JP2010202626A - Method for producing anhydrosugar - Google Patents
Method for producing anhydrosugar Download PDFInfo
- Publication number
- JP2010202626A JP2010202626A JP2009053068A JP2009053068A JP2010202626A JP 2010202626 A JP2010202626 A JP 2010202626A JP 2009053068 A JP2009053068 A JP 2009053068A JP 2009053068 A JP2009053068 A JP 2009053068A JP 2010202626 A JP2010202626 A JP 2010202626A
- Authority
- JP
- Japan
- Prior art keywords
- glucose
- anhydrosugar
- acid catalyst
- catalyst
- solid acid
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 12
- 239000008103 glucose Substances 0.000 claims abstract description 12
- 239000011973 solid acid Substances 0.000 claims abstract description 11
- 150000002772 monosaccharides Chemical class 0.000 claims abstract description 6
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 claims abstract description 5
- 239000002798 polar solvent Substances 0.000 claims abstract description 5
- GYNYBVOAJFHCRG-IVMDWMLBSA-N (1r,2r,6r,7r)-4,8-dioxabicyclo[3.2.1]octane-2,6,7-triol Chemical compound O1C2OC[C@@H](O)[C@]1([H])[C@H](O)[C@H]2O GYNYBVOAJFHCRG-IVMDWMLBSA-N 0.000 claims abstract description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical group C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 5
- 239000011949 solid catalyst Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 229960001031 glucose Drugs 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- GYNYBVOAJFHCRG-QZABAPFNSA-N (1r,2r,5r,6r,7r)-4,8-dioxabicyclo[3.2.1]octane-2,6,7-triol Chemical compound O1[C@@]2([H])[C@H](O)[C@@H](O)[C@]1([H])OC[C@H]2O GYNYBVOAJFHCRG-QZABAPFNSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- PKAUICCNAWQPAU-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)acetic acid;n-methylmethanamine Chemical compound CNC.CC1=CC(Cl)=CC=C1OCC(O)=O PKAUICCNAWQPAU-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 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
- 235000013305 food Nutrition 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Saccharide Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、グルコース等の単糖から無水糖を製造する方法に関する。 The present invention relates to a method for producing anhydrosaccharides from monosaccharides such as glucose.
近年、二酸化炭素排出抑制や化石資源エネルギーから再生可能エネルギーへの転換の観点からバイオマスの有効利用が注目されている。
特に、今後は非食系バイオマス（木質系）の変換が求められている。
木質系バイオマスの多くを占めるセルロースは、加水分解により糖化し、単糖のグルコースに変換した後にバイオ燃料や各種化合物の出発原料として利用されている。
この中で、グルコースを脱水することにより得られる無水糖は抗ガン剤原料、生分解性ポリマー原料、光学分割剤等に利用されている非常に価値の高い化合物である。
これまでに提案されている無水糖の合成方法は、セルロースの熱分解、グルコースの熱分解に関するものが殆どである（特許文献１〜６，非特許文献１）。
しかし、セルロース，グルコースを高温で熱分解し、無水糖を得る方法では、高温での専用の耐熱性装置が必要であることや、高い収率を得るには急激に加熱し、数秒から数分間の反応後にまた急激な冷却が必要であるために反応制御が難しい問題がある。
In recent years, effective use of biomass has attracted attention from the viewpoint of suppressing carbon dioxide emissions and switching from fossil resource energy to renewable energy.
In particular, conversion of non-food biomass (woody) is required in the future.
Cellulose occupying most of woody biomass is saccharified by hydrolysis and converted to monosaccharide glucose, and then used as a starting material for biofuels and various compounds.
Of these, anhydrous sugar obtained by dehydrating glucose is a very valuable compound used as an anticancer agent raw material, a biodegradable polymer raw material, an optical resolution agent, and the like.
Most of the methods for synthesizing anhydrosugars proposed so far are related to pyrolysis of cellulose and pyrolysis of glucose (Patent Documents 1 to 6, Non-Patent Document 1).
However, in the method of thermally decomposing cellulose and glucose at high temperature to obtain anhydrous sugar, a dedicated heat resistant device at high temperature is required, and in order to obtain a high yield, it is heated rapidly, and it takes several seconds to several minutes. Since rapid cooling is necessary again after the reaction, there is a problem that reaction control is difficult.
本発明は、上記従来技術の熱分解法に内在する技術的課題に鑑みて、分離回収が容易な固体触媒を用い、穏やかな反応条件下にて無水糖を得る新規合成法の提供を目的とする。 In view of the technical problems inherent in the above-mentioned conventional thermal decomposition method, the present invention aims to provide a novel synthesis method for obtaining anhydrous sugar under mild reaction conditions using a solid catalyst that is easy to separate and recover. To do.
本発明は、非プロトン性極性溶媒中にて、固体酸触媒の存在下、単糖から無水糖を得ることを特徴とする。
グルコースを基質とすると、レボグルコサン（アンヒドログルコピラノース：１，６−ａｎｈｙｄｒｏ−β−Ｄ−ｇｌｕｃｏｐｙｒａｎｏｓｅ，以下、ＡＧＰと称する。）及び１，６−アンヒドログルコフラノース（１，６−ａｎｈｙｄｒｏ−β−Ｄ−ｇｌｕｃｏｆｕｒａｎｏｓｅ，以下、ＡＧＦと称する。）が得られる。
The present invention is characterized in that an anhydrous sugar is obtained from a monosaccharide in the presence of a solid acid catalyst in an aprotic polar solvent.
When glucose is used as a substrate, levoglucosan (anhydroglucopyranose: 1,6-anhydro-β-D-glucopyranose, hereinafter referred to as AGP) and 1,6-anhydroglucofuranose (1,6-anhydro-β- D-glucofuranose (hereinafter referred to as AGF)).
この場合の反応スキームを下記反応式（Ａ）に示す。
固体酸触媒は、固体酸として作用するものであれば特に限定はないが、酸触媒用のイオン交換樹脂が好ましい。
固体酸触媒としては例えば、下記化学式（１）に示すアンバーリスト−１５（ローム・アンド・ハース株式会社、アンバーリストは登録商標）及び、化学式（２）で示すナフィオン（登録商標，デュポン社）が挙げられる。
Examples of the solid acid catalyst include Amberlist-15 (Rohm and Haas Co., Amberlist is a registered trademark) represented by the following chemical formula (1) and Nafion (registered trademark, DuPont) represented by the chemical formula (2). Can be mentioned.
本発明は、固体酸触媒を用いたことにより、グルコース等の単糖を基質として、非プロトン性極性溶媒中にて、穏やかな反応条件下で、高収率に無水糖を得ることができる。
また、固体酸触媒を用いたことにより、反応後に中和、分離回収が不要で触媒はそのまま再利用できる。
In the present invention, by using a solid acid catalyst, an anhydrous sugar can be obtained in a high yield under mild reaction conditions in an aprotic polar solvent using a monosaccharide such as glucose as a substrate.
Further, by using a solid acid catalyst, neutralization and separation / recovery are unnecessary after the reaction, and the catalyst can be reused as it is.
本発明に係るプロセスの特徴を以下実験結果に基づいて説明するが、これに限定されるものではない。 The characteristics of the process according to the present invention will be described below based on experimental results, but the present invention is not limited to this.
（実験１）
各種溶媒３ｍｌ中にグルコース０．１ｇ、固体酸触媒アンバーリスト−１５，０．１ｇを加え、所定温度にて３時間反応させた結果を表１に示す。
Table 1 shows the results of adding 0.1 g of glucose and 15 g of solid acid catalyst Amberlyst-15, 0.1 g to 3 ml of various solvents and reacting at a predetermined temperature for 3 hours.
表中、ＮＭＰはＮ−メチルピロリドン、ＤＭＦはＮ，Ｎ−ジメチルホルムアミド、ＤＭＩは１，３−ジメチル−２−イミダゾリジノン、ＤＭＳＯはジメチルスルホキシドを示す。
この結果、いずれの非プロトン性極性溶媒を使用してもレボグルコサン（ＡＧＰ）及び１，６−アンヒドログルコフラノース（ＡＧＦ）がそれぞれ収率１０〜３４％，９〜３０％の高い収率で得られ、フルクトースやＨＭＦ（５−ヒドロキシメチルフルフラール）の生成は確認されなかった。
なお、分析は高速液体クロマトグラフ（ＨＰＬＣ，カラムＢｉｏ−ｒａｄ社製，Ａｍｉｎｅｘ HＰＸ−８７Ｘ）を用いた。
In the table, NMP represents N-methylpyrrolidone, DMF represents N, N-dimethylformamide, DMI represents 1,3-dimethyl-2-imidazolidinone, and DMSO represents dimethyl sulfoxide.
As a result, levoglucosan (AGP) and 1,6-anhydroglucofuranose (AGF) were obtained in high yields of 10 to 34% and 9 to 30%, respectively, using any aprotic polar solvent. The production of fructose and HMF (5-hydroxymethylfurfural) was not confirmed.
In addition, the analysis used the high performance liquid chromatograph (HPLC, the column Bio-rad company make, Aminex HPX-87X).
（実験２）
次に触媒の影響を確認すべく、溶媒としてＤＭＦ ３ｍｌを用い、グルコース０．１ｇに対して各触媒０．１ｇ加え、１００℃、３時間反応させた結果を表２に示す。
なお、アンバーリスト−１５を用いて、反応温度を１２０℃にすると、ＡＧＰ収率３３％、ＡＧＦ収率３０％に向上した。
(Experiment 2)
Next, in order to confirm the influence of the catalyst, 3 ml of DMF was used as a solvent, 0.1 g of each catalyst was added to 0.1 g of glucose, and the results of reaction at 100 ° C. for 3 hours are shown in Table 2.
In addition, when the reaction temperature was set to 120 ° C. using Amberlyst-15, the AGP yield was improved to 33% and the AGF yield to 30%.
表中、ｐ−ＴｓＯＨはｐ−トルエンスルホン酸を示し、Ｈ２ＳＯ４，ＨＣｌとともに均一系の触媒である。
また、ＨＺＳＭ−５，ＨＹはゼオライトを示す。
In the table, p-TsOH represents p-toluenesulfonic acid, and is a homogeneous catalyst together with H 2 SO 4 and HCl.
HZSM-5 and HY represent zeolite.
実験２から、触媒及び反応温度の影響が大きいことが明らかになったので、触媒の量とグルコースの量との比をモル比１：３と同一にして各反応温度で３時間反応させた結果を表３に示す。 Experiment 2 revealed that the influence of the catalyst and the reaction temperature was large, and the reaction was performed at each reaction temperature for 3 hours with the ratio of the amount of catalyst and the amount of glucose being the same as the molar ratio 1: 3. Is shown in Table 3.
この結果、固体酸触媒アンバーリスト−１５，及びナフィオンＮＲ５０は選択率が高いことが明らかになった。 As a result, it was revealed that the solid acid catalyst Amberlyst-15 and Nafion NR50 have high selectivity.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009053068A JP5871221B2 (en) | 2009-03-06 | 2009-03-06 | Method for producing anhydrous sugar |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009053068A JP5871221B2 (en) | 2009-03-06 | 2009-03-06 | Method for producing anhydrous sugar |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2010202626A true JP2010202626A (en) | 2010-09-16 |
| JP5871221B2 JP5871221B2 (en) | 2016-03-01 |
Family
ID=42964480
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009053068A Expired - Fee Related JP5871221B2 (en) | 2009-03-06 | 2009-03-06 | Method for producing anhydrous sugar |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5871221B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11342517B2 (en) | 2018-12-29 | 2022-05-24 | Ningbo Lumilan Advanced Materials Co., Ltd. | Dibenzoheterocyclic compound and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02101093A (en) * | 1988-10-07 | 1990-04-12 | Agency Of Ind Science & Technol | Purification of levoglucosan |
| JP2007106685A (en) * | 2005-10-12 | 2007-04-26 | National Institute Of Advanced Industrial & Technology | Method for producing anhydrosugar |
| JP2007217386A (en) * | 2006-02-20 | 2007-08-30 | National Institute Of Advanced Industrial & Technology | Method for producing anhydrosugar |
| JP2009067730A (en) * | 2007-09-14 | 2009-04-02 | Tokyo Institute Of Technology | Method for producing anhydrous sugar, organic acid, and furfural |
-
2009
- 2009-03-06 JP JP2009053068A patent/JP5871221B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02101093A (en) * | 1988-10-07 | 1990-04-12 | Agency Of Ind Science & Technol | Purification of levoglucosan |
| JP2007106685A (en) * | 2005-10-12 | 2007-04-26 | National Institute Of Advanced Industrial & Technology | Method for producing anhydrosugar |
| JP2007217386A (en) * | 2006-02-20 | 2007-08-30 | National Institute Of Advanced Industrial & Technology | Method for producing anhydrosugar |
| JP2009067730A (en) * | 2007-09-14 | 2009-04-02 | Tokyo Institute Of Technology | Method for producing anhydrous sugar, organic acid, and furfural |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11342517B2 (en) | 2018-12-29 | 2022-05-24 | Ningbo Lumilan Advanced Materials Co., Ltd. | Dibenzoheterocyclic compound and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5871221B2 (en) | 2016-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DK2872495T3 (en) | METHOD OF PRODUCING furfural and levulinic OF lignocellulosic biomass | |
| Breeden et al. | Microwave heating for rapid conversion of sugars and polysaccharides to 5-chloromethyl furfural | |
| EP3154927B1 (en) | Method for producing muconic acids and furans from aldaric acids | |
| US20070173651A1 (en) | Two-stage dehydration of sugars | |
| US11078173B2 (en) | Process for producing 5-hydroxymethylfurfural in the presence of an organic dehydration catalyst and a chloride source | |
| KR20140105185A (en) | Method for preparation of anhydrosugar alcohols with reduced formation of polymeric reaction byproducts | |
| EP2985280A1 (en) | A process for synthesis of furfural or derivatives thereof | |
| CN113861139A (en) | Method for preparing 5-hydroxymethylfurfural | |
| JP7085474B2 (en) | A method for producing 5-hydroxymethylfurfural in the presence of a catalyst of a homogeneous sulfonic acid system in the presence of at least one aprotic polar solvent. | |
| KR20180073654A (en) | A process for preparing 5-hydroxymethylfurfural in the presence of at least one aprotic polar solvent in the presence of a Lewis acid catalyst and / or a heterogeneous base catalyst and a homogeneous organic Bronsted acid catalyst | |
| JP5871221B2 (en) | Method for producing anhydrous sugar | |
| JP2018537427A5 (en) | ||
| JP2009215172A (en) | Production method of furfurals | |
| US20220162178A1 (en) | Process for the recovery of solvent and isolation of humin materials and compositions thereof | |
| CN102516133A (en) | Preparation method of methanesulfonic acid derivative | |
| US9802910B2 (en) | Method for preparing 5-hydroxymethyl-2-furfural using acid catalyst in presence of ethylene glycol-based compound solvent derived from biomass | |
| CN113181932A (en) | Bifunctional biomass carbon-based catalyst and application thereof in catalytic preparation of levulinate | |
| KR102560488B1 (en) | Method of preparing 5-acyloxymethyl-2-furfural from d-fructose using immobilized enzyme and solid acid catalyst | |
| US9682912B2 (en) | Method for preparing levulinic acid using solid acid catalyst in presence of ethylene glycol-based compound solvent derived from biomass | |
| US10787427B2 (en) | Synthesis of furan acids from xylonic acid | |
| Tabasso et al. | Platform Chemicals from Biomass Using Microwave Irradiation | |
| JP7278315B2 (en) | Method for producing 5-alkoxymethylfurfural | |
| US20170022122A1 (en) | Conversion of oligomeric starch, cellulose, hydrolysates or sugars to hydrocarbons | |
| KR20160127675A (en) | Preparation method of hydroxymethyl furfural using ionic liquid | |
| Heltzel et al. | Eliminating the Pathway of Humins by Acid Catalyzed Hydrolysis of Glucose |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120113 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130821 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20131016 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140217 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140402 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20140507 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140728 |
|
| A911 | Transfer of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20140812 |
|
| A912 | Removal of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A912 Effective date: 20140905 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20151023 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160105 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5871221 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |