JP5873096B2 - 1,3,5−トリオキサンの製造方法 - Google Patents
1,3,5−トリオキサンの製造方法 Download PDFInfo
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- JP5873096B2 JP5873096B2 JP2013536489A JP2013536489A JP5873096B2 JP 5873096 B2 JP5873096 B2 JP 5873096B2 JP 2013536489 A JP2013536489 A JP 2013536489A JP 2013536489 A JP2013536489 A JP 2013536489A JP 5873096 B2 JP5873096 B2 JP 5873096B2
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- trioxane
- extraction
- distillation
- distillation column
- phase
- Prior art date
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- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 title claims description 79
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 98
- 238000000605 extraction Methods 0.000 claims description 73
- 238000004821 distillation Methods 0.000 claims description 72
- 238000000066 reactive distillation Methods 0.000 claims description 41
- 239000008346 aqueous phase Substances 0.000 claims description 32
- 239000012071 phase Substances 0.000 claims description 11
- 239000007791 liquid phase Substances 0.000 claims description 3
- 238000005191 phase separation Methods 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000003377 acid catalyst Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000011973 solid acid Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 150000004904 1,3,5-trioxanes Chemical class 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D323/00—Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms
- C07D323/04—Six-membered rings
- C07D323/06—Trioxane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
- B01D3/40—Extractive distillation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
(2)上記1,3,5−トリオキサン含有蒸気を蒸留及び抽出して1,3,5−トリオキサンを留出または排出させる工程、
(3)1,3,5−トリオキサン抽出工程から排出されたストリームを相分離して水相を反応蒸留塔に戻す工程、および
(4)反応器に供給された水を系外に排出させる工程。
図1に示すような配列の反応蒸留塔20を用いて1,3,5−トリオキサンを製造した。
図1の配列において蒸留塔20の蒸留部21と抽出部22を分離し、図2に示すような配列の蒸留塔24(塔径30mm、15段、バブルキャップトレイ(Bubble-cap tray))、抽出部25(塔径50mm、20段、バブルキャップトレイ)、反応器10(5L、ヒータ付き)、デカンタ(1.5L)を使用し、蒸留塔24の上部留出蒸気中の一部を凝縮させるために、凝縮器40をさらに構成してトリオキサンを製造した。
実施例1と同一の条件でトリオキサンを製造するが、図3に示すように、蒸留塔20の塔頂から相分離された水相(f)を抽出剤供給ストリームの下段に戻して1,3,5−トリオキサンを製造した。
20 反応蒸留塔
21 蒸留部
22 抽出部
23 サイドカット部(チムニートレイセクション(Chimney-Tray Section))
24 蒸留塔
25 抽出塔
30 デカンタ(decanter)
Claims (2)
- 蒸留部(21)、前記蒸留部(21)の上部に位置したサイドカット(23)、および前記サイドカット(23)の上部に位置した抽出部(22)を全て含む蒸留塔(20)と、前記蒸留部(21)に連結された反応器(10)と、前記蒸留塔(20)に連結されたデカンタ(30)とを含む反応蒸留塔において、
前記反応器(10)から供給される1,3,5−トリオキサン含有蒸気は前記蒸留部(21)に流入した後、サイドカット(23)を経て抽出部(22)に流入し、前記抽出部(22)では流入した1,3,5−トリオキサン含有蒸気の一部が凝縮して1,3,5−トリオキサン含有液相となり、前記1,3,5−トリオキサン含有液相は前記抽出部(22)の下部に位置したサイドカット(23)のストリーム(c)として排出された後、油相(b)および水相(a)に相分離され、前記水相(a)はさらに蒸留部(21)に再循環し、
前記抽出部(22)では、流入した凝縮していない1,3,5−トリオキサン含有蒸気は前記抽出部(22)を介して蒸留塔(20)の上部に留出してデカンタ(30)に流入した後に相分離され、前記相分離された水相(f、e)のうち、一部の水相(f)は抽出剤を供給する抽出剤供給ストリーム(d)よりも上部に供給され、残りの水相(e)は排出されることを特徴とする、1,3,5−トリオキサンの製造方法。 - 前記反応蒸留塔(20)の塔頂を介して留出して相分離された水相中のホルムアルデヒドの濃度が15wt%以下であることを特徴とする、請求項1に記載の1,3,5−トリオキサンの製造方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2010-0107119 | 2010-10-29 | ||
KR1020100107119A KR101092220B1 (ko) | 2010-10-29 | 2010-10-29 | 1.3,5―트리옥산의 제조방법 |
PCT/KR2011/006061 WO2012057437A2 (ko) | 2010-10-29 | 2011-08-18 | 1,3,5-트리옥산의 제조방법 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2013542221A JP2013542221A (ja) | 2013-11-21 |
JP5873096B2 true JP5873096B2 (ja) | 2016-03-01 |
Family
ID=45506021
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2013536489A Active JP5873096B2 (ja) | 2010-10-29 | 2011-08-18 | 1,3,5−トリオキサンの製造方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US8981125B2 (ja) |
EP (1) | EP2634182B8 (ja) |
JP (1) | JP5873096B2 (ja) |
KR (1) | KR101092220B1 (ja) |
CN (1) | CN103370313B (ja) |
BR (1) | BR112013010541A8 (ja) |
WO (1) | WO2012057437A2 (ja) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101496621B1 (ko) | 2014-09-16 | 2015-02-25 | 백승용 | 트리옥산의 제조 방법 |
JP6780010B2 (ja) * | 2015-12-18 | 2020-11-04 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | 1,3,5−トリオキサンの製造方法におけるエネルギー回収 |
CN105622366B (zh) * | 2016-03-14 | 2017-09-12 | 凯瑞环保科技股份有限公司 | 一种生产聚甲氧基二甲醚dmm3‑5的装置及方法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1493997C3 (de) * | 1964-11-28 | 1973-11-08 | Fa. Josef Meissner, 5000 Koeln | Verfahren zur Herstellung von Trioxan |
DE2912767A1 (de) * | 1979-03-30 | 1980-10-09 | Hoechst Ag | Verfahren zur kontinuierlichen herstellung von trioxan |
JPH0243750B2 (ja) | 1981-06-02 | 1990-10-01 | Mitsubishi Gas Chemical Co | Toriokisannoseizohoho |
JPH06228127A (ja) | 1993-02-02 | 1994-08-16 | Asahi Chem Ind Co Ltd | トリオキサンの製造方法 |
DE19842579A1 (de) * | 1998-09-17 | 2000-03-23 | Ticona Gmbh | Abtrennung von Trioxan aus flüssigen Gemischen |
JP2001199978A (ja) | 1999-11-10 | 2001-07-24 | Toray Ind Inc | トリオキサンの製造方法 |
KR20010097592A (ko) | 2000-04-25 | 2001-11-08 | 구광시 | 트리옥산의 제조방법 |
JP2005247719A (ja) | 2004-03-02 | 2005-09-15 | Toray Ind Inc | 1,3,5トリオキサンの連続製造方法 |
-
2010
- 2010-10-29 KR KR1020100107119A patent/KR101092220B1/ko active IP Right Grant
-
2011
- 2011-08-18 BR BR112013010541A patent/BR112013010541A8/pt not_active Application Discontinuation
- 2011-08-18 EP EP11836529.5A patent/EP2634182B8/en active Active
- 2011-08-18 JP JP2013536489A patent/JP5873096B2/ja active Active
- 2011-08-18 WO PCT/KR2011/006061 patent/WO2012057437A2/ko active Application Filing
- 2011-08-18 CN CN201180063318.9A patent/CN103370313B/zh active Active
- 2011-08-18 US US13/882,034 patent/US8981125B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
US8981125B2 (en) | 2015-03-17 |
US20130261318A1 (en) | 2013-10-03 |
EP2634182A4 (en) | 2014-04-02 |
EP2634182A2 (en) | 2013-09-04 |
EP2634182B8 (en) | 2015-09-16 |
JP2013542221A (ja) | 2013-11-21 |
BR112013010541A2 (pt) | 2016-07-05 |
WO2012057437A2 (ko) | 2012-05-03 |
KR101092220B1 (ko) | 2011-12-12 |
CN103370313A (zh) | 2013-10-23 |
BR112013010541A8 (pt) | 2017-10-31 |
CN103370313B (zh) | 2015-04-01 |
WO2012057437A3 (ko) | 2012-06-21 |
EP2634182B1 (en) | 2015-08-05 |
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R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |