HK1101318A - Use of ortho-phenylphenol and/or derivatives thereof for inhibiting the asexual reproduction of fungi - Google Patents
Use of ortho-phenylphenol and/or derivatives thereof for inhibiting the asexual reproduction of fungi Download PDFInfo
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Description
The invention relates to the use of o-phenylphenol and/or derivatives thereof for inhibiting the asexual reproduction of fungi, and to filter media, adhesives, building materials, building auxiliaries, textiles, furs, paper, leather or leather products which contain o-phenylphenol and/or derivatives thereof, and also to detergents, cleaning agents, rinsing agents, hand washing agents, manual dishwashing agents, automatic dishwashing agents, and agents for finishing building materials, building auxiliaries, textiles, furs, paper, leather or leather products.
Fungi, in particular filamentous fungi, can cause considerable problems in the field of construction biology, since spores released therefrom into the indoor air are often sensitized. The risk of resistance development is increased with active biocidal substances against the fungi, and therefore after a certain time new antibacterial substances must be found which are effective against these now resistant microorganisms. Moreover, biocides are not always environmentally and toxicologically harmless. Among the effects of unwanted filamentous fungi proliferation are, inter alia, colored spore-induced stains (e.g., on walls, on compound sealants (compounds), and on bath surfaces).
Sensitive fabrics, such as silk or microfiber, are more and more often processed into garments that can only be cleaned at 30 or 40 ℃. Fungi, such as the human pathogen Candida albicans (Candidaalbicans), cannot be killed thereby. Especially after fungal infection, such fungi that adhere to the clothing and are not killed can lead to re-infection.
Therefore, antibacterial substances that either inhibit the growth of fungi (fungistats) or kill them (fungicides) have been used previously. Non-selective antibacterial substances that are simultaneously active against bacteria and fungi are often used for this purpose. A disadvantage is that these biocides or biocides used, for example in rinsing and cleaning agents, contaminate the waste water and thus also interfere with the operation of the microbiological treatment step of the sewage treatment plant.
It is known in the prior art that the use of o-phenylphenol in high concentrations is suitable for inhibiting fungal growth (fungistatic effect) or even for killing fungi (fungicidal effect). The prior art does not address the fact that orthophenylphenols can be used to inhibit the asexual reproduction (particularly sporulation) of fungi. Of course, general inhibition of growth can also lead to inhibition of asexual reproduction, in particular sporulation. It is not known in the prior art that ortho-phenylphenol can reduce and/or completely prevent the asexual reproduction, in particular sporulation, of fungi without inhibiting the growth of the fungi themselves.
Earlier international patent application PCT/EP02/14306, not previously published, describes that mono-, di-and/or diterpenes and their derivatives can be used to inhibit the asexual reproduction of fungi. Farnesol is cited as a particularly preferred active substance. There is no description of the use of o-phenylphenol for inhibiting the asexual reproduction of fungi.
Us patent 4,120,970 and 3,674,510 describe that ortho-phenylphenol can be used to preserve fruits. However, the o-phenylphenol concentration used therein is toxic to fungi. The result thus occurs is not an inhibition of the vegetative propagation itself, as occurs according to the present invention, but a simple killing of the microorganisms.
It is therefore an object of the present invention to overcome the disadvantages of the prior art and to prevent the asexual propagation of fungi, in particular of filamentous fungi, in particular on surfaces, without killing the fungi.
Surprisingly, it has been found that the use of o-phenylphenol and/or derivatives thereof on or in fungal infected materials can inhibit the propagation of fungi without killing them.
The subject of the present invention is therefore the use of orthophenylphenol and/or its derivatives for inhibiting the asexual reproduction of fungi.
According to the invention. The term "vegetative propagation" encompasses, inter alia, sporulation, budding and fission.
Included derivatives of ortho-phenylphenol, preferably esters and ethers of ortho-phenylphenol, are produced by reaction with the phenolic hydroxyl group. The carboxylic acid group of the o-phenylphenol ester may in particular be C1-18Alkyl carboxylic acids, preferably C1-12Carboxylic acid, or C6-10aryl-C1-6Alkyl carboxylic acids, such that the alkyl groups may be branched or unbranched and saturated or unsaturated. Alcohol group of o-phenylphenol ether, may be, in particular, C1-18Alcohols, preferably C1-6An alcohol. According to the invention, the derivatives of orthophenylphenol likewise include mono-or polysubstituted, preferably mono-, di-or trisubstituted orthophenylphenols, mono-or polysubstituted, preferably mono-, di-or trisubstituted orthophenylphenol ethers and orthophenylphenol esters, and also mono-or polysubstituted, in particular mono-, di-or trisubstituted biphenyls. The substituents in this case are preferably selected from C1-6Alkyl radical, C1-6Alkoxy radical, C6-10Aryl radical, C6-10aryl-C1-6Alkyl radical, C6-10aryl-C1-6Alkoxy, hydroxy, halogen, especially chlorine or fluorine, nitro, cyano, amino, mono-and di-C1-6Alkylamino and benzyl. Mention may in particular be made here of benzoates of O-phenylphenol, palmitates of O-phenylphenol, cinnamates of O-phenylphenol, acetates of O-phenylphenol and O-phenylphenol-O- β -D-glucopyranosides.
Further derivatives of o-phenylphenol which are suitable according to the invention are o-phenylphenol according to formulae (I) and (II) and/or esters of the aforementioned o-phenylphenol derivatives with silicic acid. The silicates are produced in particular by simple ester interchange of silicates of lower alcohols (n ═ 1) or silicate oligomers (n > 1) with orthophenylphenol and/or its derivatives. Depending on the reaction time and conditions, the lower alcohol is cleaved and the O-phenylphenol is bound, the alcohol along the Si-O-Si chain is more easily exchanged than the terminal alcohol.
The acid ester is according to one of the formulae (I) or (II), and/or mixtures thereof.
And
wherein at least one R is an o-phenylphenyl group or a derivative thereof and all other R's are independently selected from H, linear or branched, saturated or unsaturated, substituted or unsubstituted C1-6A hydrocarbon group, a terpene alcohol, and a polymer, and m takes on a value in the range of 1 to 20, and n takes on a value in the range of 1 to 100.
According to a further preferred embodiment, at least two or three R groups are o-phenylphenyl or a derivative thereof.
The silicate according to the invention has an oligomerization number "n" of between 1 and 20. In preferred compounds, n takes a value of between 1 and 15, preferably between 1 and 12, in particular between 1 and 10, particularly preferably the values 4,5, 6, 7 and 8.
The silicates used according to the invention are notable for good hydrolytic stability and can also be used in aqueous media and in the production of granules, sealing compounds, etc., without thus undergoing an excessive loss of activity. As a result, a slow and rather small release of the active substance from the substance according to the invention takes place, so that the non-fungicidal and non-fungistatic concentration of the active substance is released continuously from the product over a longer period of time.
According to a particularly preferred embodiment, one or more polymeric groups may be present on the silicate. These polymers containing free hydroxyl groups are preferably used for the manufacture of silicates. One or more of said polymeric groups are chosen, in particular, from starch and/or derivatives thereof, cellulose and/or derivatives thereof, polyvinyl alcohol, polyols, hydroxypolydimethylsiloxanes (very particularly α, ω -dihydroxypolydimethylsiloxane), and polyphenols, in particular polyvinyl alcohol. It is particularly preferred that the polymeric group is present as a silicate with ortho-phenylphenol. For use in sealing compounds, the use of relatively short-chain polymers is particularly preferred.
This embodiment has the advantage that the silicate can be individually adapted to the specific purpose and conditions, depending on the field of application. The polymers are particularly suitable, for example, for improving the ability of substances to be bound, for increasing the adhesion, in particular to surfaces, and for influencing the release properties as desired.
According to another embodiment, the derivative of o-phenylphenol further comprises an ester of o-phenylphenol with a polymer, or an ester of one of the aforementioned o-phenylphenol derivatives with a polymer. These substances also result in better suitability for the purpose of application, for example, conditions of better adsorption or adhesion to surfaces, or more favorable binding capacity. Hydrolysis of the ester bond, for example, upon repeated contact with water, slowly releases an active substance that can inhibit asexual reproduction of fungi thereafter.
Particularly preferably, the substance is produced by reacting orthophenylphenol or a derivative of orthophenylphenol with a polymer of this kind which bears functional groups selected in particular from the group consisting of acid groups, acid chloride groups, ester groups, primary, secondary and tertiary amide groups.
Polyacrylic acids, polyacrylates, polymethacrylic acids, polymethacrylates, polycarboxylic acids (in particular carboxymethylcellulose) and copolymers of the following monomers, including those mentioned above, as well as primary, secondary or tertiary polyacrylamides, are preferably used as polymers according to the invention. Chain lengths of about 2000 to 300,000g/mol are particularly preferred in this case.
According to another preferred embodiment, the derivative of o-phenylphenol is produced by reacting o-phenylphenol and/or one of the aforementioned o-phenylphenol derivatives with a monomer or polymer bearing one or more isocyanate groups. The carbamates formed by the reaction of the alcohol functions with the isocyanate groups likewise hydrolyze slowly and release the active substances in a controlled manner.
Preference is given to using monomeric aliphatic or aromatic mono-, di-and/or triisocyanates. The urethanes or (when isocyanates with a plurality of isocyanate groups are used) polyurethanes formed can likewise hydrolyze slowly and release the active substance.
Preferred as monoisocyanates are, for example, linear or branched aliphatic monoisocyanates having 6 to 44 carbon atoms, such as hexyl isocyanate, heptyl isocyanate, octyl isocyanate, nonyl isocyanate, decyl isocyanate, undecyl isocyanate, dodecyl isocyanate, tridecyl isocyanate, tetradecyl isocyanate, pentadecyl isocyanate, hexadecyl isocyanate, heptadecyl isocyanate, octadecyl isocyanate and the corresponding higher homologues of this series. Also preferred are aromatic monoisocyanates such as phenyl isocyanate, benzyl isocyanate, or biphenyl isocyanate.
Particular preference is given to diisocyanate (Q (NCO)2) Wherein Q is selected from aliphatic, optionally substituted hydrocarbyl having 4 to about 15 carbon atoms, aromatic, optionally substituted hydrocarbyl having 6 to about 15 carbon atoms, or optionally substituted araliphatic hydrocarbyl having 7 to about 15 carbon atoms. As used herein, there are, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, dimer fatty acid diisocyanate, 1, 4-diisocyanatocyclohexane, 1-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethylcyclohexane (IDPI), 4,4 '-diisocyanatodicyclohexylmethyl, 4, 4' -diisocyanatodicyclohexylpropane-2, 2,1, 3-and 1, 4-diisocyanatobenzene,2, 4-or 2, 6-diisocyanatotoluene or mixtures thereof, 2, 2 '-, 2, 4 or 4, 4' -diisocyanatodiphenylmethane, tetramethylxylylene diisocyanate, p-xylylene diisocyanate, and mixtures made from these compounds.
Toluene diisocyanate, hexamethylene diisocyanate, and m-tetramethylxylylene diisocyanate are particularly preferable.
Particularly suitable as triisocyanates are aromatic triisocyanates, such as tris- (p-isocyanato) phenyl thiophosphate, triphenylmethane-4, 4' -triisocyanate, and in particular the various isomeric trifunctional homologs of diphenylmethane diisocyanate (MDI).
Also suitable as the tri-isocyanate are adducts of diisocyanates and low molecular weight triols, especially adducts of aromatic diisocyanates and triols such as trimethylolpropane or glycerol. The limitations described above with respect to the content of diisocyanates, and the content of polyisocyanates having a functionality > 3, also apply to these adducts.
Aliphatic triisocyanates, for example the biuretization product of Hexamethylene Diisocyanate (HDI) or the isocyanation product of HDI, or also the same trimerization product of isophorone diisocyanate (IPDI), are also suitable for use in the compositions of the present invention.
The polyisocyanates are preferably the dimerization or trimerization products of the diisocyanates already mentioned. Examples of suitable isocyanates are diisocyanate, 2, 4-tolylene diisocyanate (2, 4-TDI), 2, 6-tolylene diisocyanate (2, 6-TDI), or mixtures of the abovementioned isomers, 2 '-diphenylmethane diisocyanate (2, 2' -MDI), 2, 4 '-diphenylmethane diisocyanate (2, 4' -MDI), 4 '-diphenylmethane diisocyanate (4, 4' -MDI), 1, 5-Naphthylene Diisocyanate (NDI), 1, 4-phenylene diisocyanate, 1, 3-tetramethylxylylene diisocyanate (TMXDI), Hydrogenated MDI (HMDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate-1, 6(HDI), 2-isocyanatopropylcyclohexyl isocyanate (IPCI), 2-butyl-2-ethylpentamethylene diisocyanate (BEPDI), Lysine Diisocyanate (LDI), 1, 12-dodecyldiisocyanate, cyclohexyl 1, 3 or 1,4 diisocyanate, 2-methylpentamethylene diisocyanate (MPDI) and the like, which contain, for example, urethane, allophanate, urea, biuret, uretdione, carbodiimide or ketimine groups such as those derived from the dimerization or trimerization of the aforementioned diisocyanates. Particularly suitable are compounds which carry oligo-or polyisocyanate groups, for example those which are produced in the isocyanate production or which remain as residues in the distillation sump during the distillation of the crude isocyanate product. Examples of particularly suitable materials in this connection are crude MDI which is obtainable directly after manufacture of the MDI and polymeric MDI which remains in the distillation sump after distillation of the MDI from the crude MDI.
Preference is given to adding the corresponding amount of orthophenylphenol or orthophenylphenol derivative to the monomers and thereby producing the corresponding monomers. For example, depending on the monomers used (monoisocyanates, diisocyanates, triisocyanates or polyisocyanates), substances can be formed which carry one or more, in particular one, two or three, o-phenylphenol groups. By the polymerization reaction, it is also possible to form a polymer chain having a terminal o-phenylphenol group.
The monomer or polymer can be used in a sealing compound, for example as an additive directly in a cartridge (cartridge) or in a separate compartment. The corresponding ortho-phenylphenol derivatives can also be added directly to the monomers of the sealing compound in the production of the sealing compound, in particular those based on urethanes. The use of reaction products of mono-, di-and/or triisocyanates with ortho-phenylphenol or derivatives thereof in sealing compounds is particularly preferred.
Suitable chain extenders which can additionally be used in the case of the polymerization for the production of the substances to be used according to the invention are, for example, polyols such as ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, trimethylolpropane, glycerol, pentaerythritol, sorbitol, mannitol or glucose. Low molecular weight polyester type diols such as di (hydroxyethyl) succinate, glutarate, or adipate, or a mixture of two or more thereof, or low molecular weight diols having an ether group such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, or tetrapropylene glycol may be used together. Amines are also suitable, such as ethylenediamine, hexamethylenediamine, piperazine, 2, 5-dimethylpiperazine, 1-amino-3-aminomethyl-3, 5, 5-trimethylcyclohexane (isophoronediamine, IPDA), 4' -diaminodicyclohexylmethane, 1, 4-diaminocyclohexane, 1, 2-diaminopropane, hydrazine hydrate, amino acid hydrazides such as 2-aminoacetic acid hydrazide, or dihydrazides such as succinic acid dihydrazide. In the case of the isocyanate polyaddition, it is also possible to use small amounts of tri-or higher-functional compounds at the same time in order to achieve a certain degree of branching, as for the same purpose it is possible to use (already mentioned) tri-or higher-functional polyisocyanates at the same time. Monoalcohols such as n-butanol or n-dodecanol and stearyl alcohol can be used simultaneously in small amounts.
According to a further preferred embodiment, support-bound forms of ortho-phenylphenol and/or the aforementioned ortho-phenylphenol derivatives can also be used according to the invention, in particular to incorporate cage molecules of ortho-phenylphenol and/or derivatives thereof.
"cage molecules" are to be understood in the context of the present invention as meaning, in particular, those organic macrocyclic molecules which have a cage-like three-dimensional structure and are capable, like the so-called host molecules, of being charged with one or more so-called guest molecules. Preferably only one guest molecule is charged in each case.
The desired slow release of the compound suitable for inhibiting the asexual reproduction of fungi can also take place through an equilibrium of bonds, which are usually not covalent bonds, or by complexing the compound from a cage molecule.
Because the cage material is a rather hydrophilic shell, the loaded cage molecules are particularly easy to incorporate into the products of the invention, especially into products that are more hydrophilic in nature.
A great advantage of using cage molecules is the fact that substances which have diffused out of the product can be replaced after an extended period of time by recharging the cage molecules. Concentrated solutions of the aforementioned active substances are particularly suitable for this purpose. In this connection, it is likewise possible to produce products whose complexed or bound state in the cage molecules does not contain free active substances beforehand, but only to load them in the case of use. This is useful in terms of manufacturing techniques, for use in areas of use known to those skilled in the art.
Cucurbiturils (cucurbiturils), calixarenes (calixaresorcinolenes), cyclodextrins, cyclopropenes, crown ethers, fullerenes, cryptophanes, caged calixarenes (carcerands), semi-caged calixarenes (hemicerrans), cyclotrices (cyclovertrylenes), globular ligands (spherans) and cryptands can be described as organic cage molecules.
Cucurbiturils, calixarenes are particularly preferred according to the invention, very particularly cucurbiturils.
Cucurbiturils and their manufacture are described in the literature, for example WO 00/68332 and EP-A1094065 and others cited therein. Cucurbiturils which can be used for the purposes of the present invention are to be understood as meaning in substance all substances described in said document as belonging to this class of compounds. By definition, cucurbiturils and substituted cucurbiturils as described in WO 00/68232, and cucurbituril derivatives as described in EP-A1094065 are included herein. Instead of homogeneous cucurbiturils, substituted cucurbiturils or cucurbituril derivatives, mixtures of two or more such compounds may also be used. When cucurbiturils are mentioned hereinafter, unless otherwise expressly indicated, chemically homogeneous cucurbiturils are likewise to be understood, or else mixtures of two or more cucurbiturils, substituted cucurbiturils and/or cucurbituril derivatives are also possible. A quantitative indication of the corresponding cucurbiturils, unless expressly indicated otherwise, always refers to the total amount of one or more cucurbiturils, substituted cucurbiturils, and/or cucurbituril derivatives.
For the purposes of the present invention, cucurbit [ n ] ureas having rings of 5 to 11 size and mixtures thereof are preferred, particularly cucurbit [6] ureas and mixtures of cucurbit [6] ureas in the major part.
Calix [ n ] arenes according to formula (III) may additionally be used:
wherein
R1Is selected from R1H, alkyl, aryl, alkenyl, alkynyl and substituted alkyl, aryl, alkenyl, alkynyl with one OR more substituents selected from-OH, -OR', -NH2、-NHR′、-NR′R″、NR′R″R*+、NO2Halogen, SO3H、SO3M (alkali metal, alkaline earth metal), carboxylic acid, ketone, aldehyde, amide, ester, -SO2NH2、-SO2NHR、-SO2NR′R″、-SO2Halogen, sulfur-, phosphorus-, silicon-group-containing radicals,
and is
R2Is selected from R2H, alkyl, aryl, alkenyl, alkynyl and substituted alkyl, aryl, alkenyl, alkynyl with one OR more substituents selected from-OH, -OR', -NH2、-NHR′、-NR′R″、NR′R″R*+、NO2Halogen, SO3H、-SO3M (alkali metal, alkaline earth metal), carboxylic acid, ketone, aldehyde, amide, ester, -SO2NH2、-SO2NHR’、-SO2NR′R″、-SO2Halogen, sulfur-, phosphorus-, silicon-group-containing groups.
R', R ", R * are independently selected from H, alkyl, aryl, alkenyl, alkynyl, substituted alkyl, aryl, alkenyl, alkynyl.
Calixarenes according to formula (III), wherein
R1Is selected from R1=H、Alkyl, aryl, alkenyl, alkynyl and substituted alkyl, aryl, alkenyl, alkynyl bearing substituents selected from-OH, -OR', -NH2、-NHR′、-NR′R″、NR′R″R*+、NO2Halogen, SO3H. Carboxylic acids, ketones, aldehydes, amides, esters, -SO2The group of NR 'R' is,
and is
R2Is selected from R2H, alkyl, aryl, alkenyl, alkynyl and substituted alkyl, aryl, alkenyl, alkynyl with one OR more substituents selected from-OH, -OR', -NH2、-NR′R″、NR′R″R*+、-NO2Halogen, SO3H. Carboxylic acids, ketones, aldehydes, amides, esters, -SO2The group of NR 'R' is,
preferably, R', R ", R * are independently selected from H, alkyl, aryl, alkenyl, alkynyl and substituted alkyl, aryl, alkenyl, alkynyl.
For the purposes of the present invention, preference is given to calix [ n ] arenes having a ring size n ═ 4 to 12 and mixtures thereof, particular preference to calix [6] -and/or calix [4] arenes and also mixtures in which calix [6] -and/or calix [4] arene is the predominant fraction.
Also useful are calix [ n ] cyclic arenes, also known as calixarenes according to formula (IV), where n denotes the number of mer units and can be 4 or 6:
wherein R is1,R2And R3Selected from:
R1h, alkyl, aryl, alkenyl, alkynyl and substituted alkyl, aryl, alkenyl, alkynyl with a substituent selected from-OH, -OR, -NH2、-NHR′、-NR′R″、 NR′R″R*+、-NO2Halogen, SO3H、SO3M (alkali metal, alkaline earth metal), carboxylic acid, ketone, aldehyde, amide, ester、SO2NH2、SO2NHR、-SO2NR2、-SO2Halogen, sulfur-, phosphorus-, silicon-group-containing radicals,
and is
R2,R3Are independently from each other selected from R2,R3H, alkyl, aryl, alkenyl, alkynyl and substituted alkyl, aryl, alkenyl, alkynyl with a substituent selected from-OH, -OR, -NH2、-NHR、-NR′R″、NR′R″R*+、-NO2Halogen, -SO3H、-SO3M (alkali metal, alkaline earth metal), carboxylic acid, ketone, aldehyde, amide, ester, -SO2NH2、-SO2NHR、-SO2NR2、-SO2Halogen, sulfur-, phosphorus-, silicon-group-containing groups.
And wherein R', R ", R * are independently selected from H, alkyl, aryl, alkenyl, alkynyl and substituted alkyl, aryl, alkenyl, alkynyl.
Calix [4] cycloarene and/or calix [6] cycloarene according to formula (IV), wherein
R1Is selected from R1H, alkyl, aryl, alkenyl, alkynyl and substituted alkyl, aryl, alkenyl, alkynyl with one OR more substituents selected from-OH, -OR', -NH2、-NHR’、-NR′R″、NR′R″R*+、NO2Halogen, SO3H. Carboxylic acids, ketones, aldehydes, amides, esters, -SO2The group of NR 'R' is,
and is
R2,R3Are independently from each other selected from R2,R3H, alkyl, aryl, alkenyl, alkynyl and substituted alkyl, aryl, alkenyl, alkynyl with one OR more substituents selected from-OH, -OR', -NH2、-NR′R″、NR′R″R*+、-NO2Halogen, -SO3H. Carboxylic acids, ketones, aldehydes, amides, esters, -SO2The group of NR 'R' is,
preferably, R', R ", R * are independently selected from H, alkyl, aryl, alkenyl, alkynyl and substituted alkyl, aryl, alkenyl, alkynyl.
It is particularly preferred if R2=R3I.e. R2And R3Represent the same substituents.
According to a further embodiment, the ortho-phenylphenol or ortho-phenylphenol derivative is contained in an amount of up to 50 wt.%, preferably 1-20 wt.%, in particular 5-15 wt.%, in a carrier-bound form.
Advantageously, in the case of the use according to the invention, the fungi are neither inhibited from growing nor killed, but only the vegetative propagation is inhibited or suppressed. Therefore, the selection pressure for creating the tolerance is low.
It has surprisingly been found that the use of o-phenylphenol and/or derivatives thereof inhibits the asexual reproduction of fungi better than farnesol, i.e. at lower concentrations.
Another advantage of the present invention is that the o-phenylphenol and/or derivatives thereof are already effective at low final concentrations compared to fungicides or fungistats, thus causing little concern for unwanted side effects.
According to a preferred embodiment of the invention, the ortho-phenylphenol and/or derivatives thereof are used for inhibiting sporulation. Sporulation is understood to be both the formation of reproductive states, such as conidia, goniocytes, sporocysts, merospores, blastospores and organs associated therewith (for example conidiophores), and of permanent states (for example chlamydospores).
Since mold spores are present in the indoor air everywhere, mold infection cannot be prevented in principle. However, inhibiting the sporulation of growing mold colonies offers the possibility of significantly reducing the risk of mold allergy and completely interrupting or significantly slowing down the propagation of the fungus. Sporulation-induced staining is likewise greatly reduced or completely prevented.
The inhibition of sporulation with o-phenylphenol and/or derivatives thereof offers the further advantage that the concentration required for the inhibition of sporulation is surprisingly determined again to be lower compared to other sesquiterpenes, such as farnesol. Thus, even with lower concentrations of active substance, comparable effects can be achieved.
According to a preferred embodiment, the orthophenylphenol and/or its derivatives are used in such a final concentration that they do not have a fungicidal (fungicidal) or fungistatic (fungistatic growth) effect. A particular advantage of this embodiment is that the risk of developing tolerance is low compared to the substances used, since the fungi are neither killed nor inhibited from growing. The minimum inhibitory concentration is readily determined in a manner known to those skilled in the art.
In another embodiment, the use of o-phenylphenol and/or derivatives thereof, optionally in carrier bound form, in combination with fungicides, especially fungicides, is used at very low, especially non-fungicidal and non-fungistatic o-phenylphenol concentrations. The combined use advantageously results in a synergistic effect, such that on the one hand the microorganisms are killed or their maturation is inhibited by the biocide and on the other hand any surviving microorganisms are inhibited from vegetative propagation by the o-phenylphenol and/or derivatives thereof. Also in this application form, the development of tolerance to o-phenylphenol is prevented due to the low concentration of o-phenylphenol. The agents described according to the invention contain, in addition to the o-phenylphenol and/or its derivatives, at least one biocide, in particular a fungicide, and are therefore also subject matter of the present invention. The biocide can be selected from, in particular, biocides as described in the following citations:
K.H. Wallhauser, "Praxis der Sterilisation, Desnfektion, Konservierung" [ Sterilization, Disinfection, preservation practice ], revision 5, 1995(ISBN3134163055), Georg Thieme Verlag, Stuttgart, in particular, Table 1.60 (page 103-105), Table 5.11 (page 406), Table 5.12 (page 407), Table 5.13, Table 5.14, Table 5.15 (page 412-414), Table 6.5, Table 6.6 (page 426), tables 6.7 and 6.8, page 434, FIGS. 6.4, 6.5, 6.6 and 6.8, Table 6.13 (page 436), and Chapter 7 ("Antimicrobijournel" [ antimicrobial active substance ], page 465 and later.),
S.S.Block, "Disinfection, Sterilization, and Preservation", 5 th edition, 2000(ISBN 0-683-30740-1), Lippincott Williams & Wilkens, Philadelphia, in particular tables 7.2, 8.1, 8.2, 9.5, 9.6, 9.7, 9.11, 9.12, 9.13, 9.14, 10.3, 12.2-12.6, 13.1-13.4, 14.1, 14.2, 14.6, 14.7, 14.8, 14.17, 14.19-14.25, 15.1, 16.2, 17.2, 17.3, 18.1, 18.2, 19.1 and 20.2, and FIGS. 13.1 and 20.1-20.4,
tested according to "Richtlinien fur die fur chemischer Designofektionsite" [ guidelines for testing chemical disinfectants ] and found by Deutsche Gesellschaft fur Hygene und Mikrobiologie [ German society for Hygiene and microbiology ] as a list of effective disinfection methods, mhp-Verlag GmbH, Wiesbaden.
The content of o-phenylphenol and/or derivatives thereof contained in the agent of the present invention is preferably from 0.000001 to 2% by weight. A particular advantage of this embodiment is that these substances need only be present in low concentrations in order to reduce or substantially completely prevent the asexual propagation of the fungus. The o-phenylphenol and/or the derivative thereof is preferably contained in an amount of 0.00001 to 1% by weight, particularly 0.00001 to 0.1% by weight. Particularly preferred ranges are between 0.00005 and 0.05 wt.%, in particular between 0.00005 and 0.005 wt.%.
In the final product, the concentration which gives rise to the desired effect is considerably lower than indicated, since for many products the dilution effect has to be taken into account. For detergents, for example, a dilution factor (detergent concentration: water ratio) of 1: 20 to 1: 200 must be taken into account. The dilution ratio of the detergent is generally between 1: 60 and 1: 100, for example 1: 80. In the final use solution, especially at concentrations of 0.001 to 1% by weight, excellent spore formation inhibition was exhibited. Preferably, 0.001 to 0.1% by weight, for example 0.001% by weight, is used.
O-phenylphenol and/or the sameThe action of the derivatives according to the invention is particularly suitable for inhibiting the action of the compounds included in DSMZ (Deutsche Stammsamlung von Mikroorganismen undZellkulturen GmbH [ German Collection of microorganisms and cell culture strains]Braunschweig) of the lines catalog "DSMZ-List of Filamentous Fungi" and "DSMZ-List of Yeasts". The directory can be browsed in the corresponding web site on the internet (http://www.dsmz.de/species/fungi.htm) And (a)http://www.dsmz.de/species/yeasts.htm)。
The substances used according to the invention, orthophenylphenol and/or derivatives thereof, are preferably used for inhibiting the asexual reproduction of fungi. Among these are, for example, the human pathogenic species of the phylum Ascomycota (Ascomycota), Basidiomycota (Basidiomycota), Deuteromycota (Deuteromycota) and Zygomycota (Zygomycota), in particular of the genera Aspergillus (Aspergillus), Penicillium (Penicillium), Cladosporium (Cladosporum), and Mucor (Mucor), all the species Candida (Candida) and Stachybotrys (Stachybotrys), Phoma (Phoma), Alternaria (Alternaria), Aureobasidium (Aureobasidium), Monospora (Ulocladium), Epicoccum (Epicoccum), Phosphaera (Stemphyllium), Penicillium (Paecilomyces), Trichoderma (Trichoderma), Scopularis (Scopularis), Wallem (Wallemia), Trichoderma (Trichoderma), Trichoderma (Chaetobacter), Chaetomium (Trichoderma), and Chaetomium (Trichoderma).
The phylum Ascomycota here includes, in particular, all species of the genera Aspergillus, Penicillium and Cladosporium. Spores formed by these fungi have a strong potential to provoke allergies upon contact with the skin or respiratory tract. Included among the Basidiomycota are, for example, Cryptococcus neoformans (Cryptococcus neoformans). Included in the incomplete phylum are all species known as filamentous fungi, particularly those species that are not assigned to Ascomycota, Basidiomycota or zygomycota because of lack of sexual stage.
The use of o-phenylphenol and/or derivatives thereof according to the invention is particularly preferred for inhibiting the sporulation of all species of the genus Aspergillus, particularly preferred species being selected from Aspergillus aculeatus (Aspergillus aculeatus), Aspergillus kawamori (Aspergillus albus), Aspergillus allii (Aspergillus allieus), Aspergillus aspergilli, Aspergillus awamori (Aspergillus awamori), Aspergillus leukawachii (Aspergillus candidus), Aspergillus carbonarius (Aspergillus carbonarius), Aspergillus carneus (Aspergillus carbonarius), Aspergillus glauceus (Aspergillus carbonarius), Aspergillus kawachii (Aspergillus kawakawari), Aspergillus awamori (Aspergillus kawakawakawakamii), Aspergillus awamori (Aspergillus var. intemperatus), Aspergillus clavatus (Aspergillus nidulans), Aspergillus niger (Aspergillus nidulans), Aspergillus nidulans (Aspergillus nidulans), aspergillus alba (Aspergillus niger), Aspergillus ochraceus (Aspergillus ochraceus), Aspergillus oryzae (Aspergillus oryzae), Aspergillus oricus (Aspergillus oryzae), Aspergillus fumigatus (Aspergillus oryzae), Aspergillus parasiticus (Aspergillus flavidus), Aspergillus fumigatus (Aspergillus niger), Aspergillus rugosus (Aspergillus rugosus), Aspergillus nidus sclerotiorum (Aspergillus sclerotiorum), Aspergillus sojae (Aspergillus sojae, Aspergillus oryzae), Aspergillus sojae (Aspergillus oryzae var. oryzae), Aspergillus oryzae (Aspergillus syphilis), Aspergillus sojae (Aspergillus oryzae), Aspergillus oryzae (Aspergillus sydowii), Aspergillus oryzae (Aspergillus niger), Aspergillus terreus (Aspergillus terreus), Aspergillus terreus (Aspergillus sydowii), Aspergillus oryzae (Aspergillus terreus), Aspergillus terreus (Aspergillus terreus) and Aspergillus terreus (Aspergillus terreus), Aspergillus terreus (Aspergillus terreus.
According to a particularly preferred embodiment, the orthophenylphenol and/or derivatives thereof are used in a particularly preferred manner to inhibit the sporulation of Aspergillus species, said Aspergillus being selected from Aspergillus flavus and Aspergillus nidulans.
Further subject matter of the invention are detergents, cleaning agents, rinsing agents, hand lotions, manual dishwashing agents, automatic dishwashing agents, agents suitable for finishing filter media, building materials, construction auxiliaries, textiles, furs, paper, leather or leather products, which contain orthophenylphenol and/or derivatives thereof, for inhibiting asexual reproduction.
The invention also relates to filter media, building materials, construction auxiliaries, textiles, furs, papers, leathers or leather products which contain orthophenylphenol and/or derivatives thereof and/or have been finished with the agents according to the invention.
Finishing of paper, textiles, wall hanger materials, furs, leather or leather products can be carried out in a manner known to the person skilled in the art, for example by dipping the paper or textile furs, leather or leather products into a solution of the agent according to the invention in an appropriate concentration.
Finishing of the filter medium, construction material or construction aid can be accomplished, for example, by mechanically bonding or applying a suitably concentrated chemical agent according to the invention into or onto the filter medium, construction material or construction aid. The ortho-phenylphenol and the solutions of ortho-phenylphenol, preferably in organic solvents, can advantageously be applied or incorporated particularly effectively onto or into the building materials and auxiliary materials. By using the chemical agents according to the invention, an auxiliary finishing of the building materials and auxiliary materials, or a recharging of previously finished building materials or auxiliary materials after a long period of use, as is the case for example with sealing compounds, will thus be possible easily.
The building materials or building auxiliaries finished according to the invention are preferably selected from the group consisting of adhesives, sealants, filling and coating compounds, plastics, lacquers, paints, wall plasters, mortars, paving plasters, concrete, insulating materials and primers. Particularly preferred building materials or building auxiliaries are joint sealing compounds (e.g.silicone-containing joint sealing compounds), wallpaper glues, wall plasters, carpet holding agents, silicone adhesives, dispersion paints, indoor and/or outdoor paint compounds, and tile adhesives.
Sealing compounds, in particular joint sealing compounds, generally contain organic polymers and, in many cases, inorganic or organic fillers and other additives.
Suitable polymers are, for example, the thermoplastic elastomers described in the applicant's DE-A-3602526, preferably polyurethanes and acrylates. Suitable polymers are also listed in the applicant's German applications DE-A-3726547, DE-A-4029504 and DE-A-4009095, and DE-A-19704553 and DE-A-4233077, which are incorporated herein by reference in their entirety.
The sealing compound (sealant or sealant mixture) according to the invention preferably contains 0.000001 to 2, in particular 0.00001 to 1, particularly preferably 0.00001 to 0.1, especially 0.00005 to 0.05, in particular 0.00005 to 0.005% by weight of orthophenylphenol and/or its derivatives.
According to the invention, finishing of the inventive sealant can be done in the cured state or in the state cured below 60 ℃. In the context of the present invention, the sealant is a material in accordance with DIN EN26927, in particular one which is shaped or cured elastically as a sealant. The sealant according to the invention can contain all the additives typical of corresponding sealing compounds, such as typical thickeners, reinforcing fillers, crosslinking agents, crosslinking catalysts, pigments, adhesives or other compatibilizers. The orthophenyl phenol and/or its derivatives may be incorporated into and a portion of the finished sealant compound or combined with one or more components of the sealant compound by dispersing in a manner known to those skilled in the art, such as by using a dispersing apparatus, blender, planetary mixer, or the like, and venting moisture and oxygen.
The treatment of the surface of the previously cured, crosslinked sealing compound, which may itself be carried out by applying a solution or suspension of the substance used according to the invention, is based on the fact that the active substance has been transferred into the sealing compound by diffusion or dispersion.
Sealants usable according to the invention can be based on silicones, urethanes and acrylics or, for example, be made based on MS-polymers. Urethane-based sealants are disclosed, for example, in Ullmann's Encyclopedia of Industrial Chemistry (8 th edition 2003, Chapter 4) and US 4,417,042. Silicone sealants are known to those skilled in the art, for example, from EP 0118030A, EP 0316591A, EP 0327847A, EP 0553143A, DE 19549425 a and US 4,417,042. Examples of acrylic sealants are also disclosed in particular in WO 01/09249 or US 5,077,360. Examples of sealants based on MS polymers are disclosed in, for example, EP 0824574, US 3,971,751, US 4,960,844, US 3,979,344, US 3,632,557, DE 4029504, EP 601021 or EP 370464.
Systems which crosslink at room temperature as described, for example, in EP 0327847 or US 5,077,360 are particularly preferred. These may be single-component or multi-component systems-in which the catalyst and the crosslinking agent may be present separately (as disclosed, for example, in U.S. Pat. Nos. 4,891,400 and 5,502,144) -or else so-called silicone RTV 2K systems, in particular platinum-free systems.
Particularly preferred are so-called one-component systems which contain all the components for forming the sealing compound, are protected from atmospheric moisture and/or atmospheric oxygen, and cure by reaction with atmospheric oxygen at the point of use. So-called neutral silicone systems are particularly preferred, in which the reaction of the crosslinking agent with water in the surrounding air does not lead to corrosive, acidic, basic or odor-intensive cleavage products. Examples of such systems are disclosed in DE 19549425, US 4,417,042 or EP 0327847.
The sealing compound and, in particular, the joint sealing compound can contain an aqueous or organic solvent. Suitable organic solvents are hydrocarbons such as cyclohexane, toluene, or also xylene or petroleum ether. Further solvents are ketones, such as methyl butyl ketone, or chlorinated hydrocarbons.
The sealing compound additionally contains more rubbery polymer. Commercially available grades of polyisobutylene, polyisoprene or also polybutadiene/styrene of relatively low molecular weight are suitable for use herein. It is also possible to use degraded natural rubber or neoprene at the same time. It is also possible to use here a rubber which is characterized by being flowable at room temperature, which is often referred to as "liquid rubber".
The sealing compound according to the invention can be used for sealing or joining a wide range of materials to one another. Use can be made here primarily of concrete, glass, plaster and/or glazed surfaces, but also of ceramics and porcelain. However, it is also possible to join or seal shaped parts or profiles made of aluminium, steel, zinc, or even plastics such as PVC or polyurethane or acrylics. Finally, sealing of wood or wooden materials with a variety of other materials may be mentioned.
The durability of the joint sealing compound is usually achieved by the addition of finely divided particulate solids, also known as fillers. These can be classified into those of organic nature and those of inorganic nature. Silicic acid/silica (coated or uncoated), chalk (coated or uncoated) and/or zeolites can be preferred as inorganic fillers. In addition, the zeolite also functions as a desiccant. Suitable organic fillers are, for example, PVC powder. The filler material generally contributes substantially to the essential inherent adhesion of the sealing compound after use, thereby preventing the sealing compound from running off or protruding from the outside of the vertical joint. The aforementioned additives or fillers can be divided into pigments and thixotropic fillers, also known as thixotropic agents.
Suitable thixotropic agents are known thixotropic agents such as bentonite, kaolin or also organic compounds such as hydrogenated castor oil with polyfunctional amines or derivatives thereof, or reaction products of stearic acid or ricinoleic acid with ethylenediamine. The silicic acid used at the same time, in particular from pyrolysis, has proven particularly suitable. In addition, expandable polymer powders are suitable as thixotropic agents. Examples thereof are polyacrylonitrile, polyurethane, polyvinyl chloride, polyacrylates, polyvinyl alcohol, polyvinyl acetate and corresponding copolymers. Particularly good results are obtained with a particulate polyvinyl chloride powder. Adhesion promoters such as, for example, mercaptosilanes, may also be used, as may thixotropic agents. The use of monomericaproalkyltrialkoxysilanes (monomericotralkyltrialkoxysilanes) has proven useful. For example, Mercaptopropyltrimethoxysilane (mercaptopropyltrysilane) is commercially available.
The properties of the seam-sealing compound can be improved even further if still further ingredients are added to the plastic powder used as thixotropic agent. These substances fall within the category of plasticizers, expanding agents and expansion aids for plastics.
In particular for urethane-based or acrylic-based sealing compounds, it may occur, for example, that the plasticizer is selected from the phthalic acid esters. Examples of suitable compounds in this substance class are dioctyl phthalate, dibutyl phthalate, and benzylbutyl phthalate. Further suitable substance classes are chlorinated paraffins, alkylsulfonates, for example phenol or cresol, and fatty acid esters.
Silicone oils, particularly preferably polydimethylsiloxanes, and also hydrocarbons and/or mixtures thereof, in particular hydrocarbons having a boiling point of above 200 ℃ and especially above 230 ℃ or mixtures thereof, are suitable as plasticizers for silicone sealing compounds.
Those low molecular weight organic substances which are miscible with the polymer powder and the plasticizer may be used as the expanding agent. Such swelling agents can be deduced from the handbooks for relevant plastics and polymers for the person skilled in the art. Esters, ketones, aliphatic hydrocarbons, aromatic hydrocarbons and aromatic hydrocarbons with alkyl substituents are used as preferred expansion aids for polyvinyl chloride powders.
The pigments and dyes used are substances known for these applications, such as titanium dioxide, iron oxide and carbon black.
To improve shelf life, it is known to add seal compound stabilizers such as benzoyl chloride, acetyl chloride, methyl tosylate, carbodiimides and/or polycarbodiimides. Olefins having 8 to 20 carbon atoms have proven to be particularly good stabilizers. In addition to the stabilizing effect, it may also perform the function of a plasticizer or bulking agent. Preference is given to olefins having from 8 to 18 carbon atoms, especially if the double bond is in the 1, 2-position. The best results are obtained when the molecular structure of these stabilizers is linear.
With the use of o-phenylphenol and/or derivatives thereof according to the invention for inhibiting the asexual reproduction of fungi, the problem of tolerance due to the biocidal active ingredient is overcome. When used in building materials and adjuvants susceptible to moulds, especially in adhesives, paint compounds, and sealing compounds, particularly preferably in joint sealing compounds, several satisfactory results can be achieved due to the inhibition of sporulation:
a) preventing stains caused by pigmented spores;
b) delay of spread of fungal infection;
c) reduce the allergic effect.
A further preferred subject of the invention is a wallpaper adhesive containing 0.000001 to 2% by weight of o-phenylphenol and/or derivatives thereof. Examples are wallpaper glues made from aqueous solutions of hydrocolloids such as methylcellulose, methylhydroxypropylcellulose or water-soluble starch derivatives. Aqueous dispersions of film-forming high molecular weight substances, such as polyvinyl acetate, can also be used, in particular in combination with the abovementioned cellulose and starch derivatives.
As regards the filter medium, all known types are available, as long as they are suitable for use in water-or air-filtration systems. Mention may in particular be made of cellulose, glass fibres, PVC fibres, polyester fibres, polyamide fibres, in particular nylon fibres, filter materials made of non-woven fibres, sintered materials and membrane filters.
The concentration of the agent of orthophenylphenol and/or a derivative thereof for inhibiting asexual propagation of fungi according to the invention can be varied widely by the person skilled in the art depending on the conditions of use of the agent.
The washing and/or cleaning agents according to the invention preferably contain 0.000001 to 2, particularly preferably 0.00001 to 1, particularly preferably 0.00001 to 0.1, in particular 0.00005 to 0.05, especially 0.00005 to 0.0005 wt.% of orthophenylphenol and/or its derivatives.
The agents according to the invention are prepared according to the usual formulations known to the person skilled in the art. The ortho-phenylphenol and/or derivatives thereof are preferably added to the reagent once it has been completely prepared, but may be added during the preparation process if desired.
Inhibiting the asexual reproduction of fungi on textile or plastic surfaces often prevents reinfection of previously infected body areas. Inhibiting the asexual reproduction of fungi on ceramics, plastics or metals, and reducing the risk of infection or reinfection without stressing the skin, mucous membranes, and waste water with bactericidal substances or bactericidal action. The use of o-phenylphenol and/or derivatives thereof in e.g. rinsing or cleaning agents may also substantially protect catheters made of plastic or metal as well as other medical devices and/or prostheses from fungal infections.
According to a further embodiment, the o-phenylphenol and/or derivatives thereof are added to the washing and/or cleaning agent. Modern textile fibers, which cannot be cleaned with full strength detergents or at high temperatures, with the customary fine fabric detergents or at washing temperatures of 30 or 40 ℃, are in particular not completely free of fungi. The advantage of using the substances suitable for use according to the invention in detergents and cleaners is that despite a low degree of wastewater influence and a low degree of risk of developing tolerance, the laundry can be protected from spore-forming fungi.
Ortho-phenylphenol and/or derivatives thereof may also be added in accordance with the present invention to cleaners for cleaning hard surfaces, e.g., floors, tiles, floor tiles, plastics and other hard surfaces in the home, especially in high moisture areas (e.g., bathrooms), or in clinical practice where they may prevent unwanted surface stains due to the formation of colored spores (e.g., black for aspergillus niger). But also protects the shower curtain and other bathroom fabrics, as well as plastics, from mold-related stains.
"detergents and cleaning agents" are to be understood in the broadest sense in the context of the present invention as preparations containing surfactants in the solid state (granules, powders, etc.), in the semi-solid state (pastes, etc.), in the liquid state (solutions, emulsions, suspensions, gels, etc.), and in the gas-like state (aerosols, etc.), which usually contain a surfactant or surfactants in addition to other ingredients usually used for their respective purpose in order to produce advantageous effects in the application. Examples of such surfactant-containing preparations are surfactant-containing detergent preparations, surfactant-containing hard-surface cleaners, or surfactant-containing brightener preparations, each of which may be solid or liquid, and may also be present in a situation in which the amounts of the components or parts thereof, including solid or liquid components, are juxtaposed to one another.
Detergents and cleaning agents can contain ingredients which may be conventionally included, such as anionic, nonionic, cationic and amphoteric surfactants, inorganic and organic builder substances, specific polymers (e.g. those having co-builder properties), suds suppressors, dyes, and optionally additional perfumes (perfumes), bleaching agents (e.g. peroxygen bleaches and chlorine bleaches), bleach activators, bleach stabilizers, bleach catalysts, enzymes, and graying inhibitors, these groups of substances not being limited by the ingredients. Important ingredients of the formulations are often also detergency builders, which are known by way of example and without limitation as optical brighteners, UV-protecting substances, so-called stain repellents (i.e.polymers which hinder recontamination of the fibres). The individual substance groups will be explained in further detail later.
In the case of formulations which are present at least partly as shaped units, binding and decomposition auxiliaries may also be present.
Anionic, nonionic, zwitterionic and cationic surfactants can be used as surfactants.
Anionic surfactants which may be used are, for example, the sulfonates and sulfates. The possibility of using sulfonates as surfactants is that C is preferred9-13Alkylbenzenesulfonates, olefin sulfonates, i.e. mixtures of olefin-and hydroxyalkane sulfonates, and disulfonates, e.g. derived from compounds having terminal or internal double bondsC12-18Monoolefins, those obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation product. Also suitable are compounds from C12-18Alkanes, for example alkane sulfonates, obtained by chlorosulfonation or sulfoxidation with subsequent hydrolysis and neutralization. Esters (ester sulfonates) of 2-sulfofatty acids, such as hydrogenated coconut oil fatty acids, palm oil fatty acids, or 2-sulfonated methyl esters of tallow fatty acids, are also suitable.
Further suitable anionic surfactants are sulfonated fatty acid glycerides. "fatty acid glycerides" is understood to mean mono-, di-and triglycerides, and mixtures thereof, which are obtained during production by esterification of monoglycerides with 1 to 3 mol of fatty acids, or by transesterification of triglycerides with 0.3 to 2 mol of glycerol. Preferred sulfonated fatty acid glycerides are the sulfonation products of saturated fatty acids having from 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
The preferred alk (en) yl sulfate is C12-C18Fatty alcohols, e.g. from coconut fatty alcohol, tallow alcohol, lauryl alcohol, myristyl alcohol, cetyl or stearyl alcohol or C10-C20Sulfuric acid half esters of oxo alcohols, and alkali salts, especially sodium salts, of those half esters of those secondary alcohols of chain length. Also preferred are alk (en) yl sulfates of the above chain lengths, containing synthetic linear alkyl groups generated on a petrochemical basis, which have decomposition properties similar to those of suitable compounds based on fatty chemical starting materials. Among the detergents and cleaners, C is preferred12-C16Alkyl sulfates and C12-C15Alkyl sulfates, and C14-C15An alkyl sulfate. For example, 2, 3-alkyl sulfates, manufactured according to U.S. Pat. Nos. 3,234,258 or 5,075,041 and available as commercial products from Shell Oil Company under the name DAN®Also suitable are anionic surfactants.
Ethoxylated with 1-6 moles of ethylene oxideStraight or branched C7-21Alcohols, e.g. 2-methyl-branched C with an average of 3.5 moles of Ethylene Oxide (EO)9-11Alcohols, or C with 1-4 EO12-18Sulfuric acid monoesters of fatty alcohols are also suitable. Due to their highly foaming properties, they are used in detergents and cleaning agents in relatively small amounts, for example in amounts of 1 to 5% by weight.
Further suitable anionic surfactants are salts of alkylsulfosuccinic acids, which are also referred to as sulfosuccinates or sulfosuccinates and represent monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols, in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C8-18Fatty alcohol groups or mixtures thereof. Particularly preferred sulfosuccinates contain fatty alcohol groups derived from ethoxylated fatty alcohols, which, in essence, represent nonionic surfactants (see description below). Secondly, particular preference is given to sulfosuccinates whose fatty alcohol radicals are derived from ethoxylated fatty alcohols having a defined homologue distribution. It is also possible to use alk (en) ylsuccinic acids having preferably 8 to 18 carbon atoms in the alk (en) yl chain, or salts thereof.
Further suitable anionic surfactants are, in particular, soaps. Salts of saturated fatty acid soaps, such as lauric, myristic, palmitic, stearic, hydrogenated erucic, and behenic acid, are suitable, such as soap mixtures from, in particular, natural fatty acids, such as coconut oil fatty acid, palm oil fatty acid, or tallow fatty acid.
Anionic surfactants, including soaps, can be present in the form of their sodium, potassium, or ammonium salts and in the form of soluble salts of organic bases, such as mono-, di-, or triethanolamine. Sodium or potassium salts, especially sodium salts, are preferred. The surfactant can also be used in the form of its magnesium salt.
In the context of the present invention, preference is given to said agents containing from 5 to 50% by weight, preferably from 7.5 to 40% by weight, in particular from 15 to 25% by weight, of one or more anionic surfactants.
The nonionic surfactant is preferably alkaneAlkoxylated, advantageously ethoxylated, in particular primary alcohols preferably having from 8 to 18 carbon atoms and having an average of from 1 to 12 mol of Ethylene Oxide (EO) per mole of alcohol, where the alcohol radical may be linear or preferably has a methyl branch in the 2-position, or can contain mixed linear or methyl-branching groups, as are usually present in oxo alcohols. However, alcohol ethoxylates having a linear radical made from alcohols of natural origin with 12 to 18 carbon atoms, such as from coconut, palm, tallow, or oleyl alcohol, and on average 2 to 8EO per mole, are particularly preferred. Preferred ethoxylated alcohols include, for example, C with 3EO or 4EO12-14Alcohols, C with 7EO9-11Alcohols, C with 3EO, 5EO, 7EO or 8EO13-15Alcohols, C with 3EO, 5EO or 7EO12-18Alcohols, and mixtures thereof, e.g. C with 3EO12-14Alcohols and C with 5EO12-18A mixture of alcohols. The degree of ethoxylation indicated represents a statistical average, which may be an integer or fractional number for a particular product. Preferably, alcohol ethoxylates exhibit a limited homolog distribution (═ narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12EO can also be used. Examples thereof are tallow alcohols with 14EO, 25EO, 30EO or 40 EO.
Other classes of nonionic surfactants which are preferably used, which can be as sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.
Another class of nonionic surfactants that can be advantageously used are Alkyl Polyglycosides (APGs). Suitable alkyl polyglycosides and the general formula RO (G)zIn accordance with the formula, where R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms in the 2-position, and G is a symbol which denotes a glycoside unit having 5 or 6 carbon atoms, preferably glucose. The glycosylation number Z is between 1.0 and 4.0, preferably between 1.0 and 2.0, in particular between 1.1 and 1.4.
It is preferred to use linear alkyl polyglycosides, i.e. alkyl polyglycosides in which the polysaccharide group is a glucose group and the alkyl group is a normal alkyl chain.
The surfactant-containing formulations according to the invention may preferably contain alkylpolyglycosides, preferably with an APG content of more than 0.2% by weight, based on the total formulation, for washing, dishwashing or cleaning purposes. It is particularly preferred that the surfactant-containing formulation contains APG in an amount of from 0.2 to 10% by weight, preferably in an amount of from 0.2 to 5% by weight, in particular in an amount of from 0.5 to 3% by weight.
Nonionic surfactants of the amine oxide type, such as N-cocoalkyl (cocalkyl) -N, N-dimethylamine oxide and N-tallowalkyl (tallowalkyl) -N, N-dihydroxyethylamine oxide, and fatty acid alkanolamides, are also suitable. The amount of these nonionic surfactants preferably does not exceed the amount of ethoxylated fatty alcohols, in particular not more than half thereof.
Further suitable surfactants are polyhydroxy fatty acid amides of the formula (IV)
Wherein R is4CO represents an aliphatic acyl group having 6 to 22 carbon atoms; r5Represents hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms; [ Z ]1]Represents a straight or branched chain polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known to be those which are generally obtainable by reductive amination of a reducing sugar with ammonia, an alkylamine, or an alkanolamine, and subsequent acylation with a fatty acid, fatty acid alkyl ester, or fatty acid chloride.
The compounds also belong to the class of polyhydroxy fatty acid amides (VI),
wherein R is6Represents a straight chain having 7 to 12 carbon atomsOr a branched alkyl or alkenyl group; r7Represents a linear, branched or cyclic alkyl or aryl group having 2 to 8 carbon atoms; r8Represents a linear, branched or cyclic alkyl or aryl or alkoxy group having 1 to 8 carbon atoms, preferably C1-4Alkyl or phenyl; [ Z ]2]Denotes straight-chain polyhydroxyalkyl groups in which the alkyl chain is substituted by at least two hydroxyl groups or is alkoxylated, preferably ethoxylated or propoxylated.
[Z2]Preferably by reductive amination of a reducing sugar, for example, glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy-or N-aryloxy-substituted compounds can then be converted into polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of alkoxides as catalysts, as described in WO-A-95/07331.
In addition to anionic and nonionic surfactants, cationic surfactants can also be preferably used.
Cationic surfactants may be mentioned in particular as fabric softening substances. Examples of cationic surfactants are, inter alia, quaternary ammonium compounds, cationic polymers and emulsifiers.
Suitable examples are quaternary ammonium compounds of the formulae (VII) and (VIII)
In (VII), RaAnd RbRepresents an acyclic alkyl group having 12 to 24 carbon atoms; rcRepresents saturated C1-C4An alkyl or hydroxyalkyl group; rdOr with Ra、RbOr RcThe same or an aryl group. X-Representing either halide, methyl sulfate, methyl phosphate, or phosphate ions, and mixtures thereof. Examples of such cationic compounds are didecyldimethylammonium chloride, bis (hydrogenated tallow alkyl) dimethylammonium chloride, or dihexadecyl ammonium chloride.
The compounds of formula (VIII) are the so-called esterquats. Esterquats are characterized by excellent biodegradability. Where R iseRepresents an aliphatic alkyl group having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds; rfRepresents H, OH or O (CO) Rh;RgIndependently represent RfH, OH or O (CO) Ri,RhAnd RiEach independently of the others, an aliphatic acyl group having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds. m, n and p each independently of one another have a value of 1, 2 or 3. X-is either a halide ion, a methyl sulfate ion, a methyl phosphate ion, or a phosphate ion, and mixtures thereof. R of preferred compoundsfContaining O (CO) RhRadical, RcAnd RhIs an alkyl group having 16 to 18 carbon atoms. Particularly preferred compounds are those wherein RgAnd further represents OH. Examples of compounds of the formula (VIII) are methyl-N- (2-hydroxyethyl) -N, N-di (tallowalkylacyloxyethyl) ammonium methosulfate, or bis- (palmitoyl) ethylhydroxyethylammonium methosulfate, or methyl-N, N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate. If quaternized compounds of the formula (VIII) having unsaturated hydrocarbyl chains are used, preferably the corresponding fatty acids of these acyl groups have an iodine value of between 5 and 80, preferably between 10 and 60, in particular between 15 and 45, and have a cis/trans isomer ratio (in% by weight) of more than 30: 70, preferably more than 50: 50, in particular more than 70: 30. Commercially available examples are methyl sulfates of methyl hydroxyalkyl dialkoxyalkylammonium acyloxyalkyl (methylhydroxyalkyldialkoxyalkylammonium methosulfates) marketed by Stepan under the trade name Stepandex®Or Dehyquat, a product known as Cognis®Or as Rewoquat, a product known as Goldschmidt-Witco®. Another preferred compound is the diester quat of formula (IX), commercially available under the name Rewoquat®W222 LM or CR 3099, providing not only softness but also stability and color protection.
RkAnd RlEach here, independently of the others, denotes an aliphatic radical having 12 to 22 carbon atoms and having 0, 1, 2 or 3 double bonds.
In addition to the above quaternary ammonium compounds, other known compounds, such as quaternary ammonium imidazoline compounds of formula (X), can also be used.
Wherein R ismRepresents H or a saturated alkyl group of 1 to 4 carbon atoms; rnAnd RoEach independently of the others, represents an aliphatic saturated or unsaturated alkyl group having 12 to 18 carbon atoms; rnMay additionally represent O (CO) RpWherein R ispRepresents an aliphatic saturated or unsaturated alkyl group having 12 to 18 carbon atoms; z represents an NH group or oxygen; x-Is an anion. q is taken to be an integer between 1 and 4.
Further suitable quaternary ammonium compounds are described by the formula (XI)
Wherein R isq,RrAnd RsIndependently of one another represent C1-4Alkyl, alkenyl or hydroxyalkyl; rtAnd RuIndependently of one another represent C8-28An alkyl group; r is a number between 0 and 5.
In addition to the compounds of the formulae (V) to (IX), short-chain water-soluble quaternary ammonium compounds can also be used, such as trihydroxyethylmethyl (methylsulfate) ammonium or alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides, and trihydrocarbylmethylammonium chlorides, such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, and tricetylmethylammonium chloride.
Protonated alkylamine compounds having softening action are also suitable, as well as non-quaternized protonated precursors of cationic emulsifiers.
Quaternized protein hydrolysates represent other cationic compounds which can be used according to the invention.
Suitable cationic polymers include polyquaternium polymers, as described in CTFAcosmetic Ingredient Dictionary (The Cosmetic, toiletty and fragrance Association, Inc., 1997), in particular polyquaternium-6, polyquaternium-7, and polyquaternium-10 polymers also known as polymerquats (Ucare Polymer IR 400; Amerchol), polyquaternium-4 copolymers, such as graft copolymers having a cellulose backbone and quaternary ammonium groups bound by allyldimethylammonium chloride, cationic cellulose derivatives such as cationic Guar, such as Guar hydroxypropyltrimonium chloride (Guar), and similar quaternized Guar derivatives (e.g., Cosmedia Guar, manufacturer: Cognis GmbH), cationic quaternized sugar derivatives (cationic alkylpolyglucosides), such as The commercially available product Glucquat®100, according to the CTFA nomenclature "laurylmethylgluceth (10) etherhydroxypropyldimethylammonium chloride", copolymers of PVP and dimethylaminomethacrylate, copolymers of vinylimidazole and vinylpyrrolidone, polymers and copolymers of aminosilicones.
Polyquaternised polymers (e.g.Luviquat Care from BASF) may also be used, as well as chitin-based cationic biopolymers and derivatives thereof, for example available under the trade name Chitosan®(manufacturer: Cognis).
Also suitable according to the invention are cationic silicone oils, for example the commercial products Q2-7224 (manufacturer: Dow Coming; stabilized trisilyldimethiconol amine), Dow Coming 929 emulsion (containing hydroxylamino-modified siloxanes, also known as aminopolydimethylsiloxanes), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker), Abil®Quat 3270 and 3272 (manufacturer: Goldschmidt-Rewo; diquaternary polydimethyl siloxane, Quaternary ammonium salt-80), and siliconequat Rewoquat®SQ 1(Tegopren®6922, manufacturer: Goldschmidt-Rewo).
Compounds of the formula (XII) are also suitable
It may be alkylamidoamines (alkylamidoamines) in their non-quaternized or quaternized forms as described. RvIt may be an aliphatic acyl group having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds. S may take a value between 0 and 5. RwAnd RxEach independently of the other represents H, C1-4Alkyl, or hydroxyalkyl. Preferred compounds are fatty acid amidoamines, such as are commercially available under the name Tego Amid®S18 stearamidopropyl dimethylamine, alternatively available under the name Stepandex®The 3-tallowaminopropyltrimethylammonium methosulfate of X9124 is characterized by not only good regulating action, but also colour conversion inhibiting action, in particular good biodegradability.
If cationic surfactants are used, they are preferably contained in the formulation in an amount of from 0.01 to 10% by weight, in particular from 0.1 to 3.0% by weight.
According to the invention, the total amount of surfactant in the agent may be between 5 and 50 wt.%, preferably between 10 and 35 wt.%.
In addition to surfactants, detergent builders are the most important ingredients in detergents and cleaners. Detergent builders commonly used in detergents and cleaning agents, i.e. in particular zeolites, silicates, carbonates, organic builders and even (if not already present against the environmental prejudice of their use) phosphates, may be included in the surfactant-containing formulations according to the invention.
Suitable plate crystalsSodium silicate having the general formula NaMSixO2x+1·H2O, wherein M represents sodium or hydrogen, x is a number between 1.9 and 4, y is a number between 0 and 20, preferably x has a value of 2, 3 or 4. Such crystalline sheet silicates are described, for example, in European patent application EP-A-0164514. Preferably, the crystalline, platelet-shaped silicate referred to by the above formula is such that M represents sodium and x is 2 or 3. Particularly preferred are beta-and delta-sodium disilicates Na2Si2O5·yH2O; betA-sodium disilicate can be obtained, for example, according to the process described in international patent application WO-A-91/08171.
Na2O∶SiO2Amorphous sodium silicates having a modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8, in particular from 1: 2 to 1: 2.6, which are delayed in dissolution and exhibit secondary washing properties, are also suitable. The dissolution delay can be generated in a variety of ways, as compared to conventional amorphous sodium silicate, such as by surface treatment, compounding, compaction/densification, or overdrying. The so-called X-amorphous silicates, which are described, for example, in German patent application DE-A-4400024, also exhibit a delay in dissolution compared with conventional water glass. The product exhibits crystallite domains of 10 to several hundred nm size, preferably up to 50nm, especially up to 20 nm. Particularly preferred are dense/compacted amorphous silicates, complex amorphous silicates, and overdried X-amorphous silicates.
If applicable, the fine-crystal synthetic zeolite containing bound water used is preferably zeolite A and/or zeolite P. Zeolite MAP®(e.g., Doucil A24, a commercial product of Crosfield Co.) is particularly preferred as the P-type zeolite. However, mixtures of zeolite X with A, X and/or P are also suitable. Also commercially available and preferably used in the context of the present invention are, for example, cocrystals of zeolite X and zeolite A (about 80% by weight of zeolite X), CONDEA Augusta S.p.A. under the trade name VEGOBOND AX®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 exhibit an average particle diameter of less than 10 μm (volume distribution; determination method: Coulter Counter) and preferably contain from 18 to 22% by weight, in particular from 20 to 22% by weight, of bound water.
It is also possible to use commonly known phosphates as builder substance, provided, of course, that the use is not to be avoided for environmental reasons. Orthophosphates, pyrophosphates and especially the sodium salts of tripolyphosphates are particularly suitable.
Suitable organic builder substances are, for example, polycarboxylic acids which can be used in the form of their sodium salts, "polycarboxylic acids" being understood as 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), as long as the use is not environmentally disadvantageous, and also mixtures thereof. Preferred salts are those of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. The acid itself can also be used. In addition to the detergency effect of the acids, they also generally have the properties of an acidifying component and further are able to establish a lower and mild pH for detergents or cleaners. Mention may be made herein of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and mixtures thereof.
Polymeric polycarboxylic acids are also suitable as builders. These are, for example, alkali metal salts of polyacrylic acids or polymethacrylic acids, for example those having a relative molecular weight of 500-70,000 g/mol.
In the context of the present invention, the molar amount indicated for the polymeric polycarboxylic acid is the weight average molar amount M of the corresponding acid formwIt is usually determined by using Gel Permeation Chromatography (GPC), a UV detector. The determination is carried out on the basis of external standard polyacrylic acid, since its structure is similar to the polymer to be investigated, giving rise to the actual molecular weight values. These values deviate significantly from the molecular weight values of polystyrene acid as standard. The molar weight determined by means of polystyrene acid is much higher than the molar weight indicated in the context of the present inventionMuch more.
Suitable polymers are, in particular, polyacrylates having a molecular weight of 2000-20,000 g/mol. Owing to their excellent solubility, short-chain polyacrylates of this group whose molar mass is 2000-10,000g/ml, particularly preferably 3000 to 5000g/mol, may in turn be preferred.
Copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid or acrylic acid or methacrylic acid with maleic acid, are likewise suitable. Copolymers of acrylic acid and maleic acid, which contain from 50 to 90% by weight of acrylic acid and from 50 to 10% by weight of maleic acid, have proven particularly suitable. The relative molecular weight, based on the free acid, is generally 70,000g/mol for 2000-50,000 g/mol, preferably 20,000-50,000g/mol, particularly preferably 30,000-40,000 g/mol.
The (co) polymeric polycarboxylates may be used either as a powder or as an aqueous solution. The content of (co) polymeric polycarboxylates in the detergents and cleaners according to the invention is preferably from 0.5 to 20% by weight, in particular from 3 to 10% by weight.
To improve the water solubility, the polymers can also contain allylsulfonic acid, allyloxybenzenesulfonic acid and methallylbenzenesulfonic acid as monomers.
Also particularly preferred are biodegradable polymers synthesized from two or more different monomer units, for example those containing as monomers salts of acrylic acid and maleic acid, and vinyl alcohol or a vinyl alcohol derivative, or those containing as monomers salts of acrylic acid and 2-alkylallyl sulfonate, and a sugar derivative.
Further preferred copolymers are those which preferably contain acrolein and acrylic acid/acrylate, or acrolein and vinyl acetate, as monomers.
Also mentioned as further preferred cleaning substances are polymeric aminodicarboxylic acids, salts thereof, or precursor substances thereof. Polyaspartic acid and its salts and derivatives, some of which have not only co-builder properties but also bleach-stabilizing action, are particularly preferred.
Other suitable cleaning substances are polyacetals which can be obtained by reacting dialdehydes with polyhydroxycarboxylic acids having from 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are derived from dialdehydes such as glyoxal, glutaraldehyde, terephthalylidene aldehyde, and mixtures thereof, and from polyhydroxycarboxylic acids such as gluconic acid and/or glucoheptonic acid.
Other suitable organic builders are dextrins, such as oligomers and polymers of carbohydrates, which can be obtained by partial hydrolysis of starch. The hydrolysis can be carried out by customary methods, such as acid-or enzyme-catalysis. Preferably, the average molar amount of hydrolysis products is in the range of 400-500,000 g/mol. Preference is given to polysaccharides having a Dextrose Equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, DE being a customary indicator of the reduction of polysaccharides compared with glucose, glucose having a DE of 100. Maltodextrin with a DE between 3 and 20 and dry glucose syrup with a DE between 20 and 37, and so-called yellow dextrins and white dextrins with higher molar amounts in the range of 2000-30,000g/mol, are all usable. Preferred are dextrins as described in British patent application 9419091.
The oxidized derivative of dextrin is the reaction product thereof with an oxidizing agent capable of oxidizing at least one alcohol function on the sugar ring to a carboxylic acid function. Oxidized oligosaccharides are also suitable; at C of the sugar ring6The oxidized products are particularly advantageous.
Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are also additionally suitable cleaning aids (co-builder). The ethylenediamine N, N' -disuccinate (EDDS) used for this is preferably in the form of its sodium or magnesium salt. Also preferred in this context are glycerol disuccinate and glycerol trisuccinate. Suitable amounts in the zeolite-and/or silicate-containing formulation are 3-15% by weight.
Other useful organic builders are, for example, acetylated hydroxycarboxylic acids and their salts, which can optionally also be present in the form of lactones and contain at least 4 carbon atoms and at least one hydroxyl group and up to two acid groups.
Other classes of substances with cleaning-aid properties are represented by phosphonates. These are, in particular, hydroxyalkane-and aminoalkane phosphonates. Among hydroxyalkane phosphonates, 1-hydroxyethane-1, 1-diphosphonate (HEDP) is very important as a cleaning aid. It is preferably used as the sodium salt, in which connection the disodium salt reacts in a neutral manner and the tetrasodium salt reacts in a basic manner (pH 9). Suitable aminoalkane phosphonates are preferably ethylenediaminetetramethylenephosphonate (DTPMP), diethylenetriaminepentamethylenephosphonate and its higher homologues. They are preferably used in the form of the sodium salts of neutral reaction, such as the hexasodium salt as EDTMP or the hepta-and octasodium salts as DTPMP. Among these phosphonates, HEDP is preferred as a builder. Furthermore, the aminoalkanephosphonates have a pronounced heavy metal binding capacity. It may therefore be preferred to use aminoalkane phosphonates, in particular DTPMP, or mixtures of the abovementioned phosphonates, in particular when the surfactant-containing preparations according to the invention also contain bleaching agents.
Furthermore, all compounds which form complexes with alkaline earth metal ions can also be used as cleaning assistants.
Production of H in water2O2Of the compounds used as bleaching agents, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other bleaching agents which may be used are, for example, sodium percarbonate, peroxypyrophosphate, hydrogen peroxide citrate, and H generation2O2Such as perbenzoate, peroxyphthalate, diperoxonanoic acid, phthalimidine peracid, or diperoxydodecanedicarboxylic acid. If cleaning or bleaching preparations for automatic dishwashing are to be produced, bleaching agents selected from organic bleaching agents may also be used. Typical organic bleaching agents are diacyl peroxides, such as benzil peroxide. Further typical organic bleaching agents are peroxyacids, alkyl peroxyacids and aryl peroxyacids, which are mentioned in particular as examples. Preferred representatives are (a) peroxybenzoic acids and ring-substituted derivatives thereof, such as alkyl peroxybenzoic acids, also peroxy-alpha-naphthoic acid and monoperoxy-o-naphthoic acidMagnesium phthalate, (b) aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, epsilon-phthalimidoperoxycaproic acid [ Phthalimidoperoxycaproic Acid (PAP)]O-carboxybenzoylaminoperoxyhexanoic acid, N-nonenamido-peroxyadipic acid, and N-nonenamido-peroxysuccinate, and (c) aliphatic and arylaliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperoxydecanoic acid, diperoxyabrassylic acid, diperoxyphthalic acid, 2-decylperoxybutane-1, 4-dicarboxylic acid, and N, N-terephthaloyl-di (6-aminoperoxyhexanoic) acid.
In order to achieve improved bleaching when washing or cleaning at temperatures of 60 ℃ and below, bleach activators may be added to the surfactant-containing formulations. In the case of perhydrolysis (perhydrolysis), compounds which yield aliphatic peroxycarboxylic acids, preferably containing 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acids can be used as bleach activators. Those having an O-and/or N-acyl group having the above-mentioned number of carbon atoms, and/or an optionally substituted benzoyl group are suitable. Preference is given to multiply acylated alkylenediamines, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1, 5-diacetyl-2, 4-dioxohexahydro-1, 3, 5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimines, in particular N-Nonanoylsuccinimide (NOSI), acylated hydroxybenzenesulfonates, in particular N-nonanoyl or isononanoyloxybenzenesulfonates (N-or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyols, in particular triacetin, ethylene glycol diacetate, and 2, 5-diacetoxy-2, 5-dihydrofuran.
In addition to or instead of traditional bleach activators, so-called bleach catalysts can also be incorporated into the surfactant-containing formulations. 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 nitrogen-containing tripod ligands, and ammine complexes of Co, Fe, Cu and Ru, are also useful as bleach catalysts.
Suitable enzymes are, in particular, those proteases, esterases, lipases, amylases, cellulases, and mixtures thereof. Particularly suitable enzyme-activating substances are obtained from strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus. Preference is given to using proteases of the subtilisin type, in particular those from Bacillus lentus (Bacillus lentus). Enzyme mixtures, such as proteases and amylases, or proteases and lipases, or proteases and cellulases, or cellulases and lipases, or proteases, amylases, and lipases or proteases, lipases and cellulases, but especially cellulase-containing mixtures, are of particular interest in this context. Peroxidases or oxidases have also proven suitable in certain cases. The enzyme may be adsorbed onto a carrier material and/or embedded in a substance with a shell in order to protect it from premature disintegration. The proportion of enzyme, enzyme mixture, or enzyme granulate in the surfactant-containing formulation according to the invention may be, for example, from about 0.1 to 5% by weight, preferably from 0.1 to about 2% by weight.
Optical brighteners are preferably suitable additives. Optical brighteners in detergents are generally used for this. Examples of optical brighteners are derivatives of diaminostilbene sulphonic acid (diaminostilbene sulfonic acid) or alkali metal salts thereof. Suitable are, for example, salts of 4,4 '-bis (2-anilino-4-morpholino-1, 3, 5-triazin-6-amino) stilbene-2, 2' -disulphonic acid or compounds of similar structure which carry a diethanolamino, methylamino, anilino or 2-methoxyethylamino group instead of a morpholino group. Substituted biphenyl styryl-type brighteners can also be present in the surfactant-containing secondary part (detergent-active formulation) according to the invention, such as the alkali salt of 4,4 ' -bis (2-thiostyryl) biphenyl, the alkali salt of 4,4 ' -bis (4-chloro-3-thiostyryl) biphenyl, or 4- (4-chlorostyryl) -4 ' - (2-thiostyryl) biphenyl. Mixtures of the above-mentioned brighteners can also be used.
Further additives which are preferred according to the invention are UV-protective substances. The UV absorber is capable of adsorbing to the treated fabric and improving the light fastness of the fiber and/or the light fastness of other formulation ingredients. "UV absorber" is understood to mean an organic substance (photoprotective filter) which absorbs ultraviolet radiation and reemit the absorbed energy in the form of long-wave radiation, such as heat. Compounds which exhibit the desired properties are, for example, compounds and derivatives of benzophenone which have substituents in the 2-and/or 4-position and which are effective by non-radiative deactivation. Also suitable are substituted benzotriazoles, for example water-soluble benzenesulfonic acid-3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Cibafast)®H) Acrylate (cinnamic acid derivative) substituted in the 3-position by phenyl and optionally in the 2-position by cyano, salicylic acid, organic Ni complexes, and natural substances such as umbelliferone and urocanic acid produced by the body. Of particular importance are biphenyl derivatives and especially 1, 2-stilbene derivatives, as described, for example, in EP 0728749A, and Tinosorb, commercially available from Ciba®FD or Tinosorb®And (6) FR. Mention may be made, as UV-B absorbers, of 3-benzylidene camphor and 3-benzylidene norcamphor and derivatives thereof, such as 3- (4-methylbenzylidene) camphor as described in EP 0693471B 1; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-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; benzophenone derivatives, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4 'methylbenzophenone, 2, 2' -dihydroxy-4-methoxybenzophenone; esters of benzalmalonic acid (benzalmalonic acid), preferably di-2-ethylhexyl 4-methoxyphenylmethylenemalonate; triazine derivatives, e.g. 2, 4, 6-trianilino- (p-carbo-2 ' -ethyl-1's described in EP 0818450A 1 '-hexyloxy) -1, 3, 5-triazine and octyl triazone, or dioctyl butanamide (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 0694521B 1. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium, and glycoammonium salts; 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 4- (2-oxo-3-bornylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidenemethyl) sulfonic acid and salts thereof.
Typical UV-A filters suitable for use are, in particular, the derivatives of benzoylmethane, such as 1- (4 '-tert-butylphenyl) -3- (4' -methoxyphenyl) propane-1, 3-dione, 4-tert-butyl-4 '-methoxybenzoylmethane (Parsol 1789), 1-phenyl-3- (4' -isopropylphenyl) propane-1, 3-dione, and enamine compounds, which are described in DE 19712033A 1 (BASF). Of course, UV-A and UV-B filters can also be used in mixtures. In addition to the above-mentioned soluble substances, insoluble photoprotective pigments, i.e. finely divided, preferably nanosized, metal oxides or salts, may also be used for this purpose. Examples of suitable metal oxides are, in particular, zinc oxide and titanium oxide, and also oxides of iron, zirconium, silicon, manganese, aluminum and cerium, and mixtures thereof. Silicates (talc), barium sulfate, or zinc stearate can also be used as salts. The oxides and salts have been used in the form of pigments in skin care and skin protection creams and cosmetics. The average particle size of the particles should be less than 100nm, preferably between 5 and 50nm, in particular between 15 and 30 nm. They may be spherical, but particles of this kind with an elliptical shape, or else particles from a spherical configuration, can also be used. The pigments can also be present in surface-treated form, i.e. hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, such as titanium dioxide T805 (Degussa) or Eusolex®T2000 (Merck). Suitable as hydrophobic coating agents are primarily silicon dioxide, and in particular trialkoxyoctylsiliconAlkanes or simethicons. Preferably micronized zinc oxide is used. Other suitable UV photoprotective filters can be inferred from the review by P.Finkel in the S FW-Journal 122, 543 (1996).
UV absorbers are generally used in amounts of from 0.01% to 5% by weight, preferably from 0.03% to 1% by weight.
Further additive packages preferred according to the invention are dyes, in particular water-soluble or water-dispersible dyes. Preference is given here to using dyes which are customarily used for improving the visual product appeal in detergents, dishwashing agents, cleaning agents and brighteners. The choice of the dyes is not difficult for the person skilled in the art, in particular because the customary dyes have an excellent shelf life and are insensitive to other ingredients of the detergent-active formulation and to light, without having a significant substantivity to textiles, in order not to dye them. According to the invention, the dyes are added to the detergents and/or cleaners according to the invention in an amount of less than 0.01% by weight.
Other classes of additives that may be added to the detergents and/or cleaners according to the invention are polymers. Suitable polymers are, on the one hand, polymers which, in the case of washing and cleaning or dishwashing, exhibit the properties of cleaning aids, i.e. for example polyacrylic acids, and also modified polyacrylic acids or corresponding copolymers. Another group of polymers are polyvinylpyrrolidone and other graying inhibitors, for example, copolymers of polyvinylpyrrolidone, cellulose ethers, and the like. Also preferred as possible polymers are the so-called antifouling agents, described in detail below.
The detergents and cleaning agents mentioned can also contain, as further additives according to the invention, so-called soil release agents, i.e. polymers which adsorb onto the fibers, have a positive effect on the ability of the fabrics to remove oils and fats and thereby clearly hinder recontamination. This effect becomes particularly pronounced when the soiled fabric has been previously washed several times with a detergent or cleaner containing the oil and fat-dissolving ingredients according to the invention. Preferred oil and fat-dissolving ingredients include, for example, nonionic cellulose ethers such as, for example, methylcellulose and methylhydroxypropylcellulose with from 15 to 30% by weight of methoxy moieties and from 1 to 15% by weight of hydroxypropyl moieties, based in each case on the nonionic cellulose ether, and also polymers of phthalic acid and/or terephthalic acid, and derivatives thereof, known from the prior art, in particular polycondensates of ethylene terephthalate and/or polyethylene terephthalate or anionically and/or nonionically modified derivatives thereof. Among them, sulfonated derivatives of phthalic acid polymers and terephthalic acid polymers are particularly preferred.
They can also contain solvents, especially when the formulations are liquids or gels. Examples of suitable solvents are mono-or polyhydric alcohols having 1 to 4 carbon atoms. Preferred alcohols are ethanol, 1, 2-propanediol, glycerol and any mixture thereof. The amount of solvent contained in the liquid formulation is 2 to 12% by weight, particularly about 1 and 5% by weight, based on the entire formulation.
The above-mentioned additives are added to the washing and/or cleaning agent in amounts of up to 30% by weight, preferably from 2 to 20% by weight.
According to a particular embodiment, liquid or solid detergents are particularly preferred. Also particularly preferred are detergents and cleaners suitable for the mild treatment of delicate or sensitive fabrics.
The list of detergent and cleaning agent components that can be present in a detergent, dishwashing agent, or cleaning agent according to the invention cannot be exhaustive, but only reproduces the necessary typical components of the chemical agent. Organic solvents can also be included in the chemical agent, particularly where the formulation is a liquid or gel. These are preferably monohydric or polyhydric alcohols having from 1 to 4 carbon atoms. Preferred alcohols in the chemical agent are ethanol, 1, 2-propanediol, glycerol and mixtures of these alcohols. In a preferred embodiment, these kinds of reagents contain 2-12 wt.% of the alcohol. The results obtained are particularly advantageous in a cleaner environment for hard surfaces when the weight ratio of surfactant to alcohol in the solution is between about 1: 1.5 and about 2: 1.
Hard surface cleaners, which can be applied to a surface in either a foaming or non-foaming form, are also particularly preferred. Advantageously, it is thereby possible to reduce or prevent mold spore propagation in the indoor air and spread of stains caused by mold spores in high-humidity areas.
In addition to the above-mentioned ingredients, the aqueous liquids used according to the invention can contain minor amounts of other active substances and additives which are normally used in detergents for hard surfaces. Examples of such active substances are lime-dissolving organic acids such as citric acid, acetic acid or lactic acid or water-soluble salts thereof, which are preferably present in the liquid in an amount of 2 to 6% by weight, based on the total aqueous liquid.
The cleaning agent which can preferably be used is used as a foam for cleaning on surfaces and as a result remains there for a longer period of time. Thereby greatly improving the cleaning effect. Foam generation is preferably generated once liquid emerges from the spray device. In the case of a manual spray pump, this can be achieved by a special configuration of the spray head which ensures that the liquid exiting the nozzle is mixed with a large amount of air, so that the liquid is impacted onto the surface as a foam. Spray pumps of corresponding construction are generally commercially available. In the case of use as an aerosol, the device must be prepared so that a sufficient amount of propellant gas always appears together with the liquid, by suitable construction taking into account the spraying mechanism of the cleaning liquid composition, and then a foam of the liquid is formed. If possible, must be shaken before use. The corresponding construction of the aerosol container, the suction tube and the valve is a routine practice for a person skilled in the art and will therefore not be described in further detail here. The amount of liquid sprayed onto the surface for cleaning during cleaning is typically between about 10g and about 60g/m2In particular from 20g to 40g/m2. The foam is generally distributed as uniformly as possible to the surface to be cleaned and then automatically exerts its cleaning action. However, it is preferred to wipe the surface clean thereafter with a wet cloth or sponge, which is occasionally rinsed with clean water in the case of large surfaces. Of course, the treated surface can be rinsed with water, but this is generally not necessary, since the residual detergent residue is completely transparent when dry and practically invisible.
The following examples are intended to illustrate the invention, but not to limit it.
Detailed description of the preferred embodiments
Example 1:
effect of o-phenylphenol (OPP) on Aspergillus niger sporulation
Each wort agar plate contained 100. mu.l of a microbial suspension of Aspergillus niger (DSM1988) (10)3CFU/ml). Different amounts of active substance (ethanol solution, final concentration see table below) have been added beforehand to the agar plates. The dishes were incubated at 25 ℃ for 3 days. Sporulation was visually assessed and the rate (%) of formation of the robe was determined. Except as otherwise indicated in the table below, the concentrations of the active substances used did not prevent the growth of the test strains. The effect of inhibiting growth or killing microorganisms can only occur at 0.05 wt.% OPP concentration. However, OPP concentrations below 50-fold have been able to completely inhibit sporulation without exhibiting growth-inhibiting effects.
Table 1:
| OPP concentration [% ]] | 0 | 0.00001 | 0.00005 | 0.0001 | 0.0005 | 0.001 | 0.005 | 0.05 | 0.1 | 1.0 |
| Sporulation [% ]] | 100 | 95 | 95 | 85 | 10 | 0 | 0 | Does not grow | Does not grow | Does not grow |
At elevated concentrations, sporulation was inhibited and was completely inhibited at the applied concentration of 0.001 wt.%.
Comparative experiment:
effect of farnesol on Aspergillus niger sporulation
Table 2:
| farnesol concentration [ mu.M ]] | 0 | 25 | 62.5 | 125 | 250 | 500 |
| Sporulation [% ]] | 100 | 90 | 75 | 50 | 10 | 0 |
Example 2:
effect of o-phenylphenol/silicate (OPP/SAE) on Aspergillus niger sporulation
Wort agar plates each contain 100. mu.l of a microbial suspension of Aspergillus niger (DSM1988) (10)3CFU/ml). Different amounts of active substance (ethanol solution, final concentration see table below) have been added beforehand to the agar plates. The dishes were incubated at 25 ℃ for 3 days. Sporulation was visually assessed and the rate (%) of formation of the robe was determined. The concentration of the active substance used does not prevent the growth of the strains examined.
Table 3: ortho-phenylphenol/silicates
| OPP/SEA concentration [% ]] | 0 | 0.00001 | 0.00005 | 0.0001 | 0.0005 | 0.001 | 0.005 | 0.01 |
| Sporulation [% ]] | 100 | 95 | 95 | 95 | 50 | 25 | 0 | 0 |
At elevated concentrations, sporulation was inhibited and was completely inhibited at the applied concentration of 0.005 wt.%.
Example 3:
| composition (I) | Measurement of |
| Methyl hydroxyethyl cellulose (300 m Pas in 2% aqueous solution, methoxy content 26%) | 500g |
| PVA acetate redispersion powder | 350g |
| Kaolin clay | 60g |
| Cellulose powder | 50g |
| Additive of 6 mol ethylene oxide and 1 mol nonyl phenol | 10g |
| Commercially available preservatives (based on isothiazoline derivatives) | 8g |
| O-phenylphenol | 0.1g |
Example 4:
| composition (I) | Measurement of |
| Methyl hydroxyethyl cellulose (5000 m Pas in 2% aqueous solution, methoxy content 19%) | 680g |
| Carboxymethyl starch (DS 0.22) | 300g |
| Additive of 4 mol ethylene oxide and 1 mol fatty alcohol | 15g |
| Commercially available preservatives (based on isothiazoline derivatives) | 10g |
| O-phenylphenol | 0.1g |
Example 5:
| composition (I) | Measurement of |
| Dispersion of commercial polyvinyl acetate (50% solids) | 500g |
| Water (W) | 200g |
| Methylhydroxyethyl cellulose (3000 m Pas in 2% aqueous solution) | 20g |
| Commercially available preservatives | 10g |
| O-phenylphenol | 0.1g |
The resulting mixture is stirred with water in a ratio of 1: 20(2) or 1: 25(3) or 1: 1(4) and used to attach commercially available wallpaper to a wall surface.
Example 6: liquid detergent
| Raw material | Amount (wt%) |
| C12-Cl8Fatty alcohol +7EO (Dehydol LT 7, Cognis) | 15 |
| C12-C14Fatty alcohol +2EO sulfate, sodium salt (Texapon N70, Cognis) | 7 |
| C8-18Fatty acid cut (cut) (coconut oil fatty acid, Edenor K12-18, Cognis) | 8 |
| Citric acid sodium salt | 1.5 |
| Enzyme | + |
| Dye material | + |
| Aromatic agent | + |
| O-phenylphenol | 0.2 |
| Water (W) | Complement 100 |
Claims (22)
1. Use of o-phenylphenol and/or derivatives thereof for inhibiting the asexual reproduction of fungi.
2. Use of a carrier-bound form of o-phenylphenol and/or derivatives thereof for inhibiting the asexual reproduction of fungi.
3. The use according to claim 2, wherein the carrier is a cage molecule.
4. Use according to any one of the preceding claims, wherein the derivative is an ester or ether of o-phenylphenol.
5. Use according to any one of the preceding claims, in which the asexual propagation of fungi selected from human pathogenic fungi, in particular from human pathogenic species in the phylum Ascomycota (Ascomycota), Basidiomycota (Basidiomycota), Deuteromycota (Deuteromycota) and Zygomycota (Zygomycota), preferably from all the species in the genera Aspergillus (Aspergillus), Penicillium (Penicillium), Cladosporium (Cladosporium) and Mucor (Mucor), and Candida (Candida) is inhibited.
6. The use according to claim 3, wherein the vegetative propagation of a fungus selected from all species of the genus Aspergillus, very particularly preferably from Aspergillus aculeatus (Aspergillus aculeatus), Aspergillus candidus (Aspergillus albus), Aspergillus allii (Aspergillus alliacea), Aspergillus aspergilli (Aspergillus awamori), Aspergillus niger (Aspergillus carbonarius), Aspergillus carneus (Aspergillus Carneus), Aspergillus awamori (Aspergillus chevalieri), Aspergillus awamori (Aspergillus awamori), Aspergillus awamori (Aspergillus niger. var. intermedius), Aspergillus clavatus (Aspergillus glacius), Aspergillus glaucus (Aspergillus glacius), Aspergillus niger (Aspergillus flavus), Aspergillus nidulans (Aspergillus nidulans), Aspergillus niger (Aspergillus nidulans, Aspergillus nidulans (Aspergillus nidulans), Aspergillus niger (Aspergillus niger) and Aspergillus nidulans (Aspergillus nidulans) are preferably used in the genus Aspergillus nidulans, Aspergillus kawakawakawakawakawakawakawakawakawakawakawakawakawakawakawar, Aspergillus alba (Aspergillus niger), Aspergillus ochraceus (Aspergillus ochraceus), Aspergillus oryzae (Aspergillus oryzae), Aspergillus oricus (Aspergillus oryzae), Aspergillus fumigatus (Aspergillus oryzae), Aspergillus parasiticus (Aspergillus oryzae), Aspergillus fumigatus (Aspergillus flavicus), Aspergillus rugosa (Aspergillus flavidus), Aspergillus nidulans (Aspergillus oryzae sclerosus) Aspergillus glactius, Aspergillus penicillicus (Aspergillus niger), Aspergillus sojae (Aspergillus sojae, Aspergillus oryzae) Aspergillus niger (Aspergillus oryzae), Aspergillus sojae (Aspergillus oryzae), Aspergillus oryzae (Aspergillus oryzae) Aspergillus oryzae, Aspergillus oryzae (Aspergillus oryzae) Aspergillus oryzae, Aspergillus oryzae (Aspergillus oryzae) Aspergillus oryzae, Aspergillus oryzae (Aspergillus oryzae) Aspergillus flavidus (Aspergillus oryzae), Aspergillus oryzae (Aspergillus niger), Aspergillus niger (Aspergillus terreus), Aspergillus terreus (Aspergillus terreus) and Aspergillus terreus (Aspergillus terreus) or Aspergillus terreus (Aspergillus terreus).
7. Use according to any one of the preceding claims, wherein the o-phenylphenol and/or derivatives thereof is used at a final concentration that has no effect on the fungicidal or fungistatic manner.
8. Use according to any of the preceding claims, wherein said use is in combination with a biocide.
9. Use according to any one of the preceding claims, wherein the o-phenylphenol and/or derivatives thereof is used in a concentration of 0.000001 to 2 wt.%.
10. Use according to any one of the preceding claims, wherein the o-phenylphenol and/or derivatives thereof are used in a formulation selected from detergents, cleaning agents, rinsing agents, hand washes, manual dishwashing agents, automatic dishwashing agents, and agents for finishing filter media, adhesives, building materials, building auxiliaries, textiles, furs, paper, leather or leather goods.
11. Use according to any of the preceding claims, wherein the asexual reproduction of fungi is inhibited in the interior or on the surface of textiles, ceramics, metals, filter media, building materials, construction auxiliaries, pelts, paper, leather products and/or plastics.
12. Detergents, cleaning agents, rinsing agents, hand washing agents, manual dishwashing agents, automatic dishwashing agents, and agents for finishing filter media, building materials, building auxiliaries, textiles, furs, paper, leather or leather products, which contain orthophenylphenol and/or derivatives thereof for inhibiting the asexual reproduction of fungi.
13. A filter medium, building material, construction aid, fabric, fur, paper, leather, or leather product finished with the agent of claim 12.
14. Washing and/or cleaning agent containing 0.000001 to 2 wt% of o-phenylphenol and/or derivatives thereof for inhibiting the asexual reproduction of fungi.
15. Washing and/or cleaning agent according to claim 14, wherein they are liquid or solid detergents.
16. Washing and/or cleaning agent according to claim 14, which refers to a cleaning agent for hard surfaces.
17. An adhesive comprising 0.000001 to 2% by weight of o-phenylphenol and/or derivatives thereof for inhibiting the asexual reproduction of fungi.
18. The adhesive of claim 17, wherein it is a water-based adhesive.
19. An adhesive according to claim 17 or 18, wherein it is an adhesive for the pasting of wallpaper and similar wall coverings.
20. A sealing compound contains 0.000001 to 2% by weight of o-phenylphenol and/or its derivatives to inhibit asexual propagation of fungi.
21. The sealing compound of claim 20, wherein it is a joint sealing compound.
22. The composition according to any one of claims 12-21, wherein it additionally comprises at least one biocide.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102004038104.6 | 2004-08-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| HK1101318A true HK1101318A (en) | 2007-10-12 |
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