CN1052142C - 水包油型乳液 - Google Patents
水包油型乳液 Download PDFInfo
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- CN1052142C CN1052142C CN93114791A CN93114791A CN1052142C CN 1052142 C CN1052142 C CN 1052142C CN 93114791 A CN93114791 A CN 93114791A CN 93114791 A CN93114791 A CN 93114791A CN 1052142 C CN1052142 C CN 1052142C
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000000839 emulsion Substances 0.000 claims abstract description 35
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 15
- 239000010452 phosphate Substances 0.000 claims abstract description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 229920000151 polyglycol Polymers 0.000 claims abstract description 7
- 239000010695 polyglycol Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 150000004657 carbamic acid derivatives Chemical class 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 4
- -1 Ammonium ion Chemical class 0.000 claims description 18
- 239000004094 surface-active agent Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 150000003014 phosphoric acid esters Chemical group 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 239000003755 preservative agent Substances 0.000 claims description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 3
- 230000002335 preservative effect Effects 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 208000031295 Animal disease Diseases 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 241000238631 Hexapoda Species 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 239000008346 aqueous phase Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000003745 diagnosis Methods 0.000 claims 1
- 238000010413 gardening Methods 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 239000012071 phase Substances 0.000 claims 1
- 230000006641 stabilisation Effects 0.000 claims 1
- 238000011105 stabilization Methods 0.000 claims 1
- 239000013543 active substance Substances 0.000 abstract description 19
- 235000021317 phosphate Nutrition 0.000 abstract 2
- 238000003898 horticulture Methods 0.000 abstract 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000012141 concentrate Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000007764 o/w emulsion Substances 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- JXSJBGJIGXNWCI-UHFFFAOYSA-N diethyl 2-[(dimethoxyphosphorothioyl)thio]succinate Chemical compound CCOC(=O)CC(SP(=S)(OC)OC)C(=O)OCC JXSJBGJIGXNWCI-UHFFFAOYSA-N 0.000 description 5
- 239000002563 ionic surfactant Substances 0.000 description 5
- 239000005949 Malathion Substances 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000000872 buffer Substances 0.000 description 4
- ZNOLGFHPUIJIMJ-UHFFFAOYSA-N fenitrothion Chemical compound COP(=S)(OC)OC1=CC=C([N+]([O-])=O)C(C)=C1 ZNOLGFHPUIJIMJ-UHFFFAOYSA-N 0.000 description 4
- 229960000453 malathion Drugs 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- PNVJTZOFSHSLTO-UHFFFAOYSA-N Fenthion Chemical compound COP(=S)(OC)OC1=CC=C(SC)C(C)=C1 PNVJTZOFSHSLTO-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical compound CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 description 3
- 239000004530 micro-emulsion Substances 0.000 description 3
- AMFGTOFWMRQMEM-UHFFFAOYSA-N triazophos Chemical compound N1=C(OP(=S)(OCC)OCC)N=CN1C1=CC=CC=C1 AMFGTOFWMRQMEM-UHFFFAOYSA-N 0.000 description 3
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 2
- TVFWYUWNQVRQRG-UHFFFAOYSA-N 2,3,4-tris(2-phenylethenyl)phenol Chemical compound C=1C=CC=CC=1C=CC1=C(C=CC=2C=CC=CC=2)C(O)=CC=C1C=CC1=CC=CC=C1 TVFWYUWNQVRQRG-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- 239000005944 Chlorpyrifos Substances 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical group OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- VJOCYCQXNTWNGC-UHFFFAOYSA-L calcium;benzenesulfonate Chemical compound [Ca+2].[O-]S(=O)(=O)C1=CC=CC=C1.[O-]S(=O)(=O)C1=CC=CC=C1 VJOCYCQXNTWNGC-UHFFFAOYSA-L 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- PAUBOMBHPVULPQ-UHFFFAOYSA-N (1-chloro-6-bicyclo[3.2.0]hepta-2,6-dienyl) dihydrogen phosphate Chemical compound ClC12C=CCC2C(=C1)OP(O)(O)=O PAUBOMBHPVULPQ-UHFFFAOYSA-N 0.000 description 1
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 1
- VJPQWIPWWWFJKR-UHFFFAOYSA-N 2-methyloxirane;2-nonylphenol;oxirane Chemical class C1CO1.CC1CO1.CCCCCCCCCC1=CC=CC=C1O VJPQWIPWWWFJKR-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005947 Dimethoate Substances 0.000 description 1
- CZGGKXNYNPJFAX-UHFFFAOYSA-N Dimethyldithiophosphate Chemical compound COP(S)(=S)OC CZGGKXNYNPJFAX-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 101001062093 Homo sapiens RNA-binding protein 15 Proteins 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- 102100029244 RNA-binding protein 15 Human genes 0.000 description 1
- ISRUGXGCCGIOQO-UHFFFAOYSA-N Rhoden Chemical compound CNC(=O)OC1=CC=CC=C1OC(C)C ISRUGXGCCGIOQO-UHFFFAOYSA-N 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- RNWGYDIGXJHCHP-UHFFFAOYSA-L calcium;dodecane-1-sulfonate Chemical compound [Ca+2].CCCCCCCCCCCCS([O-])(=O)=O.CCCCCCCCCCCCS([O-])(=O)=O RNWGYDIGXJHCHP-UHFFFAOYSA-L 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- OMYMWKVYKBYCBS-UHFFFAOYSA-N diethoxy-(6-methyl-2-propan-2-ylpyrimidin-4-yl)oxy-sulfanylidene-$l^{5}-phosphane;trihydroxy(sulfanylidene)-$l^{5}-phosphane Chemical compound OP(O)(O)=S.CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 OMYMWKVYKBYCBS-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003630 growth substance Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- AOXBDWFVBSDKNR-UHFFFAOYSA-N hept-1-enylphosphonic acid Chemical compound CCCCCC=CP(O)(O)=O AOXBDWFVBSDKNR-UHFFFAOYSA-N 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- PZXOQEXFMJCDPG-UHFFFAOYSA-N omethoate Chemical compound CNC(=O)CSP(=O)(OC)OC PZXOQEXFMJCDPG-UHFFFAOYSA-N 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- RLBIQVVOMOPOHC-UHFFFAOYSA-N parathion-methyl Chemical compound COP(=S)(OC)OC1=CC=C([N+]([O-])=O)C=C1 RLBIQVVOMOPOHC-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000010232 propyl p-hydroxybenzoate Nutrition 0.000 description 1
- 239000004405 propyl p-hydroxybenzoate Substances 0.000 description 1
- QELSKZZBTMNZEB-UHFFFAOYSA-N propylparaben Chemical compound CCCOC(=O)C1=CC=C(O)C=C1 QELSKZZBTMNZEB-UHFFFAOYSA-N 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Dentistry (AREA)
- Dispersion Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Colloid Chemistry (AREA)
- Edible Oils And Fats (AREA)
- Medicinal Preparation (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及水包油乳液。这种乳液含有0.001-70重量%、优选的是0.5-45重量%的至少一种选自磷酸酯类和/或甲氨酸酯类的有效物质、0.001-20重量%、优选的是0.1-10重量%的至少一种式Ⅰ的芳基聚乙二醇醚-磷酸酯的盐，并加水至100重量%以及需要时不加溶剂和/或添加剂。
这种水包油型乳液可用于农业和园艺上，用于家庭和卫生领域内和/或医药领域内。
Description
众所周知，含有磷酸酯类和甲氨酸酯类有效物质的一些水包油型乳液可用于农业、园艺、家庭和卫生领域和/或医药领域。
US-A-4107302提到了一些含水的乳液浓缩液(EW)。这些浓缩液除含有杀虫的有机磷有效物质和表面活性剂之外，还必须含有调节pH值的缓冲液。
EP-B-0196463说明了含有磷酸酯的一些微(滴)乳状液。为了分散有效物质，其中还使用壬基酚-环氧丙烷-环氧乙烷加合物。
从EP-B-0062181中得知，一些水包油型乳液除含有效物质外，还含有作为乳化剂的至少一种、一般多种与离子型烷基芳基磺酸盐混合的烷芳基聚乙二醇醚。
EP-B-0289909公开了水相稳定的有机磷除虫杀菌剂的均匀乳液组合物。它除含有有效物质外，还含有非离子型嵌段共聚物，混合共聚物或混合/嵌段共聚物型表面活性剂以及尿素作为增稠剂和稳定剂。
EP-A-0160182涉及含水的微乳液。这些微乳液中除含有合成的拟除虫菊酯作为有效成分外，还含有由十二烷基磺酸钙、乙氧基化的二苯乙烯基酚铵硫酸盐和乙氧基化的三苯乙烯基酚组成的乳化剂混合物。
在GB-PS-0717279和US-A-2696453中所述的乳液浓缩物(EW)中，可将一定量的有效物质溶解在有机溶剂(例如二甲苯、甲苯、煤油)中，并加入由非离子型表面活性剂和离子型表面活性剂组成的乳化剂混合物(聚亚氧烷基乙二醇/烷芳基磺酸盐)，其有效物质加入有机溶剂中的量以用水稀释此浓缩液到应用浓度时还可形成足够稳定的乳液浓度为准。但所含有的溶剂给浓缩物经常来来可燃性、毒性、植物耐受性和气味等方面的缺点。
只能够在使用附加的助剂例如增稠剂、稳定剂、缓冲剂、有机溶剂以及通常由非离子型表面活性剂和离子型表面活性剂为基础组成的表面活性剂混合物的条件下，才能制备出上述含水的乳状浓缩液(EW)。
已发现含水的乳液浓缩液(EW)形式的一些水包油型乳液，它们除含有磷酸酯类和/或甲氨酸酯类有效物质和水外，至少还必须含有一种芳基聚乙二醇醚—磷酸酯的盐作为离子型表面活性剂。而这里不一定需要使用有机溶剂、非离子型/离子型表面活性剂混合物和/或附加助剂如增稠剂、稳定剂和缓冲剂。
特别值得提出的是，本发明的含水乳液浓缩液(EW)是稳定的；而从现有技术中不能指望在没有增稠剂、稳定剂或缓冲剂、没有或只有少量有机溶剂以及只有一种类型表面活性剂时，这样一些乳液经过较长时间是稳定的。
本发明的对象是水包油型乳液，它含有0.001-70重量％、优选的是0.5-45重量％的至少一种选自磷酸酯类和/或甲氨酯酯类的有效物质，0.001-20重量％、优选的是0.1-10重量％的、至少一种式I所示的芳基聚乙二醇醚-磷酸酯的盐，并加上共至100重量％所需的水和需要时的溶剂和/或助剂。式中：R1各为氢、C1-C24-烷基，C5-C15-环烷基或C6-C24-芳基或C6-C24-烷芳基，R2为氢，-O-C1-C24-烷基，-O-C5-C15-环烷基，-O-C6-C18-芳基或A，M为一个碱金属离子，碱土金属离子或式HN(R3)3的铵离子，其中R3各为氢，C1-C4-烷基，C5-C15-环烷基，C6-C18-芳基或-(CH2)Z-OH所示基团，其中Z为1至10的一个数，X为0至80的一个数，Y为0至50的一个数，其中X加Y之和不等于零。
本发明的水包油型乳液含有至少一种农业化学的有效物质，一种消灭家庭和卫生领域中的害虫的有效物质和/或一种药理上有效的磷酸酯类和/或甲氨酸酯类物质。这些有效物质在室温下不仅可为液态的，而且可为固态的。这些有效物质都是已知的，并在英国作物保护委员会1991年“农药手册”第9版中(“ThePesticide Manual”9th edition，The British Crop Protectioncouncil，1991)已有叙述。
农业化学有效物质，就目前情况而论，是指通常在植物保护中使用的一些有效物质。这些有效物质例如有：杀虫剂、杀螨剂、杀线虫剂、杀霉菌剂、除草剂、生长调节剂和肥料。
以下分别列举出这些有效物质的一些实例：O，O-二乙基-O-〔2-异丙基-4-甲基嘧啶基-(6)〕硫代磷酸酯(二嗪磷)O，O-二乙基-O-〔3，5，6-三氯-2-吡啶基〕硫代磷酸酯(毒死蜱)2-(1-甲基丙基)苯基甲基甲氨酸酯(仲丁威)O，O-二甲基-S-甲基甲氨酰甲基-硫代磷酸酯(乐果)氯代-双环〔3.2.0〕庚-2，6-二烯-6-基磷酸酯(庚烯磷)O，O-二乙基-O-1-苯基-1H-1，2，4-三唑-3-基-硫代磷酸酯(三唑磷)乙基-2-二乙氧基膦亚硫酰氧基-5-甲基吡唑基〔1，5-α〕嘧啶-6-羧酸酯(吡嘧磷)O，O-二乙基-O-(4-硝基-苯基)-硫羰-膦酸酯O，O-二甲基-O-(4-硝基-苯基)-硫羰磷酸酯(杀螟硫磷)O-(乙基-O-(4-甲硫基-苯基)-S-丙基-二硫代磷酸酯2-异丙氧基-苯基-N-甲基甲氨酸酯2，3-二氢-2，2-二甲基-7-苯并呋喃基-甲基-甲氨酸酯3，5-二甲基-4-甲硫基苯基-N-甲基-甲氨酸酯O，O-二乙基-O-(3-氯-4-甲基-7-香豆素基)-硫代磷酸酯S-〔1，2-双(乙氧基羰基)乙基〕-O，O-二甲基-二硫代磷酸酯(马拉硫磷)O，O-二甲基-O-(4-甲基巯基-3-甲基苯基)-硫羰磷酸酯(倍硫磷)O-乙基-O-(2-异丙氧基羰基-苯基)-N-异丙基硫羰磷酸酯酰胺
消灭家庭和卫生领域中害虫用的有效物质是指通常在水中微溶的有效物质。以下分别举出这些有效物质的实例：2-异丙氧基-苯基-N-甲基甲氨酸酯O，O-二乙基-O-(4-硝基-苯基)-硫羰磷酸酯(乙基对硫磷)O，O-二甲基-O-(4-硝基-苯基)-硫羰磷酸酯(甲基对硫磷)S-〔1，2-双-(乙氧基羰基)-乙基〕-O，O-二甲基-二硫代磷酸酯O，O-二甲基-O-(3-甲基-4-硝基-苯基)-硫羰磷酸酯(杀螟硫磷)O，O-二甲基-O-(4-甲基巯基-3-甲基-苯基)-硫羰磷酸酯(倍硫磷)
药理学上的有效物质目前主要是指在兽医学领域内可使用的、在水中微溶解的一些有效物质。作为这些效物质的实例举出的是氯代-双环〔3.2.0〕庚-2，6-二烯-6-基-磷酸酯(庚烯磷)。
本发明的水包油乳液含有至少一种式I所示的芳基聚乙二醇醚-磷酸酯的盐式中R1，R2，M，X和Y具有上面所述的意义。
需要时，R1，R2和R3基可是取代的。合适的取代基是卤素如溴和氯，羟基，硝基，氨基，羧基，磺酸基或其酯基。
最好考虑这种类型的一些化合物，其中R1为C1-C6-烷基，苯基，二苯基，萘基，苯乙烯基，1-苯乙基，R2为C1-C6烷基，苯基或A，M为一个碱金属离子，单乙基铵离子，双乙基铵离子，三乙基铵离子或三乙醇铵离子，X为10至50的一个数，Y为10至35的一个数。
特别优选的表面活性剂是平均有20个ED单元(EO＝环氧乙烷)的2，4，6-三(1-苯乙基)-酚-聚乙二醇醚-磷酸单酯钾盐或其三乙基铵盐以及平均有18至20个EO单元的三苯乙烯基酚-聚乙二醇醚的磷酸单酯和二酯混合物的三乙醇胺盐。
式I所示的这些表面活性剂是已知的，但迄今将它们和其它表面活性剂组合一起使用。在这方面可参阅以下文献：EP-A-0 163 598，EP-A-0 201 417，EP-A-0 364 328，EP-A-0 432 061，EP-A-0 432 062，DE-A-3 503 706，DE-A-3 542 440，DE-A-3 614 788和DE-A-3 624 910。
水包油型乳液含有水作为连续相。如果是浓缩液，则水含量很少。如果是很稀的乳液，水含量就很多。油相(分散相)以小滴形式分散在水相中。小油滴的粒度在一定范围内变动。一般情况下，颗粒直径0.01至10μm之间，最好在0.2-5.0μm之间。在本发明的水包油型乳液中，其所含各组分的百分含量在较大的范围内变动。磷酸酯类和/或甲氨酸酯类有效物质的含量一般为0.001-70重量％、最好为0.5-45重量％。式I所示的表面活性剂的含量一般为0.001-20重量％、优选的是0.1-10重量％。
此外，这些水包油型乳液或者完全不含或者只含少量有机溶剂。因此它们不会燃烧，没有或几乎没有由于有机溶剂造成的气味，并且与按常规浓度含有有机溶剂的相应的配方比较，一般它只有少量毒性或植物毒性。
如需要采用有机溶剂时，通常考虑采用少量与水混合的、沸程在100℃和200℃之间的有机溶剂或混合溶剂。首先是芳族烃，如二甲苯，甲苯，乙苯，平均有9个碳原子的烷基苯，如著名的Solvesso(Esso化学股份有限公司)的溶剂类和二甲基萘，再者有卤代芳烃，如氯苯，此外还有脂族烃，如汽油和石油醚，再还有脂环族烃，如环己酮，此外还有醇类和酮类，如正丁醇，正己醇，正辛醇，环己醇，苯甲醇和二正丁基酮以及醚类和酯类。
有机溶剂的含量一般为乳液的0-50重量％，优选的是0-20重量％。
本发明的水包油型乳液中可能含有的添加剂是防腐剂，低温稳定剂，染料和气味改进剂。
防腐剂的一此实例有：2-羟基联苯，山梨酸，对-羟基苯甲醛，对-羟基苯甲酯，苯甲醛，苯甲酸，对-羟基苯甲酸丙酯和对-硝基苯。
此乳液中防腐剂的含量在0.01-1重量％之间。
低温稳定剂的例子有乙二醇，甘油，聚乙二醇，糖和盐，如硫酸铵和油酸钠。乳液中通常含有1-10重量％的这些低温稳定剂。
作为染料的实例有偶氮染料和酞青染料。作为气味改进剂可使用香味油。
在EP-B-0 130 370中已叙述了一种适宜的制备方法。
除前面已提到含少量有机溶剂的优点外，这些水包油型乳液的另一特点是，它们在实践可控制的条件下是稳定的。在长时间存放时，这些乳液不仅在高温(50℃)下、而且在低温(-5℃，-10℃)下都保持其物理性能稳定且其有效物质含量不变。其它优点在于：在室温下固态的或液态的有效物质都同样容易乳化。
本发明的水包油型乳液既可以事前配制好，也可在使用前稀释使用。其消耗量取决于水包油型乳液的浓度和各自的指标。
此乳液的应用方法一般为例如喷洒，喷雾或浇灌。
下表中综合的配方实施例证明了其广泛的适用性。
Solvesso 150(Esso化学股份有限公司产品)：沸程：186-205℃，芳烃含量99％。
表面活性剂1：平均有20个EO单元的2，4，6-三(1-苯基-乙基)-酚-聚乙二醇醚的磷酸单-和二酯的混合物的三乙醇胺盐。
表面活性剂2：平均有20个EO单元的2，4，6-三(苯基-乙基)-酚-聚乙二醇醚的磷酸单酯的三乙醇胺盐。
表面活性剂3：平均有20-26个EO单元的三苯乙烯基酚。
表1说明本发明的一些水包油型乳液，这些乳液经过至少三个月时间存放是稳定的(存放温度：25℃；50℃)。
表2作为对比实施例说明一些水包油型乳液，这些乳液含有一种非离子型表面活性剂(有20摩尔EO的三苯乙烯基酚)和一种离子型表面活性剂(苯磺酸钙)。这些乳液经存放二星期后，其有效物质已严重降解(＞10重量％)(存放温度：25℃；50℃)。
表1
| 实施例；以重量％计的成份数据；加水到100重量％ | |||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | |
| 表面活性剂1 | 7 | 5 | 5 | ||||||||||
| 表面活性剂2 | 7 | 10 | 7 | 4 | 5 | 7 | 10 | 5 | 3 | 3 | |||
| 二甲苯 | 20 | 20 | 10 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | |
| Solvesso150 | 10 | ||||||||||||
| 马拉硫磷 | 42 | 42 | 42 | 42 | |||||||||
| 乙基对硫磷 | 51 | 51 | 51 | 51 | |||||||||
| 杀螟硫磷 | 41,7 | 42 | 52 | ||||||||||
| 二嗪磷 | 52 | 52 | |||||||||||
| 热稳定性 | -5至50℃ | -5至50℃ | -5至50℃ | -5至50℃ | -5至50℃ | -5至50℃ | -5至50℃ | -5至50℃ | -5至50℃ | -5至50℃ | -5至50℃ | -5至50℃ | -5至50℃ |
表1(续)
| 实施例；以重量％计的数据，加水到100重量％ | |||||||||||
| 14 | 15 | 16 | 17 | 18 | 19 | 20 | 21 | 22 | 23 | 24 | |
| 表面活性剂1 | 7 | 7 | 7 | 7 | 7 | ||||||
| 表面活性剂2 | 7 | 7 | 4 | 3 | 7 | 5 | |||||
| 二甲苯 | 35 | 35 | 20 | 20 | 20 | 10 | 18 | 32 | 5 | 20 | 26 |
| Solvesso150 | 10 | ||||||||||
| 马拉硫磷 | 42 | ||||||||||
| 毒死蜱 | 24 | 24 | |||||||||
| 杀螟硫磷 | 52,4 | 52,4 | |||||||||
| 仲丁威 | 50 | 50 | |||||||||
| 庚烯磷 | 54 | ||||||||||
| 三唑磷 | 40 | ||||||||||
| 吡嘧磷 | 15 | 26 | |||||||||
| 防冻剂 | 10 | 10 | 10 | 10 | |||||||
| 热稳定性 | -5至45℃ | -5至45℃ | -5至50℃ | -5至50℃ | -5至40℃ | -10至40℃ | -10至50℃ | -10至50℃ | -10至40℃ | -5至50℃ | -10至40℃ |
表2
| 实施例；以重量％计；加水到100重量％ | ||||
| 组成 | V1 | V2 | V3 | V4 |
| 表面活性剂3 | 7,5 | |||
| Emulsogen EL 400 | 8 | 7 | ||
| 苯磺酸钙 | 4 | 4 | 7,5 | 11,2 |
| Emulsogen 3510 | 13,8 | |||
| 二甲苯 | 20 | 20 | ||
| 马拉硫磷 | 52,6 | |||
| 二嗪磷 | 61,7 | |||
| 庚烯磷 | 30 | 25 | ||
| 热稳定性 | ./. | ./. | ./. | ./. |
Claims (9)
1.水包油型乳液，它含有0.001-70重量％的至少一种选自磷酸酯类和/或氨基甲酸酯类的有效物质、0.001-20重量％的至少一种式I所示芳基聚乙二醇醚-磷酸酯的盐，并加水和，加入或不加入，溶剂和/或添加剂至100重量％
式中：
R1各为氢、C1-C24-烷基，C5-C15-环烷基，C8-C24-芳基或C6-C24-烷芳基，
R2为氢，-O-C1-C24-烷基，-0-C5-C15-环烷基或-O-C6-C18芳基或A，
M为一个碱金属离子、碱土金属离子或式HN(R3)3的铵离子，
其中
R3各为氢，C1-C4-烷基，C5-C15-环烷基，C6-C18-芳基或式-(CH2)z-OH所示的基团，其中Z为1至10的一个数，
X为0至80的一个数，Y为0至50的一个数，其中X加Y之和不等于零。
2.按权利要求1所述的乳液，其特征在于，所述的至少一种选自磷酸酯类和/或氨基甲酸酯类的有效物质的含量为0.5-45重量％，所述的至少一种式I所示芳基聚乙二醇醚-磷酸酯的盐的含量为0.1-10重量％。
3.按权利要求1所述的乳液，其特征在于，它至少含有一种农业化学用的有效物质，一种消灭家庭和卫生领域中害虫的有效物质和/或一种在药理学上的有效物质。
4.按权利要求1所述的乳液，其特征在于，使用酚-聚乙二醇醚的磷酸单酯和/或-磷酸二酯的盐作为表面活性剂。
5.按权利要求1所述的乳液，其特征在于，这些乳液含有占它们0-50重量％的溶剂。
6.按权利要求3所述的乳液，其特征在于，使用芳族、脂族或脂环族烃，醇类或酮类作为溶剂。
7.按权利要求1所述的乳液，其特征在于，含有防腐剂，低温稳定剂，气味改进剂和/或酸类。
8.按权利要求1所述的乳液，其特征在于，油相以平均颗径为0.01-10μm的小滴形式分布在水相中。
9.按权利要求1所述的水包油型乳液在农业和园艺中、在家庭和卫生领域中和/或在医药领域中的应用，但其在人类和动物的疾病的诊断和治疗中的应用不包括在内。
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| JP (1) | JPH08502991A (zh) |
| KR (1) | KR100298014B1 (zh) |
| CN (1) | CN1052142C (zh) |
| AT (1) | ATE171591T1 (zh) |
| AU (1) | AU692753B2 (zh) |
| BR (1) | BR9307475A (zh) |
| CA (1) | CA2149662A1 (zh) |
| CZ (1) | CZ287112B6 (zh) |
| DE (1) | DE59309030D1 (zh) |
| DK (1) | DK0669800T3 (zh) |
| ES (1) | ES2123749T3 (zh) |
| HU (1) | HU218975B (zh) |
| MX (1) | MX9307171A (zh) |
| MY (1) | MY111197A (zh) |
| PL (1) | PL181591B1 (zh) |
| RU (1) | RU2167522C2 (zh) |
| UA (1) | UA43329C2 (zh) |
| WO (1) | WO1994010839A1 (zh) |
| ZA (1) | ZA938575B (zh) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4343856A1 (de) * | 1993-12-22 | 1995-06-29 | Hoechst Ag | Öl-in-Wasser-Emulsionen |
| US6121478A (en) * | 1996-08-20 | 2000-09-19 | Cheminova Agro A/S | Malathion oil-in-water emulsion formulations and use of peroxide in such formulations |
| US6036945A (en) * | 1997-04-11 | 2000-03-14 | Shamrock Technologies, Inc. | Delivery systems for active ingredients including sunscreen actives and methods of making same |
| GB9816697D0 (en) * | 1998-07-31 | 1998-09-30 | Agrevo Uk Ltd | Liquid formulations |
| BRPI0916259A2 (pt) * | 2008-07-24 | 2019-09-24 | Basf Se | emulsão óleo-em-água, processo para a prepração de uma emulsão óleo-em-água, formulação agroquímica, e, método para controlar fungos fitopatpgênicos e/ou vegetação indesejada e/ou ataque indesejado por insetos ou ácaros e/ou de regular o crescimento de plantas, e, semente. |
| EP2305030A1 (de) * | 2009-09-14 | 2011-04-06 | Bayer CropScience AG | Alkylpolypropylenglycolpolyethylenglycol enthaltende agrochemische Zusammensetzungen |
| DE102010032417A1 (de) * | 2010-07-27 | 2012-02-02 | Buck- Chemie Gmbh | Haftendes saures Sanitärreinigungs- und Beduftungsmittel |
| CN105519576A (zh) * | 2016-01-08 | 2016-04-27 | 广东省农业科学院植物保护研究所 | 高含量噻唑磷水乳剂及其制备方法 |
| CN114507841A (zh) * | 2021-12-29 | 2022-05-17 | 马鞍山市鑫龙特钢有限公司 | 一种碳素钢制件多元合金共渗工艺 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3210869A1 (de) * | 1981-03-27 | 1982-10-14 | Kao Soap Co., Ltd., Tokyo | Konzentrierte, waessrige biozid-suspension und verfahren zu ihrer herstellung |
| EP0224846A1 (de) * | 1985-11-30 | 1987-06-10 | Hoechst Aktiengesellschaft | Neue wässrige Pflanzenschutzmittel-Emulsionen |
| WO1990009103A1 (fr) * | 1989-02-17 | 1990-08-23 | Roussel-Uclaf | Nouvelles emulsions aqueuses concentrees, leur procede de preparation et leur application dans le domaine pesticide |
| EP0432062A1 (fr) * | 1989-12-04 | 1991-06-12 | Rhone-Poulenc Chimie | Microemulsions concentrées de matières organiques diluables sous forme d'émulsions stables et leur procédé de préparation |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3317305A (en) * | 1963-03-14 | 1967-05-02 | Gen Aniline & Film Corp | Biocidal composition containing an electrolyte plant nutrient |
| US4107302A (en) * | 1976-11-16 | 1978-08-15 | Osaka Kasei Company Limited | Novel aqueous insecticidal concentrate composition |
| DE3111934A1 (de) * | 1981-03-26 | 1982-10-07 | Bayer Ag, 5090 Leverkusen | Oel-in-wasser-emulsionen, verfahren zu deren herstellung und deren verwendung |
| DE3319796A1 (de) * | 1983-06-01 | 1984-12-06 | Hoechst Ag, 6230 Frankfurt | Verfahren zur herstellung von fluessigen pflanzenschutzmittelkombinationen |
| CA1264566A (en) * | 1984-09-05 | 1990-01-23 | Tetsuji Iwasaki | Biocidal fine powder, its manufacturing method and a suspension for agricultural use containing the above powder |
| DE3503706A1 (de) * | 1985-02-04 | 1986-08-07 | Ciba-Geigy GmbH, 7867 Wehr | Fliessfaehiges herbizides mittel |
| DE3624910A1 (de) * | 1986-07-23 | 1988-01-28 | Hoechst Ag | Konzentrierte waessrige mikroemulsionen |
-
1993
- 1993-11-11 WO PCT/EP1993/003165 patent/WO1994010839A1/de active IP Right Grant
- 1993-11-11 EP EP94900131A patent/EP0669800B1/de not_active Expired - Lifetime
- 1993-11-11 RU RU95112574/04A patent/RU2167522C2/ru not_active IP Right Cessation
- 1993-11-11 UA UA95062816A patent/UA43329C2/uk unknown
- 1993-11-11 CA CA002149662A patent/CA2149662A1/en not_active Abandoned
- 1993-11-11 DK DK94900131T patent/DK0669800T3/da active
- 1993-11-11 DE DE59309030T patent/DE59309030D1/de not_active Expired - Fee Related
- 1993-11-11 BR BR9307475A patent/BR9307475A/pt not_active IP Right Cessation
- 1993-11-11 PL PL93309011A patent/PL181591B1/pl unknown
- 1993-11-11 AT AT94900131T patent/ATE171591T1/de not_active IP Right Cessation
- 1993-11-11 CZ CZ19951289A patent/CZ287112B6/cs unknown
- 1993-11-11 HU HU9501416A patent/HU218975B/hu not_active IP Right Cessation
- 1993-11-11 JP JP6511711A patent/JPH08502991A/ja not_active Withdrawn
- 1993-11-11 KR KR1019950701986A patent/KR100298014B1/ko not_active IP Right Cessation
- 1993-11-11 AU AU54652/94A patent/AU692753B2/en not_active Ceased
- 1993-11-11 ES ES94900131T patent/ES2123749T3/es not_active Expired - Lifetime
- 1993-11-11 US US08/436,246 patent/US5700472A/en not_active Expired - Fee Related
- 1993-11-17 MY MYPI93002410A patent/MY111197A/en unknown
- 1993-11-17 MX MX9307171A patent/MX9307171A/es not_active IP Right Cessation
- 1993-11-17 ZA ZA938575A patent/ZA938575B/xx unknown
- 1993-11-18 CN CN93114791A patent/CN1052142C/zh not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3210869A1 (de) * | 1981-03-27 | 1982-10-14 | Kao Soap Co., Ltd., Tokyo | Konzentrierte, waessrige biozid-suspension und verfahren zu ihrer herstellung |
| EP0224846A1 (de) * | 1985-11-30 | 1987-06-10 | Hoechst Aktiengesellschaft | Neue wässrige Pflanzenschutzmittel-Emulsionen |
| WO1990009103A1 (fr) * | 1989-02-17 | 1990-08-23 | Roussel-Uclaf | Nouvelles emulsions aqueuses concentrees, leur procede de preparation et leur application dans le domaine pesticide |
| EP0432062A1 (fr) * | 1989-12-04 | 1991-06-12 | Rhone-Poulenc Chimie | Microemulsions concentrées de matières organiques diluables sous forme d'émulsions stables et leur procédé de préparation |
Also Published As
| Publication number | Publication date |
|---|---|
| HU218975B (hu) | 2001-01-29 |
| MX9307171A (es) | 1994-08-31 |
| JPH08502991A (ja) | 1996-04-02 |
| CA2149662A1 (en) | 1994-05-26 |
| KR100298014B1 (ko) | 2001-11-30 |
| CN1087466A (zh) | 1994-06-08 |
| EP0669800B1 (de) | 1998-09-30 |
| UA43329C2 (uk) | 2001-12-17 |
| CZ128995A3 (en) | 1995-10-18 |
| ATE171591T1 (de) | 1998-10-15 |
| KR950703849A (ko) | 1995-11-17 |
| CZ287112B6 (en) | 2000-09-13 |
| MY111197A (en) | 1999-09-30 |
| RU95112574A (ru) | 1997-03-20 |
| EP0669800A1 (de) | 1995-09-06 |
| PL181591B1 (pl) | 2001-08-31 |
| RU2167522C2 (ru) | 2001-05-27 |
| BR9307475A (pt) | 1999-05-25 |
| ES2123749T3 (es) | 1999-01-16 |
| PL309011A1 (en) | 1995-09-18 |
| DK0669800T3 (da) | 1999-06-21 |
| AU5465294A (en) | 1994-06-08 |
| ZA938575B (en) | 1995-01-17 |
| WO1994010839A1 (de) | 1994-05-26 |
| AU692753B2 (en) | 1998-06-18 |
| US5700472A (en) | 1997-12-23 |
| HUT72038A (en) | 1996-03-28 |
| DE59309030D1 (de) | 1998-11-05 |
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