DE10352466A1 - Calixarene compounds are used in solid detergent, cleaning or disinfectant compositions to absorb or adsorb (e.g. onion or fish) odors - Google Patents

Abstract

Use is claimed of specified calixarene compounds as odor binders in solid detergent, cleaning or disinfectant compositions. Use is claimed of calixarene compounds of formula (I) as odor binders in solid detergent, cleaning or disinfectant compositions. [Image] X and Y : H, nitro, halogen, NR4>R5>, SR4> or SO3Z; R4> and R5>independently optionally substituted 1-12C alkyl or aryl or, in each case, optionally substituted 1-12C alkyl, 2-12C alkenyl, 2-12C alkinyl, aryl, aryl(1-12C alkyl) or 1-12C alkoxy (sic); Z : H, alkali metal, alkaline earth metal/2 or NH4; R1> and R2>H or optionally substituted 1-12C alkyl; R3>H or optionally substituted 1-12C alkyl, 2-12C alkenyl, 2-12C alkinyl, aryl or aryl(1-12C alkyl); n : 1-9; and m : 1 or 2.

Description

The The invention relates to the use of calixarene compounds as odor-controlling agent in solid or aqueous washing, cleaning or deodorants and corresponding agents and those containing them Products.

In many applications are already odor-binding or -absorbierende Used funds. For example, textile removers contain odor-absorbing molecules the bad smells like smoke, kitchen haze or animal odors in textiles such as upholstery, carpets, curtains, car seats or Tie clothes and neutralize them. Frequently are also fragrances contained in such agents that leave a pleasant note.

Out DE-A 100 39 100 is a deodorizing textile treatment agent known, in particular zinc ricinoleate or zinc abietate as a deodorizing Contains substance. Furthermore, in particular, agents for laundry conditioning further contain Plasticizers. The funds can in addition to the deodorization or conditioning of textiles as well for the treatment of household surfaces, shoes, waste containers, recycling containers, larger household appliances, countertops, walls, floors, bathroom surfaces and Kitchen surfaces used become. As additional odor-absorbing agents can Cyclodextrins present.

Also in automatic dishwashing detergents and rinse aids Zinc ricinoleate or zinc abietate are used. This is it is possible the unpleasant "alkali smell" when opening a dishwasher to minimize or completely to avoid. Corresponding cleaning agents in the form of rinse aids or also, in particular multi-phase, detergent tablets, are described in DE-A 100 60 533.

From the US 5,783,544 describes the use of cyclodextrins in spray compositions used for odor absorption. Again, attention is drawn to the reduction of offensive odors on household surfaces. Examples include counters, walls, floors, bathroom surfaces and kitchen surfaces.

calixarenes have been prevalent so far used for the sustained release of active substances or active substances. In DE-A 101 26 966 are systems with depot and release function for active ingredients and agents described in which, for example, calixarenes and Cyclodextrins can be used as storage media.

In EP-A 0 954 965 discloses controlled release compositions of biologically active substances. The compositions contain a biologically active compound and a calixarene compound, which controls the release of the biologically active compounds.

to Absorption more disturbing odors calixarenes have been proposed so far for industrial gaseous emissions. WO 97/31698 discloses a method for separating volatile, bad smelling low molecular weight polar substances (VLC) gas streams described, wherein the gas with a calixarene or modified Calixaren is contacted. According to one embodiment may also be a gas stream with a homogeneous or heterogeneous liquid like a solution or dispersion, the calixarenes or modified Calixarene contains. This is an organic solvent in front. Typically, a gas stream containing VLC is passed through Calixarene fixed bed guided. In addition to a physical adsorption of odor binding is particularly based on a capture complexing mechanism. Here are often defined formed supramolecular species. As industrial gas emissions are exhaust gases from animal husbandry or animal processing or out sewage treatment plants called.

The On the other hand, WO 00/50099 relates to the use of surfactant-modified Calixarene derivatives in hygiene articles. In diapers and the like solid products containing polymer fibers are said to bind so annoying odors become.

Especially In detergents, zinc ricinoleate is still the most common used as an odor-binding compound. Especially with household cleaning products, especially in the kitchen area, can be the odor binding of strong odor-causing substances such as onions or fish can still be improved.

task The present invention is the provision of odor-binding or absorbing agents for solid or aqueous Detergents, cleaners and deodorants, which are also strong odoriferous materials such as onions or fish become sustainable Odor retention or absorption and preferably the known Superior means are.

mit der Bedeutung
X, Y an jeder Position unabhängig voneinander H, Nitro, Halogen, NR⁴R⁵, SR⁴, SO₃Z mit Z = H, Alkalimetall, Erdalkalimetall/2, NH₄ und R⁴, R⁵ unabhängig voneinander, jeweils gebenenenfalls substituiertes, C_1-12-Alkyl oder Aryl,
oder, jeweils gegebenenfalls substituiertes, C_1-12-Alkyl, C_2-12-Alkenyl, C_2-12-Alkinyl, Aryl, Ar(C_1-12-alkyl), C_1-12-Alkoxy,
R¹, R² an jeder Position unabhängig voneinander H oder, jeweils gegebenenfalls substituiertes, C_1-12-Alkyl,
R³ an jeder Position unabhängig voneinander H oder, jeweils gegebenenfalls substituiertes, C_1-12-Alkyl, C_2-12-Alkenyl, C_2-12-Alkinyl, Aryl oder Ar(C_1-12-alkyl),
n Zahl im Bereich von 1 bis 9,
m an jeder Position unabhängig voneinander 1 oder 2,
als geruchsbindendes Mittel in wässrigen oder festen Wasch-, Reinigungs- oder Desodorierungsmitteln.The object is achieved according to the invention by the use of calixarene compounds of the general formula (I)

with the meaning
X, Y at each position independently of one another are H, nitro, halogen, NR ⁴ R ⁵ , SR ⁴ , SO ₃ Z with Z = H, alkali metal, alkaline earth metal / 2, NH ₄ and R ⁴ , R ⁵ independently of one another, in each case optionally substituted , C _1-12 -alkyl or aryl,
or, in each case optionally substituted, C _1-12 -alkyl, C _2-12 -alkenyl, C _2-12 -alkynyl, aryl, Ar (C _1-12 -alkyl), C _1-12 -alkoxy,
R ¹ , R ² independently of one another are H or each optionally substituted, C _1-12 -alkyl,
R ³ independently of one another at any position are H or each optionally substituted, C _1-12 -alkyl, C _2-12 -alkenyl, C _2-12 -alkynyl, aryl or Ar (C _1-12 -alkyl),
n number in the range of 1 to 9,
m at each position independently 1 or 2,
as an odor-controlling agent in aqueous or solid detergents, cleaners or deodorants.

The Task is further solved by a solid or watery Washing, cleaning or deodorising agent containing at least a calixarene compound of the general formula (I) as defined above is at least one surfactant and optionally water and pH-regulating Medium.

It was found according to the invention, that the above calixarene compounds in an advantageous manner for odor retention or absorption, especially in the household sector like the kitchen area, can be used.

Of the The term "odor-binding" refers independently of a specific chemical or physical mechanism the removal of odoriferous substances from surfaces the air or liquids, in the way that a disturbing Smell toned becomes or disappears or is avoided. The term includes thus absorption, adsorption and other binding processes.

By the introduction of calixarene compounds, for example in kitchen cleaners could during cleaning a significantly improved neutralization of bad smells, for example, fish smells and onion smells, in direct comparison to, for example, zinc ricinoleates become.

According to the invention, the aforementioned calixarene compounds of the general formula (I) used. The individual radicals X, Y, R ^1, R ^2, R ^3, R ^4, R ⁵ and m can independently have different meanings at any position. Preferably, however, all radicals X, all radicals Y, all radicals R ¹ , etc. have the same meaning. In particular, all substituted aromatic nuclei of the calixarene compounds and all bridging methylene groups have an identical substitution pattern. In other words, this means that the calixarene compounds can be built up starting from a structural unit comprising one of the shown aromatic nuclei and one of the bridging methylene groups. Depending on the method of preparation and purification of the calixarene compounds, calixarene compounds of a specific ring size or mixtures of calixarene compounds of different ring size can be obtained. The ring size is in the range of 4 to 12 such that n is a number in the range of 1 to 9. For mixtures of calixarene compounds, n indicates a mean value indicating the reduced mean ring size by 3. If only one ring size is used, then n is an integer. Preferably, n is a number in the range of 1 to 5. Particularly preferred are even-numbered rings, so that the total ring size is 4 to 12, preferably 4 to 8 (ie 4, 6 or 8), in particular 6. Accordingly, n is preferably 1, 3 or 5, more preferably 3.

mindestens eine Hydroxylgruppe und/oder Säuregruppe auf, die jeweils in Salzform vorliegen können. Vorzugsweise weist jede der genannten Einheiten mindestens zwei Substituenten auf. Gemäß einer Ausführungsform der Erfindung weist jede der Einheiten mindestens 2, vorzugsweise genau 2 Gruppen in Form einer Hydroxylgruppe und/oder Säuregruppe auf, die in Salzform vorliegen können. Gemäß einer Ausführungsform liegt, bezogen auf die gesamte Ringstruktur, eine Hydroxylgruppe oder Säuregruppe innen an den Phenylengruppen vor, so dass bei der vorstehenden flächigen Darstellung die Hydroxylgruppe oder Säuregruppe jeweils in das Ringinnere weist. Die Säuregruppe kann sich dabei von organischen oder anorganischen Säuren ableiten. Beispielsweise kann eine Sulfonsäuregruppe, eine Carboxylgruppe oder auch eine Acetatgruppe vorliegen. Gemäß einer Ausführungsform können in jeder der genannten Einheiten eine Hydroxylgruppe oder Säuregruppe und eine Alkylgruppe, insbesondere eine verzweigte Alkylgruppe, vorliegen. Es können auch jeweils eine Hydroxylgruppe und eine Säuregruppe vorliegen. Sofern in jeder der Einheiten zwei Hydroxylgruppen und keine weiteren Substituenten vorliegen, ist vorzugsweise einer der Reste R¹ und R² ein Rest (CH₂)₂SO₃Alkalimetall.The substituents X, Y and OR ³ can be present in any position on the individual phenylene groups. In the above representation, substituents may be present inside the ring as well as outside the ring. Preferably, each of the units has

at least one hydroxyl group and / or acid group, which may each be in salt form. Preferably, each of said units has at least two substituents. According to one embodiment of the invention, each of the units has at least 2, preferably exactly 2 groups in the form of a hydroxyl group and / or acid group, which may be in salt form. According to one embodiment, based on the entire ring structure, a hydroxyl group or acid group is present on the inside of the phenylene groups, so that in the above planar representation, the hydroxyl group or acid group in each case points into the interior of the ring. The acid group may be derived from organic or inorganic acids. For example, a sulfonic acid group, a carboxyl group or an acetate group may be present. According to one embodiment, in each of said units a hydroxyl group or acid group and an alkyl group, in particular a branched alkyl group, may be present. It is also possible for a hydroxyl group and an acid group to be present in each case. If two hydroxyl groups and no further substituents are present in each of the units, one of the radicals R ¹ and R ² is preferably a radical (CH ₂ ) ₂ SO ₃ alkali metal.

Particularly preferred radicals X, Y and OR ³ are selected from C (CH ₃ ) ₃ , O-CH ₂ -C (= O) O-alkali metal, OH, CH ₂ -CH ₂ -SO ₃ alkali metal.

In the meanings of the calixarene compounds of the general formula (I) the term "substituted" means that said Alkyl radicals and other radicals usual Can carry substituents. It may be halogen atoms, hydroxyl groups, as well as acid groups, for example, acetate groups or sulfonate groups. suitable Substituents are known to the person skilled in the art.

Alkyl radicals are preferably C _1-6 -alkyl radicals, in particular C _1-4 -alkyl radicals. Alkenyl radicals and alkynyl radicals are preferably C _2-6 radicals, in particular C _2-4 radicals. The same applies to alkoxy radicals and aralkyl radicals. Aryl is preferably phenyl. Alkali metals are preferably sodium or potassium, alkaline earth metals preferably magnesium and calcium.

The Calixarene compounds according to the invention are preferably bound, in particular adsorption or absorption of odor-causing used chemical compounds. These are preferably to low molecular weight organic sulfur and / or amino compounds. Such compounds are described, for example, in WO 97/31698 and are considered evil-smelling low molecular weight polar substances (VLC). Appropriate Compounds are also described in the literature cited above.

Without Being bound to a theory, the interaction between the calixarene compounds and the odorous substances as in WO 97/31698 described, done.

The used according to the invention Calixarene compounds are known per se and can according to known Processes are prepared as indicated below. they lay crystalline and can be fine as a fine powder in conventional washing, Add cleaning and deodoriser. Compared to Cyclodextrins can they bind lower molecular odorants better as they are polar Have groups. Furthermore, are used in the invention Calixarene compounds two complexing spaces above and below of the ring. By different derivatizations the Properties of these two Komplexierungsräume be adjusted specifically. It is thus possible a polar and a non-polar complexing space above or to get below the ring plane. Because the odoriferous substances (stink substances) On the polar side, it is possible, for example, perfumes bind to the non-polar side, so that absorption of the Combine odor and a release of perfumes or fragrances to let. So a dual effect can be achieved.

in the Difference to the inventively used Connections is usually used Zinkricinoleat as an oil before that in aqueous Systems poorly soluble is and can lead to an oil film during use.

According to the invention, a washing, cleaning or deodorizing agent is preferably provided which, based on the total agent,
0.03 to 10 wt .-%, particularly preferably 0.1 to 5 wt .-%, in particular 0.3 to 1 wt .-% of at least one calixarene compound of the general formula (I), 0.02 to 30 wt .-%, particularly preferably 0.05 to 10 wt .-% of at least one surfactant, 0 to 10 wt .-%, particularly preferably 0 to 4 wt .-% pH-regulating agent and at least 20 wt .-%, particularly preferably contains at least 50% by weight of water, the total amount of the ingredients being 100% by weight.

According to the invention can Calixarene compounds in all usual Washing, cleaning or deodorants are used and the deodorants previously used wholly or partly replace. With that you can the calixarene compounds also mixed with cyclodextrins or For example, zinc ricinoleate can be used. Preferably the calixarene compounds as a main ingredient or more exclusive Part of the odor absorbing compounds used.

In addition to the ingredients mentioned, builder components such as phosphonates, perfumes, solvents, dyes, opacifiers, thickeners, preservatives or mixtures of one or more of these may additionally be additionally used. Suitable ingredients are described in more detail below. It can also be up US 5,783,544 DE-A 100 39 100, DE-A 199 37 871, DE-A 100 60 533 and DE-A 101 08 460 are referred to.

The agents according to the invention can about that addition as surfactant anionic, nonionic, cationic and / or amphoteric surfactants in an amount of 0 to 30 wt .-%, more preferably 0.05 to 10 wt .-%, with nonionic surfactants due their foaming power are preferred.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkane and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.

Further Suitable anionic surfactants are sulfated fatty acid glycerol esters. Among fatty acid glycerol esters are to understand the mono-, di- and triesters and their mixtures, such as they are produced by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained. Preferred sulfated fatty acid glycerol esters are included the sulphonated products of saturated fatty acids with 6 to 22 carbon atoms, for example the caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or Behenic acid.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical having an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. Also 2,3-alkyl sulfates, which can be obtained as commercial products of the Shell Oil Company under the name DAN ^® , are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C _7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _12-18 . Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates, eg disodium laureth sulfosuccinate, contain C _8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

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

The including anionic surfactants the soaps can in the form of their sodium, potassium or Ammonium salts and as soluble Salts of organic bases, such as mono-, di- or triethanolamine, are present. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

A another class of preferred nonionic surfactants, the either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half from that.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Further suitable surfactants are polyhydroxy fatty acid amides of the formula (IX)

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

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (X)

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.

[Z] is preferably by reductive amination of a reduced sugar obtained, for example, glucose, fructose, maltose, lactose, galactose, Mannose or xylose. The N-alkoxy or N-aryloxy-substituted Connections can by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxyfatty acid amides are transferred.

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, the detergent components according to the invention for automatic dishwashing contain nonionic surfactants, in particular nonionic surfactants from the group of alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Also For example, disodium caprylamphodiacetate may be as amphoteric Surfactant are used.

The composition according to the invention may contain one or more water-soluble organic solvents In this case, water-soluble means that the organic solvent is soluble in the amount contained in the aqueous agent according to the invention.

In a preferred embodiment, the agent according to the invention may contain one or more solvents from the group comprising C ₁ to C ₄ monoalcohols, C ₂ to C ₆ glycols, C ₃ to C ₁₂ glycol ethers and glycerol, in particular ethanol. The C ₃ - to C ₁₂ glycol ethers according to the invention contain alkyl or alkenyl groups having less than 10 carbon atoms, preferably up to 8, in particular up to 6, more preferably 1 to 4 and most preferably 2 to 3 carbon atoms.

Preferred C ₁ to C ₄ monohydric alcohols are ethanol, n-propanol, isopropanol and tert-butanol. Preferred C ₂ to C ₆ glycols are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,5-pentanediol, neopentyl glycol and 1,6-hexanediol, in particular ethylene glycol and 1,2-propylene glycol. Preferred C ₃ - to C ₁₂ glycol ethers are di-, tri-, tetra- and pentaethylene glycol, di-, tri- and tetrapropylene glycol, propylene glycol monotertiary butyl ether and propylene glycol monoethyl ether and the solvents designated according to INCI butoxydiglycol, butoxyethanol, butoxyisopropanol, butoxypropanol, butyloctanol, ethoxydiglycol, Ethoxyethanol, ethyl hexanediol, isobutoxypropanol, isopentyldiol, 3-methoxybutanol, methoxyethanol, methoxyisopropanol and methoxymethylbutanol.

Especially preferred solvents are ethanol, 1,2-propylene glycol and dipropylene glycol and their Mixtures, in particular ethanol.

The inventive agent can be one or more solvents in an amount of usually 0.1 to 30% by weight, preferably 1 to 25% by weight, in particular 2 to 20% by weight, more preferably 2.5 to 10% by weight, most preferably 3 to 5 wt .-%, contained.

In a preferred embodiment contains the agent of the invention additionally one or more complexing agents.

complexing (INCI chelating agents), also called sequestering agents, are ingredients, to complex and inactivate the metal ions their adverse effects on the stability or appearance of the means, for example, cloudiness, to prevent. On the one hand, it is important to deal with many Ingredients incompatible calcium and magnesium ions of the water hardness to complex. The complexation of the ions of heavy metals such as iron or copper delayed the oxidative decomposition of the finished agents.

Suitable are, for example, the following complexing agents designated according to INCI, in the International Cosmetic Ingredient Dictionary and Handbook described in more detail are: Aminotrimethylene Phosphonic Acid, Beta-Alanine Diacetic Acid, Calcium Disodium EDTA, Citric Acid, Cyclodextrin, Cyclohexanediamine Tetraacetic Acid, Diammonium Citrate, Diammonium EDTA, Diethylenetriamine Pentamethylene Phosphonic Acid, Dipotassium EDTA, Disodium Azacycloheptane Diphosphonates, Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactic Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, methyl cyclodextrin, pentapotassium triphosphate, Pentasodium Aminotrimethylene Phosphonates, Pentasodium Ethylenediamine Tetramethylene Phosphonates, Pentasodium Pentetates, Pentasodium Triphosphates, Pentetic Acid, Phytic Acid, Potassium Citrate, Potassium EDTMP, Potassium Gluconate, Potassium Polyphosphate, Potassium Trisphosphonomethylamine Oxides, Ribonic Acid, Sodium Chitosan Methylene Phosphonates, Sodium Citrate, sodium diethylenetriamine pentamethylene phosphonate, sodium Dihydroxyethylglycinate, Sodium EDTMP, Sodium Gluceptate, Sodium Gluconate, Sodium Glycereth-1 Polyphosphate, Sodium Hexametaphosphate, Sodium Metaphosphate, Sodium Metasilicate, Sodium Phytate, Sodium Polydimethylglycinophenolsulfonates, sodium trimetaphosphates, TEA-EDTA, TEA polyphosphates, tetrahydroxyethyl, ethylenediamines, tetrahydroxypropyl Ethylenediamine, tetrapotassium etidronate, tetrapotassium pyrophosphate, Tetrasodium EDTA, Tetrasodium etidronate, Tetrasodium pyrophosphate, Tripotassium EDTA, Trisodium Dicarboxymethyl Alaninate, Trisodium EDTA, Trisodium HEDTA, Trisodium NTA and Trisodium Phosphate.

preferred Chelating agents are amines, in particular alkanolamines (amino alcohols). The alkanolamines have both amino and hydroxy and / or Ether groups as functional groups. Particularly preferred alkanolamines are monoethanolamine and triethanolamine and tetra-2-hydroxypropylethylenediamine (N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine). The complexing agents practice preferably no such interactions with the calixarene compounds which severely impair or hinder their effect. in the Difference to the inventively used Calixarene compounds is e.g. Zn ricinoleate not compatible with alkanolamines.

The inventive agent contains Complexing agent in an amount of usually 0 to 20% by weight, preferably 0.1 to 15% by weight, in particular 0.5 to 10% by weight, particularly preferably 1 to 8 wt .-%.

Of the pH of the agent according to the invention becomes common to 2 to 12, preferably 4 to 11, in particular 5 to 10 set.

to PH adjustment can be any odorless and color neutral acid or basic or buffering pH regulator (INCI pH Adjusters) become.

When Acidic pH regulators are preferably acid complexing agents, e.g. Citric acid.

preferred basic pH regulators are ammonia and the alkali metal hydroxides and the alkaline earth metal hydroxides, in particular the alkali metal hydroxides, most preferably sodium hydroxide and potassium hydroxide, most preferably Potassium hydroxide and ammonia.

Farther can the agent of the invention one or more usual Auxiliaries and additives, in particular from the group of perfumes, dyes, antimicrobial agents or preservatives, antistatic agents, and insect repellents. The mentioned Auxiliaries and additives are described, for example, in WO 96/04940 and the literature cited therein. At the qualitative such as quantitative selection of excipients and additives - as well the ingredients described above - is a sufficiently high solubility in the agent according to the invention as well as a sufficiently low residue formation.

In an embodiment contains the agent of the invention one or more perfumes in an amount of usually 0.01 to 5 wt .-%, preferably 0.05 to 2 wt .-%, in particular 0.1 to 1.5% by weight, more preferably 0.2 to 1% by weight, most preferably 0.3 to 0.6 wt .-%. The perfume reinforces the deodorizing effect of the agent according to the invention in addition to - partial or complete - odor quenching by the deodorizing agent due to its odor masking Effect. The advantage here is the indifference of the deodorizing invention Active ingredient compared to the most perfumes, so that neither the deodorizing agent binds the perfume and both components bind still deactivate the perfume by the deodorant one another Drug destroyed becomes.

dyes can in the agent according to the invention be used, the amount of one or more dyes so low to choose is that after the application of the agent no visible residues remain.

The agent according to the invention may contain one or more antimicrobial agents or preservatives in an amount of usually 0.0001 to 3% by weight, preferably 0.0001 to 2% by weight, in particular 0.0002 to 1% by weight, especially preferably 0.0002 to 0.2 wt .-%, most preferably 0.0003 to 0.1 wt .-%, contained. Antimicrobial agents or preservatives include alcohols, aldehydes, antimicrobial acids, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, substituted isothiazoles and hydrogenated isothiazole derivatives such as isothiazolines (Dihydroi sothiazolen ) and isothiazolidines, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds such as antimicrobial quaternary surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophors and peroxides, for example, phenoxyethanol, undecylenic acid, salicylic acid, benzoic acid, 2-benzyl-4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2 ' -hydroxydiphenyl ether, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) -urea, N, N '- (1,10-decanediyldi-1-pyridinyl-4-ylidene) -bis (1-octanamine n) dihydrochloride, N, N'-bis (4-chlorophenyl) -3,12-dinimino-2,4,11,13-tetraaza-tetradecandimidamide and hemiacetal-isothiazolinone preparations such as a chloro-2-methyl-3 (2H) -isothiazolone-2-methyl-3 (2H) -isothiazolone-1,2-ethanediylbis (oxy) bismethanol-N, N'-dimethylol-mixture (available under the trade name Bodoxin ^® from Bode Chemie). Antimicrobial agents and preservatives are described in greater detail, for example, by KH Wallhäußer in "Praxis der Sterilisation, Desinfektion - Konservierung: Keimidentifizierung - Betriebshigiene" (5th edition - Stuttgart, New York: Thieme, 1995).

The inventive agent is according to one embodiment sprayable and therefore can be used in a spray dispenser be used.

One The invention accordingly provides a product containing a sprayable agent according to the invention and a spray dispenser.

Prefers is the spray dispenser a manually activated spray dispenser, especially selected from the group comprising aerosol spray dispensers, self pressure building spray dispenser, Pump spray dispensers and Triggersprühspender, in particular pump spray dispenser and trigger spray dispensers with a container made of transparent polyethylene or polyethylene terephthalate.

The spray dispenser cause sputtering preferably an average droplet size in the range of 10 to 1500 μm, in particular 100 to 800 microns.

spray dispenser become more detailed in WO 96/04940 (Procter & Gamble) and the spray dispensers in it cited US patents.

The The invention also relates to the use of an agent according to the invention for deodorising an article, a surface, e.g. made of glass, porcelain, plastic, textiles, leather, lacquers or wood, or a room, preferably of textile fabrics, household surfaces, shoes, waste containers Recycling containers Air, larger household appliances, cat litter, Pets, Pet Beds, in particular of garments, Carpets, carpets, curtains, Curtains, upholstered furniture, bedding, Tents, sleeping bags, Car seats, car carpets, textile car interior linings, Counter tops, walls floors, bathroom surfaces and kitchen surfaces. Larger household appliances are for example, refrigerators, freezers, Washing machines, dishwashers, dryer, ovens and microwave ovens.

to Deodorizing an object, a surface or a room an effective amount of an agent of the invention on and / or in the object, on the surface or distributed in the space, preferably textile fabrics, household surfaces, shoes, Waste container Recycling containers, air, larger household appliances, cat litter, Pets, Pet Beds, especially clothes, Carpets, Carpets, Curtains, Curtains, upholstered furniture, bedding, Tents, sleeping bags, Car Seats, Car Carpets, Textile Car Interior Linings, Counter Surfaces, Walls, Floors, Bathroom Surfaces and Kitchen surfaces, taking Tissue and shoes do not prefers to be sprayed to saturation and the agent after drying on the object or surface practically no longer recognizable.

Under an effective amount is understood to mean an amount that is a attenuation or complete Eradication of unwanted odors causes.

In an embodiment is the agent of the invention sprayed in the room or on and / or in the article or on the surface, in particular from a distance of 10 to 100 cm, preferably 20 to 50 cm, more preferably 25 to 40 cm, most preferably about 30 cm, sprayed.

The inventive agent can be used both in a ready-to-use concentrated form and as a Concentrate should be provided before using with water to dilute is, preferably in a certain volume ratio of Water to agent from 1 to 1 to 6 to 1, especially 1 to 1 to 3 to 1, more preferably 1 to 1 to 2 to 1, and most preferably 1 to 1. A concentrate differs in composition from the ready-to-use concentrated or diluted form exclusively by the lower water content with the same absolute amount (not Relative amount in wt .-%) of the rest Ingredients.

The Cleaning agent according to the invention are particularly preferably used for cleaning hard surfaces. The washing, cleaning or deodorizing agent is preferably selected from Kitchen cleaners, softeners, Universal detergents, Gentle-washing preparations, Hair treatment preparations, Fiber treatment agents and dishwashing deodorants (dishwasher deodorants, to improve odor in dishwashers), Room air improvers and manual and automatic dishwashing detergents, Glass cleaners, bath and toilet cleaners, floor cleaners and care products.

The The invention is explained in more detail below by means of examples.

Example 1:

Use in the cleaning agent:

To the Use here preferably acetate-substituted tert-butyl calix [n] arenes (n = 6), designated as calixarene n = 6 (p-tert-butyl-calix [6] arenhexakaliumacetat).

The Synthesis of calixarene was as described in Tetrahedron, 1986, p. 2089, JACS 1989, p. 8681 and J. Chem. Soc., Chem. Comm. 1984, p. 981 described carried out.

The Calixarenes, especially the calixarene with n = 6, produce in the Formulation in detergents and cleaners has positive effects in terms of odor destruction. The test was calixarenes introduced into acidic and alkaline cleaner formulations. The Effectiveness of odor neutralization on hard surfaces was in the laboratory experiment based on the odor reduction of onion and fish smell in comparison to Zn ricinoleate determined. For this purpose, each 2 g pureed onion mass or pureed fish mass on the upper 3 cm of a wooden stick of 15 cm in length and 2 cm wide and applied for Covered for 1 h of a plastic bell. Subsequently, the pureed mass removed with the help of a disposable cloth. The wooden stick was then broken off and treated with the cleaner formulations E1V-E12V.

Tabelle 2: saure Reiniger (Bad, Toilette)

Tabelle 3: Vergleichsrezepturen

The wooden sticks were scented immediately after treatment and after 1 h by a trained expert panel (4 persons) and scored on a scale of 1 to 4 or in comparison. It was found that when treated with the detergent formulations E9V-E12V, the odor was clearly noticeable (more than 80%) immediately after application and also after 1 h. When treated with the cleanser formulations E1V, E4V, E5V and E8V, the odor was still clearly noticeable immediately after use (about 70%) and reduced to about 40% after 1 h. When treated with detergent formulations E2, E3, E6 and E7, the odor was reduced to about 30% immediately after use and completely disappeared after 1 h. Table 1: alkaline cleaners (glass, kitchen)

Table 2: acidic cleaners (bath, toilet)

Table 3: Comparative formulations

Example 2

The following cleaning agents were made up:
E13: E9V base formulation + 0.5% calix [6] arene p-hexasulfonate
E14: E9V base formulation + 0.5% calix [8] arene-p-octasulfonate
E15: E9V base formulation + 0.5% calix [4] arene-p-tetrasulfonate
E16: E9V basic formula without perfume oil + 0.5% p- ^t butylcalix [6] arene hexakaliumacetat
E17: E9V basic formula without perfume oil + 0.5% p- ^t butylcalix [4] arene tetrakalium acetate (suspension)
E18: E9V basic formula without perfume oil + 0.5% p- ^t butylcalix [4] arene tetrakalium acetate
E19: E9V basic formula + 0.5% p- ^t butylcalix [6] arene hexakalium acetate
E20: E9V base formulation + 0.5% tetrasulfonated calix [4] resorcinaren
E21: E9V basic formula + 0.5% Zn ricinoleate

The Calixarenes used in E13, E14 or E15 are commercially available as 4-sulfocalix [4] arene, 6-sulfo-calix [6] arene and 8-sulfo-calix [8] arene, respectively. The calixarenes used in E16 to E20 are available as in Tetrahedron 1986, p. 2089; J. Am. Chem. Soc. 1989, 111, p. 8681, J. Chem. Soc., Chem. Commun. 1984, p. 981.

In Example 1 was a performance comparison of different compositions carried out. The results are shown in Table 4 below.

Table 4

4:

Odor completely removed

3:

Odor almost completely removed

2:

Odor diminished / mixed odor

1:

Odor not eliminated

Claims (11)

Use of calixarene compounds of the general formula (I)

with the meaning X, Y at each position independently of one another H, nitro, halogen, NR ⁴ R ⁵ , SR ⁴ , SO ₃ Z with Z = H, alkali metal, alkaline earth metal / 2, NH ₄ and R ⁴ , R ⁵ independently of one another, each optionally substituted, C _1-12 alkyl or aryl, or, each optionally substituted, C _1-12 alkyl, C _2-12 alkenyl, C _2-12 alkynyl, aryl, Ar (C _1-12 alkyl ), C _1-12 -alkoxy, R ¹ , R ² at each position independently of one another H or, in each case optionally substituted, C _1-12 -alkyl, R ³ independently of one another H or, in each case optionally substituted, C _{1 12} -alkyl, C _2-12 -alkenyl, C _2-12 -alkynyl, aryl or Ar (C _1-12 -alkyl), n is in the range of 1 to 9, m at each position independently of one another 1 or 2, as odor-controlling agent in aqueous or solid detergents, cleaners or deodorizers. Use according to claim 1, characterized that in the calixarene compounds of the general formula (I) n is a number in the range of 1 to 5. Use according to claim 1 or 2, characterized in that in the calixarene compounds of general formula (I) each of the units

at least one hydroxyl group and / or acid group, which may be in salt form. Use according to one of Claims 1 to 3, characterized that the odor-binding agent for absorption or adsorption of low molecular weight organic sulfur and / or amino compounds serves. Solid or watery Washing, cleaning or deodorising agent containing at least a calixarene compound of the general formula (I) as described in one of the claims 1 to 3, at least one surfactant and optionally Water and pH regulating agents. Detergents, cleaners or deodorants Claim 5, containing, based on the total agent, 0.03 to 10 wt .-% of at least one calixarene compound of the general Formula (I) as defined in any one of claims 1 to 3, 0.02 up to 30% by weight of at least one surfactant, 0 to 10% by weight pH-regulating Means and at least 20% by weight of water, the total amount the ingredients are 100% by weight. Detergents, cleaners or deodorants Claim 6, in addition containing perfumes, Solvents Dyes, opacifiers, thickeners, preservatives or mixtures from two or more of them. Cleaning agent according to one of claims 6 or 7, characterized in that it serves for cleaning hard surfaces. Detergents, cleaners or deodorizers one of the claims 5 to 7, characterized in that it is selected from kitchen cleaners, softeners, Universal detergents, gentle detergents, hair treatment preparations, Fiber treatment agents, dishwashing deodorants, air fresheners, manual and automatic dishwashing detergents, glass cleaners, bathroom and toilet cleaners, floor cleaners and care products. Detergents, cleaners or deodorants one of the claims 5 to 9, characterized in that it is in sprayable form. Product containing a sprayable composition according to claim 10 and a spray dispenser.