US20070224135A1 - Stable aqueous suspension concentrate for delivery of UV-labile water-insoluble biocides - Google Patents
Stable aqueous suspension concentrate for delivery of UV-labile water-insoluble biocides Download PDFInfo
- Publication number
- US20070224135A1 US20070224135A1 US11/388,553 US38855306A US2007224135A1 US 20070224135 A1 US20070224135 A1 US 20070224135A1 US 38855306 A US38855306 A US 38855306A US 2007224135 A1 US2007224135 A1 US 2007224135A1
- Authority
- US
- United States
- Prior art keywords
- stable
- suspension concentrate
- aqueous suspension
- dispersant
- concentrate according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000012141 concentrate Substances 0.000 title claims abstract description 41
- 239000007900 aqueous suspension Substances 0.000 title claims abstract description 30
- 239000003139 biocide Substances 0.000 title claims abstract description 21
- 239000002270 dispersing agent Substances 0.000 claims abstract description 47
- 239000007787 solid Substances 0.000 claims abstract description 30
- 230000003115 biocidal effect Effects 0.000 claims abstract description 19
- 125000000129 anionic group Chemical group 0.000 claims abstract description 14
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- -1 heterocyclic vinyl lactam Chemical class 0.000 claims abstract description 14
- 239000006096 absorbing agent Substances 0.000 claims abstract description 8
- 229920001519 homopolymer Polymers 0.000 claims abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 6
- 230000005855 radiation Effects 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 45
- YFLDZPUXCOSOGU-UHFFFAOYSA-N 1-iodoprop-2-ynyl n-butylcarbamate Chemical group CCCCNC(=O)OC(I)C#C YFLDZPUXCOSOGU-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000004546 suspension concentrate Substances 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003973 paint Substances 0.000 claims description 11
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical group C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 claims description 9
- 238000004383 yellowing Methods 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 230000015556 catabolic process Effects 0.000 claims description 8
- 238000006731 degradation reaction Methods 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- 239000011976 maleic acid Substances 0.000 claims description 5
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 5
- 239000003755 preservative agent Substances 0.000 claims description 5
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
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- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical compound O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000000855 fungicidal effect Effects 0.000 claims description 3
- 239000000417 fungicide Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
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- 239000004711 α-olefin Substances 0.000 claims description 3
- HHEHWCIYDICHCG-ODZAUARKSA-N (z)-but-2-enedioic acid;methoxyethene Chemical class COC=C.OC(=O)\C=C/C(O)=O HHEHWCIYDICHCG-ODZAUARKSA-N 0.000 claims description 2
- BHFLSZOGGDDWQM-UHFFFAOYSA-N 1h-benzimidazole;carbamic acid Chemical compound NC(O)=O.C1=CC=C2NC=NC2=C1 BHFLSZOGGDDWQM-UHFFFAOYSA-N 0.000 claims description 2
- 241000726103 Atta Species 0.000 claims description 2
- 239000005909 Kieselgur Substances 0.000 claims description 2
- 229920001732 Lignosulfonate Polymers 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 150000002790 naphthalenes Chemical class 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 235000021286 stilbenes Nutrition 0.000 claims description 2
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims 1
- 235000008504 concentrate Nutrition 0.000 description 22
- 238000009472 formulation Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 8
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- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 7
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- 239000006185 dispersion Substances 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 5
- 150000003951 lactams Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000003826 tablet Substances 0.000 description 5
- 239000005822 Propiconazole Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- STJLVHWMYQXCPB-UHFFFAOYSA-N propiconazole Chemical compound O1C(CCC)COC1(C=1C(=CC(Cl)=CC=1)Cl)CN1N=CN=C1 STJLVHWMYQXCPB-UHFFFAOYSA-N 0.000 description 4
- 239000008247 solid mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000002054 inoculum Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 239000004562 water dispersible granule Substances 0.000 description 3
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- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical class CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 2
- MXRGSJAOLKBZLU-UHFFFAOYSA-N 3-ethenylazepan-2-one Chemical compound C=CC1CCCCNC1=O MXRGSJAOLKBZLU-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- 230000002538 fungal effect Effects 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 2
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- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
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- TUBQDCKAWGHZPF-UHFFFAOYSA-N 1,3-benzothiazol-2-ylsulfanylmethyl thiocyanate Chemical compound C1=CC=C2SC(SCSC#N)=NC2=C1 TUBQDCKAWGHZPF-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- YTOPFCCWCSOHFV-UHFFFAOYSA-N 2,6-dimethyl-4-tridecylmorpholine Chemical compound CCCCCCCCCCCCCN1CC(C)OC(C)C1 YTOPFCCWCSOHFV-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZSDGHWLLLGYAJV-AHEHSYJASA-N 2-[(E)-[(E)-3-[1-(2-nitrophenyl)pyrrol-2-yl]prop-2-enylidene]amino]guanidine Chemical compound NC(N)=N\N=C\C=C\C1=CC=CN1C1=CC=CC=C1[N+]([O-])=O ZSDGHWLLLGYAJV-AHEHSYJASA-N 0.000 description 1
- BZGLBXYQOMFXAU-UHFFFAOYSA-N 3-(2-methylpiperidin-1-yl)propyl 3,4-dichlorobenzoate Chemical compound CC1CCCCN1CCCOC(=O)C1=CC=C(Cl)C(Cl)=C1 BZGLBXYQOMFXAU-UHFFFAOYSA-N 0.000 description 1
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 1
- SBUKOHLFHYSZNG-UHFFFAOYSA-N 4-dodecyl-2,6-dimethylmorpholine Chemical compound CCCCCCCCCCCCN1CC(C)OC(C)C1 SBUKOHLFHYSZNG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000228245 Aspergillus niger Species 0.000 description 1
- 241000194108 Bacillus licheniformis Species 0.000 description 1
- 241000194107 Bacillus megaterium Species 0.000 description 1
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- 239000005747 Chlorothalonil Substances 0.000 description 1
- 241000588697 Enterobacter cloacae Species 0.000 description 1
- 239000005789 Folpet Substances 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- QTDRLOKFLJJHTG-UHFFFAOYSA-N Furmecyclox Chemical compound C1=C(C)OC(C)=C1C(=O)N(OC)C1CCCCC1 QTDRLOKFLJJHTG-UHFFFAOYSA-N 0.000 description 1
- WPPOGHDFAVQKLN-UHFFFAOYSA-N N-Octyl-2-pyrrolidone Chemical compound CCCCCCCCN1CCCC1=O WPPOGHDFAVQKLN-UHFFFAOYSA-N 0.000 description 1
- 229920003071 Polyclar® Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 241001136494 Talaromyces funiculosus Species 0.000 description 1
- 239000005839 Tebuconazole Substances 0.000 description 1
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- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- AHGNXJYQZLZKFZ-UHFFFAOYSA-N benzimidazol-1-yl carbamate Chemical compound C1=CC=C2N(OC(=O)N)C=NC2=C1 AHGNXJYQZLZKFZ-UHFFFAOYSA-N 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 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
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- 239000008367 deionised water Substances 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FYUWIEKAVLOHSE-UHFFFAOYSA-N ethenyl acetate;1-ethenylpyrrolidin-2-one Chemical compound CC(=O)OC=C.C=CN1CCCC1=O FYUWIEKAVLOHSE-UHFFFAOYSA-N 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- KQTVWCSONPJJPE-UHFFFAOYSA-N etridiazole Chemical compound CCOC1=NC(C(Cl)(Cl)Cl)=NS1 KQTVWCSONPJJPE-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- HKIOYBQGHSTUDB-UHFFFAOYSA-N folpet Chemical compound C1=CC=C2C(=O)N(SC(Cl)(Cl)Cl)C(=O)C2=C1 HKIOYBQGHSTUDB-UHFFFAOYSA-N 0.000 description 1
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/27—Zinc; Compounds thereof
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/325—Carbamic acids; Thiocarbamic acids; Anhydrides or salts thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
- A61K31/41—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having five-membered rings with two or more ring hetero atoms, at least one of which being nitrogen, e.g. tetrazole
- A61K31/425—Thiazoles
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/29—Titanium; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
- Y10T428/31989—Of wood
Definitions
- This invention relates to delivery systems for water-insoluble active chemicals, and, more particularly, to a stable aqueous suspension concentrate of a UV-labile, water-insoluble biocide active concentrate to stabilize such actives against the degradation effects of sunlight and UV-radiation.
- IPBC iodopropargyl butyl carbamate
- U.S. Pat. No. 6,506,794 describes an aqueous dispersion of halopropargyl compounds and a partially hydrolyzed polyvinyl alcohol.
- active dispersions are quite susceptible to degradation upon storage and/or exposure to UV-radiation.
- the decomposition of IPBC typically results in the formation of a yellow or brown by-product. The compositions thus will be unsuitable for use in certain systems in need of antimicrobial protection particularly white aqueous paints.
- U.S. Pat. No. 6,156,803 discloses the use of a partially neutralized alkyl vinyl ether-maleic acid half ester copolymer as a dispersing agent for water-insoluble agriculturally active chemicals.
- Published U.S. Patent Application US 2004/0024099 A1 describes an aqueous suspension concentrate for water insoluble chemicals comprising a mixture of an anionic polymeric suspension agent and a homo- and/or a co-polymer of a heterocyclic vinyl lactam.
- a particular object herein is to provide such stable concentrates which experience substantially no degradation or coloration upon storage and/or exposure to sunlight or UV-radiation while retaining its bioactivity.
- a stable, aqueous suspension concentrate which includes a solid polymeric dispersant comprising one or more anionic polymeric dispersing agents, optionally a co-dispersant which preferably is a homopolymer and/or a copolymer of a heterocyclic vinyl lactam, preferably in a wt. ratio of 0.1:1 to 1:0.1, respectively, a UV-labile, water-insoluble biocide active and a UV-blocker or UV-absorber to stabilize said active upon storage and/or exposure to sunlight or UV-radiation.
- a solid polymeric dispersant comprising one or more anionic polymeric dispersing agents, optionally a co-dispersant which preferably is a homopolymer and/or a copolymer of a heterocyclic vinyl lactam, preferably in a wt. ratio of 0.1:1 to 1:0.1, respectively, a UV-labile, water-insoluble biocide active and a UV-blocker or UV-absorber
- the stable, aqueous suspension concentrate includes a biocide which is a fungicide or preservative.
- the biocide is a halopropargyl compound, an isothiazolone, a triazole, a phthalimide, benzimidazol carbamate or tetrachloroisophalonitrile; more particularly, iodopropargyl butyl carbamate (IPBC), benzisothiazolone (BIT), propiconazole, N(trichloromethylthio)pthalimide, methyl benzimidazol-2-yl carbamate or tetrachloroisophalonitrile.
- IPBC iodopropargyl butyl carbamate
- BIT benzisothiazolone
- propiconazole N(trichloromethylthio)pthalimide, methyl benzimidazol-2-yl carbamate or tetrachloroisophalonitrile.
- the UV-blocker or absorber suitably is titanium dioxide, zinc oxide, stilbenes, or UV-blocking minerals and mixtures thereof.
- the UV-absorbers can be esters of aromatic or aliphatic acids with appropriate substituents, aromatic ketones, triazines, which usually are commercially available.
- the stable, aqueous suspension concentrate includes a co-dispersant which comprises a homopolymer or copolymer of vinyl pyrrolidone, and an anionic dispersing agent which is an ionic derivative of methyl vinyl ether-maleic acid half-ester.
- a feature of the invention is that the suspension concentrate exhibits essentially no degradation on storage at 50° C. for 30 days, and substantially no discoloration or yellowing on exposure to sunlight or UV-radiation.
- the invention herein further comprises a composition which includes the stable aqueous suspension concentrate, e.g. a paint composition; or a coating composition, construction material like concrete, bricks, asphalt, shingles, metals and the like; or a personal care composition.
- a composition which includes the stable aqueous suspension concentrate e.g. a paint composition; or a coating composition, construction material like concrete, bricks, asphalt, shingles, metals and the like; or a personal care composition.
- Another feature of the invention is the provision of an article which comprises a substrate coated with the suspension concentrate described alone; e.g. an article wherein said substrate is wood.
- the primary dispersant in the present solid polymeric dispersant composition of the invention is an anionic polymeric dispersant such as the sodium salt of alkyl vinyl ether/maleic acid half-ester copolymer (Easy-Sperse®) (ISP), a lignosulfonate or metal salt thereof, e.g. POLYFON® or REAX® (Westvaco); a sulfonated naphthalene/formaldehyde condensate, e.g.
- anionic polymeric dispersant such as the sodium salt of alkyl vinyl ether/maleic acid half-ester copolymer (Easy-Sperse®) (ISP), a lignosulfonate or metal salt thereof, e.g. POLYFON® or REAX® (Westvaco); a sulfonated naphthalene/formaldehyde condensate, e.g.
- MORWET® (Witco); UFOXANE® or MARESPERSE® (Lignotech); an alpha-olefin/maleic acid copolymer, a high molecular weight block copolymer with pigment affinic groups, e.g., DISPERBYCK 190 (BYK Chemie) or a polyacrylate, which is capable of dispersing hydrophobic compounds in water, and mixtures thereof.
- the monomer of the anionic polymer contains 1-4 anionic sites per mole of repeat units.
- the optional co-dispersant in the composition of the invention is a vinyl lactam which is suitably the homopolymer of vinyl pyrrolidone or vinyl caprolactam either optionally substituted on the ring or in the vinyl group with a lower alkyl (C 1 to C 4 alkyl), or a mixture of these homopolymers.
- the co-dispersant can be a copolymer of vinyl pyrrolidone and/or vinyl caprolactam, e.g.
- the vinyl lactam co-dispersant generally has a weight average molecular weight of between about 5,000 and about 100,000 consistent with a Fikentscher K-value of from about 10 to about 120.
- the codispersant can be a clay selected from naturally occurring silicates, atta clay, bentonite, diatomaceous earth, and Montmorillonite.
- the lactam polymer in the solid dispersant mixture, can coil around and coat at least a portion of an active water-insoluble ingredient thus reducing its surface hydrophobicity while retaining the intrinsic hydrophobic character of the insoluble active component.
- the lactam coating also can associate with anions of the primary dispersant to provide a composition of improved stability and permit high load active compositions for disparate hydrophobic species which are not otherwise suspendable.
- the use of the co-dispersant lactam polymer in the invention solid mixture permits the use of a lower concentration of the primary anionic polymeric dispersant component which reduces irritant properties and/or foaming. Also the presence of the lactam polymer in the solid mixture allows the use of several otherwise incompatible anionic polymeric dispersants.
- the active component of the invention compositions is a particulate, substantially water-insoluble UV-labile biocide compound, or a hydrophobic compound or mixture of such compounds, and is preferably a biocide such as a halopropargyl compound, a isothiazolone, a triazole, a phthalimide, a benzimidazole carbamate, a tetrachloroisophalonitrile and the like.
- biocide compounds usually exhibit significant degradation upon certain storage conditions and/or exposure to sunlight or UV-radiation accompanied by discoloration when used in such products as in paint, wood or personal care formulations.
- substantially insoluble it is meant that for all practical purposes, the solubility of the compound in water is insufficient to make the compound practicably usable in a spray-on or dip end use without some modification either to increase its solubility or dispersability in water, so as to increase the compound's bioavailability or avoid the use of excessively large volumes of solvent.
- Compounds having low water solubility usually include those having a solubility of less than 1 gram per 100 grams of water at room temperature conditions.
- Typical “substantially insoluble” biocides include: Iodopropargyl butyl carbamate (IPBC), Benzisothiazolone (BIT), Propiconazole, N(trichloromethylthio)pthalimide, methyl benzimidazol-2-yl carbamate, tetrachloroisophalonitrile, 2-n-octyl-3-isothiazolone, Dibromonitriloproprianamide (DBNPA), 2-(thiocyanomethylthio)benzothiazole (TCMTB), Tebuconazole, Tributyl tin benzoate, Parabens, 2,5-dimethyl-N-cyclohexyl-N-methoxy-3-furan carboxamide, 5-Ethoxy-3-trichloromethyl-1,2,4 thiadiazole, 3-(2-methyl piperidino)propyl 3,4-dichlorobenzoate, N,N′-(1,4-piperazinediy
- UV labile is meant for all practical purposes, the active ingredient is susceptible to absorption of any part of natural sunlight or exposed artificial light. Generally, any active ingredient containing Unsaturated moieties, especially with conjugation, and aromatic or heterocyclic components, will be subject to absorption of such radiation, which eventually can cause a color change degradation or loss of activity.
- UV-blocker and/or UV-absorber includes those compounds which will cause a considerable shift of an appropriate active portion of the radiation spectral component.
- the instant invention provides a suspension concentrate which is environmentally friendly, and free of organic solvents and conventional emulsifiers.
- the aqueous suspension concentrate herein can be formulated with multiple active ingredients to enhance its spectrum of activity.
- the concentrate is easily dilutable with water. A high salt content in the ground water from the field will not affect its stability on dilution.
- the suspension concentrate can be made easily by standard methods, as described below:
- Easy-Sperse® International Specialty Products Inc.
- Easy-Sperse® is the partially neutralized (NaOH) aqueous solution of methyl vinyl ether/maleic acid half-ester (ethyl/butyl) copolymer having a solids content of about 25% and a viscosity of about 6,000 cps.
- the optional co-dispersant in the composition suitably is an aqueous solution of polyvinyl pyrrolidone (20-40% solids).
- a solution/slurry of both the primary and co-dispersant is provided in a weight ratio of these ingredients of 0.1:1 to 1:0.1, respectively, preferably 1:0.5 to 1:5, and, most preferably, 1:1 to 1:4.
- the solution/slurry may be diluted with water, if necessary, to produce a viscosity particularly suitable for spray drying, e.g. 3,000 to 6,000 cps. Then the solution/slurry is spray dried suitably at an inlet temperature of about 300-480° F. and an outlet temperature of about 150-270° F.
- the product of the spray drying process is a solid polymeric dispersant concentrate suitable for delivery of UV-labile, water-insoluble biocide actives. If, however, both the primary and co-dispersants are commercially available as solids, then only simple granulation of the ingredients is required to obtain the desired solid concentrate.
- the active material then can be added in a suitable amount and processed, if desired, for water-sensitive actives, under anhydrous conditions, and made into solid delivery systems such as wettable powders, water dispersible granules and tablets.
- the solid form can be used in an aqueous medium with water of dilution, in an aqueous or suspension formulation.
- the formulation also can be coated onto hydrophobic surfaces, or printed onto sheets.
- the products of the invention are advantageous from a commercial standpoint for the following reasons.
- the suspension concentrate exhibits essentially no degradation on storage at 50° C. for 30 days, and substantially no discoloration or yellowing on exposure to sunlight or UV-radiation.
- the solid composition of the invention also may be efficiently prepared by simply homogenizing and wet-milling the components or by extrusion.
- the composition may be diluted with a desired amount of water by mixing in a high speed mixer for a period of from about 30 minutes to 1 hour.
- composition of the present invention can incorporate up to 90% of an active material in its mixture while retaining its stability for at least 1 year or more.
- the active component can have a concentration of 10 ppm to 50% in the diluted mixture while retaining suspension stability for 4 hours or more.
- the combination of the anionic dispersant with the lactam polymer has a synergistic suspension effect in that the dispersing ability of the sum of either component alone is markedly exceeded.
- Example 1 was repeated with solid Morwet® D-425 in place of a solution of Easy-Sperse®, and a solution of PVP to produce a 1:1 wt. ratio solid.
- Example 5 was repeated at a wt. ratio of 1:3 with similar results.
- Example 5 was repeated with solid Reax® 100M in place of Morwet® D-425 with similar results.
- Example 6 was repeated with solid Reax® 100M in place of Morwet® D-425 with similar results.
- IPBC active 700 g of commercial IPBC active was mixed with 80 g of the polymeric dispersant of Example 2 and 220 g of commercially available titanium dioxide in a V-blender. This solid premix was used to formulate wettable powders, suspension concentrates, water-dispersible granules and tablets of the active.
- Example 11 100 g of the charge from Example 11 was made into a paste by kneading with water (10-20 g) and was extruded in a laboratory table top extruder at maximum speed. The extrudate was dried in an oven at 70 C for a period of 8 hours. The extrudate was dispersible in water at a use level concentration of IPBC of from 0.1% to 2.0%.
- Example 12 50 g of the extrudate of Example 12 was mixed with 1.5 g of cross-linked polyvinyl pyrrolidone (Polyclar® ATF) and several tablets were made by compressing the powder in a laboratory tablet press at a pressure of 2.5 tons. Each tablet weighed about 3 g, containing approximately 1.86 g IPBC. Aqueous suspensions were made by dispersing each tablet in 186 g water by mild agitation for about 10 minutes, to produce a 1% IPBC suspension.
- Polyclar® ATF cross-linked polyvinyl pyrrolidone
- compositions of biocide suspension concentrates in suitable and preferred ranges by weight thus-prepared include: Active ingredient: 5-50%; preferred range 10-40%; polymeric dispersant; 0.2-8%, preferred: 1-5%; UV-blocker: 0.2-20%, preferred: 2-10%; thickener: 0.05-0.4%; preferred: 0.1-0.3%; wetting agent: 0-1.0%, preferred: 0-0.5%; defoamer: 0.05-0.4%, preferred: 0.1-0.3%; preservative: 0-0.5% preferred 0-0.2%; and water to 100%.
- Thickeners used are usually commercially available water soluble polymers that impart high viscosity when added at very low concentrations, such as natural gums, carbohydrates like Kelzan®, synthetic polymers like Carbopol® (polyacrylates).
- the wetting agents are used to reduce friction during high speed grinding, usually low foaming organic liquids with a low dynamic surface tension, e.g. Surfynol® series or N-octyl pyrrolidone.
- Preservatives used are commercially available registered organic compounds capable of controlling biological growth in aqueous medium during a reasonable storage period of about 1-5 years, e.g. Nuosept® series, Kathon®, Proxel® and the like.
- 1 Kg of an aqueous suspension concentrate was prepared using about 200 g of commercially available IPBC, by the general procedure described in Example 14.
- 220 g IPBC was mixed with 25 g Easy-Sperse® P 20 polymeric dispersant and 600 g deionized water.
- the charge was loaded in a blender at low speed followed by high speed blending for a period of 30 minutes.
- 1.0 g Surfynol® 104 E was added along with 1.0 g Sag 30.
- the charge was processed as in Example 14.
- the suspension concentrate was then mixed with 122 g of 1% Keizan® stock solution prepared separately, followed by addition of the remaining quantity of water (53 g) to make up a 22% IPBC concentrate.
- Example 15 A was repeated except that 50 g zinc oxide was included in the initial solid mix with water and 3 g of make-up water was used at the end instead of 53 g water.
- Example 15 B was repeated except that titanium dioxide was used in the place of zinc oxide.
- Example 15 C was repeated using 400 g IPBC instead of 200 g and 40 g Easy-Sperse® P 20 instead of 25 g and initial water was 400 g instead of 600 g, and make-up water was 23 g.
- Example 15 C was repeated except that Disperbyck 190 was used in place of Easy-Sperse.
- Example 15 A, 15 B, and 15 C were evaluated for yellowing on exposure to UV-light. The results are shown in Example 16. Examples 15 C and 15 E were evaluated for accelerated storage stability. These results are shown in Example 17. Example 15 D was evaluated as an additive in paint. These results are shown in Example 18.
- IPBC dispersion described in Example 15 C and 15 E was heat aged for 30 days at 50° C.
- the resultant IPBC levels were determined by Reversed-Phase HPLC.
- the levels of IPBC detected in Sample 15 C was 21.54 ⁇ 0.06 which is the same level as the sample analyzed at time zero, immediately after preparation of the suspension concentrate.
- Levels of IPBC detected in Sample 15 E were 20.34 ⁇ 0.2% which is the same level as the sample analyzed at time zero.
- Example 15 D The efficacy of the 40% IPBC suspension concentrate in Example 15 D, was compared to that of a commercial IPBC formulation comparable in strength following ASTM D5590 entitled “Determining the Resistance of Paint Films and Related Coatings to Fungal Defacement by Accelerated Four Week Agar Plate”. The results are shown in Table 2. Growth ratings were taken every 7 days, on a scale of “0“to “10”, where “0” corresponds to the complete absence of fungal growth and “10” corresponds to the complete coverage by fungus.
- the Mixed Inoculum contained the fungi Aspergillus niger and Penicillium funiculosum.
- Example 19 The efficacy of the BIT dispersion described in Example 19 was compared to that of a commercial BIT formulation of similar strength following ASTM D2574 entitled “Resistance of Emulsion Paints in the Container to Attack by Microorganisms”. Results are shown in Table 3. Growth ratings were taken at day 1, 2, 3 and 6 after each bacterial challenge on a scale of “0” to “4”, where “0” corresponds to no growth, “1” is less than 10 cfu/ml, “2” is 11-100 cfu/ml; “3” is 101-1,000 cfu/ml and “4” is higher than 1,000 cfu/ml.
- the mixed bacterial inoculum consisted of Pseudomonas aeruginosa, Enterobacter cloacae, Bacillus subtilis, Bacillus megaterium and Bacillus licheniformis.
- Final concentration for Challenge I was 1.52 ⁇ 10 6 cfu/ml and for Challenge II, 1.56 ⁇ 10 7 cfu/ml.
- Example 15 was repeated using propiconazole instead of IPBC. Similar results were obtained.
- Example 19 was repeated using a combination of IPBC and propiconazole in the weight ratio of 1:2. Similar results were obtained.
- Example 15 was repeated using Folpet instead of IPBC. Similar results were obtained.
- Example 15 was repeated using chlorothalonil. Similar results were obtained.
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Abstract
Description
- 1. Field of the Invention
- This invention relates to delivery systems for water-insoluble active chemicals, and, more particularly, to a stable aqueous suspension concentrate of a UV-labile, water-insoluble biocide active concentrate to stabilize such actives against the degradation effects of sunlight and UV-radiation.
- 2. Description of the Prior Art
- Numerous delivery systems and formulations have been proposed to provide aqueous dispersions of substantially water-insoluble biocide active chemicals such as iodopropargyl butyl carbamate (IPBC). For example U.S. Pat. No. 6,506,794 describes an aqueous dispersion of halopropargyl compounds and a partially hydrolyzed polyvinyl alcohol. However, such active dispersions are quite susceptible to degradation upon storage and/or exposure to UV-radiation. In particular, the decomposition of IPBC typically results in the formation of a yellow or brown by-product. The compositions thus will be unsuitable for use in certain systems in need of antimicrobial protection particularly white aqueous paints.
- Various methods and compositions have been described to stabilize biocidal compositions containing IPBC, for example, using UV absorbers and/or organic epoxides in a liquid vehicle, as shown in U.S. Pat. Nos. 4,276,211; 4,552,885; 5,938,825; 6,059,991 and 6,140,370. U.S. Pat. No. 6,616,740 teaches on the use of various glycol carriers for IPBC stabilization. However, none of these disclosures provide a stable IPBC composition as an aqueous dispersion free from yellowing on exposure to UV-radiation.
- U.S. Pat. No. 6,156,803 discloses the use of a partially neutralized alkyl vinyl ether-maleic acid half ester copolymer as a dispersing agent for water-insoluble agriculturally active chemicals. Published U.S. Patent Application US 2004/0024099 A1 describes an aqueous suspension concentrate for water insoluble chemicals comprising a mixture of an anionic polymeric suspension agent and a homo- and/or a co-polymer of a heterocyclic vinyl lactam.
- Accordingly, it is an object of this invention to provide a stable, aqueous suspension concentrate of a UV-labile biocide active for delivery of such active in stabilized form into formulations and onto substrates.
- A particular object herein is to provide such stable concentrates which experience substantially no degradation or coloration upon storage and/or exposure to sunlight or UV-radiation while retaining its bioactivity.
- What is described herein is a stable, aqueous suspension concentrate which includes a solid polymeric dispersant comprising one or more anionic polymeric dispersing agents, optionally a co-dispersant which preferably is a homopolymer and/or a copolymer of a heterocyclic vinyl lactam, preferably in a wt. ratio of 0.1:1 to 1:0.1, respectively, a UV-labile, water-insoluble biocide active and a UV-blocker or UV-absorber to stabilize said active upon storage and/or exposure to sunlight or UV-radiation.
- Preferably the stable, aqueous suspension concentrate includes a biocide which is a fungicide or preservative.
- Most preferably the biocide is a halopropargyl compound, an isothiazolone, a triazole, a phthalimide, benzimidazol carbamate or tetrachloroisophalonitrile; more particularly, iodopropargyl butyl carbamate (IPBC), benzisothiazolone (BIT), propiconazole, N(trichloromethylthio)pthalimide, methyl benzimidazol-2-yl carbamate or tetrachloroisophalonitrile.
- The UV-blocker or absorber suitably is titanium dioxide, zinc oxide, stilbenes, or UV-blocking minerals and mixtures thereof. The UV-absorbers can be esters of aromatic or aliphatic acids with appropriate substituents, aromatic ketones, triazines, which usually are commercially available.
- In one embodiment of the invention, the stable, aqueous suspension concentrate includes a co-dispersant which comprises a homopolymer or copolymer of vinyl pyrrolidone, and an anionic dispersing agent which is an ionic derivative of methyl vinyl ether-maleic acid half-ester.
- A feature of the invention is that the suspension concentrate exhibits essentially no degradation on storage at 50° C. for 30 days, and substantially no discoloration or yellowing on exposure to sunlight or UV-radiation.
- The invention herein further comprises a composition which includes the stable aqueous suspension concentrate, e.g. a paint composition; or a coating composition, construction material like concrete, bricks, asphalt, shingles, metals and the like; or a personal care composition.
- Another feature of the invention is the provision of an article which comprises a substrate coated with the suspension concentrate described alone; e.g. an article wherein said substrate is wood.
- The primary dispersant in the present solid polymeric dispersant composition of the invention is an anionic polymeric dispersant such as the sodium salt of alkyl vinyl ether/maleic acid half-ester copolymer (Easy-Sperse®) (ISP), a lignosulfonate or metal salt thereof, e.g. POLYFON® or REAX® (Westvaco); a sulfonated naphthalene/formaldehyde condensate, e.g. MORWET® (Witco); UFOXANE® or MARESPERSE® (Lignotech); an alpha-olefin/maleic acid copolymer, a high molecular weight block copolymer with pigment affinic groups, e.g., DISPERBYCK 190 (BYK Chemie) or a polyacrylate, which is capable of dispersing hydrophobic compounds in water, and mixtures thereof. Desirably the monomer of the anionic polymer contains 1-4 anionic sites per mole of repeat units.
- The optional co-dispersant in the composition of the invention is a vinyl lactam which is suitably the homopolymer of vinyl pyrrolidone or vinyl caprolactam either optionally substituted on the ring or in the vinyl group with a lower alkyl (C1 to C4 alkyl), or a mixture of these homopolymers. Alternatively, the co-dispersant can be a copolymer of vinyl pyrrolidone and/or vinyl caprolactam, e.g. vinyl pyrrolidone/vinyl caprolactam copolymer, vinyl pyrrolidone/vinyl acetate, vinyl pyrrolidone/acrylic acid, vinyl pyrrolidone/acrylate, vinyl pyrrolidone and butane, or a vinyl pyrrolidone and a C14-C24 alpha-olefin. The vinyl lactam co-dispersant generally has a weight average molecular weight of between about 5,000 and about 100,000 consistent with a Fikentscher K-value of from about 10 to about 120. The codispersant can be a clay selected from naturally occurring silicates, atta clay, bentonite, diatomaceous earth, and Montmorillonite. In the solid dispersant mixture, the lactam polymer can coil around and coat at least a portion of an active water-insoluble ingredient thus reducing its surface hydrophobicity while retaining the intrinsic hydrophobic character of the insoluble active component. The lactam coating also can associate with anions of the primary dispersant to provide a composition of improved stability and permit high load active compositions for disparate hydrophobic species which are not otherwise suspendable. The use of the co-dispersant lactam polymer in the invention solid mixture permits the use of a lower concentration of the primary anionic polymeric dispersant component which reduces irritant properties and/or foaming. Also the presence of the lactam polymer in the solid mixture allows the use of several otherwise incompatible anionic polymeric dispersants.
- The active component of the invention compositions is a particulate, substantially water-insoluble UV-labile biocide compound, or a hydrophobic compound or mixture of such compounds, and is preferably a biocide such as a halopropargyl compound, a isothiazolone, a triazole, a phthalimide, a benzimidazole carbamate, a tetrachloroisophalonitrile and the like.
- Some of these biocide compounds usually exhibit significant degradation upon certain storage conditions and/or exposure to sunlight or UV-radiation accompanied by discoloration when used in such products as in paint, wood or personal care formulations.
- By the term “substantially insoluble”, it is meant that for all practical purposes, the solubility of the compound in water is insufficient to make the compound practicably usable in a spray-on or dip end use without some modification either to increase its solubility or dispersability in water, so as to increase the compound's bioavailability or avoid the use of excessively large volumes of solvent. Compounds having low water solubility usually include those having a solubility of less than 1 gram per 100 grams of water at room temperature conditions.
- Typical “substantially insoluble” biocides include: Iodopropargyl butyl carbamate (IPBC), Benzisothiazolone (BIT), Propiconazole, N(trichloromethylthio)pthalimide, methyl benzimidazol-2-yl carbamate, tetrachloroisophalonitrile, 2-n-octyl-3-isothiazolone, Dibromonitriloproprianamide (DBNPA), 2-(thiocyanomethylthio)benzothiazole (TCMTB), Tebuconazole, Tributyl tin benzoate, Parabens, 2,5-dimethyl-N-cyclohexyl-N-methoxy-3-furan carboxamide, 5-Ethoxy-3-trichloromethyl-1,2,4 thiadiazole, 3-(2-methyl piperidino)propyl 3,4-dichlorobenzoate, N,N′-(1,4-piperazinediyl bis(2,2,2-trichloro)ethylidene)bis formamide, Tetramethyl thiuram disulfide, 0-Ethyl-S,S,diphenyl-dithiophosphate, 5,10-dihydro-5,10-dioxo naphtho(2,3,9)-p-dithiin-2,3-dicarbonitrile, α-2-[(4-chlorophenyl)ethyl]-α-(1,1-dimethyl ethyl)-1 H-1,2,4-triazole-1-ethanol 3-(3,4-dichlorophenyl)1,1 dimethylurea, N-tridecyl-2,6-dimethylmorpholine and 4-N-dodecyl-2,6-dimethylmorpholine.
- By the term “UV labile” is meant for all practical purposes, the active ingredient is susceptible to absorption of any part of natural sunlight or exposed artificial light. Generally, any active ingredient containing Unsaturated moieties, especially with conjugation, and aromatic or heterocyclic components, will be subject to absorption of such radiation, which eventually can cause a color change degradation or loss of activity.
- In this invention, the term UV-blocker and/or UV-absorber includes those compounds which will cause a considerable shift of an appropriate active portion of the radiation spectral component.
- The instant invention provides a suspension concentrate which is environmentally friendly, and free of organic solvents and conventional emulsifiers. The aqueous suspension concentrate herein can be formulated with multiple active ingredients to enhance its spectrum of activity. The concentrate is easily dilutable with water. A high salt content in the ground water from the field will not affect its stability on dilution. The suspension concentrate can be made easily by standard methods, as described below:
- The commercial product Easy-Sperse® (International Specialty Products Inc.) suitably is employed as the anionic polymeric dispersant in the solid composition of the invention. Easy-Sperse® is the partially neutralized (NaOH) aqueous solution of methyl vinyl ether/maleic acid half-ester (ethyl/butyl) copolymer having a solids content of about 25% and a viscosity of about 6,000 cps.
- The optional co-dispersant in the composition suitably is an aqueous solution of polyvinyl pyrrolidone (20-40% solids). A solution/slurry of both the primary and co-dispersant is provided in a weight ratio of these ingredients of 0.1:1 to 1:0.1, respectively, preferably 1:0.5 to 1:5, and, most preferably, 1:1 to 1:4. The solution/slurry may be diluted with water, if necessary, to produce a viscosity particularly suitable for spray drying, e.g. 3,000 to 6,000 cps. Then the solution/slurry is spray dried suitably at an inlet temperature of about 300-480° F. and an outlet temperature of about 150-270° F. The product of the spray drying process is a solid polymeric dispersant concentrate suitable for delivery of UV-labile, water-insoluble biocide actives. If, however, both the primary and co-dispersants are commercially available as solids, then only simple granulation of the ingredients is required to obtain the desired solid concentrate.
- The active material then can be added in a suitable amount and processed, if desired, for water-sensitive actives, under anhydrous conditions, and made into solid delivery systems such as wettable powders, water dispersible granules and tablets. If desired, the solid form can be used in an aqueous medium with water of dilution, in an aqueous or suspension formulation. The formulation also can be coated onto hydrophobic surfaces, or printed onto sheets.
- The products of the invention are advantageous from a commercial standpoint for the following reasons. In particular the suspension concentrate exhibits essentially no degradation on storage at 50° C. for 30 days, and substantially no discoloration or yellowing on exposure to sunlight or UV-radiation.
- The solid composition of the invention also may be efficiently prepared by simply homogenizing and wet-milling the components or by extrusion. The composition may be diluted with a desired amount of water by mixing in a high speed mixer for a period of from about 30 minutes to 1 hour.
- The composition of the present invention can incorporate up to 90% of an active material in its mixture while retaining its stability for at least 1 year or more. On dilution the active component can have a concentration of 10 ppm to 50% in the diluted mixture while retaining suspension stability for 4 hours or more. The combination of the anionic dispersant with the lactam polymer has a synergistic suspension effect in that the dispersing ability of the sum of either component alone is markedly exceeded.
- Having generally described the invention, reference is had to the following examples which illustrate preferred embodiments and comparisons of the present concentrate or formulation with those of the prior art.
- 72 g of an Easy-Sperse® solution (24.8% solids) was mixed with 176 g of PVP K-30 (30.5% solids), then homogenized at room temperature for 1 hour and concentrated in a hood overnight at room temperature followed by drying in a vacuum oven (<10 mm Hg) at 80° C. for 2 hours. The resulting solid product had a Tg of 159° C. and <1% bound water and a wt. ratio of Easy-Sperse® to PVP of 1:3.
- 240 Kg of Easy-Sperse® solution (26% solids) and 720 Kg of PVP K-30 (36.6% solids) were mixed and heated to 120° F. and then diluted with 600 lbs of water. The resulting solution was fed into a commercial spray dryer with an inlet temperature of 410° F. and an outlet temperature of 265° F. A solid was obtained in the form of a powder which passed through a 20 mesh screen. 700 lbs of dry material was obtained with 7% total (bound) water. The wt. ratio of Easy-Sperse® to PVP was 1:4.
- Examples 1 and 2 were repeated at a wt. ratio of 1:1. Similar results were obtained.
- Examples 1 and 2 were repeated at a wt. ratio of 1:2. Similar results were obtained.
- Example 1 was repeated with solid Morwet® D-425 in place of a solution of Easy-Sperse®, and a solution of PVP to produce a 1:1 wt. ratio solid.
- Example 5 was repeated at a wt. ratio of 1:3 with similar results.
- Example 5 was repeated with solid Reax® 100M in place of Morwet® D-425 with similar results.
- Example 6 was repeated with solid Reax® 100M in place of Morwet® D-425 with similar results.
- Mixture of Solid Dispersant and Biocide Active
- 700 g of commercial IPBC active was mixed with 80 g of the polymeric dispersant of Example 2 and 220 g of commercially available titanium dioxide in a V-blender. This solid premix was used to formulate wettable powders, suspension concentrates, water-dispersible granules and tablets of the active.
- 700 g commercial BIT active was mixed with 80 g of the polymeric dispersant of Example 2 and 220 g of commercially available titanium dioxide in a V-blender. This solid premix was used to formulate wettable powders, suspension concentrates, water-dispersible granules and tablets of the active.
- 300 g of commercial IPBC was mixed with 70 g of the polymeric dispersant/binder composition of Example 6 and 100 g of commercially available titanium dioxide in a V-blender. This charge was used to produce extruded granules and tablets.
- 100 g of the charge from Example 11 was made into a paste by kneading with water (10-20 g) and was extruded in a laboratory table top extruder at maximum speed. The extrudate was dried in an oven at 70 C for a period of 8 hours. The extrudate was dispersible in water at a use level concentration of IPBC of from 0.1% to 2.0%.
- 50 g of the extrudate of Example 12 was mixed with 1.5 g of cross-linked polyvinyl pyrrolidone (Polyclar® ATF) and several tablets were made by compressing the powder in a laboratory tablet press at a pressure of 2.5 tons. Each tablet weighed about 3 g, containing approximately 1.86 g IPBC. Aqueous suspensions were made by dispersing each tablet in 186 g water by mild agitation for about 10 minutes, to produce a 1% IPBC suspension.
- The following briefly describes the procedure used to prepare suspension concentrates of biocides shown in the following Examples 15A to 15D.
- Compositions of biocide suspension concentrates in suitable and preferred ranges by weight thus-prepared include: Active ingredient: 5-50%; preferred range 10-40%; polymeric dispersant; 0.2-8%, preferred: 1-5%; UV-blocker: 0.2-20%, preferred: 2-10%; thickener: 0.05-0.4%; preferred: 0.1-0.3%; wetting agent: 0-1.0%, preferred: 0-0.5%; defoamer: 0.05-0.4%, preferred: 0.1-0.3%; preservative: 0-0.5% preferred 0-0.2%; and water to 100%.
- General Procedure:
- In a vessel with Cowles mixer added about 80% of water required, followed by wetting agent, dispersant, UV-blocker, and active ingredient. Mixed at 500 rpm for 30 minutes. Defoamer and thickener were added to the above mixture and remaining water, and mixed at 2000 rpm for an additional 30 minutes. The charge was pumped into a basket mill and milled to the selected particle size, usually about 10 microns average particle size (a Hegman rating between 6 and 7).
- Thickeners used are usually commercially available water soluble polymers that impart high viscosity when added at very low concentrations, such as natural gums, carbohydrates like Kelzan®, synthetic polymers like Carbopol® (polyacrylates). The wetting agents are used to reduce friction during high speed grinding, usually low foaming organic liquids with a low dynamic surface tension, e.g. Surfynol® series or N-octyl pyrrolidone. Preservatives used are commercially available registered organic compounds capable of controlling biological growth in aqueous medium during a reasonable storage period of about 1-5 years, e.g. Nuosept® series, Kathon®, Proxel® and the like.
- 1 Kg of an aqueous suspension concentrate was prepared using about 200 g of commercially available IPBC, by the general procedure described in Example 14. 220 g IPBC was mixed with 25 g Easy-Sperse® P 20 polymeric dispersant and 600 g deionized water. The charge was loaded in a blender at low speed followed by high speed blending for a period of 30 minutes. During the blending process, 1.0 g Surfynol® 104 E was added along with 1.0 g Sag 30. The charge was processed as in Example 14. The suspension concentrate was then mixed with 122 g of 1% Keizan® stock solution prepared separately, followed by addition of the remaining quantity of water (53 g) to make up a 22% IPBC concentrate.
- Example 15 A was repeated except that 50 g zinc oxide was included in the initial solid mix with water and 3 g of make-up water was used at the end instead of 53 g water.
- Example 15 B was repeated except that titanium dioxide was used in the place of zinc oxide.
- Example 15 C was repeated using 400 g IPBC instead of 200 g and 40 g Easy-Sperse® P 20 instead of 25 g and initial water was 400 g instead of 600 g, and make-up water was 23 g.
- Example 15 C was repeated except that Disperbyck 190 was used in place of Easy-Sperse.
- The suspension concentrates described in Example 15 A, 15 B, and 15 C were evaluated for yellowing on exposure to UV-light. The results are shown in Example 16. Examples 15 C and 15 E were evaluated for accelerated storage stability. These results are shown in Example 17. Example 15 D was evaluated as an additive in paint. These results are shown in Example 18.
-
TABLE 1 Yellowing upon UV-light Exposure Formulation Degree of Yellowing Formulation 15 A +++ Formulation 15 B + Formulation 15 C −
“+” = yellowing; “−” = non-yellowing
- The IPBC dispersion described in Example 15 C and 15 E was heat aged for 30 days at 50° C. The resultant IPBC levels were determined by Reversed-Phase HPLC. The levels of IPBC detected in Sample 15 C was 21.54±0.06 which is the same level as the sample analyzed at time zero, immediately after preparation of the suspension concentrate. Levels of IPBC detected in Sample 15 E were 20.34±0.2% which is the same level as the sample analyzed at time zero.
- The efficacy of the 40% IPBC suspension concentrate in Example 15 D, was compared to that of a commercial IPBC formulation comparable in strength following ASTM D5590 entitled “Determining the Resistance of Paint Films and Related Coatings to Fungal Defacement by Accelerated Four Week Agar Plate”. The results are shown in Table 2. Growth ratings were taken every 7 days, on a scale of “0“to “10”, where “0” corresponds to the complete absence of fungal growth and “10” corresponds to the complete coverage by fungus. The Mixed Inoculum contained the fungi Aspergillus niger and Penicillium funiculosum.
TABLE 2 Efficacy of IBPC Aqueous Suspension Concentrate Mixed Inoculum % by Leached Unleached Paint Wt. 1 2 3 4 1 2 3 4 White Exterior Susp. Conc. 0.6 0 0 0 1 0 0 0 0 Commercial 0.6 0 0 0 0 0 0 0 0 Control — 5 9 10 10 3 3 3 5 Deep Tint Susp. Conc. 0.5 0 0 0 1 0 0 0 0 Commercial 0.5 0 0 0 1 0 0 0 0 Control — 7 7 8 10 4 4 8 10 - 1 Kg of an aqueous suspension concentrate was prepared with BIT following the procedure of Example 15 C.
- The efficacy of the BIT dispersion described in Example 19 was compared to that of a commercial BIT formulation of similar strength following ASTM D2574 entitled “Resistance of Emulsion Paints in the Container to Attack by Microorganisms”. Results are shown in Table 3. Growth ratings were taken at day 1, 2, 3 and 6 after each bacterial challenge on a scale of “0” to “4”, where “0” corresponds to no growth, “1” is less than 10 cfu/ml, “2” is 11-100 cfu/ml; “3” is 101-1,000 cfu/ml and “4” is higher than 1,000 cfu/ml. The mixed bacterial inoculum consisted of Pseudomonas aeruginosa, Enterobacter cloacae, Bacillus subtilis, Bacillus megaterium and Bacillus licheniformis. Final concentration for Challenge I was 1.52×106 cfu/ml and for Challenge II, 1.56×107 cfu/ml.
TABLE 3 Efficacy of BIT Aqueous Suspension Concentrate % by Challenge I Challenge II Paint Wt. 1 2 3 6 1 2 3 6 Paint A Susp. Conc. 0.05 0 0 0 0 0 0 0 0 Commercial 0.05 0 0 0 0 0 0 0 0 Control — 4 4 4 4 4 4 4 4 Paint B Susp. Conc. 0.1 0 0 0 0 1 0 0 0 Commercial 0.1 0 1 0 0 0 0 0 0 Control — 4 4 4 4 4 4 4 4 - Example 15 was repeated using propiconazole instead of IPBC. Similar results were obtained.
- Example 19 was repeated using a combination of IPBC and propiconazole in the weight ratio of 1:2. Similar results were obtained.
- Example 15 was repeated using Folpet instead of IPBC. Similar results were obtained.
- Example 15 was repeated using chlorothalonil. Similar results were obtained.
- While the invention has been described with particular reference to certain embodiments thereof, it will be understood that changes and modifications may be made which are within the skill of the art.
Claims (20)
Priority Applications (12)
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| US11/388,553 US20070224135A1 (en) | 2006-03-24 | 2006-03-24 | Stable aqueous suspension concentrate for delivery of UV-labile water-insoluble biocides |
| KR1020087025820A KR20090008262A (en) | 2006-03-24 | 2007-03-26 | Stable aqueous suspension concentrate for delivery of biocides that are labile to water and insoluble in water |
| EP07754009A EP1998739A4 (en) | 2006-03-24 | 2007-03-26 | Stable aqueous suspension concentrate for delivery of uv-labile water-insoluble biocides |
| CA2646280A CA2646280C (en) | 2006-03-24 | 2007-03-26 | Stable aqueous suspension concentrate for delivery of uv-labile water-insoluble biocides |
| EP15199852.3A EP3023089A1 (en) | 2006-03-24 | 2007-03-26 | Stable aqueous suspension concentrate for delivery of uv-labile water-insoluble biocides |
| JP2009501608A JP5306177B2 (en) | 2006-03-24 | 2007-03-26 | Stable aqueous suspension concentrates, compositions, coating compositions, personal care compositions, products and stable water dispersible solids |
| PCT/US2007/007432 WO2007112091A2 (en) | 2006-03-24 | 2007-03-26 | Stable aqueous suspension concentrate for delivery of uv-labile water-insoluble biocides |
| CNA2007800106555A CN101505600A (en) | 2006-03-24 | 2007-03-26 | Stable aqueous suspension concentrates for delivery of UV-labile water-insoluble antimicrobials |
| BRPI0709118A BRPI0709118B1 (en) | 2006-03-24 | 2007-03-26 | stable aqueous suspension concentrate, its compositions and article comprising substrate coated with said concentrate |
| AU2007230909A AU2007230909B9 (en) | 2006-03-24 | 2007-03-26 | Stable aqueous suspension concentrate for delivery of UV-labile water-insoluble biocides |
| MX2008012137A MX2008012137A (en) | 2006-03-24 | 2007-03-26 | Stable aqueous suspension concentrate for delivery of uv-labile water-insoluble biocides. |
| US12/966,623 US9044010B2 (en) | 2006-03-24 | 2010-12-13 | Stable aqueous suspension concentrate for delivery of UV-labile water-insoluble biocides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/388,553 US20070224135A1 (en) | 2006-03-24 | 2006-03-24 | Stable aqueous suspension concentrate for delivery of UV-labile water-insoluble biocides |
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| US12/966,623 Continuation US9044010B2 (en) | 2006-03-24 | 2010-12-13 | Stable aqueous suspension concentrate for delivery of UV-labile water-insoluble biocides |
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| US12/966,623 Expired - Fee Related US9044010B2 (en) | 2006-03-24 | 2010-12-13 | Stable aqueous suspension concentrate for delivery of UV-labile water-insoluble biocides |
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| US (2) | US20070224135A1 (en) |
| EP (2) | EP1998739A4 (en) |
| JP (1) | JP5306177B2 (en) |
| KR (1) | KR20090008262A (en) |
| CN (1) | CN101505600A (en) |
| AU (1) | AU2007230909B9 (en) |
| BR (1) | BRPI0709118B1 (en) |
| CA (1) | CA2646280C (en) |
| MX (1) | MX2008012137A (en) |
| WO (1) | WO2007112091A2 (en) |
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-
2007
- 2007-03-26 BR BRPI0709118A patent/BRPI0709118B1/en not_active IP Right Cessation
- 2007-03-26 CN CNA2007800106555A patent/CN101505600A/en active Pending
- 2007-03-26 KR KR1020087025820A patent/KR20090008262A/en not_active Ceased
- 2007-03-26 JP JP2009501608A patent/JP5306177B2/en not_active Expired - Fee Related
- 2007-03-26 EP EP07754009A patent/EP1998739A4/en not_active Withdrawn
- 2007-03-26 MX MX2008012137A patent/MX2008012137A/en active IP Right Grant
- 2007-03-26 AU AU2007230909A patent/AU2007230909B9/en not_active Ceased
- 2007-03-26 EP EP15199852.3A patent/EP3023089A1/en not_active Withdrawn
- 2007-03-26 WO PCT/US2007/007432 patent/WO2007112091A2/en not_active Ceased
- 2007-03-26 CA CA2646280A patent/CA2646280C/en not_active Expired - Fee Related
-
2010
- 2010-12-13 US US12/966,623 patent/US9044010B2/en not_active Expired - Fee Related
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060045914A1 (en) * | 2004-08-26 | 2006-03-02 | Isp Investments Inc. | Matrix composition for stable microemulsions |
| US20100239629A1 (en) * | 2006-07-31 | 2010-09-23 | Isp Investments Inc. | Delivery system for delivering bioactive materials |
| US8747871B2 (en) | 2006-09-28 | 2014-06-10 | Isp Investments Inc. | Synergistic matrix composite for making stable microemulsions of active ingredients |
| US20080081059A1 (en) * | 2006-09-28 | 2008-04-03 | Narayanan Kolazi S | Synergistic matrix composite for making stable microemulsions of active ingredients |
| EP2442643A4 (en) * | 2009-06-17 | 2014-08-06 | Isp Investments Inc | A process for preparation of stable, microencapsulated and sustained release biocidal actives and composition thereof |
| US20120164203A1 (en) * | 2009-06-17 | 2012-06-28 | Raman Premachandran | Process for preparation of stable, microencapsulated and sustained release biocidal actives and composition thereof |
| WO2010148158A1 (en) * | 2009-06-17 | 2010-12-23 | Isp Investments Inc. | A process for preparation of stable, microencapsulated and sustained release biocidal actives and composition thereof |
| US20130045241A1 (en) * | 2009-12-07 | 2013-02-21 | Isp Investments Inc. | Stabilized aqueous dispersion of folpet analogues, method of preparing the same and composition thereof |
| CN103392735A (en) * | 2013-06-30 | 2013-11-20 | 广东中迅农科股份有限公司 | Pesticide suspending agent containing inorganic nano-material and preparation method thereof |
| US11933048B2 (en) | 2014-02-21 | 2024-03-19 | Owens Corning Intellectual Capital, Llc | Shingles with increased hydrophobicity |
| US12276107B2 (en) | 2014-02-21 | 2025-04-15 | Owens Corning Intellectual Capital, Llc | Shingles with increased hydrophobicity |
| WO2018185710A1 (en) * | 2017-04-07 | 2018-10-11 | Sabic Global Technologies B.V. | Durable surface hardened coating or overcoating for protecting plants from pests |
| US12091859B2 (en) | 2018-06-29 | 2024-09-17 | Owens Corning Intellectual Capital, Llc | Roofing materials including a parting agent layer |
| US11359377B2 (en) * | 2018-07-11 | 2022-06-14 | Owens Corning Intellectual Capital, Llc | Shingles with increased hydrophobicity |
| US11629496B2 (en) | 2018-07-11 | 2023-04-18 | Owens Corning Intellectual Capital, Llc | Shingles with increased hydrophobicity |
| US20220023475A1 (en) * | 2019-02-15 | 2022-01-27 | Whiteley Corporation Pty Ltd | Improved endoscope disinfectant |
| US12427215B2 (en) * | 2019-02-15 | 2025-09-30 | Whiteley Corporation Pty Ltd | Endoscope disinfectant |
| CN110140721A (en) * | 2019-06-11 | 2019-08-20 | 珠海润硕生物技术有限公司 | Agent and preparation method thereof is lost in a kind of new pesticide control |
| US12065835B2 (en) | 2019-12-03 | 2024-08-20 | Owens Corning Intellectual Capital, Llc | Roofing materials including a layer of a parting agent |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5306177B2 (en) | 2013-10-02 |
| WO2007112091A3 (en) | 2009-04-09 |
| MX2008012137A (en) | 2008-10-03 |
| KR20090008262A (en) | 2009-01-21 |
| US9044010B2 (en) | 2015-06-02 |
| AU2007230909A1 (en) | 2007-10-04 |
| US20110081555A1 (en) | 2011-04-07 |
| CN101505600A (en) | 2009-08-12 |
| BRPI0709118B1 (en) | 2016-06-14 |
| AU2007230909B2 (en) | 2013-11-07 |
| EP1998739A4 (en) | 2012-10-31 |
| EP1998739A2 (en) | 2008-12-10 |
| EP3023089A1 (en) | 2016-05-25 |
| AU2007230909B9 (en) | 2014-03-27 |
| WO2007112091A2 (en) | 2007-10-04 |
| CA2646280A1 (en) | 2007-10-04 |
| CA2646280C (en) | 2014-08-05 |
| JP2009533329A (en) | 2009-09-17 |
| BRPI0709118A2 (en) | 2011-06-28 |
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