JP5050284B2 - Cation exchange membrane for salt production and method for producing the same - Google Patents
Cation exchange membrane for salt production and method for producing the same Download PDFInfo
- Publication number
- JP5050284B2 JP5050284B2 JP2008064719A JP2008064719A JP5050284B2 JP 5050284 B2 JP5050284 B2 JP 5050284B2 JP 2008064719 A JP2008064719 A JP 2008064719A JP 2008064719 A JP2008064719 A JP 2008064719A JP 5050284 B2 JP5050284 B2 JP 5050284B2
- Authority
- JP
- Japan
- Prior art keywords
- cation exchange
- group
- monomer
- exchange membrane
- polymerizable monomer
- 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
- 238000005341 cation exchange Methods 0.000 title claims description 50
- 239000012528 membrane Substances 0.000 title claims description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 32
- 150000003839 salts Chemical class 0.000 title claims description 21
- 239000000178 monomer Substances 0.000 claims description 55
- 238000010559 graft polymerization reaction Methods 0.000 claims description 19
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 18
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 18
- 125000000524 functional group Chemical group 0.000 claims description 16
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 230000005865 ionizing radiation Effects 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 230000001678 irradiating effect Effects 0.000 claims description 8
- 230000008961 swelling Effects 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000000034 method Methods 0.000 description 16
- 239000003014 ion exchange membrane Substances 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229920000307 polymer substrate Polymers 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000000909 electrodialysis Methods 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003011 anion exchange membrane Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 230000002522 swelling effect Effects 0.000 description 2
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N Methylcyclohexane Natural products CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Description
本発明は、製塩に用いられる陽イオン交換膜及びその製造方法に関する。 The present invention relates to a cation exchange membrane used for salt production and a method for producing the same.
イオン交換膜製塩法における海水濃縮工程には、陽及び陰イオン交換膜を利用した電気透析槽が用いられている。電気透析槽に利用するイオン交換膜の性能上求められているのは、膜の電気抵抗、濃縮性能、耐久性等であり、製造費低減のためには、膜の電気抵抗を増加させることなく、濃縮性能を向上させることが必要である。加えて耐久性、特に機械的強度を向上させることも必要となる。 An electrodialysis tank using positive and anion exchange membranes is used in the seawater concentration step in the ion exchange membrane salt production method. What is required in terms of the performance of ion exchange membranes used in electrodialysis tanks is membrane electrical resistance, concentration performance, durability, etc. To reduce manufacturing costs, without increasing membrane electrical resistance. It is necessary to improve the concentration performance. In addition, it is necessary to improve durability, particularly mechanical strength.
製塩用イオン交換膜の製法については従来から数多くの方法が提案されている（例えば特許文献１〜３参照）が、イオン交換基が導入可能な官能基又はイオン交換基を有するモノマー、架橋剤及び重合触媒を主たる成分として含有する混合物をポリ塩化ビニル製の織布などに塗布して重合した後、必要に応じてイオン交換基を導入する方法が広く知られている。
A number of methods have been proposed for producing an ion exchange membrane for salt production (see, for example,
しかしながら、この方法により得られたイオン交換膜は、膜の電気抵抗を増加させることなく、濃縮性能を向上させることは困難であり、かつ機械的強度についても満足できる性質のものではなかった。
かかる問題点を解決するため、ポリプロピレン繊維基材等に重合性モノマーを含浸担持させた後、電離放射線でグラフト重合しイオン交換膜を得る方法や、ポリオレフィン製基材等に重合性モノマーを含浸担持させた後、電離性放射線で一部重合を行い、続いて重合開始剤の存在下で加熱することにより、重合を完結させてイオン交換膜を得る方法が提案されている（例えば特許文献４〜６参照）。
However, the ion exchange membrane obtained by this method is difficult to improve the concentration performance without increasing the electrical resistance of the membrane, and the mechanical strength is not satisfactory.
In order to solve such problems, a method of obtaining an ion exchange membrane by impregnating and supporting a polymerizable monomer on a polypropylene fiber substrate or the like, and then graft polymerization with ionizing radiation, or impregnating and supporting a polymerizable monomer on a polyolefin substrate or the like Then, a method of partially polymerizing with ionizing radiation and subsequently heating in the presence of a polymerization initiator to complete the polymerization and obtain an ion exchange membrane has been proposed (for example,
しかし、いずれの方法も、膜の機械的強度を向上させることは可能であるが、膜の濃縮性能については満足のいく成果は見られなかった。
本発明は、製塩に用いられる陽イオン交換膜について、従来使用されている膜と比較し、電気抵抗を増加させずに、濃縮性能を向上させ、且つ機械的強度を向上させることを目的とするものである。 It is an object of the present invention to improve the concentration performance and mechanical strength of a cation exchange membrane used for salt production without increasing the electric resistance as compared with a conventionally used membrane. Is.
本発明者等は、前記課題を解決すべく鋭意研究を重ねた結果、超高分子量ポリエチレンフィルムに電離放射線を照射し、スチレン系モノマー等をグラフト重合した後、形成されるグラフト側鎖にスルホン酸基を導入することにより、従来使用されている製塩用のイオン交換膜と比較し、電気抵抗を増加させずに、濃縮性能を増加させ、且つ機械的強度を向上させた膜を提供できることを見出した。 As a result of intensive studies to solve the above-mentioned problems, the present inventors irradiate an ultrahigh molecular weight polyethylene film with ionizing radiation, graft polymerize a styrene monomer and the like, and then form sulfonic acid on a graft side chain formed. It has been found that by introducing a group, it is possible to provide a membrane with increased concentration performance and improved mechanical strength, without increasing the electrical resistance, compared to conventionally used ion exchange membranes for salt production. It was.
すなわち、本発明は、下記の構成とすることにより上記の目的を達成するに至った。
（１）超高分子量ポリエチレンフィルムに電離放射線を照射することにより、超高分子量ポリエチレンにラジカルを発生させた後、陽イオン交換基を導入可能な官能基を有する重合性単量体（ただし、陽イオン交換基を導入可能な官能基自体が陽イオン交換基である場合を除く）単独、又は該重合性単量体及び架橋性単量体の重合性混合物を用いてグラフト重合を行い、その後陽イオン交換基を付与できる化合物で処理することにより得られたことを特徴とする製塩用陽イオン交換膜。
（２）前記重合性単量体単独、又は前記重合性単量体及び架橋性単量体の重合性混合物を用いてグラフト重合を行う際に膨潤溶媒を使用することを特徴とする前記（１）記載の製塩用陽イオン交換膜。
（３）前記陽イオン交換基を導入可能な官能基を有する重合性単量体が、スルホン酸基が導入されやすい芳香族環を有する単量体であり、グラフト重合後に、スルホン酸基を付与できる化合物で処理するものである前記（１）又は（２）記載の製塩用陽イオン交換膜。
That is, the present invention has achieved the above object by adopting the following configuration.
(1) by irradiating an ionizing radiation to the ultra-high molecular weight polyethylene film, after generating the radical ultra high molecular weight polyethylene, the polymerizable monomer having a functional group introducible cation exchange group (provided that positive except where functional groups themselves introducing ion-exchange groups are cation exchange groups) alone, or have rows graft polymerization using a polymerizable mixture of polymerizable monomer and a crosslinkable monomer, followed A cation exchange membrane for salt production obtained by treating with a compound capable of imparting a cation exchange group .
(2) A swelling solvent is used when graft polymerization is performed using the polymerizable monomer alone or a polymerizable mixture of the polymerizable monomer and the crosslinkable monomer (1). ) The cation exchange membrane for salt production as described.
(3) The polymerizable monomer having a functional group capable of introducing a cation exchange group is a monomer having an aromatic ring into which a sulfonic acid group is easily introduced , and imparts a sulfonic acid group after graft polymerization. The cation exchange membrane for salt production according to the above (1) or (2), which is treated with a compound that can be produced.
（４）超高分子量ポリエチレンフィルムに電離放射線を照射することにより、超高分子量ポリエチレンにラジカルを発生させた後、陽イオン交換基を導入可能な官能基を有する重合性単量体（ただし、陽イオン交換基を導入可能な官能基自体が陽イオン交換基である場合を除く）単独、又は該重合性単量体及び架橋性単量体の重合性混合物を用いてグラフト重合を行い、その後陽イオン交換基を付与できる化合物で処理することを特徴とする製塩用陽イオン交換膜の製造方法。
（５）前記重合性単量体単独、又は前記重合性単量体及び架橋性単量体の重合性混合物を用いてグラフト重合を行う際に膨潤溶媒を使用することを特徴とする前記（４）記載の製塩用陽イオン交換膜の製造方法。
（６）前記陽イオン交換基を導入可能な官能基を有する重合性単量体が、スルホン酸基が導入されやすい芳香族環を有する単量体であり、グラフト重合後に、スルホン酸基を付与できる化合物で処理するものである前記（４）又は（５）記載の製塩用陽イオン交換膜の製造法。
(4) by irradiating the ionizing radiation to the ultra-high molecular weight polyethylene film, after generating the radical ultra high molecular weight polyethylene, the polymerizable monomer having a functional group introducible cation exchange group (provided that positive except where functional groups themselves introducing ion-exchange groups are cation exchange groups) alone, or have rows graft polymerization using a polymerizable mixture of polymerizable monomer and a crosslinkable monomer, followed A method for producing a cation exchange membrane for salt production , comprising treating with a compound capable of imparting a cation exchange group .
(5) A swelling solvent is used when graft polymerization is performed using the polymerizable monomer alone or a polymerizable mixture of the polymerizable monomer and the crosslinkable monomer (4) ) Described in the above.
(6) The polymerizable monomer having a functional group capable of introducing a cation exchange group is a monomer having an aromatic ring into which a sulfonic acid group is easily introduced , and imparts a sulfonic acid group after graft polymerization. The method for producing a cation exchange membrane for salt production according to the above (4) or (5), which is treated with a compound that can be produced.
上記から明らかなように、本発明の骨子は、下記（ａ）及び（ｂ）に存する。
（ａ）超高分子量ポリエチレンフィルムに電離放射線を照射することにより、超高分子量ポリエチレンにラジカルを発生させた後、陽イオン交換基を導入可能な官能基を有する重合性単量体単独、又は該重合性単量体及び架橋性単量体の重合性混合物を用いてグラフト重合を行い、必要に応じてクロロスルホン酸等を用いてスルホン酸基を導入する陽イオン交換膜製造方法である。
（ｂ）前記（ａ）に記載の方法で得た陽イオン交換膜である。
As is clear from the above, the gist of the present invention resides in the following (a) and (b).
(A) A polymerizable monomer having a functional group capable of introducing a cation exchange group alone after generating radicals in ultrahigh molecular weight polyethylene by irradiating ionizing radiation to the ultrahigh molecular weight polyethylene film, or This is a method for producing a cation exchange membrane wherein graft polymerization is carried out using a polymerizable mixture of a polymerizable monomer and a crosslinkable monomer, and sulfonic acid groups are introduced using chlorosulfonic acid or the like as required.
(B) A cation exchange membrane obtained by the method described in (a) above.
本発明により、現在製塩に用いられている陽イオン交換膜と比較して、電気抵抗を増加させずに、濃縮性能を増加させ、且つ機械的強度を向上させた陽イオン交換膜を提供できることから、製塩コスト低減に寄与できる。 According to the present invention, it is possible to provide a cation exchange membrane having an increased concentration performance and an improved mechanical strength without increasing the electric resistance as compared with the cation exchange membrane currently used for salt production. , Can contribute to reducing salt production costs.
本発明の陽イオン交換膜製造方法は、超高分子量ポリエチレンフィルムに電離放射線を照射することにより、超高分子量ポリエチレンにラジカルを発生させた後、陽イオン交換基を導入可能な官能基を有する重合性単量体単独、又は該重合性単量体及び架橋性単量体の重合性混合物を用いてグラフト重合を行い、必要に応じてクロロスルホン酸等を用いてスルホン酸基を導入することが特徴である。 The method for producing a cation exchange membrane of the present invention is a polymerization having a functional group capable of introducing a cation exchange group after generating a radical in an ultra high molecular weight polyethylene by irradiating an ultra high molecular weight polyethylene film with ionizing radiation. Graft polymerization using a polymerizable monomer alone or a polymerizable mixture of the polymerizable monomer and the crosslinkable monomer, and introducing a sulfonic acid group using chlorosulfonic acid or the like as necessary. It is a feature.
以下、本発明の実施の形態を詳細に説明する。
本発明で使用できる、高分子フィルム基材としては、超高分子量ポリエチレンを使用することにより、得られるイオン交換膜の耐久性が向上し、膨潤性も抑制されるが、該超高分子量ポリエチレンとしては、分子量が３０万以上であるものが好ましく、中でも分子量が１００万〜６３０万であり、厚みが２０〜１００μｍのものを用いるのが特に好ましい。それにより、得られるイオン交換膜の耐久性が向上し、膨潤性も抑制される、
Hereinafter, embodiments of the present invention will be described in detail.
As the polymer film substrate that can be used in the present invention, the use of ultra-high molecular weight polyethylene improves the durability of the obtained ion exchange membrane and suppresses the swelling property. Preferably have a molecular weight of 300,000 or more, particularly preferably a molecular weight of 1,000,000 to 6,300,000 and a thickness of 20 to 100 μm. Thereby, the durability of the obtained ion exchange membrane is improved, and the swelling property is also suppressed.
高分子基材の形態は、製塩用のイオン交換膜としての利用面からの要請から、膜（フィルム）の形態であって、その大きさ、厚さは適宜決定することができる。
超高分子量ポリエチレンフィルムの製造法による種別は特に限定するものではなく、インフレーションフィルム、スカイブフィルム等いずれのフィルムも使用可能である。インフレーションフィルムとしては、例えば、作新工業株式会社製、Ｓａｘｉｎニューライトフィルム イノベート（製品名）などがあげられる。
スカイブフィルムとしては、例えば作新工業株式会社製、Ｓａｘｉｎニューライトフィルム（製品名）があげられる。また、その他、市販の超高分子量ポリエチレンフィルムとしては、日東電工株式会社製、超高分子量ポリエチレンフィルム Ｎｏ．４４０などが挙げられる。
The form of the polymer substrate is a form of a membrane (film) from the viewpoint of utilization as an ion exchange membrane for salt production, and its size and thickness can be appropriately determined.
The type of the ultrahigh molecular weight polyethylene film according to the production method is not particularly limited, and any film such as an inflation film or a skive film can be used. Examples of the inflation film include Saxin New Light Film Innovate (product name) manufactured by Sakushin Kogyo Co., Ltd.
Examples of the skive film include Saxin New Light Film (product name) manufactured by Sakushin Kogyo Co., Ltd. In addition, as a commercially available ultra high molecular weight polyethylene film, an ultra high molecular weight polyethylene film No. 440 or the like.
本発明において使用することができる、陽イオン交換基を導入可能な官能基を有する重合性単量体としては、以下に列記する単量体が挙げられる。（１）スルホン酸基が導入されやすい芳香族環を有する単量体。例えば、スチレン、ビニルトルエン等。
本発明において、重合性単量体は、架橋性単量体又は膨潤溶媒と混合して重合性混合物として用いてもよい。
本発明において使用することができる架橋性単量体としては、以下に列記する単量体が挙げられる。架橋構造を導入できる単量体。すなわちビニル基を少なくとも２個有するもの。例えばジビニルベンゼン（ＤＶＢ）、トリビニルベンゼン、ジビニルトルエン、ジビニルナフタレン、エチレングリコールジメタクリレート。
また、本発明において使用することができる膨潤溶媒としては特に限定されないが、ベンゼン、キシレン、トルエン、ヘキサン等の炭化水素類、メタノール、エタノール、イソプロピルアルコール等のアルコール類、アセトン、メチルイソプロピルケトン、シクロヘキサン等のケトン類、ジオキサン、テトラヒドロフラン等のエーテル類、酢酸エチル、酢酸ブチル等のエステル類、イソプロピルアミン、ジエタノールアミン、Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド等の含窒素化合物等の溶媒が挙げられ、これらを適宜、少なくとも１種以上選択して使用することができる。
Examples of the polymerizable monomer having a functional group capable of introducing a cation exchange group that can be used in the present invention include the monomers listed below. (1) A monomer having an aromatic ring into which a sulfonic acid group is easily introduced. For example, styrene, vinyl toluene and the like.
In the present invention, the polymerizable monomer may be mixed with a crosslinkable monomer or a swelling solvent and used as a polymerizable mixture.
Examples of the crosslinkable monomer that can be used in the present invention include the monomers listed below. A monomer capable of introducing a crosslinked structure. That is, one having at least two vinyl groups. For example, divinylbenzene (DVB), trivinylbenzene, divinyltoluene, divinylnaphthalene, ethylene glycol dimethacrylate.
Further, the swelling solvent that can be used in the present invention is not particularly limited, but hydrocarbons such as benzene, xylene, toluene and hexane, alcohols such as methanol, ethanol and isopropyl alcohol, acetone, methyl isopropyl ketone and cyclohexane. And solvents such as ketones such as dioxane and tetrahydrofuran, esters such as ethyl acetate and butyl acetate, nitrogen-containing compounds such as isopropylamine, diethanolamine, N-methylformamide and N, N-dimethylformamide. These can be used by appropriately selecting at least one or more of them.
高分子基材への上記モノマーのグラフト重合は、基材を電離放射線照射後、モノマーと重合反応させる、いわゆる前照射法か、または基材とモノマーとに同時に照射し、重合反応させる、いわゆる同時照射法のいずれによっても行うことができる。高分子基材にグラフト重合しないホモポリマーの生成量が少ないことから、前照射法を使用することが好ましい。前照射法については２方法あり、高分子基材を不活性ガス中で照射するポリマーラジカル法と、基材を酸素の存在する雰囲気下で照射するパーオキサイト法があり、いずれも本発明において使用することができる。 The graft polymerization of the above-mentioned monomer onto the polymer substrate is a so-called pre-irradiation method in which the substrate is irradiated with ionizing radiation and then subjected to a polymerization reaction, or the substrate and the monomer are simultaneously irradiated to cause a polymerization reaction. It can be performed by any of the irradiation methods. The pre-irradiation method is preferably used because the amount of homopolymer that does not undergo graft polymerization on the polymer substrate is small. There are two pre-irradiation methods, a polymer radical method for irradiating a polymer substrate in an inert gas, and a peroxide method for irradiating the substrate in an oxygen-containing atmosphere, both of which are used in the present invention. Can be used.
前照射法の一例を以下に説明する。
まず、高分子基材を酸素不透過性ポリ袋中に挿入後、この袋内を窒素置換し、袋内酸素を除去する。次いでこの基材を含む袋に電離放射線の一つである電子線を、−１０〜８０℃、好ましくは室温付近で、１０〜４００ｋＧｙ照射する。次いで、照射済み基材を大気中で取り出し、ガラス容器に移し替えた後、容器内にモノマー液またはモノマー溶液（溶媒希釈液）を充填する。モノマー液またはモノマー溶液は、酸素の存在しない不活性ガスによるバブリングや凍結脱気などで予め酸素ガスを除いたものを使用する。照射済み基材にポリマーのグラフト鎖を導入するためのグラフト重合は、通常、室温〜８０℃、好ましくは、２５〜７０℃で実施する。
An example of the pre-irradiation method will be described below.
First, after inserting the polymer base material into an oxygen-impermeable plastic bag, the inside of the bag is purged with nitrogen to remove oxygen in the bag. Next, the bag containing the substrate is irradiated with an electron beam, which is one of ionizing radiations, at −10 to 80 ° C., preferably near room temperature, for 10 to 400 kGy. Next, after the irradiated substrate is taken out in the atmosphere and transferred to a glass container, the container is filled with a monomer solution or a monomer solution (a solvent dilution solution). As the monomer solution or monomer solution, one obtained by removing oxygen gas in advance by bubbling or freeze degassing with an inert gas containing no oxygen is used. Graft polymerization for introducing a polymer graft chain to an irradiated substrate is usually carried out at room temperature to 80 ° C, preferably 25 to 70 ° C.
これにより得られたポリマーのグラフト率（すなわち、重合前の高分子基材に対するグラフト鎖の重量パーセント）は、５〜３００質量％、より好ましくは３０〜２００質量％である。グラフト率は、照射線量、重合温度、重合時間等に依存して適宜変化させることができる。 The graft ratio of the polymer thus obtained (that is, the weight percent of the graft chain with respect to the polymer substrate before polymerization) is 5 to 300% by mass, more preferably 30 to 200% by mass. The graft ratio can be appropriately changed depending on the irradiation dose, polymerization temperature, polymerization time and the like.
グラフト鎖を導入した高分子基材には、次の段階としてスルホン酸基等の陽イオン交換基を導入する。スルホン酸基の導入は従来行われている広範な方法が何の制限もなく使用できるが、具体例を以下に示す。 As a next step, a cation exchange group such as a sulfonic acid group is introduced into the polymer base material into which the graft chain has been introduced. A wide range of conventional methods can be used for introducing sulfonic acid groups without any limitation. Specific examples are shown below.
１，２−ジクロロエタンを溶媒とする濃度１質量％〜濃度５０質量％のクロロスルホン酸溶液に、グラフト反応後の高分子基材を２５〜８０℃で１〜７２時間浸漬して反応させる。所定時間反応後、膜を十分に水洗する。その後、濃度１〜１０質量％の水酸化ナトリウム水溶液に１〜２４時間浸漬することで、加水分解した後、膜を十分に水洗する。スルホン化反応に必要なスルホン化剤としては、濃硫酸、三酸化硫黄、チオ硫酸ナトリウムなども使用することができ、これらのスルホン酸基を導入できるものであれば特に限定されない。 The polymer base material after the graft reaction is immersed in a chlorosulfonic acid solution having a concentration of 1% by mass to 50% by mass using 1,2-dichloroethane as a solvent and reacted at 25 to 80 ° C. for 1 to 72 hours. After reacting for a predetermined time, the membrane is thoroughly washed with water. Then, after hydrolyzing by immersing in a sodium hydroxide aqueous solution having a concentration of 1 to 10% by mass for 1 to 24 hours, the membrane is sufficiently washed with water. As the sulfonating agent necessary for the sulfonation reaction, concentrated sulfuric acid, sulfur trioxide, sodium thiosulfate and the like can be used, and there is no particular limitation as long as these sulfonic acid groups can be introduced.
以下、本発明の陽イオン交換膜およびその製造方法を実施例にもとづいてさらに詳細に説明する。なお、本発明はかかる実施例に限定されるものではない。 Hereinafter, the cation exchange membrane of the present invention and the production method thereof will be described in more detail based on examples. In addition, this invention is not limited to this Example.
（実施例１）
分子量１６０万、膜厚３０μｍのインフレーション法により製造された超高分子量ポリエチレン基材（作新工業株式会社製、Ｓａｘｉｎニューライトフィルム イノベート（製品名））を酸素不透過性ポリエチレン袋中に挿入後、この袋内を窒素置換し、袋内の酸素を除去する。次いでこの基材を含む袋に電子線を２５℃、加速電圧２５０ｋｅＶ、電子線電流３２．７ｍＡで、１００ｋＧｙ照射した。次いで、照射済み基材を大気中で取り出し、ガラス容器に移し替えた後、高純度窒素によりバブリングし、予め酸素ガスを除いたスチレンの４０質量％シクロヘキサン溶液を充填した。充填後、５０℃で１８０ｍｉｎグラフト重合した後、膜をガラス容器より取り出し、メタノールで洗浄し、風乾した。グラフト率は２１１％であった。
Example 1
After inserting an ultra high molecular weight polyethylene base material (manufactured by Sakushin Kogyo Co., Ltd., Saxin New Light Film Innovate (product name)) manufactured by an inflation method having a molecular weight of 1.6 million and a film thickness of 30 μm into an oxygen-impermeable polyethylene bag, The inside of the bag is purged with nitrogen to remove oxygen in the bag. Next, the bag containing the substrate was irradiated with an electron beam at 25 ° C., an acceleration voltage of 250 keV, and an electron beam current of 32.7 mA at 100 kGy. Next, the irradiated base material was taken out in the air, transferred to a glass container, and then bubbled with high-purity nitrogen, and filled with a 40% by mass cyclohexane solution of styrene excluding oxygen gas in advance. After filling, graft polymerization was performed at 50 ° C. for 180 minutes, and then the membrane was taken out of the glass container, washed with methanol, and air-dried. The graft ratio was 211%.
１，２−ジクロロエタンを溶媒とする濃度１０質量％のクロロスルホン酸溶液に、グラフト反応後の高分子基材を室温で７２時間浸漬した後、膜を十分に水洗した。その後、濃度１〜１０質量％の水酸化ナトリウム水溶液に２４時間浸漬した。得られた陽イオン交換膜はよく水洗し、０．５Ｎ−ＮａＣｌ水溶液中に保存した。合成した膜の膜厚は１０７μｍであった。得られた陽イオン交換膜の破裂強度はミューレン式破裂強度試験機により測定した。 The polymer substrate after the graft reaction was immersed in a chlorosulfonic acid solution having a concentration of 10% by mass using 1,2-dichloroethane as a solvent at room temperature for 72 hours, and then the membrane was sufficiently washed with water. Thereafter, it was immersed in an aqueous sodium hydroxide solution having a concentration of 1 to 10% by mass for 24 hours. The obtained cation exchange membrane was thoroughly washed with water and stored in 0.5N-NaCl aqueous solution. The film thickness of the synthesized film was 107 μm. The rupture strength of the obtained cation exchange membrane was measured with a Murren burst strength tester.
さらに、該陽イオン交換膜と市販の陰イオン交換膜（旭硝子（株）ＡＳＡ）を小型電気透析装置（膜面積８ｃｍ２）に装着し、濃縮試験を実施した。脱塩室流速は６ｃｍ／ｓ、電流密度３Ａ／ｄｍ２の濃縮条件で供給液は０．５Ｍの塩化ナトリウム水溶液を用いた。 Further, the cation exchange membrane and a commercially available anion exchange membrane (Asahi Glass Co., Ltd. ASA) were mounted on a small electrodialysis apparatus (membrane area 8 cm 2 ), and a concentration test was performed. A 0.5 M sodium chloride aqueous solution was used as the feed solution under the concentration conditions of a desalting chamber flow rate of 6 cm / s and a current density of 3 A / dm 2 .
実施例１と異なる基材および方法で合成した膜を実施例２〜２７、現在製塩用陽イオン交換膜として使用されている膜を比較例１〜２とし、実施例1とあわせ、合成条件及び膜特性を表１〜２に示す。 Membranes synthesized by a substrate and method different from those in Example 1 were designated as Examples 2 to 27, and membranes currently used as cation exchange membranes for salt production were designated as Comparative Examples 1 and 2, and together with Example 1, synthesis conditions and The film characteristics are shown in Tables 1-2.
また、濃縮試験の結果として膜抵抗と濃縮液の塩化ナトリウム濃度との関係を図1に示す。
表１〜２に示したとおり本発明に従って製造したいずれの膜についても、市販されている製塩用陽イオン交換膜と比較し、高い破裂強度を示した。
また、膜抵抗も市販膜とほぼ同等か、それより低い値を示した。
さらに、図１に示したとおり、本発明に従って製造したいずれの陽イオン交換膜についても、市販されている陽イオン交換膜と比較し高い濃縮性能を示した。なお、図１中に示した直線は、市販イオン交換膜と同等の濃縮性能を示す直線であり、直線より上部に示される膜性能はすべて市販膜より高い濃縮性能であるといえる。
FIG. 1 shows the relationship between the membrane resistance and the concentration of sodium chloride in the concentrated solution as a result of the concentration test.
As shown in Tables 1 and 2, all of the membranes produced according to the present invention exhibited high burst strength compared to commercially available salt-forming cation exchange membranes.
Further, the membrane resistance was almost the same as or lower than that of the commercially available membrane.
Furthermore, as shown in FIG. 1, any cation exchange membrane produced according to the present invention showed high concentration performance as compared with a commercially available cation exchange membrane. In addition, the straight line shown in FIG. 1 is a straight line which shows the concentration performance equivalent to a commercially available ion exchange membrane, and it can be said that all the membrane performance shown above a straight line is higher concentration performance than a commercial membrane.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008064719A JP5050284B2 (en) | 2007-03-14 | 2008-03-13 | Cation exchange membrane for salt production and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007065332 | 2007-03-14 | ||
| JP2007065332 | 2007-03-14 | ||
| JP2008064719A JP5050284B2 (en) | 2007-03-14 | 2008-03-13 | Cation exchange membrane for salt production and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008255350A JP2008255350A (en) | 2008-10-23 |
| JP5050284B2 true JP5050284B2 (en) | 2012-10-17 |
Family
ID=39979235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008064719A Active JP5050284B2 (en) | 2007-03-14 | 2008-03-13 | Cation exchange membrane for salt production and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5050284B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2732256C1 (en) * | 2019-03-27 | 2020-09-14 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Казанский национальный исследовательский технический университет им. А.Н. Туполева-КАИ" (КНИТУ-КАИ) | Method of laser welding of metals and device for implementation of method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5140861B2 (en) * | 2008-03-28 | 2013-02-13 | 財団法人塩事業センター | Cation exchange membrane for salt production and method for producing the same |
| JP2010227801A (en) * | 2009-03-26 | 2010-10-14 | Solt Industry Center Of Japan | Solid-state cation exchanger and method for producing the same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58463B2 (en) * | 1979-02-05 | 1983-01-06 | 日本原子力研究所 | New manufacturing method for ion exchange membranes |
| JPS6034980B2 (en) * | 1979-02-05 | 1985-08-12 | 日本原子力研究所 | Method for producing graft membranes with excellent dimensional stability using radiation graft polymerization method |
| JP3245454B2 (en) * | 1992-08-04 | 2002-01-15 | 日本原子力研究所 | Production method of ion exchange resin |
| JP3555967B2 (en) * | 1993-07-30 | 2004-08-18 | 旭化成ケミカルズ株式会社 | Method for producing elution-resistant anion-adsorbing membrane and membrane thereof |
| JP4167914B2 (en) * | 2003-03-07 | 2008-10-22 | 日本板硝子株式会社 | Ion-exchange functional membrane |
| JP4576620B2 (en) * | 2003-08-28 | 2010-11-10 | 独立行政法人 日本原子力研究開発機構 | Method for producing nanostructure control polymer ion exchange membrane |
| JP2005344263A (en) * | 2004-06-07 | 2005-12-15 | Solt Industry Center Of Japan | Method for producing anion exchange membrane and the resultant anion exchange membrane |
| JP2006007162A (en) * | 2004-06-29 | 2006-01-12 | Nittetsu Mining Co Ltd | Ion exchange filter and its production method |
-
2008
- 2008-03-13 JP JP2008064719A patent/JP5050284B2/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2732256C1 (en) * | 2019-03-27 | 2020-09-14 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Казанский национальный исследовательский технический университет им. А.Н. Туполева-КАИ" (КНИТУ-КАИ) | Method of laser welding of metals and device for implementation of method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008255350A (en) | 2008-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5050285B2 (en) | Anion exchange membrane for salt production and method for producing the same | |
| JP5196241B2 (en) | Cation exchange membrane and method for producing the same | |
| JP5196242B2 (en) | Anion exchange membrane and method for producing the same | |
| US6828386B2 (en) | Process for preparing graft copolymers and membranes formed therefrom | |
| JP5196234B2 (en) | Anion exchange membrane and method for producing the same | |
| US20140370417A1 (en) | Anion exchange membrane, method for producing the same, and fuel cell using the same | |
| JP5579365B2 (en) | Anion exchange membrane and method for producing the same | |
| CA1189018A (en) | Cation exchange membrane and process for producing the same | |
| JP5196236B2 (en) | Cation exchange membrane and method for producing the same | |
| JP5050284B2 (en) | Cation exchange membrane for salt production and method for producing the same | |
| JP2009096923A (en) | Cation exchange membrane and method for production thereof | |
| US8372894B2 (en) | Method for producing a radiation on grafted polymer | |
| JP4035106B2 (en) | Method for preparing a graft copolymer membrane | |
| KR101394417B1 (en) | Fabrication method for the fuel cell membranes by using the carbon-based membranes prepared by radiation grafting of vinyl benzyl chloride based monomers | |
| JP5120541B2 (en) | Cation exchange membrane for salt production and method for producing the same | |
| JP5626684B2 (en) | Monovalent anion selective permeation anion exchange membrane for salt production and method for producing the same | |
| JP2016193407A (en) | Ion exchange membrane for radioactive substance concentrator | |
| JP5305283B2 (en) | Production method of polymer electrolyte membrane for fuel cell, electrolyte membrane thereof, and membrane electrode assembly for fuel cell using the membrane | |
| JP5140861B2 (en) | Cation exchange membrane for salt production and method for producing the same | |
| JP2009126971A (en) | Cation exchange and anion exchange membrane, and method of manufacturing them | |
| US20040016693A1 (en) | Process for preparing graft copolymer membranes | |
| JP6665418B2 (en) | Method for producing electrolyte membrane | |
| KR101327971B1 (en) | Fabrication method for the grafted polymer membrane with vinyl ether based monomers having leaving group by simultaneous radiation | |
| JP6530630B2 (en) | Polymer alloy electrolyte membrane and method for producing the same | |
| JP2004087380A (en) | Electrolyte film for fuel cell, and its manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20090107 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100701 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110719 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110916 |
|
| 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: 20120626 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120706 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5050284 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150803 Year of fee payment: 3 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
| R370 | Written measure of declining of transfer procedure |
Free format text: JAPANESE INTERMEDIATE CODE: R370 |
|
| 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 |
|
| 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 |