WO2009115391A1 - Use of imidazolium salts in detergents and cleaning products - Google Patents

Abstract

The present invention relates to detergents and cleaning products containing imidazolium salts and to the use of said detergents and cleaning products for cleaning textiles and surfaces.

Description

 20/02/2009

1

Use of imidazolium salts in detergents and cleaners

The present invention relates to detergents and cleaning agents containing imidazolium salts and to the use of these detergents and cleaners for cleaning textiles and surfaces.

In washing and cleaning agents, a variety of active substances has already been used to improve their cleaning performance. Nevertheless, there is still a need for more effective agents, especially with regard to particularly stubborn stains. A particular problem in this case is strongly burned in dirt, which can be as a rule only with great difficulty and with great expenditure of time, such as by soaking for several hours, removed.

Surprisingly, it has now been found that imidazolium salts, in particular with respect to strongly baked-on dirt, allow a significant improvement in the cleaning performance of detergents and cleaners.

A first subject of the present invention are therefore detergents and cleaners containing at least one imidazolium salt. Cleaning agents for hard surfaces, in particular hand dishwashing detergents and automatic dishwasher detergents, are particularly preferred.

Another object of the present invention is therefore also the use of such imidazolium salts according to the invention and of detergents and cleaners containing such imidazolium salts, for the cleaning of surfaces, especially hard surfaces, as well as for the cleaning of textile fabrics.

A preferred object of the present invention is in particular the use of such imidazolium salts according to the invention and of detergents and cleaners which contain such imidazolium salts, for the removal of stubborn and / or baked-on, in particular strongly burned, stains.

A further preferred subject matter of the present application is furthermore a process for cleaning dishes in a dishwasher, in which a washing or cleaning agent according to the invention is metered into the interior of a dishwasher during the passage of a dishwashing program before the main wash cycle or during the main wash cycle. The metering or the entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered by means of the metering chamber into the interior of the dishwasher. The imidazolium salt according to the invention is preferably a salt which contains as imidazolium cation a compound of general formula (I)

characterized in that R1, R2, R3, R4 and R5 independently of one another represent trifluoromethyl, hydrogen, alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, heteroalkyl, heterocycloalkyl, alkoxy, alkoxyalkyl, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, alkanoyl, alkanoyloxy, alkoxycarbonyl, Alkylaminocarbonyl, alkylsulfanylcarbonyl, hydroxy, hydroxyalkyl, hydroxycarbonyl, amino, alkylamino, aryl, arylalkyl, aryloxy, arylamino, arylsulfanyl, arylsulfinyl, arylsulfonyl, arylcarbonyl, arylcarbonyloxy, aryloxycarbonyl, arylaminocarbonyl, arylsulfanylcarbonyl, heteroaryl, heteroarylalkyl, heteroaryloxy, heteroarylamino, heteroarylsulfanyl, heteroarylsulfonyl, Heteroarylsulfoxidyl, heteroarylcarbonyl, heteroarylcarbonyloxy, heteroaryloxycarbonyl, heteroarylaminocarbonyl, heteroarylsulfanylcarbonyl, alkoxysulfonyl, alkoxycarbinol, sulfo, sulfino, sulfeno, formyl or thioformyl, all radicals of the resulting molecule in each case independently of one another optionally also auc h may be monosubstituted or polysubstituted.

In a preferred embodiment, R 1 and R 4 are independently optionally substituted alkyl, aryl, arylalkyl, alkylcarbonylalkyl or arylcarbonylalkyl, and R 2, R 4 and R 5 are independently hydrogen or optionally substituted alkyl.

In a further preferred embodiment, in this case R1 and / or R4, preferably both R1 and R4, comprise an aromatic radical.

In a particularly preferred embodiment, R 1 and R 4 independently of one another are optionally substituted phenyl, phenyl-C 1-e-alkyl or phenylcarbonyl-C 1-e-alkyl and

Radicals R2, R4 and R5 are independently hydrogen or optionally substituted

C ^ alkyl.

In very particularly preferred embodiments, R 1 is an optionally substituted phenacyl radical and / or R 4 is an optionally substituted phenylmethyl radical

Rest. In this sense, in a very particularly preferred embodiment, the imidazohum cation is a compound according to formula (II) or formula (III)

where appropriate, said compounds may also be monosubstituted or polysubstituted.

The abovementioned substituents are preferably selected from alkyl, halogen, in particular chlorine, bromine, iodine or fluorine, hydroxypropyl, hydroxyalkyl, hydroxycarbonyl, alkoxy, alkoxyalkyl, alkoxycarbonyl, amino, alkylamino and dialkylamino.

The Anioπ of the imidazolium salt is preferably selected from Halogeπid, in particular chloride, boron, iodide or fluoride. Sulfate, sulfite, nitrate, Hydrogβncarbonat and deprotonatedβn organic acids, more preferably it is a halide, especially bromide.

It has surprisingly been found according to the invention that the washing performance can be further improved if the imidazolium salt is used in combination with salicylic acid (2-hydroxybenzoic acid), a salicylic acid or mixtures thereof.

According to the invention, the salicylic acid derivatives may be selected, in particular, from 2-hydroxybenzoic acid which is substituted by further radicals on the ring, the other radicals preferably being selected from hydroxyl, amino, halogen, in particular chlorine, bromine or fluorine, C 1 -b-alkyl, Ci-β-alkoxy, Cf-β-alkylamino and di (Ci-B-alkyl) amino. The Ca rboxyl group and the hydroxy group of 2-Hydroxybenzoesäυre and salicylic acid derivatives may also be optionally esterified or etherified, in particular by optionally substituted Ci-β-Alkaπol.

"Alkyl" according to the invention preferably represents C

^. _ie -alkyl. in accordance with the invention in each case independently of one another for all saturated linear and branched alkyl radicals having up to 18 C atoms, preference being given to C 1, B-alkyl radicals. Ci "6-alkyl is according to the invention for all saturated linear and branched alkyl radicals having up to 6 C-Atomθn, iπsbθsondθre for methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl and all isomers of pentyl and hexyl.

According to the invention, "cycloalkyl" is preferably Cs-β-cycloalkyl. Cj-β-Cycloalkyl independently of one another in each case denotes all cyclic alkyl radicals having 3 to 6 C atoms, preferably 5 to 6 C atoms, where the radicals may be saturated or unsaturated, especially for cyclopentyl, cyclohexyl or cyclopentadienyl.

"Alkenyl" is C ₂ -i erfindungsgemöß preferably _a alkenyl. C ₂ -i _fl -alkenyl erfiπduπgsgemad each independently for all linear and branched alkyl radicals having up to 18 carbon atoms, containing at least one double bond, C _2-6 alkenyl radicals are preferably C ₂ -. ₆ -alkenyl erfmduπgsgemaß for all linear and branched alkyl radicals having up to 6 carbon atoms, containing at least one double bond, in particular ethenyl, propenyl, i-propenyl and all isomers of butenyl, pentenyl and hexenyl.

"Alkynyl" is preferably θrfiπduπgsgemäß for

in accordance with the invention, in each case independently of one another, denotes all linear and branched alkyl radicals having up to 18 C atoms which contain at least one triple bond, where C ₂ . _e- alkynyl radicals are preferred. C ₂ . ₆ -Alkinyl stands erfinduπgsgemälϊ for all linear and unbranched alkyl radicals having up to 6 carbon atoms which contain at least one triple bond, in particular ethynyl, propynyl, i-Propiπyl and all isomers of Butrnyl, Peπtinyl and hexynyl.

Heteroalkyl according to the invention is in each case independently of one another for all saturated and mono- or polyunsaturated, linear or branched alkyl radicals which contain at least one, preferably exactly one heteroatom, in particular selected from O, S and N, where the sum of C and Hetero-Atomeπ preferably up to 18, more preferably up to 6 amounts.

Heterocycloalkyl according to the invention is in each case independently of one another for all cyclic alkyl radicals which contain at least one, preferably exactly one, heteroatom, in particular selected from O, S or N ₁ , wherein the ring is preferably from three to eight membered, more preferably five to six membered , Examples of these are tetrahydrofuranyl, tetrahydrothiophenyl, pyrrolidinyl, 2-thiazolinyl, tetrahydrothiazolyl, tetrahydrooxazolyl, piperidinyl, pipazrazinyl, morpholinyl and thiomorpholmyl.

According to the invention, C _1-18 -alkoxy is preferably independently of each other all saturated and unsaturated, linear and branched alkyl radicals having up to 18 C atoms which are bonded via an oxygen atom to C _1-16 -alkoxy. When C ₁ -C alkoxy radicals are preferred, C _1-6 -alkoxy, according to the invention, in each case independently of one another for all saturated and unsaturated, linear and branched alkyl radicals having up to 6 C atoms, which are bonded via an oxygen atom, in particular methoxy and ethoxy.

"Alkylöulfanyl" stands erfinduπgsgemaß preferably Ci_ig alkylsulfanyl. Ci-ie-alkylsulfanyl is erfinduπgsgemäß each independently, all saturated and _unsaturated! Linear and branched alkyl radicals having up to 18 carbon atoms bonded via a sulfur atom, where C _{1, β} -alkylsulfinyl radicals are preferred According to the invention, C ₁ -alkylsulfanyl represents all saturated and unsaturated, linear and branched alkyl radicals having up to 6 C atoms which are bonded via a sulfur atom, in particular Methysulfanyl and Ethylsulfaπyl.

According to the invention, "alkylsulfinyl" is preferably C _1- al-alkynyl [sulfinyl. C 1-6 -alkylsulfinyl according to the invention is, independently of one another, for all saturated and unsaturated, linear and branched alkyl radicals having up to 16 carbon atoms which have an SO group are bonded, said CI_ ₆ -Alkylsulfoπyl radicals are preferred. C ^ alkylsulfinyl stands according to the invention for all saturated and unsaturated, linear and branched alkyl radicals having up to 6 C-Atomeπ, which are bonded via an SO group, in particular for Mβthylsulfiπyl and ethylsulfinyl.

According to the invention, "alkylsulfonyl" is preferably C 1 -C 4 -alkylsulfonyl. C 1 -C 4 -alkylsulfonyl according to the invention in each case independently of one another for all saturated and unsaturated, linear and branched alkyl radicals having up to 18 C atoms which are bonded via a SOjj group are, where C _t -β-Alkylsulfoxidyl radicals are preferred. C ,. ₆ -AlkylsulFoπyl is erfinduπgsgemäß for all saturated and unsaturated, linear and branched alkyl radicals having up to 6 carbon atoms which bound via a SO ₂ group in particular for methylsulfonyl and ethylsulfonyl

According to the invention, C ₁ -alkyl is in each case independently of each other saturated and unsaturated, linear and branched alkyl radicals having up to 18 C atoms which, via a carbonyl _radical, represent C _1-1 -alkanoyl. Ci- ₆ -alkanoyl is according to the invention for all saturated and unsaturated, linear and branched alkyl radicals having up to 6 carbon atoms, which are bonded via a carbonyl group , in particular For Methycarboπyl and ethylcarbonyl.

According to the invention, "alkaπoyloxy" is preferably Ci_is-alkanoyloxy. Ci-iβ-alkanoyloxy in accordance with the invention in each case independently represents all saturated and unsaturated, linear and branched alkyl radicals having up to 18 C atoms which are bonded via a carboxyyloxy group, in which

are preferred.

is according to the invention for all saturated and unsaturated, linear and branched alkyl radicals having up to 6 carbon atoms, which are bonded via a Carboπyloxy group, in particular for methanoyloxy, Ethaπoyloxy, n-propanoyloxy and i-Propanoyloxy. "Alkoxycarbonyl" means erfindungsgemafl preferably C ^ _j -Alkcxvcarbonyl C _1-1β -. Erfinduπgsgemäß alkoxycarbonyl in each case independently of one another for all saturated and unsaturated, linear and branched alkyl radicals having up to 18 carbon atoms, which has a group Oxycarboπyl are attached, wherein Ci »a-Alkoxycarboπyl radicals are preferred. C- _\ .§- alkoxycarbonyl accordance with the invention for all saturated and unsaturated, linear and branched alkyl radicals having up to 6 carbon atoms which bound via an oxycarbonyl group are, in particular for methoxycarbonyl and ethoxycarbonyl

According to the invention, C _1-19 -alkylaminocarbonyl in each case independently of one another represents an aminocarbonyl group which is mono- or disubstituted by a saturated or unsaturated, linear or branched alkyl radical with up to 18 C atoms is substituted, wherein mono- or disubstituted by C ^ alkyl groups substituted aminocarbonyl radicals, in particular monomethylaminocarbonyl, Diemethylaminocarbonyl, Monoethylamiπocarboπyl and Diethylamiπocarboπyl, are preferred.

According to the invention, "alkylsulfanylcarbonyl" is preferably d-ie-alkylsulfanylcarbonyl. Ci-m-Alkylsulfanylcarbonyl is according to the invention independently of each other for all saturated and unsaturated, linear and branched alkyl radicals having up to 18 C atoms, which have a thiocarbony] group are attached, wherein C _1-β -Alkylsulfanylcarbonyl radicals are preferably C _1-6 -. Alkylsulfanylcarboπyl is according to the invention for all saturated and unsaturated, linear and branched alkyl radicals having up to 6 carbon atoms which bound via a group Thiocarboπyl are, in particular for methylthiocarbonyl and ethylthiocarbonyl.

"Alkylamino" is erfind ungsgernäß preferably (Ci-ia alkyl) NH. _{Fl CM alkyl) NH erfindungsgsmäß each independently, all saturated and unsaturated, linear and branched alkyl groups having up to 18 carbon atoms, which has a Hydrogenamino group are bonded, wherein _(a CI_ alkyl) NH is preferred (Ci. alkyl _a) NH according to the invention for all saturated and unsaturated, linear and branched alkyl radicals having up to 6 carbon atoms, which has a Hydrogenamino Group are bound, in particular for CH ₃ NH and C ₂ H _S NH.

According to the invention, "dialkylamine" is preferably di (C ₁ -alkyl) N, di- (C ₁ -isalkyl) N is according to the invention in each case independently of each other all saturated and unsaturated, linear and branched alkyl radicals having up to 18 C atoms which are bonded via a (C 1-10 -alkylamino group, preference being given to di- (C 1-8 -alkyl) N, where the two alkyl radicals may be identical or different from one another. alkyl) N is according to the invention for all saturated and unsaturated, linear and branched alkyl groups having up to 6 C-atoms, which amiπo group are bonded via a (Ci-β- alkyl), especially for (CHj) ₂ N and (C ₂ H ₆ ) ₂ N. According to the invention, aryl preferably represents C _β . _{1 [r} aryl. C 1-10 aryl is according to the invention, in particular also in C _6-10 aryl-C _1-12 -alkyl, Cβ-m-aryloxy, Ce. ₁₀ arylamino, C _a-10 -Arylβulfanyl, C _M0 - arylsulfonyl, C _6- io-Arylsulfoxidyl, Ce-io-arylcarbonyl, C-io arylcarbonyloxy, C-io aryloxycarbonyl, Cβ-io-Arylamiπocarbonyl and

preferably phenyl or naphthyl, particularly preferably phenyl.

Heteroaryl is erfgπdungsgβmäß, in particular also in heteroaryl-CM2-alkyl, heteroaryloxy, heteroarylamino, Heteroarylsulfaπyl, Heteroarylsulfonyl, Heteroarylsulfoxidyl, Hθteroarylcarbonyl, Heteroarylcarboπyloxy, Heteroaryloxycarbonyi, Heteroarylaminocarboπyl and Hθteroarylsulfanylcarbonyl, unless otherwise indicated, for at least one heteroatom selected from O, S and N. containing aromatic radical having 5 to 10, preferably 5 or 6, ring members, preferably selected from furanyl, thienyl, thiophenyl, pyrrolyl, isopyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isothiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, benzofuranyi, Benzothiophenyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, indazolyl, pyridofuranyl and pyridothienyl.

In arylalkyl, in particular C _0-10 -aryl-C _1-1S -alkyl, and heteroarylalkyl, the alkyl radical may be saturated or unsaturated, branched or unbranched. Preferred radicals are benzyl, phenylethyl, naphthylmethyl and naphthylethyl,

"Amino" according to the invention stands for any substituted or unsubstituted amino group, in particular -NH ₂ , -NH (C _1-1B -alkyl), -N (C _1-1 -alkyl) -alkyl, -NH ₂ -alkyl-aryl) or -N (C _6-10 -AfyI) ₂ , especially preferred for -NH _£ .

According to the invention, "ammonium" represents any substituted or unsubstituted ammonium group, in particular -NH ₃ ^W , -NH ₂ (C ₁ -18 -alkyl) -NH (C ₁ -alkyl) ₂ ^W or -N (C _1-18 -AikyI) ₃ ",

"Sulfato" according to the invention is in particular Wr -OS (O) ₂ -OR ₁ "sulfo" for -S (O) ₂ -OR, "amidosulfo" for -O-S (O) ₂ -NR ₂ , "phosphato" for 0-P (O) (OR) ₂ , "phosphono" for -P (O) (OR) ₂ "amidophosphono" for -O-P (O) (NRj) ₂ or -OP (O) (OR) (NO ₂₎ and "amidocarbonyl" -C (O) -NR ₂ wherein each R is independently ^(H, M ⁺⁾ _F Ci-ie-alkyl, Ce-io-aryl or Ci-is- alkyl-C _{e- 10} -aryl stands.

Imidazolium salts to be used according to the invention are preferably present in the inventive compositions in an amount of from 0.01 to 5.0% by weight, more preferably in an amount of from 0.1 to 3.0% by weight, especially in an amount from 0.2 to 2.0% by weight. A washing or cleaning agent according to the invention and in particular a machine dishwashing detergent according to the invention may contain further washing or cleaning-active ingredients as well as other ingredients customary for detergents and cleaners.

Detergents or cleaners according to the invention generally contain one or more builders, in particular zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological reasons against their use, the phosphates. The latter are particularly preferred builders to be used in automatic dishwashing detergents.

With preferred crystalline layered silicates of general formula NaMSi _x O _{2x + I} ^■ y H ₂ O are used, wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, wherein particularly preferred Values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline layered silicates of the formula NaMSi _x O _{2x + 1} ^■ y H ₂ O are sold for example by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 _(Na2 Sb2θ ₄ 5 ^■ x H ₂ O, kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ ^■ x H ₂ O, magadiite), Na-SKS 3 (Na ₂ Si ₈ O ₁₇ ^.xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ .H ₂ O, makatite).

The agents according to the invention furthermore preferably contain surfactants, in particular selected from nonionic, anionic, cationic and amphoteric surfactants. Surfactants used according to the invention are preferably nonionic, anionic and / or amphoteric surfactants.

As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) _x in which R corresponds to a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a 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 an arbitrary number between 1 and 10; preferably x is 1, 2 to 1, 4.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain. Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Further suitable surfactants are polyhydroxy fatty acid amides of the formula

wherein R is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical 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.

The group of polyhydroxy fatty acid amides also includes compounds of the formula

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 oxy-alkyl radical having 1 to 8 carbon atoms, wherein Cw-alkyl or phenyl radicals are preferred and [Z] is 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 obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. The detergents according to the invention also contain bleaches in a preferred embodiment. Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further useful bleaching agents are, for example, peroxopyrophosphates, citrate perhydrates and peroxygenic salts or peracids which yield H ₂ O ₂ , such as persulfates or persulfuric acid. The urea peroxohydrate percarbamide, which can be described by the formula H ₂ N-CO-NH ₂ H ₂ O ₂ , is also useful , Especially when using the MiUeI for cleaning hard surfaces, for example with automatic dishwashing _! If desired, they may also contain bleaches from the group of organic bleaches, although their use is in principle also possible with detergents. Typical organic bleaches are the diacyl peroxides. such as dibenzoyl peroxide. Further typical organic bleaching agents are the peroxyacids, examples of which are the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) peroxybenzoic acid and its substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate. (B) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid (phthalimidoperoxyhexanoic acid, PAP), o-carboxybenzamidoperoxycaproic acid, N-nonenylamidopipradadic acid and N-nonenylamidoper succinate, and (c) aliphatic and araliphatic peroxydicarboxylic acid, such as 1,12-diperoxycarboxylic acid , 1,9-Diperoxyazelaic acid. Diperoxysebacic. Diperoxybrassylic. the diperoxyphthalic acids, 2-decyldiperoxybutane-1, 4-diacid, N, N-terephthaloyl-di (6-aminopercaproic acid).

As a bleaching agent and chlorine or bromine releasing substances can be used. Examples of suitable chlorine or bromine-releasing materials are heterocyclic N-bromo and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid B, dibromoisocyanuric acid and / or dichloroisocyanic acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

With regard to inventive replaceable further ingredients, in particular with regard to inventively preferably usable Geruststoffen, surfactants, polymers, bleaching agents, especially Bieichaktivatoren and / or bleach catalysts, enzymes, especially amylases, proteases and Amadoriasen, solvents, thickeners, sequestering agents, electrolytes, optical brighteners, grayness inhibitors, Glaskorrosionsiπhibitoreπ, Corrosioπsinhibitoren, Farbubertragungsinhibitorsen, Schaumiπhibitoreπ, Disintegrationshilfsmitteln, abrasives, dyes or dyes, perfumes, perfume carriers, microbial agents, UV absorbents, enzyme stabilizers, "Soil-Release" -W rkstoffen, Acidifiziemπgsmiitelπ and Propellants and with regard to their preferred Einsatzππ reference is made to Offenlegiiπgsschnft WO2008 / 101810.

A separate subject matter of the invention is a process for the mechanical cleaning of textiles or of hard surfaces, in which at least in one of the process steps an imidazolium salt according to the invention, preferably in combination with salicylic acid or a salicylic acid derivative, is used.

This includes both manual and mechanical processes, with mechanical processes being preferred on account of their more precise controllability, for example with regard to the quantities and reaction times used.

Processes for the cleaning of textiles are generally distinguished by the fact that various cleaning-active substances are applied to the items to be cleaned in a plurality of process steps and washed off after the reaction time, or the product to be treated is otherwise treated with a detergent or a solution of this agent. The same applies to processes for the purification of all materials other than textiles, which are summarized under the term "hard surfaces." All conceivable washing or cleaning processes can be carried out in at least one of the process steps around an inventive imidazolium salt, preferably in combination with salicylic acid or a salicylic acid Derivative, and then constitute embodiments of the present invention.

A separate subject of the invention is the use of imidazolium salts according to the invention, preferably in combination with salicylic acid or a salicylic acid derivative, for the purification of textiles or hard surfaces.

Accordingly, the above-mentioned concentration ranges apply correspondingly for these uses.

Because erfiπduπgsgemälϊe imidazolium salts and corresponding combinations with salicylic acid and salicylic acid derivatives can, in particular according to the properties described above and the methods described above, be used to remove stains from textiles or hard surfaces. Examples of embodiments include hand washing, manual removal of stains from textiles or hard surfaces, or use in conjunction with a machine process. In a preferred embodiment of this use, the imidazolium salts and salicylic acid derivatives according to the invention are in this case provided in the context of one of the above formulations for agents according to the invention, preferably detergents or cleaners.

Another object of the present invention is also a product comprising a composition according to the invention or a detergent or cleaning agent according to the invention, in particular a hard surface cleaner according to the invention, and a spray dispenser. In the case of the product, this can be both a chamber chamber and a multi-chamber container, in particular a two-chamber container. The spray dispenser is preferably a manually activated spray dispenser, in particular selected from the group comprising aerosol sprayers (pressurized gas containers, also called spray cans), pressure-building spray dispensers, pump spray dispensers and trigger spray dispensers, in particular pump spray dispensers and trigger sprayers with a container made of transparent polyethylene or polyethylene terephthalate. Spray dispensers are described in more detail in WO 96/04940 (Procter & Gamble) and the US patents cited therein on spray dispensers, to which reference is made in this regard and the contents of which are hereby incorporated by reference. Triggersprühspender and pump sprayer have over compressed gas tanks the advantage that no propellant must be used. By means of suitable particles-passing attachments, nozzles, etc. (so-called "nozzle valves") on the spray dispenser, optionally contained enzyme in this embodiment can optionally also be added to the composition in a form immobilized on particles and thus metered in as a cleaning foam.

Machine dishwashing agents particularly preferred according to the invention comprise

From 5 to 70% by weight, preferably from 10 to 60% by weight and in particular from 20 to 50% by weight, of aggregate (s), with the exception of washing and cleaning-active polymers, preferably phosphates, from 2 to 28% by weight, preferably from 4 to 20 wt .-% and in particular 6 to 15 wt .-% washing and rÄinigungsaktivβ polymers;

0.5 to 10% by weight, preferably 1 to 9% by weight and in particular 2 to 6% by weight of surfactant (s), preferably nonionic and / or amphoteric surfactant (s), more preferably nonionic (s) surfactant (s);

From 0.5 to 8% by weight, preferably from 1 to 7% by weight and in particular from 2 to 6% by weight of enzyme (s), preferably selected from amylases, proteases and amadoriases;

From 2 to 20% by weight, preferably from 4 to 15% by weight and in particular from 6 to 12% by weight of bleaching agent, preferably percarbonate;

0.01 to 5% by weight, preferably 0.02 to 4% by weight and in particular 0.05 to 3% by weight of bleach catalysts;

0.01 to 5% by weight, preferably 0.02 to 4% by weight, and in particular 0.05 to 3% by weight, of imidazolium salts; such as optionally 0.01 to 5 wt .-%, preferably 0.02 to 4 wt .-% and in particular 0.05 to 3 wt .-% salicylic acid and / or salicylic acid derivatives.

Very particularly preferred automatic dishwashing detergents comprise

From 5 to 70% by weight, preferably from 10 to 60% by weight and in particular from 20 to 50% by weight

Phosphate;

2 to 28 wt .-%, preferably 4 to 20 wt .-% and in particular 6 to 15 wt .-% washing and cleaning-active polymers;

0.5 to 10% by weight, preferably 1 to 8% by weight and in particular 2 to 6% by weight of nonionic surfactant (s);

0.5 to 8 wt .-%, preferably 1 to 7 wt .-% and in particular 2 to 6 wt .-% enzyme (s) selected from amylases, proteases and amadoriases;

2 to 20% by weight, preferably 4 to 15% by weight and in particular 6 to 12% by weight

percarbonate;

0.01 to 5 wt .-%, preferably 0.02 to 4 wt .-% and in particular 0.05 to 3 wt .-%

Bleach catalysts; such as

0.01 to 5 wt .-%, preferably 0.02 to 4 wt .-% and in particular 0.05 to 3 wt .-%

Imidazolium salts; and optionally 0.01 to 5 wt .-%, preferably 0.02 to 4 wt .-% and in particular 0.05 to 3 wt .-% salicylic acid and / or salicylic acid derivatives.

The preparation of automatic dishwashing agents according to the invention can take place in different ways. The compositions according to the invention can be present in solid or liquid form as well as a combination of solid and liquid forms.

Powder, granules, extrudates or compactates, in particular tablets, are particularly suitable as firm supply forms. The liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels.

Inventive agents can be formulated in the form of single-phase or multi-phase products. In particular, automatic dishwashing detergents with one, two, three or four phases are preferred. Machine dishwashing detergent, characterized in that it is in the form of a prefabricated dosing unit with two or more phases, are particularly preferred.

The individual phases of multiphase agents may have the same or different states of aggregation. Machine dishwashing detergents which have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one solid phase are preferred. Automatic dishwasher detergents according to the invention are preferably prefabricated to form metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 16 and 22 g.

The volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.

The automatic dishwasher detergents according to the invention, in particular the prefabricated metering units, have a water-soluble coating, with particular preference.

The following examples further illustrate the invention without being limited thereto.

embodiments

Example 1: Synthesis of imidazolium salts

General procedure for the preparation of imidazolium salts AA1:

Scheme:

0.1 mol bromoacetophenone or chloroacetophenone are abs. In 60 ml. Under N ₂ is heated to about 70 ⁰ C and 0.06 mol of imidazole derivative in 15 ml of abs. Ethyl acetate was added dropwise.

Stir the reaction mixture for 3h at reflux. It is then cooled to room temperature, whereby a white solid precipitates. This is filtered off with suction and washed with a little cold ethyl acetate. Recrystallization of the solid from 30 ml of ethanol gives white crystals in about 80% yield.

Following procedure AA1 described above, the following compounds were synthesized: Phenacylbenzylimidazolium bromide Huc-Ve-9329-182

Formula Weight = 3572438314

¹ H-NMR (400MHz, DMSO): δ = 10.04 (s, 1H), 7.98 (d, 2H), 7.68 (s, 1H), 7.55 (dd, 1H), 7.34 (m, 8H), 6.31 (s , 2H), 5.45 (s, 2H)

Phenacylbenzylimidazolium chloride Huc-Ve-9329-184

Formula Weight = 3127928314

¹ H-NMR (400MHz, DMSO): δ = 10.32 (s, 1H), 8.00 (d, 2H), 7.60 (m, 2H), 7.38 (m, 7H), 7.24 (d, 1H), 6.32 (s , 2H), 5.44 (s, 2H)

Phenacylbenzylethylimidazolium chloride Huc-Ve-9329-195

Formula Weight = 3268194114

¹ H-NMR (400 MHz, DMSO): δ = 8.16 (m, 2H), 7.75 (s, 1H), 7.65 (m, 1H), 7.55 (m, 2H), 7 , 42 (m, 2H), 7, 28 (m, 4H), 6.45 (s, 2H), 5.41 (s, 2H) Methylphenacylbenzylmethylimidazolium bromide Huc-Ve-9660-035

Formula Weight = 385 2969914

¹ H-NMR (400 MHz, DMSO): δ = 7.96 (d, 2H), 7.49 (m, 6H), 7.41 (s, 1H), 7.34 (d, 2H), 5.47 (s, 2H), 2.52 (s, 3H), 2.45 (s, 3H).

Example 2: Checking the Washing Performance on Stubborn Test Dirt

The test soil is obtained by baking a mixture of cream, whole egg and cornstarch on a glazed ceramic surface. This test dirt is then rinsed with a dishwasher G 698 SC Plus from sensor. Miele in Intensivspülprogramm (50 ⁰ C, 107 minutes). The amount of soil removed is determined gravimetrically and the result is expressed in percent based on the improvement in the washing result compared to a commercial reference dishwashing detergent.

The addition of the respective detergency enhancers on-top to the reference machine dishwashing detergent (reference MGSM) results in the improved relative soil removals (relative to the reference MGSM) shown in Table 1.

Table 1: Improvement of soil release over reference MGSM

As shown in the table, the addition of imidazolium salts leads to a significant improvement in soil release from the ceramic surfaces (lines 1 and 2). However, the soil release could be significantly improved by additional addition of salicylic acid or salicylic acid derivatives (lines 4 and 5). This was surprising in particular insofar as the addition of salicylic acid alone does not lead to an improvement in soil release (line 3), so that a synergistic effect of the imidazolium salt in combination with salicylic acid and / or its derivative must be assumed.

Claims

claims

1. washing or cleaning agent containing at least one imidazolium salt.

2. washing or cleaning agent according to claim 1, characterized in that it is the imidazolium cation of the imidazolium salt to a compound of general formula (I)

R4

characterized in that R 1, R 2, R 3, R 4 and R 5 independently of one another represent trifluoromethyl, hydrogen, alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, heteroalkyl, heterocycloalkyl, alkoxy, alkoxyalkyl, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, alkanoyl, alkanoyloxy, Alkoxycarbonyl, alkylaminocarbonyl, alkylsulfanylcarbonyl, hydroxy, hydroxyalkyl, hydroxycarbonyl, amino, alkylamino, aryl, arylalkyl, aryloxy, arylamino, arylsulfanyl, arylsulfinyl, arylsulfonyl, arylcarbonyl, arylcarbonyloxy, aryloxycarbonyl, arylaminocarbonyl, arylsulfanylcarbonyl, heteroaryl, heteroarylalkyl, heteroaryloxy, heteroarylamino, heteroarylsulfanyl, Heteroarylsulfonyl, heteroarylsulfoxide, heteroarylcarbonyl, heteroarylcarbonyloxy, heteroaryloxycarbonyl, heteroarylaminocarbonyl, heteroarylsulfanylcarbonyl, alkoxysulfonyl, alkoxycarbinol, sulfo, sulfino, sulfeno, formyl or thioformyl, all of the resulting molecule being independently given if one or more times can be substituted.

3. washing or cleaning agent according to claim 2, characterized in that R1 and R4 independently of one another represent optionally substituted alkyl, aryl, arylalkyl, Alkylcarbonylalkyl or Arylcarbonylalkyl and R2, R3 and R5 are independently hydrogen or optionally substituted alkyl.

4. washing or cleaning agent according to claim 2 or 3, characterized in that R1 comprises an aromatic radical.

5. washing or cleaning agent according to one of claims 2 to 4, characterized in that R4 comprises an aromatic radical.

6. washing or cleaning agent according to one of claims 2 to 5, characterized in that R1 and R4 independently of one another represent optionally substituted phenyl, phenyl-Ci-6-alkyl or phenylcarbonyl-Ci-e-alkyl and the radicals R2, R3 and R5 is hydrogen or optionally substituted C-ι_ ₆ alkyl independently of one another.

7. washing or cleaning agent according to one of claims 2 to 6, characterized in that R1 represents an optionally substituted phenacyl radical.

8. washing or cleaning agent according to one of claims 2 to 7, characterized in that R4 is an optionally substituted phenylmethyl radical.

9. washing or cleaning agent according to one of claims 1 to 8, characterized in that it is the imidazolium cation of the imidazolium salt to a compound of formula (II) or according to formula (IM)

where appropriate, said compounds may also be monosubstituted or polysubstituted.

10. Washing or cleaning agent according to one of claims 2 to 9, characterized in that the substituents are selected from alkyl, halogen, hydroxy, hydroxyalkyl, hydroxycarbonyl, alkoxy, alkoxyalkyl, alkoxycarbonyl, amino and alkylamino.

11. Washing or cleaning agent according to one of the preceding claims, characterized in that the anion is selected from chloride, bromide, iodide, fluoride, sulfate, sulfite, nitrate and bicarbonate.

12. Washing or cleaning agent according to one of the preceding claims, characterized in that it contains salicylic acid, a salicylic acid derivative or mixtures thereof.

13. washing or cleaning agent according to claim 12, characterized in that it is the salicylic acid derivative is 2-hydroxybenzoic acid, which by at least one further radical selected from hydroxy, amino, halogen, in particular chlorine, bromine or fluorine, Ci- 6-alkyl, Ci-6-alkoxy, Ci-6-alkylamino or di- (Ci-6-alkyl) amino substituted.

14. Washing or cleaning agent according to one of the preceding claims, characterized in that it contains at least one surfactant.

15. Washing or cleaning agent according to one of the preceding claims, characterized in that it contains at least one enzyme selected from amylases, proteases and amadoriases.

16. Washing or cleaning agent according to one of the preceding claims, characterized in that it is a cleaning agent for hard surfaces.

17. Washing or cleaning agent according to claim 16, characterized in that it is a machine dishwashing detergent or a hand dishwashing detergent.

18. Washing or cleaning agent according to claim 17, characterized in that the automatic dishwashing detergent is in tablet form.

19. Washing or cleaning agent according to one of claims 1 to 15, characterized in that it is a textile washing agent.

20. Washing or cleaning agent according to one of the preceding claims, characterized in that it is a multi-phase agent.

21. Use of a washing or cleaning agent according to one of claims 1 to 20 for cleaning hard surfaces.

22. Use of a washing or cleaning agent according to one of claims 1 to 20 for cleaning textile fabrics.

23. Use according to claim 21 or 22 for the removal of baked-on and / or persistent stains.

24. A method for cleaning dishes in a dishwasher, wherein a detergent or cleaning agent is metered according to one of claims 1 to 20 during the passage of a dishwashing program before the start of the main wash cycle or in the course of the main wash cycle in the interior of a dishwasher.

25. Imidazolium salt, characterized in that it comprises as imidazolium cation a compound of general formula (II) or general formula (III)

optionally, said compound may also be mono- or polysubstituted.