JPH02108602A - Stable oil-in-water type emulsified agricultural chemical composition - Google Patents
Stable oil-in-water type emulsified agricultural chemical compositionInfo
- Publication number
- JPH02108602A JPH02108602A JP63261317A JP26131788A JPH02108602A JP H02108602 A JPH02108602 A JP H02108602A JP 63261317 A JP63261317 A JP 63261317A JP 26131788 A JP26131788 A JP 26131788A JP H02108602 A JPH02108602 A JP H02108602A
- Authority
- JP
- Japan
- Prior art keywords
- composition
- water
- agricultural chemical
- poly
- oil
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 239000003905 agrochemical Substances 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 13
- -1 ethylene, propylene Chemical group 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 15
- 238000002844 melting Methods 0.000 claims abstract description 14
- 230000008018 melting Effects 0.000 claims abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 10
- 230000008025 crystallization Effects 0.000 claims abstract description 10
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims abstract description 3
- 239000000575 pesticide Substances 0.000 claims description 18
- 239000007764 o/w emulsion Substances 0.000 claims description 13
- 238000003860 storage Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 abstract description 6
- YWYHGNUFMPSTTR-UHFFFAOYSA-N 1-methyl-4-(4-methylphenoxy)benzene Chemical compound C1=CC(C)=CC=C1OC1=CC=C(C)C=C1 YWYHGNUFMPSTTR-UHFFFAOYSA-N 0.000 abstract description 2
- 241000196324 Embryophyta Species 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 18
- 239000000839 emulsion Substances 0.000 description 15
- 239000013078 crystal Substances 0.000 description 14
- 239000003995 emulsifying agent Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 239000008399 tap water Substances 0.000 description 5
- 235000020679 tap water Nutrition 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- XCSGPAVHZFQHGE-UHFFFAOYSA-N alachlor Chemical compound CCC1=CC=CC(CC)=C1N(COC)C(=O)CCl XCSGPAVHZFQHGE-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- UXZAJSZFFARTEI-GUMHCPJTSA-N methyl (2R,3S)-3-(methanesulfonamido)-2-[(4-phenylcyclohexyl)oxymethyl]piperidine-1-carboxylate Chemical compound COC(=O)N1CCC[C@H](NS(C)(=O)=O)[C@@H]1COC1CCC(CC1)c1ccccc1 UXZAJSZFFARTEI-GUMHCPJTSA-N 0.000 description 3
- 235000019645 odor Nutrition 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical group C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- XJFIKRXIJXAJGH-UHFFFAOYSA-N 5-chloro-1,3-dihydroimidazo[4,5-b]pyridin-2-one Chemical group ClC1=CC=C2NC(=O)NC2=N1 XJFIKRXIJXAJGH-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 239000005945 Chlorpyrifos-methyl Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012872 agrochemical composition Substances 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229920006127 amorphous resin Polymers 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 125000006353 oxyethylene group Chemical group 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 229950004959 sorbitan oleate Drugs 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- RIGGBTNEASBFER-UHFFFAOYSA-N 1,2-dimethyl-3,4-bis(1-phenylethyl)benzene Chemical group C=1C=C(C)C(C)=C(C(C)C=2C=CC=CC=2)C=1C(C)C1=CC=CC=C1 RIGGBTNEASBFER-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- 101100235626 Caenorhabditis elegans hlb-1 gene Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 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 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940009868 aluminum magnesium silicate Drugs 0.000 description 1
- WMGSQTMJHBYJMQ-UHFFFAOYSA-N aluminum;magnesium;silicate Chemical compound [Mg+2].[Al+3].[O-][Si]([O-])([O-])[O-] WMGSQTMJHBYJMQ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000013011 aqueous formulation Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical class OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical group CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- GTCAXTIRRLKXRU-UHFFFAOYSA-N carbamic acid methyl ester Natural products COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000013583 drug formulation Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- DIRFUJHNVNOBMY-UHFFFAOYSA-N fenobucarb Chemical compound CCC(C)C1=CC=CC=C1OC(=O)NC DIRFUJHNVNOBMY-UHFFFAOYSA-N 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000003966 growth inhibitor Substances 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- BOTNYLSAWDQNEX-UHFFFAOYSA-N phenoxymethylbenzene Chemical compound C=1C=CC=CC=1COC1=CC=CC=C1 BOTNYLSAWDQNEX-UHFFFAOYSA-N 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 230000000885 phytotoxic effect Effects 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229940071089 sarcosinate Drugs 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical group CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は新規な水中油型乳濁状１％薬製剤に関するもの
である。更に、詳しくは、０〜５０℃付近に融点を有す
る疎水性農薬を水中に乳濁状となし、かつ、長期にわた
って低温に於ける結晶化を抑制されて、安定化された組
成物の製造に関するものである。本発明は溶剤を使用す
ることなく、水を用いる農薬組成物であるため、使用者
に対しても安全であり、希釈施用でも、又微量散布によ
る直接施用にも有効な水性製剤を提供するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel oil-in-water emulsion 1% drug formulation. More specifically, it relates to the production of a composition in which a hydrophobic pesticide having a melting point in the vicinity of 0 to 50°C is emulsified in water and is stabilized by suppressing crystallization at low temperatures for a long period of time. It is something. Since the present invention is an agrochemical composition that uses water without using a solvent, it is safe for users and provides an aqueous formulation that is effective even when applied diluted or directly applied by spraying in a small amount. It is.
〈従来技術及び問題点〉
農薬は実用にあたっては、一般に粉剤、水和剤、粒剤、
乳剤、液剤、流動剤等に製剤化されるが、近年、省資源
化、毒性及び薬害の軽減、引火及び悪臭防止、漂流飛散
や流口防止などの見地から、有機溶剤や鉱物微粉末担体
を使用することなく、製剤とする技術として、水又は水
性媒体を用いる流動剤が開発され、実用化されてきた。<Prior art and problems> In practical use, agricultural chemicals are generally prepared as powders, wettable powders, granules,
It is formulated into emulsions, solutions, flow agents, etc., but in recent years, organic solvents and fine mineral powder carriers have been used to save resources, reduce toxicity and chemical damage, prevent ignition and bad odors, and prevent drifting and scattering. A fluidizing agent using water or an aqueous medium has been developed and put into practical use as a technique for preparing a formulation without the use of water or an aqueous medium.
この水性流動剤には、融点が６０〜７０℃以上である疎
水性固体農薬を水中に０．５〜５ミクロン程度の粒子を
なし、これに分散剤（界面活性剤）、増粘剤（水溶性高
分子物質又は無機増粘剤）等を含有させ、更に必要なら
ば氷結防止剤、結晶成長防止剤、分解防止剤、消泡剤、
防腐剤等を加用した固体懸濁剤（フロアブル、ゾル）、
融点が通常０℃付近以下であって、常温では液状である
疎水性農薬を乳化剤（界面活性剤）、増粘剤（同上）を
用いて、水中に微細な乳化粒子となし、更に、必要なら
ば上記各種補助添加成分を加用した乳濁製剤（エマルシ
ョン剤）及び両者を併存させたサスポ−エマルション剤
がある。This aqueous flow agent consists of a hydrophobic solid pesticide with a melting point of 60 to 70°C or higher, formed into particles of about 0.5 to 5 microns in water, and a dispersant (surfactant) and a thickener (water-soluble polymeric substances or inorganic thickeners), and if necessary, anti-icing agents, crystal growth inhibitors, decomposition inhibitors, antifoaming agents, etc.
Solid suspensions containing preservatives (flowables, sols),
Hydrophobic agricultural chemicals, which have a melting point usually below 0°C and are liquid at room temperature, are made into fine emulsified particles in water using emulsifiers (surfactants) and thickeners (same as above), and further, if necessary. For example, there are emulsion preparations (emulsions) to which the above-mentioned various auxiliary additive components are added, and suspension emulsions in which both are present together.
これら流動剤は通常−５℃〜４０℃又は５０℃程度の長
期にわたる保存中、懸濁粒子又は乳濁粒子の凝集、合−
及び結晶成長などが生ずるために、懸濁製剤では有効成
分の沈降、凝結、粒径増大、等が、又、乳濁製剤では、
クリーム分離、油層分離、凝集等が生じ易く、この現象
の防止に多大の工夫がなされてきた。These fluidizing agents usually cause suspended particles or emulsified particles to aggregate or coalesce during long-term storage at temperatures between -5°C to 40°C or 50°C.
and crystal growth, etc., occur in suspension preparations, precipitation, coagulation, particle size increase, etc. of the active ingredient, and in emulsion preparations,
Cream separation, oil layer separation, aggregation, etc. tend to occur, and many efforts have been made to prevent these phenomena.
しかしながら、融点が０〜５０℃付近にある疎水性農薬
の場合には、−５℃〜４０℃又は５０℃の保存条件では
、農薬の結晶化と溶融が不可避的に伴なうために、組成
物が極度に不安定化し易く、結晶成長、粒子凝結、乳化
破壊、油層分離等が速やかに進行するため、安定な組成
物を得ることが困難である場合が通常であり、解決方法
が強く望まれてきた。However, in the case of hydrophobic pesticides with melting points in the vicinity of 0 to 50°C, storage conditions of -5 to 40°C or 50°C will inevitably lead to crystallization and melting of the pesticide; It is common for it to be difficult to obtain stable compositions because crystal growth, particle coagulation, demulsification, oil layer separation, etc. proceed rapidly, and a solution is strongly desired. It has become rare.
この問題を解決する試みとして２〜３の方法が考案され
てきた。特開昭６２−１６７７０２号公報には多芳香環
溶剤が、又、特開昭６２−２４０６０１号公報には、エ
ステル類、トルアミド類、塩素化パラフィン、塩素化ベ
ンゼン、高級脂肪酸類。A few methods have been devised in an attempt to solve this problem. JP-A-62-167702 discloses polyaromatic ring solvents, and JP-A-62-240601 describes esters, toluamides, chlorinated paraffins, chlorinated benzene, and higher fatty acids.
ナフタレン誘導体等を水中油型懸濁剤の結晶防止剤とし
て使用することが記載されている。これら記載の化合物
は、いずれも主として溶剤として、常温では固体の疎水
性農薬と加温して融解して溶解させるため、即ち、本来
、対象となる疎水性農薬の溶解度が不十分なこれら記載
の化合物中に加温溶解した後、水中油型乳濁状組成物と
なすため、短期の保存では、安定な乳濁状組成を得るこ
とができても、長期に渡る保存や低温（−５〜−１Ｏ℃
）での保存又は、変温保存では農薬が結晶析出・成長す
る場合がほとんどであり、保存安定性の良好な水中油型
乳濁状組成物を作成することが困難であり、主要な原因
となってきた。The use of naphthalene derivatives and the like as crystallization inhibitors for oil-in-water suspensions has been described. All of these compounds are mainly used as solvents to melt and dissolve hydrophobic pesticides, which are solid at room temperature, by heating. After heating and dissolving the compound, it forms an oil-in-water emulsion composition. -1O℃
) or variable temperature storage, pesticides often precipitate and grow as crystals, making it difficult to create oil-in-water emulsion compositions with good storage stability, and this is the main cause. It has become.
従って、これら結晶防止溶剤を多量に含有させたり、又
農薬の含有率を低下させたりする欠点があり、実用的見
地から更に改良が望まれてきた。Therefore, there are disadvantages in that a large amount of these crystallization-preventing solvents are contained and the content of agricultural chemicals is reduced, and further improvements have been desired from a practical standpoint.
〈発明が解決しようとする間層点〉
本発明は０〜５０℃付近に融点をもつ疎水性農薬の水中
油型乳濁状組成物を製造するに際し、主として溶剤を使
用する従来技術では十分に実現することが出来なかった
常温以下、特に−５℃程度の長期存在中の結晶化を抑制
して外観上も又、組成上も均一で安定な農薬組成物を作
成することにある。<Interlayer Point to be Solved by the Invention> The present invention solves the problem in producing an oil-in-water emulsion composition of a hydrophobic agricultural chemical having a melting point in the vicinity of 0 to 50°C. The object of this invention is to suppress crystallization during long-term presence at temperatures below room temperature, particularly at about -5° C., and to create a stable agrochemical composition that is uniform in appearance and composition.
本発明者らは、鋭意研究を重ね、こ゛の問題を解決する
ための添加すべき化合物とその実用化技術をみいだして
、本発明を完成するに至ったものである。The inventors of the present invention have conducted intensive research and have discovered the compound to be added to solve this problem and the technology for its practical application, and have completed the present invention.
く間層点を解決するための手段〉
本発明は従来技術が本来、溶解度が十分でない溶剤と常
温で固体の農薬を、その農薬の融点以上に一度加温して
融解して溶解させてから、水中油型乳濁状組成物となす
ために、組成物の常温以下、特に−５℃程度の保存に於
いては過飽和状態であるので、徐々に農薬の結晶化が生
ずる点を解決するため、下記■〜ｍで表示される化合物
と、０〜５０℃付近に融点を有する疎水性農薬を５０〜
６０℃程度に加温・融解した後、混合・溶解し、更に水
中油型乳濁状組成物とするものであるが、１〜ｍで示さ
れる化合物は次の様な特性を有するものである。即ち常
温では粘稠な液体であるが５０〜６０℃の加温状態では
比較的低粘度となる。又、芳香環を３〜５ケ有するため
に、疎水性農薬とはいかなる率でも相溶することができ
、常温以下、特に−５℃程度では、極めて粘度の高い非
晶質性樹脂状態を形成することが出来る。従って、５０
〜６０℃程度に加温されて融解した疎水性農薬はＩ〜■
で表示される化合物と相溶混合物を形成し、常温又は−
５℃附近では、相溶した疎水性農薬を結晶化に導くこと
なく、高粘性の不水溶性非晶質樹脂状態となって農薬の
結晶化や結晶成長を抑制すると考えられる。Means for Solving Interlayer Points> The present invention is based on the conventional technology, in which a solvent that does not have sufficient solubility and a pesticide that is solid at room temperature are heated once above the melting point of the pesticide to melt and dissolve. To solve the problem that, in order to form an oil-in-water emulsion composition, when the composition is stored below room temperature, especially at around -5°C, it is in a supersaturated state, so that the pesticide gradually crystallizes. , Compounds shown in
After heating and melting to about 60°C, they are mixed and dissolved to form an oil-in-water emulsion composition, and the compounds represented by 1 to m have the following characteristics. . That is, it is a viscous liquid at room temperature, but becomes relatively low in viscosity when heated to 50 to 60°C. In addition, since it has 3 to 5 aromatic rings, it can be miscible with hydrophobic pesticides at any rate, and forms an extremely viscous amorphous resin state below room temperature, especially at around -5°C. You can. Therefore, 50
Hydrophobic pesticides that have been heated to ~60°C and melted are I~■
Forms a compatible mixture with the compound represented by and at room temperature or -
At around 5° C., it is thought that the hydrophobic agricultural chemicals dissolved in the resin become a highly viscous water-insoluble amorphous resin state, suppressing the crystallization and crystal growth of the agricultural chemicals, without leading them to crystallization.
又、１〜ｍで表示される化合物中の酸化アルキレン附加
部分は、これら化合物を水溶性に導びかないようにすべ
きである。特に酸化エチレンは、１〜ｍで表示される化
合物を水溶性に導びかない程度にその附加を止めるべき
である。これら酸化アルキレンの付加は、Ｉ〜■で表示
される化合物の低温に於ける高粘度化、常温以上に於る
低粘度化に重要な作用を示す。Also, the alkylene oxide adduct in the compounds represented by 1 to m should not lead to water solubility of these compounds. In particular, the addition of ethylene oxide should be stopped to such an extent that the compounds represented by 1 to m do not become water-soluble. The addition of these alkylene oxides has an important effect on increasing the viscosity of the compounds represented by I to ① at low temperatures and decreasing the viscosity at temperatures above room temperature.
■ ：
（Ｉ及び■中、Ｒ１はエチレン、プロビレ又はブチレン
、Ｒ８は水素、ベンジル又はα−メチルベンジル、Ｒ３
は水素、炭素数１〜９のアルキル又はフェニル、Ｒ４は
炭素数１〜５のアルキレン、ｒｎは１〜１０の整数、ｎ
は１〜３の整数を示す）■：樹脂酸又は不均化樹脂酸の
エチレンオキシド、プロピレンオキシド又はブチレンオ
キシド附加反応物（付加モル数１〜１０）。■: (In I and ■, R1 is ethylene, propylene or butylene, R8 is hydrogen, benzyl or α-methylbenzyl, R3
is hydrogen, alkyl or phenyl having 1 to 9 carbon atoms, R4 is alkylene having 1 to 5 carbon atoms, rn is an integer of 1 to 10, n
(indicates an integer of 1 to 3) ■: Addition reaction product of resin acid or disproportionated resin acid with ethylene oxide, propylene oxide, or butylene oxide (number of moles added is 1 to 10).
これら■〜■で表示される化合物は、化学的に極めて安
定であると共に、引火点は２００℃以上であり、かつ低
臭性であるため、溶剤類にみられる欠点がないのも有利
な点である。These compounds represented by ■ to ■ are chemically extremely stable, have a flash point of 200°C or higher, and have low odor, so they have the advantage of not having the drawbacks found in solvents. It is.
本発明に係る１〜ｍで表示される化合物はすでに公知の
方法で容易に合成することができるものである。即ち、
■及び■の化合物は出発物質としてフェノール、クレゾ
ール、ブチルフェノール、オクチルフェノール、ノニル
フェノール、フェニルフェノール類及び各種ビスフェノ
ール類を用い、フリーデルクラフト触媒（例えば、塩化
アルミニウム、塩化亜鉛、弗化朋素、リン酸、硫酸等）
存在下に塩化ベンジル又はスチレンと７０〜１００℃で
反応させた（過剰の塩化ベンジル又はスチレンは減圧下
に除去することができる）後、アルカリ触媒下に酸化ア
ルキレン（エチレン、プロピレン、ブチレン）を２〜１
０気圧、１５０〜１８０℃の条件で附加することによっ
て得ることができるものである。又、■の化合物は、通
常、蒸留ロジン（樹脂酸主体）をそのまま用いるか、又
はパラジウムブラック等を触媒として不均化反応（２８
０〜３００℃）を行なわせた不均化ロジンを用い。The compounds represented by 1 to m according to the present invention can be easily synthesized by known methods. That is,
Compounds (1) and (2) use phenol, cresol, butylphenol, octylphenol, nonylphenol, phenylphenols, and various bisphenols as starting materials, and use Friedel-Crafts catalysts (e.g., aluminum chloride, zinc chloride, fluoride, phosphoric acid, sulfuric acid, etc.)
After reacting with benzyl chloride or styrene at 70-100 °C in the presence of alkylene oxides (ethylene, propylene, butylene) in the presence of an alkali catalyst (excess benzyl chloride or styrene can be removed under reduced pressure) ~1
It can be obtained by adding under the conditions of 0 atm and 150 to 180°C. In addition, for the compound (2), usually distilled rosin (mainly resin acid) is used as is, or a disproportionation reaction (28
0 to 300°C) was used.
式（１）〜（２）化合物と同様に、酸化アルキレン（エ
チレン、プロピレン、ブチレン）を附加することによっ
て大量に得ることが出来る。Similar to the compounds of formulas (1) and (2), they can be obtained in large quantities by adding alkylene oxide (ethylene, propylene, butylene).
Ｉ〜■で表示される化合物の中より、一般に有用な具体
例として次のものを挙げることができる。Among the compounds represented by I to ■, the following are generally useful specific examples.
■の具体例 （）内の数字はオキシアルキレン基の平均
附加モル数を示す）
■ ポリ（３）オキシプロピレンジベンジルクレジルエ
ーテル
■ ポリ（２）オキシエチレントリベンジルフェニルエ
ーテル
■ ポリ（８）オキシプロピレントリα−メチルベンジ
ルフェニルエーテル
■ ポリ（３）オキシブチレンジα−メチルベンジルオ
クチルフェニルエーテル
■の具体例
■ ポリ（４）オキシプロピレンビスフェノールＡ■
ポリ（２）オキシエチレンポリ（４）オキシプロピレン
ビスフェノールＢ
■ ポリ（８）オキシプロピレンジベンジルビスフェノ
ールＡ
■ ポリ（２）オキシブチレンモノα−メチルベンジル
ビスフェノールＡ
■の具体例
■ ポリ（３）オキシプロピレン樹脂酸エステル［相］
ボ１バ３）オキシエチレンポリバ３）オキシブチレン
樹脂酸エステル
■ ポリ（８）オキシプロピレン不均化樹脂酸エステル
■ ポリ（３）オキシブチレン不均化樹脂酸エステ実用
的な水中油型乳濁状組成物を作成するに当っては、本発
明に係るＩ〜■で表示される化合物の１種又は２種以上
を０〜５０℃附近に融点を有する疎水性農薬１００部に
対して一般的に３０〜１５０％程度、好ましくは、５０
〜ｌＯＯ％程度で十分である場合が多い、予め５０〜６
０℃に加温した０〜５０℃附近に融点をもつ疎水性農薬
と１〜ｍで表示される化合物から選ばれた化合物を混線
し相溶させた後、主として界面活性剤から成る乳化剤を
混合し、更に増粘剤、氷結防止剤、更に必要に応じて分
解防止剤、比重調整剤、ｐＨ緩衡剤、防腐剤、消泡剤等
を含有する水を加え、各種乳化器を用いて、乳濁化して
組成物となすことができる。Specific examples of ■ (The numbers in parentheses indicate the average number of moles added to the oxyalkylene group) ■ Poly(3) oxypropylene dibenzyl cresyl ether ■ Poly(2) oxyethylene tribenzyl phenyl ether ■ Poly(8) oxypropylene Triα-methylbenzylphenyl ether■ Specific example of poly(3) oxybutylene diα-methylbenzyloctylphenyl ether■ Poly(4) oxypropylene bisphenol A■
Poly(2) oxyethylene poly(4) oxypropylene bisphenol B ■ Poly(8) oxypropylene dibenzyl bisphenol A ■ Specific examples of poly(2) oxybutylene mono α-methylbenzyl bisphenol A ■ Poly(3) oxypropylene Resin acid ester [phase]
Bo1ba 3) Oxyethylene polyba3) Oxybutylene resin acid ester ■ Poly(8) oxypropylene disproportionated resin acid ester ■ Poly(3) oxybutylene disproportionated resin acid ester Practical oil-in-water emulsion When preparing a composition, one or more of the compounds represented by I to ■ according to the present invention are generally added to 100 parts of a hydrophobic pesticide having a melting point around 0 to 50°C. About 30 to 150%, preferably 50%
~lOO% is often sufficient, 50~6 in advance
A hydrophobic pesticide with a melting point in the vicinity of 0 to 50 degrees Celsius heated to 0 degrees Celsius is mixed with a compound selected from compounds represented by 1 to m to make them compatible, and then an emulsifier mainly consisting of a surfactant is mixed. Then, add water containing a thickener, an anti-icing agent, and if necessary, an anti-decomposition agent, a specific gravity adjuster, a pH buffer, a preservative, an anti-foaming agent, etc., and use various emulsifiers. It can be emulsified into a composition.
乳化剤としては、一般に界面活性剤と増粘剤としての水
溶性高分子化合物の単用又は併用によって、乳濁状組成
物を得ることができる。乳化剤を構成する界面活性剤は
一般にノニオン性界面活性剤及びアニオン性界面活性剤
の１種又は２種以上が選択されて用いられる。As an emulsifier, an emulsified composition can generally be obtained by using a surfactant and a water-soluble polymer compound as a thickener alone or in combination. As the surfactant constituting the emulsifier, one or more of nonionic surfactants and anionic surfactants are generally selected and used.
ノニオン性界面活性活性剤としては、ソルビタン脂肪酸
エステル、ポリオキシエチレン（以下Ｐ。Nonionic surfactants include sorbitan fatty acid ester and polyoxyethylene (hereinafter referred to as P).
Ｅ）ソルビタン脂肪酸エステル、蔗糖脂肪酸エステル、
ＰＯＥアルキルエーテル、ＰＯＥ肪脂酸エステル、ＰＯ
Ｅ植物油、ＰＯＥアルキルアミン、ＰＯＥ肪脂酸アミド
、ＰＯＥモノ及びジフェニルエーテル、ＰＯＥアルキル
フェニルエーテル−ホルムアルデヒド縮合物、ポリオキ
シアルキレン（エチレン及びプロピレン、以下ＰＯＡ）
ベンジル（又はスチリル、又はシクロヘキシル）化フェ
ニル（又はクレジル又はフェニルフェニル）エーテル、
ＰＯＥアビエチン酸エステル、ポリオキシエチレンーポ
リオキシブロビレンブロックボリマー、ＰＯＥビスフェ
ノール等が又、アニオン性界面活性剤としてはアルキル
サルフェート、アルキルベンゼンスルホネート、アルキ
ルナフタレンスルホネ゛−ト、ナフタレンスルホネート
ホルムアルデヒド縮合物、ジアルキルスルホサクシネー
ト、ＡＯ５、ＰＯＥアルキルフェニルエーテルサルフェ
ート及びフォスフェート、ＰＯＥアルキルエーテルサル
フェート及びフォスフェート、Ｎ−メチル肪脂酸タウリ
ド、肪脂酸ザルコシネート、ＰＯＥベンジル（又はスチ
リル又はシクロヘキシル）化フェノール（又はクレジル
又はフェニルフェニル）エーテルサルフェート又はフェ
オスフエート、ポリオキシエチレンーポリオキシプロピ
レンブロックポリマーサルフエート又はフォスフェート
、リグニンスルネート等が選択・配合されて゛使用され
る。E) Sorbitan fatty acid ester, sucrose fatty acid ester,
POE alkyl ether, POE fatty acid ester, PO
E vegetable oil, POE alkylamine, POE fatty acid amide, POE mono- and diphenyl ether, POE alkylphenyl ether-formaldehyde condensate, polyoxyalkylene (ethylene and propylene, hereinafter referred to as POA)
benzyl (or styryl, or cyclohexyl) phenyl (or cresyl or phenylphenyl) ether,
POE abietic acid ester, polyoxyethylene-polyoxybrobylene block polymer, POE bisphenol, etc., and anionic surfactants such as alkyl sulfate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, naphthalene sulfonate formaldehyde condensate, Dialkyl sulfosuccinate, AO5, POE alkyl phenyl ether sulfate and phosphate, POE alkyl ether sulfate and phosphate, N-methyl fatty acid tauride, fatty acid sarcosinate, POE benzylated (or styryl or cyclohexyl) phenol (or cresyl) Alternatively, phenyl phenyl) ether sulfate or pheosphate, polyoxyethylene-polyoxypropylene block polymer sulfate or phosphate, lignin sulfate, etc. are selected and blended for use.
又、増粘性高分子物質を用いる場合には、水溶性高分子
物質としては、Ｐ、Ｖ、Ａ、Ｃ，Ｍ、Ｃ，Ｍ。In addition, when using a thickening polymer substance, examples of the water-soluble polymer substance include P, V, A, C, M, C, and M.
Ｃ，Ｈ，Ｅ、Ｃ、アルギン酸、カラギーナン、ゼラチン
、アラビアガム、グアガム、ザンサンガム、トラガカン
トガム、ポリアクリレート、アクリレ−トルメチルメタ
アクリレート共重合体、セルロース硫酸、ポリスチレン
スルホン酸等が、又、無機性高分子としてはポリリン酸
、ポリシリケート、ベントナイト、アルミニウムマグネ
シウムシリケート、合成ケイ酸等が選択・配合される。Inorganic high As molecules, polyphosphoric acid, polysilicate, bentonite, aluminum magnesium silicate, synthetic silicic acid, etc. are selected and blended.
本発明に係る水中油型乳濁状組成物の一船釣組成一、デ
ィスパーザ−で十分であり、通常２０００〜ｉｏ、ｏｏ
Ｏｒｐｍ、５〜ｌＯ分間の乳化でＯ９１〜１ミクロン程
度及び２００−１０００ ｃ Ｐ ｓの粘性を有する乳
濁状組成物を容易に得ることができる。One boat fishing composition of the oil-in-water emulsion composition according to the present invention, a disperser is sufficient, and usually 2000 to io, oo
By emulsifying the emulsion for 5 to 10 minutes, an emulsion composition having an O91 to 1 micron and a viscosity of 200 to 1000 cPs can be easily obtained.
このようにして作成された乳濁状組成物は、通常実用に
際しては一般に倉庫等に１〜３年程度保管されるため、
低温時−５℃〜−１０℃、高温時３０〜３５℃、室温等
を考慮して、長期保存試験条件としては一般に一５℃、
室温、４０℃又は５０℃に於る経時試験が２〜３ケ月実
施される場合が多い。この場合、保存試験中に農薬の結
晶化や結晶成長や乳化粒子の肥大化及び乳化破壊（クリ
ーミング、油層分離）又は大量の水層分離等が生じたり
、又農薬の分解、着色、ｐＨ変化が許容範囲を越えない
よう組成物の構成を調整１選択する必要がある。The emulsion composition created in this way is generally stored in a warehouse for about 1 to 3 years during practical use.
Taking into consideration -5℃ to -10℃ at low temperature, 30 to 35℃ at high temperature, room temperature, etc., long-term storage test conditions are generally -5℃,
A time test at room temperature, 40°C or 50°C is often carried out for 2 to 3 months. In this case, crystallization or crystal growth of the pesticide, enlargement of emulsified particles, destruction of the emulsification (creaming, oil layer separation), or large amount of water layer separation may occur during the storage test, or decomposition, coloration, or pH change of the pesticide may occur. It is necessary to adjust the composition of the composition so as not to exceed the permissible range.
〈作用及び発明の効果〉
本発明に係る０〜５０℃附近に融点をもつ疎水性１％薬
の水中油型乳濁状組成物は常温以下、特に−５℃程度の
低温における長期にわたる保存中、農薬を液状に保持し
ており、従って農薬の結晶析出を効果的に抑制するので
、−５℃〜４０℃又は５０℃の温度域にわたって、乳濁
状態を安定に保持することができ、かつ乳濁状態の不安
定化、例えばクリーミングや油層分離の生じない均一で
安定な水中油型組成物を得ることができる。<Operation and Effects of the Invention> The oil-in-water emulsion composition of the hydrophobic 1% drug having a melting point around 0 to 50°C according to the present invention is stable during long-term storage at room temperature or below, especially at a low temperature of about -5°C. , since the pesticide is kept in a liquid state, and therefore the precipitation of pesticide crystals is effectively suppressed, the emulsion state can be stably maintained over the temperature range of -5°C to 40°C or 50°C, and A homogeneous and stable oil-in-water composition that does not cause destabilization of the emulsion, such as creaming or oil layer separation, can be obtained.
このようにして作成された水中油型乳濁状組成物は、所
定の倍率に水中に希釈したり、微量散布（ＵＬＶ）とし
て希釈することなく散布したり、又他の製剤例えば水和
剤、乳剤、流動剤、液剤等と混用散布することもできる
。The oil-in-water emulsion composition prepared in this way can be diluted in water to a predetermined ratio, sprayed without dilution as a microscopic application (ULV), or used in other preparations such as hydrating powders, etc. It can also be mixed and sprayed with emulsions, flow agents, liquids, etc.
又この組成物は、水を媒体とする水性組成物であるため
、引火性や臭気がなく（又は少なく）、毒性や薬害作用
も低くなる利点があると共に、農薬の結晶化が防止され
て液状化しているため、雑草や作物への吸収移行が増大
する傾向を有し、薬効増強の可能性も大きくなる場合が
ある。In addition, since this composition is an aqueous composition using water as a medium, it has the advantage of having no (or little) flammability and odor, and low toxicity and phytotoxic effects. Because of this, absorption and transfer to weeds and crops tends to increase, and the possibility of enhancing medicinal efficacy may also increase.
く実 施 例〉
（実施例−１）
０−ｓｅｅ−ブチルフェニルメチルカーバメート（ＢＰ
ＭＣｍ、ｐ、３１〜３２℃）７５ ｇ ｒ、具体例−■
３７ｇｒ及び乳化剤（ＰＯＥスチリルフェニルエーテ
ル（ＨＬＢ １５）３５％重量＋ＰＯＥひまし油（）
［ＬＢ １２）６５％混合物）９ ｇ ｒをホモミキ
サー（日本精機製ユニバーサル型）の乳化容器（ステン
レス製３００ｍＭ）中に仕込み、約６０℃に加温して十
分に混合した後、プロピレングリコール６ｇｒ及び水道
水５３ｇｒを入れ、室温で８．００Ｏｒｐｍで１０分間
撹拌を行って乳化させ、ＢＰＭＣ４０％を含有する水中
油型乳濁状組成物１８０ｇｒを得た。（以下、乳化操作
は同様である。）
（実施例−２）
ジエチル−２，３，５−トリクロロ−６−ビリシルホス
フオロチオエート（クロルビリフォスｍ。Example (Example-1) 0-see-butylphenyl methyl carbamate (BP
MCm, p, 31-32℃) 75 g r, specific example-■
37gr and emulsifier (POE styryl phenyl ether (HLB 15) 35% by weight + POE castor oil ()
[LB 12) 65% mixture) 9 g was placed in an emulsifying container (stainless steel, 300 mM) of a homo mixer (universal type manufactured by Nippon Seiki), heated to approximately 60°C and mixed thoroughly, and then mixed with 6 g of propylene glycol. Then, 53g of tap water was added, and the mixture was emulsified by stirring at room temperature at 8.00 rpm for 10 minutes to obtain 180g of an oil-in-water emulsion composition containing 40% BPMC. (Hereinafter, the emulsification operation is the same.) (Example-2) Diethyl-2,3,5-trichloro-6-bilicylphosphorothioate (chlorbirifos m.
ｐ、４２〜４３℃）３８ｇｒ、具体例−■ ３０ｇｒ及
び乳化剤（ＰＯＥソルビタンオレート（ＨＬＢ １５
）４０％士ソルビタンオレート６０％混合物）１８ｇｒ
を乳化容器に仕込み、約６０℃に加温して混合、溶解し
た後、エチレングリコール７ｇｒ、キサンタンガム２％
水容液１８ｇｒ及び水道水６９ｇｒを入れて室温で乳化
させた。クロルビリフォス２０％を含有する乳濁状組成
物１８０ｇｒを得た。p, 42-43°C) 38gr, Specific example-■ 30gr and emulsifier (POE sorbitan oleate (HLB 15
) 40% sorbitan oleate 60% mixture) 18 gr
Place the ingredients in an emulsifying container, mix and dissolve by heating to about 60℃, then add 7g of ethylene glycol and 2% xanthan gum.
18g of aqueous liquid and 69g of tap water were added and emulsified at room temperature. 180 gr of an emulsion composition containing 20% chlorbilifos was obtained.
（実施例−３）
０、Ｏ−ジエチル−〇−（４−メチル−クマリン−７−
イル）フォスフォロチオエート（ボタサン、ｍ、ｐ、３
８〜３９℃）６０ ｇ ｒ、具体例−■、４５ｇｒ、及
び乳化剤（ＰＯＥ ベンジルフェニルエーテル（ＨＬＢ
１４）５０％＋ＰＯＥノ二ルフ二二ルエーテル（Ｈ
ＬＢ １３）５０％混合物）１５ｇｒを乳化容器に仕
込み、約６０℃に加温して混合・溶解した後プロピレン
グリコール３ｇｒ及びＭｃ Ｉ ｌ ｖａ ｉ ｎｅ
＠清液（ｐ Ｈ５，０）５７ ｇ ｒを加えて室温で乳
化させた。ボタサン３０％を含有する乳濁状組成物１８
０ｇｒを得た。(Example-3) 0,O-diethyl-〇-(4-methyl-coumarin-7-
il) phosphorothioate (botasan, m, p, 3
8-39℃) 60gr, specific example-■, 45gr, and emulsifier (POE benzyl phenyl ether (HLB
14) 50%+POE nonylphyl ether (H
LB 13) 50% mixture) 15g was placed in an emulsification container, heated to approximately 60°C, mixed and dissolved, and then 3g of propylene glycol and McIlva ine.
57 g of @clear liquid (pH 5,0) was added and emulsified at room temperature. Emulsion composition 18 containing 30% Botasan
I got 0gr.
（実施例−４）
ジメチル−２，３，５−トリクロロ−６−ビリシルホス
フオロチオエート（クロルピリホスメチル、ｍ、ｐ、４
５〜４７℃）３８ ｇ ｒ、具体例−０３０ｇｒ及び乳
化剤（ＰＯＥスチリルフェニルエーテル（ＨＬＢ １
４）６０％＋ポリオキシエチレン（６８）ポリオキシプ
ロピレン（１２０）ブロックポリマー４０％混合物）１
５ｇｒを乳化容器に仕込み約６０℃に加温して混合・溶
解した後、プロピレングリコール１２ｇｒ、ＰＶＡｌ０
％水溶液４５ｇｒ及び水道水４０ｇｒを加えて室温で乳
化させた。クロルピリホスメチル２０％を含有する乳濁
状組成物１．８０ ｇ ｒを得た。(Example-4) Dimethyl-2,3,5-trichloro-6-bilysylphosphorothioate (chlorpyrifosmethyl, m, p, 4
5-47°C) 38 gr, specific example-030 gr and emulsifier (POE styryl phenyl ether (HLB 1
4) 60% + polyoxyethylene (68) polyoxypropylene (120) block polymer 40% mixture) 1
After putting 5gr into an emulsification container and heating it to about 60℃ to mix and dissolve, add 12gr of propylene glycol and PVAl0.
% aqueous solution and 40 gr of tap water were added and emulsified at room temperature. 1.80 g of an emulsified composition containing 20% chlorpyrifos-methyl was obtained.
（実施例−５）
２−クロロ−２゛、６°−ジエチル−Ｎ−メトキシメチ
ルアセトアニリド（アラクロール、ｍ、ｐ。(Example-5) 2-chloro-2',6'-diethyl-N-methoxymethylacetanilide (alachlor, m, p.
４０〜４１’Ｃ）６８ｇｒ、具体例−■ ４５ｇｒ及び
乳化剤（ツルポール３２０ 東邦化学工業（株）登録
商標）９ ｇ ｒを乳化容器に仕込み約６５℃に加温し
て溶解させた後、ジエチレングリコール７ｇｒ及び水道
水５１ｇｒを加えて室温で乳化させた。アラクロール３
５％を含有する乳濁状組成物１８０ｇｒを得た。40~41'C) 68gr, Specific example-■ 45gr and emulsifier (Tsurupol 320, registered trademark of Toho Chemical Industries, Ltd.) 9gr were placed in an emulsification container, heated to about 65°C to dissolve, and diethylene glycol 7gr. Then, 51g of tap water was added and emulsified at room temperature. Alachlor 3
180 gr of an emulsion composition containing 5% were obtained.
〈比較例〉
（比較例−１）
実施例−１の内、具体例−■をメチルナフタリンに置き
換えたもの。<Comparative Example> (Comparative Example-1) Of Example-1, Specific Example-■ was replaced with methylnaphthalene.
（比較例−２）
実施例−２の内、具体例−〇をビス−（メチルベンジル
）キシレンに置き換えたもの。(Comparative Example-2) Of Example-2, Specific Example-2 was replaced with bis-(methylbenzyl)xylene.
（比較例−３）
実施例−３の内、具体例−■を１．１−ジフェニルエタ
ンに置き換えたもの。(Comparative Example-3) Of Example-3, Specific Example-■ was replaced with 1.1-diphenylethane.
（比較例−４）
実施例−４の内、具体例−〇をフタル酸ジオクチルエス
テルに置き換えたもの。(Comparative Example 4) Of Example 4, Specific Example 〇 was replaced with phthalic acid dioctyl ester.
（比較例−５）
実施例−５の内、具体例−〇をリン酸トリブチルエステ
ルに置き換えたもの。(Comparative Example-5) Of Example-5, Specific Example-〇 was replaced with tributyl phosphoric acid ester.
〈試験方法〉
（１）長期保存安定性試験法
各実施例及び比較例５０ｇＩＱを白色５０ａ＋ｌｌｌ密
栓付きシリンダー（１ｍＱ目盛り付き）に入れ、密栓を
した上、−５℃及び４０℃に６０日間保存した。<Test method> (1) Long-term storage stability test method Each Example and Comparative Example 50 g IQ was placed in a white 50a + lll sealed cylinder (with 1 mQ scale), sealed tightly, and stored at -5°C and 40°C for 60 days. .
その後、取り出し各測定を行った。After that, it was taken out and various measurements were performed.
（２）外観観察試験
油層、クリーム層、及び水層の分離状態を肉眼にて観察
した。(2) Appearance observation test The state of separation of the oil layer, cream layer, and water layer was observed with the naked eye.
分離層容積を目盛からよみとり ％とじた。The volume of the separated layer was read from the scale and expressed as a percentage.
（３）乳濁粒子測定
１０回シリンダーをゆっくり倒立させて均一としたサン
プル５マイクロリツターを１００ＩＩＱの生理的食塩水
（０，９０ｗ／ｖ ＮａＣＱ溶液）に希釈し、コールタ
−カウンター（日科機（株）製モデルＺＢ型）を用いて
２０℃の粒子径分布を測定し、平均粒子径を算出した。(3) Emulsion particle measurement 10 times 5 microliters of the sample, made homogeneous by slowly inverting the cylinder, was diluted with 100 IIQ physiological saline (0.90 w/v NaCQ solution) and placed in a Coulter counter (Nikikaki). The particle size distribution at 20° C. was measured using a model ZB model manufactured by Co., Ltd., and the average particle size was calculated.
（４）結晶試験
サンプル１００ｓ１２を２５０メツシュ分析篩（ＪＩＳ
規格）に移し、少量の水道水で洗浄して、篩上に残る結
晶の量を肉眼で観察し、次の表示法で記録した。(4) Pass 100s12 of the crystal test sample through a 250 mesh analysis sieve (JIS
After washing with a small amount of tap water, the amount of crystals remaining on the sieve was observed with the naked eye and recorded using the following notation method.
： 結晶なし
± ： 極めて僅かに結晶あり
十 二 明らかに少量の結晶あり
十十： 篩上全体に渉って少量の結晶あり十十＋：
篩上に相当量の結晶あり
評価結果を表に纏めて示したが、本発明品が農薬製剤の
結晶化を十分に抑制していることが明らかである。: No crystals ± : Very few crystals 12 Obviously a small amount of crystals 10 : A small amount of crystals throughout the sieve 10+ :
There was a considerable amount of crystals on the sieve.The evaluation results are summarized in the table, and it is clear that the product of the present invention sufficiently suppresses crystallization of the agricultural chemical formulation.
特許出願人 東邦化学工業株式会社Patent applicant: Toho Chemical Industry Co., Ltd.
Claims (1)
IIIで表示される化合物の１種又は２種以上を含有させ
ることを特徴とする、結晶化を抑制された、保存安定性
の良好なる水中油型乳濁状農薬組成物 I ：式（１） ▲数式、化学式、表等があります▼ II：式（２） ▲数式、化学式、表等があります▼ 〔式（１）及び（２）中、Ｒ＿１はエチレン、プロピレ
ン、又はブチレン、Ｒ＿２はＨ、ベンジル又はα−メチ
ルベンジル、Ｒ＿３は水素、炭素数１〜９のアルキル又
はフェニル、Ｒ＿４は炭素数１〜５のアルキレン、ｍは
１〜１０の整数、ｎは１〜３の整数を示す。〕 III：樹脂酸又は不均化樹脂酸のエチレンオキシド、プ
ロピレンオキシド、又はブチレンオキシド付加物（付加
モル数１〜１０）。[Claims] Hydrophobic agricultural chemicals having a melting point around 0 to 50°C include the following I to
Oil-in-water emulsion pesticide composition I with suppressed crystallization and good storage stability, characterized by containing one or more of the compounds represented by III: Formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ II: Formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In formulas (1) and (2), R_1 is ethylene, propylene, or butylene, R_2 is H, benzyl or α-methylbenzyl, R_3 is hydrogen, alkyl or phenyl having 1 to 9 carbon atoms, R_4 is alkylene having 1 to 5 carbon atoms, m is an integer of 1 to 10, and n is an integer of 1 to 3. ] III: Ethylene oxide, propylene oxide, or butylene oxide adduct of resin acid or disproportionated resin acid (additional mole number 1 to 10).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63261317A JPH02108602A (en) | 1988-10-19 | 1988-10-19 | Stable oil-in-water type emulsified agricultural chemical composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63261317A JPH02108602A (en) | 1988-10-19 | 1988-10-19 | Stable oil-in-water type emulsified agricultural chemical composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02108602A true JPH02108602A (en) | 1990-04-20 |
Family
ID=17360123
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63261317A Pending JPH02108602A (en) | 1988-10-19 | 1988-10-19 | Stable oil-in-water type emulsified agricultural chemical composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02108602A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0669078A1 (en) * | 1994-02-22 | 1995-08-30 | Makhteshim Chemical Works Limited | Low ecotoxic emulsifiable concentrate formulations of pesticides |
| EP0670113A1 (en) * | 1994-02-22 | 1995-09-06 | Makhteshim Chemical Works Limited | Low ecotoxic formulations of pesticides |
| JPH08151302A (en) * | 1994-11-25 | 1996-06-11 | Kao Corp | Efficacy potentiator composition for agrochemical and agrochemical composition |
| WO1999033340A1 (en) * | 1997-12-30 | 1999-07-08 | Aquatrols Holding Co., Inc. | Agrochemical emulsifiable concentrates |
| WO2003075657A1 (en) * | 2002-03-14 | 2003-09-18 | Makhteshim Chemical Works Ltd. | Pesticidal composition comprising a lactate ester as crystal growth inhibitor |
| JP2011511010A (en) * | 2008-02-04 | 2011-04-07 | ダウ アグロサイエンシィズ エルエルシー | Stabilized oil-in-water emulsions containing active agricultural ingredients |
| JP2018062498A (en) * | 2016-10-11 | 2018-04-19 | フマキラー株式会社 | Herbicide |
| JP2018080137A (en) * | 2016-11-18 | 2018-05-24 | フマキラー株式会社 | Pest control composition |
-
1988
- 1988-10-19 JP JP63261317A patent/JPH02108602A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0669078A1 (en) * | 1994-02-22 | 1995-08-30 | Makhteshim Chemical Works Limited | Low ecotoxic emulsifiable concentrate formulations of pesticides |
| EP0670113A1 (en) * | 1994-02-22 | 1995-09-06 | Makhteshim Chemical Works Limited | Low ecotoxic formulations of pesticides |
| JPH08151302A (en) * | 1994-11-25 | 1996-06-11 | Kao Corp | Efficacy potentiator composition for agrochemical and agrochemical composition |
| WO1999033340A1 (en) * | 1997-12-30 | 1999-07-08 | Aquatrols Holding Co., Inc. | Agrochemical emulsifiable concentrates |
| WO2003075657A1 (en) * | 2002-03-14 | 2003-09-18 | Makhteshim Chemical Works Ltd. | Pesticidal composition comprising a lactate ester as crystal growth inhibitor |
| JP2005526752A (en) * | 2002-03-14 | 2005-09-08 | マクテシム・ケミカル・ワークス・リミテツド | Agrochemical composition containing lactic acid ester as crystal growth inhibitor |
| JP4657607B2 (en) * | 2002-03-14 | 2011-03-23 | マクテシム・ケミカル・ワークス・リミテツド | Agrochemical composition containing lactic acid ester as crystal growth inhibitor |
| JP2011511010A (en) * | 2008-02-04 | 2011-04-07 | ダウ アグロサイエンシィズ エルエルシー | Stabilized oil-in-water emulsions containing active agricultural ingredients |
| JP2011511009A (en) * | 2008-02-04 | 2011-04-07 | ダウ アグロサイエンシィズ エルエルシー | Stabilized oil-in-water emulsion containing meptyldinocup |
| JP2015078219A (en) * | 2008-02-04 | 2015-04-23 | ダウ アグロサイエンシィズ エルエルシー | Agriculturally active ingredient containing stabilized oil-in-water type emulsion |
| US9426982B2 (en) | 2008-02-04 | 2016-08-30 | Dow Agrosciences Llc | Stabilized oil-in-water emulsions including agriculturally active ingredients |
| JP2018062498A (en) * | 2016-10-11 | 2018-04-19 | フマキラー株式会社 | Herbicide |
| JP2018080137A (en) * | 2016-11-18 | 2018-05-24 | フマキラー株式会社 | Pest control composition |
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