NZ724922B2 - A wood preservative - Google Patents
A wood preservative Download PDFInfo
- Publication number
- NZ724922B2 NZ724922B2 NZ724922A NZ72492212A NZ724922B2 NZ 724922 B2 NZ724922 B2 NZ 724922B2 NZ 724922 A NZ724922 A NZ 724922A NZ 72492212 A NZ72492212 A NZ 72492212A NZ 724922 B2 NZ724922 B2 NZ 724922B2
- Authority
- NZ
- New Zealand
- Prior art keywords
- metal
- compound
- wood
- formulation
- triazole
- Prior art date
Links
- 239000003171 wood protecting agent Substances 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims abstract description 115
- 229910052751 metal Inorganic materials 0.000 claims abstract description 87
- 239000002184 metal Substances 0.000 claims abstract description 87
- 230000002335 preservative Effects 0.000 claims abstract description 58
- 239000003755 preservative agent Substances 0.000 claims abstract description 56
- 239000002023 wood Substances 0.000 claims abstract description 52
- 238000009472 formulation Methods 0.000 claims abstract description 47
- 239000010949 copper Substances 0.000 claims abstract description 45
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052802 copper Inorganic materials 0.000 claims abstract description 41
- 239000005839 Tebuconazole Substances 0.000 claims abstract description 39
- PXMNMQRDXWABCY-UHFFFAOYSA-N Tebuconazole Chemical compound C1=NC=NN1CC(O)(C(C)(C)C)CCC1=CC=C(Cl)C=C1 PXMNMQRDXWABCY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000005822 Propiconazole Substances 0.000 claims abstract description 33
- 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 abstract description 33
- 230000003115 biocidal Effects 0.000 claims abstract description 30
- 239000011701 zinc Substances 0.000 claims abstract description 29
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 27
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 26
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 25
- KAESVJOAVNADME-UHFFFAOYSA-N pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 57
- -1 copper(II) compound Chemical class 0.000 claims description 52
- 230000000855 fungicidal Effects 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 33
- 239000000417 fungicide Substances 0.000 claims description 29
- 150000002500 ions Chemical class 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 19
- 150000003852 triazoles Chemical class 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000008365 aqueous carrier Substances 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000006184 cosolvent Substances 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 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- 239000011135 tin Substances 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 150000001880 copper compounds Chemical class 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229950000294 Azaconazole Drugs 0.000 claims description 5
- AKNQMEBLVAMSNZ-UHFFFAOYSA-N azaconazole Chemical compound ClC1=CC(Cl)=CC=C1C1(CN2N=CN=C2)OCCO1 AKNQMEBLVAMSNZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 241000894007 species Species 0.000 claims description 5
- 239000010875 treated wood Substances 0.000 claims description 5
- 239000005749 Copper compound Substances 0.000 claims description 4
- STMIIPIFODONDC-UHFFFAOYSA-N Hexaconazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(O)(CCCC)CN1C=NC=N1 STMIIPIFODONDC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910052803 cobalt Inorganic materials 0.000 claims description 4
- FBOUIAKEJMZPQG-BLXFFLACSA-N diniconazole-M Chemical compound C1=NC=NN1/C([C@H](O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1Cl FBOUIAKEJMZPQG-BLXFFLACSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 230000002195 synergetic Effects 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 239000011121 hardwood Substances 0.000 claims description 3
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 239000011122 softwood Substances 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 150000003752 zinc compounds Chemical class 0.000 claims description 3
- YNWVFADWVLCOPU-MDWZMJQESA-N (1E)-1-(4-chlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pent-1-en-3-ol Chemical compound C1=NC=NN1/C(C(O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1 YNWVFADWVLCOPU-MDWZMJQESA-N 0.000 claims description 2
- ZMYFCFLJBGAQRS-IRXDYDNUSA-N (2R,3S)-epoxiconazole Chemical compound C1=CC(F)=CC=C1[C@@]1(CN2N=CN=C2)[C@H](C=2C(=CC=CC=2)Cl)O1 ZMYFCFLJBGAQRS-IRXDYDNUSA-N 0.000 claims description 2
- URDNHJIVMYZFRT-UONOGXRCSA-N (2S,3S)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)pentan-3-ol Chemical compound C([C@@H]([C@@H](O)C(C)(C)C)N1N=CN=C1)C1=CC=C(Cl)C=C1Cl URDNHJIVMYZFRT-UONOGXRCSA-N 0.000 claims description 2
- PPDBOQMNKNNODG-NTEUORMPSA-N (5E)-5-(4-chlorobenzylidene)-2,2-dimethyl-1-(1,2,4-triazol-1-ylmethyl)cyclopentanol Chemical compound C1=NC=NN1CC1(O)C(C)(C)CC\C1=C/C1=CC=C(Cl)C=C1 PPDBOQMNKNNODG-NTEUORMPSA-N 0.000 claims description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 2
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 claims description 2
- LQDARGUHUSPFNL-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)-3-(1,1,2,2-tetrafluoroethoxy)propyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(COC(F)(F)C(F)F)CN1C=NC=N1 LQDARGUHUSPFNL-UHFFFAOYSA-N 0.000 claims description 2
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 claims description 2
- UFNOUKDBUJZYDE-UHFFFAOYSA-N 2-(4-chlorophenyl)-3-cyclopropyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol Chemical compound C1=NC=NN1CC(O)(C=1C=CC(Cl)=CC=1)C(C)C1CC1 UFNOUKDBUJZYDE-UHFFFAOYSA-N 0.000 claims description 2
- YABFPHSQTSFWQB-UHFFFAOYSA-N 2-(4-fluorophenyl)-1-(1,2,4-triazol-1-yl)-3-(trimethylsilyl)propan-2-ol Chemical compound C=1C=C(F)C=CC=1C(O)(C[Si](C)(C)C)CN1C=NC=N1 YABFPHSQTSFWQB-UHFFFAOYSA-N 0.000 claims description 2
- MNHVNIJQQRJYDH-UHFFFAOYSA-N 2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound N1=CNC(=S)N1CC(C1(Cl)CC1)(O)CC1=CC=CC=C1Cl MNHVNIJQQRJYDH-UHFFFAOYSA-N 0.000 claims description 2
- OVFHHJZHXHZIHT-UHFFFAOYSA-N 3-(2,4-dichlorophenyl)-2-(1,2,4-triazol-1-yl)quinazolin-4-one Chemical compound ClC1=CC(Cl)=CC=C1N1C(=O)C2=CC=CC=C2N=C1N1N=CN=C1 OVFHHJZHXHZIHT-UHFFFAOYSA-N 0.000 claims description 2
- RQDJADAKIFFEKQ-UHFFFAOYSA-N 4-(4-chlorophenyl)-2-phenyl-2-(1,2,4-triazol-1-ylmethyl)butanenitrile Chemical compound C1=CC(Cl)=CC=C1CCC(C=1C=CC=CC=1)(C#N)CN1N=CN=C1 RQDJADAKIFFEKQ-UHFFFAOYSA-N 0.000 claims description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N 8-Hydroxyquinoline Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000005741 Bromuconazole Substances 0.000 claims description 2
- 239000005757 Cyproconazole Substances 0.000 claims description 2
- 239000005760 Difenoconazole Substances 0.000 claims description 2
- 239000005767 Epoxiconazole Substances 0.000 claims description 2
- 239000005775 Fenbuconazole Substances 0.000 claims description 2
- 239000005785 Fluquinconazole Substances 0.000 claims description 2
- FQKUGOMFVDPBIZ-UHFFFAOYSA-N Flusilazole Chemical compound C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 FQKUGOMFVDPBIZ-UHFFFAOYSA-N 0.000 claims description 2
- ULCWZQJLFZEXCS-KGLIPLIRSA-N Furconazole-cis Chemical compound O1[C@@H](OCC(F)(F)F)CC[C@@]1(C=1C(=CC(Cl)=CC=1)Cl)CN1N=CN=C1 ULCWZQJLFZEXCS-KGLIPLIRSA-N 0.000 claims description 2
- 239000005796 Ipconazole Substances 0.000 claims description 2
- 239000005868 Metconazole Substances 0.000 claims description 2
- 239000005811 Myclobutanil Substances 0.000 claims description 2
- HZJKXKUJVSEEFU-UHFFFAOYSA-N Myclobutanil Chemical compound C=1C=C(Cl)C=CC=1C(CCCC)(C#N)CN1C=NC=N1 HZJKXKUJVSEEFU-UHFFFAOYSA-N 0.000 claims description 2
- 239000005813 Penconazole Substances 0.000 claims description 2
- 239000005825 Prothioconazole Substances 0.000 claims description 2
- 239000005840 Tetraconazole Substances 0.000 claims description 2
- 229940035295 Ting Drugs 0.000 claims description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N Triadimefon Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005846 Triadimenol Substances 0.000 claims description 2
- 239000005859 Triticonazole Substances 0.000 claims description 2
- HJJVPARKXDDIQD-UHFFFAOYSA-N bromuconazole Chemical compound ClC1=CC(Cl)=CC=C1C1(CN2N=CN=C2)OCC(Br)C1 HJJVPARKXDDIQD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002144 chemical decomposition reaction Methods 0.000 claims description 2
- 238000007385 chemical modification Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 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 claims description 2
- DWRKFAJEBUWTQM-UHFFFAOYSA-N etaconazole Chemical compound O1C(CC)COC1(C=1C(=CC(Cl)=CC=1)Cl)CN1N=CN=C1 DWRKFAJEBUWTQM-UHFFFAOYSA-N 0.000 claims description 2
- IJJVMEJXYNJXOJ-UHFFFAOYSA-N fluquinconazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1N1C(=O)C2=CC(F)=CC=C2N=C1N1C=NC=N1 IJJVMEJXYNJXOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- AGKSTYPVMZODRV-UHFFFAOYSA-N imibenconazole Chemical compound C1=CC(Cl)=CC=C1CSC(CN1N=CN=C1)=NC1=CC=C(Cl)C=C1Cl AGKSTYPVMZODRV-UHFFFAOYSA-N 0.000 claims description 2
- QTYCMDBMOLSEAM-UHFFFAOYSA-N ipconazole Chemical compound C1=NC=NN1CC1(O)C(C(C)C)CCC1CC1=CC=C(Cl)C=C1 QTYCMDBMOLSEAM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- XWPZUHJBOLQNMN-UHFFFAOYSA-N metconazole Chemical compound C1=NC=NN1CC1(O)C(C)(C)CCC1CC1=CC=C(Cl)C=C1 XWPZUHJBOLQNMN-UHFFFAOYSA-N 0.000 claims description 2
- 125000005609 naphthenate group Chemical group 0.000 claims description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 2
- 238000010422 painting Methods 0.000 claims description 2
- 239000011120 plywood Substances 0.000 claims description 2
- 239000005871 repellent Substances 0.000 claims description 2
- 230000002940 repellent Effects 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- 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 claims description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims 2
- ULCWZQJLFZEXCS-UHFFFAOYSA-N 1-[[2-(2,4-dichlorophenyl)-5-(2,2,2-trifluoroethoxy)oxolan-2-yl]methyl]-1,2,4-triazole Chemical compound O1C(OCC(F)(F)F)CCC1(C=1C(=CC(Cl)=CC=1)Cl)CN1N=CN=C1 ULCWZQJLFZEXCS-UHFFFAOYSA-N 0.000 claims 1
- XOVQZRBUHDLLEG-UHFFFAOYSA-N 2-ethylhexanoic acid;octanoic acid Chemical compound CCCCCCCC(O)=O.CCCCC(CC)C(O)=O XOVQZRBUHDLLEG-UHFFFAOYSA-N 0.000 claims 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N Abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 abstract description 21
- 239000000969 carrier Substances 0.000 abstract description 12
- 150000003851 azoles Chemical class 0.000 description 22
- 230000014759 maintenance of location Effects 0.000 description 20
- 230000035515 penetration Effects 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 239000011780 sodium chloride Substances 0.000 description 17
- 150000003839 salts Chemical class 0.000 description 13
- 229940120693 copper naphthenate Drugs 0.000 description 11
- 229960000490 Permethrin Drugs 0.000 description 10
- 238000004166 bioassay Methods 0.000 description 10
- RLLPVAHGXHCWKJ-HKUYNNGSSA-N (3-phenoxyphenyl)methyl (1R,3R)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CC1(C)[C@@H](C=C(Cl)Cl)[C@H]1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-HKUYNNGSSA-N 0.000 description 9
- DPQXAUXLLDWUMQ-UHFFFAOYSA-L zinc;naphthalene-2-carboxylate Chemical compound [Zn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 DPQXAUXLLDWUMQ-UHFFFAOYSA-L 0.000 description 8
- 241001674280 Coniophora olivacea Species 0.000 description 7
- 230000000749 insecticidal Effects 0.000 description 7
- 239000002917 insecticide Substances 0.000 description 7
- 241000233866 Fungi Species 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 6
- 241000238631 Hexapoda Species 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 229940027983 antiseptics and disinfectants Quaternary ammonium compounds Drugs 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 239000003139 biocide Substances 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 230000002538 fungal Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 241000408174 Fomitopsis lilacinogilva Species 0.000 description 3
- 235000008577 Pinus radiata Nutrition 0.000 description 3
- 241000218621 Pinus radiata Species 0.000 description 3
- 230000000996 additive Effects 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000001638 boron 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
- 239000008139 complexing agent Substances 0.000 description 3
- AYWHENVLARCQQQ-UHFFFAOYSA-N copper;1H-pyrrole Chemical compound [Cu].C=1C=CNC=1 AYWHENVLARCQQQ-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 230000002633 protecting Effects 0.000 description 3
- 239000002424 termiticide Substances 0.000 description 3
- 241000221198 Basidiomycota Species 0.000 description 2
- 239000005874 Bifenthrin Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N Boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000005946 Cypermethrin Substances 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
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 239000005892 Deltamethrin Substances 0.000 description 2
- OWZREIFADZCYQD-NSHGMRRFSA-N Deltamethrin Chemical compound CC1(C)[C@@H](C=C(Br)Br)[C@H]1C(=O)O[C@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 OWZREIFADZCYQD-NSHGMRRFSA-N 0.000 description 2
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N 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
- RAXXELZNTBOGNW-UHFFFAOYSA-N Imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 241000256602 Isoptera Species 0.000 description 2
- 241000229754 Iva xanthiifolia Species 0.000 description 2
- 240000000233 Melia azedarach Species 0.000 description 2
- YWFWDNVOPHGWMX-UHFFFAOYSA-N N,N-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N Pentachlorophenol Chemical class OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 241000233647 Phytophthora nicotianae var. parasitica Species 0.000 description 2
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- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- YNWVFADWVLCOPU-MAUPQMMJSA-N uniconazole P Chemical compound C1=NC=NN1/C([C@@H](O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1 YNWVFADWVLCOPU-MAUPQMMJSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229940100888 zinc compounds Drugs 0.000 description 1
- MXODCLTZTIFYDV-ZTYDOUOLSA-L zinc;(1S,4aR,4bS)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [Zn+2].C([C@H]12)CC(C(C)C)=CC1=CCC1[C@]2(C)CCC[C@]1(C)C([O-])=O.C([C@H]12)CC(C(C)C)=CC1=CCC1[C@]2(C)CCC[C@]1(C)C([O-])=O MXODCLTZTIFYDV-ZTYDOUOLSA-L 0.000 description 1
Abstract
Disclosed is a low metal/high preservative formulation for use in treating wood or other cellulosic formulations, said formulation comprising: at least one biocidal metal compound (e.g., copper or zinc); at least one organic compound (e.g., tebuconazole or propiconazole; and a carrier, wherein the ratio of the metal to the organic compound is between about 5:1 and about 1:10 w/w. atio of the metal to the organic compound is between about 5:1 and about 1:10 w/w.
Description
A WOOD PRESERVATIVE
Related ation
This application claims the t of Australian Provisional Patent
Application AU 5439, dated 23 December 2011, the content of which is
incorporated herein by reference.
Field of the Invention
The present invention relates to the treatment of wood products and
other osic substrates with a preservative formulation. More ically,
the invention relates to the treatment of wood with a preservative mixture,
which comprises “inverse” tions ofmetal and organic compound, relative
to those presently used in the art. That is, the inventive formulation comprises a
generic “high organic compound/low metal nd” ratio of biocidal agents.
The invention has been developed primarily for use in treating timber
which is used in residential applications. For example, treatment of decking
timbers with the inventive formulation renders the treated wood resistant to
insect and fungal decay over a predetermined period. Although the invention
will be described hereinafter with reference to this application, it will be
appreciated that it is not limited to this particular field of use.
Background of the Invention
Any discussion of the prior art throughout the specification should in no
way be considered as an admission that such prior art is widely known or forms
part of the common general knowledge in the field.
Wood is a staple construction formulation used throughout the world.
However, it is prone to degradation from elements ing the natural
nment, weather , insects, rot and fire. Accordingly, a range of
chemical treatments has been developed to improve the durability and working
lifetime of wooden structures.
To treat and prevent infestations, timber is often impregnated with a
preservative or preservative mixture comprising ide/s and/or or
insecticide/s. The preservative is typically t in a carrier, with the e
being applied to the surface of the timber, for example by dipping, spraying,
brushing or pressure treatment, such that the carrier and preservative are
absorbed in to the timber.
The treatment of timber or timber products with preservative compounds
involves the introduction of stable chemicals into the ar structure of the
timber. This, in turn, protects the timber from hazards such as fungi, insects and
other wood—destroying organisms. Preservative treatments may also include the
introduction of chemicals that improve resistance to degradation by fire.
vative treatment of wood is sometimes carried out at increased
pressure so as to force the liquid preservative solution into the pores of the
wood. A vacuum may be applied prior to the uction of the treatment
solution in order to increase penetration. Irrespective of whether they are
subject to pressure—based application methods, preservative solutions are
generally of relatively low viscosity in order to facilitate the penetration of the
treatment solution.
Increased penetration of the vative solution can also be achieved
by diffusion, which despite involving less expensive ent, requires a
longer time period and greater levels of stock holding. Diffusion time is also
influenced by the initial wood moisture content, especially when dealing with
aqueous carriers.
Table 1
Minimum preservative retention in the penetration zone: Hazard Class 3 (H3)
Light c solvent preservatives/waterborne
Preservative Minimum Retention (TAE, % m/m)
CCA 0.38
Cu + DDAC Softwood 0.35; Hardwood 0.39
Copper azole 0.229
Creosote 8
0.08 (tin, vertically d); 0.16 (tin,
TBTN or TBTO
horizontally exposed)
Propiconazole & Tebuconazole Softwood 0.06 (total azole)
Copper naphthenate 0.1 (copper)
Permethrin 0.02; Cypermethrin 0.03;
Synthetic pyrethroids Deltamethrin 0.002; Bifenthrin 0.0047
In Australia, the ent of timber is ed by the Australian
standard “AS 1604—2010”. Hazard Class H3 is defined as being for protection
against “moderate fungal decay and e hazard for decking, fascia, cladding,
window reveals, and or structure timber”. Decking is one such example.
The timber is exposed to the weather or not fully protected. It is clear from the
2012/001556
ground and the area is well d and ventilated. H3 treatment is designed to
prevent attack by insects, including termites, and decay.
Hazard Class H4 defines e decay, borers and termites, fence posts,
greenhouses, pergolas (in ground and landscaping timbers)”. The timber is in
contact with the ground or is continually damp so there is a severe decay hazard.
The treatment stops attack by s, including es, and severe decay.
“Penetration” is defined under the H3/H4 Standards as: “All preservative—
treated wood shall show evidence of distribution of the preservative in the
penetration zone in accordance with the following ements: (a) If the
species of timber used is of natural durability class 1 or 2, the preservative shall
penetrate all the sapwood. vative penetration of the heartwood is not
required; (b) If the species of timber used is of natural durability class 3 or 4, the
preservative shall penetrate all of the sapwood and, in addition one of the
following requirements shall apply; (bi) Where the lesser cross—sectional
dimension is greater than 35 mm, the penetration shall be not less than 8 mm
from any surface. Where the lesser cross—sectional dimension is equal or less
than 35 mm, the penetration shall be not less than 5 mm from any surface; and
(bii) Unpenetrated heartwood shall be permitted, provided that it comprises less
than 20% of the cross—section of the piece and does not extend more than
halfway through the piece from one surface to the opposite surface and does not
exceed half the dimension of the side in the cross—section on which it occurs”.
As mentioned above, a carrier must be used in order to facilitate
penetration of the preservative into the . As shown in the lian
Standards, the carriers presently available can be characterised broadly as
“water—bome” or “solvent—bome” systems.
A carrier must be capable of providing sufficient penetration of the
preservative into the wood, thereby to provide an effective barrier against
ation. Other considerations in the choice of carrier include the desired rate
of penetration, cost, environmental, health and safety considerations. A carrier
may provide for a “complete penetration” formulation, or for an “envelope
penetration” formulation in which a defined migration of one or more
vatives into the wood is achieved.
The preservatives commonly used in timber treatment can be
terised according to the carrier vehicle used to carry preservatives into the
timber, and by the active chemicals protecting against the s hazards. The
final step in the preservation process is often that a solvent, if used in or as the
carrier, must then be removed before the timber is made available for use.
Light c solvent—borne preservatives ) comprise a light
organic solvent, typically white spirits, to carry the preservative into the timber.
The solvent is drawn out in the final stages of treatment, with the preservative
remaining within the wood. Such preservatives are typically fungicides, having
copper, tin, zinc, azoles and pentachlorophenols (PCPs) as major toxicants.
Synthetic pyrethroids such as permethrin may be incorporated within the
preservative composition if an insect hazard is also t. One principal
advantage of LOSP treatment is that the treated timber does not swell, making
such treatment quite suitable for “finished” items such as mouldings and
joinery. The ty of LOSPs used in wood treatment also contain
insecticides and/or waxes so as to give the surface water repellent properties.
However, odour and exposure to VOCs (volatile c compounds) are
significant environmental/occupational health and safety issues. Accordingly,
whilst effective, LOSP treatments are ng singly undesirable.
However, the LOSP procedure does have an advantage in that it does not add
moisture back into the timber. Excessive re uptake can affect the
dimensions of timber.
Water—based systems lly require a significant uptake of any water—
based treatment composition in order to provide the required penetration
through to the core of the timber. This results in an increase of the moisture
t of the timber, which in turn affects the dimensional stability of the
timber and may also require that the timber be redried prior to use.
The use of biocidal metal ions in wood preservation is well known.
There are also many compounds containing an azole group which are known to
possess biocidal ties. Indeed, it is known from WO 93/02557 that a metal
compound and a fungicidal compound containing a triazole group may exhibit
synergistic fungicidal ty. This document bes preservative
compositions comprising a biocidal metal compound, most preferably in the
form of copper; and a fungicidal triazole compound. 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 ed. However, preferably the ratio by weight of metal
to triazole compound is less than 1000:l, e.g., no greater than 750:1. More
preferably, the weight ratio of metal: triazole compound should be between
750:1 and 1:1, particularly preferably between 500:1 and 2:1; most preferably
the ratio is between 50:1 and 5:1, especially about 25:1. Most preferably, the
metal is copper and the triazole is tebuconazole, or a mixture of les
nazole and propiconazole.
The concentration required for preservative treatment depends on the
ratio of metal to triazole nd 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 es present. In general, the level of metal
required will be in the range 0.01-5% and the level of le will be in the
range 25 ppm to 1.0%. The preferred range for waterborne treatments is to have
a metal concentration of 0. l—5% and a triazole level of 50 ppm to 5000 ppm.
It will thereby be iated that WO 93/02557 describes generic “high
metal/low organic compound” biocidal formulations. These formulations can
be used in waterborne pressure treatment processes. Commercially, it is a
preservative mixture that contains copper, boric acid and tebuconazole. Such a
ation was introduced in Australia as a replacement for copper—chrome—
arsenate (“CCA”) for treatments having external applications.
W0 95/14558 teaches that although “high metal/low azole”
formulations are exemplified and indeed “preferred”, the c “low
metal/high azole” proportions are nonetheless optional — at least within a w/w
ratio of about 1:25.
It will be understood that the metal compound may be present in a form
such that metal ions are free in solution, may form part of a complex, or may be
micronised. Similarly, the le compound may be free in solution or may be
present in the form of a salt or a complex. For e, the le compound
could be present in the form of a complex with part of the biocidal metal ion.
The metal compound may be a compound of any biocidally—active metal
including copper, aluminium, manganese, iron, cobalt, nickel, zinc, gold, 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 above.
The most preferred metal is copper, particularly as the Cu(II) ion. The metal
may be solubilised in the aqueous carrier or micronised.
In cases where zinc is used instead of copper, it is know that typically
three times as much zinc (cf. copper) is required for control of decay organisms.
Accordingly, the optimum ratio in the case of zinc may be l:l total zinczazole.
nic boron compounds have been used to protect the sapwood of
susceptible hardwoods against lyctid or “powder post” borers. Such treatment
ts of g freshly—sawn unseasoned timber in solutions of boron salts.
The salts diffuse through the timber, thereby ng it, and after such treatment, the
timber is allowed to dry. However, boron salts are readily soluble in aqueous
solutions and can be leached relatively easily from the wood once treated. This
largely restricts boron-treated timber to interior uses such as flooring or joinery,
wherein it is protected from the external environment.
It is an object of the present invention to overcome or ameliorate at least one
of the disadvantages of the prior art, or to provide a useful alternative. The t
invention thereby seeks to provide a wood treatment ation that meets the
industry-specific standards of active ingredient retention and penetration. The
treated wood should preferably have good dimensional stability. The ages in
obtaining an rially-effective “low high preservative” formulation may
be both economic and environmental.
The present invention result in effective penetration for a variety of different
biocidally-effective active agents having an antifungal or other biocidal role having
singly r exposure times to yield a moisture content of the treated timber
of less than 25% and preferably less than 20% w/w. The present invention
recognises many different actives can be d into the wood without the need for
resins and/or curing agents in the aqueous carrier. The present invention recognises
the option of including a wetting agent and/or surfactant. Preferred actives include
fungicides, mouldicides, insecticides and termiticides.
Despite the many and varied techniques for the treatment of wood, there
remains a need to satisfy the “dry after” requirement for treated timber, having less
than 15% moisture content, whilst achieving the required penetration of active
compounds into the wood.
Unless the context y requires otherwise, hout the description and
the claims, the words “comprise”, “comprising”, and the like are to be construed in
an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in
the sense of ding, but not limited to”.
Although the invention will be described with reference to specific es
it will be appreciated by those skilled in the art that the invention may be embodied
in many other forms.
Summary of the Invention
According to a first aspect of the present invention there is provided a
preservative formulation for use in ng wood or other cellulosic materials, said
ation comprising:
at least one azole fungicide;
at least one metal compound having a biocidal effect; and
an aqueous carrier,
wherein the ratio of said at least one metal to said at least one azole fungicide
is between 1:3 and about 1:5 w/w.
Most preferably, the ratio of said at least one metal to said at least one
preservative is about 1:3.1 w/w.
In a preferred ment, the preservative ation achieves
substantially full sapwood penetration in compliance with the lian Standard
In a preferred embodiment, the metal compound is a compound of a metal
selected from the group ting of: copper, aluminium, manganese, iron, cobalt,
nickel, zinc, silver, cadmium, tin, antimony, mercury, lead and bismuth. ably,
the metal compound is a compound of copper or zinc. More preferably, the copper
compound is a copper(II) compound.
In a preferred embodiment, the copper or zinc compound is selected from the
group consisting of: copper or zinc naphthenate, copper or zinc octanoate (2-
ethylhexanoate), copper or zinc abietate, copper or zinc tallate and copper or zinc
oxine or a copper or zinc soap.
The organic compound is a fungicide; the Applicant has observed a synergy
between metals and fungicides. Alternatively, the one or more organic compounds
are selected from the group consisting of: insecticides, termiticides, fungicides,
mouldicides, or the like, and mixtures thereof. ably the preservative is
selected from the group consisting of: synthetic pyrethroids (such as allethrin,
bifenthrin, cypermethrin, cyphenothrin, deltamethrin, permethrin, prallethrin,
resmethrin, sumithrin, tetramethrin, ethrin, transfluthrin, imiprothrin), azoles,
triazoles, copper azole-based compounds, organic biocides, thiachloprid,
imidachloprid or the like, and mixtures f, triazoles, copper azole-based
compounds, organic biocides, iodopropynylbuthylcarbamate , organic tin
compounds such as tributyltin naphthenate (TBTN), organic copper compounds
such as copper 8 quinolinolate, copper naphthenate, organic zinc compounds,
quaternary ammonium compounds, tertiary ammonium compounds, azolones,
boron nds, 3-benzothienyl-5,6-dihydro-1,4,2-oxathiazineoxide
(Bethogard®) and bis-(N-cyclohexyldiazenuimdioxy) copper DO”)”, and
mixtures thereof.
O R3
R2 CH2 CH2 R1
CH2 O CH2
N N
N N
N (I) N (II)
In a preferred embodiment, the preservative is a triazole compound of
formulae (I) or (II), above, wherein R1 represents a branched or straight chain C1-
5alkyl group; R2 represents a phenyl group optionally substituted by one or more
substituents ed from halogen, C1-3alkyl, C1-3alkoxy, phenyl and nitro; R3 is as
defined for R2; and R4 represents a hydrogen atom or a branched or straight chain
C1-5alkyl. Preferably, the triazole compound of formula (I) is nazole (-[2-(4-
chlorophenyl)ethyl]--(l,1-dimethylethyl)-1H-1,2,4-triazole-l-ethanol) or
hexaconazole (α-butyl-α-(2,4-dichlorophenyl)-1H-1,2,4-triazoleethanol). Most
ably, the triazole nd of formula (I) is tebuconazole.
In a preferred embodiment, the triazole compound of formula (II) is
propiconazole (1-[[2-(2,4-dichlorophenyl)propyl-1,3-dioxolanyl]methyl]-lH-
1,2,4-triazole); azaconazole (l-[[2,4-dichlorophenyl)-1,3-dioxolanyl]methyl]-lH-
l,2,4-triazole); or difenaconazole (1-[2-[2-chloro(4-chlorophenoxy)phenyl]
methyl-1,3-dioxolanylmethyl]-1H-1,2,4-triazole).
In a preferred embodiment, the preservative is a triazole nd ed
from the group consisting of: azaconazole, bromuconazole, cyproconazole,
diclobutrazol, difenoconazole, diniconazole, diniconazole-M, epoxiconazole,
etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, azole,
furconazole-cis, hexaconazole, imibenconazole, ipconazole, metconazole,
myclobutanil, penconazole, propiconazole, prothioconazole, quinconazole,
simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole,
uniconazole, and uniconazole-P.
In a particularly preferred ment, the organic compound is
tebuconazole (-[2-(4-chlorophenyl)ethyl]--(l,1-dimethylethyl)-1H-1,2,4-triazolel-ethanol
) and/or propiconazole (1-[[2-(2,4-dichlorophenyl)propyl-1,3-dioxolan-
2-yl]methyl]-lH-1,2,4-triazole).
In a red embodiment, the aqueous carrier is water. Alternatively, the
formulation may further comprise one or more water-miscible compounds selected
from the group consisting of: glycerol, propylene glycol, ethylene glycol and the
like, and mixtures thereof glycols, amine oxides, quaternary ammonium compounds,
glycol , esters, alcohols, s, diols, triols, ketones, carbamates, amides,
sulfoxides, amines, acids (e.g. amino acids), modified cellulosics or the like, or
ations thereof, polymer/resins (e.g. polyvinyl alcohol), PEGs, water
dispersible alkyds, polyesters, proteins, etc.
In a preferred embodiment, the formulation is applicable to engineered wood
composites selected from the group consisting of: plywood, laminated veneer
lumber, glue-laminated lumber am”), cross-laminated lumber, oriented strand
board or I-joists.
In a preferred embodiment, the ation ses below about 10% w/w
preservative (organic compound and metal compound, combined) content;
preferably below about 5%, more preferably below about 2%; and; more preferably
still below about 1% w/w preservative ic compound and metal compound,
combined) t.
In a preferred embodiment, the biocidal metal compound is t in
unmodified or modified (i.e., soluble or solid particulate) form. The soluble or solid
particulate form preferably comprises a chemical modification providing relatively
sed stability against environmental conditions such as heat and/or chemical
degradation. The soluble or solid particulate form may be a microencapsulated form
and/or a micronised form. The formulation may further comprise colour/s, water
ents and/or vents.
Particularly preferred form of the present invention may comprise
tebuconazole and propiconazole (1:1 as the organic compound) in an approximate
3.1:1 w/w ratio with copper; tebuconazole and propiconazole (1:1 as the organic
compound), in an approximate 2.6:1 to 3.0:1 w/w ratio with copper; tebuconazole
and propiconazole (1:1 as the organic compound), in an approximate 3.1:1 to 4.9:1
w/w ratio with copper; and tebuconazole and propiconazole (1:1 as the organic
compound), in an imate 5.0:1 to 10:1 w/w ratio with copper. In a preferred
ment, the copper compound is (II) naphthenate.
According to a second aspect of the present invention there is ed a
method of treating a substrate of wood or other cellulosic formulation which
comprises applying to the substrate a preservative formulation as defined according
to the first aspect of the invention.
Preferably the step of contacting said wood is performed by means selected
from the group consisting of: pressure application, vacuum application, spraying,
dipping, rolling, painting, or any combination f.
According to a third aspect of the present invention there is provided treated
wood, when so-treated by a method defined according to the second aspect of the
invention.
According to a fourth aspect of the invention there is ed a method of
making a ation for treating wood, said method comprising the step of
admixing at least one azole fungicide and at least one metal compound in a ratio of
between about 1:3 and about 1:5 w/w, with an aqueous carrier.
According to a fifth aspect of the invention there is provided a formulation
for treating wood, when made by a method defined according to the fourth aspect of
the invention.
According to a sixth aspect of the t invention there is provided a
method of treating wood, said method comprising the steps of:
contacting said wood with at least one azole fungicide;
contacting said wood at least one metal nd having a biocidal
effect; and
wherein said at least one azole fungicide and said at least one metal
compound are operatively associated with one or more aqueous carriers,
wherein the ratio of said at least one metal to said at least one azole
fungicide is between about 1:3 and about 1:5 w/w.
In a preferred embodiment, the steps of contacting said wood with at least
one organic compound and contacting said wood at least one metal compound are
performed simultaneously such that both said organic compound and said metal
compound are distributed ntially homogeneously throughout said carrier.
In a preferred embodiment, the metal compound is biocidal.
The Inventors have found that compositions according to the present
invention may possess certain advantageous properties. In particular, the metal
nd and the fungicidal compound ning the triazole group (hereinafter,
“the triazole compound”) may exhibit synergistic fungicidal activity.
It will be tood 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 le compound could be present in the form of a
complex with part of the biocidal metal ion.
The compositions according to the invention may be used to treat substrates
such as wood or other cellulosic substrates (such as cotton, hessian, rope and
e). For convenience, the invention will be described hereinafter with
reference to the treatment of wood, but it will be appreciated that the other
formulations may be treated analogously.
The metal compound may include copper, aluminium, manganese, iron,
cobalt, nickel, zinc, gold, silver, cadmium, tin, antimony, y, lead and bismuth
compounds. These may be either used alone or in mixtures. The preferred metals
are copper and zinc used alone, in ation with each other or with one or more
of the metals listed previously. The most red metal is copper, particularly
Cu(II) ion.
The triazole compound may be any compound which contains a triazole
group and which possesses biocidal activity. Preferably, the triazole compound
ns the triazole group (A) (see, below)
Advantageously, the le compound is selected from compounds of
formula (I) wherein R1 represents a branched or ht chain C1_5alkyl group
(e.g., t—butyl) and R2 represents a phenyl group optionally substituted by one or
more substituents selected from n (e.g., chlorine, fluorine or e)
atoms and C1_3alkyl (e.g., ), koxy (e.g., methoxy), phenyl and nitro
groups. A particularly preferred compound of formula (I) is tebuconazole: 0t—
[2—(4—chlorophenyl)ethyl] —0t—(l, l —dimethylethyl) —lH— l ,2,4—triazole—l—ethanol
(i.e., R1 = l; R2 = p—chlorophenyl).
0 R3
CH2 0
l [\i R4 Cng
N \ \
\< \N \T N \< N
NJ(A) NJ
(1) (11)
Alternatively, the triazole compound is advantageously selected from
compounds of formula (11) wherein R3 is as defined for R2 above; and R4
represents a hydrogen atom or a branched or straight chain C1_5alkyl group (e.g.,
n—propyl). Particularly preferred compounds of formula (II) are propiconazole:
l—[[2—(2,4—dichlorophenyl)—4—propyl— l ,3 —dioxolan—2—yl] methyl] —lH— l ,2,4—triazole
(i.e., R3 = o,p—dichlorophenyl; R4 = n—propyl); and azaconazole: l—[[2,4—
dichlorophenyl)—l,3—dioxolan—2—yl]methyl]—lH—l,2,4—triazole (i.e., R3 = o,p—
dichlorophenyl; R4 = H).
The ive compositions may contain more than one le
compound for example, they may contain tebuconazole and propiconazole, or a
mixture of tebuconazole, propiconazole and azaconazole.
The present Inventors have found that the biocidal metal may
advantageously be incorporated into the ition in the form of inorganic
salts of the metal ion, e.g., in the form of the metal carbonate, sulfate, chloride,
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 may exhibit 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 x with, a larger more complex
WO 90995
organic compound which itself possesses biocidal properties. Alternatively, the
metal may be in micronised form.
The m weight ratio of metal ion to triazole compound varies
depending on the particular formulation or product to which the composition is
d and the type of organism against which protection is required.
ably, the ratio by weight of metal to triazole compound is between about
1:1 and about 1:10, most preferably around l:3.l w/w. More preferably still,
the metal is Cu(II) ion and/or Zn(lI) ion, and the le compound is
nazole and/or propiconazole.
The concentration required for preservative treatment of wood s
on the ratio of metal to triazole compound ed, 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 25 ppm to 5%
w/w and the level of triazole will be in the range 25 ppm to 5.0% w/w. The
red range for waterborne treatments is to have a metal concentration of 50
ppm to 5000 ppm and a triazole level of 50 ppm to 5000 ppm, depending upon
the metal to azole ratio desired.
The compositions of the present invention may 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 microemulsions 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 lves biocidal and so they enhance the overall biocidal
activity of the composition. These nds also improve penetration of the
biocidal metal ion and triazole nd into the timber.
The composition in accordance with the invention comprises water as
solvent/carrier. ations can be prepared as concentrates ed to be
diluted at the treatment facility, or the formulations can be prepared in the form
of dilute treatment solutions. Optionally, 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 dilution.
le ations 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 metal ion would be for example, polyphosphoric acids such as
tripolyphosphoric acid, ammonia, water soluble amines and alkanolamines
capable of complexing with biocidal s; arboxylic acids such as
e, glutamic acid, ethylenediaminetetraacetic acid, 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, lactic acid, hydroxybutyric acid, glycollic acid, gluconic acid
and glucoheptonic acid; phosphonic acids such as nitrilotrimethylene
onic acid, ethylenediaminetetra(methylenephosphonic acid),
hydroxyethylidene phonic acid. Where the 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.
Suitable surfactants for triazole compounds include, for example,
cationic, nonionic, anionic, Zwitterionic or eric surfactants.
Suitable formulations can also be prepared, for example, by adding an
emulsified formulation of the le compound to an aqueous solution of a
metal salt, such as copper sulfate or zinc acetate. At certain ratios of metal ion
to azole, the solubility of the azole may be sufficient to se the azole in the
formulation using a le co—solvent.
Alternatively, formulations can be prepared employing only organic
solvents. To prepare such formulations, a biocidal metal salt of a carboxylic
acid (e. g., decanoic or octanoic acid) is ed 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 alcohol, aliphatic or aromatic hydrocarbon, glycol ether,
glycol or ketone.
Concentrated formulations containing organic solvents can be diluted
with water to form an emulsion which can be ised with surfactants if
necessary.
Compositions in accordance with the invention can optionally contain
other additives conventionally employed in timber preservation such as water
ents, colour additives, viscosity modifiers or corrosion inhibitors.
The compositions of the invention may contain other organic
compounds including fungicides, mouldicides, termiticides, insecticides and
bacteriocides. Such organic compounds include ylic acids such as
naphthenic acids and branched 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 a salts; polyhalogenated
phenols such as pentachlorophenol or tribromophenol and their alkali metal or
ammonia salts; quaternary ammonium salts and ry amine salts such as
didecyl dimethyl ammonium chloride, octyl decyl yl ammonium
chloride, dodecyl dimethyl benzyl ammonium de, dodecyl benzyl
trimethyl ammonium chloride, l dimethyl amine acetate, dodecyl
dimethyl amine lactate, dodecyl dimethyl amine salicylate, cyl methyl
amine chloride; isothiazolone derivatives such as 4,5—dichloro—2—(n—octyl)—4—
isothiazolin—3—one or 2—methyl—4—isothiazolin—3—one, yl—4—isothiazolin—3—
one and mixtures of those and other related compounds; sulfamide derivatives
such as N,N—dimethyl—N—phenyl—(N—fluorodichloro—methylthio)—sulfonamide,
N,N—dimethyl—N—tolyl—N—(dichlorofluoro—methylthio)—sulfamide; azoles such as
imidazole; MBT (methylene—bis thiocyanate); IPBC o—2—propanyl—butyl—
carbamate); carbendazim and chlorothalonil; N—nitrosophenylhydroxylamine
and N—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—dichioroethenyl)—2,2—
yl cyclopropanecarboxylate, (3—phenoxyphenyl)methyl—3—(2,2—dichloro—
ethyenyl)—2,2—dimethyl—cyclopropanecarboxylate, cyano—(3—phenoxy—phenyl)—
methyl—2—(4—chlorophenyl)—3—methylbutyrate, and mixtures thereof; organo—
phosphorous, carbamate and organochlorine insecticides such as lindane.
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
silicafluorides.
Particularly preferred compositions in accordance with the invention
comprise copper(II) ion, one or more triazole compounds which may be
tebuconazole and/or onazole, and optionally an alkanolamine, as well as
optionally borate ion and/or a quaternary ammonium nd or a mixture of
quaternary ammonium compounds.
ing to a further form of the present ion there is provided a
method of treating timber or another cellulosic substrate of the type
—l6-
hereinbefore described, which ses applying to the substrate a
composition as defined above.
The skilled person 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, spraying,
deluging, brushing, vacuum impregnation, pressure impregnation and/or any
other applicable method. Other types of substrate may be treated analogously.
Brief Description of the Figures
A preferred embodiment of the invention will now be described with
nce to the accompanying Figures, in which:
Figure l is a plot of m ive retentions (MER) of copper
naphthenate, “A2” = an approximate l:l w/w mixture of tebuconazole and
propiconazole, and the 1:3 w/w combination of total Cu/Az (see, Example 4).
This plot demonstrates a synergy for the formulation tested such that the
preservative effect is beyond that expected for the individual (i.e., additive)
preservatives.
Figure 2 is a plot of the s obtained from a decay trial ing
various timber preservatives against Fomitopsis lilacinogilva (see, Example 6,
below). In Figure, 2, A: Untreated control; B: ZnN, 0.1% m/m (as Zn ;
C: ZnN, 0.2% m/m; D: ZnN, 0.3% m/m; E: Az, 0.06% m/m; F: Az/ZnN (1:1),
0.06/0.06% m/m; and G: Az/ZnN (1 :2), 0.06/0.12% m/m); “AZ” 2 an
approximate l:l w/w mixture of tebuconazole and propiconazole. ZnN = zinc
naphthenate, where Az/ZnN ratio given as azole to zinc metal.
Figure 3 is a plot of the s obtained from a decay trial involving
s timber preservatives t Coniophora olivacea (see, Example 6,
below). In Figure 3, A: Untreated control; B: ZnN, 0.1% m/m (as Zn metal); C:
ZnN, 0.2% m/m; D: ZnN, 0.3% m/m; E: Az, 0.06% m/m; F: Az/ZnN (1:1),
0.06/0.06% m/m; and G: Az/ZnN (1:2), 0.06/0.12% m/m ); “Az” = an
approximate l:l w/w e of tebuconazole and propiconazole. ZnN = zinc
naphthenate, where Az/ZnN ratio given as azole to zinc metal.
Example 1
A ready to use solution; metal to azole ratio 1:4, prepared combining the
various raw materials in an appropriate solvent or mixture of solvents.
Com n onent
Tebuconazole
Pro o iconazole
Permethrin
Co o oer (as co o oer naohthenate)
Co-solvent
Example 2
A ready to use solution; metal to azole ratio 1:3
Tebuconazole
Propiconazole
Permethrin
Copper (as copper naphthenate)
Co-solvent
Example 3
A ready to use solution; metal to azole ratio 1:2.6
Component % w/v
nazole 0.45
Propiconazole 0.45
Permethrin 0.32
Copper (as copper naphthenate) 0.35
0-75
1.00
1.00
Balance
It will be appreciated that the illustrated ready—to—use solvent—based
formulations used in the treatment of wood achieves the required ation of
the wood with s that are stable in these formulations. It will be further
appreciated that the inventive ation substantially mes or
ameliorates many of the disadvantages inherent in the art.
Example 4
The synergy between the azoles tebuconazole/propiconazole and copper,
is demonstrated by way of the results of field trials in Hawaii, where the decay
hazard is known to be very severe. Radiata pine sapwood panels (200 x 70 x 25
—18-
mm) were treated with various preservatives and exposed on racks at 45°, using
a method generally described as the “flat panel test” (Reference: Australasian
Wood vation Committee, Protocols for Assessment of Wood
Preservatives, March 2007 Revision, . Untreated controls, solvent—
treated controls and panels treated with reference preservatives (e.g., CCA)
were also included in this field test. The treatments of interest are ised
in Table 2, below.
Table 2
Results of Hawaiian Field Trials
Retention (% m/m) Cu/Azole ratio
Copper naphthenate
0.11 n/a Heav1ly decayed.
(CuN)
Tebuconazole/ 0.04, 0.02 (total Lowest retention
oro oiconazole ( 1: 1) azole) rated 7
nazole/ 0-03/0-01 (total
Lowest retention
propiconazole (1: 1), C11) 13
rated 7
CuN 0006/0002
Note: All formulations contained the insecticide permethrin at a
concentration sufficient to deliver approximately 0.02% m/m active in the
treated panels. After approximately three years outdoor exposure in Hawaii, the
specimens were rated using a typical 0 to 10 rating system (e.g., Evaluation
rd E25, AWPA Book of Standards, 2010, American Wood Protection
Association, gham, Alabama), where 7 is the lowest score where the
specimen is deemed still to be serviceable. A score of 7 indicates that 10—30%
of the cross—section has been d.
Several observations became apparent upon inspection of the specimens
after three years exposure. Firstly copper naphthenate (CuN) alone performs
very poorly at this field test site. Copper naphthenate d specimens were
heavily decayed, even at a copper ion of 0.11 % m/m Cu. The minimum
effective retention of CuN to prevent decay was, at the three year inspection,
>0.11 % m/m. The minimum effective retention of azoles tebuconazole and
propiconazole, to prevent decay was 0.02% m/m (total azole). If the anti—fungal
effectiveness of the combination of azole and copper was additive, then it would
be expected that the minimum effective retention would fall approximately on
the al line shown graphically in Figure 3, that ts the minimum
effective retention of tebuconazole/propiconazole (1:1) on the vertical axis and
the minimum effective retention of copper (as CuN) on the horizontal axis.
However the combination of copper naphthenate and
tebuconazole/propiconazole at a 1:3 ratio (total copper metal to azole) gave
surprisingly superior s, even at low retentions. The minimum effective
retention of the copper naphthenate and tebuconazole/propiconazole at a 1:3
ratio (total copper metal to azole) was approximately 0.006 % m/m total azole
(and 0.002 % m/m copper). The synergy between this combination of actives is
readily apparent. Synergy is also apparent for the approximate 5:3 w/w
combination of actives.
Example 5
“Hi Azole, Lo Copper” — In a tory bioassay, the benefit of
combining relatively low levels of metal ions with azoles was demonstrated.
The bioassay was carried out in accordance with recognised methods (see,
Protocols for the ment ofWood vatives, lasian Wood
Preservation Committee, March 2007 Revision, Ensis, Clayton).
Radiata pine sapwood (20 x 20 x 10 mm) specimens were d with
various preservative formulations. After drying the specimens were saturated
with water and leached in a shaking water—bath at 35 0C for seven days, with
daily changes of water. After leaching, the specimens were vacuum oven dried,
before being sterilised in readiness for the fungal bioassay. The bioassay was
carried out in accordance with standard tory techniques, by an
independent research provider.
Mass loss was used to determine the effectiveness of a preservative
treatment. In general, the more effective the preservative treatment the lower the
mass loss. Decay is deemed to have been prevented if the mass loss is less than
Some basidiomycete decay fungi are more tolerant to azoles that others.
In this bioassay, a selection of brown rot fungi were chosen. One of those
, Coniophora olivacea, is relatively ant to azoles. The l:l
combination of tebuconazole and onazole at a ion of 0.03% m/m
(total azole) was found to be decayed by C. olivacea, with a mean mass loss of
8.6% recorded.
However, the incorporation of copper, in the form of copper
naphthenate, at an amount to give a total azole to copper ratio of 4:1, reduced
the mass loss to 4.9%. The total azole retention was 0.03% m/m. Although
decay was not prevented entirely, it was reduced significantly.
A 5:1 azole to copper ratio (total azole retention 2 0.03% m/m) also
produced a lower mean mass loss than for azoles alone. The untreated controls
were heavily decayed, with a mass loss of 61%.
Example 6
In a laboratory bioassay, the t of combining relatively low levels
of metal ions with azoles was demonstrated. The bioassay was carried out in
accordance with recognised methods (see, Protocols for the Assessment of
Wood Preservatives, Australasian Wood Preservation Committee, March 2007
Revision, Ensis, Clayton).
Radiata pine d (20 x 20 x 10 mm) specimens were treated with
various preservative formulations. After drying the specimens were saturated
with water and leached in a shaking water—bath at 35 0C for seven days, with
daily changes of water. After leaching, the specimens were vacuum oven dried,
before being sterilised in ess for the fungal bioassay. The bioassay was
carried out in accordance with standard laboratory techniques, by an
independent research provider.
Mass loss was used to determine the effectiveness of a preservative
treatment. Generally, the more effective the preservative treatment the lower the
mass loss. Decay is deemed to have been prevented if the mass loss is less than
Some basidiomycete decay fungi are more tolerant to azoles that others.
In this bioassay, a selection of brown rot fungi were chosen. One of those
chosen, Coniophora olivacea, is relatively ant to azoles. The l:l
combination of tebuconazole and propiconazole at a retention of 0.06% m/m
(total azole) was found to be decayed by C. olivacea, with a mean mass loss of
0% recorded.
However, the incorporation of zinc, in the form of zinc naphthenate, at
an amount to give a total azole to zinc ratio of 1:2, also ed 0% mass loss.
The total azole retention was 0.06% m/m. As used in this example, the
expression “azoles” refers to a 1:1 mixture of tebuconazole and onazole.
A l:l azole to zinc ratio (total azole retention 0.06% m/m) also ed a
lower mean mass loss than for azoles alone (0.4%) The untreated ls were
heavily decayed, with a mass loss of 61.2%.
Fomitopsis nogilva is a wood—rotting bracket fungus common in
many places of Gondwanaland origin. It is found on logs, stumps, and some
outdoor wooden uctions. It forms fans, s, pads or crusts, to 100
_ 21 _
mm across, is hairy, crusted above, zoned pinkish and brownish. The results
against Fomitopsis lilacinogilva were less cular. Azole/zinc 1:2 gave
% mass loss; 1:1 gave 15.9% mass loss; and azoles alone gave 19.9% mass
loss versus the control (71.5% mass loss).
Table 3
Metal—Azole formulations against F. nogilva and C. ea
' C. olivacea
Mass Loss (%)
. 61-2
II ZnN, 0.1% m/m . 50.5
ZnN, 0.2% m/m . 42.8
II ZnN, 0.3% m/m . 28.4
AZ, 0.06% m/m . 0
F Az/ZnN (1:1), 0.06/0.06% m/m 15.9 0.4
G Az/ZnN (1:2), 0.06/0.12% m/m 10 0
“AZ” = tebuconazole/propiconazole (l :1)
The above results hint at a potential synergy between the azoles
tebuconazole/propiconazole and zinc. As can be seen from the above data, zinc
naphthenate, used alone, has a weak vative effect (i.e., at 0.3% m/m,
53.5% against F. nogilva and 28.4% against C. olivacea). However, when
just 20% of this retention (i.e., 0.06% m/m) is used in a 1:2 ratio with a
combination with azoles (i.e., a 1:1 mixture of tebuconazole and propiconazole
at 0.12% m/m total azoles), the decay falls to 10% for F. lilacinogilva; this
appears to be more than merely additive — and suggests that some degree of
fungicide synergy may be operative.
Example 7
A ready to use water—based solution; metal to azoles ratio 1:10, prepared
combining the various raw materials in an appropriate solvent or mixture of
solvents.
WO 90995
_ 22 _
Example 8
A ready to use based emulsion; metal to azoles ratio 1:1, prepared
combining the various raw als in an appropriate solvent or mixture of
solvents.
Com n onent
Tebuconazole
Pro o iconazole
Permethrin
Emulsifier
Co-solvent
Co 0061‘ (as co o oer ethanolamine)
Example 9
A ready to use solvent—based solution, metal to azole ratio 2:1, prepared
by combining the various raw materials in an appropriate solvent or mixture of
solvents.
Comment —
Tebuconazole —
onazole —
Permethrin —
Zinc (as zinc naphthenate) —
Co-solvent —
Wax —
Example 10
A ready to use solvent—based solution, metal to azole ratio 5:1, prepared
by combining the various raw materials in an riate solvent or mixture of
solvents.
Com n onent
Tebuconazole
Propiconazole
Permethrin
Zinc (as zinc naphthenate)
Co-solvent
White spirit
Although the ion has been described with reference to specific
es it will be appreciated by those skilled in the art that the invention may
be embodied in many other forms.
nce throughout the specification and claims to ranges, e.g., “the
ratio of said at least one metal to said at least one organic compound is between
about 5:1 and about 1:10 w/w” should be construed as encompassing the quoted
limits (plus a reasonable tolerance appropriate to the art) — and all ratios in
between.
Reference throughout this specification to “one embodiment” or “an
embodiment” means that a particular feature, structure or characteristic
described in connection with the embodiment is included in at least one
embodiment of the present ion. Thus, the phrases “in one embodiment”
or “in an embodiment” throughout this specification are not necessarily all
referring to the same embodiment, but may. Furthermore, the ular
features, structures or characteristics may be combined in any suitable manner,
as would be apparent to one of ordinary skill in the art from this disclosure.
In the description provided herein, numerous specific details are set
forth. However, it is understood that embodiments of the invention may be
practiced without these specific details. Thus, while there has been described
what are ed to be the preferred embodiments of the invention, those
skilled in the art will recognise that other and further cations may be
made thereto without departing from the spirit of the invention, and it is
intended to claim all such changes and cations as fall within the scope of
the ion. For example, any formulas given above are merely representative
of procedures that may be used.
Claims (30)
1. A preservative formulation for use in ng wood or other cellulosic materials, said formulation comprising: 5 at least one azole fungicide; at least one metal compound having a biocidal ; and an aqueous carrier, wherein the ratio of said at least one metal to said at least one azole fungicide is between 1:3 and about 1:5 w/w.
2. A formulation according to claim 1, wherein the ratio of said at least one metal to said at least one azole fungicide is about 1:3.1 w/w.
3. A formulation according to any one of the preceding claims, wherein said 15 metal compound is a compound of a metal selected from the group consisting of: copper, aluminium, manganese, iron, cobalt, nickel, zinc, silver, cadmium, tin, antimony, mercury, lead and bismuth.
4. A formulation according to any one of the preceding claims, wherein said 20 metal compound is a compound of copper or zinc.
5. A formulation ing to claim 4, wherein said copper compound is a copper(II) compound. 25
6. A formulation according to claim 4, wherein said copper or zinc compound is selected from the group consisting of: naphthenate, octanoate (2- ethylhexanoate), abietate, rosin, tallate, oxine or a copper or zinc soap.
7. A formulation according to claim 1, n said azole ide is a 30 triazole compound of formulae (I) or (II): O R3 R2 CH2 CH2 R1 R4 O CH2 N N N N N (I) N (II) wherein R1 ents a branched or straight chain C1-5alkyl group; R2 represents a phenyl group optionally substituted by one or more 5 substituents selected from halogen, C1-3alkyl, C1-3alkoxy, phenyl and nitro; R3 is as defined for R2; and R4 represents a hydrogen atom or a branched or straight chain C1-5alkyl.
8. A formulation according to claim 7, wherein said triazole nd of 10 formula (I) is tebuconazole (-[2-(4-chlorophenyl)ethyl]--(l,1- dimethylethyl)-1H-1,2,4-triazole-l-ethanol) or hexaconazole (α-butyl-α- (2,4-dichlorophenyl)-1H-1,2,4-triazoleethanol).
9. A formulation according to claim 8, n said triazole compound of 15 formula (I) is tebuconazole.
10. A formulation according to claim 7, wherein said triazole compound of formula (II) is propiconazole -(2,4-dichlorophenyl)propyl-1,3- anyl]methyl]-lH-1,2,4-triazole); azole (l-[[2,4-dichloro- 20 phenyl)-1,3-dioxolanyl]methyl]-lH-l,2,4-triazole); or difenaconazole (1- [2-[2-chloro(4-chlorophenoxy)phenyl]methyl-1,3-dioxolan ylmethyl]-1H-1,2,4-triazole).
11. A formulation according to claim 7, wherein said azole fungicide is a 25 triazole compound selected from the group consisting of: azaconazole, bromuconazole, cyproconazole, diclobutrazol, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, afol, furconazole, furconazole-cis, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, quinconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, and azole-P.
12. A formulation according to any one of the preceding claims, n said azole fungicide is tebuconazole (4-chlorophenyl)ethyl]--(l,1- dimethylethyl)-1H-1,2,4-triazole-l-ethanol) and/or propiconazole (1-[[2- ichlorophenyl)propyl-1,3-dioxolanyl]methyl]-lH-1,2,4-triazole).
13. A formulation ing to any one of the preceding claims, wherein said aqueous carrier is water.
14. A formulation according to any one of the preceding claims, wherein said
15 formulation is able to hardwood and/or softwood species and/or engineered wood composites selected from the group consisting of: plywood, laminated veneer lumber, glue-laminated lumber (“glulam”), cross-laminated lumber, oriented strand board or I-joists. 20 15. A formulation according to any one of the preceding claims, sing below about 10% w/w preservative (azole fungicide and metal, combined) content.
16. A formulation according to any one of the preceding , comprising 25 below about 5% w/w preservative (azole fungicide and metal, combined) content.
17. A formulation according to any one of the preceding claims, comprising below about 2% w/w preservative (azole fungicide and metal, combined) 30 content.
18. A formulation according to any one of the ing claims, comprising below about 1% w/w vative (azole fungicide and metal, combined) content. 5
19. A ation according to any one of the preceding claims, wherein said metal compound is present in soluble or solid particulate form.
20. A ation according to claim 19, n said soluble or solid particulate form comprises a chemical modification providing relatively 10 increased stability against environmental ions such as heat and/or chemical degradation.
21. A formulation according to claim 19 or claim 20, wherein said solid particulate form is a microencapsulated form and/or a micronised form.
22. A formulation according to any one of the preceding claims, further comprising mouldicide/s, colour/s, water repellent/s and/or co-solvent/s.
23. A formulation according to any one of the preceding claims, wherein the 20 biocidal metal compound and the azole fungicide have a synergistic preservative effect.
24. A method of treating a substrate of wood or other cellulosic formulation which comprises applying to the substrate a preservative formulation as 25 defined ing to any one of the preceding claims.
25. A method according to claim 24, wherein said step of contacting said wood is performed by means selected from the group ting of: pressure and vacuum application, spraying, dipping, g, painting, or any 30 combination thereof.
26. Treated wood, when so-treated by a method defined according to claim 24 or claim 25.
27. A method of making a ation for treating wood, said method comprising the step of admixing at least one azole fungicide and at least one metal compound having a biocidal effect in a ratio of between about 5 1:3 and about 1:5 w/w, with an aqueous carrier.
28. A formulation for treating wood, when made by a method defined according to claim 27. 10
29. A method of ng wood, said method comprising the steps of: contacting said wood with at least one azole fungicide; contacting said wood at least one metal compound having a biocidal effect; and wherein said at least one azole fungicide and said at least one metal 15 compound are operatively associated with one or more aqueous carriers, wherein the ratio of said at least one metal to said at least one azole fungicide is between about 1:3 and about 1:5 w/w.
30. A method according to claim 29, n the steps of contacting said wood 20 with at least one azole fungicide and contacting said wood at least one metal compound are performed simultaneously such that both said azole fungicide and said metal compound are distributed substantially neously throughout said aqueous carrier. Dated this 2nd day of November 2017 on IP Attorneys for: Arch Wood Protection Pty Ltd
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2011905439 | 2011-12-23 | ||
AU2011905439A AU2011905439A0 (en) | 2011-12-23 | A wood preservative | |
NZ62725612 | 2012-12-19 |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ724922A NZ724922A (en) | 2018-04-27 |
NZ724922B2 true NZ724922B2 (en) | 2018-07-31 |
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