DE102005020759A1 - Halomethylene alkanones and furanones as biofilm blockers - Google Patents

Abstract

The present invention relates to the use of halomethylene alkanones and furanones as biofilm blockers, and to methods of controlling processes based on microbial interaction using these biofilm blockers and agents containing these biofilm blockers in the industrial or institutional field.

Description

The The present invention relates to the use of halomethylene alkanones and furanones as biofilm blockers and methods of control of microbial interaction based processes using these biofilm blockers and agents containing these biofilm blockers in the industrial or institutional area.

microorganisms communicate with each other via a variety of different signals. In particular, the communication and interaction mechanisms in bacteria are in the art described in detail.

In the documents WO 00/56154; EP 0881297 ; US 6287836 ; EP 0909820 and US 6001600 special histidine kinases or homologous proteins are described for the purpose of screening for antibacterial substances. The kinases are derived exclusively from gram-positive organisms.

In WO 01/49708 is used to block a response regulator Peptide with at least 6 but less than 200 amino acids used. However, it is not signal molecules that are blocked but activation the next Proteins in the signal chain.

The Training of mature biofilms on or with bacteria is by communication between bacterial cells over various extracellular Signaling dependent.

Depending on the cell number density more adherent Bacteria causes the transgression a minimum concentration of these messengers activation of the Biofilm formation as well as an activation of further virulence genes. This phenomenon will be "quorum Called "Sensing" and open in principle the possibility for the control of biofilms, without the biofilm living germs kill.

So far were numerous signaling molecules identified in Gram-negative and Gram-positive bacteria [Miller, M.B., Bassler, B.L. (2001) Quorum sensing in bacteria. Annu Rev Microbiol. 55, 165-199; Kleerebezem, M., Quadri, L.E. (2001) Peptides pheromone-donor Regulation of antimicrobial peptide production in Gram-positive bacteria: a case of multicellular behavior. Peptides 22, 1579-1596].

The Structure of these signaling molecules is especially well studied in gram-negative organisms. In the case of the signaling substances (pheromones) used by these organisms they are common to representatives from a group of different N-Acyl-L-Homoserinlactone (AHL), which itself through the length the N-acyl side group as well as by modifications of the C-3 position (3-oxo or 3-hydroxy group) [Greenberg, E.P. (1997) Quorum sensing in Gram-negative bacteria. ASM News 63, 371-377].

at Gram-positive bacteria, the mechanisms are even less well known. Often here smaller peptides are described as signaling molecules. [Kleerebezem, M., Quadri, L.E. (2001) Peptide pheromone-dependent regulation of antimicrobial peptide production in Gram-positive bacteria: a case of multicellular behavior. Peptides 22, 1579-1596].

The However, the basic principle is similar. The respective signaling molecule is derived from specific, usually membrane-bound, cellular receptors recognized and bound (two-component systems).

at Gram-negative bacteria function, inter alia. special histidine kinases as said receptors. These histidine kinases are components so-called two-component systems. The second component is in each case by the so-called response regulator educated. If a signal molecule binds to such a histidine kinase, this is the response regulator activated. The activated response regulator then acts in turn as activator of various cellular processes [Chang C, Stewart, The two-component system. Regulation of various signaling pathways in prokaryotes and eukaryotes. Plant Physiol. 1998 Jul; 117 (3): 723-31.]

While there are a variety of such two-component systems with a wide variety of functions in all cells, Gram-negative bacteria are mainly responsible for intracellular transcription activator proteins ("LuxR proteins") The LuxR-Classh is able to bind AHLs, but also interacts with To take control domains of DNA molecules. [Eberl L, N-acyl homoserine lactone-mediated gene regulation in Gram-negative bacteria, Syst Appl Microbiol. 1999 Dec; 22 (4): 493-506 .; Michael B, Smith JN, Swift S, Heffron F, Ahmer BM. SdiA of Salmonella enterica is a LuxR homologous that detects mixed microbial communities. J Bacteriol. 2001 Oct; 183 (19): 5733-42; Gray KM, Garey JR., The Evolution of Bacterial Lux and Lux Quorum Sensing Microbiology. 2001 Aug; 147 (Pt 8): 2379-87.].

since recently it is known that for binding the AHL molecules only the N-terminal part of the transcriptional activator protein (ca. 200 amino acids) responsible for. [Zhang RG, Pappas T, Brace JL, Miller PC, Oulmassov T, Molyneaux JM, Anderson JC, Bashkin JK, Winan's SC, A., Structure of a bacterial quorum-sensing transcription factor complexed with pheromones and DNA. Nature. 2002 Jun 27; 417 (6892): 971-4.].

• 1. Spaltung der Botenstoffe durch Enzyme z.B. Lactonasen. Kürzlich wurden verschiedene Enzyme aus gram-positiven Bacillen isoliert, die AHL-Moleküle spezifisch spalten und somit diese Signalwege ausschalten können („Quorum Quenching"). Diese Lactonasen sind mehrfach beschrieben worden [Dong YH, Wang LH, Xu JL, Zhang HB, Zhang XF, Zhang LH. (2001) Quenching quorum-sensingdependent bacterial infection by an N-acyl homoserine lactonase. Nature. 411, 813–817; WO 01/85664; WO 02/16623].
• 2. Blockierung/Bindung der Botenstoffe selbst z.B. mit Antikörpern. Eine weitere Möglichkeit zur Verhinderung von Biofilmen ist der Einsatz von AHL-spezifischen Antikörpern. Nach Bindung eines solchen Antikörpers an den Botenstoff ist dieser nicht mehr in der Lage an seinen ursprünglichen Rezeptor (=Histidin-Kinase) zu binden [WO01/94543]. Auf Grund der hohen Kosten für die Antikörperherstellung ist diese Methode allerdings bestenfalls für medizinische Zwecke praktikabel.
• 3. Blockierung der zellulären Rezeptoren der Botenstoffe z.B. durch strukturanaloge Substanzen. Als strukturanaloge Substanzen sind hier insbesondere Furanone und Furanonderivate bekannt. [Manefield M, de Nys R, Kumar N, Read R, Givskov M, Steinberg P, Kjelleberg., Evidence that halogenated furanones from Delisea pulchra inhibit acylated homoserine lactone (AHL)-mediated gene expression displacing the AHL signal from its receptor protein. Microbiology. 1999 Feb;145 (Pt 2):283–91; WO96/29392; WO01/68091; WO01/68090; WO01/76594].

Essentially, three different concepts for biofilm prevention or control are described in the prior art:

• 1. Cleavage of messenger substances by enzymes such as lactonases. Recently, several enzymes have been isolated from gram-positive bacilli that specifically cleave AHL molecules and thus can switch off these signaling pathways (quorum quenching) .These lactonases have been described several times [Dong YH, Wang LH, Xu JL, Zhang HB, Zhang XF, Zhang LH (2001) Quenching quorum sensing-dependent bacterial infection by on N-acyl homoserine lactonase, Nature 411, 813-817, WO 01/85664, WO 02/16623].
• 2. Blocking / binding of messenger substances themselves, eg with antibodies. Another way to prevent biofilms is the use of AHL-specific antibodies. After binding such an antibody to the messenger, it is no longer able to bind to its original receptor (= histidine kinase) [WO01 / 94543]. However, due to the high cost of antibody production, this method is at best practicable for medical purposes.
• 3. Blocking of the cellular receptors of messenger substances, for example by structurally analogous substances. In particular, furanone and furanone derivatives are known as structurally analogous substances. [Manefield M, de Nys R, Kumar N, Read R, Givskov M, Steinberg P, Kjelleberg., Evidence that halogenated furanones from Delisea pulchra inhibit acylated homoserine lactone (AHL) -mediated gene expression displacing the AHL signal from its receptor protein. Microbiology. 1999 Feb; 145 (Pt 2): 283-91; WO96 / 29392; WO01 / 68091; WO01 / 68090; WO01 / 76594].

furanones They represent AHL analogues in terms of their structure. They interrupt the signal transmission path, by competitively displacing the AHL signaling substances and even to the intracellular target molecule (intracellular transcription activator protein) tie. The growth of the affected germs is due to the furanone exposure not inhibited at low concentrations.

Next the use of furanones in individual cases, the use of antibodies or antibody fragments mentioned. [Bryers, J.D., 2001, Gene therapy approach to colonization of biomaterials, abstracts of papers, 222nd ACS National Meeting]

und andererseits Halomethylen-Alkanone der allgemeinen Formel (II)

geeignete Biofilmblocker darstellen, die auch nach Einarbeitung in eine markttaugliche Rezeptur dazu in der Lage sind, die Biofilmbildung wirksam zu unterdrücken.Surprisingly, it has now been found that, on the one hand, furanones of the general formula (I)

and on the other hand, halomethylene-alkanones of the general formula (II)

represent suitable biofilm blocker, which are even after incorporation into a marketable formulation to be able to effectively suppress biofilm formation.

object The present invention therefore provides the use of furanones of the general formula (I) and / or of halomethylene alkanones of general formula (II) for controlling microbial interaction based operations, in particular for the control of the formation and / or maturation of biofilms, particularly preferred biofilms containing Gram-negative bacteria involved in the industrial and / or institutional field, especially in the field of industrial and / or institutional Hygiene.

In the formulas (I) and (II) in this case are both the radicals R ₁ , R ₂ and R ₃ , which may be different or identical, as well as the radicals Ra, Rb, Rc and Rd, which may also be different or identical independently of one another selected from halogen, in particular chlorine, bromine, fluorine or iodine, trifluoromethyl, hydrogen, alkyl, in particular C _1-12 -alkyl, cycloalkyl, in particular C _3-8 -cycloalkyl, alkenyl, in particular C _2-12 -alkenyl, Alkynyl, in particular C _2-12 -alkynyl, heteroalkyl, alkoxy, in particular C _1-12 -alkoxy, alkylsulfanyl, in particular C _1-12 -alkylsulfanyl, alkylsulfonyl, in particular C _1-12 -alkylsulfonyl, alkylsulfoxidyl, in particular C _1-12 Alkylsulfoxidyl, alkanoyl, in particular C _1-12 -alkanoyl, acyl, alkoxycarbonyl, in particular C _1-12 -alkoxycarbonyl, alkylaminocarbonyl, in particular C _1-12 -alkylaminocarbonyl, alkylsulfanylcarbonyl, in particular C _1-12 -alkylsulfanylcarbonyl, hydroxy, monoalkylamino, in particular ( C _1-12 alkyl) NH, dialkyl amino, in particular di- (C _1-12 -alkyl) N, aryl, in particular C _6-10 -aryl, heteroaryl, heterocycloalkyl, arylalkyl, in particular C _6-10 -aryl-C _1-4 -alkyl, arylsulfonyl, in particular C _6-10 -arylsulfonyl, arylsulfoxidyl, in particular C _6-10 -arylsulfoxidyl, arylcarbonyl, in particular C _6-10 -arylcarbonyl, aryloxycarbonyl, in particular C _6-10 -aryloxycarbonyl, arylaminocarbonyl, in particular C _6-10 -arylaminocarbonyl, formyl and cyano,
particularly preferably from hydrogen, halogen, in particular fluorine, chlorine, bromine or iodine, C _1-12 -alkyl, C _1-12 -alkoxy, C _2-12 -alkenyl, C _2-12 -alkynyl, C _6-14 -aryl and C _6-14 -aryl-C _1-4 -alkyl,
wherein the alkyl, cycloalkyl, alkenyl, alkynyl, heteroalkyl, heterocycloalkyl, alkoxy, alkylsulfanyl, alkylsulfonyl, alkylsulfoxidyl, alkanoyl, alkoxycarbonyl, alkanoyloxy, alkylaminocarbonyl, alkylsulfanylcarbonyl, (C _{1 12-} alkyl) NH, di- (C _1-12 -alkyl) N, aryl, C _6-10 -aryl-C _1-4 -alkyl and heteroaryl radicals are each, independently of one another, optionally also mono- or polysubstituted , in particular mono-, di- or tri-substituted, in particular by substituents selected from halogen, in particular chlorine, bromine or fluorine, trifluoromethyl, C _1-12 -alkyl, C _3-8 -cycloalkyl, C _2-12 -alkenyl , C _2-12 -alkynyl, heteroalkyl, heterocycloalkyl, C _1-12 -alkoxy, C _1-12 -alkylsulfanyl, C _1-12 -alkylsulfonyl, C _1-12 -alkylsulfoxidyl, C _1-12 -alkanoyl, C _{1- 12} alkoxycarbonyl, C _1-12 alkanoyloxy, C _1-12 alkylaminocarbonyl, C _1-12 alkylsulfanylcarbonyl, hydroxy, (C _1-12 alkyl) NH, di (C _1-12 alkyl) N, C _6-10 -aryl, heteroaryl, C _6-10 -aryl-C _1-4 -alkyl, C _6-10 -arylsul vinyl, C _6-10 -arylsulfoxidyl, C _6-10 -arylcarbonyl, C _6-10 -aryloxycarbonyl or C _6-10 -arylaminocarbonyl, preferably C _1-6 -alkyl, C _1-6 -alkoxy, halogen or hydroxyl,
and wherein the total number of substituents in the molecule is preferably up to 5, more preferably up to three, in particular one, two or three,
and X is halogen, in particular fluorine, chlorine, bromine or iodine, preferably bromine,

In a preferred embodiment, R ₁ and R _{2 are} independently selected from C _1-4 alkyl, in particular methyl, ethyl, i-propyl and n-propyl, especially methyl and ethyl, R ₃ is hydrogen and X is bromine , Particularly preferred here is R _{1 is} ethyl and R _{2 is} methyl.

In another preferred embodiment, Ra is a halogen, in particular bromine, Rb is C _1-12 -alkyl, in particular C _4-10 -alkyl, especially n-heptyl, Rc is hydrogen or C _1-4 -alkyl, preferably hydrogen, and Rd Halogen, in particular bromine, particularly preferred here are Ra and Rd bromine, Rb n-heptyl and Rc hydrogen.

In another preferred embodiment, R a is C _1-12 -alkyl, especially C _4-10 -alkyl, especially n-heptyl, Rb is halogen, in particular bromine, Rc is hydrogen or C _1-4 -alkyl, preferably hydrogen, and Rd is halogen , in particular bromine, particularly preferably Rb and Rd are bromine, Ra n-heptyl and Rc is hydrogen.

The alkyl group is preferably (C ₁ -C ₁₈ ) -alkyl, more preferably (C ₁ -C ₁₂ ) -alkyl, in particular (C ₁ -C ₆ ) -alkyl. The alkyl group may be straight-chain or branched. The alkyl group may in particular be selected from methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, isobutyl and tert-butyl. The alkyl group may also be mono- or polysubstituted, in particular by radicals ("substituents") selected from the group consisting of alkyl, cycloalkyl, alkenyl, alkynyl, halo, haloalkyl, haloalkenyl, haloalkynyl, hydroxy, alkoxy, alkenyloxy, haloalkoxy, haloalkenyloxy , Nitro, amino, nitroalkyl, Ni troalkenyl, nitroalkynyl, nitroheterocyclyl, alkylamino, dialkylamino, alkenylamino, alkynylamino, acyl, alkenoyl, alkynyl, acylamino, diacylamino, acyloxy, alkylsulfonyloxy, heterocyclyl, heterocycloxy, heterocycloamino, haloheterocyclyl, alkylsulfenyl, alkylcarbonyloxy, alkylthio, acylthio, phosphorus-containing groups such as phosphono and phosphinyl, where, when the substituent carries an alkyl group, it preferably comprises up to 18, more preferably up to 12, especially up to 6 carbon atoms.

The alkoxy group is preferably (C ₁ -C ₁₈ ) -alkoxy, more preferably (C ₁ -C ₁₂ ) -alkoxy, in particular (C ₁ -C ₆ ) -alkoxy. The alkyl radical of the alkoxy group may be straight-chain or branched. The alkyl radical may in particular be selected from methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, isobutyl and tert-butyl. The alkyl group may also be mono- or polysubstituted, in particular by the abovementioned substituents.

The alkenyl group is preferably (C ₂ -C ₁₈ ) -alkenyl, particularly preferably (C ₂ -C ₁₂ ) -alkenyl, in particular (C ₂ -C ₆ ) -alkenyl. The alkenyl radical may be straight-chain or branched. The alkenyl radical may in particular be selected from vinyl, allyl, 1-methylvinyl, butenyl, isobutyl, 3-methyl-2-butenyl, 1-pentenyl, cyclopentenyl, 1-methylcyclopentyl, 1-hexenyl, 3-hexenyl, cyclohexenyl , 1-heptenyl, 3-heptenyl, 1-octenyl, cyclooctenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 3-decenyl, 1,3-butadienyl, 1,4-pentadienyl, 1.3 Cyclopentadienyl, 1,3-hexadienyl, 1,4-hexadienyl, 1,3-cyclohexadienyl, 1,4-cyclohexadienyl, 1,3-cycloheptadienyl, 1,3,5-cycloheptatrienyl and 1,3,5,7-cyclooctatetraenyl ,

The Alkenyl group may also be mono- or polysubstituted, in particular by the previously mentioned substituents.

at the halogen is preferably fluorine, chlorine, bromine or Iodine, more preferably bromine or fluorine.

at the heteroatom is preferably oxygen, nitrogen or sulfur.

The acyl group may be an aliphatic acyl group ("alkanoyl group") or an acyl group containing a heterocyclic ring ("heterocyclic acyl group"). It is preferably a (C ₁ -C ₁₈ ) alkanoyl group, particularly preferably a (C ₁ -C ₁₂ ) alkanoyl group, in particular a (C ₁ -C ₆ ) alkanoyl group. The alkyl radical of the alkanoyl group may be straight-chain or branched. The acyl group may also be mono- or polysubstituted, in particular by the abovementioned substituents. The acyl group may in particular be selected from carbamoyl, formyl, acetyl, propanoyl, butanoyl, 2-methylpropanoyl, pentanoyl, 2,2-dimethylpropanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, t-pentyloxycarbonyl , heptyloxycarbonyl, cyclopropanecarbonyl, cyclobutanecarbonyl, cyclopentanecarbonyl, cyclohexanecarbonyl, methanesulfonyl, ethanesulfonyl, methoxysulfonyl, ethoxysulfonyl, Heterocycloalkancarbonyl, Heterocyclyoalkanoyl, particularly Pyrrolidinylacetyl, Pyrrolidinylpropanoyl, Pyrrolidinylbutanoyl, Pyrrolidinylpentanoyl, Pyrrolidinylhexanoyl or Thiazolidinylacetyl, Heterocyclylalkenoyl, particularly Heterocyclylpropenoyl, Heterocyclylbutenoyl, Heterocyclylpentenoyl or Heterocyclylhexenoyl and Heterocyclylglyoxyloyl, in particular thiazolidinylglyoxyloyl or pyrrolidinylglyoxyloyl.

C _3-8 -cycloalkyl according to the invention in each case independently of one another for all cyclic alkyl radicals having 3 to 8 C-atoms, preferably having 5 to 6 C-atoms, in particular for cyclopentyl and cyclohexyl.

According to the invention, C _2-12 -alkynyl is, independently of one another, independently of all linear and unbranched alkyl radicals having up to 12 C atoms which contain at least one triple bond, preference being given to C _2-6 -alkynyl radicals. C _2-6 -alkynyl according to the invention represents all linear and unbranched alkyl radicals having up to 6 C atoms which contain at least one triple bond, in particular ethynyl, propynyl, i-propynyl and all isomers of butynyl, pentynyl and hexynyl.

heteroalkyl is according to the invention respectively independently each other for all saturated and mono- or polyunsaturated, linear or branched alkyl radicals which are at least one, preferably contain exactly one heteroatom, in particular O, S or N, where the sum of C and hetero atoms up to 12, preferably up to 6, is.

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 O, S or N, where the ring is from three to eight membered, preferably five to six membered. Examples are tetrahydrofuranyl, Tetrahydrothiophenyl, pyrrolidinyl, 2-thiazolinyl, tetrahydrothiazolyl, tetrahydrooxazolyl, piperidinyl, piperazinyl, morpholinyl and thiomorpholinyl.

According to the invention, C _1-12 -alkylsulfanyl in each case independently of one another represents all saturated and unsaturated, linear and branched alkyl radicals having up to 12 C atoms which are bonded via a sulfur atom, preference being given to C _1-6 -alkylsulfanyl radicals are. According to the invention, C _1-6 -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 for methylsulfanyl and ethylsulfanyl.

According to the invention, C _1-12 -alkylsulfonyl in each case independently of one another represents all saturated and unsaturated, linear and branched alkyl radicals having up to 12 C atoms which are bonded via an SO group, preference being given to C _1-6 -alkylsulfonyl radicals are. According to the invention, C _1-6 -alkylsulfonyl represents all saturated and unsaturated, linear and branched alkyl radicals having up to 6 C atoms which are bonded via an SO group, in particular for methysulfonyl and ethylsulfonyl.

C _1-12 -alkylsulfoxidyl is according to the invention in each case independently of one another for all saturated and unsaturated, linear and branched alkyl radicals having up to 12 C atoms, which are bonded via an SO ₂ group, where C _1-6 alkylsulfoxidyl radicals are preferred. According to the invention, C _1-6 -alkylsulfoxidyl represents all saturated and unsaturated, linear and branched alkyl radicals having up to 6 C atoms which are bonded via an SO ₂ group, in particular for methylsulfoxidyl and ethylsulfoxidyl.

According to the invention, C _1-12 -alkanoyl in each case independently of one another represents all saturated and unsaturated, linear and branched alkyl radicals having up to 12 C atoms which are bonded via a carbonyl group, preference being given to C _1-6 -alkanoyl radicals are. According to the invention, C _1-6 -alkanoyl represents all saturated and unsaturated, linear and branched alkyl radicals having up to 6 C atoms which are bonded via a carbonyl group, in particular for methycarbonyl and ethylcarbonyl.

According to the invention, C _1-12 -alkoxycarbonyl in each case independently of one another represents all saturated and unsaturated, linear and branched alkyl radicals having up to 12 C atoms, which are bonded via an oxycarbonyl group, preference being given to C _1-6 -alkoxycarbonyl radicals are. C _1-6 -alkoxycarbonyl is according to the invention for all saturated and unsaturated, linear and branched alkyl radicals having up to 6 C-atoms, which are bonded via an oxycarbonyl group, in particular for methoxycarbonyl and ethoxycarbonyl.

According to the invention, C _1-12 -alkanoyloxy in each case independently of one another represents all saturated and unsaturated, linear and branched alkyl radicals having up to 12 C atoms which are bonded via a carbonyloxy group, preference being given to C _1-6 -alkanoyloxy radicals are. According to the invention, C _1-6 -alkanoyloxy represents all saturated and unsaturated, linear and branched alkyl radicals having up to 6 C atoms which are bonded via a carbonyloxy group, in particular methanoyloxy, ethanoyloxy, n-propanoyloxy and i-propanoyloxy ,

According to the invention, C _1-12 -alkylaminocarbonyl in each case independently of one another represents an aminocarbonyl group which is monosubstituted or disubstituted by a saturated or unsaturated, linear or branched alkyl radical having up to 12 C atoms, wherein one or two times C _1-6 alkyl groups substituted aminocarbonyl radicals, especially monomethylaminocarbonyl, diemethylaminocarbonyl, monoethylaminocarbonyl and diethylaminocarbonyl, are preferred.

According to the invention, C _1-12 -alkylsulfanylcarbonyl in each case independently of one another represents all saturated and unsaturated, linear and branched alkyl radicals having up to 12 C atoms which are bonded via a thiocarbonyl group, preference being given to C _1-6 -alkylsulfanylcarbonyl radicals are. C _1-6 -alkylsulfanylcarbonyl according to the invention represents all saturated and unsaturated, linear and branched alkyl radicals having up to 6 C atoms which are bonded via a thiocarbonyl group, in particular methylthiocarbonyl and ethylthiocarbonyl.

(C _1-12 -alkyl) According to the invention, in each case independently of one another, NH 4 represents, independently of one another, all saturated and unsaturated, linear and branched alkyl radicals having up to 12 C atoms which are bonded via a hydrogenamino group, where (C _1-6 -alkyl) NH is preferred. (C _1-6 -alkyl) NH is according to the invention for all saturated and unsaturated, linear and branched alkyl radicals having up to 6 C-atoms, which are bonded via a hydrogenamino group, in particular for CH ₃ NH and C ₂ H ₅ NH.

According to the invention, di- (C _1-12 -alkyl) N is, independently of one another, for all saturated and un saturated saturated, linear and branched alkyl radicals having up to 12 carbon atoms, which are bonded via a (C _1-12 alkyl) amino group, with di- (C _1-6 alkyl) N is preferred. The two alkyl radicals here may be the same or different from each other. Di- (C _1-6 -alkyl) N is according to the invention for all saturated and unsaturated, linear and branched alkyl radicals having up to 6 C atoms, which are bonded via a (C _1-6 alkyl) amino group, in particular for (CN ₃ ) ₂ N and (C ₂ H ₅ ) ₂ N.

C _6-10 aryl according to the invention is in particular phenyl and naphthyl, preferably phenyl.

In C _6-10 arylC _1-4 alkyl, the alkyl radical may be saturated or unsaturated, branched or unbranched. Preferred radicals are benzyl, phenylethyl, naphthylmethyl and naphthylethyl.

heteroaryl is according to the invention, if not otherwise stated, for at least one heteroatom selected from O, S and N. aromatic radical having 5 to 10, preferably 5 or 6, ring members, especially selected from furanyl, thienyl, thiophenyl, pyrrolyl, isopyrrolyl, pyrazolyl, Imidazolyl, oxazolyl, thiazolyl, isothiazolyl, pyridinyl, pyridazinyl, Pyrimidinyl, pyrazinyl, triazinyl, benzofuranyl, benzothiophenyl, Indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, indazolyl, pyridofuranyl and pyridothienyl.

The aforementioned alkyl, cycloalkyl, alkenyl, alkynyl, heteroalkyl, heterocycloalkyl, alkoxy, alkylsulfanyl, alkylsulfonyl, alkylsulfoxidyl, alkanoyl, alkoxycarbonyl, alkanoyloxy, alkylaminocarbonyl, alkylsulfanylcarbonyl, (C _{1 -12} alkyl) NH-, di (C _1-12 alkyl) N-, aryl, C _6-10 arylC _1-4 alkyl and heteroaryl radicals may each independently optionally mono- also or more than once, in particular mono-, di- or trisubstituted, in particular by substituents selected from halogen, in particular chlorine, bromine or fluorine, trifluoromethyl, C _1-12 -alkyl, C _3-8 -cycloalkyl, C _2-12 - Alkenyl, C _2-12 alkynyl, heteroalkyl, heterocycloalkyl, C _1-12 alkoxy, C _1-12 alkylsulfanyl, C _1-12 alkylsulfonyl, C _1-12 alkyl sulfoxide, C _1-12 alkanoyl, C _{1 -12-} alkoxycarbonyl, C _1-12 -alkanoyloxy, C _1-12 -alkylaminocarbonyl, C _1-12 -alkylsulfanylcarbonyl, hydroxy, (C _1-12 -alkyl) NH, di- (C _1-12 -alkyl) N, C _6-10 aryl, heteroaryl, C _6-10 arylC _1-4 alkyl, C _{6-1 0-} arylsulfonyl, C _6-10 -arylsulfoxidyl, C _6-10 -arylcarbonyl, C _6-10 -nanxycarbonyl or C _6-10 -arylaminocarbonyl, preferably by C _1-6 -alkyl, C _1-6 -alkoxy, chlorine, Bromine, fluorine or hydroxy.

In a preferred embodiment is the total number of substituents on the residues in the sum over all Remains in the molecule not bigger than 5, in particular, it is not larger than 3 or is exactly 1, exactly 2 or exactly 3.

It can according to the invention in a preferred embodiment also be a fluorophilic compound. The term "fluorophilic" refers to the affinity to alkyl groups, which carry many fluorine atoms, such as perfluoroalkanes and perfluoroalkane polymers.

hergestellt, wobei R₁, R₂, R₃ und X die oben angegebenen Bedeutungen haben, und wobei die Decarboxylierung in Gegenwart einer schwachen Base durchgeführt wird. Grundsätzlich sind alle Stereoisomere der Verbindungen der Formel (III) als Ausgangsstoffe verwendbar.The halomethylene alkanones to be used according to the invention are preferably prepared by decarboxylation of compounds of the formula (III)

prepared, wherein R _1, R _2, R ₃ and X have the meanings indicated above, and wherein the decarboxylation is carried out in the presence of a weak base. In principle, all stereoisomers of the compounds of the formula (III) can be used as starting materials.

Of the weakly basic catalyst can be soluble in the reaction medium or also not soluble be. examples for insoluble in the reaction medium Basic catalysts are basic resins, basic salts and basic ones Polymers.

Examples for im Reaction medium soluble basic catalysts are triethylamine, pyridine, 1,4-diazabicyclo [2.2.2] octane (DABCO), 4- (dimethylamino) pyridine (DMAP) and 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU).

Preferably, the decarboxylation is carried out using triethylamine or DBU or from Mi scans of these bases with other bases. Most preferably, the reaction is carried out in the presence of triethylamine.

The Decarboxylation can be carried out with a mild base in the presence or in Absence of a solvent carried out become. For the solvent it can be any solvent. According to the invention preferred solvent are alkyl acetates, aromatic hydrocarbons, chlorinated alkanes, Tetrahydrofuran, diethyl ether and dioxane.

Especially Preferably, the solvent is an alkyl acetate or a chlorinated alkane, especially dichloromethane, Dichloroethane or trichloroethane.

The Reaction is preferably carried out at mild temperatures. Of the Cyclization step is preferably carried out at temperatures between -20 and 150 ° C performed. The Reaction time is preferably between 2 and 12 hours. The Reaction conditions will vary depending on the particular Substrates and the desired Reaction rate adjusted.

The brominated keto acids according to formula (III) obtained by bromination of the corresponding 4-oxo-2-alkene acids become.

microorganisms whose quorum sensing is interrupted are preferably selected below Aeromonas hydrophila, Aeromonas salmonicida, Agrobacterium tumefaciens, Burkholderia cepacia, Chromobacterium violaceum, Enterobacter agglomerans, Erwinia carotovora, Erwinia chrysanthemi, Escherichia coli, Nitrosomona europaea, Obesumbacterium proteus, Pantoea stewartii, Pseudomonas aeruginosa, Pseudomonas aureofaciens, Pseudomonas fluorescens, Pseudomonas syringae, Ralstonia solanacearum, Rhizobium etli, Rhizobium leguminosarum, Rhodobacter sphaeroides, Salmonella enterica, Serratia liquefaciens, Vibrio anguillarum, Vibrio fish, Xenorhabdus nematophilus, Yersinia enterolytica, Yersinia pestis, Yersinia pseudotuberculosis, Yersinia ruckeri.

Also according to the invention gram-positive bacteria suitable microorganisms.

At the most important are germs, which are particularly involved in biofilm formation in aqueous solutions are. These are primarily germs from the large pseudomonad group (especially P. aeruginosa as particular target germ), Burkholderia cepacia, Serratia, Rhizobium, E. coli. Other important biofilm germs are aqua bacteria, Xanthomonas.

• – Steuerung der Expression der Biolumineszenzgene (z.B. Photobacterium fischeri)
• – Produktion des β-Lactam-Antibiotikums Carbapenem (Erwinia carotovora) und AB-Produktion in Pseudomonas aureofaciens
• – Konjugativer Plasmidtransfer (traI/traR aus Agrobacterium tumefaciens),
• – Starvation response (z.B. Pseudomonas)
• – Bakterielle Fortbewegung (swrI/swrR aus Serratia liquefaciens) und bei P. aeruginosa
• – Ausbildung differenzierter Biofilme (P aeruginosa, B. cepacia)
• – Produktion verschiedenster Virulenzfaktoren (zellassoziierte Virulenzfaktoren bei P. aeruginosa, z.B. extrazelluläre Faktoren, wie Proteasen (LasB-Elastase, alkalische Protease und LasA-Protease), Hämolysine (Rhamnolipid und Phosoholipase) und Toxine (Exotoxin A und Exoenzym S)
• – Interspezifische Zell-Zell-Kommuniation ("cross-talk" zwischen verschiedenen Bakterienspezies) z.B. zwischen P. cepacia und P. aeruginosa

In most cases, the bacterial communication systems do not control morphological changes of individual cells, but influence the pathogenicity of the respective organisms. Some of the most significant features of these communication systems are listed below by way of example:

• Control of the expression of the bioluminescence genes (eg Photobacterium fischeri)
• Production of the β-lactam antibiotic carbapenem (Erwinia carotovora) and AB production in Pseudomonas aureofaciens
• Conjugative plasmid transfer (traI / traR from Agrobacterium tumefaciens),
• - Starvation response (eg Pseudomonas)
• - Bacterial locomotion (swrI / swrR from Serratia liquefaciens) and P. aeruginosa
• - Development of differentiated biofilms (P aeruginosa, B. cepacia)
• Production of various virulence factors (cell-associated virulence factors in P. aeruginosa, eg extracellular factors such as proteases (LasB elastase, alkaline protease and LasA protease), hemolysins (rhamnolipid and phosoholipase) and toxins (exotoxin A and exoenzyme S)
• Interspecific cell-cell communication ("cross-talk" between different bacterial species) eg between P. cepacia and P. aeruginosa

According to the invention microbial interaction selected under the formation and / or maturation of biofilms, multicellular swarming behavior, the concerted training of antibiotic resistance, the concerted Synthesis of antibiotics, the concerted synthesis of pigments, the concerted production of extracellular enzymes, in particular hydrolytic Enzymes, as well as the concerted production of virulence factors, preferably the formation and / or maturation of biofilms.

Another object of the invention is the use of the compounds of the invention for the control of processes based on microbial interaction, in particular for controlling the formation and / or maturation of biofilms, more preferably of biofilms in which Gram-negative bacteria be are involved.

advantageously, kill those Compounds of the invention In contrast to antibiotics, the bacteria do not decrease but inhibit only their communication system, so that there is no training of one mature, slimy biofilm is coming. It is particularly advantageous that the microorganisms can not develop resistance to these compounds that Represent structural analogues to the AHL molecules they use themselves, otherwise they severely affect your own communication system would.

The Compounds of the invention can used in pure form or as effective components of mixtures become.

In the majority of cases contain the for the practical application of certain mixtures a total of 0 to about 99, preferably 90 to 10 wt .-% of other commonly used ingredients, depending on the intended use and the purpose of use selected become.

For liquid preparations for example, come as a solvent water-miscible organic solvents, for example Ethanol, isopropanol and ethylene glycol, propylene glycol, ethyl ethylene glycol, Propylpropylene glycol 20 and water immiscible solvents such as white spirit, benzene, toluene, ethyl acetate or dimethylene chloride.

Preferred dimensions done the use according to the invention therefore applicable in the institutional and / or industrial field Sterilization, disinfection, impregnation, preservation, washing, dishwasher or cleaning agents, cooling, coolants or corrosion inhibitors (technical application solutions), in the field of water purification / water treatment and in detergents to the equipment or Treatment of surfaces, Food, filter media, adhesives, building materials, building aids, Ceramics, plastics, metals, textiles, furs, paper, skins, Polymers, leather or packaging. In particular, the application may here in the pharmaceutical, food, brewery, dairy, Medical, paint, wood, textile, cosmetic, leather, tobacco, Fur, rope, paper, pulp, plastic, fuel, oil, rubber, Automotive, polymer, steel or Mechanical engineering industry.

Another The present invention accordingly also relates to compositions Preparations and materials - im the following also simply called "means" -, the substances according to the invention contained and / or coated with substances according to the invention or equipped are.

The agents according to the invention are selected here in particular from institutional and / or industrial sterilization, disinfection, impregnating, Preservative, corrosion protection, washing, dishwashing or Cleaning agents, cooling or cooling lubricants and water treatment agents containing substances according to the invention.

at The agents may according to the invention further example, for example act on filter media, adhesives, building materials, building aids, Textiles, furs, paper, furs, leather, ceramics, plastics, Polymers, packaging or metals as well as means for equipment or Treatment of surfaces, Food, filter media, adhesives, building materials, building aids, Ceramics, plastics, metals, textiles, furs, paper, skins, Polymers, leather or packaging. When the surfaces are These are in particular surfaces of equipment and Industrial and / or institutional equipment as well around surfaces of automobiles.

In another preferred according to the invention embodiment used for biofilm control in medical devices, instruments and apparatus, especially for catheters and endoscopes. object The present invention are therefore also by a corresponding Treatment available medical equipment, Instruments and apparatus, in particular catheters and endoscopes.

The substances according to the invention can in the inventive compositions be contained and / or the agents according to the invention can with coated and / or equipped with these, wherein the substances according to the invention covalently or non-covalently bound to the agents.

In a particular embodiment of the invention, the effect according to the invention is achieved here by a surface modification of the apparatuses, machines and / or devices, wherein surface modification means that the substances according to the invention are fixed to the surface of the corresponding apparatuses, machines and / or devices, wherein every kind of bond, in particular covalent bond is conceivable.

The Compounds of the invention are suitable for inhibiting microbial growth wherever this Growth unwanted is, e.g. in aqueous Systems in a range of industrial applications such as papermaking.

A Series of important industries is characterized by the activity of this Bacteria, algae and fungi on the raw materials used to various aspects of their manufacturing activities or on the final products produced severely impaired. Belong to these industries the colors, wood, textile, cosmetics, leather, tobacco, fur, rope, Paper, pulp, plastics, fuel, oil, rubber and machinery industries.

To important applications of the compounds of the invention include: prevention the bacterial contamination of air conditioners, inhibiting growth of bacteria and fungi in adhesives, latex emulsions and potting compounds; Wood preservatives; Bohrölkonservierung; fight slime-producing bacteria and fungi in pulp and paper mills and Cooling water; as a spray or dip treatment for Textiles and leather for preventing mold growth; protection of processing equipment against slime deposits in the production of cane and beet sugar; Prevention of accumulation and deposition of microorganisms in exhaust air scrubber systems and in industrial fresh water supply systems; Combating the Contamination with and deposition of microorganisms in oil drilling fluids and sludges as well as in secondary Crude oil refining process; Inhibition of bacterial and fungal growth in paper coating processes, that's the quality could affect the paper coating; Fight against Bacterial and fungal growth and deposition during production various special cardboard, z. B. solid board and chipboard; prevention the cell juice discoloration freshly cut wood of various kinds; Fight against Bacterial and fungal growth in clay and pigment sludge different Kind of the later Use for example in paper coating and paint production be prepared and during storage and transport the degradation subject to microorganisms; as institutional and / or Industrial disinfectant for hard surfaces Preventing the growth of bacteria and fungi on walls, floors, etc. and in swimming pools to prevent algae growth.

Especially important is the fight of bacteria and fungi in water systems of pulp and paper mills, the aqueous Dispersions of fibers for papermaking included. The uncontrolled Enrichment of mucus by the accumulation of bacteria and fungi leads to poor quality production, reduced production due breaks and higher Cleaning frequency, Increased consumption of raw materials and higher maintenance costs. The problem of slime deposits is in the paper industry by the widespread use of closed white water systems worse.

One another important area in which is the fight against bacterial and fungal growth The decisive factor is the clay and pigment sludge. These sludges exist of different clays, e.g. Kaolin, and pigments, e.g. calcium carbonate and titanium dioxide. They usually become produced at a location different from that of the final use, e.g. in paper coating and paint making, is removed and then to the later Transport stored at the final destination. The high quality standards for the paper and paint end products in which the sludge is used require that the sound or Pigment sludge has a very small amount of microorganisms, so he used for paper coating or paint production can be.

One another important area for combating microbial growth are cooling systems, like those with circulating cooling towers. These Systems set a big one Amount of water considerably long of the atmosphere from under conditions that do not provide adequate ventilation and do not involve sufficient exposure to sunlight, that microbial growth, especially bacterial and fungal growth would be fought. Lots Put cooling towers also a filling from beads made of synthetic polymer or other materials to the Heat exchange surface to enlarge. These Construction aggravates the problem of microbial growth as it the ideal physical environment for the reproduction of annoying microbes provides. blank Fight these microorganisms thrive and produce colonies that are sufficient the heat exchange surfaces with block a biofilm and the components of the water transport device, to operate the cooling system used to be clogged. The compounds of the invention make an excellent fight of microbial growth in these systems.

The compounds according to the invention are particularly suitable for controlling the harmful effects of microorganisms in water or aqueous media. Systems that circulating water or around The use of aqueous media in progress infects microorganisms and significantly affects their effectiveness as microorganism deposits accumulate in the system. The deposits called slimes coat the walls of containers and other vessels, any machinery and processing equipment used, and create obstructions in pipes and valves. The formation of slime promotes the corrosion of metal surfaces and facilitates the rotting of wooden towers. The slimes also cause discoloration and other defects in all manufactured products and force costly business interruptions. The control of microorganisms in aqueous media is particularly important if they contain dispersed particles or fines, for example dispersed cellulose fibers and dispersed fillers and pigments in papermaking.

For the production Ready-to-use disinfectants and preservatives can be used alongside liquid Concentrates also solid products, preferably in powder or granular form be provided containing the substances of the invention.

The agents according to the invention can in every conceivable institutional and / or industrial area be used, for example, in hospitals, hotels, schools, swimming pools, bathing establishments, Cisterns, public Transportation, public Buildings, public sanitary Facilities, saunas, sports facilities or in doctor's or massage practices, in commercial and industrial plants, in particular for Clean hard surfaces, such as soils, Tiles, tiles and plastics.

Farther can the compounds of the invention in the preservation of technical products still to be processed such as glazes, adhesives and glues, drilling and cutting oils or Products of the paper, cardboard or leather processing industry as well as for the preservation of industrial and service water application Find.

The Application can be done by spraying, Brushing, brushing, knife coating, dipping or pressure or vacuum impregnation respectively

The Compounds of the invention according to formula (I) or (II) are preferably in a concentration in the range from 1 ppm to 1000 ppm, especially 20 to 500 ppm, more preferably 20 to 50 ppm used.

The equipment the surfaces, Filter media, adhesives, building materials, building aids, ceramics, plastics, Metals, textiles, furs, papers, furs, polymers, leather parts or packaging with the substances according to the invention takes place in the Expert known manner, for example by immersion in a suitably concentrated solution an agent according to the invention or by spraying with such a solution. So can for example, works of art on paper, parchment, wood and / or Canvas before infestation by microorganisms, in particular mold, protected or freed from this. The equipment of filter media, building materials or Bauhilfsstoffe done for example by applying or by mechanical incorporation of the substances according to the invention or a suitable concentrated solution of substances according to the invention on or in the filter media, building materials or building aids. The substances according to the invention can so mechanically into the relevant materials prior to their use, e.g. by stirring, be incorporated or you can alternatively already during the preparation of the materials are incorporated into this.

Building and construction aids

In a preferred embodiment are the building materials equipped according to the invention or building aids under adhesives, sealants, fillers and paints, plastics, Paints, paints, plaster, mortar, Screed, concrete, insulating materials and primers. Especially preferred building materials or building aids are jointing compounds (For example, silicone-containing jointing compounds), wallpaper paste, plaster, Carpet fixer, silicone adhesive, tile adhesive.

sealants and in particular jointing compounds typically contain organic polymers as well as in many cases mineral or organic fillers and other additives.

Suitable polymers are for example thermoplastic elastomers, as in DE 3602526 described, preferably polyurethanes and acrylates. Suitable polymers are also in the published patent applications DE 3726547 . DE 4029504 and DE 4009095 as in DE 19704553 and DE 4233077 to which reference is hereby incorporated by reference.

The sealing compounds according to the invention (Sealants or sealant mixtures) preferably contain 0.001-3.0% by weight substances according to the invention according to formula (I) and / or (II). Particularly preferred amounts are between 0.01 and 1.0% by weight.

According to the invention, the equipment the sealants of the invention both in the uncured or at below 60 ° C hardened Condition done. Sealants are materials in the context of the invention according to DIN EN 26927, in particular those which are plastic or elastic as sealants Harden. The sealants according to the invention can all for the corresponding sealants typical additives, such. typical thickeners, reinforcing fillers, crosslinkers, crosslinking catalysts, Pigments, adhesives or other volume extender. The Applying or introducing the nonionic surfactants can by Dispersing in a manner known to those skilled in the art, e.g. through the use of dispersers, kneaders, planetary mixers, etc., below Exclusion of moisture and oxygen both in the finished as well as in parts of these sealants or together with a or more components of the sealants.

Even the treatment of already cured, crosslinked sealant surfaces can by Applying solutions or suspensions of the substance used according to the invention are carried out by the active ingredient by swelling or diffusion into the sealant is transported.

Sealants which can be used according to the invention can be produced both on silicone, urethane and on acrylic base or about on MS polymer basis. Urethane-based sealants are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry (8th Edition 2003, Chapter 4) and in US 4,417,042 disclosed. Silicone sealants are known in the art, for example. From the EP 0 118 030 A . EP 0 316 591 A . EP 0 327 847 A . EP 0 553 143 A . DE 195 49 425 A and US 4,417,042 , Examples of acrylic sealants are inter alia in WO 01/09249 or the US 5,077,360 disclosed. Examples of MS polymer-based sealants are described, for example, in US Pat EP 0 824 574 . US 3,971,751 . US 4,960,844 . US 3,979,344 . US 3,632,557 . DE 4029504 . EP 601,021 or the EP 370 464 disclosed.

In particular, at room temperature crosslinking systems, such as. In the EP 0 327 847 or US 5,077,360 described, preferred. These may be single-component or multi-component systems, it being possible for catalyst and crosslinker to be present separately in the multicomponent systems (for example disclosed in the patents US 4,891,400 and US 5,502,144 ), or other so-called silicone RVT 2K systems, in particular platinum-free systems.

Particular preference is given to so-called one-component systems which contain all ingredients for the construction of a sealant, are stored with the conclusion of atmospheric moisture and / or atmospheric oxygen and cure on site under reaction with atmospheric oxygen and / or atmospheric moisture. Particularly preferred are the so-called silicone neutral systems, in which the reaction of crosslinking agents with the water of the ambient air does not lead to corrosive, acidic, basic or odor-intensive cleavage products. Examples of such systems are in the DE 195 49 425 , of the US 4,417,042 or the EP 0 327 847 disclosed.

The Sealants and in particular jointing compounds may be aqueous or organic solvents contain. As organic solvents come hydrocarbons such as cyclohexane, toluene or xylene or petroleum ether in question. Other solvents include ketones like Methyl butyl ketone or chlorinated hydrocarbons.

Farther can the sealants still contain other rubbery polymers. Here come relatively low molecular weight, commercially available types of polyisobutylene, Polyisoprene or polybutadiene styrene in question. Also the co-use of degraded natural rubber or neoprene rubber is possible. Here can even at room temperature still flowable types are used, which often be referred to as "liquid rubber".

The sealing compounds according to the invention can be used to different materials with each other to connect or seal. Here is primarily to use on concrete, on glass, on plaster and / or enamel as well as ceramics and Porcelain thought. But also the joining or sealing of molded parts or profiles made of aluminum, steel, zinc or even of plastics such as PVC or polyurethanes or acrylic resins is possible. Finally, be the sealing of wood or wood materials with the most diverse mentions other materials.

The Stability of jointing compounds is usually through Adding finely divided solids - also called fillers - achieved. These can be in such organic and inorganic type differ. As inorganic fillers, for example, silica / silica (coated or uncoated), chalk - coated or uncoated - and / or Zeolites are preferred. The latter can also be used as a desiccant act. As organic filler comes for example PVC powder into consideration. The fillers generally wear essential to the sealing compound after use possesses a necessary internal support, so that leakage or Discharging the sealant from vertical joints is prevented. The aforementioned additives or fillers can be reduced to pigments and thixotropic fillers, also abbreviated as Thixotropic agent referred to, divide.

When Thixotropic agents are the known thixotropic agents such as bentones, kaolins or organic compounds such as hydrogenated castor oil or derivatives thereof with polyfunctional amines or the reaction products of stearic acid or ricinoleic acid with ethylenediamine. As particularly favorable has the concomitant use of silicic acid, especially of silicic acid proved from the pyrolysis. Furthermore come as a thixotropic agent substantially swellable polymer powder into consideration. Examples are polyacrylonitrile, polyurethane, polyvinyl chloride, polyacrylate, Polyvinyl alcohols, polyvinyl acetates and the corresponding copolymers. Particularly good results can be achieved with finely divided polyvinyl chloride powder receive. In addition to the thixotropic agents, it is also possible to use additional adhesion promoters such as mercaptoalkylsilane. Here it has proven to be appropriate to use a Monomercaptoalkyltrialkoxysilane. Commercially available for example, the mercaptopropyltrimethoxysilane.

The Properties of a jointing compound can be further developed improve when the plastic powder used as thixotropic agent additional components are added. These are substances under the category of for Plastics used plasticizers or swelling agents and swelling aids fall.

It come for example Plasticizers, in particular for the sealing compounds based on urethane or acrylic the class of phthalates into consideration. examples for applicable compounds from this class of substances are dioctyl phthalate, Dibutyl phthalate and benzyl butyl phthalate. Further suitable substance classes are Chloroparaffins, alkylsulfonic acid esters such as the phenols or cresols and fatty acid esters.

For the silicone sealants are silicone oils as plasticizers, particularly preferred polydimethylsiloxanes, and hydrocarbons and / or mixtures thereof, especially hydrocarbons or their mixtures with a boiling point of greater than 200 ° C, especially greater 230 ° C, well suited.

When Swelling aids are such low molecular weight organic substances can be used, which is miscible with the polymer powder and the plasticizer are. Such source aids can be submitted to the relevant plastic and polymer manuals for the Remove specialist. As preferred swelling aids for polyvinyl chloride powder serve esters, ketones, aliphatic hydrocarbons, aromatic Hydrocarbons and aromatic hydrocarbons with alkyl substituents.

When Pigments and dyes become known for these uses Substances such as titanium dioxide, iron oxides and soot used.

to Improvement of storage stability become known the sealants stabilizers such as benzoyl chloride, acetyl chloride, toluenesulfonate, Carbodiimides and / or polycarbodiimides added. As special good stabilizers have olefins with 8 to 20 carbon atoms proved. In addition to the stabilizing effect, these can also be tasks of Meet plasticizers or swelling agents. Preference is given to olefins with 8 to 18 carbon atoms, especially when the double bond is arranged in 1,2-position. Best results are obtained, if the molecular structure of these stabilizers is linear.

A further preferred embodiment The present invention is a wallpaper adhesive containing preferably 0.000001 to 3 wt .-% of substances according to the invention according to formula (I) and / or (II). The wallpaper adhesives may be this Wallpaper paste from aqueous solutions of hydrocolloids such as methylcellulose, methylhydroxypropylcellulose or water-soluble starch derivatives or about watery Dispersions of film-forming high molecular weight such as polyvinyl acetate, in particular in connection with the already mentioned cellulose and starch derivatives, act.

As filter media, all known types can be used, as long as they are suitable for use in water or air filter systems, in particular for air conditioners or humidifiers. Insbeson These include filter materials of cellulose, glass fibers, PVC fibers, polyester fibers, polyamide fibers, in particular nylon fibers, nonwovens, sintered materials and membrane filters.

Cleaning and disinfecting agents

The inventive cleaning and / or disinfectant containing the biofilm blockers of the invention contains is in a preferred embodiment biocides, but may also contain biocides.

The Detergent may in particular be liquid, gel or pasty aqueous and may be common, for example Contain detergent ingredients. To these ingredients counting especially surfactants, but also builders, acids, alkalis, hydrotropes, Solvent, Thickeners, abrasives and other auxiliaries and additives such as dyes, perfumes, corrosion inhibitors or skin care products.

The optionally used surfactants are preferably selected from the group anionic surfactants, nonionic surfactants and / or amphoteric Surfactants. In this case, preference is given to anionic and / or nonionic Surfactants used. If used, come anionic Surfactants preferably in amounts of 0.1 to 15 wt .-%, nonionic Surfactants preferably in amounts of 0.1 to 10 wt .-% and amphoteric Surfactants are preferably used in amounts of from 0.1 to 4% by weight, in each case based on the total composition. In a less preferred embodiment can In addition, cationic surfactants, in particular in amounts of up to 2% by weight, based on the total composition. In a preferred embodiment is the detergent due to the cationic surfactants outgoing biocidal action, however, free of these.

To the inventively usable include anionic surfactants in particular aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, Dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkanesulfonates, α-olefinsulfonates, Ether sulfonates, n-alkyl ether sulfonates, sulfonated fatty acids, ester sulfonates and lignosulfonates. Also in the context of the present invention usable are alkylbenzenesulfonates, fatty acid salts (soaps), fatty acid cyanamides, Sulfosuccinates (Sulfobernsteinsäuremono- and dialkyl esters), sulfosuccinamates, sulfosuccinamides, carboxylic acid amide ether sulfates, Alkyl polyglycol ether carboxylates, fatty acid isethionates, acylaminoalkanesulfonates (Taurides, N-acyltaurides), fatty acid sarcosinates, ether and alkyl (ether) phosphates and α-sulfofatty acid salts, Acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate, and finally their mixtures.

in the The present invention relates to fatty acids or fatty alcohols or their derivatives - insofar not stated otherwise - representative for branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms, in particular 8 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms, most preferred 12 to 16 carbon atoms, for example 12 to 14 carbon atoms. The fatty acids / alcohols or their derivatives with even number of carbon atoms are in particular because of their vegetable base than on renewable resources based on ecological establish preferred, but without limiting the teaching of the invention to them. Especially are also available, for example, according to the ROELEN's oxo synthesis Oxo-alcohols or their derivatives having preferably 7 to 19 carbon atoms, in particular 9 to 19 carbon atoms, particularly preferably 9 to 17 carbon atoms, especially 11 to 15 carbon atoms, for example 9 to 11, 12 to 15 or 13 to 15 carbon atoms, respectively used.

They are in the form of their alkali metal and alkaline earth metal salts, in particular sodium, potassium and magnesium salts, as well as ammonium and mono-, di-, tri- or tetraalkylammonium salts and in the case of the sulfonates also in the form of their corresponding acid, for example dodecylbenzenesulfonic acid, used. Due to their production, the alkyl ether sulfates always contain residual contents of non-alkoxylated fatty alcohol sulfates, especially at low degrees of ethoxylation. Furthermore, the compositions according to the invention may also comprise soaps, ie alkali or ammonium salts of saturated or unsaturated C ₆ -C ₂₂ -fatty acids.

Prefers The anionic surfactants are selected from the group comprising Fatty alcohol sulfates in amounts of up to 5% by weight, alkylbenzenesulfonates in amounts of up to 7.5% by weight and soaps in amounts of up to 2 wt .-%, each based on the total composition, and mixtures the same.

Suitable nonionic surfactants are, for example, C ₈ -C ₁₈ -alkyl alcohol polyglycol ethers, alkyl polyglycosides and nitrogen-containing surfactants or mixtures thereof, in particular the first two.

C ₈ -C ₁₈ alkyl alcohol polypropylene glycol / polyethylene glycol ethers may be represented by the formula R ¹ O- (CH ₂ CH (CH ₃ ) O) _p (CH ₂ CH ₂ O) _e -H in which R ^{1 is} a linear or branched, aliphatic alkyl and / or alkenyl radical having 8 to 18 carbon atoms, p is 0 or numbers from 1 to 3 and e is numbers from 1 to 20. They are obtained by addition of propylene oxide and / or ethylene oxide to alkyl alcohols, preferably to fatty alcohols. Furthermore, end-capped C ₈ -C ₁₈ alkyl alcohol polyglycol ethers can also be used, ie alkyl alcohol polyalkylene glycol ethers according to the above formula in which the free OH group has been etherified.

Inventive cleaner can Alkyl alcohol polyglycol ether in amounts of 0.1 to 4 wt .-%, based on the total composition.

Preferred nonionic surfactants are also alkyl polyglycosides (APG) of the formula R ² O [G] _x , in which R ^{2 is} a linear or branched, saturated or unsaturated alkyl radical having 8 to 22 carbon atoms, [G] is a glycosidically linked sugar radical and x is a number from 1 to 10. The index number x indicates the degree of oligomerization (DP degree), ie the distribution of monoglycerides and oligoglycosides. While x in a given compound always has to be an integer, and above all can assume the values x = 1 to 6, the value x for a given alkyl glycoside is an analytically determined arithmetic variable, which usually represents a fractional number. Preferably, alkyl glycosides having a mean degree of oligomerization x of 1.1 to 3.0 are used. From an application point of view, those alkyl glycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.6 are preferred. The glycosidic sugar used is preferably xylose, but especially glucose. The alkyl or alkenyl radical R ² can be derived from primary alcohols having 8 to 18, preferably 8 to 14 carbon atoms. Typical examples are caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol, and technical mixtures thereof, such as those obtained during the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from ROELEN's oxosynthesis. Preferably, however, the alkyl or alkenyl radical R ² is derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol. Also to be mentioned are elaidyl alcohol, petroselinyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and technical mixtures thereof.

Alkylpolyglykoside can in cleaners according to the invention in amounts of 0.1 to 6 wt .-%, based on the total composition.

When other nonionic surfactants can containing nitrogen-containing surfactants, e.g. fatty acid polyhydroxy amides, For example, glucamides, and ethoxylates of alkylamines, vicinalen Diols and / or carboxylic acid amides, the alkyl groups having 10 to 22 carbon atoms, preferably 12 to 18 C atoms, own. The degree of ethoxylation of these compounds is usually between 1 and 20, preferably between 3 and 10. Preferred are ethanolamide derivatives of alkanoic acids with 8 to 22 C atoms, preferably 12 to 16 C atoms. To the particular include suitable compounds the lauric acid, myristic and palmitic acid monoethanolamides.

The amphoteric surfactants (amphoteric surfactants, zwitterionic surfactants) which can be used according to the invention include, inter alia, betaines, amine oxides, alkylamidoalkylamines, alkyl-substituted amino acids and acylated amino acids. Preferred amphoteric surfactants are, for example, betaines of the formula (R ³ ) (R ⁴ ) (R ⁵ ) N ⁺ CH ₂ COO ^- , in which R ^{3 is} an optionally interrupted by hetero atoms or heteroatom groups alkyl radical having 8 to 25, preferably 10 to 21 carbon atoms and R ⁴ and R ^{5 are} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ alkyl dimethylcarboxymethylbetain and C ₁₁ -C ₁₇ -Alkylamidopropyl dimethylcarboxymethyl betaine.

If cationic surfactants are included in the composition, these are preferably the quaternary ammonium compounds of the formula (R ⁶ ) (R ⁷ ) (R ⁸ ) (R ⁹ ) N ⁺ X ^- , in which R ⁶ to R ^{9 are} four identical or different, in particular two long and two short-chain, alkyl radicals and X ^{- are} an anion, in particular a halide ion, for example didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecylammonium chloride and their mixtures. Preferably, however, the detergent composition is free of cationic surfactants.

at The choice of suitable surfactants must be taken to ensure that, if additionally Enzymes are contained in the detergent, then they are used with the Enzymes are compatible. Preferably, the enzyme activity is during a typical medium exposure time of 15 minutes by no more than 50% reduced, in particular not more than 30%. So have trials show that the as denaturing known sodium dodecyl sulfate (SDS) the activity of corolase already in a concentration of 1% within 15 minutes drops below 30% while the activity xylanase decreases to less than 40% with only 0.1% SDS, see above that this Surfactant for the use in cleaning agents according to the invention is not preferred. Should this or a similar acting surfactant nevertheless are used, it is preferable to a spatial separation while the storage, for example by encapsulation of the enzymes or by using a multi-chamber bottle, so that enzymes and surfactants only immediately before or during use with each other get in touch. On the other hand, alkyl polyglycosides are good for use in enzyme-containing agents according to this Invention suitable. So the activity of the Corolase also remains with 3% APG 600 still clearly over 50% experiencing xylanase even an increase in activity through the addition of APG 600 (more than 150% activity with 0.1% surfactant) and still shows more than 80% with 3% APG activity on.

Farther can the agents according to the invention Builder included. Suitable builders are, for example, alkali metal gluconates, citrates, nitrilotriacetates, carbonates and bicarbonates, in particular Sodium gluconate, citrate and nitrilotriacetate and sodium and potassium carbonate and bicarbonate, and alkali metal and alkaline earth metal hydroxides, especially sodium and potassium hydroxide, ammonia and amines, in particular mono- and triethanolamine, or mixtures thereof. This includes as well the salts of glutaric acid, Succinic acid, adipic acid, tartaric acid and benzene hexacarboxylic acid as well as phosphonates and phosphates. The agents can be builders in quantities to the composition, from 0.1 to 5 wt .-%.

Furthermore, the agents according to the invention may contain acids and / or alkalis. These serve on the one hand as pH regulators, on the other hand, the acids can also contribute to the removal of limescale from the surfaces to be cleaned. The acids which can be used according to the invention may be inorganic mineral acids, for example hydrochloric acid, and / or C _1-6 -mono-, di-, tri- or polycarboxylic acids or -hydroxycarboxylic acids such as, for example, formic acid, acetic acid, lactic acid, citric acid, gluconic acid, glutaric acid , Succinic acid, adipic acid, tartaric acid or else malic acid, as well as other organic acids such as salicylic acid or amidosulfonic acid. However, the citric acid is particularly preferably used; also mixtures of several acids can be used. Acids can be present in the inventive detergent in amounts of up to 6 wt .-%, based on the total composition.

To the optionally usable bases include alkanolamines, for example Mono- or diethanolamine, and ammonium or alkali metal hydroxides, especially sodium hydroxide. The cleaning agent according to the invention may contain bases in amounts of up to 2.5% by weight, based on the overall composition.

The agent according to the invention can furthermore contain one or more thickeners for viscosity regulation. Suitable thickeners are natural and synthetic polymers and inorganic thickeners. The polymers which can be used include polysaccharides or heteropolysaccharides and other organic natural thickeners, including the polysaccharide gums such as gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, eg propoxylated Guar, and their mixtures, as well as pectins, polyoses, carob seed flour, starch, dextrins, gelatin, casein. Furthermore, organic modified natural substances such as carboxymethyl cellulose and cellulose ethers, hydroxyethyl and propyl cellulose and the like or cellulose acetate and core flour ethers can be used. Homogeneous and copolymeric polycarboxylates, especially polyacrylic and polymethacrylic compounds, as well as vinyl polymers, polycarboxylic acids, polyethers, polyimines or else polyamides can serve as organic fully synthetic thickeners. Suitable inorganic thickeners include polysilicic acids, clay minerals such as montmorillonites, zeolites, silicic acid and various nanoparticulate inorganic compounds such as nanoparticulate metal oxides, oxide hydrates, hydroxides, carbonates and phosphates and silicates having an average particle size of 1 to 200 nm, based on the Particle diameter in the longitudinal direction, ie in the direction of the largest expansion of the particles. These nano-particulate substances can optionally in a further embodiment of the invention be treated with one or more surface modifiers. The surface modification is carried out in known manner to the skilled person with mono- and polybasic carboxylic acids or C _2-8 hydroxycarboxylic acids, functional silanes of the type (OR) _4-n SiR _n (R = org. Radicals having functional groups such as hydroxyl, carboxyl, ester , Amine, epoxy, etc.), quaternary ammonium compounds or amino acids as well as other substances which can be used for this purpose.

Next the previously mentioned thickening agents, the inventive detergent Electrolyte salts included. These can also contribute to an increase in viscosity. Electrolyte salts in the context of the present invention are salts, in the aqueous agent according to the invention disintegrate into their ionic constituents. Preference is given to the salts, in particular alkali metal and / or alkaline earth metal salts, an inorganic Acid, preferably an inorganic acid from the group comprising the hydrohalic acids, nitric acid and sulfuric acid, in particular the chlorides and sulfates. Within the scope of the teaching of the invention For example, an electrolyte salt may also be used in the form of its corresponding acid / base pair be, for example, hydrochloric acid and sodium hydroxide instead of sodium chloride.

in the agents according to the invention can organic and / or inorganic thickener in quantities of total up to 2% by weight, based on the total composition.

The inventive agent can advantageously additionally one or more water-soluble organic solvents usually in an amount of up to 6% by weight, based on the total composition. The solvent is within the scope of the teaching of the invention as required in particular as hydrotrope, viscosity regulator and / or cold stabilizer used. It has a solution-promoting effect especially for Surfactants and electrolyte as well as perfume and dye and so contributes their incorporation at, prevents the formation of liquid-crystalline Phases and contributes to the formation of clear products. The viscosity of the agent according to the invention decreases with increasing amount of solvent. Too much solvent However, it can cause excessive viscosity drop.

Finally sinks with increasing amount of solvent the Kältetrübungs- and Clear point of the agent according to the invention.

Suitable solvents are, for example, saturated or unsaturated, preferably saturated, branched or unbranched C _1-20 -hydrocarbons, preferably C _2-15 -hydrocarbons, having at least one hydroxy group and optionally one or more ether functions COC, ie the carbon atom chain interrupting oxygen atoms. However, preferred solvents are the - optionally unilaterally etherified with a C _1-6 alkanol - C _2-6 alkylene glycols and poly-C _2-3 alkylene glycol having an average of 1 to 9 identical or different, preferably identical, alkylene glycol groups per molecule, for example Ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dimethoxy diglycol, dipropylene glycol, propylene glycol butyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, and PEG. Further preferred solvents are the C _1-6 -alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, etc., more preferably ethanol and / or isopropanol is used.

When solubilizers can except the solvents described above for example, alkanolamines and alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical, e.g. Xylene or cumene sulfonate be used. Other useful hydrotropes are e.g. octyl or butyl glucoside. The agent according to the invention may contain these hydrotropes in amounts of, based on the total composition, up to 4 wt .-% contain.

In an embodiment can the agents according to the invention Containing abrasives. As Abrasivkomponente this can be solid water-soluble and water-insoluble, preferably inorganic compounds and mixtures thereof are used. These include for example, alkali carbonates, alkali bicarbonates and alkali sulfates, Alkaline borates, alkali phosphates, silica, crystalline or amorphous alkali metal silicates and phyllosilicates, fine crystalline sodium aluminum silicates and calcium carbonate. The advantage of water-soluble abrasive components consists in a virtually residue-free rinsability of the agent. Besides these inorganic substances can also Abrasives obtained from animate nature, for example minced nutshells or woods, and abrasion-resistant plastics, for example polyethylene beads, or ceramic or glass beads Find use. The cleaning agent according to the invention can abrasives in amounts of up to 2 wt .-%, based on the total composition.

In addition to the abovementioned components, the compositions according to the invention may contain one or more other auxiliaries and additives, such as are customary, above all, in hard surface cleaners. These include in particular UV stabilizers, corrosion inhibitors, cleaning enhancers, antistatic agents, preservatives (eg 2-bromo-2-nitropropane-1,3-diol or an isothiazolinone Bromnitropropandiol preparation), perfume, dyes, pearlescing agents (for example, glycol distearate) and opacifiers or also skin protection agents, such as those in EP 522 506 are described. The amount of such additives is usually not more than 12 wt .-% in the detergent. The lower limit of the use depends on the nature of the additive and can be up to 0.001 wt .-% and below, for example, in the case of dyes. The amount of auxiliaries is preferably between 0.01 and 7% by weight, in particular 0.1 and 4% by weight.

When Dyes can all in detergents usually used dyes are used. Also with the fragrances can all usual perfumes be used. Preference is given to fruity scents, for example Citrus, pine (Pine) and mint, as well as floral scents. preservative have a biocidal effect, so that it is desirable in detergents according to the invention only low concentrations, but preferably no preservatives use.

It is advantageous if the agent contains no complexing agent; of the Addition of a bleaching agent for the cleaning agent according to the invention is not required.

Of the pH value of the agents according to the invention is preferably between 1 and 7.5, more preferably between 2 and 5, in particular between 2.5 and 4.5. It is in multiphase Means below the pH of the agent, the pH of the resulting after shaking temporary To understand emulsion, for means offered in multi-chambered bottles the pH of the agent is the pH of the common intended dosage obtained from the components stored in the various chambers Solution. Thus, it is meant in each case the pH of the ready-to-use cleaning solution.

Provided it is a liquid This agent preferably has a viscosity of up to to 1000 mPas. Gel-like or pasty Cleaning agents can In contrast, viscosities of up to 150,000 mPas. The viscosity measurements are carried out at 20 ° C in the Brookfield viscometer LVDV II with a rotor frequency of 20 rpm (spindle no. 31, conc. 100%).

The Detergent may contain one or more propellants (INCI Propellants), usually in an amount of 1 to 80% by weight, preferably 1.5 to 30% by weight, in particular 2 to 10 wt .-%, particularly preferably 2.5 to 8 wt .-%, most preferably 3 to 6 wt .-%, contained.

propellant are customary according to the invention Propellant gases, especially liquefied or compressed gases. The choice depends on the product to be sprayed and the field of application. When using compressed gases such as nitrogen, carbon dioxide or nitrous oxide, in general in the liquid Detergent insoluble are, the operating pressure decreases with each valve actuation. In the detergent soluble or even as a solvent acting liquefied Gases (liquefied gases) as blowing agents offer the advantage of constant operating pressure and even distribution, because in the air the propellant vaporizes and takes up a hundredfold Volume.

Suitable are the following according to INCI Propellants: Butanes, Carbon Dioxide, Dimethyl Carbonate, Dimethyl Ethers, ethanes, hydrochlorofluorocarbon 22, hydrochlorofluorocarbon 142b, hydrofluorocarbon 152a, hydrofluorocarbon 134a, hydrofluorocarbon 227ea, Isobutane, Isopentane, Nitrogen, Nitrous Oxide, Pentane, Propane.

On Chlorofluorocarbons (chlorofluorocarbons, CFCs) as However, propellant is hard because of its harmful effect on the - UV radiation protective - ozone shield the atmosphere, the so-called ozone layer, preferably largely and in particular Completely waived.

preferred Propellants are liquefied gases. Liquid are gases, which are converted at mostly already low pressures and 20 ° C from gaseous to liquid state can. In particular, under liquefied gases but the - in oil refineries as by-products of distillation and cracking of crude oil as well in natural gas processing arising in the gasoline separation - hydrocarbons propane, Propene, butane, butene, isobutane (2-methylpropane), isobutene (2-methylpropene, Isobutylene) and mixtures thereof.

Especially preferably contains the cleaning agent as one or more propellants propane, butane and / or Isobutane, especially propane and butane, most preferably propane, butane and isobutane.

One Cleaning agent according to the invention may further contain enzymes, in particular selected from polysaccharidases, Proteases and nucleases, which are suitable for biofilm degradation are.

at the polysaccharidase may in particular be a β-glucanase, Cellulase, hemicellulase, arabinase, xylanase, amylase, dextranase, Glucosidase, galactosidase, pectinase, chitinase, lysozyme, alginate lyase or any mixtures thereof. With the protease it can especially subtilisin, thermolysin, pepsin, a carboxypeptidase, an acidic protease, a serine proteinase or mixtures act on it. The nucleases can be any DNAse or RNAse act.

The in addition in the sense of this invention Enzymes which can be used in the enzyme preparations can be prepared by customary biochemical methods be obtained from the corresponding organisms. But you are too commercially available, For example, from the companies Novozymes, Genencor International, Sigma, AB Enzymes or ASA enzymes. In this case, the enzyme preparations also of technical quality and consist of several different enzyme activities. The presence from partially not closer characterized ancillary activities may be due to the hydrolysis of complex biofilm polymers also a cheap one Have influence.

The Hygienic effect of the cleaning agent according to the invention can optionally be supplemented by the addition of antimicrobial agents. Suitable germ-inhibiting agents here are in particular isothiazolein mixtures, Sodium benzoate and / or salicylic acid. Further examples are substances with specific activity against gram-positive Bacteria such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether, Chlorhexidine (1,6-di- (4-chlorophenyl-biguanido) -hexane) or TCC (3,4,4'-trichlorocarbanilide). Also numerous fragrances and essential oils have antimicrobial properties on. Typical examples are the active ingredients Eugenol, Menthol and Thymol in cloves, mint and Thyme oil. An interesting natural germ repellent is the terpene alcohol farnesol (3,7,11-trimethyl-2,6,10-dodecatrien-1-ol), which is present in linden flower oil is and a lily of the valley smell Has. Glycerol monolaurate has also proven itself as a bacteriostat. The Amount of these germ-inhibiting agents depends greatly on the effectiveness the respective compound and may be up to 5 wt .-% amount.

When Preservatives are also suitable e.g. Benzoic acid or Benzoate, salicylic acid or salicylate, sorbic acid or sorbate, formic acid or formate, propionic acid or propionate, formaldehyde, glutaraldehyde, o-phenylphenol, pHB esters (e.g., butyl 4-hydroxybenzoates, methyl 4-hydroxybenzoates, ethyl 4-hydroxybenzoates, Propyl-4-hydroxy-benzoate), 10-undecylenic acid, hexetidine, Bronidox, bronopol, trichlorocarbanilide, p-chloro-m-cresol, triclosan, imidazolidinylurea, 2-phenoxyethanol, dimethyldimethylolhydantoin, Benzyl alcohol, dibromocyanobutane, isothiazolinone mixtures, 2-chloroacetamide, Chlorhexidine gluconate, diazolidinyl urea, benzalkonium chloride, 1,2-benzisothiozolone, benzyl alcohol monochemiformal, 2- (2-hydroxypropyl) aminomethanol, Methylene bis-thiocyanate, (thiocyanomethylthio) benzothiazole, dithio-2,2'-bis (benzmethylamide), Silver chloride on TiO2 support, Didecyldimethylene ammonium chloride, N, N-bis-33-aminopropyl-C 12 -amine, Na hydroxymethylglycinate, dehydroacetic, Ethylene glycol formal, 2,4-dichlorobenzyl alcohol, 2-phenoxypropanol, 3- (4-chlorophenoxy) -1,2-propanediol, 4-chloro-3,5-dimethylphenol, Hexadecylpyridinium chloride and / or 3-iodopropynyl-butyl-carbamate.

Preferably are the germ-inhibiting substances in amounts up to 10, preferably between 0.01 and 5 wt .-%. As stated earlier, can in a preferred embodiment However, the addition of antibacterial agents are completely dispensed with.

One Another object of the present invention is a product, containing a cleaning agent according to the invention and a spray dispenser. The spray dispenser is preferred a manually activated spray dispenser, especially selected from the group comprising aerosol spray dispensers (pressurized gas containers; et al referred to as spray can), even pressure-building spray dispensers, Pumpsprühspender and trigger spray dispensers, in particular pump spray dispenser and trigger spray dispensers with a container made of transparent polyethylene or polyethylene terephthalate. spray dispenser become more detailed in WO 96/04940 (Procter & Gamble) and the spray dispensers in it cited US patents, all of which are incorporated herein by reference and its contents are hereby incorporated into this application is described. Triggersprühspender and pump sprayer own opposite Compressed gas containers the advantage that no Propellant must be used.

In a further preferred embodiment, however, the agent according to the invention, in particular when enzymes are present, is not atomized as an aerosol, since in this case, if appropriate, small amounts of the Enzymes may enter the respiratory tract and may cause allergic reactions there. By means of suitable particles-passing attachments, nozzles, etc. (so-called "nozzle valves") on the spray dispenser, the enzyme can be added to the agent in a form immobilized on particles and dosed as a cleaning foam. In producing these compact foams, no respirable particles are formed so that the danger of inhaling allergens is substantially eliminated.

Yet Another subject of the invention is a method for hydrolysis biofilms on hard surfaces, in which the vitality the microbial cells are not damaged. For this purpose, the inventive enzyme preparation or the cleaning agent according to the invention, optionally using a product according to the invention, on the biofilm-coated area applied and optionally after a contact time of 1 to 30 minutes, with stronger Infest also for a few hours or over Night, rinsed with clean water. The preparation or the agent may also be washed before rinsing a cloth, a sponge, a brush or some other Cleaning suitable utensil on the biofilm infested surface blurs or triturated, which is e.g. in the presence of abrasives Improved cleaning performance in the cleaning agent. Finally will the surface dried with a dry cloth. In case of very strong infestation of surface with biofilm, the cleaning process can then be repeated.

Cooling lubricant and anti-corrosion agent

In one according to the invention especially preferred embodiment the use of the compounds according to the invention is carried out in a cooling lubricant or anti-corrosion agent, in particular in a reactor circulation or open cooling system, its metal surfaces be protected against corrosion and hardness deposition have to. The use is preferably carried out in a zinc-free composition. Of the Use of the composition is preferably carried out in a pH range from 8.2 to 9.0. To be protected metal surfaces it is preferably steel, copper or non-ferrous metal surfaces. The composition contains preferably at least one dispersant component, at least one, preferably different, phosphonic acids and / or polycarboxylic acids, and preferably at least one non-ferrous metal inhibitor.

The explain the following examples the invention without, however, limiting it to:

General procedural regulation for the preparation of Dibromoxoalkanoylsäuren

A solution of bromine (0.06 mol) in dry dichloromethane (8 ml) becomes slow to an iced solution of 4-oxo-2-alkenoic acid (0.03 mol) in dry dichloromethane (30 ml). The Mix will be first Stirred for 30 minutes in an ice bath and subsequently another 30 minutes at room temperature. The solution thus obtained becomes with watery Sodium metabisulphite (0.5 M, 30 ml) and washed with brine (30 ml). The solution will over Dried sodium sulfate and concentrated to dryness. The yield of crude pale brownish oily 2,3-dibromo-4-oxoalkanoylic acid is intermediate 60 and 65%. The crude product can be used for the following reaction steps to be used without purification.

General procedural regulation for the Preparation of 3- (bromomethylene) -2-alkanones and 2-bromo-4-oxo-2-alkenoic acids

A solution of triethylamine (8.7 mmol) in dichloromethane (5 ml) is added dropwise with stirring to an iced solution of dibromo-4-oxoalkanoylic acid (3.5 mmol) in dry dichloromethane (10 ml). The so obtained mixture is first on ice for Stirred for 2 hours and subsequently at room temperature Night. The mixture is then poured into dilute hydrochloric acid (50 ml, 2M) and then with dichloromethane (3 x 20 ml). The combined dichloromethane extracts are washed with brine (100 ml), over dried anhydrous sodium sulfate and then to concentrated to dryness. The thus obtained 3- (bromomethylene) -2-alkanone shows a slightly brownish Colour. The crude product is purified on silica gel using dichloromethane chromatographed as eluant. The yield of colorless 3- (bromomethylene) -2-alkanone ö1 is between 52 and 70%. On continuation elution with dichloromethane / ethyl acetate in the ratio 3 : 1 receives 2-bromo-4-oxo-2-alkenoylic acid in a yield of 20 to 30% as an oil, which upon standing at Room temperature is fixed.

Example:

A) The following furanone compounds and halomethylene-alkanone derivative (123) were tested:

B) Use of QSB active ingredients in technical fluids for the reduction of P. aeruginosa biofilms on glass surfaces

Execution:

The seed Pseudomonas aeruginosa DSM 939 is grown overnight on Caso agar at 37 ° C. A CFU (Colony Forming Unit) from the solid medium is incubated in 50 ml Caso Broth for 7 h at 37 ° C and 150 rpm (1st passage). From the grown liquid culture 100 .mu.l germs are transferred to 50 ml of fresh Caso-nutrient medium and incubated for about 16h at 37 ° C and 150 upm. (2nd passage). From this second passage, a bacterial count of 10 ⁶ cfu / ml is used in the biofilm test. For the biofilm experiment, the germs in the above-mentioned concentration are pipetted together with a diluted complete medium (20 times DGYM-diluted TBY) into a microtiter plate (6-well chamber), which is used as a miniaturized biofilm test system. To the mixture (3ml) are the active substances to be tested in the ge desired concentration added, in addition run controls without drug or without cells. Negative controls are approaches with active ingredient, but without germ, as the active ingredients could already have an intrinsic color. As a positive control, diluted complete medium with germ, but without active ingredient (furanone derivative) is used. In addition, 1 sterile glass slide (coverslip for microscopy) of size 18 × 18 is placed in the 6-well chambers, on the surface of which the biofilm growth is examined.

In addition, will a commercial one Water treatment agent added in its presence (50 ppm use concentration) the effect of the furanone or the open-chain halomethylene-alkanone derivative to be examined. The commercial water treatment agent is a liquid, Zinc-free combination product based on various phosphonic acids, polycarboxylic acids and a non-ferrous metal inhibitor. It works in the pH range from 8.2 to 9.0 corrosion-inhibiting on steel, copper and non-ferrous metal surfaces and prevents deposits by a dispersant component Pipe walls and thus provides the guarantee for the training of an optimal Corrosion protection film.

From each approach, triple determinations are made, ie, three coverslips are tested per batch. The 6-well plates are shaken for 6h or 24h at 30 ° C and 60 rpm. After the given incubation times, 1 ml each per batch is taken for germ count determination, diluted in tryptone-NaCl solution and plated out on caso-agar. The resulting plates are incubated at 37 ° C for 24 h and then counted. The coverslips are removed from the 6-wells at room temperature to dry and then stained for 15 minutes in new 6-wells containing 3 ml of 0.01% safranine-O solution (prepared with distilled water). Thereafter, the staining solution is filtered off with suction, removed with H ₂ Obidest non-bound dye from the glasses and the colored coverslips dried. The stained and dried surfaces of the coverslips are scanned and evaluated with Corel Draw Paint 9. In order to be able to subtract the background value (caused by the glass) from the measured value, additionally untreated coverslips are scanned.

Results and explanation of the pictures:

Five different substances (50 ppm) were tested for their ability to suppress the biofilm of P. aeruginosa ( 1 ). After 6 hours of incubation, differences in biofilm formation in the control (in 1 ) compared to the approaches with the QSB active substances. The three best acting substances (105, 123, 139) were tested in two concentrations (5 ppm and 50 ppm) alone and in addition to the commercial water treatment agent to find the most effective compound. In each case 5 ppm (first column) and 50 ppm (second column) QSB concentrations were added to the batches in the absence (in 2A ) or present (in 2 B ) of the water treatment agent. The batch with 50 ppm substance 123 showed a biofilm reduction of almost 70% without the addition of the water treatment agent, while in the presence of the water treatment agent the biofilm reduction was still 50%. When using 5 ppm substance 123, only small biofilm reductions (about 10%) were observed in batches without and with water treatment agent compared to the control.

Without Water treatment agents showed, besides compound 123, the furanones 105 and 139 the best effect (a biofilm reduction of over 30%). In combination with the water treatment agent leaves the effect of the substances 105 and 139, but they still have a significant one Effectiveness. However, by far the best effectiveness shows the Substance 123.

This new finding was confirmed by a concentration series of substance 123 in the presence of the water treatment agent ( 3 ). There is a clear dependency between biofilm reduction and the active ingredient concentration used, since with the use of 25 ppm of substance 123, a significant reduction in biofilm (approx. 30%) could be achieved, in contrast to the approach of 5 ppm.

The Effect of a QSB agent depends on its concentration as well as the chemical composition of the liquid in which it is used shall be.

The Tent growth was in all approaches not disturbed, i.e. Biofilm reduction is based on a non-biocidal effect.

Claims (19)

Use of one or more compounds selected from compounds of the formula (I)

and compounds of the formula (II)

for the control of processes based on microbial interaction, in particular for the control of the formation and / or maturation of biofilms, particularly preferably of biofilms in which Gram-negative bacteria are involved, in the industrial and / or institutional field, wherein the radicals R ₁ , R ₂ and R ₃ , which may be different or identical, and the radicals Ra, Rb, Rc and Rd, which may also be different or identical, are independently selected from halogen, in particular chlorine, bromine, fluorine or iodine, trifluoromethyl, hydrogen , Alkyl, cycloalkyl, alkenyl, alkynyl, heteroalkyl, alkoxy, alkylsulfanyl, alkylsulfonyl, alkylsulfoxidyl, alkanoyl, acyl, alkoxycarbonyl, alkylaminocarbonyl, alkylsulfanylcarbonyl, hydroxy, monoalkylamino, dialkylamino, aryl, heteroaryl, heterocycloalkyl, arylalkyl, arylsulfonyl, arylsulfoxidyl, arylcarbonyl, aryloxycarbonyl , Arylaminocarbonyl, formyl and cyano, and wherein X is halogen, in particular fluorine, chlorine, B rom or iodine, stands. Use according to claim 1, characterized in that the radicals R ₁ , R ₂ and R ₃ and the radicals Ra, Rb, Rc and Rd are independently selected from halogen, C _1-12 -alkyl, C _1-12 -alkoxy, C _2-12 alkenyl, C _2-12 alkynyl, C _6-14 aryl and C _6-14 arylC _1-4 alkyl. Use according to claim 1 or 2, characterized in that R ₁ and R _{2 are} independently selected from C _1-4 alkyl, R _{3 is} hydrogen and X is bromine. Use according to claim 1 or 2, characterized in that Ra is halogen, Rb is C _1-12 -alkyl, Rc is hydrogen or C _1-4 -alkyl and Rd is halogen. Use according to claim 1 or 2, characterized in that Ra is C _1-12 -alkyl, Rb is halogen, Rc is hydrogen or C _1-4 -alkyl and Rd is halogen. Use according to one of claims 1 to 5, characterized that the Use in institutional and / or industrial sterilization, Disinfecting, impregnating, Preservative, corrosion protection, washing, dishwashing or Cleaning agents, cooling or cooling lubricants (technical application solutions) or in the field of water purification / water treatment. Use according to one of claims 1 to 5, characterized that use in means for finishing or treating surfaces, foods, Filter media, adhesives, building materials, building aids, ceramics, Plastics, metals, textiles, furs, paper, hides, polymers, Leather or packaging in industrial and / or institutional Area is done. Use according to one of claims 1 to 7, characterized that the application in the pharmaceutical, food, brewery, Milk, medical, paint, wood, textile, cosmetics, leather, Tobacco, fur, rope, paper, pulp, plastic, fuel, oil, rubber, Automotive, polymer, steel or mechanical engineering industry. Use according to one of claims 1 to 5, characterized that the Application in medical devices, Instruments and apparatus, in particular for catheters or endoscopes he follows. Use according to one of claims 1 to 5, characterized that the application in industrial and / or institutional machinery, Apparatus or equipment is done. Use according to one of claims 1 to 7, characterized that the application in hospitals, Hotels, schools, swimming pools, Bathing establishments, cisterns, public Transportation, public Buildings, public sanitary Facilities, saunas, sports facilities or in doctor or massage practices. Use according to one of claims 1 to 11, characterized that the Compound or compounds of formula (I) and / or according to formula (II) in a concentration in the range of 1 ppm to 1000 ppm, in particular 2 to 500 ppm and more preferably 5 to 50 ppm are used. Composition containing, equipped and / or coated with at least one substance selected from compounds of the formula (I)

and compounds of the formula (II)

where the radicals R ₁ , R ₂ and R ₃ , which may be different or identical, and the radicals R a, R _b , R _c and R d, which may likewise be different or identical, are independently selected from halogen, in particular chlorine, bromine, Fluorine or iodine, trifluoromethyl, hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, heteroalkyl, alkoxy, alkylsulfanyl, alkylsulfonyl, alkylsulfoxidyl, alkanoyl, acyl, alkoxycarbonyl, alkylaminocarbonyl, alkylsulfanylcarbonyl, hydroxy, monoalkylamino, dialkylamino, aryl, heteroaryl, heterocycloalkyl, arylalkyl, Arylsulfonyl, arylsulfoxidyl, arylcarbonyl, aryloxycarbonyl, arylaminocarbonyl, formyl and cyano, and wherein X is halogen, in particular fluorine, chlorine, bromine or iodine, characterized in that it is an institutional and / or industrial sterilization, disinfection, Impregnating, preserving, washing, dishwashing or cleaning agents, cooling or cooling lubricants or a Wasserbehandlungsmit tel acts. Composition according to Claim 13, characterized that it is an anti-corrosive agent which is at least a dispersant component, at least one, preferably different, phosphonic acids and / or polycarboxylic and at least one non-ferrous metal inhibitor. Composition comprising, equipped and / or coated with at least one substance selected from compounds of the formula (I) and compounds of the formula (II) where the radicals R ₁ , R ₂ and R ₃ , which may be different or identical, and the radicals Ra , Rb, Rc and Rd, which may also be different or identical, are independently selected from halogen, in particular chlorine, bromine, fluorine or iodine, trifluoromethyl, hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, heteroalkyl, alkoxy, alkylsulfanyl, alkylsulfonyl , Alkylsulfoxidyl, alkanoyl, acyl, alkoxycarbonyl, alkylaminocarbonyl, alkylsulfanylcarbonyl, hydroxy, monoalkylamino, dialkylamino, aryl, heteroaryl, heterocycloalkyl, arylalkyl, arylsulfonyl, arylsulfoxidyl, arylcarbonyl, aryloxycarbonyl, arylaminocarbonyl, formyl and cyano, and where X is halogen, in particular fluorine, Chlorine, bromine or iodine, is, characterized in that it is filter media, adhesives, building materials, Bauhilfsstoff e, textiles, furs, paper, hides, leather, ceramics, plastics, polymers, packaging or metals. Composition containing, equipped and / or coated with at least one substance selected from compounds of the formula (II) and compounds of the formula (II) where the radicals R ₁ , R ₂ and R ₃ , which may be different or identical, and the radicals Ra , Rb, Rc and Rd, which may also be different or identical, are independently selected from halogen, in particular chlorine, bromine, fluorine or iodine, trifluoromethyl, hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, heteroalkyl, alkoxy, alkylsulfanyl, alkylsulfonyl , Alkylsulfoxidyl, alkanoyl, acyl, alkoxycarbonyl, alkylaminocarbonyl, alkylsulfanylcarbonyl, hydroxy, monoalkylamino, dialkylamino, aryl, heteroaryl, heterocycloalkyl, arylalkyl, arylsulfonyl, arylsulfoxidyl, arylcarbonyl, aryloxycarbonyl, arylaminocarbonyl, formyl and cyano, and where X is halogen, in particular fluorine, Chlorine, bromine or iodine, characterized in that it is a means of equipping or treating Ob surfaces, foods, filter media, adhesives, building materials, building aids, ceramics, plastics, metals, textiles, furs, paper, hides, polymers, leather or packaging in the industrial and / or institutional area. Method of controlling for microbial interaction based operations in the industrial and / or institutional field, characterized in that that he a) determines the interacting microorganisms, if any, b) optionally among the compounds according to formula (I) and formula (II) selects the appropriate compound or compounds, and c) the compound or compounds of formula (I) and / or formula (II) in for the desired Control sufficient amount of the medium in which the microbial Interaction takes place. Method according to claim 17, characterized in that that the Microorganisms selected are among bacteria, algae or fungi, especially bacteria, preferably among gram-negative bacteria. Method according to claim 17 or 18, characterized that the microbial interaction selected is under the formation and / or maturation of biofilms, multicellular swarming behavior, the concerted training of antibiotic resistance, the concerted Synthesis of antibiotics, the concerted synthesis of pigments, the concerted production of extracellular enzymes, in particular hydrolytic Enzymes, as well as the concerted production of virulence factors, preferably the formation and / or maturation of biofilms.