CA2078412A1 - Water-based, solvent- and emulsifier-free, microbicidal active compound combination - Google Patents
Water-based, solvent- and emulsifier-free, microbicidal active compound combinationInfo
- Publication number
- CA2078412A1 CA2078412A1 CA002078412A CA2078412A CA2078412A1 CA 2078412 A1 CA2078412 A1 CA 2078412A1 CA 002078412 A CA002078412 A CA 002078412A CA 2078412 A CA2078412 A CA 2078412A CA 2078412 A1 CA2078412 A1 CA 2078412A1
- Authority
- CA
- Canada
- Prior art keywords
- active compound
- compound combination
- acid
- combination according
- preservation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 230000003641 microbiacidal effect Effects 0.000 title claims abstract description 12
- 238000004321 preservation Methods 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000417 fungicide Substances 0.000 claims abstract description 11
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims abstract description 7
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- -1 sulphuric acid anions Chemical class 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000002023 wood Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- PXMNMQRDXWABCY-UHFFFAOYSA-N 1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol Chemical compound C1=NC=NN1CC(O)(C(C)(C)C)CCC1=CC=C(Cl)C=C1 PXMNMQRDXWABCY-UHFFFAOYSA-N 0.000 claims description 8
- 239000005839 Tebuconazole Substances 0.000 claims description 8
- 150000001556 benzimidazoles Chemical class 0.000 claims description 8
- 239000002855 microbicide agent Substances 0.000 claims description 8
- 230000000855 fungicidal effect Effects 0.000 claims description 7
- 239000010985 leather Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012770 industrial material Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 244000005700 microbiome Species 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000003085 diluting agent Substances 0.000 claims description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005822 Propiconazole Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 239000012433 hydrogen halide Substances 0.000 claims description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 3
- 229940124561 microbicide Drugs 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- STJLVHWMYQXCPB-UHFFFAOYSA-N propiconazole Chemical compound O1C(CCC)COC1(C=1C(=CC(Cl)=CC=1)Cl)CN1N=CN=C1 STJLVHWMYQXCPB-UHFFFAOYSA-N 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- AKNQMEBLVAMSNZ-UHFFFAOYSA-N azaconazole Chemical compound ClC1=CC(Cl)=CC=C1C1(CN2N=CN=C2)OCCO1 AKNQMEBLVAMSNZ-UHFFFAOYSA-N 0.000 claims description 2
- 229950000294 azaconazole Drugs 0.000 claims description 2
- 150000007980 azole derivatives Chemical class 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 claims description 2
- 125000000335 thiazolyl group Chemical group 0.000 claims description 2
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- 229940058303 antinematodal benzimidazole derivative Drugs 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- 239000011877 solvent mixture Substances 0.000 description 7
- 238000007792 addition Methods 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 238000001720 action spectrum Methods 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 3
- 241000228245 Aspergillus niger Species 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 241000233866 Fungi Species 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 241000228143 Penicillium Species 0.000 description 3
- 241000589516 Pseudomonas Species 0.000 description 3
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 3
- 241000223261 Trichoderma viride Species 0.000 description 3
- 239000008272 agar Substances 0.000 description 3
- 229940027983 antiseptic and disinfectant quaternary ammonium compound Drugs 0.000 description 3
- 150000003851 azoles Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000002917 insecticide Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- YFLDZPUXCOSOGU-UHFFFAOYSA-N 1-iodoprop-2-ynyl n-butylcarbamate Chemical compound CCCCNC(=O)OC(I)C#C YFLDZPUXCOSOGU-UHFFFAOYSA-N 0.000 description 2
- AVGVFDSUDIUXEU-UHFFFAOYSA-N 2-octyl-1,2-thiazolidin-3-one Chemical compound CCCCCCCCN1SCCC1=O AVGVFDSUDIUXEU-UHFFFAOYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- 241000223602 Alternaria alternata Species 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 241000222120 Candida <Saccharomycetales> Species 0.000 description 2
- 241000222122 Candida albicans Species 0.000 description 2
- 241001515917 Chaetomium globosum Species 0.000 description 2
- 241000222290 Cladosporium Species 0.000 description 2
- 241000588722 Escherichia Species 0.000 description 2
- 241000220150 Eucryphia lucida Species 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 241001236817 Paecilomyces <Clavicipitaceae> Species 0.000 description 2
- 241001123663 Penicillium expansum Species 0.000 description 2
- 241000223254 Rhodotorula mucilaginosa Species 0.000 description 2
- 241000235070 Saccharomyces Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 241000223259 Trichoderma Species 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000013011 aqueous formulation Substances 0.000 description 2
- 244000052616 bacterial pathogen Species 0.000 description 2
- RIOXQFHNBCKOKP-UHFFFAOYSA-N benomyl Chemical compound C1=CC=C2N(C(=O)NCCCC)C(NC(=O)OC)=NC2=C1 RIOXQFHNBCKOKP-UHFFFAOYSA-N 0.000 description 2
- MITFXPHMIHQXPI-UHFFFAOYSA-N benzoxaprofen Natural products N=1C2=CC(C(C(O)=O)C)=CC=C2OC=1C1=CC=C(Cl)C=C1 MITFXPHMIHQXPI-UHFFFAOYSA-N 0.000 description 2
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- 229940095731 candida albicans Drugs 0.000 description 2
- TWFZGCMQGLPBSX-UHFFFAOYSA-N carbendazim Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 description 2
- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- NMCCNOZOBBWFMN-UHFFFAOYSA-N davicil Chemical compound CS(=O)(=O)C1=C(Cl)C(Cl)=NC(Cl)=C1Cl NMCCNOZOBBWFMN-UHFFFAOYSA-N 0.000 description 2
- WURGXGVFSMYFCG-UHFFFAOYSA-N dichlofluanid Chemical compound CN(C)S(=O)(=O)N(SC(F)(Cl)Cl)C1=CC=CC=C1 WURGXGVFSMYFCG-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- DIRFUJHNVNOBMY-UHFFFAOYSA-N fenobucarb Chemical compound CCC(C)C1=CC=CC=C1OC(=O)NC DIRFUJHNVNOBMY-UHFFFAOYSA-N 0.000 description 2
- NYPJDWWKZLNGGM-UHFFFAOYSA-N fenvalerate Chemical compound C=1C=C(Cl)C=CC=1C(C(C)C)C(=O)OC(C#N)C(C=1)=CC=CC=1OC1=CC=CC=C1 NYPJDWWKZLNGGM-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- JWZXKXIUSSIAMR-UHFFFAOYSA-N methylene bis(thiocyanate) Chemical compound N#CSCSC#N JWZXKXIUSSIAMR-UHFFFAOYSA-N 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- XTEGVFVZDVNBPF-UHFFFAOYSA-N naphthalene-1,5-disulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1S(O)(=O)=O XTEGVFVZDVNBPF-UHFFFAOYSA-N 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- ZCVAOQKBXKSDMS-AQYZNVCMSA-N (+)-trans-allethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OC1C(C)=C(CC=C)C(=O)C1 ZCVAOQKBXKSDMS-AQYZNVCMSA-N 0.000 description 1
- YLZGKZDEFJIHIJ-UHFFFAOYSA-N (1-methylbenzimidazol-2-yl) carbamate Chemical compound C1=CC=C2N(C)C(OC(N)=O)=NC2=C1 YLZGKZDEFJIHIJ-UHFFFAOYSA-N 0.000 description 1
- KAATUXNTWXVJKI-NSHGMRRFSA-N (1R)-cis-(alphaS)-cypermethrin Chemical compound CC1(C)[C@@H](C=C(Cl)Cl)[C@H]1C(=O)O[C@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 KAATUXNTWXVJKI-NSHGMRRFSA-N 0.000 description 1
- YATDSXRLIUJOQN-SVRRBLITSA-N (2,3,4,5,6-pentafluorophenyl)methyl (1r,3s)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(Cl)Cl)[C@H]1C(=O)OCC1=C(F)C(F)=C(F)C(F)=C1F YATDSXRLIUJOQN-SVRRBLITSA-N 0.000 description 1
- OJFZCPMENWLPRI-UHFFFAOYSA-N (2-ethylphenyl)-phenylmethanone Chemical compound CCC1=CC=CC=C1C(=O)C1=CC=CC=C1 OJFZCPMENWLPRI-UHFFFAOYSA-N 0.000 description 1
- GHPYJLCQYMAXGG-WCCKRBBISA-N (2R)-2-amino-3-(2-boronoethylsulfanyl)propanoic acid hydrochloride Chemical compound Cl.N[C@@H](CSCCB(O)O)C(O)=O GHPYJLCQYMAXGG-WCCKRBBISA-N 0.000 description 1
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- RYAUSSKQMZRMAI-ALOPSCKCSA-N (2S,6R)-4-[3-(4-tert-butylphenyl)-2-methylpropyl]-2,6-dimethylmorpholine Chemical compound C=1C=C(C(C)(C)C)C=CC=1CC(C)CN1C[C@H](C)O[C@H](C)C1 RYAUSSKQMZRMAI-ALOPSCKCSA-N 0.000 description 1
- XVSNMNYYRHUVGL-UHFFFAOYSA-N (4-methyl-1h-benzimidazol-2-yl) carbamate Chemical compound CC1=CC=CC2=C1NC(OC(N)=O)=N2 XVSNMNYYRHUVGL-UHFFFAOYSA-N 0.000 description 1
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- VUWCWMOCWKCZTA-UHFFFAOYSA-N 1,2-thiazol-4-one Chemical class O=C1CSN=C1 VUWCWMOCWKCZTA-UHFFFAOYSA-N 0.000 description 1
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- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
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- WEYSQARHSRZNTC-UHFFFAOYSA-N 1h-benzimidazol-2-ylcarbamic acid Chemical compound C1=CC=C2NC(NC(=O)O)=NC2=C1 WEYSQARHSRZNTC-UHFFFAOYSA-N 0.000 description 1
- RULKYXXCCZZKDZ-UHFFFAOYSA-N 2,3,4,5-tetrachlorophenol Chemical compound OC1=CC(Cl)=C(Cl)C(Cl)=C1Cl RULKYXXCCZZKDZ-UHFFFAOYSA-N 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 1
- YTOPFCCWCSOHFV-UHFFFAOYSA-N 2,6-dimethyl-4-tridecylmorpholine Chemical compound CCCCCCCCCCCCCN1CC(C)OC(C)C1 YTOPFCCWCSOHFV-UHFFFAOYSA-N 0.000 description 1
- CLVALLQETQTQMV-UHFFFAOYSA-N 2-(1,2,4-triazol-1-yl)ethanol Chemical compound OCCN1C=NC=N1 CLVALLQETQTQMV-UHFFFAOYSA-N 0.000 description 1
- STMIIPIFODONDC-UHFFFAOYSA-N 2-(2,4-dichlorophenyl)-1-(1H-1,2,4-triazol-1-yl)hexan-2-ol Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(O)(CCCC)CN1C=NC=N1 STMIIPIFODONDC-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- NCDBYAPSWOPDRN-UHFFFAOYSA-N 2-[dichloro(fluoro)methyl]sulfanylisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(SC(Cl)(Cl)F)C(=O)C2=C1 NCDBYAPSWOPDRN-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- LNRVTEQEGXVMEF-UHFFFAOYSA-N 2-hydroxy-2-methylpropanedioic acid Chemical compound OC(=O)C(O)(C)C(O)=O LNRVTEQEGXVMEF-UHFFFAOYSA-N 0.000 description 1
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- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- BSCCSDNZEIHXOK-UHFFFAOYSA-N phenyl carbamate Chemical compound NC(=O)OC1=CC=CC=C1 BSCCSDNZEIHXOK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- TVLSRXXIMLFWEO-UHFFFAOYSA-N prochloraz Chemical compound C1=CN=CN1C(=O)N(CCC)CCOC1=C(Cl)C=C(Cl)C=C1Cl TVLSRXXIMLFWEO-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- QHGVXILFMXYDRS-UHFFFAOYSA-N pyraclofos Chemical compound C1=C(OP(=O)(OCC)SCCC)C=NN1C1=CC=C(Cl)C=C1 QHGVXILFMXYDRS-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- YBBJKCMMCRQZMA-UHFFFAOYSA-N pyrithione Chemical compound ON1C=CC=CC1=S YBBJKCMMCRQZMA-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229940108410 resmethrin Drugs 0.000 description 1
- VEMKTZHHVJILDY-FIWHBWSRSA-N resmethrin Chemical compound CC1(C)[C@H](C=C(C)C)C1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-FIWHBWSRSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- CSABAZBYIWDIDE-UHFFFAOYSA-N sulfino hydrogen sulfite Chemical compound OS(=O)OS(O)=O CSABAZBYIWDIDE-UHFFFAOYSA-N 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000004308 thiabendazole Substances 0.000 description 1
- 235000010296 thiabendazole Nutrition 0.000 description 1
- 229960004546 thiabendazole Drugs 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- BAKXBZPQTXCKRR-UHFFFAOYSA-N thiodicarb Chemical compound CSC(C)=NOC(=O)NSNC(=O)ON=C(C)SC BAKXBZPQTXCKRR-UHFFFAOYSA-N 0.000 description 1
- HYVWIQDYBVKITD-UHFFFAOYSA-N tolylfluanid Chemical compound CN(C)S(=O)(=O)N(SC(F)(Cl)Cl)C1=CC=C(C)C=C1 HYVWIQDYBVKITD-UHFFFAOYSA-N 0.000 description 1
- BAZVSMNPJJMILC-UHFFFAOYSA-N triadimenol Chemical compound C1=NC=NN1C(C(O)C(C)(C)C)OC1=CC=C(Cl)C=C1 BAZVSMNPJJMILC-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000003171 wood protecting agent Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/16—Inorganic impregnating agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/343—Heterocyclic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/38—Aromatic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Peptides Or Proteins (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Steroid Compounds (AREA)
Abstract
Water-based, solvent- and emulsifier-free microbicidal active compound combination A b s t r a c t Microbicidal, optionally solvent- and emulsifier-free active compound combinations of known azole and/or benzimidazole fungicides and quaternary ammonium compounds and their use in the preservation of materials are described.
Le A 28 628
Le A 28 628
Description
2~78~2 ThP present invention relates to new, preferably aqueous, optionally organic solvent- and emulsifier-free micro-bicidal active compound combinations of known azole fungicides and/or benzimidazole derivatives and quater-nary ammonium compounds.
It is known that imidazole or triazole fungicides, such as, for example, ~-[2-(4-chlorophenyl~-ethyl]-~-(1,1-dimethylethyl)-1-H-1,2,4-triazole-1-ethanol (tebucon-azole), 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1,2,3-triazol-l~yl)-propan~2-ol and 1-E[2-(2,~-di-chlorophenyl)-4-n-propyl-1,3-dioxolan-2-yl]-methyl]-1-H
1,2,4-triazole (propiconazole) can be used as such or in the form of their salts for protecting plants and seeds (compare, for example, EP-A 0 040 345 and EP-A 0 052 424).
It is furthermore known that these compounds are also ~,~
suitable for use in the preservation of materials for combating microbes which destroy materials or discolour materials (comparel for example, DE-OS (German Published Specification) 3 621 494 and US 4 07~ 062).
However, the azole fungicides, such as the tebuconazole mentionedj have gaps in their action against some germs relevant to the preservation of materials, such as, for example, Trichoderma cpec.
;
:
:' ~ .
Le A 28 628 - 1 -~' . . - :
; - : : . :
, 2~7~12 Furthermore, because of the often low water-solubility of azoles, their use in some fields of application, such as, for example, leather, water-based preservation of wood, disinfection, cooling water treatment, the paper indus-try, metal processing and industrial preservation ofwater-containing products, is limited or impossible.
It is fur~hermore known that b~nzimidazole derivatives, such as methyl benzimidazolecarbamate (BCM, carbendazim), methyl l-(butylcarbamoyl)-2-benzimidazolecarbamate 1~ (benomyl), 2-(2~-furyl)-lH-benzimidazole (uberidazole) and 2-(4'-thiazolyl)-benzimidazole have a fungicidal activity (Farm Chemicals Handbook). These can also be used in the preservation of materials.
Benzimidazole derivatives such as, for example, BCM are sparingly soluble in the customary organic solvents and virtually insoluble in water. They moreover have yaps in ~- their action spectrum, which can make their use in the preservation of materials difficulk because of the breadth of the action spectrum required in that sector.
On the basis of the solubility data, direct use in water-based systems is practically excluded.
Quaternary ammonium salts have been known for a lony time as broad-action microbicides and are used, for example, in disinfection and textile pre~ervation.
Althou~h these active compounds are usually readily water-soluble, they tend to foam severely at the use Le A 28 628 - 2 -, ~ ~ . .. . .
2~7~
concentrations, which causes trouble in many fields of use. Because of their cationic properties, they can moreover react with anionic components, such as soaps, surfactants and the like. Their profile of properties can be adversely influenced in this way, or they can become deactivated. It is furthermore known that quaternary ammonium salts are easily deactivated by the presence of protein and dirt.
For many uses in the practice of the preservation of materials it is desirable to employ the active compounds in liquid formulations which are free from organic solvents or in which the corresponding solvent content is reduced drastically.
Water-insoluble solven~s are incompatible with aqueous products, such as leather liquors, emulsion paints, cooling and process waters and disinfectants.
~, ~ ., The users are also often not equipped to handle products in the form of solutions in organic solvents, since particular devices, associated with high investment costs, are required ~or application from the solvent and recovery thereo~, which is essential in order to avoid ecological problems.
,~
Water-soluble solvents would be suitable in principle as solubilising agents in aqueous systems. However, if they Z5 enter the waste water, they can cause ecological problems. In addition, solvents manifest themselves ::
.~
Le A 28 628 - 3 -.. . ..
~, :
. . , ~ . .. ~ : - .
2~78~2 adversely in the products to be preserved.
Another solubilisation possibility for the preparation of water-based active compound formulations is the use of emulsifiers. In the case of highly water-insoluble compounds, such as azoles and benzimidazole derivatives, large amounts of emulsifier are as a rule required for this, which should be avoided for ecological reasons. The activity of microbicidal active compounds can also ba severely impaired by the use of emulsifiers. Usability for certain systems can also be limited.
The object of the invention was therefore to provide new, preferably water-based, solvent- and emulsifier-free microbicidal act.ive compound formulations which are based on azole fungicides and/or benzimidazole derivatives and can easily be diluted with water and in this form give storage-stable use solutions.
It has now been found ~hat new active compound combina-tions of at least one metal salt and/or at least one acid addition compound of at least one azole fungicide, 20 preferably :
- 1-(4-chlorophenoxy)-3,3-dim~thyl-1-(lH-1,2,4-tri-azol-1-yl)-2-butanone (triadimefon) (4-chlorophenoxy)-~-(l,l~dimethyl-ethyl~-lH-1,2,4-triazole-1-ethanol (triadimenol) Le A 28 628 - 4 -' :
, 2~78~12 [2-(4 chlorophenyl)-ethyl]~ dLmethylethyl)-lH~1,2,4-triazole-1-ethanol (tebuconazole) ; - (RS)-2-(2,4-dichlorophenyl)-1-(lH-1,2,4-triazol-1-~ 5 yl)-hexan-2-ol .: (hexaconazole) - l-(N-propyl-N-(2-(2,4,6-(trichlorophenoxy)-ethyl)~
carbamoyl)-imidazole (prochloraz), - 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol ~ 1-[[2-(2,4-dichlorophenyl)-4 propyl-1,3-dioxolan-2-yl]-methyl]-lH-lj2,4-triazole ~propiconazole~
lo [ 2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl-methyl]-lH-1,2,4-triaxole (azaconazole) wherein, in the cases where the compounds have asymmetric carbon atoms, the isomers and isomer mixtures of the most diverse compositions are also included;
:especially preferably +~-[2-(4-chlorophenyl~-ethyl]-~-(1,1-dimethylethyl)-lH-1j2,4-triazole-1-ethanol ~tebuconazole) ..,~ :
, :
~: : and/or at least one metal salt and/or at least one acid addition aompound of~at~least one benzimidazole fungi-cide, preferably of the formula (I) ' :
Le A 28_628~ 5 -:
:: : . . :~:: : ,. - - ~ . , ; .
2~7~12 N
I 1.1 1 (I) !
in which Rl represents carbamic acid ester groups, or furyl or thiazolyl rings which are optionally further substi-- 5 tuted and R2 represents H or carbamic acid ester groups, and at least one preferably fungicidal, quaternary ammonium compound, p~eferably of the formula (II~
~: R1 I
R2_N~_K3 xe (II) : ~: : R4 :~
in which R1, R2, R3 and R4 are identical or different and in each : ` case represent unsubstituted or substituted, ~; straight-chain or branched, saturated or unsaturated alkyl groups having 1 20 carbon atoms, alkylaryl or 15: aralkyl groups:having 5~10 carbon atoms in the aryl part and 1-20 carbon atoms in the alkyl`part or aryl :~ -: groups; having 5-10 carbon atoms, and optionally : ~ mono- or polyalkoxylated derivatlves thereof;
possible substituent3 being halogenl C~-C~-alkyl and C1 C4-alkoxy; and in which 2 or 3 radicals Rl to R4 of :~
: ' ~ ' : I,e A 28 628 - 6 -:
~:
.. .
`::: : ~ . . : . . -. ,, 2~78~1~
-the quaternary centre, if appropriate with further hetero atoms, can form a saturated or unsaturated 5-, 6- or 7-membered (heterocyclic) ring and X represents an anion which promotes water-solubility, such as, for example, halide, sulphate, alkyl-sulphonate or optionally substituted arylsulphonate, have a particularly high microbicidal activity and at the same time are completely water-soluble and give stable solutions in water.
Such aqueous formulations avoid the abovementioned ecologicaI and use-related disadvantages of solvent-based or emulsifier-mediated formulations and in this respect represent a useful enrichment of the prior art.
~ Benzimidazole derivatives which may be mentioned are, ; ~15 preferably:
methyl benzimidazolylcarbamate (BCM), methyl 1-~butyl-carbamoyl)-2-benzimidazolecarbamate (benomyl), 2-~2'-furyl)-lH-benzimidazole (fuberidazole) an~ 2-(4'-thia-zolyl)benzimidazole (thiabendazole).
:: : 20 Methyl~ benzimidazolylcarbamate lBCM) is particularly preerred. : ~ :
.~ .
Quaternary ammonium compounds which may be mentioned are, preferably, ammonium salts ~uch as .
: :~
, :
Le A 28 628 - 7 - :
.
:
2~78~12 - C12-cl4-alkYl-benzyl-dimethylammonium chloride - trimethyl-coconut-ammonium chloride - didecyldimethylammonium chloride.
C12-Cl4-Alkyl-benzyl-dimethylammonium chloride is parti-cularly preferred.
The a~ole derivatives and the benzimidazole derivatives lie in each case in the form of their metal salt com-plexes or are present as acid addition salts. Possible metal salts are, preferably, salt~ of metals of main groups II to IV and sub-groups I and II and I~ to VII of the periodic system, coppsr, zinc, manganese, magnesium, tin, iron, calcium, aluminium, lead, chromium, cobalt and nickel being mentioned as examples.
~' Possible anions of ~he salts are those which are prefer-ably dsrived from the followinq acids: hydrogen halide acids, such as, for example, hydrochloric acid and hydrobromic acid, and }urther re phosphoric acid, nitric acid and sulphuric acid or sulphonic acids~
; A combination of tebuconazoles and/or BCM, preferably in ;~ 20 the ~form of their hydxohalides, and C12-C14-alkyl-benzyl-~ dimethylammonium chloride i8 especially preferred.
~: .
The metal salt compIexes can be obtained in a simple manner by customary processes, thus, for example, by dissolving the metal salt in alcohol, for example etha-nol, and adding the solution to the azole derivative or ', - :
.
Le A 28 628 - 8 -:
~78~2 ben~imida~oi~ d~rivative. Metal salt complexes can D~
isolated in a ~.nown manner, for example by filtration, and if appropriate purified by recrystallisation.
The following acids are preferably suitable for the preparation of acid addition salts: the hydrogen halide acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, and furthermore phosphoric acid, nitric acid, sulphuric acid, mono- and bifunctional carboxylic acids and hydroxy-carboxylic acids, such as, for example, acetic acid,propionic acid, butyric acid, mandelic acid, oxalic acid, succinic acid, 2 hydroxy-ethane-dicarboxylic acid, maleic acid, fumaric acid, tartaric acid, citric acid, sal:icylic acid, sorbic acid and lactic acid, and sulphonic acids, such as, for example, p-toluenesulphonic acid, 1,5-naphthalenedisulphonic acid and alkanesulphonic acids, and optionally sub~tituted benzoic acids.
The acid addition salts of the compounds can be obtained in a simple manner by customary salt formation methods, for example by dissolving a compound in a suitable inert solvent and adding the acid, for example hydrochloric acid, and they can be~isolated in a known manner, for example by filtrationj and if appropriate purified by wa~hing with an inert organic solvent.
The weight ratios of the active compounds in the active compound combinations can be varied within xelatively wide ranges.
Le A 28_628 - 9 .
, ;
~ , - , : :
- -:: .
~784:l2 The weight ratio of azole compounds (A) to benzimidazole derivatives (B) can thus be in the range from 1:99 to 99:1, and the weight ratio of A:B is preferably 1~9 to 9:1, especially preferably 1:5 to 5:1. The weight ratio of the compounds ~A) or (~) or of the sum o~ (A)+(B) to the content of quaternary ammonium compounds (C) can be in the range from 1:99 to 99:1, 1:9 to 9:1 being preferred and the weight ratio especially preferably being 1:5 to 5:1.
The active compound combinations according to the inven-tion have a potent action against microorganisms. The : active compound combinations according to the invention are used in the preservation of materials to preserve industrial materials; they are active above all against moulds, wood- and leather-discolouring and wood- and : : leather-destroying fungi and bacteria, and against yeasts, algae and slime organisms. The following genera of microorganisms may be mentioned as examples - but without implying a limitation:
Alternaria, such as Alternaria tenuis, Aspergillus, such as Aspergillus niger and Aspergillus terreus, Aureo-: basidium, such as Aureobasidium pullulans, Chaetomium, ; such as Chaetomium globosum, Cladosporium, such as Cladosporium herbarum, Coniophora, such as Coniophora puteana, Gliocladium, such as Gliocladium virens, . Lentinus, such as Lentinus tigrinus, Paecilomyces, such as Paecilomyces varioti, Penicillium, such as Penicillium Le A 28 628 - 10 ~
.
: :: . . . ~ : . :.
2~7~2 brevicaule, Penicillium glaucum and Penicillium pino-philum, Polyporus, such as Polyporus versicolor, Sclero-phoma, such as Sclerophoma pityophila, Streptoverti-cillium, such as Streptoverticillium reticulum, Tricho-derma, such as Trichoderma viride and Trichophyton, suchas Trichophyton mentagrophytes;
Escherichia, such as Escherichia coli, Pseudomonas, such as Pseudomonas areuginosa and Staphylococcus, such as Staphylococcus aureus; and Candida, such as Candida albicans.
The amount of the active compound combinations employed depends on the nature and the occurrence of the micro organisms, the germ count and on the medium. The optimum amount to be used for the application can be determined in each case by test series. In general, however, it is sufficient to employ 0.001 to 20% by weight, preferably 0.05 to 10% by weight, in particular 0.05 to 2% by weight, of the active compound mixtures, based on the material to be preserved.
- 20 The new active compound combinations can be used as such or in the form of concentrates or generally customary formulations, such as powders, granules, soIutions, suspensions, emulsions or pastes.
:: :
The formulations mentioned can be prepared in a manner which is known per se, for example by mixing the active Le A 28 628 : :
~: - ~ . . : .
, ~ .
.
.~
compounds with a solvents or diluents, emulsifiers, dispersants and/or of a binder or fixing agent, if appropriate siccatives and W stabilisers and if appropriate dyestuffs and pigments, as well as other processing auxiliaries.
Possible solvents and diluents are organochemical sol-vents or solvent mixtures and/or a polar organic solvent or solvent mixtures and/ox an oily or oil-like organo-chemical solvent or solvent mixture and/or water with at least one emulsifier and/or wetting agent. Customary water-insoluble oily or oil-like solvents of low volatil-ity which are used are preferably the particular mineral oils/solvent mixtures containing mineral oils or aromatic fractions thereof. Examples which may be mentioned are white spirit, petroleum or alkylbenzenes, and in addition spindle oil and monochloronaphthalene. The boiling ranges of these solvents or solvent mixtures of low volatility cover the range from about 17~C to not more than 350C.
, :
The oily or oil-like solvents of low volatility described ahove can be replaced in part by organochemical solvents of higher volatility.
To prepare a wood preservative, some of the solvent or solvent mixture described above is preferably replaced by a polar organochemical solvent or solvent mixture.
Solvents which contain hydroxyl groups, es~er g:roups, ether groups or mixture~ of this functionality are preferably employed here. Examples which may be mentioned .
~, : - . ~ : ..
2~7~4~2 are esters or glycol ethers. Binders are understood according to the invention as synthetic resins which are water-dilutable or soluble, dispersible or emulsifiable in organochemical solvents, or binding drying oils~ for example based on acrylic resins, vinyl resins, polyester resins, polyurethane resins, alkyl resins, phenolic resins, hydrocarbon resins or silicone resins. The binder used can be employed as a solution, emulsion or dispersion. Mixtures of alkyd resins and drying vegetable oil are preferably used. Alkyd resins having an oil content of between 45 and 70% are particularly preferred.
All or some of the binder mentioned can be replaced by a fixing agent (mixture) or a plasticiser (mixture). These additions are intended to prevent evaporation of the active compounds and crystallisation or precipitation.
They preferably replace 0.01 to 30% of the binder (based on 100~ of the binder employed).
.
The plasticisers originate fro~ the chemical classes or phthalic aci~ esters, such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters, such as tributyl phosphate, adipic acid esters, such as di-(2-ethylhexyl)-adipate, stearates, such as butyl stearate and amyl stearate, oleates, such as butyl oleate, glycerol ethers or higher molecular weight glycol ethers, glycerol esters and p-toluenesulphonic acid esters.
::
` Fixing agents are based chemically on polyvinyl alkyl el:hers, such as, ~or example, polyvinyl methyl ether, or Le A 28 628 - 13 -: . , . ,, :
. . .
.
~ .
2~7~12 ketones, such as benzophenone or ethylbenzophenone.
Possible solvents or diluents are, pre~erably, water, if appropriate mixed with one or more of the abovementioned solvents or diluents, emulsifiers and dispersing agents.
According to the invention, industrial materials are non-living materials which have been prepared for use in industry. Industrial materials which are to be protected by the active compounds according to the invention from microbial change or destruction can be, for example, adhesives, sizes, papers and cardsl textiles, leather wood, paints and articles of plastic, cooling lubricants and other materials which can be attacked or destroyed by microorganisms. Components of production plantsi, for ; example cooling water circulations, which may be impaired by multiplication of microorganisms, may also be men-tion~d in the context of the materials to be preserved.
Preferred industrial materials in the context of the invention are adhesives, sizes, papers and cards, leather wood, paints, cooling lu~ricants, aqueous hydraulic fluids and cooling circulations.
,~
The active compound combinations, agents and concentrates according to the invention are preferably employed for preserving leather, wood and wood materials against microorganismsj for example against leather- and wood-destroying or leather- and wood-discolouring fungi, in particular in the temporary pxeservation of wood.
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By wood which can be preserved by the mixtures accordin~
to the invention there is to be understood, for example:
building timber, wood~n beams, railway sleepers, bridge components, boat jetties, wooden vehicles, crates, pallets, containers, telephone poles, wooden fences, wood panelling, wooden windows and doors, plywood, chipboard, joinery work or timber products which are used quite generally in house construction or building joinery.
Particularly effective preservation of wood is achieved by large-scale industrial impregnation processes, for example vacuum, double vacuum or pressure process~s.
The activity and the action spectrum of the active compound combination according to the invention and the agents, concentrates or quite generally formulations which can be prepared therefrom is increased if, as appropriate, other antimicrobially active substances, fun~icides, insecticides or other acti~e compounds are added to increase the active compound spectrum or achieve particular effects, such as, for example, the additional protection against insects. Particularly favourable mixing partners are, for example, the following compounds:
sulphenamides, such as dichlofluanid (Euparen), tolyl-fluanid ~Methyleuparen), folpet and fluorofolpet; thio-cyanates, ~uch as thiocyanatomethylthiobenzothiazole(TCMTB) and methylene bisthiocyanate (MBT); morpholine derivatives,suchasCll-Cl4-4-alkyl-2,6-dimethylmorpholine Le A 28 628 - 15 - -.
2~7~2 homologues(tridemorph),(+)-cis-4-[3-tert.-butylphenyl)-2-methylpropyl]-2,6-dimethylmorpholine (fenpropimorph) and falimorph; phenols, such as o-phenylphenol, halogen~
ated cresols, tribromophenol, tetrachlorophenol, penta-chlorophenol and 3-methyl~4-chlorophenol; dichlorophen;
iodopropargyl derivatives, such as iodopropargyl butyl-carbamate (IPBC) t chlorophenyl formal, phenylcarbamate, hexylcarbamate and cyclohexylcarbamate; isothiazolinones, such as N-methylisothiazolin-3-one, 5-chloro-N-methyl-isothiazolin-3-one, 4,5-dichloro-N~octylisothiazolin-3-one and N-octylisothiazolin-3-one (octhilinone); pyrid-ines, such as 1-hydroxy-2-pyridinethione (and its Na, Fe, Mn and Zn salts) tetrachloro-4-methyl-sulphonylpyridine and tetrachloro-4-methyl-sulphonylpyridine; metal soaps, such as tin, copper or zinc naphthenate, octoate, 2-ethylhexanoate, olete, phosphate, benzoate or oxide;
zinc salts of dialkyldithiocarbamates; tetramethyldiuram disulphite (TMTD); 2,4,5,6-tetrachloroisophthalonitrile (chlorthalonil); benzothiazoles, such as 2-mercapto-benzothiazole; thiazolyl-benzimidazole; quinolines, such as ~-hydroxyquinoline; benzyl alcohol mono(poly)hemi-formal; tris-N-(cyclohexyldiazeniumdioxy)-aluminium and N-(cyclohexyldiaæeniumdioxy)-tributyl tin.
: Insecticides which are preferably added are:
phosphoric acid esters, such as azinphos-ethyl, azinphos-: methyl, 1-(4-chlorophenyl)-4-(0-ethyl r S-propyl)phos-phoryloxypyrazole (TIA-230), chlorpyrifos, coumaphos, demeton, demeton S-methyl, Diazinon, dichlorvos and Le A 28 628 - 16 -... , . . , . . ~ . . . . :
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.
2~7~12 dimethoate, and carbamate~, such as aldicarb, bendiocarb, BPMC (2-(1-methylpropyl)phenyl methylcarbamate), buto-carboxim, butoxycarboxim, carbaryl, carbofuran, carbo-sulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pyrimicarb, promecarb, propoxur and thiodicarb;
pyrethroids, such as allethrin, alphamethrin, biores-methrin, byfenthrin (FMC 54 800), cycloprothrin, cyflu-thrin, decamethrion, cyhalcthrin, cypermethrin, delta-methrin, alpha-cyano-3-phenyl-2-methylbenzyl 2,2-dimeth-yl-3 (2-chloro-2-trifluoromethylvinyl)cyclopropane-carboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin and resmethrin; and nitroimides, such as 1-[(6-chloro-3~
pyridinyl)-methyl]-4,5-dihydro-N-nitro-lH-imidazol-2-anine (imidacloprid).
Possible other active compounds are algicides, mollusci-cides, and active compounds against "sea animals" which colonise, for example, paint films on ships' bottoms.
The microbicidal agents or concentrates used for preser-vation of the industrial materials comprise the active compound combinations according to the invention in a concentration of 0.01 to 95~ by weight, in particular 0.01 to 60~ by weight, and in addition if approp:riate ~ 0.001 to 10% by weight of a suitable further fungicide, : 25 insecticide or a further active compound as mentioned above.
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The active compound combinations or agents according to the invention advantageously allow the microbicidal agents hitherto available to be replaced by more effec-tive and more environmentally compatible agents. They exhibit a good stability and advantageously have a broad action spectrum.
The following examples serve to illustrate the invention, without limiting it thereto. Parts and percentage data denote parts by weight and percentages by weight.
Example 1 Microbicidal mixture based on tebuconazole, BCM and Cl2/Cl4-alkyl-benzyldimethyl-a~monium chloride 21.6 g of C12/C14-alkyl-benzyl-dimethylammonium ch:Loride are initially dissolved in 845 ml of water. 34 g of concentrated hydrochloric acid are added, while stirring.
80 g of tebuconazole and 20 g of BCM are added to this mixture. Ater the mixture has been stirred at 65-70C
for 2 hours, a clear, st~ble aqueous formulation of the active compou~d mixture which can be further diluted with water as desired is obtained.
, Example 2 Microbicidal activity of the active compound mixtures according to the invention !
Le A 28 ~28 - 18 -': .' .. . ' . . - `.- - ~ .
~7~2 This activity can be documented with the aid of the MIC
(minimum inhibitory concentration) values.
~etermination of the MIC values:
To demonstrate the activity against fungi, yeasts and bacteria, the minimum inhibitory concentrations (MIC) of mixtures according to the invention were determined:
Active compounds according to the invention are added in concentrations of 0.1 mg/l to 5000 ml/l to an agar prepared by beer wort and peptone. After the agar has solidified, it is contaminated with pure cultures of the test organisms shown in the table. After storage at 28C
and 60 to 70% relative atmospheric humidity for 2 weeks, the MIC is determined. The MIC is the lowest concentration of active compound at which no growth at all of the species of microbe used takes place; it is shown in the following Table l.
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~7~ 2 Table 1 MIC values of the mxiture against moulds, yeasts and bacteria Test germsMixture according toExample 1 MIC values in mgfl Penicillium brevic. 50 Chaetomium globosum 10 Aspergillus niger 50 Lentius tigrinus 5 Sclerophoma pityoph. 5 Trichoderma viride 75 Cladosporium herb. 5 Alternaria tenuis 400 Aureobasidum pull. 5 Escherichia coll 800 Pseudomonas fluorescens >800 Bacillus subtilis 50 Aeromonas punctata 100 Proteus mirabilis >800 Aerobacter Aerogenes250 Bacillus mycoides 75 Leuconostoc mesenteroides 100 Staphylococc. aureus 50 Pseudomonas aerug. >800 Rhodotorula mucilaginosa 100 Candida albicans 75 Candida krusel 35 Saccharomyces bailil7.5 Torula rubra lO0 Saccharomyces cerivisiae 250 Torula utilis 35 Example 3 Preservation of leather The activity of the mixture according to Example 1 in preserving damp chrome leather (wet-blue) is tested. The mixture according to Example 1 is added during chrome he A 28 628 - 20 -.;. ..
.
~, 2û7~12 tanning of cattle hideO Circular samples (~ 3 cm) are then taken ~rom the resulting wet-blue and are placed on contaminated agar in Petri dishes in the agar diffusion test in accordance with the Swiss test standard SNV 195 921. The test germs Aspergillus niger, Trichoderma viride and Penicillium glaucum are used for the contamination.
The samples are stored in an incubating cabinet at 28C/80-100% atmospheric humidity. The period over which the wet-blue sample~ remain unattacked by mould is tested.
Result: next page Le A 28 628 - 21 -- . ~
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2 ~ 1 2 ) 14.4% of tebuconazole 1.0% of BCM
It is known that imidazole or triazole fungicides, such as, for example, ~-[2-(4-chlorophenyl~-ethyl]-~-(1,1-dimethylethyl)-1-H-1,2,4-triazole-1-ethanol (tebucon-azole), 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1,2,3-triazol-l~yl)-propan~2-ol and 1-E[2-(2,~-di-chlorophenyl)-4-n-propyl-1,3-dioxolan-2-yl]-methyl]-1-H
1,2,4-triazole (propiconazole) can be used as such or in the form of their salts for protecting plants and seeds (compare, for example, EP-A 0 040 345 and EP-A 0 052 424).
It is furthermore known that these compounds are also ~,~
suitable for use in the preservation of materials for combating microbes which destroy materials or discolour materials (comparel for example, DE-OS (German Published Specification) 3 621 494 and US 4 07~ 062).
However, the azole fungicides, such as the tebuconazole mentionedj have gaps in their action against some germs relevant to the preservation of materials, such as, for example, Trichoderma cpec.
;
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Le A 28 628 - 1 -~' . . - :
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, 2~7~12 Furthermore, because of the often low water-solubility of azoles, their use in some fields of application, such as, for example, leather, water-based preservation of wood, disinfection, cooling water treatment, the paper indus-try, metal processing and industrial preservation ofwater-containing products, is limited or impossible.
It is fur~hermore known that b~nzimidazole derivatives, such as methyl benzimidazolecarbamate (BCM, carbendazim), methyl l-(butylcarbamoyl)-2-benzimidazolecarbamate 1~ (benomyl), 2-(2~-furyl)-lH-benzimidazole (uberidazole) and 2-(4'-thiazolyl)-benzimidazole have a fungicidal activity (Farm Chemicals Handbook). These can also be used in the preservation of materials.
Benzimidazole derivatives such as, for example, BCM are sparingly soluble in the customary organic solvents and virtually insoluble in water. They moreover have yaps in ~- their action spectrum, which can make their use in the preservation of materials difficulk because of the breadth of the action spectrum required in that sector.
On the basis of the solubility data, direct use in water-based systems is practically excluded.
Quaternary ammonium salts have been known for a lony time as broad-action microbicides and are used, for example, in disinfection and textile pre~ervation.
Althou~h these active compounds are usually readily water-soluble, they tend to foam severely at the use Le A 28 628 - 2 -, ~ ~ . .. . .
2~7~
concentrations, which causes trouble in many fields of use. Because of their cationic properties, they can moreover react with anionic components, such as soaps, surfactants and the like. Their profile of properties can be adversely influenced in this way, or they can become deactivated. It is furthermore known that quaternary ammonium salts are easily deactivated by the presence of protein and dirt.
For many uses in the practice of the preservation of materials it is desirable to employ the active compounds in liquid formulations which are free from organic solvents or in which the corresponding solvent content is reduced drastically.
Water-insoluble solven~s are incompatible with aqueous products, such as leather liquors, emulsion paints, cooling and process waters and disinfectants.
~, ~ ., The users are also often not equipped to handle products in the form of solutions in organic solvents, since particular devices, associated with high investment costs, are required ~or application from the solvent and recovery thereo~, which is essential in order to avoid ecological problems.
,~
Water-soluble solvents would be suitable in principle as solubilising agents in aqueous systems. However, if they Z5 enter the waste water, they can cause ecological problems. In addition, solvents manifest themselves ::
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2~78~2 adversely in the products to be preserved.
Another solubilisation possibility for the preparation of water-based active compound formulations is the use of emulsifiers. In the case of highly water-insoluble compounds, such as azoles and benzimidazole derivatives, large amounts of emulsifier are as a rule required for this, which should be avoided for ecological reasons. The activity of microbicidal active compounds can also ba severely impaired by the use of emulsifiers. Usability for certain systems can also be limited.
The object of the invention was therefore to provide new, preferably water-based, solvent- and emulsifier-free microbicidal act.ive compound formulations which are based on azole fungicides and/or benzimidazole derivatives and can easily be diluted with water and in this form give storage-stable use solutions.
It has now been found ~hat new active compound combina-tions of at least one metal salt and/or at least one acid addition compound of at least one azole fungicide, 20 preferably :
- 1-(4-chlorophenoxy)-3,3-dim~thyl-1-(lH-1,2,4-tri-azol-1-yl)-2-butanone (triadimefon) (4-chlorophenoxy)-~-(l,l~dimethyl-ethyl~-lH-1,2,4-triazole-1-ethanol (triadimenol) Le A 28 628 - 4 -' :
, 2~78~12 [2-(4 chlorophenyl)-ethyl]~ dLmethylethyl)-lH~1,2,4-triazole-1-ethanol (tebuconazole) ; - (RS)-2-(2,4-dichlorophenyl)-1-(lH-1,2,4-triazol-1-~ 5 yl)-hexan-2-ol .: (hexaconazole) - l-(N-propyl-N-(2-(2,4,6-(trichlorophenoxy)-ethyl)~
carbamoyl)-imidazole (prochloraz), - 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol ~ 1-[[2-(2,4-dichlorophenyl)-4 propyl-1,3-dioxolan-2-yl]-methyl]-lH-lj2,4-triazole ~propiconazole~
lo [ 2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl-methyl]-lH-1,2,4-triaxole (azaconazole) wherein, in the cases where the compounds have asymmetric carbon atoms, the isomers and isomer mixtures of the most diverse compositions are also included;
:especially preferably +~-[2-(4-chlorophenyl~-ethyl]-~-(1,1-dimethylethyl)-lH-1j2,4-triazole-1-ethanol ~tebuconazole) ..,~ :
, :
~: : and/or at least one metal salt and/or at least one acid addition aompound of~at~least one benzimidazole fungi-cide, preferably of the formula (I) ' :
Le A 28_628~ 5 -:
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I 1.1 1 (I) !
in which Rl represents carbamic acid ester groups, or furyl or thiazolyl rings which are optionally further substi-- 5 tuted and R2 represents H or carbamic acid ester groups, and at least one preferably fungicidal, quaternary ammonium compound, p~eferably of the formula (II~
~: R1 I
R2_N~_K3 xe (II) : ~: : R4 :~
in which R1, R2, R3 and R4 are identical or different and in each : ` case represent unsubstituted or substituted, ~; straight-chain or branched, saturated or unsaturated alkyl groups having 1 20 carbon atoms, alkylaryl or 15: aralkyl groups:having 5~10 carbon atoms in the aryl part and 1-20 carbon atoms in the alkyl`part or aryl :~ -: groups; having 5-10 carbon atoms, and optionally : ~ mono- or polyalkoxylated derivatlves thereof;
possible substituent3 being halogenl C~-C~-alkyl and C1 C4-alkoxy; and in which 2 or 3 radicals Rl to R4 of :~
: ' ~ ' : I,e A 28 628 - 6 -:
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-the quaternary centre, if appropriate with further hetero atoms, can form a saturated or unsaturated 5-, 6- or 7-membered (heterocyclic) ring and X represents an anion which promotes water-solubility, such as, for example, halide, sulphate, alkyl-sulphonate or optionally substituted arylsulphonate, have a particularly high microbicidal activity and at the same time are completely water-soluble and give stable solutions in water.
Such aqueous formulations avoid the abovementioned ecologicaI and use-related disadvantages of solvent-based or emulsifier-mediated formulations and in this respect represent a useful enrichment of the prior art.
~ Benzimidazole derivatives which may be mentioned are, ; ~15 preferably:
methyl benzimidazolylcarbamate (BCM), methyl 1-~butyl-carbamoyl)-2-benzimidazolecarbamate (benomyl), 2-~2'-furyl)-lH-benzimidazole (fuberidazole) an~ 2-(4'-thia-zolyl)benzimidazole (thiabendazole).
:: : 20 Methyl~ benzimidazolylcarbamate lBCM) is particularly preerred. : ~ :
.~ .
Quaternary ammonium compounds which may be mentioned are, preferably, ammonium salts ~uch as .
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Le A 28 628 - 7 - :
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2~78~12 - C12-cl4-alkYl-benzyl-dimethylammonium chloride - trimethyl-coconut-ammonium chloride - didecyldimethylammonium chloride.
C12-Cl4-Alkyl-benzyl-dimethylammonium chloride is parti-cularly preferred.
The a~ole derivatives and the benzimidazole derivatives lie in each case in the form of their metal salt com-plexes or are present as acid addition salts. Possible metal salts are, preferably, salt~ of metals of main groups II to IV and sub-groups I and II and I~ to VII of the periodic system, coppsr, zinc, manganese, magnesium, tin, iron, calcium, aluminium, lead, chromium, cobalt and nickel being mentioned as examples.
~' Possible anions of ~he salts are those which are prefer-ably dsrived from the followinq acids: hydrogen halide acids, such as, for example, hydrochloric acid and hydrobromic acid, and }urther re phosphoric acid, nitric acid and sulphuric acid or sulphonic acids~
; A combination of tebuconazoles and/or BCM, preferably in ;~ 20 the ~form of their hydxohalides, and C12-C14-alkyl-benzyl-~ dimethylammonium chloride i8 especially preferred.
~: .
The metal salt compIexes can be obtained in a simple manner by customary processes, thus, for example, by dissolving the metal salt in alcohol, for example etha-nol, and adding the solution to the azole derivative or ', - :
.
Le A 28 628 - 8 -:
~78~2 ben~imida~oi~ d~rivative. Metal salt complexes can D~
isolated in a ~.nown manner, for example by filtration, and if appropriate purified by recrystallisation.
The following acids are preferably suitable for the preparation of acid addition salts: the hydrogen halide acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, and furthermore phosphoric acid, nitric acid, sulphuric acid, mono- and bifunctional carboxylic acids and hydroxy-carboxylic acids, such as, for example, acetic acid,propionic acid, butyric acid, mandelic acid, oxalic acid, succinic acid, 2 hydroxy-ethane-dicarboxylic acid, maleic acid, fumaric acid, tartaric acid, citric acid, sal:icylic acid, sorbic acid and lactic acid, and sulphonic acids, such as, for example, p-toluenesulphonic acid, 1,5-naphthalenedisulphonic acid and alkanesulphonic acids, and optionally sub~tituted benzoic acids.
The acid addition salts of the compounds can be obtained in a simple manner by customary salt formation methods, for example by dissolving a compound in a suitable inert solvent and adding the acid, for example hydrochloric acid, and they can be~isolated in a known manner, for example by filtrationj and if appropriate purified by wa~hing with an inert organic solvent.
The weight ratios of the active compounds in the active compound combinations can be varied within xelatively wide ranges.
Le A 28_628 - 9 .
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~784:l2 The weight ratio of azole compounds (A) to benzimidazole derivatives (B) can thus be in the range from 1:99 to 99:1, and the weight ratio of A:B is preferably 1~9 to 9:1, especially preferably 1:5 to 5:1. The weight ratio of the compounds ~A) or (~) or of the sum o~ (A)+(B) to the content of quaternary ammonium compounds (C) can be in the range from 1:99 to 99:1, 1:9 to 9:1 being preferred and the weight ratio especially preferably being 1:5 to 5:1.
The active compound combinations according to the inven-tion have a potent action against microorganisms. The : active compound combinations according to the invention are used in the preservation of materials to preserve industrial materials; they are active above all against moulds, wood- and leather-discolouring and wood- and : : leather-destroying fungi and bacteria, and against yeasts, algae and slime organisms. The following genera of microorganisms may be mentioned as examples - but without implying a limitation:
Alternaria, such as Alternaria tenuis, Aspergillus, such as Aspergillus niger and Aspergillus terreus, Aureo-: basidium, such as Aureobasidium pullulans, Chaetomium, ; such as Chaetomium globosum, Cladosporium, such as Cladosporium herbarum, Coniophora, such as Coniophora puteana, Gliocladium, such as Gliocladium virens, . Lentinus, such as Lentinus tigrinus, Paecilomyces, such as Paecilomyces varioti, Penicillium, such as Penicillium Le A 28 628 - 10 ~
.
: :: . . . ~ : . :.
2~7~2 brevicaule, Penicillium glaucum and Penicillium pino-philum, Polyporus, such as Polyporus versicolor, Sclero-phoma, such as Sclerophoma pityophila, Streptoverti-cillium, such as Streptoverticillium reticulum, Tricho-derma, such as Trichoderma viride and Trichophyton, suchas Trichophyton mentagrophytes;
Escherichia, such as Escherichia coli, Pseudomonas, such as Pseudomonas areuginosa and Staphylococcus, such as Staphylococcus aureus; and Candida, such as Candida albicans.
The amount of the active compound combinations employed depends on the nature and the occurrence of the micro organisms, the germ count and on the medium. The optimum amount to be used for the application can be determined in each case by test series. In general, however, it is sufficient to employ 0.001 to 20% by weight, preferably 0.05 to 10% by weight, in particular 0.05 to 2% by weight, of the active compound mixtures, based on the material to be preserved.
- 20 The new active compound combinations can be used as such or in the form of concentrates or generally customary formulations, such as powders, granules, soIutions, suspensions, emulsions or pastes.
:: :
The formulations mentioned can be prepared in a manner which is known per se, for example by mixing the active Le A 28 628 : :
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compounds with a solvents or diluents, emulsifiers, dispersants and/or of a binder or fixing agent, if appropriate siccatives and W stabilisers and if appropriate dyestuffs and pigments, as well as other processing auxiliaries.
Possible solvents and diluents are organochemical sol-vents or solvent mixtures and/or a polar organic solvent or solvent mixtures and/ox an oily or oil-like organo-chemical solvent or solvent mixture and/or water with at least one emulsifier and/or wetting agent. Customary water-insoluble oily or oil-like solvents of low volatil-ity which are used are preferably the particular mineral oils/solvent mixtures containing mineral oils or aromatic fractions thereof. Examples which may be mentioned are white spirit, petroleum or alkylbenzenes, and in addition spindle oil and monochloronaphthalene. The boiling ranges of these solvents or solvent mixtures of low volatility cover the range from about 17~C to not more than 350C.
, :
The oily or oil-like solvents of low volatility described ahove can be replaced in part by organochemical solvents of higher volatility.
To prepare a wood preservative, some of the solvent or solvent mixture described above is preferably replaced by a polar organochemical solvent or solvent mixture.
Solvents which contain hydroxyl groups, es~er g:roups, ether groups or mixture~ of this functionality are preferably employed here. Examples which may be mentioned .
~, : - . ~ : ..
2~7~4~2 are esters or glycol ethers. Binders are understood according to the invention as synthetic resins which are water-dilutable or soluble, dispersible or emulsifiable in organochemical solvents, or binding drying oils~ for example based on acrylic resins, vinyl resins, polyester resins, polyurethane resins, alkyl resins, phenolic resins, hydrocarbon resins or silicone resins. The binder used can be employed as a solution, emulsion or dispersion. Mixtures of alkyd resins and drying vegetable oil are preferably used. Alkyd resins having an oil content of between 45 and 70% are particularly preferred.
All or some of the binder mentioned can be replaced by a fixing agent (mixture) or a plasticiser (mixture). These additions are intended to prevent evaporation of the active compounds and crystallisation or precipitation.
They preferably replace 0.01 to 30% of the binder (based on 100~ of the binder employed).
.
The plasticisers originate fro~ the chemical classes or phthalic aci~ esters, such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters, such as tributyl phosphate, adipic acid esters, such as di-(2-ethylhexyl)-adipate, stearates, such as butyl stearate and amyl stearate, oleates, such as butyl oleate, glycerol ethers or higher molecular weight glycol ethers, glycerol esters and p-toluenesulphonic acid esters.
::
` Fixing agents are based chemically on polyvinyl alkyl el:hers, such as, ~or example, polyvinyl methyl ether, or Le A 28 628 - 13 -: . , . ,, :
. . .
.
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2~7~12 ketones, such as benzophenone or ethylbenzophenone.
Possible solvents or diluents are, pre~erably, water, if appropriate mixed with one or more of the abovementioned solvents or diluents, emulsifiers and dispersing agents.
According to the invention, industrial materials are non-living materials which have been prepared for use in industry. Industrial materials which are to be protected by the active compounds according to the invention from microbial change or destruction can be, for example, adhesives, sizes, papers and cardsl textiles, leather wood, paints and articles of plastic, cooling lubricants and other materials which can be attacked or destroyed by microorganisms. Components of production plantsi, for ; example cooling water circulations, which may be impaired by multiplication of microorganisms, may also be men-tion~d in the context of the materials to be preserved.
Preferred industrial materials in the context of the invention are adhesives, sizes, papers and cards, leather wood, paints, cooling lu~ricants, aqueous hydraulic fluids and cooling circulations.
,~
The active compound combinations, agents and concentrates according to the invention are preferably employed for preserving leather, wood and wood materials against microorganismsj for example against leather- and wood-destroying or leather- and wood-discolouring fungi, in particular in the temporary pxeservation of wood.
Le A 28 628 - 14 -:
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By wood which can be preserved by the mixtures accordin~
to the invention there is to be understood, for example:
building timber, wood~n beams, railway sleepers, bridge components, boat jetties, wooden vehicles, crates, pallets, containers, telephone poles, wooden fences, wood panelling, wooden windows and doors, plywood, chipboard, joinery work or timber products which are used quite generally in house construction or building joinery.
Particularly effective preservation of wood is achieved by large-scale industrial impregnation processes, for example vacuum, double vacuum or pressure process~s.
The activity and the action spectrum of the active compound combination according to the invention and the agents, concentrates or quite generally formulations which can be prepared therefrom is increased if, as appropriate, other antimicrobially active substances, fun~icides, insecticides or other acti~e compounds are added to increase the active compound spectrum or achieve particular effects, such as, for example, the additional protection against insects. Particularly favourable mixing partners are, for example, the following compounds:
sulphenamides, such as dichlofluanid (Euparen), tolyl-fluanid ~Methyleuparen), folpet and fluorofolpet; thio-cyanates, ~uch as thiocyanatomethylthiobenzothiazole(TCMTB) and methylene bisthiocyanate (MBT); morpholine derivatives,suchasCll-Cl4-4-alkyl-2,6-dimethylmorpholine Le A 28 628 - 15 - -.
2~7~2 homologues(tridemorph),(+)-cis-4-[3-tert.-butylphenyl)-2-methylpropyl]-2,6-dimethylmorpholine (fenpropimorph) and falimorph; phenols, such as o-phenylphenol, halogen~
ated cresols, tribromophenol, tetrachlorophenol, penta-chlorophenol and 3-methyl~4-chlorophenol; dichlorophen;
iodopropargyl derivatives, such as iodopropargyl butyl-carbamate (IPBC) t chlorophenyl formal, phenylcarbamate, hexylcarbamate and cyclohexylcarbamate; isothiazolinones, such as N-methylisothiazolin-3-one, 5-chloro-N-methyl-isothiazolin-3-one, 4,5-dichloro-N~octylisothiazolin-3-one and N-octylisothiazolin-3-one (octhilinone); pyrid-ines, such as 1-hydroxy-2-pyridinethione (and its Na, Fe, Mn and Zn salts) tetrachloro-4-methyl-sulphonylpyridine and tetrachloro-4-methyl-sulphonylpyridine; metal soaps, such as tin, copper or zinc naphthenate, octoate, 2-ethylhexanoate, olete, phosphate, benzoate or oxide;
zinc salts of dialkyldithiocarbamates; tetramethyldiuram disulphite (TMTD); 2,4,5,6-tetrachloroisophthalonitrile (chlorthalonil); benzothiazoles, such as 2-mercapto-benzothiazole; thiazolyl-benzimidazole; quinolines, such as ~-hydroxyquinoline; benzyl alcohol mono(poly)hemi-formal; tris-N-(cyclohexyldiazeniumdioxy)-aluminium and N-(cyclohexyldiaæeniumdioxy)-tributyl tin.
: Insecticides which are preferably added are:
phosphoric acid esters, such as azinphos-ethyl, azinphos-: methyl, 1-(4-chlorophenyl)-4-(0-ethyl r S-propyl)phos-phoryloxypyrazole (TIA-230), chlorpyrifos, coumaphos, demeton, demeton S-methyl, Diazinon, dichlorvos and Le A 28 628 - 16 -... , . . , . . ~ . . . . :
~, : . , . . :, - ~ ~
.
2~7~12 dimethoate, and carbamate~, such as aldicarb, bendiocarb, BPMC (2-(1-methylpropyl)phenyl methylcarbamate), buto-carboxim, butoxycarboxim, carbaryl, carbofuran, carbo-sulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pyrimicarb, promecarb, propoxur and thiodicarb;
pyrethroids, such as allethrin, alphamethrin, biores-methrin, byfenthrin (FMC 54 800), cycloprothrin, cyflu-thrin, decamethrion, cyhalcthrin, cypermethrin, delta-methrin, alpha-cyano-3-phenyl-2-methylbenzyl 2,2-dimeth-yl-3 (2-chloro-2-trifluoromethylvinyl)cyclopropane-carboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin and resmethrin; and nitroimides, such as 1-[(6-chloro-3~
pyridinyl)-methyl]-4,5-dihydro-N-nitro-lH-imidazol-2-anine (imidacloprid).
Possible other active compounds are algicides, mollusci-cides, and active compounds against "sea animals" which colonise, for example, paint films on ships' bottoms.
The microbicidal agents or concentrates used for preser-vation of the industrial materials comprise the active compound combinations according to the invention in a concentration of 0.01 to 95~ by weight, in particular 0.01 to 60~ by weight, and in addition if approp:riate ~ 0.001 to 10% by weight of a suitable further fungicide, : 25 insecticide or a further active compound as mentioned above.
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The active compound combinations or agents according to the invention advantageously allow the microbicidal agents hitherto available to be replaced by more effec-tive and more environmentally compatible agents. They exhibit a good stability and advantageously have a broad action spectrum.
The following examples serve to illustrate the invention, without limiting it thereto. Parts and percentage data denote parts by weight and percentages by weight.
Example 1 Microbicidal mixture based on tebuconazole, BCM and Cl2/Cl4-alkyl-benzyldimethyl-a~monium chloride 21.6 g of C12/C14-alkyl-benzyl-dimethylammonium ch:Loride are initially dissolved in 845 ml of water. 34 g of concentrated hydrochloric acid are added, while stirring.
80 g of tebuconazole and 20 g of BCM are added to this mixture. Ater the mixture has been stirred at 65-70C
for 2 hours, a clear, st~ble aqueous formulation of the active compou~d mixture which can be further diluted with water as desired is obtained.
, Example 2 Microbicidal activity of the active compound mixtures according to the invention !
Le A 28 ~28 - 18 -': .' .. . ' . . - `.- - ~ .
~7~2 This activity can be documented with the aid of the MIC
(minimum inhibitory concentration) values.
~etermination of the MIC values:
To demonstrate the activity against fungi, yeasts and bacteria, the minimum inhibitory concentrations (MIC) of mixtures according to the invention were determined:
Active compounds according to the invention are added in concentrations of 0.1 mg/l to 5000 ml/l to an agar prepared by beer wort and peptone. After the agar has solidified, it is contaminated with pure cultures of the test organisms shown in the table. After storage at 28C
and 60 to 70% relative atmospheric humidity for 2 weeks, the MIC is determined. The MIC is the lowest concentration of active compound at which no growth at all of the species of microbe used takes place; it is shown in the following Table l.
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~7~ 2 Table 1 MIC values of the mxiture against moulds, yeasts and bacteria Test germsMixture according toExample 1 MIC values in mgfl Penicillium brevic. 50 Chaetomium globosum 10 Aspergillus niger 50 Lentius tigrinus 5 Sclerophoma pityoph. 5 Trichoderma viride 75 Cladosporium herb. 5 Alternaria tenuis 400 Aureobasidum pull. 5 Escherichia coll 800 Pseudomonas fluorescens >800 Bacillus subtilis 50 Aeromonas punctata 100 Proteus mirabilis >800 Aerobacter Aerogenes250 Bacillus mycoides 75 Leuconostoc mesenteroides 100 Staphylococc. aureus 50 Pseudomonas aerug. >800 Rhodotorula mucilaginosa 100 Candida albicans 75 Candida krusel 35 Saccharomyces bailil7.5 Torula rubra lO0 Saccharomyces cerivisiae 250 Torula utilis 35 Example 3 Preservation of leather The activity of the mixture according to Example 1 in preserving damp chrome leather (wet-blue) is tested. The mixture according to Example 1 is added during chrome he A 28 628 - 20 -.;. ..
.
~, 2û7~12 tanning of cattle hideO Circular samples (~ 3 cm) are then taken ~rom the resulting wet-blue and are placed on contaminated agar in Petri dishes in the agar diffusion test in accordance with the Swiss test standard SNV 195 921. The test germs Aspergillus niger, Trichoderma viride and Penicillium glaucum are used for the contamination.
The samples are stored in an incubating cabinet at 28C/80-100% atmospheric humidity. The period over which the wet-blue sample~ remain unattacked by mould is tested.
Result: next page Le A 28 628 - 21 -- . ~
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~ ~ ~U
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.,1 0 Co C~ C~ ~ U~ ~ ~ ~7 i ,1 ~ N N
.- ~ ~¢ A A A
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Le A28 628 - 22 -, :
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2 ~ 1 2 ) 14.4% of tebuconazole 1.0% of BCM
3.3% of dodecylbenzenesulphonic acid 61.3~ of propylene glycol mono-methyl ether 20.0% of ethoxylated nonylphenol (about 10 mol of ethylene oxide) b~ ) alkyl (C12JC14)-benzyldimethyl-ammonium chloride The results demonstrate the outstanding activity of the microbicide mixture of Example 1 according to the invention.
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Claims (11)
1. Active compound combination of at least one metal salt and/or at least one acid addition compound of at least one azole derivative and/or at least one metal salt and/or at least one acid addition com-pound of at least one benzimidazole derivative and at least one quaternary ammonium compound.
2. Active compound combination according to Claim 1, comprising at least one of the following azole fungicides:
- 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-(triadimefon) - .beta.-(4-chlorophenoxyl-.alpha.-(1,1-dimethyl-ethyl)-1H-1,2,4-triazoles-1-ethanol - ?,2-(4-chlorophenyl)-ethyl]-.alpha.-(1,1-dimethyl-ethyl)-lH-1,2,4-triazole-1-ethanol - (RS)-2-(2,4-dichlorophenyl)-1-(1H-1,2,4-tri-azol-1-yl)-hexan-2-ol - 1-(N-propyl-N-(2-(2,4,6-(trichlorophenoxy)-ethyl)-carbamoyl)-imidazole - 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol - 1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxo-lan-2-yl]~methyl]-1H-1,2,4-triazole (propicon-azole) - 1-[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl-methyl]-1H-1,2,4-triazole (azaconazole) Le A 28 628 - 24 -and/or at least one benzimidazole fungicide of the formula (I) (I) in which R1 represents carbamic acid ester groups, or furyl or thiazolyl rings which are optionally further substituted and R2 represents H or carbamic acid ester groups, and at least one quaternary ammonium compound, of the formula (II) (II) in which R1, R2, R3 and R4 are identical or different and in each case represent unsubstituted or substi-tuted, straight-chain or branched, saturated or unsaturated alkyl groups having 1-20 carbon atoms, alkylaryl or aralkyl groups each having 5-10 carbon atoms in the aryl part and 1-20 carbon atoms in the alkyl part or aryl group having 5-10 carbon atoms, and optionally Le A 28 628 - 25 -mono or polyalkoxylated derivatives thereof;
possible substituents being halogen, C1-C4-alkyl and C1-C4-alkoxy; and in which 2 or 3 of the substituents of the quaternary centre, if appropriate with further hetero atoms, can form a saturated or unsaturated 5-, 6- or 7-membered (heterocyclic) ring and X represents an anion which promotes water-solubility.
- 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-(triadimefon) - .beta.-(4-chlorophenoxyl-.alpha.-(1,1-dimethyl-ethyl)-1H-1,2,4-triazoles-1-ethanol - ?,2-(4-chlorophenyl)-ethyl]-.alpha.-(1,1-dimethyl-ethyl)-lH-1,2,4-triazole-1-ethanol - (RS)-2-(2,4-dichlorophenyl)-1-(1H-1,2,4-tri-azol-1-yl)-hexan-2-ol - 1-(N-propyl-N-(2-(2,4,6-(trichlorophenoxy)-ethyl)-carbamoyl)-imidazole - 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol - 1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxo-lan-2-yl]~methyl]-1H-1,2,4-triazole (propicon-azole) - 1-[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl-methyl]-1H-1,2,4-triazole (azaconazole) Le A 28 628 - 24 -and/or at least one benzimidazole fungicide of the formula (I) (I) in which R1 represents carbamic acid ester groups, or furyl or thiazolyl rings which are optionally further substituted and R2 represents H or carbamic acid ester groups, and at least one quaternary ammonium compound, of the formula (II) (II) in which R1, R2, R3 and R4 are identical or different and in each case represent unsubstituted or substi-tuted, straight-chain or branched, saturated or unsaturated alkyl groups having 1-20 carbon atoms, alkylaryl or aralkyl groups each having 5-10 carbon atoms in the aryl part and 1-20 carbon atoms in the alkyl part or aryl group having 5-10 carbon atoms, and optionally Le A 28 628 - 25 -mono or polyalkoxylated derivatives thereof;
possible substituents being halogen, C1-C4-alkyl and C1-C4-alkoxy; and in which 2 or 3 of the substituents of the quaternary centre, if appropriate with further hetero atoms, can form a saturated or unsaturated 5-, 6- or 7-membered (heterocyclic) ring and X represents an anion which promotes water-solubility.
3. Active compound combination according to Claim 1 characterised in that the salts are in the form of the hydrogen halide acid, phosphoric acid/ nitric acid and/or sulphuric acid anions.
4. Active compound combination according to Claim 1, comprising tebuconazole and/or BCM and C12-C14-alkyl-benzyldimethyl-ammonium chloride in the form of their hydrohalides.
5. Microbicidal agents for the preservation of mater-ials, comprising an active compound combination according to Claim 1, solvents or diluents and if appropriate processing auxiliaries and if approp-riate other active compounds.
6. Microbicidal agents according to Claim 5, comprising water.
7. Microbicidal agents according to Claim 5, for Le A 28 628 - 26 -preservation of leather and wood.
8. Method of combating microorganisms, characterised in that the active compound combination according to Claim 1 is allowed to act on microbes or their environment.
9. Use of the active compound combination according to Claim 1 as a microbicide for the preservation of industrial materials.
10. Use according to Claim 9, as a fungicide for the preservation of leather and wood.
11. Use of the active compound combination according to Claim 1 for the preparation of stable, optionally organic solvent- and emulsifier-free aqueous micro-bicidal agents, Le A 28 626 - 27 -
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4131184.1 | 1991-09-19 | ||
DE4131184A DE4131184A1 (en) | 1991-09-19 | 1991-09-19 | WATER-BASED, SOLVENT-FREE AND EMULSIFY-FREE MICROBICIDES ACTIVE SUBSTANCE COMBINATION |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2078412A1 true CA2078412A1 (en) | 1993-03-20 |
Family
ID=6440979
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002078412A Abandoned CA2078412A1 (en) | 1991-09-19 | 1992-09-16 | Water-based, solvent- and emulsifier-free, microbicidal active compound combination |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0533016B1 (en) |
JP (1) | JPH05194117A (en) |
AT (1) | ATE129384T1 (en) |
CA (1) | CA2078412A1 (en) |
DE (2) | DE4131184A1 (en) |
DK (1) | DK0533016T3 (en) |
FI (1) | FI924165A (en) |
NO (1) | NO180663C (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5855817A (en) * | 1993-06-09 | 1999-01-05 | Lonza, Inc. | Waterproofing and preservative compositions and preparation thereof |
US6464764B1 (en) | 1998-02-06 | 2002-10-15 | Lonza Ag | Protective agents for wood |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4139637A1 (en) * | 1991-12-02 | 1993-06-03 | Bayer Ag | FUNGICIDAL ACTIVE COMPOUNDS |
AU732685B2 (en) * | 1995-12-20 | 2001-04-26 | Nigel Paul Maynard | Solubilizing biocides using anhydrous "onium" compounds as solvent |
DE19648888A1 (en) * | 1996-11-26 | 1998-05-28 | Remmers Bauchemie Gmbh | Stable, water-dilutable concentrate for protecting wood |
WO2002081159A2 (en) * | 2001-04-03 | 2002-10-17 | Lonza Ag | Method for the protective treatment of wood and derived timber products |
JP4849743B2 (en) * | 2001-06-26 | 2012-01-11 | 日本エンバイロケミカルズ株式会社 | Industrial composition |
NZ523237A (en) * | 2002-12-18 | 2005-10-28 | Lanxess Deutschland Gmbh | Improvements in preservatives for wood-based products |
CA2529611C (en) | 2002-12-20 | 2009-12-15 | Pfizer Products Inc. | Pyrimidine derivatives for the treatment of abnormal cell growth |
GB2438404A (en) * | 2006-05-24 | 2007-11-28 | Arch Timber Protection Ltd | Preserving wood with an amine oxide, an azole and a specified amine or quaternary ammonium compound, in synergistic proportions |
JP5457782B2 (en) * | 2009-10-15 | 2014-04-02 | 日本エンバイロケミカルズ株式会社 | Industrial antibacterial agent |
JP5457793B2 (en) * | 2009-10-29 | 2014-04-02 | 日本エンバイロケミカルズ株式会社 | Industrial antibacterial agent |
US9255194B2 (en) * | 2013-10-15 | 2016-02-09 | International Business Machines Corporation | Methods and materials for depolymerizing polyesters |
WO2018026468A1 (en) * | 2016-08-03 | 2018-02-08 | Koppers Performance Chemicals Inc. | Stable wood preservative formulations |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2368223A1 (en) * | 1976-10-19 | 1978-05-19 | Sandoz Sa Produits | water-soluble methyl benzimidazole-2-carbamate carbendazim fungicide- comprises carbendazim, a strong mineral acid and water |
DE2951498A1 (en) * | 1979-12-20 | 1981-07-02 | Esbjerg Kemikaliefabrik A/S, Esbjerg | LIQUID SEEDING AGENT FOR SEED |
DE3004249A1 (en) * | 1980-02-06 | 1981-08-13 | Desowag-Bayer Holzschutz GmbH, 4000 Düsseldorf | WOOD PROTECTIVE CONCENTRATE AND PRODUCT MADE THEREOF FOR THE PRESERVATION OF WOOD AND WOOD MATERIALS |
DE3333411A1 (en) * | 1983-09-16 | 1985-04-04 | Bayer Ag, 5090 Leverkusen | FUNGICIDAL AGENT |
DE3502939A1 (en) * | 1985-01-30 | 1986-07-31 | Dr. Wolman Gmbh, 7573 Sinzheim | FUNGICIDE AGENT |
DE3605551A1 (en) * | 1986-02-21 | 1987-09-10 | Bayer Ag | FUNGICIDAL AGENT |
BE904660A (en) * | 1986-04-23 | 1986-08-18 | Janssen Pharmaceutica Nv | Synergistic wood preservatives - comprising ammonium salt and imidazole or triazole deriv. |
DE3614909A1 (en) * | 1986-05-02 | 1987-11-05 | Wolman Gmbh Dr | Methylene dirhodanide- and thiabendazole-containing wood preservatives |
GB8613913D0 (en) * | 1986-06-07 | 1986-07-09 | Ciba Geigy Ag | Microbicidal agrochemical compositions |
FR2626740B1 (en) * | 1988-02-08 | 1990-10-19 | Xylochimie | EMULSIONABLE CONCENTRATES OF BIOCIDAL MATERIALS, THE AQUEOUS MICROEMULSIONS OBTAINED AND THE APPLICATION OF THESE MICROEMULSIONS TO THE TREATMENT OF WOOD |
ATE126666T1 (en) * | 1988-04-08 | 1995-09-15 | Janssen Pharmaceutica Nv | SYNERGISTIC COMPOSITIONS CONTAINING IMAZALIL. |
-
1991
- 1991-09-19 DE DE4131184A patent/DE4131184A1/en not_active Withdrawn
-
1992
- 1992-08-26 NO NO923330A patent/NO180663C/en unknown
- 1992-09-07 AT AT92115276T patent/ATE129384T1/en not_active IP Right Cessation
- 1992-09-07 EP EP92115276A patent/EP0533016B1/en not_active Expired - Lifetime
- 1992-09-07 DK DK92115276.5T patent/DK0533016T3/en active
- 1992-09-07 DE DE59204120T patent/DE59204120D1/en not_active Expired - Fee Related
- 1992-09-16 CA CA002078412A patent/CA2078412A1/en not_active Abandoned
- 1992-09-17 FI FI924165A patent/FI924165A/en unknown
- 1992-09-17 JP JP4273819A patent/JPH05194117A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5855817A (en) * | 1993-06-09 | 1999-01-05 | Lonza, Inc. | Waterproofing and preservative compositions and preparation thereof |
US6464764B1 (en) | 1998-02-06 | 2002-10-15 | Lonza Ag | Protective agents for wood |
Also Published As
Publication number | Publication date |
---|---|
NO180663C (en) | 1997-05-28 |
NO923330D0 (en) | 1992-08-26 |
ATE129384T1 (en) | 1995-11-15 |
FI924165A (en) | 1993-03-20 |
EP0533016A1 (en) | 1993-03-24 |
JPH05194117A (en) | 1993-08-03 |
EP0533016B1 (en) | 1995-10-25 |
DK0533016T3 (en) | 1996-02-19 |
NO180663B (en) | 1997-02-17 |
DE4131184A1 (en) | 1993-03-25 |
DE59204120D1 (en) | 1995-11-30 |
NO923330L (en) | 1993-03-22 |
FI924165A0 (en) | 1992-09-17 |
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Legal Events
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EEER | Examination request | ||
FZDE | Discontinued |