JP5561759B2 - 油中水型エマルジョン、その製造方法およびその使用方法 - Google Patents
油中水型エマルジョン、その製造方法およびその使用方法 Download PDFInfo
- Publication number
- JP5561759B2 JP5561759B2 JP2009236887A JP2009236887A JP5561759B2 JP 5561759 B2 JP5561759 B2 JP 5561759B2 JP 2009236887 A JP2009236887 A JP 2009236887A JP 2009236887 A JP2009236887 A JP 2009236887A JP 5561759 B2 JP5561759 B2 JP 5561759B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- oil
- group
- hydrogen
- carbon atoms
- 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.)
- Active
Links
- 238000000034 method Methods 0.000 title claims description 22
- 239000007762 w/o emulsion Substances 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 229920000642 polymer Polymers 0.000 claims description 98
- 239000000178 monomer Substances 0.000 claims description 70
- 239000003921 oil Substances 0.000 claims description 64
- 239000000839 emulsion Substances 0.000 claims description 55
- 229930195733 hydrocarbon Natural products 0.000 claims description 35
- 150000002430 hydrocarbons Chemical class 0.000 claims description 35
- 239000004215 Carbon black (E152) Substances 0.000 claims description 34
- 239000001257 hydrogen Substances 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 33
- 238000006116 polymerization reaction Methods 0.000 claims description 33
- 125000000217 alkyl group Chemical group 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- 239000003995 emulsifying agent Substances 0.000 claims description 16
- -1 2-ethylhexyl Chemical group 0.000 claims description 14
- 239000004094 surface-active agent Substances 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000010802 sludge Substances 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 5
- 239000002480 mineral oil Substances 0.000 claims description 5
- 230000004931 aggregating effect Effects 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 3
- 101100235626 Caenorhabditis elegans hlb-1 gene Proteins 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 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 claims description 2
- 238000004065 wastewater treatment Methods 0.000 claims description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- 125000002091 cationic group Chemical group 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 125000000129 anionic group Chemical group 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 11
- 238000004090 dissolution Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 7
- 238000010790 dilution Methods 0.000 description 7
- 239000012895 dilution Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000002296 dynamic light scattering Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 150000005215 alkyl ethers Chemical class 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000012674 dispersion polymerization Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000004533 oil dispersion Substances 0.000 description 4
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000001593 sorbitan monooleate Substances 0.000 description 3
- 235000011069 sorbitan monooleate Nutrition 0.000 description 3
- 229940035049 sorbitan monooleate Drugs 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- VBZBISQOWJYWCC-UHFFFAOYSA-N 2-(2-carboxypropan-2-yldiazenyl)-2-methylpropanoic acid Chemical compound OC(=O)C(C)(C)N=NC(C)(C)C(O)=O VBZBISQOWJYWCC-UHFFFAOYSA-N 0.000 description 2
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007877 V-601 Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000011978 dissolution method Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- CDDDRVNOHLVEED-UHFFFAOYSA-N 1-cyclohexyl-3-[1-[[1-(cyclohexylcarbamoylamino)cyclohexyl]diazenyl]cyclohexyl]urea Chemical compound C1CCCCC1(N=NC1(CCCCC1)NC(=O)NC1CCCCC1)NC(=O)NC1CCCCC1 CDDDRVNOHLVEED-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- ZVUAMUKZHFTJGR-UHFFFAOYSA-N 1-piperazin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCNCC1 ZVUAMUKZHFTJGR-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- VMSBGXAJJLPWKV-UHFFFAOYSA-N 2-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=C VMSBGXAJJLPWKV-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- FVPMLCUKLBYBSV-UHFFFAOYSA-M 2-hydroxypropyl-dimethyl-(prop-2-enoyloxymethyl)azanium;chloride Chemical compound [Cl-].CC(O)C[N+](C)(C)COC(=O)C=C FVPMLCUKLBYBSV-UHFFFAOYSA-M 0.000 description 1
- RIAVQNCBHNMYFJ-UHFFFAOYSA-M 2-hydroxypropyl-dimethyl-[phenyl(prop-2-enoyloxy)methyl]azanium;chloride Chemical compound [Cl-].CC(O)C[N+](C)(C)C(OC(=O)C=C)C1=CC=CC=C1 RIAVQNCBHNMYFJ-UHFFFAOYSA-M 0.000 description 1
- AUZRCMMVHXRSGT-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CC(C)CS(O)(=O)=O AUZRCMMVHXRSGT-UHFFFAOYSA-N 0.000 description 1
- DWSMBORYMHSAEA-UHFFFAOYSA-N 3-[(4-amino-4-iminobutan-2-yl)diazenyl]butanimidamide;dihydrochloride Chemical compound Cl.Cl.NC(=N)CC(C)N=NC(C)CC(N)=N DWSMBORYMHSAEA-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- HDWNKEWYEDOKIZ-UHFFFAOYSA-N 5-(diethylamino)-2-methylidenepentanamide Chemical compound CCN(CC)CCCC(=C)C(N)=O HDWNKEWYEDOKIZ-UHFFFAOYSA-N 0.000 description 1
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 239000007875 V-40 Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000012726 Water-in-Oil Emulsion Polymerization Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- ZGCZDEVLEULNLJ-UHFFFAOYSA-M benzyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 ZGCZDEVLEULNLJ-UHFFFAOYSA-M 0.000 description 1
- QBZPCMKUFMJWAN-UHFFFAOYSA-N benzyl-dimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C=CC(=O)NCCC[N+](C)(C)CC1=CC=CC=C1 QBZPCMKUFMJWAN-UHFFFAOYSA-N 0.000 description 1
- GYCUTPICSQQWKP-UHFFFAOYSA-N bis[2-(5-methyl-4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene Chemical compound N1C(C)CN=C1C(C)(C)N=NC(C)(C)C1=NCC(C)N1 GYCUTPICSQQWKP-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000013207 serial dilution Methods 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Treatment Of Sludge (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Colloid Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
(R1:水素又はメチル基 R2:水素、炭素数1〜4のアルキル基又はフェニル基 n:2〜100の整数)
(R3:水素又はメチル基 R4:炭素数4〜18のアルキル基、アルケニル基、アリール基又はCOOR5、ここではR5炭素数4〜18のアルキル基)
(R6は水素又はメチル基、R7、R8は炭素数1〜3のアルキルあるいはアルコキシル基、R9は水素、炭素数1〜3のアルキル基、アルコキシル基あるいはベンジル基であり、同種でも異種でも良い、Aは酸素またはNH、Bは炭素数2〜4のアルキレン基またはアルコキシレン基を表わす、X1 −は陰イオンをそれぞれ表わす。)
(R10は水素又はメチル基、R11、R12は炭素数1〜3のアルキル基、アルコキシ基あるいはベンジル基、X2 −は陰イオンをそれぞれ表わす。)
(R13は水素、メチル基またはカルボキシメチル基、QはSO3 −、C6H4SO3 −、CONHC(CH3)2CH2SO3 −、C6H4COO−あるいはCOO−、R14は水素またはCOO−Y1 +、Y1 +およびY2 +は水素イオンまたは陽イオンをそれぞれ表す。)
(R1:水素又はメチル基 R2:水素、炭素数1〜4のアルキル基又はフェニル基 n:2〜100の整数)
(R3:水素又はメチル基 R4:炭素数4〜18のアルキル基、アルケニル基、アリール基又はCOOR5、ここではR5炭素数4〜18のアルキル基)
(R6は水素又はメチル基、R7、R8は炭素数1〜3のアルキルあるいはアルコキシル基、R9は水素、炭素数1〜3のアルキル基、アルコキシル基あるいはベンジル基であり、同種でも異種でも良い、Aは酸素またはNH、Bは炭素数2〜4のアルキレン基またはアルコキシレン基を表わす、X1 −は陰イオンをそれぞれ表わす。)
(R10は水素又はメチル基、R11、R12は炭素数1〜3のアルキル基、アルコキシ基あるいはベンジル基、X2 −は陰イオンをそれぞれ表わす。)
(R13は水素、メチル基またはカルボキシメチル基、QはSO3 −、C6H4SO3 −、CONHC(CH3)2CH2SO3 −、C6H4COO−あるいはCOO−、R14は水素またはCOO−Y1 +、Y1 +およびY2 +は水素イオンまたは陽イオンをそれぞれ表す。)
AMG:メトキシポリエチレングリコールアクリレート(n=9)
HA:2−エチルへキシルアクリレート
DMM:ジメチルアミノエチルメタクリレート
AAC:アクリル酸
油中水型高分子エマルジョンの単量体組成:DMQ/AAM=20/80(モル%)
効果発現率:十分な効果を発揮する希釈条件である段階希釈液の効果に対する各直接希釈液の効果の割合。
フロック径:mm、ケーキ含水率:質量%、添加量:対ss質量%
濾布剥離性:○>△>×の順に良いことを示す。
Claims (8)
- 下記一般式(3)、(4)、(5)で表わされる単量体および非イオン性単量体から選択される一種以上であるビニル系水溶性単量体を含む水相と水に非混和性のパラフィン類あるいは鉱油あるいは炭化水素系合成油から選択される一種以上の炭化水素系溶媒を乳化した後、重合して製造される油中水型高分子エマルジョンであって、該油中水型高分子エマルジョンを製造する際、下記一般式(1)および(2)の構造単位を有し、前記水に非混和性の炭化水素系溶媒と同種の炭化水素系溶媒中で重合した油溶性高分子として、メトキシ又はフェノキシポリエチレングリコール(n=3〜23)(メタ)アクリレート5〜30mol%、2−エチルへキシル(メタ)アクリレート50〜95mol%、ジアルキルアミノアルキル(メタ)アクリレート0〜15mol%、(メタ)アクリル酸0〜15mol%の共重合物を乳化剤として使用することを特徴とする溶解性に優れた油中水型高分子エマルジョン。
(R1:水素又はメチル基 R2:水素、炭素数1〜4のアルキル基又はフェニル基 n:2〜100の整数)
(R3:水素又はメチル基 R4:炭素数4〜18のアルキル基、アルケニル基、アリール基又はCOOR5、ここではR5炭素数4〜18のアルキル基)
(R6は水素又はメチル基、R7、R8は炭素数1〜3のアルキルあるいはアルコキシル基、R9は水素、炭素数1〜3のアルキル基、アルコキシル基あるいはベンジル基であり、同種でも異種でも良い、Aは酸素またはNH、Bは炭素数2〜4のアルキレン基またはアルコキシレン基を表わす、X1 −は陰イオンをそれぞれ表わす。)
(R10は水素又はメチル基、R11、R12は炭素数1〜3のアルキル基、アルコキシ基あるいはベンジル基、X2 −は陰イオンをそれぞれ表わす。)
(R13は水素、メチル基またはカルボキシメチル基、QはSO3 −、C6H4SO3 −、CONHC(CH3)2CH2SO3 −、C6H4COO−あるいはCOO−、R14は水素またはCOO−Y1 +、Y1 +およびY2 +は水素イオンまたは陽イオンをそれぞれ表す。) - 前記油溶性高分子の分子量が3000〜5万であることを特徴とする請求項1に記載の油中水型高分子エマルジョン。
- 乳化剤として前記油溶性高分子に加え、HLB1〜9の界面活性剤を併用することを特徴とする請求項1〜2のいずれかに記載の油中水型高分子エマルジョン。
- 乳化剤として前記油溶性高分子に加え、HLB10〜20の界面活性剤を併用することを特徴とする請求項1〜2のいずれかに記載の油中水型高分子エマルジョン。
- 下記一般式(3)、(4)、(5)で表わされる単量体および非イオン性単量体から選択される一種以上であるビニル系水溶性単量体を含む水相と水に非混和性のパラフィン類あるいは鉱油あるいは炭化水素系合成油から選択される一種以上の炭化水素系溶媒を乳化した後、重合し油中水型高分子エマルジョンを製造する際、下記一般式(1)および(2)の構造単位を有し、前記水に非混和性の炭化水素系溶媒と同種の炭化水素系溶媒中で重合した油溶性高分子として、メトキシ又はフェノキシポリエチレングリコール(n=3〜23)(メタ)アクリレート5〜30mol%、2−エチルへキシル(メタ)アクリレート50〜95mol%、ジアルキルアミノアルキル(メタ)アクリレート0〜15mol%、(メタ)アクリル酸0〜15mol%の共重合物を乳化剤として使用することを特徴とする溶解性に優れた油中水型高分子エマルジョンの製造方法。
(R1:水素又はメチル基 R2:水素、炭素数1〜4のアルキル基又はフェニル基 n:2〜100の整数)
(R3:水素又はメチル基 R4:炭素数4〜18のアルキル基、アルケニル基、アリール基又はCOOR5、ここではR5炭素数4〜18のアルキル基)
(R6は水素又はメチル基、R7、R8は炭素数1〜3のアルキルあるいはアルコキシル基、R9は水素、炭素数1〜3のアルキル基、アルコキシル基あるいはベンジル基であり、同種でも異種でも良い、Aは酸素またはNH、Bは炭素数2〜4のアルキレン基またはアルコキシレン基を表わす、X1 −は陰イオンをそれぞれ表わす。)
(R10は水素又はメチル基、R11、R12は炭素数1〜3のアルキル基、アルコキシ基あるいはベンジル基、X2 −は陰イオンをそれぞれ表わす。)
(R13は水素、メチル基またはカルボキシメチル基、QはSO3 −、C6H4SO3 −、CONHC(CH3)2CH2SO3 −、C6H4COO−あるいはCOO−、R14は水素またはCOO−Y1 +、Y1 +およびY2 +は水素イオンまたは陽イオンをそれぞれ表す。) - 請求項1〜4のいずれかに記載の油中水型エマルジョンを汚泥脱水処理における凝集処理剤として使用することを特徴とする油中水型高分子エマルジョンの使用方法。
- 請求項1〜4のいずれかに記載の油中水型エマルジョンを抄紙工程における歩留向上剤として使用することを特徴とする油中水型高分子エマルジョンの使用方法。
- 請求項1〜4のいずれかに記載の油中水型エマルジョンを一般廃水処理における凝集処理剤として使用することを特徴とする油中水型高分子エマルジョンの使用方法。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009236887A JP5561759B2 (ja) | 2008-10-17 | 2009-10-14 | 油中水型エマルジョン、その製造方法およびその使用方法 |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008268033 | 2008-10-17 | ||
JP2008268033 | 2008-10-17 | ||
JP2009236887A JP5561759B2 (ja) | 2008-10-17 | 2009-10-14 | 油中水型エマルジョン、その製造方法およびその使用方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2010116551A JP2010116551A (ja) | 2010-05-27 |
JP5561759B2 true JP5561759B2 (ja) | 2014-07-30 |
Family
ID=42304390
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2009236887A Active JP5561759B2 (ja) | 2008-10-17 | 2009-10-14 | 油中水型エマルジョン、その製造方法およびその使用方法 |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP5561759B2 (ja) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5729717B2 (ja) * | 2010-11-30 | 2015-06-03 | ハイモ株式会社 | 汚泥の濃縮方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2742447B2 (ja) * | 1989-06-27 | 1998-04-22 | 株式会社日本触媒 | 逆相懸濁重合用分散剤および該分散剤を用いた親水性重合体の製造方法 |
-
2009
- 2009-10-14 JP JP2009236887A patent/JP5561759B2/ja active Active
Also Published As
Publication number | Publication date |
---|---|
JP2010116551A (ja) | 2010-05-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4167969B2 (ja) | 凝集処理剤及びその使用方法 | |
JP5103395B2 (ja) | 凝集剤組成物およびその製造方法 | |
JP5557366B2 (ja) | 粉末からなるイオン性水溶性高分子とその製造方法およびその用途 | |
JP5622263B2 (ja) | 汚泥の脱水方法 | |
JP2012254430A (ja) | 凝集処理剤およびそれを用いた汚泥脱水方法 | |
JP5142210B2 (ja) | 汚泥の脱水方法 | |
JP6257079B2 (ja) | 凝集処理剤及びそれを用いた汚泥の脱水方法 | |
JP4840995B2 (ja) | 油中水型分散液の希釈液、その調製方法及びその使用方法 | |
JP3886098B2 (ja) | 汚泥脱水剤及び汚泥脱水方法 | |
JP4167974B2 (ja) | 有機汚泥の脱水方法 | |
JP4167972B2 (ja) | 有機汚泥の脱水方法 | |
JP4897523B2 (ja) | 汚泥脱水剤および汚泥脱水方法 | |
JP5258639B2 (ja) | 汚泥の脱水方法 | |
JP5283253B2 (ja) | 製紙スラッジを脱水する方法 | |
JP4167919B2 (ja) | 汚泥の脱水処理方法 | |
JP5561759B2 (ja) | 油中水型エマルジョン、その製造方法およびその使用方法 | |
JP2008025054A (ja) | 抄紙用薬剤 | |
JP5995534B2 (ja) | 凝集処理剤および排水処理方法 | |
JP7101947B2 (ja) | 溶解性且つ安定性に優れた油中水型分散液 | |
JP5187927B2 (ja) | 水溶性高分子分散液及びその製造方法 | |
JP2000159969A (ja) | エマルジョンおよびその用途 | |
JP4167973B2 (ja) | 有機汚泥の脱水方法 | |
JP5709257B2 (ja) | 汚泥処理剤および汚泥脱水処理方法 | |
JP2011178818A (ja) | 水溶性高分子架橋剤、それを用いて製造される水溶性重合体、およびこれらの製造方法 | |
JP2014233647A (ja) | 凝集処理剤及び汚泥の脱水方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120914 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130826 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130829 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130909 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20131219 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140106 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140310 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140325 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140605 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140605 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5561759 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |