as the already mentioned high molecular weight polyethylene glycols or polyvinylpyrrolidone. Denture adhesives can be offered as powders, creams, foils or liquids and support the adhesion of the prostheses.

As active ingredients natural and synthetic swelling substances are suitable. As natural swelling agents, besides alginates, plant gums, such as e.g. Gum arabic, tragacanth and karaya gum as well as natural rubber. In particular, alginates and synthetic bulking agents, e.g. Sodium carboxymethyl cellulose, high molecular weight ethylene oxide copolymers, salts of poly (vinyl ether-co-maleic acid) and polyacrylamides.

As adjuvants for pasty and liquid products are particularly hydrophobic bases, in particular hydrocarbons, such as white Vaseline (DAB) or paraffin oil.

The following examples illustrate the invention without, however, limiting it to:

Example 1 Examination of Enzyme Concentrates for the Presence of Amadoriase Activity with a Highly Denatured Soil as Substrate

Sample: Enzyme concentrate from Bacillus licheniformis

Stains as substrate:

1. From EMPA: Blood / Milk / Ink on Cotton Product No. 116 available from the company Eidgenössische Material- und Prüfanstalt (EMPA) Testmaterialien AG, St. Gallen (Switzerland)

2. Whole egg / pigment on cotton: Product No. 10N available from the company wfk Testgewebe GmbH; Bruggen-Bracht, Germany.

Preparation of soiling:

The stains were cut into 2mm x 4mm pieces, each

Approach approx. 50 mg scraps of fabric were used. Of the? Nladhweis of the amadoriase activity is due to the insert of a H ₂ O ₂ -

Detection plate. The plate was set as follows:

1 g of agar is boiled in 50 ml_ 120 mM Tris-HCl buffer pH 8.5. In a second

Solution are 26.8 mg of 4-chloronaphthol and horseradish peroxidase (2 mL of a

54 U / mL solution) in 50 mL redist. Water dissolved. After combining the solutions, the agar plates are poured. If these are cold, small holes are punched

(about 0.5 cm diameter) into which the enzyme sample is added.

Literature: Simon Delagrave, Dennis J. Murphy, Jennifer L. Rittenhouse Pruss, Anthony

M. Maffia, III, Barry L. Marrs, Edward J. Bylina, William J. Coleman, Christina L. Grek,

Michael R. Dilworth, Mary M. Yang & Douglas C. Youvan "Application of a very high-throughput digital imaging screen to evolve the enzyme galactose oxidase" protein

Engineering 2001 vol.14, no.4, pp261-267

Bylina, EJ. , Grek, C.L., Coleman, WJ. & Youvan, D.C. "Directed evolution and solid phase enzyme screening" Proc. SPIE 2000 Vol. 3926, p. 186-191, Advances in

Nucleic acid and protein analysis, manipulation, and sequencing

Execution of the test:

In 2.2 mL Eppendorf Cups 50 mg of soiling are submitted. Be on it

700 μL of 120 mM Tris HCl buffer pH 8.5 and 30 μL of a 30 mM

Hydroxylamine sulfate solution as catalase inhibitor (1 mM in the reaction). Of the

Culture supernatants are given 300 μL aliquots, of the enzyme concentrates per 100 μL in the cups.

The incubation takes place at 37 ° C., the agar plates being incubated on a shaker (Intelli).

Mixer RM-2L from LFT-Labortechnik, program F1, 40 rpm) for up to 22 hours. After 2.5 and 22 hours of incubation, 30 μL of sample are taken per cup and placed on an H ₂ O ₂ detection plate (see above). A blue color indicates a positive H ₂ O ₂ detection.

Result: The enzyme concentrate shows a distinct blue coloration with both soiling. This corresponds to detection of amadoriase activity.

Example 2: Examination of enzyme concentrates for the presence of amadoriase activity with synthesized Amadori crude products as substrate Substrate: Amadori compound-containing products: Synthesis Description Incubate 0.5 M glucose, 0.1 M glycine, 10 g sodium metabisulfite and 10 mL water for 4 hours in a water bath at 95 ° C. In parallel, the production of a negative control, which contains the same substances, but is not heated. (Hironaga Hashiba "Participation of amadori rearrangement products and carbonyl compounds in oxygen-dependent browning of soy sauce", J Agric. Food Chem., 1976 VoI 24, p.70-74)

Sample:

The enzyme concentrate is used to test the substrate (synthesis products + negative control) in two concentrations each.

Approach: 100 μL sample

100 or 500 μL substrate

30 μL 30 mM hydroxylamine sulfate ad 1 mL 120 mM Tris-HCl pH 8.5

Incubation at 37 ⁰ C, 40 rpm, for 1, 15 h. Test of 30 μL each using H ₂ O ₂ detection plate.

Result:

The enzyme concentrate shows a blue color with the substrate.

With this method, the minimum detectable H ₂ O ₂ concentration is one

Enzyme activity producing 1, 5 ng H ₂ O ₂ in 30 minutes.

Amadoriase activity assay

The amadoriase activity was measured at 37 ° C by formation of a quinone dye A555 (ε, 39.2 cm 2 / mol) using a suitable spectrophotometer. The reaction mixture contained 100 mM potassium phosphate (pH 8.0); 2.7 purple galactin units peroxidase; 0.45 mM 4-aminoantipyrine; 0.5mM Λ / ethyl Λ / - (2-hydroxy-3-sulfopropyl) -m-toluidine, and 5.0mM Amadori product in a total volume of 3mL. Under these conditions, the reaction proceeded over a period of time from 1 to 3 minutes linear. An enzyme activity unit was defined as the amount of enzyme that produced 0.5 μmol of quinone dye per minute. (Ryoichi Sakaue & Naoki Kajiyama ^' s ^{; •} '<< f 5 -'>, \ i

Thermoέtabilisation of bacterial fructosyl-amino-acid oxidase by directed evolution "Appl. Environ. Micro., Vol. 69, 2003, 139-145)"

Example 3: Amadoriase - washing test

Enzymes: o Amadoriase available from Sigma-Aldrich Corporation, Box

14508, St. Louis Missouti 63178 USA o Protease concentrate from Bacillus licheniformis (examples are BLAP-S or

BLAP-X from HENKEL KGaA) o Catalase available from Merck KGaA, Darmstadt, Germany

Buffer: o 100 mM Tris / HCl pH8.5 (enzyme solution)

Stains: o Blood milk / ink on cotton: Product No. C5 from CFT B.V. Vlaardingen,

Holland o Full egg / pigment on cotton: Product No. 10N available from wfk

Test fabric GmbH; Brüggen-Bracht, Germany, cut into small pieces

Detergent matrix:

Table 1: Frame formulation for a laundry detergent

Test batch (1ml) in 48-well plates:

Incubation: 60 min., 4O ⁰ C, ca. 600rpm

After incubation: Rinse (3x) the stains, dry and fix Brightness measurement with colorimeter Cm508d (Minolta)

To carry out this test, round pieces of the test tissues (diameter 10 mm) were incubated in a 24-well microtiter plate in 1 ml of wash liquor for 30 min at 37 ^° C. and a shaking frequency of 100 rpm. The wash contained protease (protease concentrate from Bacillus licheniformis, examples are BLAP-S or BLAP-X Darmstadt, Germany) and / or amadoriase (available from Sigma-Aldrich Corporation, Box 14508, St. Louis Missouri 63178 USA). Each experiment was carried out in triplicate against a triplicate control with catalase alone.

After washing, the whiteness of the washed fabrics was measured in comparison to a white standard (d / 8, 8mm, SCI / SCE) normalized to 100% (determination of L value). The measurement was carried out on a colorimeter (Minolta Cm508d) with an illumination setting of 107D65. The results obtained are expressed as percent power, with the difference in remission values from the basic detergent without enzymes to that with protease and with catalase standardized to 100%.

The results of the washing test were compiled in FIG. Fig. 2 shows the experiments of a washing test which corresponds to that shown in Fig. 1, in which the protease concentrate from Bacillus licheniformis but was purified using conventional biochemical methods.

The results show a clearly superior performance of the combination according to the invention with amadoriase over that without amadoriase. The better result was achieved with the BMT stain. This seems logical considering the composition and production of BMT stain: In the BMT stain more Amadori product is expected than in the egg soot stain because significantly more sugars (for example, glucose from blood and lactose from milk) with a lot of protein (Membrane protein) can react.

Claims

claims

1. Detergent, detergent, rinse aid, hand detergent, hand dishwashing detergent or machine dishwashing detergent, containing at least one Amadoriase.

2. Body care preparations, hair care products, shampoos, mouth, tooth and denture care products, braces, cosmetics, therapeutics, brightening agents, bleaching agents, disinfectants and agents for bleaching or disinfecting treatment of filter media, textiles, furs, paper, skins or leather, containing at least one amadoriase.

3. Composition according to claim 1 or 2, characterized in that it additionally contains at least one protease.

4. Composition according to one of claims 1 to 3, characterized in that it additionally contains at least one amylase.

5. Composition according to one of the preceding claims, characterized in that it additionally contains at least one cellulase.

6. Composition according to one of the preceding claims, characterized in that it additionally contains at least one surfactant and at least one perhydrolase.

7. Composition according to one of the preceding claims, characterized in that it additionally contains at least one bleach activator.

8. Composition according to one of the preceding claims, characterized in that it additionally contains at least one bleach catalyst.

9. Composition according to one of the preceding claims, characterized in that the Amadoriase is obtained from fungi or bacteria, in particular from the species Aspergillus and Bacillus. "

10. Composition according to one of the preceding claims, characterized in that the Amadoriase is obtained from organisms selected from Agrobacterium tumefaciens, Agrobacterium tumefaciens, Arthrobacter sp., Aspergillus clavatus, Aspergillus fumigatus, Aspergillus nidulans, Aspergillus oryzae, Aspergillus terreus, Bacillus halodurans, Candida boidinii, Coniochaeta sp., Corynebacterium sp., Cryptococcus neoformans, Debaryomyces hansenii, Eupenicillium terrenum, Filobasidiella neoformans, Gibberella zeae, Neosartorya fischeri, Ulocladium sp., Fusarium oxysporum, Acremonium, Bacillus cereus, Bacillus clausii; Brevibacterium linens, Thermobifidafusca; Bacillus anthracis, Bacillus thuringiensis, Eobacillus kaustophilus, Bacillus subtilis, Oceanobacillus iheyensis, Geobacillus kaustophilus, Penicillium spp., Penicillium janthinellum, Pichia sp., Bacillus licheniformis and Schizosaccharomyces pombe.

11. Composition according to one of the preceding claims, characterized in that the amadoriase is selected from amadoriases whose amino acid sequences comprise a sequence or consist of a sequence which coincide with the amino acid sequences given in SEQ ID NO: 1 to 26 to at least 80%.

12. Composition according to one of the preceding claims, characterized in that it is present as a free-flowing powder having a bulk density of 300 g / l to 1200 g / l, in particular 500 g / l to 900 g / l.

13. Composition according to one of claims 1 to 11, characterized in that it is in the form of a single- or multi-phase, in particular two-phase liquid and sprayable agent or a pasty or liquid detergent, preferably in a single or multi-chamber bottle, in particular in a or multi-chamber bottle with spray system.

14. Composition according to one of claims 1 to 11, characterized in that it is in the form of a non-aqueous liquid detergent or a non-aqueous paste.

15. Composition according to one of claims 1 to 11, characterized in that it is in the form of an aqueous liquid detergent or a water-containing paste and is packaged in an air-impermeable container, from which it is released shortly before use or during the washing process.

16. Composition according to one of claims 1 to 11, characterized in that the amadoriase and / or the substrate for this enzyme is coated with a at room temperature or in the absence of water for the enzyme and / or its substrate impermeable substance, which under use conditions the agent becomes permeable to the enzyme and / or its substrate.

17. Use of an amadoriase for the enzymatic degradation of Amadori products, in particular as a constituent of detergents, dishwashing detergents and cleaning agents.

18. Use of an amadoriase for the enzymatic generation of hydrogen peroxide in situ, in particular for bleaching, for color transfer inhibition and for disinfection.