NZ243460A - Synergistic fungicides containing a biocidal metal compound and a triazole derivative; preservatives for wood and other cellulosic materials - Google Patents
Synergistic fungicides containing a biocidal metal compound and a triazole derivative; preservatives for wood and other cellulosic materialsInfo
- Publication number
- NZ243460A NZ243460A NZ243460A NZ24346092A NZ243460A NZ 243460 A NZ243460 A NZ 243460A NZ 243460 A NZ243460 A NZ 243460A NZ 24346092 A NZ24346092 A NZ 24346092A NZ 243460 A NZ243460 A NZ 243460A
- Authority
- NZ
- New Zealand
- Prior art keywords
- composition
- tebuconazole
- copper
- compound
- ratio
- Prior art date
Links
- 230000003115 biocidal effect Effects 0.000 title claims description 21
- 230000002195 synergetic effect Effects 0.000 title claims description 17
- 239000002023 wood Substances 0.000 title claims description 15
- 239000003755 preservative agent Substances 0.000 title claims description 12
- 239000000463 material Substances 0.000 title claims description 10
- 150000003852 triazoles Chemical class 0.000 title claims description 10
- 150000002736 metal compounds Chemical class 0.000 title claims description 7
- 239000000417 fungicide Substances 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims description 84
- 239000010949 copper Substances 0.000 claims description 60
- 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 47
- 239000005839 Tebuconazole Substances 0.000 claims description 46
- 150000001875 compounds Chemical class 0.000 claims description 43
- 229910052802 copper Inorganic materials 0.000 claims description 42
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 41
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 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 22
- 239000005822 Propiconazole Substances 0.000 claims description 21
- AKNQMEBLVAMSNZ-UHFFFAOYSA-N azaconazole Chemical compound ClC1=CC(Cl)=CC=C1C1(CN2N=CN=C2)OCCO1 AKNQMEBLVAMSNZ-UHFFFAOYSA-N 0.000 claims description 16
- 229950000294 azaconazole Drugs 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 230000000855 fungicidal effect Effects 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 230000002335 preservative effect Effects 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 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 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 235000010288 sodium nitrite Nutrition 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000005749 Copper compound Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 150000001880 copper compounds Chemical class 0.000 claims 1
- 231100000331 toxic Toxicity 0.000 description 35
- 230000002588 toxic effect Effects 0.000 description 35
- -1 triazole compound Chemical class 0.000 description 29
- 238000009472 formulation Methods 0.000 description 18
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 16
- 229910021645 metal ion Inorganic materials 0.000 description 14
- 239000012141 concentrate Substances 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000011282 treatment Methods 0.000 description 10
- 239000004480 active ingredient Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 241000233866 Fungi Species 0.000 description 7
- 125000000129 anionic group Chemical group 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 241001492489 Postia placenta Species 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 229940116318 copper carbonate Drugs 0.000 description 5
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 241001600095 Coniophora puteana Species 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 241001070947 Fagus Species 0.000 description 3
- 235000010099 Fagus sylvatica Nutrition 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 3
- 239000012874 anionic emulsifier Substances 0.000 description 3
- 229940027983 antiseptic and disinfectant quaternary ammonium compound Drugs 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
- 239000008139 complexing agent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 3
- 229940005654 nitrite ion Drugs 0.000 description 3
- 239000012875 nonionic emulsifier Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000010734 process oil Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000005946 Cypermethrin Substances 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- JGFDZZLUDWMUQH-UHFFFAOYSA-N Didecyldimethylammonium Chemical compound CCCCCCCCCC[N+](C)(C)CCCCCCCCCC JGFDZZLUDWMUQH-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 229960000686 benzalkonium chloride Drugs 0.000 description 2
- XIWFQDBQMCDYJT-UHFFFAOYSA-M benzyl-dimethyl-tridecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 XIWFQDBQMCDYJT-UHFFFAOYSA-M 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 2
- 229960005424 cypermethrin Drugs 0.000 description 2
- KAATUXNTWXVJKI-UHFFFAOYSA-N cypermethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 KAATUXNTWXVJKI-UHFFFAOYSA-N 0.000 description 2
- 229940078672 didecyldimethylammonium Drugs 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
- JWZXKXIUSSIAMR-UHFFFAOYSA-N methylene bis(thiocyanate) Chemical compound N#CSCSC#N JWZXKXIUSSIAMR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-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
- 229960000490 permethrin Drugs 0.000 description 2
- RLLPVAHGXHCWKJ-UHFFFAOYSA-N permethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 1
- YGKOYVNJPRSSRX-UHFFFAOYSA-M (4-dodecylphenyl)methyl-trimethylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCC1=CC=C(C[N+](C)(C)C)C=C1 YGKOYVNJPRSSRX-UHFFFAOYSA-M 0.000 description 1
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical class O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 description 1
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-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
- PJYMYGYDYGFUHM-UHFFFAOYSA-N 2-(4-chlorophenyl)-4-cyano-2,3-dimethyl-3-(3-phenoxyphenyl)butanoic acid Chemical compound C=1C=C(Cl)C=CC=1C(C)(C(O)=O)C(CC#N)(C)C(C=1)=CC=CC=1OC1=CC=CC=C1 PJYMYGYDYGFUHM-UHFFFAOYSA-N 0.000 description 1
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 description 1
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- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- KUZYYSNLEIAJQJ-UHFFFAOYSA-N 4,4,6-trimethyl-2-[(4,4,6-trimethyl-1,3,2-dioxaborinan-2-yl)oxy]-1,3,2-dioxaborinane Chemical compound O1C(C)CC(C)(C)OB1OB1OC(C)(C)CC(C)O1 KUZYYSNLEIAJQJ-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
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- 101100111458 Arabidopsis thaliana BHLH63 gene Proteins 0.000 description 1
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005747 Chlorothalonil Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
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- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 1
- 239000005760 Difenoconazole Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241001492300 Gloeophyllum trabeum Species 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 241000222355 Trametes versicolor Species 0.000 description 1
- MTGCVJULGAYJMI-UHFFFAOYSA-N [2-(1-iodoethyl)-3-oxopentyl]carbamic acid Chemical compound CCC(=O)C(C(C)I)CNC(O)=O MTGCVJULGAYJMI-UHFFFAOYSA-N 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- XKXHCNPAFAXVRZ-UHFFFAOYSA-N benzylazanium;chloride Chemical compound [Cl-].[NH3+]CC1=CC=CC=C1 XKXHCNPAFAXVRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229940063013 borate ion Drugs 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000000073 carbamate insecticide Substances 0.000 description 1
- JNPZQRQPIHJYNM-UHFFFAOYSA-N carbendazim Chemical compound C1=C[CH]C2=NC(NC(=O)OC)=NC2=C1 JNPZQRQPIHJYNM-UHFFFAOYSA-N 0.000 description 1
- 239000006013 carbendazim Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- VNZQQAVATKSIBR-UHFFFAOYSA-L copper;octanoate Chemical compound [Cu+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O VNZQQAVATKSIBR-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- YMGUBTXCNDTFJI-UHFFFAOYSA-M cyclopropanecarboxylate Chemical compound [O-]C(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-M 0.000 description 1
- QQODLKZGRKWIFG-UHFFFAOYSA-N cyfluthrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OC(C#N)C1=CC=C(F)C(OC=2C=CC=CC=2)=C1 QQODLKZGRKWIFG-UHFFFAOYSA-N 0.000 description 1
- SCXCDVTWABNWLW-UHFFFAOYSA-M decyl-dimethyl-octylazanium;chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCC SCXCDVTWABNWLW-UHFFFAOYSA-M 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229960004670 didecyldimethylammonium chloride Drugs 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- BQYJATMQXGBDHF-UHFFFAOYSA-N difenoconazole Chemical compound O1C(C)COC1(C=1C(=CC(OC=2C=CC(Cl)=CC=2)=CC=1)Cl)CN1N=CN=C1 BQYJATMQXGBDHF-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- JLYXXMFPNIAWKQ-GNIYUCBRSA-N gamma-hexachlorocyclohexane Chemical compound Cl[C@H]1[C@H](Cl)[C@@H](Cl)[C@@H](Cl)[C@H](Cl)[C@H]1Cl JLYXXMFPNIAWKQ-GNIYUCBRSA-N 0.000 description 1
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N gamma-hexachlorocyclohexane Natural products ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229960002809 lindane Drugs 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- LXCJGJYAOVCKLO-UHFFFAOYSA-N n-cyclohexyl-n-hydroxynitrous amide Chemical compound O=NN(O)C1CCCCC1 LXCJGJYAOVCKLO-UHFFFAOYSA-N 0.000 description 1
- UWHRNIXHZAWBMF-UHFFFAOYSA-N n-dodecyl-n-methyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)CCCCCCCCCCCC UWHRNIXHZAWBMF-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 1
- 239000003992 organochlorine insecticide Substances 0.000 description 1
- 239000004306 orthophenyl phenol Substances 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- WSHYKIAQCMIPTB-UHFFFAOYSA-M potassium;2-oxo-3-(3-oxo-1-phenylbutyl)chromen-4-olate Chemical compound [K+].[O-]C=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 WSHYKIAQCMIPTB-UHFFFAOYSA-M 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- FMYOMWCQJXWGEN-UHFFFAOYSA-M sodium;2,3,4,5,6,7-hexahydroxyheptanoate Chemical compound [Na+].OCC(O)C(O)C(O)C(O)C(O)C([O-])=O FMYOMWCQJXWGEN-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
- 239000002689 soil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical class NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- 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
- B27K3/20—Compounds of alkali metals or ammonium
-
- 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
- B27K3/22—Compounds of zinc or copper
-
- 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
- B27K3/40—Aromatic compounds halogenated
-
- 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
Description
<div class="application article clearfix" id="description">
<p class="printTableText" lang="en">24 3 4 o <br><br>
Priority Date(s): <br><br>
Com"ffpcciifcot^n f :.i: Clai-* \*)..0.-..!,. ,0> <br><br>
J.-.-.5..;— <br><br>
, n , Z7"J(JN "1995' <br><br>
w | ?-r| <br><br>
Patents Form No. 5 <br><br>
NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION <br><br>
PRESERVATIVES FOR WOOD AND OTHER CELLULOSIC MATERIALS <br><br>
WE, HICKSON INTERNATIONAL PLC, a British company of <br><br>
Wheldon Road, Castleford, West Yorkshire, WF10 2JT, <br><br>
UNITED KINGDOM <br><br>
hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: <br><br>
- 1 - // f h T * V ^ <br><br>
(followed by page la) /v 0\. <br><br>
X-f v f. ^ ^ <br><br>
56391B.320 <br><br>
-ia~ <br><br>
243 4 60 <br><br>
Preservatives for wood and other cellulosic materials <br><br>
This invention relates to preservatives for wood and other cellulosic materials. <br><br>
The use of biocidal metal ions in wood preservation is well known. There are also many compounds containing a tria/.ole group which are known to possess biocidal 1 (j properties. <br><br>
According to the present invention there are provi<i<"l in •/it ! vc i 'or'}" >:• 11 i ■ >ps comp! isln'j a svnerg i St ic mixture ot a biocidal metal compound and a fungicidal compound containing a triazole group selected from: 1a) compounds oi formula (A): <br><br>
OH I <br><br>
K —CHi-CHa-C- H <br><br>
(A) <br><br>
CH2 <br><br>
wherein R, represents a branched or straight chain c, 5 alkyl group and R2 represents a phenyl group optionally substituted by one or more substituents' selected from halogen atoms and alkyl, C1-3 alkoxy, phenyl and nitro groups; <br><br>
b) compounds of formula (B): <br><br>
35 <br><br>
(B) <br><br>
wherein R3 is as defined for R, above and R i r»pi e.senl s a hydrogen atom or a branched or st iniqht chain C1 alkyl group; and <br><br>
-) <br><br>
15 <br><br>
20 <br><br>
25 <br><br>
30 <br><br>
35 <br><br>
243460 <br><br>
c) hexaconazole and ditenoconaxoie; <br><br>
wherein the weight: ratio of metal atom: fungicidal compound containing the triazole group is at J east 5:1; with the specific exception of composition (a) which 5 con tains 1.320% by weight of sodiuin nitrite, 1.190% by weight of copper sulphate 5H20, 0.400% by weight of boric acid, 0.625% by weight of sodium heptonate, 0.390% by weight of. sodium hydroxide, 0.012% by weight of Lebuconazole 0.391% by weight of surfactant blend in 10 xvlene and 95.702% by weight of water. <br><br>
We have found that compositions according to the invention possess advantageous properties: in particular, it has been found that the metal compound and the fungicidal compound containing the triazole group (hereinafter "the triazole compound") exhibit synergistic fungicidal activity. <br><br>
It will be understood that the metal compound may be present in a form such that metal ions are free in solution or may form part of a complex. Similarly, the triazole compound may be free in solution or may be present in the form of a salt or a complex. For example, the triazole compound could be present in the form of a complex with part of the biocidal metal ion. <br><br>
The compositions according to the invention may be used to treat substrates such as wood or other cellulosic materials (such as cotton, hessian, rope and cordage). For convenience, the invention will be described hereinafter with reference to the treatment of wood but it will be appreciated that the other materials may be treated analogously. <br><br>
The metal compound may be a compound of any biocidally active metal including copper, aluminium, manganese, iron, cobalt, nickel, zinc, silver, cadmium, tin, antimony, mercury, lead and bismuth. These may be either used alone or in mixtures. The preferred metals are copper and zinc used alone, in combination with each other or with one or more of the metals listed previously. The most preferred metal is copper, f particularly Cu (II) ion. jf <br><br>
24346 <br><br>
3 <br><br>
Advantageously, the triazole compound is selected from compounds of formula (A): <br><br>
5 <br><br>
OH I <br><br>
R?—CHi-CH2-C- R. <br><br>
i i <br><br>
(A) <br><br>
CH2 <br><br>
10 <br><br>
wherein R, represents a branched or straight chain <br><br>
15 C15 alkyl group (e.g. t-butyl) and R? represents a phenyl group optionally substituted by one or more substituents selected from halogen (e.g. chlorine, fluorine or bromine) atoms and C,.3 alkyl (e.g. methyl), C, 3 alkoxy (e.g. methoxy)j phenyl and nitro groups. 20 A particularly preferred compound of formula (A) is tebuconazole: <br><br>
alpha-[2-(4-chlorophenyl)ethyl]-alpha(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol. <br><br>
25 advantageously selected from compounds of formula (B): <br><br>
Alternatively, the triazole compound is <br><br>
30 <br><br>
(B) <br><br>
35 <br><br>
243 45 <br><br>
- 4 - <br><br>
wherein R3 is as defined for R2 above and R4 represents a hydrogen atom or a branched or straight chain alkyl group (e.g. n-propyl). <br><br>
Particularly preferred compounds of formula (B) 5 are: propiconazole (1-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4- triazole) and azaconazole (1-[[ 2,4-dichlorophenyl)-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole). <br><br>
Hexaconazole and difenoconazole are examples of 10 further triazole compounds which may be used in the compositions of the invention. <br><br>
Compositions nay contain more than one triazole compound for example, they may contain tebuconazole and propiconazole, or a mixture of tebuconazole, 15 propiconazole and azaconazole. <br><br>
We have found that the biocidal metal may advantageously be incorporated into the composition in the form of inorganic salts of the metal ion e.g. in the form of the metal carbonate, sulphate, chloride, 20 hydroxide, borate, fluoride or oxide. Alternatively the metal may be used in the form of the metal salt of a simple organic compound e.g. in the form of a salt of a carboxylic acid such as a metal acetate. Thus, it has been found that the biocidal triazole compounds exhibit 25 synergistic properties when the metal ion is present in the form of such simple salts, and it is not necessary to add the metal ion in the form of a salt of, or complex with, a larger more complex organic compound which itself possesses biocidal properties. 30 The optimum weight ratio of metal ion to triazole compound varies depending on the particular material or product to which the composition is applied and the type of organism against which protection is required. Preferably the ratio by weight of metal to 35 triazole compound is less than 1000:1, e.g. no greater than 750:1. More preferably, the weight ratio of metaj triazole compound should be between 750:1 and 5:1, <br><br>
- b - <br><br>
particularly preferably between 500:1 and 5:1; most preferably the said ratio is between 50:1 and 5:1, especially about 25:1. <br><br>
The concentration required for preservative treatment depends on the ratio of metal to triazole compound selected, the metal chosen, the method of treatment employed, the timber species, the level of protection required and the nature and quantity of any other biocides present. The levels necessary can be determined readily by one skilled in the art. In general, the level of metal required will be in the range 0.01-5% and the level of triazole will be in the range 25 ppm to 1.0%. The preferred range for waterborne treatments is to have a metal concentration of 0.1-5% and a triazole level of 50 ppm to 5000 ppm. <br><br>
Compositions in accordance with the invention may if desired additionally contain nitrite ion. Alternatively, there can be advantages associated with the omission of nitrite ion from the compositions for example, by leaving out nitrite ion the formation of certain noxious gases is prevented. <br><br>
The compositions of the present invention advantageously contain a biocidally active quaternary ammonium compound or tertiary amine salt. These compounds aid in the formation of emulsions of triazole compounds in aqueous solutions of biocidal metal ion. Compositions containing quaternary ammonium compounds or tertiary amine salts can form micro-emulsions which are particularly useful in the treatment of timber. In addition, the presence of these compounds may mean that additional organic solvents are not necessary to solubilise the triazole compound. Furthermore, the quaternary ammonium compounds and tertiary amine salts are themselves biocidal and so they enhance the overall biocidal activity of the composition. These compounds also improve penetration of the biocidal metal ion anc^ triazole compound into the timber. <br><br>
24 34 6 <br><br>
The composition in accordance with the invention may contain water as solvent, or an organic solvent or a mixture of solvents. Formulations can be prepared as concentrates intended to be diluted at the treatment 5 facility, or the formulations can be prepared in the form of dilute treatment solutions. Optionally, <br><br>
separate solutions of biocidal metal ion and triazole compound can be provided e.g. in the form of two concentrates intended to be mixed before or after 10 dilution. <br><br>
Suitable formulations may be prepared, for example, by preparing aqueous solutions of metal ion complexes and subsequently adding an emulsified formulation of the triazole compound. Suitable complexing agents for the 15 metal ion would be for example, polyphosphoric acids such as tripolyphosphoric acid, ammonia, water soluble amines and alkanolamines capable of complexing with biocidal cations; aminocarboxylic acids such as glycine, glutamic acid, ethylenediaminetetra-acetic acid, 20 hydroxyethyldiamine triacetic acid, nitrilotriacetic acid and N-dihydroxy ethylglycine; polymeric compounds which contain groups capable of complexing with metallic cations such as polyacrylic acids; hydroxycarboxylic acids such as tartaric acid, citric acid, malic acid, 2d lactic acid, hydroxybutyric acid, glycollic acid, <br><br>
gluconic acid and glucoheptonic acid; phosphonic acids such as nitrilotrimethylene phosphonic acid, ethylenediaminetetra (methylene phosphonic acid), hydroxyethylidene diphosphonic acid. Where the 30 complexing agents are acidic in nature they may be employed either as free acids or as their alkali metal or ammonium salts. These complexing agents may be used either alone or in combination with each other. <br><br>
Suitable surfactants for triazole compounds include, for 35 example, cationic, nonionic, anionic or amphoteric surfactants. <br><br>
Suitable formulations can also be prepared, for <br><br>
24 3 4 <br><br>
example, by adding an emulsified formulation of the triazole compound to an aqueous solution of a metal salt, such as copper sulphate or zinc acetate. At high ratios of metal ion to azole, the solubility of the 5 azole may be sufficient to disperse the azole in the formulation using a suitable co-solvent. <br><br>
Alternatively, formulations can be prepared employing only organic solvents. To prepare such formulations, a biocidal metal salt of a carboxylic acid 10 (e.g. decanoic or octanoic acid) is prepared and dissolved in a suitable organic solvent to form a concentrate. The triazole compound can then be added directly to the concentrate or to a solution diluted with a suitable solvent such as an ester, alcohol, ester 15 alcohol, aliphatic or aromatic hydrocarbon, glycol ether, glycol or ketone. <br><br>
Concentrated formulations containing organic solvents can optionally be mixed with water to form an emulsion which can be stabilised with surfactants if 2 0 necessary. <br><br>
Compositions in accordance with the invention can optionally contain other additives conventionally employed in timber preservation such as water repellents, colour additives, viscosity modifiers or 25 corrosion inhibitors. <br><br>
The compositions of the invention may contain other organic compounds including fungicides, insecticides and bacteriocides. Such organic compounds include carboxylic acids such as naphthenic acids and branched 30 aliphatic acids and their metal salts such as copper and zinc naphthenate, phenols and substituted phenols such as orthophenyl phenol and its alkali metal or ammonia salts; polyhalogenated phenols such as pentachlorophenol or tribromophenol and their alkali metal or ammonia 35 salts; quaternary ammonium salts and tertiary amine salts such as didecyl dimethyl ammonium chloride, octyl decyl dimethyl ammonium chloride, dodecyl dimethyl <br><br>
24 3 4 <br><br>
- 3 - <br><br>
benzyl ammonium chloride, dodecyl benzyl trimethyl ammonium chloride, dodecyl dimethyl amine acetate, dodecyl dimethyl amine lactate, dodecyl dimethyl amine salicylate, didodecyl methyl amine chloride; <br><br>
5 isothiazolone derivatives such as 4,5-dichloro-2-(n- <br><br>
octyl)-4-isothiazolin-3-one or 2-methyl-4-isothiazolin-3-one, 2n-octyl-4-isothiazolin-3-one and mixtures of those and other related compounds; sulphamide derivatives such as N,N-dimethyl-N-pnenyl-(N-10 fluorodichloro-methylthio)-sulphonamide, N,N-dimethyl-N-tolyl-N-(dichlorofluoro-methylthio)-sulphamide; azoles such as imidazole; MST (methylene-bis thiocyanate); IPBC (3-iodo-2-propanyl-butyl-carbamate); carbendazim and chlorothalonil; N-nitrosophenylhvdroxylamine and N-15 nitroso cyclohexyl hydroxylamine, either as their metal salts or as metal chelates; pyrethroid type insecticides selected from the group consisting of cyano-(4-fluoro-3-phenoxyphenyl)-methyl-3-(2,2-dichloroethenyl)-2,2-dimethyl-cyclopropanecarboxylate, (3-phenoxyphenyl)-2 0 methyl-3-(2,2-dichloroethyenyl)-2,2-dimethyl- <br><br>
cyclopropanecarboxylate, cyano-(3-phenoxyphenvl)-methyl-2-(4-chlorophenyl)-3-methylbutyrate, and mixtures thereof; organo-phosphorous, carbamate and organochlorine insecticides such as lindane. 25 Other biocidally active elements may also be present such as boron, in any form, for example boric acid, boron or boron esters and also fluorides and si 1icafluorides. <br><br>
Particularly preferred compositions in accordance 30 with the invention comprise copper (II) ion, a triazole compound which is tebuconazole or propiconazole, and an alkanolamine, as well as borate ion and/or a quaternary ammonium compound or a mixture of quaternary ammonium compounds. <br><br>
35 According to a further aspect of the invention there is provided a method of treating a substrate of the type hereinbefore defined which comprises applying <br><br>
243460 <br><br>
- 9 - <br><br>
to the substrate a composition as defined above. Also within the scope of the invention is a method of treating a substrate of the type hereinbefore defined which comprises applying to the substrate composition 5 (b) as defined above. <br><br>
The skilled man will be well acquainted with the various methods of treating the substrates with aqueous solutions. For example, the compositions according to the invention may be applied to wood by dipping, 10 spraying, deluging, brushing and by vacuum and/or pressure impregnation. Other types of substrate may be treated by analogous methods. <br><br>
The following non-limiting Examples further illustrate the invention. <br><br>
24 3460 <br><br>
- 10 - <br><br>
Examples <br><br>
The compositions of Examples 1 to 3 may be prepared by adding an emulsified formulation of the triazole compound to an aqueous solution of a metal complex. <br><br>
Example 1 A concentrate formulation; metal to azole ratio 25:1 <br><br>
% w/w <br><br>
Basic copper carbonate 10.9 <br><br>
10 Monoethanolamine 23.1 <br><br>
Boric acid 16.9 <br><br>
Tebuconazole 0.24 <br><br>
Xylene 3.76 <br><br>
Process oil 4.00 <br><br>
15 Anionic/non-ionic emulsifier 1.00 <br><br>
Water 40.10 <br><br>
Example 2 A ready to use solution; metal to azole ratio 10:1 <br><br>
% w/w <br><br>
Copper sulphate pentahydrate <br><br>
1.13 <br><br>
Lactic acid <br><br>
2.13 <br><br>
Sodium nitrite <br><br>
1.31 <br><br>
Boric acid <br><br>
0.79 <br><br>
Ammonium hydroxide <br><br>
0.57 <br><br>
Tebuconazole <br><br>
0.03 <br><br>
Cypermethrin <br><br>
0.05 <br><br>
Methyl dioxitol <br><br>
0.64 <br><br>
Anionic/non-ionic emulsifier <br><br>
0.08 <br><br>
Water <br><br>
93.22 <br><br>
24 3 46 0 <br><br>
- n - <br><br>
Example 3 A ready to use solution; metal to azole ratio 5:1 <br><br>
% w/w <br><br>
Basic copper carbonate 0.55 <br><br>
5 Ammonium hydroxide 0.65 <br><br>
Ammonium bicarbonate 0.33 <br><br>
Propiconazole 0.06 <br><br>
Naphthenic acid 0.15 <br><br>
Anionic/non-ionic emulsifiers 0.21 <br><br>
10 Methyl dioxitol 0.48 <br><br>
Water 97.624 <br><br>
Example 4 A ready to use solution; metal to azole ratio 5:1 The compositions of Examples 4 and 5 may be prepared by 15 adding an emulsified formulation of the triazole compound to an aqueous solution of the metal ion. <br><br>
% w/w <br><br>
Copper acetate 0.43 <br><br>
Zinc acetate 0.34 <br><br>
20 Tebuconazole 0.06 <br><br>
Ester alcohol 0.03 <br><br>
2-ethyl hexanoic acid 0.03 <br><br>
Process oil 0.03 <br><br>
Anionic/non-ionic emulsifier 0.06 <br><br>
25 Water 98.52 <br><br>
Example 5 A ready to use solution, metal to azole ratio 30:1 <br><br>
% w/w <br><br>
Copper sulphate pentahydrate 1.18 <br><br>
30 Azaconazole 0.01 <br><br>
Methyl dioxitol 0.08 <br><br>
Anionic/non-ionic emulsifiers 0.01 <br><br>
Water 98.72 <br><br>
35 Example 6 Two pack system <br><br>
% w/w <br><br>
Pack A : Copper carbonate 14.5 <br><br>
Monoethanolamine 30.7 <br><br>
Water 54.8 <br><br>
- 12 - <br><br>
/ T ,r r* <br><br>
4 0 it. 0 <br><br>
% w/w <br><br>
Pack B : Tebuconazole 10 <br><br>
Ester glycol 50 <br><br>
2-ethyl hexanoic acid 10 <br><br>
5 Process oil 10 <br><br>
Anionic/non-ionic emulsifiers 20 The ratio of copper to Tebuconazole resulting from the mixing of Pack A and Pack B can vary from 5:1 to 750:1 parts by weight. <br><br>
10 The separate packs are intended to be mixed together at the treatment facility and diluted with water. <br><br>
Examples 7 to 11 contain organic solvents. <br><br>
Example 7 A concentrate 15 % w/w <br><br>
Zinc versatate 15.0 <br><br>
Tebuconazole 0.5 <br><br>
Glycol ether 10.0 <br><br>
White spirit 74.5 <br><br>
2 0 <br><br>
Example 8 A concentrate % w/w <br><br>
Copper caprylate 25.0 <br><br>
Tebuconazole 0.05 <br><br>
Shellsol A 74.75 <br><br>
25 Permethrin 0.2 <br><br>
Example 9 A concentrate % w/w <br><br>
Copper acypetacs 15.0 <br><br>
Hexylene glycol biborate 10.0 30 Cypermethrin 0.1 Tebuconazole 0.1 <br><br>
White spirit 74.8 <br><br>
Example 10 A concentrate % w/w <br><br>
35 Zinc octoate 50.0 Azaconazole 1.0 <br><br>
Glycol ether 49.0 <br><br>
243460 <br><br>
- 13 - <br><br>
Example 11 A ready to use solution I w/w <br><br>
Copper versatate 5.0 <br><br>
Propiconazole 0.01 <br><br>
Permethrin 0.1 <br><br>
5 White spirit 94.39 <br><br>
The compositions of Examples 12 and 13 each contain a biocidally active quaternary ammonium compound. These compounds stabilise the triazole compound in the treatment solution obtained by diluting the concentrated 10 compositions. <br><br>
Example 12 A concentrate <br><br>
15 <br><br>
% w/w <br><br>
Monoethanolamine <br><br>
19.23 <br><br>
Basic copper carbonate <br><br>
7.27 <br><br>
Benzalkonium chloride (50% active) <br><br>
8 . 0 <br><br>
Tebuconazole <br><br>
0.8 <br><br>
Boric acid <br><br>
11.3 <br><br>
20 Weight ratio Cu: benzalkonium chloride:Tebuconazole 5:5:1 <br><br>
Example 12(a) A concentrate was made having the same formulation as Example 12 except that monoethanolamine was replaced by ethylenediamine. <br><br>
Example 13 A concentrate w/w <br><br>
Monoethanolamine 30.77 <br><br>
Basic copper carbonate 14.50 30 Didecyldimethylammonium methyl sulphate (50% active) 8.0 <br><br>
Propiconazole 0.32 <br><br>
Weight ratio Cu:Didecyldimethylammonium methyl sulphate: 35 Propiconazole 2:1:0.08 <br><br>
Example 13(a) A concentrate was made having the same formulation as Example 13 except that monoethanolamine was replaced by diethanolamine. <br><br>
2 4 3 4 5 0 <br><br>
- 14 - <br><br>
Synergistic Action of Mixtures Formulated According to the Invention <br><br>
The toxic limit value for a particular biocidal 5 compound is the concentration of the compound which is required to prevent degradation (defined as >3% mass loss) of a substrate by a target organism. Toxic limits are normally expressed as two experimentally-determined concentrations that span the pass/fail point of the 10 test. The toxic index is the midpoint of these two values. Where a preservative composition contains two biocidal compounds at a particular ratio, the toxic index is the estimated minimum concentration of each biocide required for effective protection of the 15 substrate from the target organism. In Figure 1 of the accompanying drawings, points A and B are the toxic index values for biocidal compounds Y and X respectively and the straight line between these two points illustrates the toxic index values which would be 20 obtained if the biocidal effects of compounds X and Y are merely additive. If, for any particular ratio of X:Y, the toxic index value is found to be below the straight line (e.g. at point C) , then compounds X and Y are synergistic at that particular ratio. 25 A convenient method of assessing the synergistic properties of a formulation is to use a 'synergistic index'. This may be defined as: <br><br>
Synergistic Index (SI) = Theoretical toxic index 30 Actual toxic index <br><br>
The theoretical toxic index may be calculated by interpolation to the theoretical line of action. A SI of 1 indicates no synergism. As the SI increases, so 35 the degree of synergism also increases. <br><br>
L H <br><br>
< /, <br><br>
- 15 - <br><br>
A) Compositions containing tebuconazole <br><br>
(i) Fungicidal effect on basidiomvcete <br><br>
Fungicidal activity was measured according to the test method pr EN113. This method involves treating small wood blocks with the preservative compounds and then exposing them to the decay fungi in a small test 10 vessel. Using a range of treatment concentrations, <br><br>
estimation of performance is determined after a 12 week exposure period by measuring the weight loss of the blocks. Average values for weight loss for replicate samples allow the determination of an estimated 15 concentration or loading of preservative in the wood which will be effective against the target fungus. In order to demonstrate synergism, results have been obtained using tebuconazole alone, a substituted cupramnonium compound and then together as a mixture, 20 the constituents of which are given as Example 1. The copper to tebuconazole ratio for this example was 25:1. All tests were carried out after cold water leaching according to the method published as EN84. Although boron was included in these formulations, this leaching 25 procedure is sufficient to remove all of the boron. There is therefore no contribution of this active ingredient to overall efficacy in the tests. Results are given in Tables 1 and 2 for the individual active ingredients and Table 3 for the mixture. <br><br>
30 <br><br>
7k34 60 <br><br>
- 16 - <br><br>
TABLE 1 Toxic limit values for Tebuconazole as determined by EN113 (kgm'1 active ingredient) <br><br>
Toxic Limit kgm'3 <br><br>
Toxic Index kgm"3 <br><br>
10 <br><br>
P. placenta C. Versicolor C. puteana <br><br>
0.3 - 0.5 0.2 - 0.4 0.05 - 0.2 <br><br>
0.4 0.3 0. 125 <br><br>
TABLE 2 Toxic limit values for substitute cuprammonium compounds determined by EN113 (kgm"3 copper) <br><br>
15 <br><br>
Toxic Limit kgm"3 <br><br>
Toxic Index kgm'3 <br><br>
20 <br><br>
P. placenta G. trabeum C. puteana <br><br>
> 4.62 <br><br>
> 4.49 3.1 - 5.4 <br><br>
Estimated value 5.0 " "5.0 <br><br>
4.25 <br><br>
30 <br><br>
These results clearly indicate the differential performance between tebuconazole and the cuprammonium compounds. For the most aggressive fungus (Poria placenta) about 0.4 kgm'3 Tebuconazole is required for effectiveness whilst approximately 5.0 kgm'3 of copper is required to prevent decay. <br><br>
Further results for tests using a 25:1 mixture of copper to tebuconazole are given in Table 3. Poria placenta was used as this is the most aggressive fungus in the full EN113 test towards these two compounds. <br><br>
Lk 3 4 6 0 <br><br>
- 17 - <br><br>
TABLE 3 Toxic Unit values for a 25:1 copper:tebuconazole mixture as determined bv EN113. (Toxic limit <br><br>
values given as kqa'3 Cu) <br><br>
5 Toxic Limit Toxic Index kgm"3 Cu kgm"5 Cu <br><br>
P. placenta 1.4 - 2.2 1.8 <br><br>
10 These results have been plotted in diagrammatic form in Figure 2 of the accompanying drawings. <br><br>
In Figure 2, the dotted line illustrates the expected concentration of cuprammonium compound and tebuconazole which would be needed in a composition containing copper 15 and tebuconazole at a weight ratio of 25:1 if the performance of copper and tebuconazole were merely additive (3.2 kgm'3 copper and 0.13 kgm"3 tebuconazole). The solid line illustrates the actual concentrations found to be required. These concentrations are considerably 20 lower than expected (1.8 kgn"3 copper and 0.072 kgm'3 tebuconazole), producing a synergistic index of 1.73. <br><br>
ii) Fungicidal effect of various copper:tebuconazole rat ios <br><br>
25 The above tests have been extended to delineate the range of ratios over which synergism exists between cuprammonium compounds and tebuconazole. A shortened version of the test prEN113 was used: the duration of the test was 6 weeks; the target fungus was C.puteana as the 30 growth rate of this copper tolerant fungus is reliable in a six week exposure test. All blocks were cold-water leached according to prEN84. The compositions tested were obtained by mixing the packs A and B described in Example 6 to obtain the copper: Tebuconazole ratios shown in Table 35 4, which also shows the toxic and synergistic indices found at these ratios. <br><br>
- 18 - <br><br>
24346 <br><br>
10 <br><br>
TABLE 4 Fornulat ion <br><br>
Tebuconazole <br><br>
Cuprammonium compound <br><br>
1:10 <br><br>
25:1 <br><br>
500: 1 <br><br>
1000: 1 <br><br>
Toxic Index (kgm"3) 0.048 ai 4.91 CU <br><br>
0.048 ai <0.48 Cu <1.90 Cu 4.3 4 CU <br><br>
Theoretical Toxic Synergistic <br><br>
Index (kgm-3) <br><br>
0.048 ai 0.9 5 Cu 4.10 Cu 4.40 Cu <br><br>
Index <br><br>
1.00 >2 .08 >2.10 <br><br>
1.01 <br><br>
N.B. Ratios given as Copper:Tebuconazole ai - active ingredient <br><br>
15 These values clearly show the surprising differences in fungicidal activity exhibited by different ratios of Cu:tebuconazole; they are shown in diagrammatic form in Figure 3. Whereas at 1:10 and 1000:1 the fungicidal activity of Cu and tebuconazole are purely additive, at <br><br>
20 25:1 and 500:1 the formulations are significantly synergistic. <br><br>
iii) Fungicidal effect against soft rot <br><br>
The mixture used in the previous test was further 25 tested in a fungal cellar test where activity against soft rot was assessed. Results from this test are particularly important in assessing the suitability of wood preservatives for use in ground contact. <br><br>
Small stakes of wood (15 x 3 x 100mm) of Beech were 30 exposed in unsterile soil to nine-tenths of their length. The exposure period was six months. Leached samples were used. The strength loss was used as the main criteria for assessment. 80% of residual strength was used as the level at which toxic limits were determined. 35 Toxic thresholds on Beech against soft rot for individual components and mixtures after leaching are given below (in this table, the toxic limit and toxic index for the cuprammonium compound are given in kg of Cu per m3) . <br><br>
24 3 4 6 0 <br><br>
19 <br><br>
TABLE 5 <br><br>
Toxic Limit Toxic Index <br><br>
(kgm'3 active (kgm'3 active ingredient) ingredient) <br><br>
Tebuconazole <br><br>
> 9.09 <br><br>
> 9.09 <br><br>
Cuprammonium compound > 8.44 <br><br>
CoppenTebuconazole 25:1 1.65 - 3 .25 <br><br>
> 8.44 <br><br>
> 8.44 <br><br>
2.45 <br><br>
The interaction between the copper and tebuconazole for performance on Beech against soft rot is shown in Figure 4 of the accompanying drawings. <br><br>
In Figure 4, the dotted line illustrates the expected concentrations of copper and tebuconazole needed in a composition containing copper and tebuconazole at a weight ratio of 25:1 if the performance of copper and tebuconazole were merely additive (> 8.44 kgm'3 copper and > 0.33 kgm'3 tebuconazole). The solid line illustrates the actual concentrations found to be required. These concentrations are considerably lower than expected (2.44 kgm'3 copper and 0.01 kgm'3 tebuconazole). <br><br>
These results show that the synergistic index of copper:tebuconazole combined at a ratio of 25:1 is > 3.58 when tested against soft rot fungi. <br><br>
2b <br><br>
243 450 <br><br>
- 20 - <br><br>
B) Compositions containing either propiconazole or <br><br>
Azaconazole <br><br>
Tests to evaluate efficacy against basidiomycetes 5 were carried out on Propiconazole and Azaconazole singly and in mixtures with copper using ratios within the scope of the invention. The tests were carried out according to both EN 113 and the method published as IRG/WP/2329, and toxic limits were identified as 10 described above for the fungus Coniophora puteana. <br><br>
The toxic limits are given in the table below (in this table, the toxic limit and toxic index for the cuprammonium compound are given in kg of Cu per m3) : <br><br>
15 TABLE 6 <br><br>
Active ingredient Toxic Limit Toxic Index <br><br>
(kgm'3 total (kgm'3 total active ingredient) active ingredient) <br><br>
20 Cuprammonium compound 3.1-5.4 4.25 <br><br>
Propiconazole 0.3-0.7 0.5 <br><br>
Azaconazole 0.7 - 1.3 1.0 <br><br>
Cu:Propiconazole 5:1 < 0.504 < 0.504 <br><br>
Cu:Azaconazole 5:1 1.008 - 2.04 1.52 <br><br>
The interaction between the propiconazole and copper is illustrated in Figure 5; and that for azaconazole and copper is illustrated in Figure 6. <br><br>
In Figure 5, the dotted line illustrates the 30 expected concentrations of copper and propiconazole in a composition containing copper at a weight ratio of 5:1 if the performance of copper and propiconazole were merely additive (1.6 kgm'3 copper and 0.3 kgm'5 propiconazole). The solid line illustrates the actual 35 concentrations found to be required. These concentrations are considerably lower than expected (< 0.42 kgm'3 copper and < 0.084 kgm"3 propiconazole). A synergistic of index of > 3.77 was calculated from these results for Cu:Propiconazole combined at a ratio of 5:1. <br><br>
\ <br><br>
24 3 4 M <br><br>
- 21 - <br><br>
In Figure 6, the dotted line illustrates the expected concentrations of copper and azaconazole needed in a composition containing copper at a weight ratio of 5:1 if the performance of copper and azaconazole were 5 merely additive (2.5 kgm'3 copper and 0.5 kgm"3 <br><br>
azaconazole). The solid line illustrates the actual concentrations found to be required. These concentrations are considerably lower than expected (1.26 kgm'3 copper and 0.25 kgm'3 azaconazole). <br><br>
10 These results suggest that copper: azaconazole mixtures combined of a ratio of 5:1 are synergistic with a synergistic index of 1.97. <br><br></p>
</div>
Claims (18)
1. Preservative compositions comprising a synergistic mixture ot a biocidal metal compound and a fungicidal compound containing a triazole group selected from: a) compounds of formula (A):<br><br> OH I<br><br> —CHi-CHj-C- r<br><br> 1 (a)<br><br> CH2<br><br> 1 ; ,<br><br> f ■<br><br> wherein R1 represents a branched or straight chain C,.5 alkyl group and represents a phenyl group optionally substituted by one or more substituents selected 1 rom halogen atoms and C, 3 alkyl, C13 alkoxy, phenyl and nitro groups;<br><br> b) compounds of formula (B) :<br><br> r—0<br><br> R-<br><br> R<br><br> 30<br><br> y o ch2<br><br> n n<br><br> n 1<br><br> (b)<br><br> 2 4 3 4 5 0<br><br> wheioin R3 i a a:-: defined ior K? above and R4 lepresents a hydroc.-n atom or a branched or straight chain C15 alkyl qroup; and c) hexaoonazole and aifenoconazole;<br><br> b wherein the wi-icht ratio of metal atom: fungicidal compound containing the triazole group is at least 5:1; with the specific exception of composition (a) which cont.u p.:; by v:eight oi sodium nitrite, 1.190% by wr'iqht ot copper sulphate bH?0, 0.400% by weight of boi_ic<br><br> ]( 0.(>:V.-A by woiqr.t oi sodiurr. heptonate, 0.390% by v:> ;«jilt i i urn hv •: rox i d-'-, 0.012°i by weight of tebuconazole 0.3 91% by weight of surfactant blend in xy i >•!)*• and (>b.7G2?o t,y weight of water.<br><br> lb .
A composition as claimed in claim 1 in which the nu t -i 1 compound is a compound of a metal selected from: copper, aluminium, manganese, iron, cobalt, nickel,<br><br> zinc, silver, cadmium, tin, antimony, mercury, lead and bi smuth.<br><br> lie.<br><br>
3. A composition as claimed in claim 2 in which the metal compound is a copper compound.<br><br> A.
A composition as claimed in any one of the preceding claims in which the compound containing a tiiazole group is selected from tebuconazole, propiconazole, azaconazole, hexaconazole and di fenoconazole.<br><br> JO b.
A composition as claimed in any one of the preceding claims wherein the fungicidal compound containing a triazole group is selected from tebuconazole, propiconazole and azaconazole.<br><br> 3b
6. A composition as claimed in claim 5 which contains tebuconazole and propiconazole.<br><br> I<br><br> 243460<br><br> 24<br><br>
7. A composition as claimed in any one of the preceding claims wherein the weight ratio of metal atom: fungicidal compound containing a triazole group is between 5:1 and 500:1.<br><br>
8. A composition as claimed in claim 7 wherein said ratio is between 5:1 and 113.5:1.<br><br>
9. A composition as claimed in claim 8 wherein said 10 ratio is between 5:1 and 50:1.<br><br>
10. A composition as claimed in claim 9 wherein said ratio is between 10:1 and 30:1.<br><br> 15
11. A composition as claimed in claim 10 wherein said ratio is about 25:1.<br><br>
12. A method of treating a substrate of wood or other cellulosic material which comprises applying to the<br><br> 20 substrate a composition as claimed in any one of the, precedinq claims.<br><br>
13. A substrate of wood or other cellulosic material treated with a composition as claimed in any one of claims 1 to 11.<br><br>
14. A preservative composition as claimed in claim l substantially as herein described.<br><br>
15. A preservative composition substantially as described herein with reference to any one of the Examples.<br><br>
16. A method as claimed in claim 12 substantially as herein described.<br><br> 5<br><br> / v -<br><br> u<br><br> 'A -/<br><br> V<br><br> - 25 -<br><br> ^ *' T » n /%<br><br> £ 'i 4 0 0<br><br>
17. A method of treating a substrate of wood or other cellulosic material substantially as herein described with reference to any one of the Examples.<br><br>
18 . A substrate as claimed in claim 13 substantially as herein described.<br><br> bkdtseo.. \a&(x^2cQLAg^—<br><br> ■"'/ the r. *ur" ised agents<br><br> • • i •' <» \ i<br><br> </p> </div>
Priority Applications (17)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19920916694 EP0641164B1 (en) | 1991-08-01 | 1992-08-03 | Preservatives for wood and other cellulosic materials |
PCT/GB1992/001427 WO1993002557A1 (en) | 1991-08-01 | 1992-08-03 | Preservatives for wood and other cellulosic materials |
US08/190,108 US5527384A (en) | 1991-08-01 | 1992-08-03 | Preservatives for wood and other cellulosic materials |
ES92916694T ES2142828T3 (en) | 1991-08-01 | 1992-08-03 | PRESERVATIVES FOR WOOD AND OTHER CELLULOSIC MATERIALS. |
CA 2114644 CA2114644C (en) | 1991-08-01 | 1992-08-03 | Preservatives for wood and other cellulosic materials |
DK92916694T DK0641164T3 (en) | 1991-08-01 | 1992-08-03 | Preservatives for wood and other cellulose materials |
BR9206324A BR9206324A (en) | 1991-08-01 | 1992-08-03 | Compositions for the conservation of wood and cellulosic materials, and, process for the treatment of a wooden substrate or other cellulosic material |
AT92916694T ATE188341T1 (en) | 1991-08-01 | 1992-08-03 | PRESERVATIVES AND METHODS FOR TREATING WOOD |
JP50340593A JP3391449B2 (en) | 1991-08-01 | 1992-08-03 | Preservatives for wood and other cellulosic materials |
AU23797/92A AU659203C (en) | 1991-08-01 | 1992-08-03 | Preservatives for wood and other cellulosic materials |
DE1992630540 DE69230540T2 (en) | 1991-08-01 | 1992-08-03 | PRESERVATIVES AND METHOD FOR TREATING WOOD |
US09/190,109 USRE36798E (en) | 1991-08-01 | 1992-08-03 | Preservatives for wood and other cellulosic materials |
NO940324A NO309671B1 (en) | 1991-08-01 | 1994-01-31 | Preservative mixtures and their use |
FI940452A FI109323B (en) | 1991-08-01 | 1994-01-31 | A protective composition and a method for treating a substrate of wood or other cellulosic material |
US08/465,512 US5634967A (en) | 1991-08-01 | 1995-06-05 | Preservatives for wood and other cellulosic materials |
US08/867,261 US5916356A (en) | 1991-08-01 | 1997-06-02 | Preservatives for wood and other cellulosic materials |
GR20000400760T GR3033071T3 (en) | 1991-08-01 | 2000-03-27 | Preservatives for wood and other cellulosic materials. |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB919116672A GB9116672D0 (en) | 1991-08-01 | 1991-08-01 | Preservatives for wood and other cellulosic materials |
Publications (1)
Publication Number | Publication Date |
---|---|
NZ243460A true NZ243460A (en) | 1995-06-27 |
Family
ID=10699389
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NZ243460A NZ243460A (en) | 1991-08-01 | 1992-07-06 | Synergistic fungicides containing a biocidal metal compound and a triazole derivative; preservatives for wood and other cellulosic materials |
Country Status (6)
Country | Link |
---|---|
US (1) | USRE36798E (en) |
GB (1) | GB9116672D0 (en) |
MY (1) | MY120192A (en) |
NZ (1) | NZ243460A (en) |
PT (1) | PT100707B (en) |
ZA (1) | ZA925135B (en) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AUPR211400A0 (en) | 2000-12-15 | 2001-01-25 | Koppers-Hickson Timber Protection Pty Limited | Material and method for treatment of timber |
US6416789B1 (en) | 2001-01-05 | 2002-07-09 | Kop-Coat, Inc. | Synergistic combination of fungicides to protect wood and wood-based products from fungal decay, mold and mildew damage |
US6818317B2 (en) * | 2001-05-02 | 2004-11-16 | Potlach Corporation | Termite resistant and fungal resistant oriented strand board and methods for manufacturing |
CA2357392C (en) * | 2001-09-17 | 2010-12-21 | Genics Inc. | Method of manufacture of a liquid pesticide containing copper and a liquid pesticide containing copper |
WO2004011215A2 (en) * | 2002-07-26 | 2004-02-05 | Osmose, Inc. | Polymeric wood preservative compositions |
US7056919B2 (en) | 2003-01-24 | 2006-06-06 | Kopcoat, Inc. | Synergistic combination of fungicides to protect wood and wood-based products and wood treated by such combination as well as methods of making the same |
US8637089B2 (en) | 2003-04-09 | 2014-01-28 | Osmose, Inc. | Micronized wood preservative formulations |
NZ542889A (en) | 2003-04-09 | 2010-02-26 | Osmose Inc | Micronized wood preservative formulations comprising dispersions of micronized metal or metal compounds |
US20050000387A1 (en) * | 2003-07-02 | 2005-01-06 | Ying Wang | Wood preservative with alkaline copper quaternary |
US20050227956A1 (en) * | 2004-04-13 | 2005-10-13 | Ying Wang | Control of mold growth on wood |
US20070021385A1 (en) * | 2005-07-21 | 2007-01-25 | Jun Zhang | Compositions and methods for wood preservation |
US20080175913A1 (en) * | 2007-01-09 | 2008-07-24 | Jun Zhang | Wood preservative compositions comprising isothiazolone-pyrethroids |
GB0700857D0 (en) * | 2007-01-17 | 2007-02-21 | Betts John A | Preservative compositions for wood and like materials |
US7816343B2 (en) * | 2007-03-08 | 2010-10-19 | Hwd Acquisition, Inc. | Wood preservative composition |
US20090162410A1 (en) * | 2007-12-21 | 2009-06-25 | Jun Zhang | Process for preparing fine particle dispersion for wood preservation |
Family Cites Families (43)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2041655A (en) * | 1933-11-24 | 1936-05-19 | Celcure Corp | Wood treating preparation |
SE396032B (en) * | 1973-04-27 | 1977-09-05 | Boliden Ab | WATER-SOLUBLE IMPREGENT, CONTAINING AMINE-FORMED METAL, POLYPHOSPHATE AND CHLORINATED PHENOLES, FOR THREE AND OTHER ORGANIC MATERIALS |
DE2410603C2 (en) * | 1974-03-06 | 1982-12-23 | Basf Ag, 6700 Ludwigshafen | Fungicide for wood protection |
AU519146B2 (en) * | 1977-04-29 | 1981-11-12 | Commonwealth Scientific And Industrial Research Organisation | Ethanolamine etal based wood preservative compositions |
US4288249A (en) * | 1979-02-26 | 1981-09-08 | Reichhold Chemicals, Inc. | Water soluble pentachlorophenol and tetrachlorophenol wood treating systems |
EP0044270B1 (en) * | 1980-06-30 | 1984-07-25 | Ciba-Geigy Ag | Intumescent fire-retarding composition and its use in the fireproofing of substrates and as fire-tighting agent |
US5216007A (en) * | 1980-10-01 | 1993-06-01 | Rohm And Haas Company | Substituted ethylene imidazole and triazoles |
SE459164B (en) * | 1981-05-08 | 1989-06-12 | Kenogard Ab | WOOD PROTECTIVE BASED ON CONSERVATIVE METALS AND ORGANIC NITROGEN CONTAINING COMPOUNDS AND USE OF THE MEDICINE |
DE3208142A1 (en) * | 1982-03-06 | 1983-09-08 | Bayer Ag, 5090 Leverkusen | FUNGICIDAL AGENT |
US4461721A (en) * | 1982-04-12 | 1984-07-24 | Basf Aktiengesellschaft | Wood preservative |
MA19798A1 (en) * | 1982-06-08 | 1983-12-31 | Novartis Ag | PLANT DISEASE CONTROL AGENT; ITS PREPARATION AND ITS APPLICATION TO THE PROTECTION OF PLANTS. |
DE3231347A1 (en) * | 1982-08-24 | 1984-03-01 | Basf Ag, 6700 Ludwigshafen | BETA TRIAZOLYL KETALS, METHOD FOR THE PRODUCTION THEREOF AND FUNGICIDES CONTAINING THEM |
DE3234624A1 (en) * | 1982-09-18 | 1984-03-22 | Bayer Ag, 5090 Leverkusen | FUNGICIDAL AGENT |
US4420542A (en) * | 1982-10-25 | 1983-12-13 | Reilly Tar & Chemical Corp. | Article and method for wood preservation |
WO1985000040A1 (en) * | 1983-06-17 | 1985-01-03 | Koppers Australia Pty. Limited | Preservative composition |
DE3333412A1 (en) * | 1983-09-16 | 1985-04-04 | Bayer Ag, 5090 Leverkusen | FUNGICIDAL AGENT |
DE3333411A1 (en) * | 1983-09-16 | 1985-04-04 | Bayer Ag, 5090 Leverkusen | FUNGICIDAL AGENT |
US4648988A (en) * | 1983-12-21 | 1987-03-10 | Janssen Pharmaceutica, N.V. | Water-dilutable wood-preserving liquids |
DE3511411A1 (en) * | 1985-03-29 | 1986-10-02 | Basf Ag, 6700 Ludwigshafen | USE OF AZOLYLMETHYLOXIRANES TO COMBAT VIRAL DISEASES |
DE3520394A1 (en) * | 1985-06-07 | 1986-12-11 | Dr. Wolman Gmbh, 7573 Sinzheim | WOOD PRESERVATIVES |
US5078912A (en) * | 1985-06-07 | 1992-01-07 | Dr. Wolman Gmbh | Wood preservative |
PH24256A (en) * | 1985-12-20 | 1990-05-04 | Rhone Poulenc Agrochimie | Fungicide with triazole and oligoether group and association |
DE3609317A1 (en) * | 1986-03-20 | 1987-09-24 | Wolman Gmbh Dr | WOOD PRESERVATIVES |
DE3621361A1 (en) * | 1986-06-26 | 1988-01-14 | Wolman Gmbh Dr | WOOD PRESERVATIVES CONTAINING COPPER AND ORGANO TIN CONNECTIONS |
DE3621494A1 (en) * | 1986-06-27 | 1988-01-07 | Bayer Ag | USE OF 1-ARYL-3-HYDROXY-3-ALKYL-4- (1,2,4-TRIAZOL-1-YL) -BUTANE DERIVATIVES AS MICROBICIDES FOR MATERIAL PROTECTION |
GB2194752B (en) * | 1986-09-04 | 1990-01-10 | Mikhail Petrovich Zverev | Method for producing anion exchange fibres |
DE3641554C2 (en) * | 1986-12-05 | 1995-04-06 | Solvay Werke Gmbh | Wood preservatives |
DE3737888A1 (en) * | 1987-11-07 | 1989-05-18 | Basf Ag | PROCESS FOR INFLUENCING PLANT GROWTH THROUGH AZOLYL METHYLOXIRANE |
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 |
FR2628295B1 (en) * | 1988-03-09 | 1991-05-10 | Soyez Jean Louis | LIQUID FUNGICIDAL COMPOSITIONS BASED ON COPPER TALLATES |
US5013746A (en) * | 1988-04-08 | 1991-05-07 | Janssen Pharmaceutica N.V. | Imazalil containing synergistic compositions |
NZ226377A (en) * | 1988-09-28 | 1992-06-25 | Nigel Paul Maynard | Water-insoluble biocidal or preservative composition comprising a borate organic complex ion and a biocidally active cationic species |
US5223524A (en) * | 1989-04-19 | 1993-06-29 | Janssen Pharmaceutica N.V. | Synergistic compositions containing propiconazole and tebuconazole |
DE3934935A1 (en) * | 1989-10-20 | 1991-04-25 | Wolman Gmbh Dr | WOOD PRESERVATIVES CONTAINING POLYMER NITROGEN COMPOUNDS |
NZ236976A (en) * | 1990-02-02 | 1991-11-26 | Hickson Int Plc | Aqueous preservative compositions containing a biocidal cation and nitrite ions with ph above 6.5 |
DE4008837A1 (en) * | 1990-03-20 | 1991-09-26 | Desowag Materialschutz Gmbh | Prevention of wood from being stained by mould growth - using mixt. of azole and organo:aluminium cpd. |
DE4009740A1 (en) * | 1990-03-27 | 1991-10-02 | Desowag Materialschutz Gmbh | MEDIUM OR CONCENTRATE FOR PROTECTING SAWN WOOD AGAINST WOOD-MOLDING MUSHROOMS |
DE4013524A1 (en) * | 1990-04-27 | 1991-10-31 | Bayer Ag | USE OF COPPER SALT AS A CRYSTALIZATION INHIBITOR |
US5230892A (en) * | 1990-08-24 | 1993-07-27 | Bayer Aktiengesellschaft | Solid formulations |
US5223178A (en) * | 1990-12-10 | 1993-06-29 | Rohm And Haas Company | Use of certain triazoles to protect materials from fungal attack, articles and compositions |
DE4113158A1 (en) * | 1991-04-23 | 1992-10-29 | Bayer Ag | MICROBICIDAL COMBINATIONS OF ACTIVE SUBSTANCES |
DE69230540T2 (en) * | 1991-08-01 | 2000-07-06 | Hickson Int Plc | PRESERVATIVES AND METHOD FOR TREATING WOOD |
US5252594A (en) * | 1992-06-17 | 1993-10-12 | Rohm And Haas Company | Fungicidal (2-aryl-2-substituted)ethyl-1,2,4-triazoles |
-
1991
- 1991-08-01 GB GB919116672A patent/GB9116672D0/en active Pending
-
1992
- 1992-07-06 NZ NZ243460A patent/NZ243460A/en not_active IP Right Cessation
- 1992-07-09 ZA ZA925135A patent/ZA925135B/en unknown
- 1992-07-20 PT PT100707A patent/PT100707B/en not_active IP Right Cessation
- 1992-07-22 MY MYPI92001302A patent/MY120192A/en unknown
- 1992-08-03 US US09/190,109 patent/USRE36798E/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
PT100707A (en) | 1993-10-29 |
GB9116672D0 (en) | 1991-09-18 |
PT100707B (en) | 1999-07-30 |
ZA925135B (en) | 1994-01-10 |
MY120192A (en) | 2005-09-30 |
USRE36798E (en) | 2000-08-01 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
RENW | Renewal (renewal fees accepted) | ||
RENW | Renewal (renewal fees accepted) | ||
EXPY | Patent expired |