HK1070788A - Inhibition of the asexual reproduction of fungi - Google Patents

Description

Inhibiting vegetative propagation of fungi

no marking

The invention relates to the inhibition of the asexual reproduction of fungi by the use of monoterpenes, sesquiterpenes and/or diterpenes and derivatives thereof and to filter media comprising monoterpenes, sesquiterpenes and/or diterpenes or derivatives thereof, adhesives, building materials, building aids, textiles, furs, paper, fur or leather, detergents, cleaners, rinses, hand-wash preparations, artificial dishwashing agents, machine dishwashing agents, and compositions for polishing building materials, building aids, textiles, furs, paper, fur or leather.

Fungi, especially moulds, cause serious problems in the field of architectural biology, since spores that they release into the air are often allergens. Combating such fungi with antimicrobial agents often involves an increased risk of resistance and therefore new antimicrobial agents have to be sought after some time to combat the currently resistant microorganisms. Moreover, antimicrobial agents are not always ecologically and toxicologically safe. Undesirable effects of mold transmission include, among others, stains caused by colored spores (e.g., on walls, adhesives, and other bathroom floors).

Delicate textiles, such as silk or microfiber, for example, are increasingly being used to make garments that can only be laundered at 30 or 40 ℃. However, fungi such as, for example, Candida albicans, which are pathogenic to humans, cannot be killed at this temperature. Especially after fungal infection, these fungi that attach to the garment can cause re-infection.

Thus, antimicrobial agents that inhibit the growth of fungi (fungistats) or kill fungi (bactericides) have been used to date. Antimicrobial agents used for these purposes are often non-selective, i.e., not only antibacterial but also antifungal. A disadvantage of such non-selective biocides is that the corresponding biocides or biostatics used, for example, in laundry detergents and cleaning agents contaminate the waste water and thus also functionally impair the microbiological phase of the waste water treatment plant.

It has surprisingly been found that by using monoterpenes, sesquiterpenes and/or diterpenes or derivatives thereof on or in a substance infected with fungi, the spread of the fungi is inhibited, although they are not actually killed.

The present invention therefore relates to the inhibition of vegetative propagation of fungi by the use of monoterpenes, sesquiterpenes and/or diterpenes and their derivatives.

In the context of the present invention, the term "asexual propagation" includes, inter alia, sporulation, germination and fission.

Preferably, the use according to the invention neither inhibits the growth nor kills the fungus; merely inhibit or stop vegetative propagation. Thus the selection pressure for resistance enhancement is minimal.

Another advantage of the present invention is that monoterpenes, sesquiterpenes and/or diterpenes or derivatives thereof are active at low final concentrations compared to bactericidal or antifungal agents, and therefore have a low risk of unwanted side effects.

In a preferred embodiment of the invention, sporulation is inhibited by using monoterpenes, sesquiterpenes and/or diterpenes and their derivatives. Sporulation in the context of the present invention refers to the generation of two reproductive forms, such as conidia, goniocysts, sporocysts, arthrospores, blastospores and their related structures (such as conidiophores), and their fixed forms (such as chlamydospores).

Since mold spores are ubiquitous in the air of a room, mold infestation cannot be substantially prevented. However, the sporulation of the fungal colonies that inhibit growth can significantly reduce the risk of mold allergy and completely halt or significantly delay the spread of the fungus. Stains caused by sporulation are also greatly reduced or completely avoided.

In a particular embodiment, the monoterpene, sesquiterpene and/or diterpene or derivative thereof may be selected from alcohols, such as farnesol and ethers thereof, acids, such as farnesoic acid, and esters thereof and other monoterpenes, sesquiterpenes and diterpenes having functional groups. Both trans and cis isomers are suitable. Likewise included are alpha-farnesene (3, 7, 11-trimethyl-1, 3, 6, 10-dodecatetraene) and beta-farnesene (7, 11-dimethyl-3-methylene-1, 6, 10-dodecatriene and nerolidol (3, 7, 11-trimethyl-1, 6, 10-dodecatriene-3-ol) and bisabolene, sesquiterpinene, zingiberene, piperylene, aryl tomerone, xanthorrhiazole, vulgare and beta-cnedene, preferred monoterpenes are, for example, alpha-and beta-ocimene, linalool, linalyl acetate, carene, abienol, nerol, neroli acid, geraniol, alpha-and beta-phellandrene and/or thujone, especially preferred alcohols, linalool and/or jambolane, examples of diterpenes are geranyl alcohol (3, 7, 11, 15-tetramethyl-2, 6, 10, 14-hexadecatrien-1-ol) and isomers and derivatives thereof. Plant extracts containing mono-, sesqui-and/or diterpenes (e.g., geranium oil, rose oil, neroli oil, lavender oil, jasmine oil, clove basil oil, citronella oil, cedar leaf oil, coriander oil, rosewood oil, capsicum oil, ginger oil or clove oil) may also be used. In a particularly preferred embodiment, the monoterpene, sesquiterpene and/or diterpene or derivative thereof is selected from farnesol and farnesoic acid, farnesol being most particularly preferred.

In a particular embodiment, the monoterpene, sesquiterpene and/or diterpene is used at a final concentration that is neither fungicidal (i.e., does not kill the fungus) nor fungistatic (i.e., inhibits the growth of the fungus). A particular advantage of this embodiment is that the risk of a gradual increase in resistance to the substances used is relatively small, since the fungi are neither killed nor growth-inhibited. The minimum concentration at which growth is not inhibited yet and the minimum inhibitory concentration itself can be readily determined according to known methods.

In another particular embodiment, the monoterpene, sesquiterpene and/or diterpene is present in a concentration of 0.000001 to 3 wt%. A particular advantage of this embodiment is that only low concentrations of these substances are required to reduce or substantially completely prevent asexual propagation of the fungus. The monoterpene, sesquiterpene and/or diterpene or derivative thereof is preferably used in a concentration of 0.00001 to 1 wt.%, more particularly in a concentration of 0.0001 to 0.5 wt.%. Concentrations of 0.0001 to 0.1 wt.% are particularly preferred.

The concentrations that give the desired result in the final product are significantly lower than those mentioned, since many products have to take into account dilution problems. For laundry detergents, a dilution factor (concentrated detergent to water ratio) of 1: 20 to 1: 200 may be considered. The dilution ratio of the laundry detergent is often between 1: 60 and 1: 100, for example 1: 80. Concentrations of 0.0001 to 1 wt.% have particularly good adhesion-inhibiting effects in the end-use solutions. Concentrations of 0.001 to 0.1 wt.%, for example 0.01 wt.%, are preferably used.

For farnesol, concentrations of 0.001 to 1.5 wt.%, more preferably 0.01 to 0.8 wt.%, will be suitable.

Sheets useful in the inventionThe terpenes, sesquiterpenes and/or diterpenes or derivatives thereof are particularly suitable for inhibiting the vegetative propagation of all fungi listed in the "list of DSMZ-filamentous fungi" and the "list of DSMZ-yeasts" of the stock catalog DSMZ (Deutsche Stammsamming von Mikroorganismen und Zellkulturen GmbH, Braunschweig). The catalog can be found in the following web site:http://www.dsmz.de/species/fungi.htmorhttp://www.dsmz.de/species/yeasats.htm。

The monoterpenes, sesquiterpenes and/or diterpenes or derivatives thereof used according to the invention are particularly suitable for inhibiting the asexual reproduction of fungi. Such fungi include, for example, ascomycetes, basidiomycetes, deuteromycetes and human-pathogenic species of the zygomycetes classes, more specifically any species of the genera aspergillus, penicillium, amycolatopsis and mucor, as well as human pathogenic forms of the genera candida.

The ascomycetes include, in particular, Aspergillus gennini, Penicillium and Cladosporium. These fungal forms have spores of strong allergens that may come into contact with the skin or respiratory tract. Basidiomycetes include, for example, Cryptococcus neoformans. Fungi imperfecti include all genera known as molds, especially those that cannot be classified as either ascomycetes, basidiomycetes or zygomycetes due to lack of sexual stage.

The monoterpenes, sesquiterpenes and/or diterpenes or derivatives thereof useful in the present invention are particularly useful for inhibiting sporulation of all species of Aspergillus, in particular from the group consisting of Aspergillus aculeatus, Aspergillus aculualbus, Aspergillus cepacia, Aspergillus kawachii, Aspergillus awamori, Aspergillus kawachii, Aspergillus chevalius intervarietal, Aspergillus clavatus, Aspergillus ficuus, Aspergillus flavus, Aspergillus foetidus, Aspergillus fumigatus, Aspergillus saprophyticus, Aspergillus intermedium, Aspergillus japonicus, Aspergillus nidulans, Aspergillus niger, Aspergillus niveus, Aspergillus ochraceus, Aspergillus oryzae, Aspergillus porosa, Aspergillus parasiticus, Aspergillus paragonicus var.

In a particularly preferred embodiment, the monoterpene, sesquiterpene and/or diterpene or derivative thereof useful in the present invention is most particularly preferably used for inhibiting sporulation in a species of aspergillus selected from aspergillus flavus and aspergillus nidulans.

The invention also relates to laundry detergents, cleaning agents, rinsing agents, hand washing preparations, artificial dishwashing agents, machine dishwashing agents and compositions for treating filter media, building materials, building auxiliaries, textiles, furskins, paper, skin or leather, comprising monoterpenes, sesquiterpenes and/or diterpenes or derivatives thereof which are suitable for inhibiting the asexual reproduction of fungi.

The invention also relates to a filter medium, building material, building aid, textile, fur, paper, skin or leather comprising a monoterpene, sesquiterpene and/or diterpene or derivative thereof suitable for inhibiting the asexual reproduction of fungi and/or which has been treated with a composition according to the invention.

Paper, textiles, fur, skin or leather are treated in a known manner, for example by immersion in a suitable concentrate of the components according to the invention.

The filter medium, construction material or construction aid is treated, for example, by mechanically incorporating or applying a suitable concentrate according to the invention to the filter medium, construction material or construction aid.

The building materials or building auxiliaries treated by the invention are preferably selected from the group consisting of adhesives, sealants, surface compounds and coating components, plastics, lacquers, paints, plasters, mortars, screeds, concrete, release materials and primers. Particularly preferred building materials or building aids are adhesives (e.g. silicone containing adhesives), wallpaper pastes, plasters, carpet adhesives, silicone adhesives, tile adhesives.

Sealants and in particular adhesives typically contain organic polymers and, in many cases, mineral or organic fillers and other additives.

Suitable polymers are, for example, the thermoplastic elastomers described in DE-A-3602526 of the applicant, preferably polyurethanes and acrylates. Suitable polymers are also described in the Applicant's DE-A3726547, 4029504 and 4009095 and in DE-A19704553 and DE-A4233077, all of which are incorporated herein by reference.

The sealant and, in particular, the adhesive may comprise water or an organic solvent. Suitable organic solvents are hydrocarbons, such as cyclohexane, toluene or even xylene or petroleum ether. Other solvents are ketones, such as methyl butyl ketone, and chlorinated hydrocarbons.

The sealant may also contain other rubbery polymers including the relatively low molecular weight, commercially available types of polyisobutylene, polyisoprene, and even polybutadiene styrene. Degraded natural rubber or neoprene may also be used. Even the type that remains liquid at room temperature, commonly referred to as "liquid rubber", can be used.

The sealant according to the present invention can be used to bond or seal various different kinds of materials to each other. The above materials are mainly concrete, glass, plaster and/or enamel, ceramics and porcelain. However, it is also possible to glue or seal molds or profiles of aluminium, steel, zinc or even plastics, such as polyvinyl chloride (PVC) or polyurethane or acrylics. Finally, sealing wood or lumber to various other materials is also described.

The stability of the binder is generally attributed to the added fine-particulate solids, also known as fillers. These fillers can be divided into organic as well as inorganic types. Preferred inorganic fillers are, for example, chalk (coated or uncoated) and/or zeolites. Zeolites may also act as desiccants. Suitable organic fillers are, for example, polyvinyl chloride powders.

The filler material, after application, generally has a critical effect on the sealing compound with the necessary internal adhesion so that it does not flow or protrude from the vertical seam. Said additives or fillers can be divided into pigments and thixotropic fillers, which are referred to in short as thixotropic agents.

Suitable thixotropic agents may be of any known type, such as organic bentonites, kaolins or even organic compounds, such as hydrogenated castor oil or derivatives thereof with polyfunctional amines or reaction products of stearic acid or ricinoleic acid with ethylenediamine. Silica has proven particularly suitable, and pyrogenic silica has proved to be particularly suitable. Other suitable thixotropic agents are substantially expandable polymer powders, such as polyacrylonitrile, polyurethane, polyvinyl chloride, polyacrylates, polyvinyl alcohol, polyvinyl acetate and corresponding copolymers. Particularly good results are obtained with fine-grained polyvinyl chloride powder. In addition to the thixotropic agent, for example, a coupling agent such as mercaptoalkyl may be used. For example, mercaptopropyltrimethoxysilane is commercially available.

The properties of the adhesive may be further improved by adding further components to the polymer powder used as thixotropic agent. Such components fall within the category of plasticizers or expanding agents and expansion aids used in plastics. Plasticizers from, for example, phthalates may be used. Examples of suitable compounds from this class are dioctyl phthalate, dibutyl phthalate and butyl benzyl phthalate. Other suitable classes of compounds are chlorinated paraffins, alkyl sulfonates, such as carbolic acid or cresols, and fatty acid esters.

Suitable expansion aids are low molecular weight organics that are miscible with the polymer powder and the plasticizer. Typical expansion aids can be found by the person skilled in the art on relevant textbooks on plastics and polymers. Preferred expansion aids for polyvinyl chloride powders are esters, ketones, aliphatic hydrocarbons, aromatic hydrocarbons and alkyl-substituted aromatic hydrocarbons.

The pigments and dyes used may be of any type that has been used for the application in question, such as titanium dioxide, iron oxides and carbon black.

To improve the storage stability, stabilizers such as benzoyl chloride, acetyl chloride, methyl tosylate, carbodiimides and/or polycarbodiimides may be added to the known sealing adhesives. Olefins containing from 8 to 20 carbon atoms have proven to be particularly effective stabilizers. In addition to their stabilizing effect, these stabilizers can also act as plasticizers or bulking agents. Preferred stabilizers are olefins containing from 8 to 18 carbon atoms, in particular with the double bond in the 1, 2-position. The best results are obtained when the molecular structure of these stabilizers is linear.

By inhibiting the vegetative propagation of fungi using the monoterpenes, sesquiterpenes and/or diterpenes and their derivatives of the invention, the problem of increased resistance to fungicides is avoided. When monoterpenes, sesquiterpenes and/or diterpenes or derivatives thereof are used in building materials and building aids susceptible to mould infections, especially in sealing adhesives and in particular adhesives, some desirable effects are obtained by inhibiting sporulation:

a) preventing the colored spores from forming stains,

b) the spread of the mould infection is delayed,

c) reducing the release of allergens.

In another preferred embodiment, the present invention relates to a wallpaper adhesive suitable for inhibiting fungal asexual reproduction comprising 0.000001 to 3 wt% of a monoterpene, a sesquiterpene and/or a derivative thereof. Wallpaper pastes hydrocolloids, such as aqueous solutions of methyl cellulose, methyl hydroxypropyl cellulose or water-soluble starch derivatives, film-forming high molecular weight aqueous dispersions, such as polyvinyl acetate, may also be used, in particular together with the above-mentioned cellulose and starch derivatives.

The filter media used may be of any known type, provided that they are suitable for water or air filtration. Mention may in particular be made of filters of cellulose, glass fibres, polyvinyl chloride fibres, polyester fibres, polyamide fibres, in particular nylon fibres, nonwovens, sintered materials and filters for filter membranes.

The concentration of the monoterpenes, sesquiterpenes and/or diterpenes or derivatives suitable for inhibiting the asexual propagation of fungi in the composition according to the invention may vary within wide limits by the expert depending on the conditions under which the preparation is carried out.

The laundry and/or cleaning agents of the present invention comprise 0.000001 to 3% by weight of monoterpenes, sesquiterpenes and/or derivatives thereof, suitable for inhibiting the asexual reproduction of fungi. Concentrations of 0.00001 to 1.0% by weight, in particular 0.0001 to 0.5% by weight, are particularly preferred. In a most particularly preferred embodiment, laundry detergents and cleaning agents comprise from 0.0001 to 0.05% by weight of these compounds.

The compositions of the present invention are prepared in standard formulations well known to the expert. Mono-, sesquiterpene and/or diterpene or derivatives thereof suitable for inhibiting the asexual reproduction of fungi are preferably added to the ready-to-use composition although, if desired, they may also be added during the production process.

Inhibiting the asexual reproduction of fungi on textiles or on plastic surfaces often prevents reinfection of the body with partial infection. Inhibiting the asexual reproduction of fungi on ceramics, plastics or metals reduces the risk of re-infection without contaminating the skin, mucous membranes or waste water with bactericide or fungistatic components. Catheters and other surgical instruments and/or prostheses or metal cans made of plastic may also be substantially protected from contamination by fungi by using monoterpenes, sesquiterpenes and/or diterpenes or derivatives thereof suitable for inhibiting fungi.

In another particular embodiment, a monoterpene, sesquiterpene and/or diterpene or derivative thereof suitable for inhibiting the asexual reproduction of fungi is added to the detergent and/or cleanser. In particular, modern textile fibers that cannot be washed with heavy duty detergents or high temperatures cannot be completely cleared of fungi by typical light duty detergents or washing temperatures of 30 or 40 ℃. One advantage of using such materials according to the invention for laundry and cleaning agents is that despite the lowest risk of wastewater contamination and lower resistance enhancement, the clothes can be cleaned of fungi.

According to the present invention, monoterpenes, sesquiterpenes and/or diterpenes or derivatives thereof suitable for use in inhibiting the asexual reproduction of fungi may also be added to detergents for cleaning hard surfaces such as floors, tiles, plastics and other hard surfaces in homes, especially in wet rooms (e.g. bathrooms) or medical practices. Here, they are able to prevent unwanted stains on the surface, which are produced by stained spores (e.g. black from aspergillus niger). Faded shower curtains and other bathroom textiles are also protected from the creation of spore stains.

In the context of the present invention, laundry and cleaning agents are understood in a broad sense as surfactants comprising the following formulations in the form: solid formulations (granules, powders, etc.), semi-solid forms (pastes, etc.), liquid forms (solutions, emulsions, suspensions, gels, etc.), and gas-like forms (aerosols, etc.), often containing one or more surfactants in addition to other typical components specifically applied, in order to obtain a beneficial effect in the application. Examples of such surfactant-containing formulations are surfactant-containing laundry detergents, surfactant-containing detergents for hard surfaces or surfactant-containing fabric conditioning formulations, which may be solid or liquid or even in a form present in a partial amount comprising solid and liquid components or mutual components.

Laundry and cleaning agents may contain typical ingredients such as anionic, nonionic, cationic and amphoteric surfactants, inorganic and organic components, specialty polymers (e.g. those with co-builder properties), suds suppressors, dyes and optionally additional perfumes, bleaching agents (e.g. peroxygen and chlorine bleaches), bleach activators, bleach stabilizers, bleach catalysts, enzymes and redeposition inhibitors, without limitation of the ingredients in these groups. Other important ingredients of such formulations are detergency builders, including, for example, optical brighteners, UV absorbers, soil repellents, i.e., polymers that resist fiber backfill. The individual substance groups are explained in more detail below.

When the preparation is present in the form of an at least partially shaped body, a binder and a decomposition aid may also be present.

The surfactants used may be anionic, nonionic, zwitterionic and cationic surfactants.

Suitable ionic surfactants are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are preferably C_9-13Of alkylbenzenesulfonates, olefinic sulfonates, i.e. mixtures of alkenes and hydroxyalkanesulfonates, and of the type obtained, for example, from C_12-18Disulfonates of monoolefins, which carry internal or terminal double bonds obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation product. Other suitable surfactants of the sulfonate type are those obtained from C_12-18Alkyl sulfonates of alkanes, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Esters (sulfonates) of 2-sulfonated fatty acids, such as the 2-sulfonated methyl esters of hydrogenated coconut oil, palm oil or tallow fatty acids, are also suitable.

Other suitable ionic surfactants are sulfonated fatty acid glycerides. The fatty acid glycerides in the context of the present invention are mono-, di-and triesters and mixtures thereof, produced by esterification of monoglycerides with 1 to 3 mol of fatty acids or by exchange with triglycerides of 0.3 to 2 mol of glycerol. Preferred sulfonated fatty acid glycerides are the sulfonation products of saturated fatty acids containing from 6 to 22 carbon atoms, such as caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Preferred alkyl (alkenyl) sulfates are alkali metal salts and, in particular, C_12-18Sodium salts of fatty alcohol sulfuric acid half-esters, e.g. coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C_10-20Oxidized alcohols and the corresponding half-esters of secondary alcohols having the same chain length. Other preferred alkyl (alkenyl) sulfates have the chain lengths described above and contain linear, petrochemical-based compoundsAlkyl chains and which behave in degradation similar to the corresponding compounds based on oleophilic starting materials. C_12-16Alkyl sulfates, C_12-15Alkyl sulfates and C_14-15Alkyl sulfates are preferably used in laundry and cleaning agents. Other suitable ionic surfactants are 2, 3-alkyl sulfates which can be produced, for example, according to US 3,234,258 or US 5,075,041 and are available as DAN from Shell oil company^*Trade-name products are commercially available.

Linear or branched C ethoxylated with 1 to 6 moles of ethylene oxide_7-21Sulfuric acid monoesters of alcohols, such as 2-methyl branched C containing an average of 3.5 moles of Ethylene Oxide (EO)_9-11Alcohols or C containing 1 to 4 EO_12-18Fatty alcohols are also suitable. In view of their high foaming capacity, only relatively low amounts are used, for example 1 to 5% by weight in laundry and cleaning agents.

Other suitable ionic surfactants are alkyl sulfosuccinates, also known as sulfosuccinates or sulfosuccinates, and also mono-and/or diesters of alcohols, preferably of sulfosuccinic acid of fatty alcohols and, more particularly, ethoxylated fatty alcohols. Preferred sulfosuccinates comprise C_8-18Fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates comprise fatty alcohol residues derived from ethoxylated fatty alcohols, which represent nonionic surfactants in view of isolation (see description below). Of these sulfosuccinates, those in which the fatty alcohol residue is derived from a narrow range of ethoxylated fatty alcohols are particularly preferred. Alkyl (alkenyl) succinic acids preferably containing 8 to 18 carbon atoms in the alkyl (alkenyl) chain or a salt thereof may also be used.

Other suitable anionic surfactants are, in particular, soaps. Suitable soaps are saturated fatty acid soaps, such as the salts of lauric, myristic, palmitic, stearic, hydrogenated erucic and behenic acid, and also mixtures of soaps, in particular from natural fatty acids, for example coconut, palm or tallow fatty acids.

Anionic surfactants, including soaps, may be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as the soluble salts of mono-, di-or triethanolamine. The anionic surfactant is preferably present in the form of its sodium or potassium salt and preferably in the form of its sodium salt.

Preferred compositions according to the invention comprise from 5 to 50% by weight, preferably from 7.5 to 40% by weight, more preferably from 15 to 25% by weight of one or more anionic surfactants.

Preferred nonionic surfactants are primary alcohols which are alkoxylated, preferably ethoxylated, more particularly preferably contain from 8 to 18 carbon atoms and, on average, from 1 to 12 moles of Ethylene Oxide (EO) per mole of alcohol, where the alcohol component may be linear or, preferably, carry a methyl branch in the 2-position or may contain residues of linear and methyl branches in the form of mixtures, which are usually present in the oxidized alcohol residue. However, fatty alcohol ethoxylates, such as coconut oil, palm oil, tallow or oleyl alcohol, which comprise linear residues of alcohols of natural origin having from 12 to 18 carbon atoms and containing an average of from 2 to 8 EO per mole of alcohol, are particularly preferred. Preferred ethoxylated alcohols include, for example, C with 3 EO or 4 EO_12-14Alcohol, C containing 7 EO_9-11Alcohols, C containing 3 EO, 5 EO, 7 EO, or 8 EO_13-15Alcohols, C containing 3 EO, 5 EO or 7 EO_12-18Alcohols and mixtures thereof, such as C containing 3 EO_12-14Alcohols and C containing 5 EO_12-18A mixture of alcohols. The degree of ethoxylation represents a statistical average and may be an integer or fractional number for a particular product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols containing more than 12 EO may also be used, examples include tallow fatty alcohols containing 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferred nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters preferably containing from 1 to 4 carbon atoms in the alkyl chain, more particularly fatty acid methyl esters, wherein the nonionic surfactant may be used as the sole nonionic surfactant or in combination with other nonionic surfactants.

Another class of nonionic surfactants that may be preferably used are Alkyl Polyglycosides (APGs). Suitable alkyl polyglycosides correspond to the formula RO (G)_zWherein R is a linear or branched, especially 2-methyl-branched, saturated or unsaturated aliphatic radical containing from 8 to 22, preferably from 12 to 18, carbon atoms and G represents a monosaccharide unit containing 5 or 6 carbon atoms, preferably glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0, more preferably between 1.1 and 1.4.

Preferably, linear alkyl polyglucosides, i.e., alkyl polyglycosides, wherein the polyglucosyl component is a glucose monomer and the alkyl component is an alkyl group, are used.

The surfactant containing formulations of the present invention may preferably contain alkyl polyglycosides, an APG content of more than 0.2% by weight based on the total formulation being preferred for laundry, dishwashing or cleaning agents. Especially preferred formulations comprising surfactants contain APG in an amount of 0.2 to 10% by weight, preferably in an amount of 0.2 to 5% by weight, more preferably in an amount of 0.5 to 3% by weight.

Nonionic surfactants of the amine oxide type, such as N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and fatty acid alkanolamides, are also suitable. Wherein the amount of non-ionic surfactant used is preferably not more than the amount wherein the ethoxylated fatty alcohol is used, more preferably not more than half of those amounts.

Other suitable surfactants are polyhydroxy fatty acid amides corresponding to the following formula (I):

wherein R is⁴CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R⁵Is hydrogen, an alkyl or hydroxyalkyl radical comprising 1 to 4 carbon atoms, [ Z ]¹]Is a linear or branched polyhydroxyalkyl group comprising 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. Polyhydroxy fatty acid amides are known substances which are generally obtained by reductive amination with ammonia, alkylamines or reducing sugars of alkanolamines and subsequent acylation with fatty acids, fatty acid alkyl esters or fatty acid chlorides.

The group of polyhydroxy fatty acid amides also includes compounds corresponding to the following formula (II):

wherein R is⁶Is a linear or branched alkyl or alkenyl radical comprising from 7 to 12 carbon atoms, R⁷Is a linear, branched or cyclic alkyl or aryl group comprising 2 to 8 carbon atoms, R⁸Is a linear, branched or cyclic alkyl or aryl or oxyalkyl radical comprising from 1 to 8 carbon atoms, preferably C_1-4Alkyl or phenyl, [ Z ]²]Is a linear polyhydroxyalkyl group in which the alkyl chain is substituted with at least two hydroxyl groups, or an alkoxylated, preferably ethoxylated or propoxylated, derivative of this group.

[Z²]Preferably by reductive amination of a reducing sugar, such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy-or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alcoholate as catalyst, for example as taught in International patent application WO-A-95/07331.

In another preferred embodiment, cationic surfactants may be used in addition to anionic as well as nonionic surfactants.

The fabric softening material comprises, inter alia, a cationic surfactant. Examples of cationic surfactants are, inter alia, quaternary ammonium compounds, cationic polymers and emulsifiers.

Further suitable examples are quaternary ammonium compounds corresponding to the following formulae (III) and (IV):

wherein R In (IV)^aAnd R^bRepresents a non-cyclic alkyl group comprising 12 to 24 carbon atoms, R^cIs saturated with C_1-4Alkyl or hydroxyalkyl radical, R^dAnd R^a、R^bOr R^cIdentical or represents an aryl group. X^-Is halide, dimethyl sulfate, dimethyl phosphate or phosphate ion or their mixture. Examples of cationic compounds corresponding to formula (III) are didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dicetylammonium chloride.

The compounds corresponding to formula (IV) are the so-called esterquats. An advantage of Esterquat is its excellent biodegradability. In this formula, R^eIs an aliphatic alkyl radical comprising 12 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, R^fIs H, OH or O (CO) R^h，R^gIndependently of R^fRepresents H, OH or O (CO) Rⁱ，R^hAnd RⁱIndependently of one another, represent an aliphatic acyl group comprising 12 to 22 carbon atoms and 0, 1, 2 or 3 double bonds. m, n and p independently of one another may be 1, 2 or 3. X^-May be halide, dimethyl sulfate, dimethyl phosphate or phosphate ions or mixtures thereof. Preferred compounds for R^fIncluding the group O (CO) R^hFor R^cAnd R^hSaid includes C_16-18An alkyl group. Particularly preferred compounds are R^gCompounds which are also OH. Examples of compounds corresponding to formula (IV) are methyl-N- (2-hydroxyethyl) -N, N-di (tallowoyloxyethyl) -aminodimethyl sulfate, bis- (palmitoyl) -ethylhydroxyethylmethylaminodimethyl sulfate or methyl-N, N-bis- (acyloxyethyl) -N- (2-hydroxyethyl) -aminodimethyl sulfate. If used, corresponds to the formula (IV) packageQuaternized compounds comprising unsaturated alkyl chains, preferably corresponding fatty acids having an iodine value of 5 to 80, preferably 10 to 60, more preferably 15 to 45, and a cis: acyl groups having a t-trans isomer ratio (in weight%) of greater than 30: 70, preferably greater than 50: 50, more preferably greater than 70: 30. A commercially available example is methyl hydroxyalkyl dialkoyloxylkyl dimethyl sulfamate, marketed by Stepan as Stepatex^*Or Dehyquart^*Cognis product under the trade name or Rewoquat^*Sold as Goldschmidt-Witco product. Other preferred compounds are the diesterquats corresponding to formula (III), which are known under the trade name Rewoquat^*W222 LM or CR3099, which in addition to softness also provides stability and color protection.

In the formula (V), R^kAnd R^lEach represents an aliphatic acyl group comprising 12 to 22 carbon atoms and 0, 1, 2 or 3 double bonds.

In addition to the quaternary compounds described above, other known compounds may also be used, including for example quaternary imidazoline compounds corresponding to formula (VI):

wherein R is^mRepresents H or a saturated alkyl radical comprising from 1 to 4 carbon atoms, RⁿAnd R^oEach represents an aliphatic saturated or unsaturated alkyl group containing 12 to 18 carbon atoms, RⁿOptionally also represents O (CO) R^p，R^pIs an aliphatic saturated or unsaturated alkyl radical comprising 12 to 18 carbon atoms, Z is an NH group or oxygen, X^-Is an anion. q may be an integer from 1 to 4.

Other suitable quaternary compounds correspond to the following formula (VII):

wherein R is^q、R^rAnd R^sIndependently of one another, represent C_1-4Alkyl, alkenyl or hydroxyalkyl, R^tAnd R^uEach represents C_8-28Alkyl, r is a number from 0 to 5.

In addition to the compounds corresponding to formulae (III) and (VII), short-chain water-soluble quaternary ammonium compounds, including trihydroxy and methylaminodimethyl sulfate or alkyltrimethylammonium chloride dihydrocarbyldimethylammonium chloride and trialkylmethylammonium chlorides, such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, can also be used.

Also suitable are protonated alkylamine compounds having fabric softening benefits and non-quaternized protonated precursors of cationic emulsifiers.

Other cationic compounds suitable for use in the present invention are quaternized protein hydrolysates.

Suitable cationic polymers are the polyquaternary polymers listed in the CTFA cosmetic ingredient dictionary (the cosmetic, Toiletry and Fragrance Association, Inc, Inc., 1997), especially polyquaternium-6, polyquaternium-7 and polyquaternium-10 polymers (UcarePolyquaternium IR 400, Amerchol), also known as merquats, polyquaternium-4 copolymers, such as graft copolymers having a cellulose backbone and quaternary ammonium groups attached by allyldimethylammonium chloride, cationic cellulose derivatives, such as cationic Guar gums, such as Guar hydroxypropyltriammonium chloride, and similar quaternized Guar derivatives (e.g. Cosmedia Guar, Cognis GmbH), cationic quaternary sugar derivatives (cationic alkylpolyglucosides), such as the commercial product Glucquat quat^*100(CTFA name: lauryl methyl Gluceth-10 hydroxypropyl Dimonium chloride), copolymers of polyvinylpyrrolidone and dimethylaminomethacrylate, vinylimidazole and vinylpyrroleCopolymers of alkanones, aminosilane polymers and copolymers.

Polyquaternised polymers (e.g. Luviquat Care, BASF) and chitin-based cationic biopolymers and derivatives thereof, e.g. the commercially available Chitosan^*(Cognis) polymers are also suitable.

Cationic silicone oils are also suitable for this purpose, including, for example, the commercially available products Q2-7224 (a stable trimethylsilyl amodimethicone, Dow Corning), Dow Corning929 emulsion (including hydroxylamino-modified silicone resin also known as amodimethicone), SM-2059 (Universal electric), SLM-55067(Wacker), Abil^*Quat 3270 and 3272 (diquaternary polydimethylsiloxane Quaternary-80, Goldschmidt-Rewo) and siliconequat Rewoquat^*SQ 1(Tegopren^*6922，Goldschmidt-Rewo)。

Other suitable compounds correspond to the following formula (VIII):

and alkylamides which may be in non-quaternized form or, as illustrated, in quaternized form. In the formula (VI), R^vAliphatic acyl groups comprising 12 to 22 carbon atoms and 0, 1, 2 or 3 double bonds are possible. s may assume a value of 0 to 5. R^wAnd R^xRepresent H, C independently of each other_1-4Alkyl or hydroxyalkyl. Preferred compounds are fatty acid amides such as stearamidopropyl dimethylamine, available under the trade name Tego Amid^*S18 or 3-Butylosylamidopropyltrimethyldimethylsulfate, as Stepandex^*X9124 was obtained, and in addition to good conditioning effect, there were advantages in dye transfer inhibition effect and rapid biodegradability.

If cationic surfactants are used, they are preferably present in the formulation in an amount of 0.01 to 10% by weight, more preferably 0.1 to 3.0% by weight.

The surfactant content of the composition of the invention may be between 5 and 50% by weight, preferably between 10 and 35% by weight.

Next to surfactants, builders are the most important ingredients of detergents and cleaners. The surfactant-containing formulations of the present invention may comprise any builder conventionally used in detergents, i.e. especially zeolites, silicates, carbonates, organic co-builders and provided that the use of phosphates is not ecologically objectionable.

Suitable sodium silicates in the form of crystalline layers correspond to the formula NaMSi_xO_2x+1·H₂O, where M is sodium or hydrogen, X has a value of 1.9 to 4, y has a value of 0 to 20, and X is preferably 2, 3 or 4. Such as crystalline layered silicates are described in European patent application EP-A-0164514. Preferred crystalline layered silicates corresponding to the above formula wherein M is sodium and X is assumed to be 2 or 3. Sodium b-and d-disilicate Na is particularly preferred₂Si₂O₅·y H₂Sodium O, b-disilicate is obtainable from the process described in international patent application WO a-91/08171.

Other effective builders are amorphous sodium silicates having a modulus (Na 2O: SiO2 ratio) of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and more preferably 1: 2 to 1: 2.6, which dissolve slowly and exhibit multiple wash cycle characteristics. The delay in dissolution associated with conventional amorphous sodium silicates can be achieved in a number of ways, for example by surface treatment, synthesis, compression or overdrying. So-called X-ray amorphous silicates which also retard dissolution compared with conventional soluble glasses are described, for example, in German patent application DE-A-4400024. The product preferably has crystallite regions of 10 and several hundred nanometres in size, up to 50 nanometres, more particularly up to 20 nanometres in size. Compressed amorphous silicates, complex amorphous silicates and overdried X-ray-amorphous silicates are particularly preferred.

The fine crystalline synthetic zeolite containing bound water optionally used is preferably zeolite a and/or zeolite P. Zeolite MAP^*(for example Soucil A24 is available from Crosfield) isA particularly preferred P-type zeolite. However, mixtures of zeolites X and A, X and/or P are also suitable. According to the invention, preference is also given to using, for example, cocrystals of zeolite X and zeolite A (approximately 80% by weight of zeolite X) under the trade name VEGOBOND AX from CONDEA Augusta S.p.A^*Sold and can be described by the following formula:

nNa₂O·(1-n)K₂O·Al₂O₃·(2-2.5)SiO₂·(3.5-5.5)H₂O.

suitable zeolites have an average particle size (volume distribution determined by the Coulter Counter Method) of less than 10 mm and preferably contain 18 to 22% by weight, more preferably 20 to 22% by weight, of bound water.

It is generally known that phosphates can of course be used as builders for detergents, provided that their use will not be avoided on ecological grounds. Particularly suitable are orthophosphates, pyrophosphates and the sodium salts of all the tripolyphosphates mentioned above.

Suitable organic builders are, for example, polycarboxylic acids which can be used in the form of their sodium salts, by which is understood carboxylic acids having the function of more than one acid, such as citric acid, adipic acid, succinic glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, saccharinic aminocarboxylic acid, nitrilotriacetic acid (NTA), as long as they are ecologically safe in use, and mixtures thereof. Preferred salts are salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. The acid itself may also be used. In addition to their builder effect, acids typically have the characteristics of an acid-changing component and, therefore, are also used to determine relatively low and mild pH values in surfactant-containing formulations. Mention may be made in particular in this connection of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and mixtures thereof.

Other suitable builders are polymeric polycarboxylates, for example alkali metal salts of polyacrylic or polymethacrylic acids, for example those having a relative molar amount of from 500 to 70,000 g/mole.

The molecular weights of the polymeric polycarboxylates mentioned in this specification are those of a particular acid type weight average molecular weight M_wIt is determined by Gel Permeation Chromatography (GPC) using a UV detector. This determination provides an actual molecular weight value by virtue of a structural relationship to the polymer under study, as compared to an external polyacrylic acid standard. These values are greatly different from the molecular weight values in which polystyrene sulfonic acid acids are used as standards. The molecular weight measured using polystyrene sulfonic acid as a standard is generally higher than the molecular weight mentioned in the description of the present invention.

Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of from 12,000 to 30,000 g/mol. Within this group, short chain polyacrylates having a molecular weight of 2,000 to 10,000 g/mole, more preferably 3,000 to 5,000 g/mole, are preferred due to their superior solubility.

Other suitable polymers are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid or acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid and maleic acid comprising from 50 to 90% by weight of acrylic acid and from 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molar amount, based on the free acid, is generally in the range of from 2,000 to 70,000 g/mole, preferably in the range of from 20,000 to 50,000 g/mole, more preferably in the range of from 30,000 to 40,000 g/mole.

The (co) polymeric polycarboxylates may be used as powders or in the form of aqueous solutions. The content of (co) polymeric polycarboxylates in the detergents/cleaners of the invention is preferably between 0.5 and 20% by weight, more preferably between 3 and 10% by weight.

To improve solubility in water, the polymer may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.

Other particularly preferred polymers are biodegradable polymers of more than two different monomer units, for example those comprising salts of acrylic acid and maleic acid as monomers and vinyl alcohol or vinyl alcohol derivatives as monomers or those comprising acrylic acid and 2-alkylallyl sulfonic acid and sugar derivatives as monomers.

Other preferred copolymers are copolymers preferably comprising acrolein and acrylic acid/acrylate or acrolein and vinyl acetate as monomers.

Other preferred builders are polymeric aminodicarboxylic acids, salts or precursors thereof. Polyaspartic acids or salts and derivatives thereof which have a bleach-stabilizing action in addition to their co-builder properties are particularly preferred.

Other suitable builders are polyacetals, obtainable by reacting dialdehydes with polyhydric alcohol carboxylic acids containing from 5 to 7 carbon atoms and at least three 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.

Other suitable organic builders are dextrins, for example oligomers or polymers of carbohydrates obtainable by partial hydrolysis of starch. Hydrolysis may be carried out by standard methods, such as acid or enzyme catalyzed methods. The end product is preferably a hydrolysate having an average molecular weight of 400 to 500,000 g/mole. Preferred are glycans having a glycation Degree (DE) of 0.5 to 40, more particularly 2 to 30, the DE being an acceptable measure of the reduction of glycans compared to glucose having a DE of 100. Maltodextrins having a DE of 3 to 20 and dry glucose syrups having a DE of 20 to 37 and so-called yellow dextrins and white dextrins having a relatively high molecular weight of 2,000 to 30,000 can be used. Preferred dextrins are described in british patent application 9419091.

Oxidized derivatives of such dextrins are their reaction products with oxidizing agents capable of oxidizing at least one functional group of the sugar ring to a carboxylic acid functional group. Oxidized oligosaccharides are also suitable;sugar ring C₆The products of the oxidation are particularly advantageous.

Other suitable co-builders are hydrogen oxysuccinate and derivatives thereof, preferably ethylenediamine hydrogen succinate. ethylenediamine-N, N' -disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salt. Glyceryl succinate and glyceryl tristuccinate are particularly preferred in this regard. The zeolite-containing and/or silicate-containing preparations are used in amounts of 3 to 15% by weight.

Other effective organic co-builders are, for example, acetylated hydroxycarboxylic acids and esters thereof, optionally present in the form of lactones and containing at least 4 carbon atoms, at least one hydroxyl group and up to two acidic groups.

Another material with co-builder properties is a phosphonate, more particularly a hydroxyalkylaminoalkane phosphonate. Of the hydroxyalkanophosphonates, 1-hydroxyethane-1, 1-diphosphonate (HEDP) is particularly important as a cobuilder. Preferably used in the form of the sodium salt, the disodium salt showing a neutral reaction and the tetrasodium salt showing a basic dosing (pH 9). Preferred aminoalkanephosphonates are ethylenediamine 1, 4-butylidene phosphonate (EDTMP), diethylenetriamine cyclopentane phosphonate (DTPMP) and higher homologs thereof. They are preferably used in the form of neutral reactive sodium salts, for example the hexasodium salt as EDTMP and the heptasodium and octasodium salts as DTPMP. In the phosphonate ester, HEDP is preferably used as a component. Aminoalkanephosphonates also exhibit significant heavy metal binding. Thus, when the surfactant-containing formulation of the invention also contains a bleaching agent, it is advantageous to use aminoalkanephosphonates, in particular DTPMP, or mixtures of said phosphonates.

In addition, any compound capable of forming a complex with an alkaline earth metal ion may also be used as a co-builder.

Production of H in water as a bleaching agent₂O₂Of particular importance are sodium perborate tetrahydrate and sodium perborate monohydrate. Other effective bleaches are, for exampleSodium percarbonate, peroxopyrophosphates, citrate perhydrate and H production₂O₂Such as perbenzoate, peroxyphthalate, perazelaic acid, phthalimide peracid or diperoxydodecanedioic acid. If detergents or bleaching preparations for dish washers are produced, bleaching agents from organic bleaches can also be used. Typical organic bleaching agents are diacyl peroxides, such as, for example, dibenzoyl peroxide. Other typical organic bleaching agents are peroxyacids, of which alkyl acids as well as aryl peroxyacids are particularly mentioned examples. Preferred representatives are (a) perbenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acid, peroxy-alpha-naphthoic acid and magnesium monophthalate, (b) aliphatic or substituted aliphatic peroxoacids, such as lauric peroxide, stearic peroxide, epsilon-phthalimidoperoxycarboxylic acid [ Phthalimidoperoxycaproic Acid (PAP)]Ortho-carboxybenzoylaminoperoxyhexanoic acid, N-nonenamido peroxyadipic acid and N-nonenamido peroxysuccinic acid and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperoxydecanoic acid, diperoxyphthalic acid, 2-decyldiperoxybutane-1, 4-dioic acid, N, N-terephthaloyl-bis (6-aminoperoxyhexanoic acid).

To obtain improved bleaching, i.e. washing at temperatures of 60 ℃ or less, bleach activators may be added to the surfactant-containing formulations. The bleach activator may be an aliphatic peroxycarboxylic acid formed comprising preferably from 1 to 10 carbon atoms, more preferably from 2 to 4 carbon atoms and/or optionally substituted perbenzoic acid under perhydrolysis conditions. Ortho-and/or normal acyl groups and/or optionally substituted benzoyl groups having the above-mentioned number of carbon atoms are suitable. Preferred bleach activators are the compounds of the class of the compounds of the formula I, which are preferably selected from the group consisting of the compounds of the formula I, the compounds of the formula II, and the compounds of the formula I.

In addition to the conventional bleach activators described above, so-called bleach catalysts can also be incorporated into formulations containing surfactants. Bleach catalysts are transition metal salts or transition metal complexes which promote bleaching such as, for example, manganese-, iron-, cobalt-, ruthenium-or molybdenum-salen complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium, and copper complexes and cobalt-, iron-, copper-, and ruthenium-ammonia complexes with nitrogen-containing tripod ligands may also be used as bleach catalysts.

Suitable enzymes are enzymes from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus, are particularly suitable. Proteases of the subtilisin type are preferred, proteases obtained from Bacillus subtilis being particularly preferred. Enzyme mixtures, for example protease and amylase or protease and lipase or a mixture of protease and cellulase, or cellulase and lipase or a mixture of protease, amylase and lipase, or a mixture of protease, lipase and cellulase, especially a mixture comprising cellulase, are particularly preferred. Peroxidases or oxidases have also proven suitable in some cases. The enzyme may be adsorbed onto a support and/or encapsulated in a membrane material to prevent premature decomposition. The percentage of enzyme, enzyme mixture or enzyme particle in the surfactant containing formulation of the present invention may be, for example, from about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

Preferably suitable additives are optical brighteners. Optical brighteners commonly used in laundry detergents may be used. Examples of optical brighteners are diamino-stilbenediphenoldisulfonic acids or alkali metal salts thereof. Suitable optical brighteners are, for example, salts of 4, 4 '-bis- (2-anilino-4-morpholino-1, 3, 5-triazin-6-amino))) -1-2-stilbene-2, 2' -disulfonic acid or compounds of similar composition which contain a dihydroxyethylamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of a morpholino group. In addition, brighteners of the substituted biphenylstyryl type, for example alkali metal salts of 4, 4 ' -bis- (2-sulfostyryl) -biphenyl, 4, 4 ' -bis- (4-chloro-3-sulfostyryl) -biphenyl or 4- (4-chlorostyryl) -4 ' - (2-sulfostyryl) -biphenyl, may also be present in part of the components of the formulations according to the invention containing surfactants (detergent formulations). Mixtures of the above-mentioned brighteners may also be used.

Another group of additives preferred for the purposes of the present invention are uv absorbers. The uv absorber can absorb onto the treated textile and can improve the photostability of the fiber and/or the photostability of another formulation component. Ultraviolet absorbers are organic substances (optical filters) that are capable of absorbing ultraviolet light and releasing energy as longer-wave radiation, such as heat. Compounds having these desired properties are, for example, compounds which act by non-radiative deactivation and benzophenone derivatives having substituents in the 2-and/or 4-position. Other suitable UV absorbers are substituted azaindolines, such as, for example, the water-soluble benzenedisulfonic acid-3- (2H-benzothiazol-2-yl) -4-hydroxy-5- (methylpropyl) -monosodium salt (Cibafast)^*H) 3-phenyl-substituted acrylates (cinnamic acid derivatives) optionally having a cyano group in the 2-position, salicylates, organonickel complexes and natural substances such as pseudomorphic ketones and imidazole acrylic acid contained in the body. Of particular importance is attributed to the biphenyl radical and, above all, the 1-2-stilbene derivatives, described, for example, in EP 0728749A, commercially available as Tinosorb^*FD and Tinosorb^*FR exCiba. Suitable UV-B absorbers include 3-benzylidene camphor or 3-benzylidene norcamphor and derivatives thereof, such as 3- (4-methylbenzylidene) -camphor as described in EP-B10693471; 4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) -benzoic acid-2-ethylhexyl ester2-octyl 4- (dimethylamino) -benzoate and amyl 4- (dimethylamino) -benzoate; esters of cinnamic acid, preferably 2-ethylhexyl 4-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 '-methoxybenzophenone, 2, 2' -dihydroxy-4-methoxybenzophenone; esters of benzylidene benzenedioic acid, preferably 4-methoxybenzylidene benzenedioic acid-di-2-ethylhexyl ester; triazine derivatives such as, for example, 2, 4, 6-trianilino- (p-carbon-2 '-ethyl-1' -hexyloxy) -1, 3, 5-triazine and octyltriazone, described in EP 0818450A 1 or dioctylbutylaminotriazinone (Uvasorb)^*HEB); propane-1, 3-diones such as, for example, 1- (4-tert-butylphenyl) -3- (4' -methylphenyl) -propane-1, 3-dione; ketotricyclo (5.2.1.0) decane derivatives, described in EP 0694521B 1. Other suitable UV-B absorbers are 2-phenylbenzimidazole-5-sulfonic acid and also the alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts thereof; sulfonic acid derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and salts thereof; sulfonic acid derivatives of 3-benzylidene camphor such as, for example, 4- (2-oxo-3-bornylidenemethyl) -benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) -sulfonic acid and salts thereof.

Typical UV-A filters are, in particular, derivatives of benzoylmethane, such as, for example, 1- (4 '-tert-butylphenyl) -3- (4' -methylphenyl) -propane-1, 3-dione, 4-tert-butyl-4 '-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4' -isopropylphenyl) -propane-1, 3-dione and enamine compounds, as described in DE 19712033A 1 (BASF). Of course, the UV-A and UV-B filters can also be used in the form of mixtures. In addition to the soluble substances mentioned, insoluble photo-block pigments, i.e.finely divided, preferably "nanosized" metal oxides or salts, can also be used in the context of the present inventionThe purpose is. Examples of suitable metal oxides are, inter alia, zinc oxide and titanium dioxide and also iron oxide, zirconium oxide, silicon, manganese, aluminum and cerium and mixtures thereof. Silicates (talc), barium sulfate and zinc stearate can also be used as salts. The oxides and salts are used in the form of pigments for skin care and emulsions and cosmetics for protecting the skin. The average diameter of the particles is less than 100nm, preferably between 5 and 50nm, more preferably between 15 and 30 nm. Although ellipsoidal or other non-spherical particle shapes may be used, they may also be spherical. The pigments may also be surface-treated, i.e. hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, such as Titandioxid T805 (Degussa) and Eusolex^*T2000 (Merck). Suitable hydrophobic coating materials are, above all, siloxanes, in particular trialkoxyoctylsilanes or polydimethylsiloxanes. It is preferred to use micronized zinc oxide. Other suitable UV filters can be found in review S * FW-Journal 122, 543(1996) by P.Finkel.

The ultraviolet absorber is generally used in an amount of 0.01 to 5% by weight and preferably in an amount of 0.03 to 1% by weight.

Another group of additives which are preferably used for the purposes of the present invention are dyes, in particular water-soluble or water-dispersible dyes. Preferred dyes are of the type commonly used in laundry and dishwashing agents, detergents and fabric conditioners to improve their appearance. Dyes such as these, which are readily selected by the person skilled in the art, have a high storage stability which is not influenced by other ingredients comprising surfactant preparations or by light and do not have any substantive dyeability to dye textile fibers. According to the invention, the amount of dye present in the inventive washing and/or cleaning agents is less than 0.01% by weight.

Another class of additives that can be incorporated into detergents and/or cleaners according to the present invention are polymers. Suitable polymers are, on the one hand, those which exhibit co-builder properties during washing or dishwashing, i.e. for example polyacrylic acids, on average modified polyacrylic acids or corresponding copolymers. Another group of polymers are polyvinylpyrrolidone and other redeposition inhibitors such as copolymers of polyvinylpyrrolidone, cellulose ethers, and the like. Other preferred polymers are soil repellents described in detail below.

The detergents/cleaners may also comprise the soil repellent of the invention as a further additive. Soil repellents are polymers that adsorb onto the fibers and have a positive effect on removing oils and fats from textiles by washing to resist back filling. These effects can be partially removed when the textile which has been repeatedly cleaned with the detergent comprising oil-and fat-soluble components according to the invention is soiled. Preferred dissolved oil-and fat components include, for example, nonionic cellulose ethers, such as methyl cellulose and methyl hydroxypropyl cellulose based on nonionic cellulose ethers containing from 15 to 30% by weight of methoxyl groups and from 1 to 15% by weight of hydroxypropoxyl groups, and polymers of phthalic acid and/or terephthalic acid or derivatives thereof, especially polymers of ethylene terephthalate and/or polyethylene glycol terephthalate or ionically and/or non-ionically modified derivatives thereof, which are well known in the art. Among these, sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

Especially when they are liquids or gels, the formulations may also contain solvents. Examples of suitable solvents are mono-or polyhydric alcohols containing 1 to 4 carbon atoms. Preferred alcohols are ethanol, 1, 2-propanediol, glycerol and mixtures thereof. The solvent may be present in the liquid formulation in an amount of from 2 to 12% by weight based on the final formulation, more particularly between about 1 and 5% by weight.

The amount of said additives which can be added to the washing and/or cleaning agent amounts to up to 30% by weight, preferably to 2 to 20% by weight.

In a particular embodiment, liquid or solid lotions are particularly preferred. Light duty laundry detergents suitable for the careful treatment of delicate textiles are also particularly preferred.

The list of detergent ingredients that may be present in the laundry/dishwashing or cleaning agent of the present invention is by no means complete and merely shows typical key components of such a composition. Organic solvents may also be present in the composition, especially when they are liquids or gels. These organic solvents may be mono-or polyhydric alcohols containing from 1 to 4 carbon atoms. Preferred alcohols are ethanol, 1, 2-propanediol, glycerol and mixtures of these alcohols. In a preferred embodiment, the composition comprises from 2 to 12% by weight of these alcohols. The overall effectiveness of the hard surface cleaner is achieved when the weight ratio of surfactant to alcohol in the solution is between 1: 1.5 and about 2: 1.

Hard surface cleaners which may be applied to a surface in a foamed or non-foamed form are also particularly preferred. In this way, the propagation of mold spores in the room air and the propagation of stains caused by mold spores in the humid chamber can be advantageously reduced or prevented.

In addition to the components mentioned, the aqueous solutions used in the present invention may contain other active components and small amounts of typical hard surface cleaner additives. Examples of such active ingredients are lime-dissolving organic acids, such as citric acid, acetic acid or lactic acid or their water-soluble salts, which are preferably present in an amount of 2 to 6% by weight, based on the total aqueous solution.

It is advantageous to use a cleaning agent which is applied as a foam to the surface to be cleaned and which is capable of remaining on the surface for a relatively long time. The cleaning effect can thus be significantly enhanced. The liquid preferably produces foam immediately after exiting the spray applicator. As regards the manual sprayer pump, this effect is obtained by specially designing the spray head of the sprayer, which guarantees an intensive mixing of the aqueous solution flowing down from the nozzle with the air, the liquid actually striking the surface in the form of a foam. Correspondingly designed jet pumps are commercially available. It is important to ensure-by proper design with a view to the mechanism of the spray of the washing liquid component-that a sufficient amount of propellant always accompanies the liquid flow and then causes the liquid to foam. Shaking may be necessary prior to administration. Spray container, suction nozzle and valve designed accordinglyAre conventional to those skilled in the art and therefore need not be further explained herein. The amount of liquid sprayed onto the surface to be cleaned during the cleaning process is typically between about 10g and about 60g/m²More particularly between 20g and 40g/m²In the meantime. The foam is preferably evenly distributed over the surface to be cleaned and can automatically exhibit its cleaning effect. Preferably, however, the surface is then wiped with a damp cloth or sponge, which requires periodic rinsing in fresh water for relatively large areas of the surface. It is of course also possible to rinse the treated surface with water, although this is usually not necessary, since the residues of the cleaning agent are completely transparent and virtually invisible after drying.

The following examples are intended to illustrate the invention and are not intended to limit it in any way.

Examples

Example 1

Effect of farnesol on sporulation by Aspergillus niger

100. mu.l of Aspergillus niger cell suspension (1.5. multidot.10)⁷Cells/ml) were inoculated on wort agar extract (Merck), to which different amounts of farnesol have been added: 0; 25; 62.5; 125; 250 and 500. mu.M. The dishes were incubated at 25 ℃ for 5 days, then sporulation was assessed by appearance and inhibition of sporulation was assessed (see, table 1). None of the farnesol concentrations inhibited growth, however sporulation was inhibited with increasing concentration and completely at 500 μ M.

Table 1: sporulation at different concentrations

Concentration of farnesol [ μ M ]]	0	25	62.5	125	250	500
							Formation of spores [% ]]	100	90	75	50	10	0

Examples 2 to 4: wallpaper adhesive

Example 2

Composition (I)	Measurement of
		Methylcellulose (300 m. pas in 2% aqueous solution, methoxy content 26%)	500g
PV acetate redispersion powder	350g
		Kaolin clay	60
Cellulose powder	50g
		Adduct of 6mol of ethylene oxide and 1mol of nonylphenol	10g
Commercially available preservatives (based on isothiazolipine derivatives)	8g
		Farnesol	0.2g

Example 3

Composition (I)	Measurement of
		Methylcellulose (5000 m. pas in 2% aqueous solution, methoxy content 19%)	680g
Carboxymethyl starch (DS 0.22)	300g
		Adduct of 4mol of ethylene oxide and 1mol of nonylphenol	15g
Preservatives available on the market (based on isothiazoline derivatives)	10g
		Farnesol	0.2g

Example 4

Composition (I)	Measurement of
		Commercially available polyvinyl acetate dispersions (50% solids)	500g
Water (W)	200g
		Methylcellulose (3000 m.pas in 2% aqueous solution)	20g
Commercially available preservatives	10g
		Farnesol	0.15g

The obtained mixture is made into paste with water in the ratio of 1: 20(2) or 1: 25(3) or 1: 1(4) and used for hanging wall paper.

Example 5: liquid detergent

Raw materials	In wt.%
		C12-18Fatty alcohol +7 EO (Dehydol LT 7, Cognis)	15
C12-14Fatty alcohol +2 EO sulfate, sodium salt (Texpaon N70, Cognis)	7
		C8-18Fatty acid oil component (coconut fatty acid, Edenor K12-18, Cognis)	8
Citric acid sodium salt	1.5
		Enzyme	+
Dye material	+
		Perfume	+
Farnesol	0.4
		Water (W)	To 100 of

Claims (18)

1. Use of a monoterpene, a sesquiterpene and/or a diterpene and derivatives thereof for inhibiting the asexual reproduction of fungi.

2. Use according to claim 1, characterized in that the monoterpene, sesquiterpene and/or diterpene or derivative thereof is selected from the group consisting of geraniol, linalool, nerol, thujone, farnesol, farnesoic acid, α -farnesene, β -farnesene, nerolidol, bisabolone, sesquiterestrene, zingiberene, piperylene, aryl tomerone, xanthorrhizole, vulgare, β -cnidium and geranylgeraniol, more particularly from the group consisting of farnesol and farnesoic acid, preferably farnesol.

3. Use according to claim 1 or 2, characterized in that the asexual reproduction of fungi selected from the group of human-pathogenic fungi, more particularly from the human pathogenic species of ascomycetes, basidiomycetes, zygomycetes, deuteromycetes and zygomycetes, preferably from all species of the genera aspergillus, penicillium, amycolatopsis and mucor and the human pathogenic forms of candida, is inhibited.

4. Use according to any one of the preceding claims, characterized in that the asexual reproduction of fungi selected from all the species of Aspergillus, more particularly from the following species, is inhibited: aspergillus aculeatus, Aspergillus albus, Aspergillus cepacia, Aspergillus oryzae, Aspergillus awamori, Aspergillus kawachii, Aspergillus carbonarius, Aspergillus carneus, Aspergillus chevalii, Aspergillus chekiangensis intervarietal, Aspergillus clavatus, Aspergillus ficuum, Aspergillus flavus, Aspergillus foetidus, Aspergillus fumigatus, Aspergillus megaterium, Aspergillus saprophyticus, Aspergillus niger, Aspergillus intemermedius, Aspergillus japonicus, Aspergillus nidulans, Aspergillus niger, Aspergillus niveus, Aspergillus ochraceus, Aspergillus oryzae, Aspergillus poreus, Aspergillus parasiticus, Aspergillus pratense var.

5. Use according to any of the preceding claims, characterized in that the monoterpene, sesquiterpene and/or diterpene or derivative thereof is used at a final concentration which is non-fungicidal or non-fungistatic.

6. Use according to any of the preceding claims, characterized in that the monoterpene, sesquiterpene and/or diterpene or derivative thereof is used in a concentration of 0.000001 to 3 wt% by weight.

7. Use according to any of the preceding claims, characterized in that the monoterpene, sesquiterpene and/or diterpene is used in a preparation selected from the group consisting of: laundry detergents, cleaning agents, rinsing agents, hand washing preparations, artificial dishwashing agents, machine dishwashing agents and also preparations for treating filter media, adhesives, building materials, building auxiliaries, textiles, furs, paper, skin or leather.

8. Use according to any of the preceding claims, characterized in that the asexual reproduction of fungi in or on textiles, ceramics, metals, filter media, building materials, building aids, pelts, paper, skin, leather and/or plastics is inhibited.

9. Laundry detergents, cleaning agents, rinsing agents, hand washing preparations, artificial dishwashing agents, machine dishwashing agents and preparations for treating filter media, building materials, building auxiliaries, textiles, furs, paper, skin or leather, which contain monoterpenes, sesquiterpenes and/or diterpenes or derivatives thereof suitable for inhibiting the asexual reproduction of fungi.

10. A filter medium, building material, construction aid, textile, fur, paper, skin or leather treated with the formulation of claim 9.

11. Laundry and/or detergent compositions comprising 0.000001 to 3% by weight of a monoterpene, sesquiterpene and/or diterpene or derivative thereof suitable for inhibiting the asexual reproduction of fungi.

12. A laundry and/or detergent composition as claimed in claim 11, characterised in that it is a liquid or solid laundry detergent.

13. A laundry and/or detergent composition as claimed in claim 11, characterised in that it is a detergent composition for hard surfaces.

14. An adhesive comprising 0.000001 to 3% by weight of a monoterpene, sesquiterpene and/or diterpene or derivative thereof suitable for inhibiting the asexual reproduction of fungi.

15. The adhesive as claimed in claim 14, characterized in that it is diluted with water.

16. An adhesive as claimed in claim 14 or 15, characterized in that it is an adhesive for hanging wall papers and similar wall coverings.

17. A sealant comprising 0.000001 to 3% by weight of a monoterpene, sesquiterpene and/or diterpene or a derivative thereof suitable for inhibiting the asexual reproduction of fungi.

18. A sealant according to claim 17, characterized in that it is an adhesive.