JP2015044705A - Manufacturing method of nanoparticle of cuprous oxide - Google Patents
Manufacturing method of nanoparticle of cuprous oxide Download PDFInfo
- Publication number
- JP2015044705A JP2015044705A JP2013176437A JP2013176437A JP2015044705A JP 2015044705 A JP2015044705 A JP 2015044705A JP 2013176437 A JP2013176437 A JP 2013176437A JP 2013176437 A JP2013176437 A JP 2013176437A JP 2015044705 A JP2015044705 A JP 2015044705A
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- cuprous oxide
- light
- wavelength
- manufacturing
- 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
Images
Abstract
Description
本発明は、亜酸化銅ナノ粒子の製造方法に関するものである。 The present invention relates to a method for producing cuprous oxide nanoparticles.
亜酸化銅は、赤色の粉末顔料で、船底へのフジツボなどの付着を防止する船底塗料用防汚剤として使用されているが、古くから半導体材料としても知られており、昨今では、光起電力素子として利用されている。 Cuprous oxide is a red powder pigment that has been used as an antifouling agent for ship bottom paint to prevent barnacles from sticking to the ship bottom, but it has long been known as a semiconductor material. It is used as a power element.
亜酸化銅の製造方法としては、銅塩含有溶液にアルカリ溶液と還元糖を添加して亜酸化銅粉末を製造する方法や、塩酸含有塩化銅溶液に金属銅などを溶解させて塩化第二銅を塩化第一銅に還元し、得られた溶液をアルカリ溶液と反応させて亜酸化銅を生成する方法などが知られている。 As a method for producing cuprous oxide, a method of producing a cuprous oxide powder by adding an alkali solution and a reducing sugar to a copper salt-containing solution, or a method of dissolving cuprous chloride by dissolving metal copper or the like in a hydrochloric acid-containing copper chloride solution. There is known a method for reducing cuprate to cuprous chloride and reacting the resulting solution with an alkaline solution to produce cuprous oxide.
あるいは、銅化合物と、錯化剤と、水酸化アルカリとを溶解した溶液中に光触媒を添加して、光照射することにより溶液中の銅イオンを還元し、亜酸化銅粉末を製造する方法も提案されている(例えば、特許文献1参照。)。 Alternatively, a method of producing a cuprous oxide powder by adding a photocatalyst to a solution in which a copper compound, a complexing agent, and an alkali hydroxide are dissolved, and reducing the copper ions in the solution by light irradiation. It has been proposed (see, for example, Patent Document 1).
本発明者らは、単層カーボンナノチューブに酢酸銅を担持させ、真空加熱処理することにより、一価の銅イオンが増加する現象をX線吸収分光法(XAFS)により見出した。 The present inventors have found a phenomenon that monovalent copper ions are increased by X-ray absorption spectroscopy (XAFS) when copper acetate is supported on single-walled carbon nanotubes and subjected to vacuum heat treatment.
このことから、単層カーボンナノチューブに酢酸銅を液相で吸着させた後、150℃で真空加熱脱気し、さらに水蒸気を飽和蒸気圧にまで吸着させることによって、亜酸化銅が生成可能であることを確認した。 From this fact, cuprous oxide can be produced by adsorbing copper acetate on the single-walled carbon nanotubes in the liquid phase, then vacuum degassing at 150 ° C., and further adsorbing water vapor to the saturated vapor pressure. It was confirmed.
このように亜酸化銅の作製に関する新規なメカニズムを見出したものの、単層カーボンナノチューブを用いた場合には、製造コストが高コスト化しやすく、安価な材料の利用を検討する必要があった。 Thus, although a novel mechanism related to the production of cuprous oxide was found, when single-walled carbon nanotubes were used, it was easy to increase the manufacturing cost, and it was necessary to consider the use of inexpensive materials.
そこで、単層カーボンナノチューブの代替として活性炭を利用することを検討し、研究開発を行う中で、本発明を成すに至ったものである。 Therefore, the present invention has been accomplished while studying the use of activated carbon as an alternative to single-walled carbon nanotubes and conducting research and development.
本発明の亜酸化銅の製造方法では、活性炭に酢酸銅を液相で吸着させる第1の工程と、酢酸銅の銅を吸着させた活性炭を真空加熱脱気する第2の工程と、真空加熱脱気された活性炭に対して水蒸気を飽和蒸気圧まで吸着させる第3の工程と、活性炭に可視光を照射する第4の工程とを有するものである。 In the cuprous oxide production method of the present invention, the first step of adsorbing copper acetate on the activated carbon in the liquid phase, the second step of vacuum heating and degassing the activated carbon adsorbed copper of copper acetate, and vacuum heating It has a 3rd process which makes water vapor adsorb | suck to saturated vapor pressure with respect to the deaerated activated carbon, and a 4th process which irradiates visible light to activated carbon.
さらに、本発明の亜酸化銅の製造方法では、可視光が500〜530nmの波長域の光であること、第1〜3の工程を500〜530nmの波長の光が除去された環境下で行うこと、活性炭に形成されている微細孔の直径の平均を1nm以下としていることにも特徴を有するものである。 Furthermore, in the method for producing cuprous oxide of the present invention, visible light is light having a wavelength range of 500 to 530 nm, and the first to third steps are performed in an environment where light having a wavelength of 500 to 530 nm is removed. In addition, the average diameter of the micropores formed in the activated carbon is also set to 1 nm or less.
本発明によれば、安価な活性炭を利用して亜酸化銅を製造することができ、亜酸化銅の製造コストを低減することができる。しかも、可視光による還元反応によって亜酸化銅を生成することができ、還元剤レスの製造を可能とすることができることによっても、製造コストを低減することができる。 According to the present invention, cuprous oxide can be manufactured using inexpensive activated carbon, and the manufacturing cost of cuprous oxide can be reduced. In addition, cuprous oxide can be generated by a reduction reaction using visible light, and the manufacturing cost can be reduced by enabling the production of a reducing agent-less.
本発明の亜酸化銅の製造方法は、活性炭に酢酸銅を液相で吸着させる第1の工程と、酢酸銅の銅を吸着させた活性炭を真空加熱脱気する第2の工程と、真空加熱脱気された活性炭に対して水蒸気を飽和蒸気圧まで吸着させる第3の工程と、活性炭に可視光を照射する第4の工程とを有し、可視光による還元反応によって亜酸化銅を生成しているものである。以下において実施例を示しながら、本発明を詳説する。 The method for producing cuprous oxide of the present invention includes a first step of adsorbing copper acetate in a liquid phase on activated carbon, a second step of vacuum heating and degassing the activated carbon adsorbed copper of copper acetate, and vacuum heating. It has a third step of adsorbing water vapor to the saturated vapor pressure on the degassed activated carbon and a fourth step of irradiating the activated carbon with visible light, and produces cuprous oxide by a reduction reaction with visible light. It is what. Hereinafter, the present invention will be described in detail with reference to examples.
まず、可視光による還元反応によって亜酸化銅が生成された事例を説明する。ここでは、活性炭ではなく単層カーボンナノチューブを用いている。 First, the case where cuprous oxide was produced | generated by the reduction reaction by visible light is demonstrated. Here, single-walled carbon nanotubes are used instead of activated carbon.
暗所下で、単層カーボンナノチューブに酢酸銅の銅を担持させ、150℃で真空加熱脱気し、さらに水蒸気を飽和蒸気圧にまで吸着させた。 In the dark, single-walled carbon nanotubes were loaded with copper acetate, vacuum degassed at 150 ° C., and water vapor was adsorbed to the saturated vapor pressure.
酢酸銅の銅を担持した単層カーボンナノチューブに、次の4種類の処理をそれぞれ施し、XRDにより亜酸化銅の生成の確認を行った。4種類の処理のち、処理(a)では、暗所下で100℃まで加熱した。処理(b)では、500〜600nmの波長の光をカットする波長カットフィルターを通してキセノンランプの光を照射した。処理(c)では、425〜530nmの波長の光をカットする波長カットフィルターを通してキセノンランプの光を照射した。処理(d)では、470nm以上の波長の光をカットする波長カットフィルターを通してキセノンランプの光を照射した。 The single-walled carbon nanotube carrying copper acetate was subjected to the following four types of treatment, and the production of cuprous oxide was confirmed by XRD. After the four types of treatments, the treatment (a) was heated to 100 ° C. in the dark. In the process (b), the light of the xenon lamp was irradiated through a wavelength cut filter that cuts light having a wavelength of 500 to 600 nm. In the process (c), light from a xenon lamp was irradiated through a wavelength cut filter that cuts light having a wavelength of 425 to 530 nm. In the treatment (d), light from a xenon lamp was irradiated through a wavelength cut filter that cuts light having a wavelength of 470 nm or more.
処理(a)〜(d)に対する結果を図1に示す。図1において、横軸の36 2θ/deg近傍で現れるピークが亜酸化銅の生成を示すピークであり、500〜530nmの波長の光を照射することにより亜酸化銅が生成されることが確認できた。 The results for the processes (a) to (d) are shown in FIG. In FIG. 1, the peak appearing in the vicinity of 36 2θ / deg on the horizontal axis is a peak indicating the production of cuprous oxide, and it can be confirmed that cuprous oxide is produced by irradiating light with a wavelength of 500 to 530 nm. It was.
まず、活性炭として、サンプルA、サンプルB、サンプルC、サンプルDの4種類の活性炭を準備した。サンプルAは、αs解析の結果、平均細孔サイズが0.63nmであった。サンプルBは、αs解析の結果、平均細孔サイズが1.03nmであった。サンプルCは、図2に示す細孔径分布を示すものであった。サンプルDは、図3に示す細孔径分布を示すものであった。 First, four types of activated carbons, Sample A, Sample B, Sample C, and Sample D, were prepared as activated carbon. As a result of α s analysis, Sample A had an average pore size of 0.63 nm. As a result of α s analysis, Sample B had an average pore size of 1.03 nm. Sample C showed the pore size distribution shown in FIG. Sample D showed the pore size distribution shown in FIG.
<第1の工程>
各活性炭を50mgずつアンプル管内に入れ、0.26Mの酢酸銅水溶液を5ml加えて、アンプル管の口を封じ、30℃において24時間以上撹拌しながら活性炭に酢酸銅の銅を吸着させた。その後、撹拌させた活性炭を吸引濾過して洗浄した。このとき、吸引濾過を行いながらピペットを用いて20mlの蒸留水を滴下することにより洗浄した。
<First step>
50 mg of each activated carbon was placed in an ampule tube, 5 ml of a 0.26 M copper acetate aqueous solution was added, the mouth of the ampule tube was sealed, and copper acetate was adsorbed on the activated carbon while stirring at 30 ° C. for 24 hours or more. Then, the activated carbon which was stirred was filtered by suction and washed. At this time, it was washed by dropping 20 ml of distilled water using a pipette while performing suction filtration.
<第2の工程>
第1の工程において酢酸銅の銅を吸着させた活性炭を真空加熱脱気した。このとき、真空度は10-4torr以下とすることが望ましく、温度は200℃以下でよく、好適には120〜180℃程度が望ましい。真空加熱脱気の処理時間は長ければ長いほどよい。
<Second step>
In the first step, the activated carbon on which copper acetate was adsorbed was vacuum-heated and degassed. At this time, the degree of vacuum is preferably 10 −4 torr or less, the temperature may be 200 ° C. or less, and preferably about 120 to 180 ° C. The longer the processing time for vacuum heating and degassing, the better.
<第3の工程>
真空加熱脱気された活性炭に対して水蒸気を飽和蒸気圧まで吸着させた。なお、後段の工程で光照射を行うため、暗所下で行った。
<Third step>
Water vapor was adsorbed to the saturated vapor pressure on the activated carbon degassed by vacuum heating. In addition, in order to perform light irradiation in the latter process, it performed in the dark place.
<第4の工程>
水蒸気を飽和蒸気圧まで吸着させた活性炭に、キセノンランプを用いて可視光を照射した。
<4th process>
Visible light was irradiated to activated carbon in which water vapor was adsorbed to a saturated vapor pressure using a xenon lamp.
図4は、サンプルA(平均細孔サイズ0.63nm)のXRDパターンのグラフである。特に、上側のグラフは、500nm以上の波長の光を照射した場合であり、下側のグラフは、400〜500nm以上の波長の光を照射した場合である。図4より、亜酸化銅が生成されることが確認できた。特に、500nm以下の波長の光が照射された場合でも、亜酸化銅が生成されている。 FIG. 4 is a graph of the XRD pattern of Sample A (average pore size 0.63 nm). In particular, the upper graph is a case where light having a wavelength of 500 nm or more is irradiated, and the lower graph is a case where light having a wavelength of 400 to 500 nm or more is irradiated. From FIG. 4, it was confirmed that cuprous oxide was produced. In particular, cuprous oxide is generated even when light having a wavelength of 500 nm or less is irradiated.
図5は、サンプルB(平均細孔サイズ1.03nm)のXRDパターンのグラフである。特に、上側のグラフは、500nm以上の波長の光を照射した場合であり、下側のグラフは、400〜500nm以上の波長の光を照射した場合である。図5より、500nm以上の波長の光の照射により、かろうじて亜酸化銅が生成されていることが確認できる。 FIG. 5 is a graph of the XRD pattern of Sample B (average pore size 1.03 nm). In particular, the upper graph is a case where light having a wavelength of 500 nm or more is irradiated, and the lower graph is a case where light having a wavelength of 400 to 500 nm or more is irradiated. From FIG. 5, it can be confirmed that cuprous oxide is barely generated by irradiation with light having a wavelength of 500 nm or more.
図6は、サンプルCのXRDパターンのグラフであり、第4の工程で385〜740の波長の光を照射したが、亜酸化銅の生成は確認できなかった。 FIG. 6 is a graph of the XRD pattern of Sample C, and irradiation with light having a wavelength of 385 to 740 was performed in the fourth step, but formation of cuprous oxide could not be confirmed.
図7は、サンプルDのXRDパターンのグラフであり、第4の工程で385〜740の波長の光を照射したが、亜酸化銅の生成は確認できなかった。 FIG. 7 is a graph of the XRD pattern of Sample D, and irradiation with light having a wavelength of 385 to 740 was performed in the fourth step, but formation of cuprous oxide could not be confirmed.
以上のことから、500〜530nmの波長の可視光による還元反応によって亜酸化銅が生成可能であることが確認でき、特に、活性炭のような安価なカーボン材料を用いても亜酸化銅を生成可能であることから、亜酸化銅をより安価に製造することが可能となる。しかも還元剤レスとすることができることによっても、製造コストをより低減することができる。 From the above, it can be confirmed that cuprous oxide can be generated by a reduction reaction with visible light having a wavelength of 500 to 530 nm. In particular, cuprous oxide can be generated even using an inexpensive carbon material such as activated carbon. Therefore, cuprous oxide can be produced at a lower cost. In addition, the manufacturing cost can be further reduced by the fact that no reducing agent can be used.
なお、活性炭はできるだけ微細な細孔を有していることが望ましく、細孔の直径の平均が1nm以下であることが望ましい。特に、図4から明らかなように、細孔の直径が小さくなることで、可視光による還元反応が生じる波長域を広げることができ、反応効率の向上が期待できる。 The activated carbon desirably has as fine pores as possible, and the average pore diameter is desirably 1 nm or less. In particular, as can be seen from FIG. 4, by reducing the diameter of the pores, it is possible to widen the wavelength range in which the reduction reaction by visible light occurs and to improve the reaction efficiency.
また、可視光による還元反応を利用する関係上、その前工程では、還元反応が生じない環境下で行われることが望ましく、第1〜3の工程を、500〜530nmの波長の光が除去された環境下で行うことにより、第4の工程での効率を向上させることができる。 In addition, because of the use of a visible light reduction reaction, it is desirable that the previous process be performed in an environment where no reduction reaction occurs, and the light having a wavelength of 500 to 530 nm is removed in the first to third processes. By performing it under a different environment, the efficiency in the fourth step can be improved.
Claims (4)
前記酢酸銅の銅を吸着させた活性炭を真空加熱脱気する第2の工程と、
真空加熱脱気された活性炭に対して水蒸気を飽和蒸気圧まで吸着させる第3の工程と、
活性炭に可視光を照射する第4の工程と
を有する亜酸化銅の製造方法。 A first step of adsorbing copper acetate on activated carbon in a liquid phase;
A second step of vacuum heating and degassing the activated carbon adsorbed copper of the copper acetate;
A third step of adsorbing water vapor to saturated vapor pressure with respect to the activated carbon degassed by vacuum heating;
And a fourth step of irradiating activated carbon with visible light.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013176437A JP6363827B2 (en) | 2013-08-28 | 2013-08-28 | Method for producing cuprous oxide nanoparticles |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013176437A JP6363827B2 (en) | 2013-08-28 | 2013-08-28 | Method for producing cuprous oxide nanoparticles |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2015044705A true JP2015044705A (en) | 2015-03-12 |
JP6363827B2 JP6363827B2 (en) | 2018-07-25 |
Family
ID=52670587
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2013176437A Active JP6363827B2 (en) | 2013-08-28 | 2013-08-28 | Method for producing cuprous oxide nanoparticles |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP6363827B2 (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004262941A (en) * | 2003-02-13 | 2004-09-24 | Asahi Kasei Chemicals Corp | Deodorizing, antibacterial and antifungal coating composition |
US20070140951A1 (en) * | 2003-12-11 | 2007-06-21 | The Trustees Of Columbia University In The City Of New York | Nano-sized particles, processes of making, compositions and uses thereof |
JP2011074485A (en) * | 2009-09-04 | 2011-04-14 | National Institute Of Advanced Industrial Science & Technology | Method of manufacturing spherical nanoparticle and spherical nanoparticle obtained by the manufacturing method |
JP2012523224A (en) * | 2009-04-09 | 2012-10-04 | ベースクリック ゲーエムベーハー | Click chemistry with heterogeneous catalysts |
-
2013
- 2013-08-28 JP JP2013176437A patent/JP6363827B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004262941A (en) * | 2003-02-13 | 2004-09-24 | Asahi Kasei Chemicals Corp | Deodorizing, antibacterial and antifungal coating composition |
US20070140951A1 (en) * | 2003-12-11 | 2007-06-21 | The Trustees Of Columbia University In The City Of New York | Nano-sized particles, processes of making, compositions and uses thereof |
JP2012523224A (en) * | 2009-04-09 | 2012-10-04 | ベースクリック ゲーエムベーハー | Click chemistry with heterogeneous catalysts |
JP2011074485A (en) * | 2009-09-04 | 2011-04-14 | National Institute Of Advanced Industrial Science & Technology | Method of manufacturing spherical nanoparticle and spherical nanoparticle obtained by the manufacturing method |
Non-Patent Citations (1)
Title |
---|
T. OKUBO ET AL.: "Water-initiated ordering around a copper ion of copper acetate confined in slit-shaped carbon microp", MICROPOROUS AND MESOPOROUS MATERIALS, vol. 154, JPN6017009160, 14 September 2011 (2011-09-14), NL, pages 82 - 86, ISSN: 0003821479 * |
Also Published As
Publication number | Publication date |
---|---|
JP6363827B2 (en) | 2018-07-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Li et al. | Insight into photocatalytic activity, universality and mechanism of copper/chlorine surface dual-doped graphitic carbon nitride for degrading various organic pollutants in water | |
He et al. | Mechanistic insight into photocatalytic pathways of MIL-100 (Fe)/TiO2 composites | |
Park et al. | Visible-light photocatalysis by carbon-nano-onion-functionalized ZnO tetrapods: degradation of 2, 4-dinitrophenol and a plant-model-based ecological assessment | |
Asadzadeh-Khaneghah et al. | Decoration of carbon dots and AgCl over g-C3N4 nanosheets: novel photocatalysts with substantially improved activity under visible light | |
Xie et al. | Solar‐inspired water purification based on emerging 2D materials: status and challenges | |
Hou et al. | Highly efficient photocatalytic hydrogen evolution in ternary hybrid TiO2/CuO/Cu thoroughly mesoporous nanofibers | |
Zhang et al. | A facile ultrasonic-assisted fabrication of nitrogen-doped carbon dots/BiOBr up-conversion nanocomposites for visible light photocatalytic enhancements | |
Tran et al. | Unusual synthesis of safflower-shaped TiO2/Ti3C2 heterostructures initiated from two-dimensional Ti3C2 MXene | |
Ge et al. | TiO 2 nanotube arrays loaded with reduced graphene oxide films: facile hybridization and promising photocatalytic application | |
Yang et al. | Tuning the morphology of g-C3N4 for improvement of Z-scheme photocatalytic water oxidation | |
Ghosh et al. | The characteristic study and sonocatalytic performance of CdSe–graphene as catalyst in the degradation of azo dyes in aqueous solution under dark conditions | |
McEvoy et al. | Synthesis and characterization of Ag/AgCl–activated carbon composites for enhanced visible light photocatalysis | |
Bao et al. | Adsorption of dyes on hierarchical mesoporous TiO2 fibers and its enhanced photocatalytic properties | |
Qian et al. | Low-temperature nitrogen doping in ammonia solution for production of N-doped TiO2-hybridized graphene as a highly efficient photocatalyst for water treatment | |
Wu et al. | Hydrothermal carbonization of carboxymethylcellulose: One-pot preparation of conductive carbon microspheres and water-soluble fluorescent carbon nanodots | |
Tien et al. | One-pot synthesis of a reduced graphene oxide–zinc oxide sphere composite and its use as a visible light photocatalyst | |
Jing et al. | Novel Ag 2 S quantum dot modified 3D flower-like SnS 2 composites for photocatalytic and photoelectrochemical applications | |
Ong et al. | Hybrid organic PVDF–inorganic M–rGO–TiO 2 (M= Ag, Pt) nanocomposites for multifunctional volatile organic compound sensing and photocatalytic degradation–H 2 production | |
Jaafar et al. | Visible-light photoactivity of plasmonic silver supported on mesoporous TiO2 nanoparticles (Ag-MTN) for enhanced degradation of 2-chlorophenol: Limitation of Ag-Ti interaction | |
Khasevani et al. | Synthesis of BiOI/ZnFe2O4–metal–organic framework and g-C3N4-based nanocomposites for applications in photocatalysis | |
Guo et al. | Layered and poriferous (Al, C)-Ta2O5 mesocrystals supported CdS quantum dots for high-efficiency photodegradation of organic contaminants | |
Lin et al. | Ultrasonic chemical synthesis of CdS-reduced graphene oxide nanocomposites with an enhanced visible light photoactivity | |
Darwish et al. | Functionalized nanomaterial for environmental techniques | |
González-Poggini et al. | Two-dimensional nanomaterials for the removal of pharmaceuticals from wastewater: a critical review | |
JP2006265005A (en) | Method for manufacturing activated carbon carrying nano-sized metal or metal oxide with high efficiency |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160624 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20170310 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170328 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20171017 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180117 |
|
A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20180131 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180227 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180427 |
|
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: 20180626 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20180629 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6363827 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |