Adhesion inhibition of moldno marking
The present invention relates to the use of monoterpenes, sesquiterpenes and/or diterpenes and derivatives thereof for reducing fungal adhesion to surfaces and to filter media, adhesives, building materials, auxiliary building materials, textiles, furs, paper, skin or leather, detergents, cleaning compositions, rinses, hand, machine dishwashing agents, and for finishing building materials, auxiliary building materials, textiles, furs, paper, skin or leather and compositions containing monoterpenes, sesquiterpenes and/or diterpenes or derivatives thereof.
Mold may be found everywhere in the home, for example in a kitchen or in a wet room such as a bathroom. Mold can cause serious problems because it often releases spores into the air causing allergies. The elimination of such fungi with biocides often causes an increase in the build-up of resistance, so that after a period of time new antimicrobial agents must be found to combat resistant microorganisms. In addition, biocides are not always ecologically and toxicologically safe.
Thus, antibacterial agents that exhibit the effect of inhibiting the growth of fungi (inhibiting fungicides) or eliminating them (fungicides) have been used. The antibacterial agents used for this purpose are often non-selective, i.e. destroy not only bacteria but also fungi. The disadvantage is that the corresponding biocides or biostatic agents used, for example, in detergents and cleaning agents contaminate the waste water and thus also damage the microbiological activity sites of the waste water treatment plants.
Thus, the problem to be solved by the present invention is to selectively remove moulds from or away from surfaces without fouling the surfaces, or to selectively remove moulds from or away from waste water, with fungicides and/or antimycotics.
This problem can be solved by using monoterpenes, sesquiterpenes and/or diterpenes to reduce the adhesion of the mould to the surface.
It has surprisingly been found that the use of monoterpenes, sesquiterpenes and/or diterpenes or derivatives thereof on or in materials infected with fungi can reduce or largely prevent the adhesion of the mould without damaging the mould.
By "reduced adhesion" is understood a significant reduction in the number of adhering moulds. Ideally, sticking is completely prevented. Preferably, adhesion of mold is reduced or substantially completely prevented.
An advantage of the present invention is that these substances are effective at lower final concentrations than fungicides or antimycotics, so that there is hardly any possibility and/or sign of side effects.
Furthermore, a reduction in adhesion by reducing contact of the human body, in particular the respiratory tract, with moulds or their spores can also lead to a reduction in the potential for causing allergies.
In particular embodiments, the monoterpene, sesquiterpene and/or diterpene or derivative thereof may be selected from alcohols, such as farnesol, and ethers thereof; acids, such as farnesoic acid, and esters thereof, and other monoterpenes, sesquiterpenes, and diterpenes that contain functional groups. Both trans and cis isomers thereof are suitable. Also included are alpha-farnesene (3, 7, 11-trimethyl-1, 3, 6, 10-dodecatetraene), beta-farnesene (7, 11-dimethyl-3-methylene-1, 6, 10-dodecatriene), nerolidol (3, 7, 11-trimethyl-1, 6, 10-dodecatriene-3-ol), bisabolene, sesquiterpinene, zingiberene, cadinene, arylturmerone, turmerone, curcumene (xanthorrhbizole), vulgare, and beta-cnidiene. Preferred monoterpenes are for example alpha-and beta-ocimene, linalool, linalyl acetate, carene, terpineol, nerol, neric acid, geraniol, geranic acid, alpha-and beta-phellandrene and/or thujone; geraniol, linalool and/or thujone are particularly preferred. An example of a diterpene is geranylgeraniol (3, 7, 11, 15-tetramethyl-2, 6, 10, 14-hexadecatetraen-1-ol) and isomers and derivatives thereof. Plant extracts containing mono-, di-and/or diterpenes (e.g. grass leaf oil, rose oil, neroli oil, lavender oil, jasmine oil, basil oil, citronella oil, cedar oil, coriander oil, rosewood oil, capsicum oil, ginger oil or clove oil) may also be used.
In a particular embodiment, the final concentration of monoterpene, sesquiterpene and/or diterpene used is neither fungicidal (i.e. does not destroy the fungus) nor fungistatic (i.e. inhibits the growth of the fungus). A particular advantage of this embodiment is that the cumulative resistance to the substances used is considerably less likely, since the mould is neither destroyed nor inhibited from growing. The minimum concentration at which production is not inhibited yet and the minimum inhibitory concentration itself can be readily determined in a known manner.
In another particular embodiment, the concentration of monoterpenes, sesquiterpenes and/or diterpenes is 0.000001 to 3% by weight. A particular advantage of this embodiment is that only small concentrations of these substances are required to reduce or substantially completely prevent adhesion of mold to the surface. The concentration is preferably 0.00001 to 1% by weight, more preferably 0.0001 to 0.5% by weight, and particularly preferably 0.0001 to 0.1% by weight.
For many products dilution considerations must be taken into account, so that the concentrations which give the desired results in the final product are significantly lower than those mentioned. For laundry detergents, dilution factors (ratio of detergent concentrate to water) of 1: 20 to 1: 200 are contemplated. The dilution ratio of the laundry detergent is often 1: 60 to 1: 100, for example 1: 80. The concentration of farnesol is preferably 0.01 to 5% by weight, more preferably 0.1 to 1.5% by weight. Particularly good adhesion inhibition is achieved in the end-use solutions, especially at concentrations of 0.0001 to 1% by weight. Preferably, a concentration of 0.001 to 0.1% by weight, for example 0.01% by weight, is used.
In the context of the present invention, mould is understood to be a fungus which lives in dirt, on human and/or animal food, or in concentrated nutrient solutions, forms common mycelium and is capable of deriving nutrients from their decomposable organic matter (humus or saprophytic organisms). Furthermore, they are propagated asexually, mainly by spores (in particular sporangiospores or asexual spores), and if necessary form still small sexual reproductive organs.
Such moulds include, for example, species originating from Ascomycota, Basidiomycetes (Basidiomycota), Deuteromycota and Zygomycota, more particularly any species originating from Aspergillus (Aspergillus), Penicillium (Penicillium), Cladosporium (Cladosporum) and Mucor (Mucor).
Ascomycetes include in particular all the species of the genera Aspergillus, Penicillium and Cladosporium. By contact with the skin or respiratory tract, these fungi form spores with a strong tendency to cause allergy. Basidiomycetes include, for example, Cryptococcus neoformans. Deuteromycetes include all genera known as moulds, in particular those which cannot be classified as ascomycetes, basidiomycetes or zygomycetes due to the lack of sexual stage.
Monoterpenes, sesquiterpenes and/or diterpenes or derivatives thereof are particularly suitable for reducing the adhesion of all species of the genus aspergillus to a surface, in particular selected from the following species: more particularly, it is selected from the group consisting of Aspergillus aculeatus, Aspergillus albus, Aspergillus cepacia, Aspergillus glaucomatosus, Aspergillus awamori, Aspergillus kawachii, Aspergillus carneus, Aspergillus chekiangensis, Aspergillus chevalieri intermorpha, Aspergillus clavatus, Aspergillus ficuum, Aspergillus niger, Aspergillus flavus, Aspergillus foetidus, Aspergillus fumigatus, Aspergillus megaterium, Aspergillus saprophytus, Aspergillus intermedus, Aspergillus japonicus, Aspergillus nidulans, Aspergillus niger, Aspergillus niveus, Aspergillus ochraceus, Aspergillus oryzae, Aspergillus porosus, Aspergillus parasiticus, Aspergillus parasaticus var.
In a particularly preferred embodiment, adhesion of Aspergillus fiavus and Aspergillus nidulans is reduced or substantially completely prevented.
In another particularly preferred embodiment, the adhesion of mold to surfaces such as textiles, ceramics, metals, wood and/or plastics is reduced. Furthermore, the adhesion of mold to the food-contact surface can be reduced.
The invention also relates to detergents, cleaning compositions, rinses, hand, machine dishwashing agents and compositions for finishing surfaces and/or packaging, in particular compositions which come into contact with foodstuffs, filter media, building materials, auxiliary building materials, textiles, furs, paper, skin or leather and which contain monoterpenes, sesquiterpenes and/or diterpenes or derivatives thereof and are suitable for reducing the adhesion of moulds to surfaces.
In another particularly preferred embodiment, the monoterpenes, sesquiterpenes and/or diterpenes of the invention are used in detergents and cleaners to reduce the adhesion of moulds to surfaces.
According to the invention, the monoterpenes, sesquiterpenes and/or diterpenes or derivatives thereof according to the invention can also be added to or mixed in cleaning compositions used for cleaning hard surfaces, such as floors, tiles, plastics and other surfaces, in the household, especially in wet rooms (e.g. bathrooms) or medical rooms.
In the present invention laundry detergents and cleaning compositions are to be understood in the broadest sense as surfactant-containing preparations which may be in solid form (granules, powders, etc.), in semisolid form (pastes, etc.), in liquid form (solutions, emulsions, suspensions, gels, etc.) and in gaseous form (aerosols, etc.), which usually contain one or more surfactants for effective action in use, in addition to other ingredients contained in the particular application. Examples of such surfactant-containing preparations are surfactant-containing detergents, surfactant-containing detergents for hard surfaces or surfactant-containing fabric conditioning preparations, which may be in the form of solids or liquids, or contain solid and liquid components or fractions of one another.
Laundry and cleaning agents may contain conventional ingredients such as anionic, nonionic, cationic and amphoteric surfactants, inorganic and organic builders, specialty polymers (e.g. those with built-in cleaning properties), suds suppressors, dyes and optionally other perfumes, bleaches (e.g. peroxygen bleaches and chlorine bleaches), bleach activators, bleach stabilizers, bleach catalysts, enzymes and redeposition inhibitors, but the ingredients are not limited thereto. Other important ingredients of such formulations are often detergency builders, such as optical brighteners, UV absorbers, anti-soiling agents, i.e.polymers which prevent recontamination of the fibres. The substances of each group are described in detail below.
In the case of preparations which are at least partly shaped bodies, adhesion and decomposition aids may also be present.
The surfactants used may be anionic, nonionic, zwitterionic and cationic surfactants.
Suitable anionic surfactants are, for example, those of the sulfonate and sulfate type. A suitable sulfonate surfactant is preferably C9-13Alkylbenzenesulfonates, olefinsulfonates, i.e. mixtures of olefin and hydroxyalkanesulfonates, and disulfonates, e.g. by havingC of internal or terminal double bonds12-18The monoolefin and gaseous sulfur trioxide are subjected to sulfonation reaction, and then the sulfonation product is subjected to alkali or acid hydrolysis to obtain the sulfonated monoolefin. Other suitable sulfonate surfactants are alkane sulfonates, which may be, for example, C12-18Chlorosulfonation or sulfoxidation of alkanes, and subsequent hydrolysis or neutralization. Esters (sulfonates) of 2-sulfofatty acids are also suitable, for example hydrogenated coconut oil, palm kernel oil or 2-sulfonated methyl esters of tallow fatty acids.
Other suitable anionic surfactants are sulfonated fatty acid glycerides. In the present invention, the fatty acid glyceride refers to a mono-ester, a di-ester, a tri-ester and a mixture thereof, which can be obtained by esterifying mono-glycerol with 1 to 3mol of fatty acid or transesterifying triglyceride with 0.3 to 2mol of glycerol. Preferred sulfonated fatty acid glycerides are sulfonated products of saturated fatty acids having 6 to 22 carbon atoms, such as caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
Preferred alk (en) yl sulfates are alkali metal salts, especially C12-18Sodium salts of fatty alcohol sulfuric acid half esters, e.g. coconut fatty alcohol, tallow fatty ester, lauryl, myristyl, cetyl, stearyl, or C10-20Oxo alcohols, and the corresponding half esters of secondary alcohols having the same chain length. Other preferred alk (en) yl sulfates are those having the chain lengths mentioned above, which contain synthetic linear alkyl groups based on petrochemistry, the degradation properties of which are similar to those of the corresponding compounds based on oil chemical feedstocks. For detergents and cleaners, C12-16Alkyl sulfates, C12-15Alkyl sulfates and C14-15Alkyl sulfates are preferred. Other suitable anionic surfactants are 2, 3-alkyl sulfates, which can be prepared, for example, according to US 3,234,258 or US 5,075,041, and also commercially available as DAN from Shell Oil company*The trade name of (a).
Straight-chain or branched C ethoxylated with 1-6 mol of ethylene oxide7-21Sulfuric monoesters of alcohols are also suitable, e.g. containing on average 3.5mol of Ethylene Oxide (EO)2-methyl-branched C9-11Alcohol or fatty alcohol containing 1-4 EO. Due to their high foaming capacity in laundry and cleaning agents, they are used in relatively small amounts, for example in amounts of 1 to 5% by weight.
Other suitable anionic surfactants are salts of alkyl sulfosuccinic acids, also known as sulfosuccinates or sulfosuccinates, which are monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols, more preferably ethoxylated fatty alcohols. Preferred sulfosuccinates contain C8-18Fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain fatty alcohol residues from ethoxylated fatty alcohols, which represent nonionic surfactants in view of isolation (see description below). Among these sulfosuccinates, fatty alcohol residues derived from a narrow range of ethoxylated fatty alcohols are particularly preferred. Alk (en) ylsuccinic acids having 8 to 18 carbon atoms in the alk (en) yl chain or salt thereof may also be used.
Other particularly suitable anionic surfactants are soaps. Suitable soaps are the salts of saturated fatty acid soaps, such as lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and especially soap mixtures derived from natural fatty acids, for example coconut oil, palm kernel oil or tallow fatty acids.
Anionic surfactants, including soaps, may be present in the form of their sodium, potassium or ammonium salts or in the form of soluble salts of organic bases such as mono-, di-or triethanolamine. The anionic surfactant is preferably present in the form of its sodium or potassium salt, more preferably in the form of its sodium salt.
Preferred compositions of the invention contain 5 to 50% by weight of one or more anionic surfactants, preferably 7.5 to 40% by weight, more preferably 15 to 25% by weight.
Preferred nonionic surfactants are alkoxylated, preferably ethoxylated, primary alcohols, preferably containing from 8 to 18 carbon atoms and an average of from 1 to 12 moles of epoxy per mole of alcoholEthane (EO), wherein the alcohol component may be linear, or preferably methyl branched at the 2-position, or may contain both linear and methyl branched residues, typically in the form of a mixture of residues present in oxo alcohols. However, particularly preferred are alcohol ethoxylates containing a natural alcohol straight-chain residue and having from 12 to 18 carbon atoms, such as coconut oil, palm oil, tallow or oleyl alcohol, with an average of from 2 to 8EO per mole of alcohol. Preferred ethoxylated alcohols include, for example, C with 3EO or 4EO12-14Alcohol, C containing 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 is expressed as a statistical average and may be an integer or fractional number for a particular product. Preferred alcohol ethoxylates have a narrow homology distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols containing more than 12EO may also be used, examples of which include tallow fatty alcohols containing 14EO, 25EO, 30EO or 40 EO.
Other classes of preferred nonionic surfactants which may be used as the sole nonionic surfactant or in admixture with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably containing from 1 to 4 carbon atoms in the alkyl chain, more preferably fatty acid methyl esters.
Another class of nonionic surfactants that may preferably be used are Alkyl Polyglycosides (APGs). Suitable alkylpolyglycosides correspond to the general formula RO (G) z, wherein R is a linear or branched, especially 2-methyl branched, saturated or unsaturated aliphatic radical having from 8 to 22, preferably from 12 to 18, carbon atoms and G represents a monosaccharide unit having 5 or 6 carbon atoms, preferably glucose. The degree of glycosylation z is 1.0 to 4.0, preferably 1.0 to 2.0, and more preferably 1.1 to 1.4.
It is preferable to use a linear alkyl polyglycoside, that is, an alkyl polyglycoside in which the polysaccharide-based component is a glucose unit and the alkyl component is an n-alkyl group.
The surfactant-containing formulations of the present invention preferably contain alkyl polyglycosides in an amount of APG of more than 0.2% by total weight of the formulation, which is preferred for detergents, dishwashing agents or cleaning agents. Particularly preferred surfactant-containing formulations have an APG amount of 0.2 to 10% by weight, preferably 0.2 to 5% by weight, more preferably 0.5 to 3% by weight.
Nonionic surfactants of the amine oxide type and of the fatty acid alkanolamide type are also suitable, for example N-cocoalkyl-N, N-dimethyl amine oxide and N-tallowalkyl-N, N-dihydroxyethyl-amine oxide. The amount of nonionic surfactant used is preferably not more than the amount of ethoxylated fatty alcohol used, more preferably not more than half of its amount.
Further suitable surfactants are polyhydroxy fatty acid amides corresponding to the general formula (I)
Wherein R is4CO is an aliphatic acyl group having 6 to 22 carbon atoms, R5Is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms, [ Z ]1]Is a straight chain or branched chain polyhydroxyalkyl group containing 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. Polyhydroxy fatty acid amides are known substances which are generally obtainable by reductive amination of reducing sugars with ammonia, alkylamines or alkanolamines and subsequent acylation with fatty acids, fatty acid alkyl esters or fatty acid chlorides.
The polyhydroxy fatty acid amides also include compounds corresponding to the following formula (II):
wherein R is6Is a straight or branched alkyl or alkenyl group having 7 to 12 carbon atoms, R7Is a straight-chain, branched or cyclic alkyl or aryl group containing 2 to 8 carbon atoms, R8Is a straight-chain, branched or cyclic alkyl or aryl or alkoxy radical having 1 to 8 carbon atoms, C1-4Alkyl or phenyl is preferred, [ Z ]2]Is a straight-chain polyhydroxy radical or a derivative of this radical, in which the alkyl chain is substituted by at least two hydroxyl groups or is alkoxylated, preferably ethoxylated or propoxylated.
[Z2]Preferably, the sugar is obtained by reductive amination of a reducing sugar such as glucose, fructose, maltose, lactose, galactose, mannose, or xylose. The N-alkoxy-or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of alkoxides as catalysts, for example according to the process taught in International patent application WO-A-95/07331.
In another preferred embodiment, cationic surfactants may be used in addition to anionic and nonionic surfactants.
The fabric softening material comprises in particular a cationic surfactant. Examples of cationic surfactants are, inter alia, quaternary ammonium compounds, cationic polymers and emulsifiers.
Suitable examples are quaternary ammonium compounds corresponding to the general formulae (III) and (IV):
wherein R In (IV)aAnd RbRepresents an acyclic alkyl group having 12 to 24 carbon atoms, RcIs saturated C1-4Alkyl or hydroxyalkyl radical, RdIs or with Ra、RbOr RcThe same or represent an aromatic group. X-Is a halide, dimethyl sulfate, dimethyl phosphate or phosphate ion, or a mixture thereof. Examples of cationic compounds corresponding to the general formula (III) are didecyl dimethyl ammonium chloride, ditallowdimethyl ammonium chloride or di-hexadecaneAlkyl dimethyl ammonium chloride.
The compounds corresponding to formula (IV) are known as ester quats. Ester quats are distinguished by excellent biodegradability. In the general formula, ReIs an aliphatic alkyl group having 12 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, RfIs H, OH or O (CO) Rh，RgIndependently of RfRepresents H, OH or O (CO) Ri，RhAnd RiIndependently of one another, represents an aliphatic acyl group having 12 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, and m, n and p independently of one another represent 1, 2 or 3. X-Can be a halide, dimethyl sulfate, dimethyl phosphate or phosphate ion, or a mixture thereof. Preferred compounds for RfContaining the group O (CO) RhFor RcAnd RhSaid contains C16-18An alkyl group. Particularly preferred compounds are those in which R8Those that are OH. Examples of compounds corresponding to formula (IV) are methyl-N- (2-hydroxyethyl) -N, N-di (tallowoylethoxy) -dimethylammonium sulfate, bis- (palmitoyl) -ethylhydroxyethyl-methylammonium dimethyl sulfate, or methyl-N, N-bis- (acylethoxy) -N- (2-hydroxyethyl) -dimethylammonium sulfate. If quaternary ammonium compounds corresponding to formula (IV) and containing unsaturated alkyl chains are used, the acyl group of the corresponding fatty acid has an iodine value of 5 to 80, preferably 10 to 60, more preferably 15 to 45, and the ratio (in% by weight) of cis-to trans-isomer is greater than 30: 70, preferably greater than 50: 50, more preferably greater than 70: 30. Commercially available examples are methylhydroxyalkyldialkanoylalkoxydimethylammonium sulfates, which are manufactured by Stepan as Stepatex*Is put on the market or is Cognis brand name Dehyquart*Or the product of (1) is under the trade name Rewoquat (R) under the trademark Goldschmidt-Witco*The product of (1). Other preferred compounds are diester quats corresponding to the general formula (III), which may be referred to under the trade name Rewoquat*W222 LM or CR 3099, which, in addition to having flexibility, also has stability and color protection.
In the general formula (V), RkAnd R1Independently of one another and each represents an aliphatic acyl group having 12 to 22 carbon atoms and 0, 1, 2 or 3 double bonds.
In addition to the quaternary ammonium compounds mentioned above, other known compounds can also be used, including, for example, quaternary ammonium compounds corresponding to the general formula (VI):
wherein R ismRepresents H or a saturated alkyl group having 1 to 4 carbon atoms, RnAnd RoIndependently of one another, represents an aliphatic saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, RnOptionally also represents O (CO) Rp，RpIs an aliphatic saturated or unsaturated alkyl group having 12 to 18 carbon atoms, Z is an NH group or oxygen, X-Is an anion. q may be an integer of 1 to 4.
Other suitable quaternary ammonium compounds correspond to general formula (VII):
wherein R isq、RrAnd RsIndependently of one another represent C1-4Alkyl, alkenyl or hydroxyalkyl. RtAnd RuIndependently of one another represent C8-28Alkyl, r is a number from 0 to 5.
In addition to the compounds corresponding to the general formulae (III) and (VII), short-chain water-soluble quaternary ammonium compounds, including trihydroxyethylmethylammonium sulfate, or alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, can also be used.
Non-quaternized protonated precursors of protonated alkylamine compounds and cationic emulsifiers that have fabric softening effects are also suitable.
Other cationic compounds suitable for use in the present invention are quaternized protein hydrolysates.
Suitable cationic polymers are The polyquaternary ammonium polymers listed in CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry and Fragrance Association, inc., 1997), in particular polyquaternary ammonium-6, polyquaternary ammonium-7 and polyquaternary ammonium-10 polymers (ucarne polymer IR 400, Amerchol), which are also known as merquats; polyquaternary-4 copolymers, such as graft copolymers containing a cellulose skeleton and quaternary ammonium bound by propenyl dimethyl ammonium chloride, cationic cellulose derivatives, such as cationic guar gums, such as guar gum hydroxypropyl triammonium chloride, and similar quaternized guar gum derivatives (e.g. Cosmedia guar gum, Cognis GmbH), cationic quaternary ammonium sugar derivatives (cationic alkyl polyglycosides), e.g. the commercial product Glucqut*100(CTFA name: lauryl methyl Gluceth-10 hydroxypropyl dimethyl ammonium chloride), copolymers of PVP and methyl dimethylaminoacrylate, copolymers of vinylimidazole and vinylpyrrolidone, aminosilicone polymers and copolymers.
Polyquaternary ammonium polymers (e.g. Luviquat Care, BASF) and chitin-based cationic biopolymers and derivatives thereof, e.g. as available commercially as Chitosan*(Cognis) derived polymers are also suitable.
Cationic silicone oils are also suitable for the purposes of the present invention and include, for example, the commercially available products Q2-7224 (stabilized trimethylsilyl amodimethicone, Dow Corning), Dow Corning 929 emulsion (containing hydroxylamino-modified silicone resin, which is also known as amodimethicone), SM-2059(General Electric), SLM-55067(Wacker), Abil*Quat 3270 and 3272 (diquaternary polydimethyl ammonium)Siloxanes, Quaternary ammonium-80, Goldschmidt-Rewo) and silicon Quaternary ammonium Rewoquat*SQ1(Tegopren*6922，Goldschmidt-Rewo)。
Other suitable compounds correspond to general formula (VIII):
can be an alkylamido amine, which can be in a non-quaternized form or in a quaternized form as shown. In the general formula (VI), RvCan be an aliphatic acyl group having 12 to 22 carbon atoms and 0, 1, 2 or 3 double bonds. S may be a value of 0 to 5. RwAnd RxRepresent H, C independently of each other1-4Alkyl or hydroxyalkyl. Preferred compounds are fatty acid amidoamines, such as stearyl amidopropyl dimethylamine, which may be under the trade name Tego Amid*S18 or 3-tallow amidopropyl trimethyl ammonium dimethyl sulfate, which may be Stepatex*X9124, which has, in addition to good conditioning, also dye transport inhibiting properties and easy biodegradability.
If cationic surfactants are used, they are preferably present in the formulation in an amount of 0.01 to 10% by weight, more preferably 0.1 to 3.0% by weight.
The total surfactant content of the composition of the invention may be from 5 to 50% by weight, preferably from 10 to 35% by weight.
Builders are second only to surfactants in detergent and cleaning compositions. The surfactant-containing preparations of the invention may contain any builders customary in detergents, especially zeolites, silicates, carbonates, organic builders and phosphates insofar as their use is not ecologically disadvantageous.
Suitable sodium silicates in the form of crystalline layers correspond to the general formula NaMSixO2x+1·H2O, where M is sodium or hydrogen, x is a number from 1.9 to 4, and y is 0 to 20The number, preferably the value of x is 2, 3 or 4. Such crystalline layered silicates are disclosed, for example, in European patent application EP-A-0164514. Preferred crystalline phyllosilicates corresponding to the above formula are those in which M is sodium and x is 2 or 3. Beta-and delta-sodium disilicate Na2Si2O5·yH2O is particularly preferred, and betA-sodium disilicate can be obtained, for example, by the process described in International patent application WO-A-91/08171.
Other suitable builders are the proportion (Na)2O∶SiO2Ratio) of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8, more preferably 1: 2 to 1: 2.6, which can delay dissolution and exhibit multiple wash cycle performance. The delay in dissolution compared to conventional amorphous sodium silicates can be obtained by various methods, for example by surface treatment, mixing, compacting, or overdrying. Known as X-ray amorphous silicates also show a delayed dissolution compared to conventional waterglass and are disclosed, for example, in German patent application DE-A-4400024. The product has crystallite domains of 10 to several hundred nanometres in size, preferably at most 50nm, more preferably at most 20 nm. Particularly preferred are compact amorphous silicates, mixed amorphous silicates and overdried X-ray amorphous silicates.
The finely crystalline synthetic zeolites optionally used, which contain water of crystallization, are preferably zeolite A and/or zeolite P. Zeolite MAP*(for example Soucil A24 available from Crosfield) is a particularly preferred P-type zeolite. However, mixtures of zeolites X and A, X and/or P are also suitable. Preference is also given according to the invention to using, for example, cocrystals of zeolite X and zeolite A (about 80% by weight of zeolite X) which are prepared from CONDEA Augusta S.p.A. under the trade name VEGOBOND AX*Marketed, it can be illustrated by the following general formula:
nNa2O·(1-n)K2O·Al2O3·(2-2.5)SiO2·(3.5-5.5)H2O
suitable zeolites have an average particle diameter of less than 10 μm (volume distribution, measured by the Coulter Counter method) and contain preferably from 18 to 22% by weight of bound water, more preferably from 20 to 22% by weight of bound water.
The known phosphates can of course also be used as builders in detergents, provided their use is not avoided for ecological reasons. Sodium salts of orthophosphoric acid, pyrophosphoric acid and tripolyphosphoric acid are particularly suitable.
Suitable organic builders are, for example, the polycarboxylic acids used in the form of their sodium salts, by which is to be understood carboxylic acids containing more than one acid function, such as citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA) which is ecologically safe for its use, and mixtures thereof. Preferred salts are salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. These acids may also be used by themselves. In addition to its builder action, acids generally also have the properties of acidifying components and are therefore also used to determine relatively low and moderate pH values in surfactant-containing formulations. In this connection, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and mixtures thereof are to be mentioned in particular.
Other suitable builders are polymeric polycarboxylates, for example alkali metal salts of polyacrylic or polymethacrylic acids, for example those having a relative molecular weight of from 500 to 70,000 g/mol.
For polymeric polycarboxylates, the molecular weight referred to in this specification is the weight average molecular weight M of the particular acid formwIt can be determined essentially by Gel Permeation Chromatography (GPC) using a UV detector. The measurement is made with reference to an external polyacrylic acid standard, which provides a true molecular weight value by its structural relationship to the polymer to be measured. These values are clearly different from the molecular weight using polystyrene sulfonic acid as a standard. The molecular weight measured with reference to polystyrenesulfonic acid is generally higher than in the present specification.
Suitable polymers are, in particular, polyacrylates, preferably having a molecular weight of from 12,000 to 30,000 g/mol. Within this range, short chain polyacrylates having a molecular weight of 2,000 to 10,000g/mol, more preferably 3,000 to 5,000g/mol, are preferred due to their higher solubility.
Other suitable polymers are copolymerized polycarboxylates, in particular those of acrylic acid with methacrylic acid or acrylic acid or methacrylic acid with maleic acid. The copolymer of acrylic acid and maleic acid contains 50-90% by weight of acrylic acid and 50-10% by weight of maleic acid, and has proved to be particularly suitable. Their relative molecular weight, calculated as free acid, is generally from 2,000 to 70,000g/mol, preferably from 20,000 to 50,000g/mol, more preferably from 30,000 to 40,000 g/mol.
The (co) polymerized polycarboxylic acid salt can be used in the form of a powder or an aqueous solution. The content of the (co) polymerized polycarboxylic acid salt in the detergent/cleaner of the present invention is preferably 0.5 to 20% by weight, more preferably 3 to 10% by weight.
To increase the solubility of the polymer in water, the polymer may also contain, as monomers, allylsulfonic acids, such as allyloxybenzenesulfonic acid, methallylsulfonic acid.
Other particularly preferred polymers are biodegradable polymers of more than two different monomer units, for example those containing salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives as monomers, or those containing acrylic acid and 2-allylsulfonic acid and sugar derivatives as monomers.
Other preferred copolymers are those which preferably contain acrolein and acrylic acid/acrylate or acrolein and vinyl acetate as monomers.
Other preferred builders are polymeric aminodicarboxylic acids, salts or precursors thereof. Polyaspartic acid or salts and derivatives thereof are particularly preferred, since they have a bleach-stabilizing action in addition to cleaning-assisting properties.
Other suitable builders are polyacetals which are obtainable by reacting dialdehydes with polyhydroxycarboxylic acids having from 5 to 7 carbon atoms and at least three hydroxyl groups. Preferred polyacetals may be obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and polyhydroxycarboxylic acids such as gluconic acid and/or glucoheptonic acid.
Other suitable organic builders dextrins, such as oligomers or polymers of carbohydrates, are obtainable by partial hydrolysis of starch. Hydrolysis may be carried out by standard methods such as acid or enzyme catalyzed methods. The end product is preferably a hydrolysate having an average molecular weight of 400 to 500,000 g/mol. Preferred polysaccharides have a Dextrose Equivalent (DE) of 0.5 to 40, more preferably 2 to 30, DE being a recognized measure of polysaccharide reduction compared to dextrose having a DE of 100. Maltodextrin with DE of 3-20 and dry glucose syrup with DE of 20-37, also known as yellow dextrin and white dextrin, and molecular weight of 2,000-30,000 can also be used. Preferred dextrins are described in british patent application 9419091.
The oxidized derivatives of dextrins are the reaction products thereof with oxidizing agents which oxidize at least one alcohol function of the sugar ring to a carboxylic acid function. Oxidized oligosaccharides are also suitable, C at the sugar ring6The products of the oxidation are particularly effective.
Other suitable builders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Preference is given to using ethylenediamine-N, N' -disuccinate (EDDS) in the form of its sodium or magnesium salt. Glycerol disuccinates and glycerol trisuccinates are particularly preferred. The amount of the zeolite-containing and/or silicate-containing agent is 3-15% by weight.
Other useful organic builders are, for example, acetylated hydroxycarboxylic acids and salts thereof, optionally in the form of lactones, which contain at least 4 carbon atoms, at least one hydroxyl group and at most two acid groups.
Another class of materials which act as cleaning aids are phosphates, preferably hydroxyalkane and aminoalkane phosphates. Of the hydroxyalkylphosphates, 1-hydroxyethane-1, 1-diphosphonate (HEDP) is particularly important as a cleaning aid. Preferably, the sodium salt is used in the form of the disodium salt indicating neutralization and the tetrasodium salt indicating the basicity (pH 9). Preferred aminoalkane phosphates are Ethylenediaminetetramethylenephosphate (EDTMP), Diethylenetriaminepentamethylenephosphate (DTPMP), and higher homologs thereof. The sodium salt forms of their neutralization reactions are preferably used, such as the hexasodium salt of EDTMP, the heptasodium salt and octasodium salt of DTPMP. In the phosphate range, HEDP is preferably used as a builder. Aminoalkane phosphates also exhibit significant heavy metal bonding capability. Thus, it is advantageous to use aminoalkane phosphates, especially DTPMP, or mixtures of said phosphates, especially when bleaching agents are also present in the surfactant-containing formulations of the present invention.
In addition, any compound that can form a complex with an alkaline earth metal ion can be used as a cleaning assistant.
Can generate H in water2O2The compounds of (4) are useful as bleaching agents, of which sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphate, citrate perhydrate, hydrogen peroxide2O2Such as peroxybenzoic acid, peroxyphthalic acid, diperoxyazelaic acid, phthalimidoperonic acid or diperoxydodecanedioic acid. If detergents or bleaching agents for dish washers are prepared, bleaching agents selected from organic bleaching agents may also be used. Commonly used organic bleaching agents are diacyl peroxides, such as dibenzoyl peroxide. Other commonly used organic bleaching agents are peroxyacids, of which alkyl and aryl peroxyacids are specifically mentioned as examples. Preferred examples are (a) perbenzoic acid and its ring-substituted derivatives, such as alkyl peroxybenzoic acids, alpha naphthoic peroxide and magnesium monoperphthalate, (b) aliphatic or substituted aliphatic peroxy acids, such as lauric peroxide, stearic peroxide, epsilon-phthalimidoperoxycaproic acid [ Phthalimidoperoxycaproic Acid (PAP)]O-carboxyphenylamidoperoxycaproic acid, N-nonylamidoadipic acidPersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, peroxydidecanoic acid, diperoxytidecanedioic acid, diperoxyphthalic acid, 2-decyldiperoxybutane-1, 4-dioic acid, N-terephthaloyl-bis (6-aminoperoxyacetic acid).
In order to achieve improved bleaching action in washing at temperatures of 60 ℃ or less, bleach activators may be incorporated in the surfactant-containing formulations. The bleach activator may be a compound which under perhydrolysis conditions forms an aliphatic peroxycarboxylic acid containing preferably from 1 to 10 carbon atoms, more preferably from 2 to 4 carbon atoms, and/or an optionally substituted peroxybenzoic acid. Substances containing O-and/or N-acyl groups and having the abovementioned number of carbon atoms and/or optionally substituted benzoyl groups are suitable. Preferred bleach activators are polyacylated alkanediamines, more preferably Tetraacetylethylenediamine (TAED), acylated triazine derivatives, more preferably 1, 5-diacetyl-2, 4-dioxohexahydro-1, 3, 5-triazine (DADHT), acylated glycolurils, more preferably Tetraacetylglycoluril (TAGU), N-imides, more preferably N-Nonanoylsuccinimide (NOSI), acylated phenolsulfonates, more preferably N-nonanoyl or isononanoyloxybenzenesulfonates (N-or iso-NOBS), carboxylic anhydrides, more preferably phthalic anhydride, acylated polyhydric alcohols, more preferably triacetin, ethylene glycol diacetate, and 2, 5-diacetoxy-2, 5-dihydrofuran.
In addition to or instead of the conventional bleach activators described above, so-called bleach catalysts can also be mixed in the surfactant-containing preparations. The bleach catalyst is a transition metal salt or transition metal complex which can drive bleaching, for example a manganese, iron, cobalt, ruthenium or molybdenum salen complex or a carbonyl complex. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with three-membered ligands and cobalt, iron, copper and ruthenium ammine complexes may also be used as bleach catalysts.
Suitable enzymes are selected from proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type are preferred, and proteases derived from bradybacillus are particularly preferred. Enzyme mixtures of, for example, protease and amylase, or protease and lipase, or protease and cellulase, or cellulase and lipase, or protease, amylase and lipase, or protease, lipase and cellulase are of particular interest, especially cellulase-containing mixtures. Peroxidases or oxidases have proven suitable in certain cases. The enzymes may be adsorbed on a carrier and/or encapsulated in a membrane material to prevent their premature decomposition. The percentage of enzyme, enzyme mixture or enzyme granulate in the surfactant-containing formulation of the invention is, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
Preferred suitable additives are optical brighteners. Generally, optical brighteners used in detergents may be used. Examples of optical brighteners are derivatives of diamino-stilbene disulfonic acid or alkali metal salts thereof. Suitable optical brighteners are, for example, salts of 4, 4 '-bis- (2-anilino-4-morpholinyl-1, 3, 5-triazin-6-amino) -stilbene-2, 2' -disulfonic acid or compounds of similar composition which contain diethanolamino, methylamino, anilino or 2-methoxyethylamino groups instead of morpholinyl groups. Furthermore, substituted diphenylstyryl-type brighteners may also be present in the part of the surfactant-containing formulations of the invention (cleaning formulations), for example the alkali metal salts of 4, 4 ' -bis- (2-sulfonated styryl) -diphenyl, 4 ' -bis- (4-chloro-3-sulfonated styryl) -diphenyl or 4- (4-chlorostyryl) -4 ' - (2-sulfonated styryl) -diphenyl. Mixtures of the above-mentioned brighteners may also be used.
Another additive preferred for the purposes of the present invention is a UV absorber. UV absorbers can be absorbed onto the treated textile, which can improve the photostability of the fibers and/or the photostability of other formulation ingredients. UV absorbers are organic substances (optical filters) that absorb ultraviolet light and can release the absorbed energy by means of longer-wave radiation, such as heat. Compounds having these desired properties are, for exampleCompounds acting by non-radiative deactivation and derivatives substituted in the 2-and/or 4-position of benzophenone. Other suitable UV absorbers are substituted benzotriazoles, for example water-soluble benzenesulfonic acid-3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) -monosodium salt (Cibafast)*H) 3-phenyl-substituted acrylates (cinnamic derivatives) optionally having a cyano group in the 2-position, salicylates, organic Ni complexes, natural substances such as umbelliferone and urocanic acid of the body itself. Of particular importance are substances which are linked to biphenyl, most importantly stilbene derivatives such as those described in EP 0728749A, which are commercially available from Ciba under the trade name Tinosorb*FD and Tinosorb*FR was purchased. Suitable UV-B absorbers include 3-benzylidene camphor or 3-benzylidene norcamphor and derivatives thereof, such as 3- (4-methylbenzylidene) -camphor as disclosed in EP-B10693471; 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 (monophenylacrylic acid monoester); esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate; derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4 '-methylbenzophenone, 2' -dihydroxy-4-methoxybenzophenone; esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxyphenylmalonate; triazine derivatives, for example 2, 4, 6-trianilino- (p-carbonyl-2 '-ethyl-1' -hexyloxy) -1, 3, 5-triazine and octyltriazone, or dioctylbutylaminotriazinone (Uvasorb), disclosed in EP 0818450A 1*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 disclosed in EP 0694521B 1. Other suitable UV-B absorbers are 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts; sulfonic acid of benzophenoneAcid derivatives, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and salts thereof; sulfonic acid derivatives of 3-benzylidenecamphor, such as 4- (2-oxo-3-bornylmethyl) -benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornyl) -sulfonic acid and salts thereof.
Commonly used UV-A filters are in particular derivatives of benzoylmethane, such as 1- (4 '-tert-butylphenyl) -3- (4' -methoxyphenyl) -propane-1, 3-dione, 4-tert-butyl-4 '-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4' -isopropylphenyl) -propane-1, 3-dione and enamine compounds as disclosed in DE 19712033A 1 (BASF). The UV-A and UV-B filters can of course also be used in the form of mixtures thereof. In addition to the above-mentioned soluble substances, insoluble light-blocking pigments, i.e. finely divided, preferably "nanosized" metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are, in particular, zinc oxide and titanium dioxide, and also oxides of iron, zirconium, silicon, magnesium, aluminum, cerium and mixtures thereof. Silicates (talc), barium sulfate and zinc stearate can be used as salts. The oxides and salts can be used in the form of skin care supplements, skin protection emulsions and cosmetics. The average diameter of the particles should be less than 100nm, preferably 5 to 50nm, more preferably 15 to 30 nm. They may be spherical or may use ellipsoidal or other non-spherical particles. The pigments may also be surface treated, i.e. hydrophilic or hydrophobic. Common examples are coated titanium dioxides, such as Titandioxid T805 (Degussa) and Eusolex*T2000(Merck) suitable hydrophobic coating materials are silicones, among which in particular trialkoxyoctylsilanes or simethicons. Preferably micronized zinc oxide is used. Other suitable UV filters are disclosed in P.Finkel' S review, S * FW-Journal 122, 543 (1996).
The UV absorbers are generally used in amounts of from 0.01% to 5% by weight, preferably from 0.03% to 1% by weight.
Another preferred additive for the purposes of the present invention is a dye, in particular a water-soluble or water-dispersible dye. Preferred dyes are those commonly used in laundry detergents, dishwashing agents, detergents and fabric conditioners to improve their appearance. The skilled person can easily select dyes which have a high storage stability and are not affected by other ingredients in the surfactant-containing formulation or by light, without any significant direct dyeing of the textile fibers, so that they do not discolor. According to the invention, the amount of dye in the inventive washing and/or cleaning agents is less than 0.01% by weight.
Another class of additives that may be incorporated in the detergents and/or cleaners of the present invention are polymers. Suitable polymers are polymers which exhibit cleaning aid properties during washing and dishwashing, i.e. for example polyacrylic acids, even modified polyacrylic acids or corresponding copolymers. Another polymer is polyvinylpyrrolidone and other redeposition inhibitors such as copolymers of polyvinylpyrrolidone, cellulose ethers, and the like. Other preferred polymers are the soil release agents which will be described in detail below.
The detergent/cleaner may also contain an anti-fouling agent as an additive in the present invention. Soil-resistant agents are polymers that can be absorbed onto the fibers and have a positive effect on the removal of oils and greases from textiles by washing, thereby preventing recontamination. This effect is particularly evident when the textile articles which have been washed repeatedly with the detergent of the invention containing soluble oil and fat components are soiled. Preferred oil and fat soluble ingredients include, for example, nonionic cellulose ethers such as methyl cellulose, methylhydroxypropyl cellulose containing from 15 to 30% methoxy groups and from 1 to 15% hydroxypropoxy groups, based on the weight of the nonionic cellulose ether, polymers of phthalic acid and/or terephthalic acid or derivatives thereof known in the art, more preferably polymers of ethylene terephthalate and/or polyethylene terephthalate, or anionically and/or nonionically modified derivatives thereof. Sulfonated derivatives of phthalic and terephthalic acid polymers are particularly preferred.
Especially when the formulation is a liquid or gel, it may also contain a solvent. Examples of suitable solvents are monohydric or polyhydric alcohols having from 1 to 4 carbon atoms. Preferred alcohols are ethanol, propane-1, 2-diol, glycerol and mixtures thereof. In the liquid preparation, the amount of the solvent is 2-12% by weight of the final preparation.
The above-mentioned additives are added to the washing and/or cleaning agents in amounts of up to 30% by weight, preferably in amounts of 2 to 20% by weight.
The list of detergent ingredients that can be used in the detergent/dishwashing or cleaning compositions of the present invention is by no means exhaustive and is intended to indicate only the key ingredients in such compositions. In particular, when the composition is a liquid or gel, an organic solvent may also be present in the composition. These organic solvents may be monohydric or polyhydric alcohols containing 1 to 4 carbon atoms. Preferred alcohols are ethanol, propane-1, 2-diol, glycerol and mixtures of these alcohols. In a preferred embodiment, the composition contains 2-12% by weight of an alcohol.
In a preferred embodiment, the detergent and/or cleaning composition of the present invention contains 0.000001 to 3% by weight of a monoterpene, a sesquiterpene and/or a diterpene. The concentration is preferably 0.00001 to 1.0% by weight, more preferably 0.0001 to 0.5% by weight. In a most particularly preferred embodiment, the detergent contains from 0.0001 to 0.05% by weight of these substances.
The detergent of the present invention may preferably contain the above-mentioned substances in a relatively small amount without contaminating wastewater. Since they are used in concentrated form and diluted in the washing solution to relatively active concentrations, the active substances must be used in relatively high concentrations. The common usage is that the detergent is diluted to 1: 40-1: 200 by water.
The invention also relates to packaging, more preferably packaging material for food, filter media, building materials, auxiliary building materials, textiles, skins, paper, skin or leather, which contains a monoterpene, sesquiterpene and/or diterpene or derivatives thereof and/or which has been treated with a composition according to the invention to reduce the adhesion of moulds to surfaces.
The packaging, surface, textile, fur, skin or leather is treated in a known manner, for example by dipping in or spraying with a solution of the composition according to the invention of suitable concentration. For example, paint on paper, parchment, wood and/or canvas may prevent or eliminate mold staining. The filter medium, construction material or auxiliary construction material can be treated, for example by mechanical mixing, or by applying a solution of the composition of the invention in a suitable concentration to or to the filter medium, construction material or auxiliary construction material.
The building materials or auxiliary building materials treated according to the invention are preferably selected from the group consisting of adhesives, sealing compounds, surface compounds and coating compositions, plastics, pigments, paints, plasters, mortars, concretes, insulating materials and primers. Particularly preferred building materials or auxiliary building materials are cements (e.g. silicone-containing cements), wallpaper pastes, plasters, felt adhesives, silicone adhesives, tile adhesives.
Sealing compounds, in particular cements, generally contain organic polymers and in many cases also mineral or organic extenders and other additives.
Suitable polymers are, for example, the thermoplastic elastomers described in DE-A-3602526 of the applicant, preferably polyurethanes and acrylates. Suitable polymers are also disclosed in the Applicant's DE-A3726547, 4029504 and 4009095, also in DE-A19704553 and DE-A4233077, the entire contents of which are incorporated herein.
The sealing compound, in particular the bonding agent, may contain an aqueous or organic solvent. Suitable organic solvents are hydrocarbons, such as cyclohexane, toluene or xylene, or petroleum ether. Other solvents are ketones, such as methyl butyl ketone and chlorinated hydrocarbons.
The sealing compound may also contain other rubbery polymers including the relatively low molecular weight commercial types of polyisobutylene, polyisoprene or polybutadiene styrene. Degradable natural rubber or neoprene may also be used. Even those that are still liquid at room temperature and are commonly referred to as "liquid rubbers" may be used.
The sealing compounds of the present invention can join different classes of materials together or seal them. The materials are highly concrete, glass, plaster and/or enamel, ceramics and porcelain. However, it is also possible to join or seal molds or profiles made of aluminum, steel, zinc or plastics such as PVC, polyurethane, acrylic. Finally, sealing of wood or timber to other materials is also contemplated.
The stability of the sealant is generally dependent on the addition of fine particulate solids, also referred to as extenders. The additives can be divided into organic and inorganic types. Preferred inorganic additives are, for example, limestone (coated or uncoated) and/or zeolites. Zeolites may also act as desiccants. Suitable organic additives are, for example, PVC powder.
The additives generally play a critical role in providing the necessary internal adhesion of the sealing compound after application so that the compound does not swell out of the vertical joint. The additives or extenders mentioned can be divided into pigments and thixotropic extenders, the latter also being referred to as thixotropic agents for short.
Suitable thixotropic agents may be of any type, such as bentonite, kaolin or organic compounds, such as hydrogenated castor oil or its derivatives with polyfunctional amines, or the reaction products of stearic acid or ricinoleic acid with ethylenediamine. The use of silica has proven particularly advantageous, more preferably pyrogenically decomposed silica. Other suitable thixotropic agents are essentially swellable polymer powders, such as polyacrylonitrile, polyurethane, polyvinyl chloride, polyacrylates, polyvinyl alcohol, polyvinyl acetate and corresponding copolymers. Particularly good results are obtained with finely divided polyvinyl chloride powder. In addition to the thixotropic agent, a linking agent, such as a mercaptoalkylsilane, may also be used. The use of monothioalkyltrialkoxysilanes has proven effective in this regard. Mercaptopropyltrimethoxysilane is commercially available.
The properties of the sealant can be further improved by adding further ingredients to the polymer powder used as further thixotropic agent. Such ingredients include plasticizers or swelling agents and swelling aids for plastics. Useful plasticizers are, for example, phthalates. Examples of suitable compounds of this type are dioctyl phthalate, dibutyl phthalate and benzyl butyl phthalate. Other suitable compounds are chloroparaffins, alkyl sulfonates, such as phenol or cresol, and fatty acid esters.
Suitable swelling aids are low molecular weight organic substances which can be mixed with the polymer powder and the plasticizer. Examples of swelling aids can be found by the skilled person in relevant textbooks on plastics and polymers. Preferred swelling aids for polyvinyl chloride powders are esters, ketones, aliphatic hydrocarbons, aromatic hydrocarbons and alkyl-substituted aromatic hydrocarbons.
The pigments and dyes used may be any of those already used in such applications, such as titanium dioxide, iron oxides and carbon black.
To improve the storage stability, stabilizers, such as benzoyl chloride, acetyl chloride, methyl tosylate, carbodiimides and/or polycarbodiimides, may be added to the sealing compound. Olefins containing 8 to 20 carbon atoms have proven to be particularly effective stabilizers. In addition to the stabilizing effect, the stabilizer may also act as a plasticizer or swelling agent. Preferred stabilizers are olefins having from 8 to 18 carbon atoms, especially those having a double bond in the 1, 2 position. The best results are obtained when the structure of the stabilizer is linear.
By using the monoterpenes, sesquiterpenes and/or diterpenes and derivatives thereof of the invention to reduce the adhesion of the mould to a surface, the problem of increased biocide resistance can be avoided. If monoterpenes, sesquiterpenes and/or diterpenes and their derivatives are used in building materials and auxiliary building materials which are sensitive to moulds, more preferably in sealing compounds, especially in cements, several desired effects can be obtained by reducing the adhesion of the mould to the surface:
a) the color of the colored spores is prevented from being changed,
b) the spread of the mould is delayed by the time,
c) the release of allergens is reduced.
In other preferred embodiments, the invention relates to wallpaper containing 0.000001-3% by weight of monoterpenes, sesquiterpenes and/or derivatives thereof. Wallpaper pastes are aqueous solutions of hydrocolloids, such as methyl cellulose, methyl hydroxypropyl cellulose or water-soluble starch derivatives. Film-forming, high molecular weight aqueous dispersions, such as polyvinyl acetate, can also be used, in particular in combination with the cellulose and starch derivatives mentioned.
The filter media used may be of any known type, provided 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, more preferably nylon fibres, non-woven fabrics, sintered materials and membrane filters.
The concentration of monoterpene, sesquiterpene and/or diterpene or derivatives thereof used to reduce the adhesion of the mold to a surface in the composition of the invention may be varied by the skilled person depending on the conditions used for the formulation.
The compositions of the invention can be prepared by the skilled person as standard formulations. Monoterpenes, sesquiterpenes and/or diterpenes or derivatives thereof suitable for reducing the adhesion of the mould to a surface are preferably added to the ready-to-use composition, although they may also be added during the preparation process if desired.