JP5467252B2 - Silver nanowire manufacturing method and silver nanowire - Google Patents
Silver nanowire manufacturing method and silver nanowire Download PDFInfo
- Publication number
- JP5467252B2 JP5467252B2 JP2009114671A JP2009114671A JP5467252B2 JP 5467252 B2 JP5467252 B2 JP 5467252B2 JP 2009114671 A JP2009114671 A JP 2009114671A JP 2009114671 A JP2009114671 A JP 2009114671A JP 5467252 B2 JP5467252 B2 JP 5467252B2
- Authority
- JP
- Japan
- Prior art keywords
- silver
- aqueous solution
- silver nanowire
- manufacturing
- nanowire
- 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.)
- Expired - Fee Related
Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 69
- 239000002042 Silver nanowire Substances 0.000 title claims description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 34
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 18
- 239000000460 chlorine Substances 0.000 claims description 18
- 229910052801 chlorine Inorganic materials 0.000 claims description 18
- 150000002772 monosaccharides Chemical class 0.000 claims description 18
- 239000003638 chemical reducing agent Substances 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 14
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 14
- 239000012736 aqueous medium Substances 0.000 claims description 11
- 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 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000008103 glucose Substances 0.000 claims description 10
- 238000010191 image analysis Methods 0.000 claims description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 7
- 229930091371 Fructose Natural products 0.000 claims description 7
- 239000005715 Fructose Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 4
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 3
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 34
- 238000000034 method Methods 0.000 description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 239000002070 nanowire Substances 0.000 description 9
- 239000011780 sodium chloride Substances 0.000 description 9
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004917 polyol method Methods 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- -1 For example Chemical compound 0.000 description 1
- LKDRXBCSQODPBY-AMVSKUEXSA-N L-(-)-Sorbose Chemical compound OCC1(O)OC[C@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-AMVSKUEXSA-N 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Landscapes
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Description
本発明は、銀ナノワイヤーの製造方法及びその製造方法により得られた銀ナノワイヤーに関する。さらに詳しくは、塩化銀を含む前駆体と、単糖類からなる還元剤と、水媒体とを用いたハイドロサーマル法により、フロー式粒子像分析装置を用いた画像解析による測定において、平均（最大垂直長／最大長）比が０.６５程度以下の形状を有する異方性の銀ナノワイヤーを効率よく製造する方法に関するものである。 The present invention relates to a method for producing silver nanowires and a silver nanowire obtained by the production method. More specifically, in the measurement by image analysis using a flow-type particle image analyzer by the hydrothermal method using a precursor containing silver chloride, a reducing agent consisting of a monosaccharide, and an aqueous medium, the average (maximum vertical) The present invention relates to a method for efficiently producing anisotropic silver nanowires having a shape with a (long / maximum length) ratio of about 0.65 or less.
複合材料におけるフィラーの添加は、各種性能面で重要であるが、性能を発揮するには十分な添加量が必要であり、特に導電性や熱伝導性、電磁波シールド性材料などでは導電フィラーによるネットワーク形成が重要である。したがって、マトリックス成分の性能を損なうことなく、十分な性能を発揮するためには、できるだけ少ない添加量でネットワークを形成することが必要である。そこで、異方性ナノフィラーは、サイズ効果による比表面積の増大と、高アスペクト比による接触面積の増大により少ない添加量でネットワークを形成することができることから、このような異方性ナノフィラーとして、カーボンナノチューブや金属ナノワイヤーが現在多く研究されている。 Addition of fillers in composite materials is important in terms of various performances, but a sufficient amount of addition is necessary to demonstrate performance, especially in conductive, thermal conductive, electromagnetic shielding materials, etc. Formation is important. Therefore, in order to exhibit sufficient performance without impairing the performance of the matrix component, it is necessary to form a network with the smallest possible addition amount. Therefore, since the anisotropic nanofiller can form a network with a small addition amount due to an increase in specific surface area due to the size effect and an increase in contact area due to a high aspect ratio, as such an anisotropic nanofiller, Many researches are currently being made on carbon nanotubes and metal nanowires.
従来、金属ナノワイヤーの製造方法としては、主として、鋳型（テンプレート）法が用いられている。このテンプレート法は、カーボンナノチューブ、ポーラスな（多孔質）シリカやアルミナ、界面活性剤、あるいはブロック共重合体をテンプレートとするものであるが、いずれも多数の工程や数〜数十時間におよぶ反応時間を必要とする複雑なものである。また、得られる金属ナノワイヤーは、必ずしも好適な太さと長さを有するものではなかった。カーボンナノチューブを使用したテンプレート法については、例えば特許文献１に開示されている。 Conventionally, as a method for producing metal nanowires, a template method has been mainly used. This template method uses carbon nanotubes, porous (porous) silica or alumina, a surfactant, or a block copolymer as a template, all of which involve a number of steps and reactions ranging from several to several tens of hours. It is a complicated thing that requires time. Moreover, the metal nanowire obtained did not necessarily have suitable thickness and length. A template method using carbon nanotubes is disclosed in Patent Document 1, for example.
また、鋳型に依らない方法として、電子線照射方法（例えば、特許文献２参照）や、紫外線照射方法（例えば特許文献３参照）が提案されているが、これらの方法は操作が煩雑で、コスト的にも不利である。
近年、鋳型に依らない金属ナノワイヤーの製造方法として、操作が簡単な化学還元法による方法の研究が行なわれており、その中でも、有機錯体を多価アルコールで還元することにより単分散ナノ粒子やナノワイヤーの合成を行うポリオール法が盛んに研究されている。
このポリオール法の多くは、前駆体として硝酸銀、分散剤にポリビニルピロリドン、溶媒且つ還元剤としてエチレングリコールを使用する（例えば、特許文献４、非特許文献１参照）。これら配合の中で特に分散剤であるポリビニルピロリドンの分子量が金属結晶の成長に依存することで、異方性のある金属ナノワイヤーが生成されるということが報告されている（例えば、非特許文献２参照）。これらの研究は、分散剤として比較的分子量の高いポリマーを使用しており、且つ有機溶媒であるエチレングリコールを使用している。また、塩化銀を前駆体としたハイドロサーマル法による銀ナノワイヤーの合成も報告されている（例えば、非特許文献３参照）。
Further, as methods that do not depend on the mold, an electron beam irradiation method (for example, see Patent Document 2) and an ultraviolet irradiation method (for example, see Patent Document 3) have been proposed, but these methods are complicated in operation and costly. It is also disadvantageous.
In recent years, as a method for producing metal nanowires that do not depend on the template, methods of chemical reduction methods that are easy to operate have been studied. Among them, monodisperse nanoparticles and organic dispersions can be obtained by reducing organic complexes with polyhydric alcohols. The polyol method for synthesizing nanowires has been actively studied.
Many of the polyol methods use silver nitrate as a precursor, polyvinylpyrrolidone as a dispersant, and ethylene glycol as a solvent and a reducing agent (see, for example,
前記非特許文献３の方法においては、塩化銀を含む前駆体を硝酸銀水溶液と塩化ナトリウム水溶液とを用いて調製する際に、使用する塩化ナトリウム水溶液の濃度が０.０２モル／Ｌと低いために、径が細く長い形状を有する異方性の銀ナノワイヤーが得られにくいという問題がある。
本発明は、このような状況下になされたもので、フロー式粒子像分析装置を用いた画像解析による測定において、平均（最大垂直長／最大長）比が、０.６５程度以下になるような形状を有する異方性の銀ナノワイヤーを効率よく製造する方法を提供することを目的とするものである。
In the method of Non-Patent Document 3, when the precursor containing silver chloride is prepared using an aqueous silver nitrate solution and an aqueous sodium chloride solution, the concentration of the aqueous sodium chloride solution used is as low as 0.02 mol / L. There is a problem in that it is difficult to obtain anisotropic silver nanowires having a thin and long shape.
The present invention has been made under such circumstances, and in measurement by image analysis using a flow type particle image analyzer, the average (maximum vertical length / maximum length) ratio is about 0.65 or less. An object of the present invention is to provide a method for efficiently producing anisotropic silver nanowires having various shapes.
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、特定の方法で得られた塩化銀を含む前駆体と、単糖類からなる還元剤とを、水媒体中において、所定の温度で加熱処理すること（ハイドロサーマル法とも云う）により、その目的を達成し得ることを見出した。本発明は、かかる知見に基づいて完成したものである。
すなわち、本発明は、
（１）塩化銀を含む前駆体と、単糖類からなる還元剤とを、水媒体中において、１３０〜２００℃の温度で加熱処理する銀ナノワイヤーの製造方法であって、前記の塩化銀を含む前駆体が、濃度０.０１〜０.１０モル／Ｌの銀塩水溶液と、濃度０.１０〜０.７０モル／Ｌの塩素含有物水溶液とを、銀塩と塩素含有物のモル比が１：１〜１：７になるように用い、かつ、前記の銀塩水溶液と塩素含有物水溶液との合計量に対して、新たに水媒体を３〜１０体積倍加えることにより得られたものであることを特徴とする、銀ナノワイヤーの製造方法、
（２）銀塩水溶液が硝酸銀水溶液である、上記(１)項に記載の銀ナノワイヤーの製造方法、
（３）塩素含有物水溶液が、アルカリ金属塩化物水溶液又は塩酸水溶液である、上記(１)又は(２)項に記載の銀ナノワイヤーの製造方法、
（４）銀塩水溶液中の銀塩と単糖類とのモル比が１：１〜１：１０である、上記(１)〜(３)項のいずれかに記載の銀ナノワイヤーの製造方法、
（５）得られる銀ナノワイヤーが、フロー式粒子像分析装置を用いた画像解析による測定において、最大長が１μｍ以上である粒子１００個以上の平均（最大垂直長／最大長）比が０.６５以下である形状を有する、上記(１)〜(４)項のいずれかに記載の銀ナノワイヤーの製造方法、
（６）単糖類がグルコース及び／又はフルクトースである、上記(１)〜(５)項のいずれかに記載の銀ナノワイヤーの製造方法、及び
(７)上記(１)〜(６)項のいずれかに記載の製造方法により得られたことを特徴とする銀ナノワイヤー、
を提供するものである。
As a result of intensive studies to achieve the above object, the inventors of the present invention have prepared a specific method in which a precursor containing silver chloride obtained by a specific method and a reducing agent consisting of a monosaccharide are added in an aqueous medium. It was found that the object can be achieved by heat treatment at a temperature of (also referred to as hydrothermal method). The present invention has been completed based on such findings.
That is, the present invention
(1) A silver nanowire manufacturing method in which a precursor containing silver chloride and a reducing agent comprising a monosaccharide are heat-treated at a temperature of 130 to 200 ° C. in an aqueous medium, A precursor containing a silver salt aqueous solution having a concentration of 0.01 to 0.10 mol / L and a chlorine containing material aqueous solution having a concentration of 0.10 to 0.70 mol / L, a molar ratio of the silver salt to the chlorine containing material. Obtained by adding 3 to 10 times the volume of the aqueous medium with respect to the total amount of the silver salt aqueous solution and the chlorine-containing material aqueous solution. A method for producing silver nanowires, characterized in that
(2) The method for producing silver nanowires according to (1) above, wherein the aqueous silver salt solution is an aqueous silver nitrate solution,
(3) The method for producing silver nanowires according to (1) or (2) above, wherein the chlorine-containing substance aqueous solution is an alkali metal chloride aqueous solution or a hydrochloric acid aqueous solution,
(4) The method for producing silver nanowires according to any one of (1) to (3) above, wherein the molar ratio of silver salt to monosaccharide in the aqueous silver salt solution is 1: 1 to 1:10,
(5) The average (maximum vertical length / maximum length) ratio of 100 or more particles having a maximum length of 1 μm or more in the measurement by image analysis using a flow-type particle image analyzer of the obtained silver nanowire is 0. The method for producing silver nanowires according to any one of (1) to (4) above, having a shape of 65 or less,
(6) The method for producing silver nanowires according to any one of (1) to (5) above, wherein the monosaccharide is glucose and / or fructose, and
(7) A silver nanowire obtained by the production method according to any one of (1) to (6) above,
Is to provide.
本発明の銀ナノワイヤーの製造方法によれば、塩化銀を含む前駆体と、単糖類からなる還元剤と、水媒体とを用いたハイドロサーマル法により、フロー式粒子像分析装置を用いた画像解析による測定において、平均（最大垂直長／最大長）比が０.６５程度以下の形状を有する異方性の銀ナノワイヤーを効率よく製造することができる。
本発明の方法で得られた異方性の銀ナノワイヤーは、特に導電性や熱伝導性、電磁波シールド性材料などにおいて、少量の添加でネットワークを形成し得るフィラーとして有用である。
According to the method for producing silver nanowires of the present invention, an image using a flow-type particle image analyzer by a hydrothermal method using a precursor containing silver chloride, a reducing agent comprising a monosaccharide, and an aqueous medium. In measurement by analysis, anisotropic silver nanowires having an average (maximum vertical length / maximum length) ratio of about 0.65 or less can be efficiently produced.
The anisotropic silver nanowire obtained by the method of the present invention is useful as a filler capable of forming a network with a small amount of addition, particularly in conductive, thermal conductive, electromagnetic shielding materials and the like.
本発明の銀ナノワイヤーの製造方法においては、下記の方法で調製した塩化銀を含む前駆体と、単糖類からなる還元剤とを、水媒体中において、１３０〜２００℃の温度で加熱処理する。
［塩化銀を含む前駆体の調製］
本発明の方法においては、まず以下に示す方法により、塩化銀を含む前駆体を調製する。
すなわち、濃度０.０１〜０.１０モル／Ｌの銀塩水溶液と、濃度０.１０〜０.７０モル／Ｌの塩素含有物水溶液とを、銀塩と塩素含有物のモル比が１：１〜１：７になるように用い、かつ前記の銀塩水溶液と塩素含有物水溶液との合計量に対して、新たに水媒体を３〜１０体積倍加えることにより、塩化銀を含む前駆体を調製する。
本発明においては、前記の銀塩水溶液濃度、塩素含有物濃度、銀塩と塩素含有物のモル比、及び新たに加える水媒体の量の中のいずれか１つが前記範囲を逸脱すると、フロー式粒子像分析装置を用いた画像解析による測定において、平均（最大垂直長／最大長）比を０.６５以下にすることが困難となり、径が細く長い形状の異方性の銀ナノワイヤーが得られない。なお、上記の平均（最大垂直長／最大長）比の測定方法については、後で詳述する。
In the method for producing silver nanowires of the present invention, a precursor containing silver chloride prepared by the following method and a reducing agent comprising a monosaccharide are heat-treated at a temperature of 130 to 200 ° C. in an aqueous medium. .
[Preparation of precursor containing silver chloride]
In the method of the present invention, first, a precursor containing silver chloride is prepared by the following method.
That is, a silver salt aqueous solution having a concentration of 0.01 to 0.10 mol / L and a chlorine containing aqueous solution having a concentration of 0.10 to 0.70 mol / L have a molar ratio of silver salt to chlorine containing material of 1: Precursor containing silver chloride by adding an aqueous medium 3 to 10 times by volume with respect to the total amount of the silver salt aqueous solution and the chlorine-containing material aqueous solution. To prepare.
In the present invention, when any one of the silver salt aqueous solution concentration, the chlorine-containing material concentration, the molar ratio between the silver salt and the chlorine-containing material, and the amount of the newly added aqueous medium deviates from the above range, the flow formula In measurement by image analysis using a particle image analyzer, it becomes difficult to reduce the average (maximum vertical length / maximum length) ratio to 0.65 or less, and an anisotropic silver nanowire having a narrow diameter and a long shape is obtained. I can't. The method for measuring the average (maximum vertical length / maximum length) ratio will be described in detail later.
前記銀塩水溶液としては、得られる銀ナノワイヤーにおける異方性などの性状の観点から、硝酸銀水溶液が好ましく、またその濃度は０.０１〜０.０５モル／Ｌの範囲が好ましい。
前記塩素含有物水溶液としては、得られる銀ナノワイヤーにおける異方性などの性状の観点から、アルカリ金属塩化物水溶液が好ましく、さらに塩化ナトリウムがより好ましく、また塩酸も好ましく用いられる。また、その濃度は、０.１０〜０.５モル／Ｌの範囲が好ましい。
さらに、得られる銀ナノワイヤーにおける異方性などの性状の観点から、前記銀塩と塩素含有物のモル比は１：２〜１：５の範囲が好ましく、また、新たに加える水媒体の量は、前記の銀塩水溶液と塩素含有物水溶液との合計量に対して、４〜７体積倍が好ましい。
The silver salt aqueous solution is preferably a silver nitrate aqueous solution from the viewpoint of properties such as anisotropy in the obtained silver nanowire, and the concentration is preferably in the range of 0.01 to 0.05 mol / L.
From the viewpoint of properties such as anisotropy in the obtained silver nanowire, the chlorine-containing material aqueous solution is preferably an alkali metal chloride aqueous solution, more preferably sodium chloride, and hydrochloric acid is also preferably used. The concentration is preferably in the range of 0.10 to 0.5 mol / L.
Furthermore, from the viewpoint of properties such as anisotropy in the obtained silver nanowire, the molar ratio of the silver salt to the chlorine-containing material is preferably in the range of 1: 2 to 1: 5, and the amount of the aqueous medium to be newly added Is preferably 4 to 7 times by volume with respect to the total amount of the silver salt aqueous solution and the chlorine-containing material aqueous solution.
本発明においては、このようにしてコロイド状の塩化銀が生成された分散液が調製される。この分散液を前駆体とし、該前駆体液と、単糖類からなる還元剤とを、１３０〜２００℃の温度で加熱処理すること（ハイドロサーマル法）により、異方性の銀ナノワイヤーを製造する。
［単糖類］
塩化銀に対する還元剤として用いられる単糖類としては特に制限はなく、例えばグルコース、フルクトース、キシロース、ソルボース、ガラクトースなどが挙げられ、これらは単独で用いてもよいし、２種類以上を組み合わせて用いてもよいが、これらの中で、得られる銀ナノワイヤーにおける異方性などの性状の観点から、グルコース及び／又はフルクトースが好ましい。
また、当該単糖類の使用量は、還元剤としての効果の観点から、前記銀塩水溶液中の銀塩と当該単糖類とのモル比が１：１〜１：１０になるような量が好ましく、１：１.５〜１：５になるような量がより好ましい。
In the present invention, a dispersion in which colloidal silver chloride is produced in this way is prepared. Using this dispersion as a precursor, anisotropic silver nanowires are produced by heat-treating the precursor liquid and a reducing agent comprising a monosaccharide at a temperature of 130 to 200 ° C. (hydrothermal method). .
[Monosaccharide]
There is no restriction | limiting in particular as monosaccharide used as a reducing agent with respect to silver chloride, For example, glucose, fructose, xylose, sorbose, galactose etc. are mentioned, These may be used independently and are used in combination of 2 or more types. Of these, glucose and / or fructose are preferable from the viewpoint of properties such as anisotropy in the obtained silver nanowire.
The amount of the monosaccharide used is preferably such that the molar ratio of the silver salt in the silver salt aqueous solution to the monosaccharide is 1: 1 to 1:10 from the viewpoint of the effect as a reducing agent. An amount such as 1: 1.5 to 1: 5 is more preferred.
［加熱処理条件］
本発明においては、前記のコロイド状塩化銀を含む前駆体液と単糖類からなる還元剤とを混合して、１３０〜２００℃の温度で加熱処理する。この温度が１３０℃未満では、塩化銀の金属体への還元が進行しにくく、一方２００℃を超えると還元された金属体の再融着が進行するため、得られる銀ナノワイヤーの径が大きくなる傾向がある。
好ましい加熱処理温度は、使用する単糖類の分解温度近辺であり、例えば単糖類としてグルコースを使用する場合には、１５０〜２００℃の範囲の温度が好ましく、フルクトースを使用する場合には、１３０〜１８０℃の範囲の温度が好ましい。
反応装置としては、耐圧密閉容器を用い、反応圧力は自発圧力でよい。反応時間は反応温度などに左右され、一概に定めることはできないが、通常２０〜７２時間程度で充分である。
このようにして得られた反応液に、遠心分離などの固液分離手段を施したのち、固相を水洗処理することにより、目的の異方性の銀ナノワイヤーを取得することができる。
[Heat treatment conditions]
In the present invention, the precursor liquid containing colloidal silver chloride and a reducing agent composed of monosaccharide are mixed and heat-treated at a temperature of 130 to 200 ° C. If the temperature is less than 130 ° C., the reduction of silver chloride to the metal body is difficult to proceed, whereas if the temperature exceeds 200 ° C., the re-fusion of the reduced metal body proceeds, so that the diameter of the obtained silver nanowire is large. Tend to be.
A preferable heat treatment temperature is around the decomposition temperature of the monosaccharide to be used. For example, when glucose is used as the monosaccharide, a temperature in the range of 150 to 200 ° C. is preferable, and when fructose is used, 130 to A temperature in the range of 180 ° C. is preferred.
As the reaction apparatus, a pressure-resistant sealed container is used, and the reaction pressure may be a spontaneous pressure. The reaction time depends on the reaction temperature and cannot be generally defined, but about 20 to 72 hours is usually sufficient.
The target anisotropic silver nanowire can be obtained by subjecting the reaction solution thus obtained to solid-liquid separation means such as centrifugation and then washing the solid phase with water.
［銀ナノワイヤーの性状］
前述した本発明の方法においては、得られる銀ナノワイヤーとして、フロー式粒子像分析装置を用いた画像解析による測定において、最大長が１μｍ以上である粒子１００個以上の平均（最大垂直長／最大長）比が、０.６５以下になる形状を有する異方性の銀ナノワイヤーを製造することができる。
なお図１２は、得られる銀ナノワイヤーについての前記フロー式粒子像分析装置を用いた画像解析による二次元模式図であり、前記最大垂直長及び最大長は、この図１２に示すとおりである。
また、得られる異方性の銀ナノワイヤーの平均直径及び平均長さは、走査型電子顕微鏡（ＳＥＭ）写真により求めることができ、平均直径は、通常１００〜６００ｎｍ程度、平均長さは、通常２０〜１００μｍであり、平均アスペクト比（平均長さ／平均直径）は５０〜２５０程度である。
また、得られるナノワイヤーが銀であることは、Ｘ線回折（ＸＲＤ）により、確認することができる。
[Properties of silver nanowires]
In the method of the present invention described above, the average of 100 or more particles having a maximum length of 1 μm or more (maximum vertical length / maximum) in the measurement by image analysis using a flow type particle image analyzer as the obtained silver nanowires. An anisotropic silver nanowire having a shape with a (long) ratio of 0.65 or less can be produced.
FIG. 12 is a two-dimensional schematic diagram of the obtained silver nanowire by image analysis using the flow type particle image analyzer, and the maximum vertical length and the maximum length are as shown in FIG.
Moreover, the average diameter and average length of the obtained anisotropic silver nanowire can be calculated | required with a scanning electron microscope (SEM) photograph, an average diameter is about about 100-600 nm normally, and average length is normal. The average aspect ratio (average length / average diameter) is about 50 to 250.
Moreover, it can confirm that the nanowire obtained is silver by X-ray diffraction (XRD).
このような本発明の方法により、異方性の銀ナノワイヤーを、効率よく製造することができる。この異方性の銀ナノワイヤーは、導電性や熱伝導性、電磁波シールド性材料などのフィラーとして、添加量が少なくても、容易にネットワークを形成することができ、有用である。 By such a method of the present invention, anisotropic silver nanowires can be efficiently produced. This anisotropic silver nanowire is useful because it can easily form a network as a filler such as a conductive material, a heat conductive material, or an electromagnetic wave shielding material, even if the addition amount is small.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
なお、各例で得られた銀ナノワイヤーの性状は、下記の方法により求めた。
（１）平均（最大垂直長／最大長）比
フロー式粒子像分析装置［ＳＹＳＭＥＸ社製、機種名「ＦＰＩＡ−３０００」］を使用し、明細書本文記載の方法に従って求めた。
（２）平均直径及び平均長さ
走査型電子顕微鏡（ＳＥＭ）［日立製作所(株)社製、機種名「Ｓ−２３８０」］写真により、測定した。またこのデータを用い、平均アスペクト比（平均長さ／平均直径）を算出した。
（３）ナノワイヤーの材質の確認
Ｘ線回折装置［理学(株)社製、機種名「ＲＵ２００Ｂ型」］を用いてＸ線回折（ＸＲＤ）を行い、銀であることを確認した。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the property of the silver nanowire obtained in each example was calculated | required with the following method.
(1) Average (maximum vertical length / maximum length) ratio A flow type particle image analyzer [manufactured by SYSMEX, model name “FPIA-3000”] was used and was determined according to the method described in the specification.
(2) Average diameter and average length It measured with the scanning electron microscope (SEM) [Hitachi Ltd. make, model name "S-2380"] photograph. Further, using this data, an average aspect ratio (average length / average diameter) was calculated.
(3) Confirmation of Nanowire Material X-ray diffraction (XRD) was performed using an X-ray diffractometer [manufactured by Rigaku Corporation, model name “RU200B type”] to confirm that the material was silver.
実施例１
テフロン製内筒へ３０ｍｌの脱イオン水を入れ、これに銀塩原料として０.０２モル／Ｌ硝酸銀水溶液５ｍｌと塩素含有物として０.２モル／Ｌ塩化ナトリウム水溶液１.０ｍｌを滴下し、単糖の還元剤としてグルコースを０.４ミリモル添加した。その後、テフロン製内筒をステンレス製の耐圧反応器へ入れた後、１６０℃にて２４時間反応させた。さらに、得られた反応液を遠心分離機［(株)久保田製作所社製、機種名「卓上小型遠心機」］（４００００ｒｐｍ、４０分間）により沈殿物を取り出して純水で洗浄し、遠心分離、洗浄の工程を３回繰り返した。
その後、得られた沈殿物をＳＥＭ観察にて確認したところ、直径５０〜３００ｎｍ程度（平均直径１８６ｎｍ）のナノワイヤー構造を有する物質を確認することができた。さらに得られた沈殿物のＸＲＤ回折を確認したところ、得られたものが銀であることが確認された。反応条件及び結果をそれぞれ第１表及び第２表に示す。
Example 1
30 ml of deionized water is put into a Teflon inner cylinder, and 5 ml of 0.02 mol / L silver nitrate aqueous solution as a silver salt raw material and 1.0 ml of 0.2 mol / L sodium chloride aqueous solution as a chlorine-containing material are added dropwise. As a sugar reducing agent, 0.4 mmol of glucose was added. Then, after putting the Teflon inner cylinder into a stainless steel pressure-resistant reactor, it was reacted at 160 ° C. for 24 hours. Further, the resulting reaction solution was centrifuged with a centrifuge [manufactured by Kubota Corporation, model name “desktop small centrifuge”] (40000 rpm, 40 minutes), washed with pure water, centrifuged, The washing process was repeated three times.
Then, when the obtained deposit was confirmed by SEM observation, the substance which has a nanowire structure about 50-300 nm in diameter (average diameter 186 nm) was able to be confirmed. Further, when XRD diffraction of the obtained precipitate was confirmed, it was confirmed that the obtained precipitate was silver. Reaction conditions and results are shown in Tables 1 and 2, respectively.
実施例２
実施例１において添加する塩化ナトリウム水溶液の量を２.５ｍｌ、グルコースの添加量を０.２ミリモル、反応温度を１８０℃に変更した以外は、実施例１と同様にして反応を行った。反応条件及び結果をそれぞれ第１表及び第２表に示す。
Example 2
The reaction was carried out in the same manner as in Example 1 except that the amount of sodium chloride aqueous solution added in Example 1 was changed to 2.5 ml, the added amount of glucose was changed to 0.2 mmol, and the reaction temperature was changed to 180 ° C. Reaction conditions and results are shown in Tables 1 and 2, respectively.
実施例３
実施例１において還元剤をフルクトース０.２ミリモルに変更し、さらに反応温度を１４０℃にした以外は、実施例１と同様にして反応を行った。反応条件及び結果をそれぞれ第１表及び第２表に示す。
Example 3
The reaction was conducted in the same manner as in Example 1 except that the reducing agent was changed to 0.2 mmole of fructose in Example 1 and the reaction temperature was 140 ° C. Reaction conditions and results are shown in Tables 1 and 2, respectively.
実施例４
実施例１において、反応温度を１８０℃に変更した以外は、実施例１と同様にして反応を行った。反応条件及び結果をそれぞれ第１表及び第２表に示す。
Example 4
In Example 1, the reaction was performed in the same manner as in Example 1 except that the reaction temperature was changed to 180 ° C. Reaction conditions and results are shown in Tables 1 and 2, respectively.
実施例５
実施例１において、グルコースの添加量を０.２ミリモルに変更し、反応温度を１８０℃に変更した以外は、実施例１と同様にして反応を行った。反応条件及び結果をそれぞれ第１表及び第２表に示す。
Example 5
In Example 1, the reaction was performed in the same manner as in Example 1 except that the amount of glucose added was changed to 0.2 mmol and the reaction temperature was changed to 180 ° C. Reaction conditions and results are shown in Tables 1 and 2, respectively.
実施例６
実施例１において、添加する塩素含有物を塩化ナトリウムから塩酸に変更し、添加する塩酸水溶液の量を０.５ｍｌに変更した以外は、実施例１と同様にして反応を行った。反応条件及び結果をそれぞれ第１表及び第２表に示す。
比較例１
実施例１において、塩化ナトリウム水溶液を添加することなく、反応温度を１８０℃にした以外は、実施例１と同様にして、硝酸銀水溶液の還元を行った。反応条件及び結果をそれぞれ第１表及び第２表に示す。
Example 6
In Example 1, the reaction was performed in the same manner as in Example 1 except that the chlorine-containing material to be added was changed from sodium chloride to hydrochloric acid, and the amount of the aqueous hydrochloric acid solution to be added was changed to 0.5 ml. Reaction conditions and results are shown in Tables 1 and 2, respectively.
Comparative Example 1
In Example 1, the silver nitrate aqueous solution was reduced in the same manner as in Example 1 except that the reaction temperature was changed to 180 ° C. without adding the sodium chloride aqueous solution. Reaction conditions and results are shown in Tables 1 and 2, respectively.
比較例２
実施例１において、硝酸銀水溶液の濃度を０.１モル／Ｌ、塩化ナトリウム水溶液の濃度を０.１モル／Ｌ、反応温度を１８０℃に変更した以外は、実施例１と同様にして反応を行った。反応条件及び結果をそれぞれ第１表及び第２表に示す。
Comparative Example 2
In Example 1, the reaction was conducted in the same manner as in Example 1 except that the concentration of the aqueous silver nitrate solution was changed to 0.1 mol / L, the concentration of the aqueous sodium chloride solution was changed to 0.1 mol / L, and the reaction temperature was changed to 180 ° C. went. Reaction conditions and results are shown in Tables 1 and 2, respectively.
比較例３
実施例１において、還元剤としてフルクトース、反応温度を１２０℃に変更した以外は、実施例１と同様にして反応を行った。反応条件及び結果をそれぞれ第１表及び第２表に示す。
Comparative Example 3
In Example 1, the reaction was performed in the same manner as in Example 1 except that fructose was used as the reducing agent and the reaction temperature was changed to 120 ° C. Reaction conditions and results are shown in Tables 1 and 2, respectively.
比較例４
実施例１において、還元剤であるグルコースを未添加にした以外は、実施例１と同様にして反応を行った。反応条件及び結果をそれぞれ第１表及び第２表に示す。
Comparative Example 4
In Example 1, the reaction was performed in the same manner as in Example 1 except that glucose as a reducing agent was not added. Reaction conditions and results are shown in Tables 1 and 2, respectively.
比較例５
実施例１において、塩化ナトリウム水溶液の濃度を０.０２モル／Ｌ、添加量を５ｍｌ、還元剤であるグルコースの添加量を０.２ミリモル、反応温度を１８０℃に変更した以外は、実施例１と同様にして反応を行った。反応条件及び結果をそれぞれ第１表及び第２表に示す。
Comparative Example 5
In Example 1, the concentration of the aqueous sodium chloride solution was 0.02 mol / L, the addition amount was 5 ml, the addition amount of glucose as a reducing agent was 0.2 mmol, and the reaction temperature was changed to 180 ° C. The reaction was carried out in the same manner as in 1. Reaction conditions and results are shown in Tables 1 and 2, respectively.
第２表から分かるように、銀ナノワイヤーのフロート式粒子像分析装置を用いた画像解析による測定において、平均（最大垂直長／最大長）比は、本発明の方法（実施例１〜６）で得られた銀ナノワイヤーにおいては、いずれも０.６５未満であり、一方比較例１〜５で得られた銀ナノワイヤーにおいては、いずれも０.６５より高い。 As can be seen from Table 2, the average (maximum vertical length / maximum length) ratio in the measurement by image analysis using a silver nanowire float type particle image analyzer is the method of the present invention (Examples 1 to 6). In the silver nanowires obtained in the above, all are less than 0.65, while in the silver nanowires obtained in Comparative Examples 1 to 5, all are higher than 0.65.
本発明の銀ナノワイヤーの製造方法は、異方性の銀ナノワイヤーを効率よく製造することができ、得られた異方性の銀ナノワイヤーは、導電性や熱伝導性、電磁波シールド性材料などのフィラーとして有用である。 The method for producing silver nanowires of the present invention can efficiently produce anisotropic silver nanowires, and the obtained anisotropic silver nanowires are conductive, thermally conductive, and electromagnetic shielding materials. It is useful as a filler.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009114671A JP5467252B2 (en) | 2009-05-11 | 2009-05-11 | Silver nanowire manufacturing method and silver nanowire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009114671A JP5467252B2 (en) | 2009-05-11 | 2009-05-11 | Silver nanowire manufacturing method and silver nanowire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2010261090A JP2010261090A (en) | 2010-11-18 |
| JP5467252B2 true JP5467252B2 (en) | 2014-04-09 |
Family
ID=43359422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009114671A Expired - Fee Related JP5467252B2 (en) | 2009-05-11 | 2009-05-11 | Silver nanowire manufacturing method and silver nanowire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5467252B2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102724910A (en) | 2010-11-24 | 2012-10-10 | 奥林巴斯医疗株式会社 | Chemical bottle for endoscope cleaning and disinfecting device |
| JP5846598B2 (en) * | 2011-06-01 | 2016-01-20 | 国立大学法人大阪大学 | Synthesis method of nanoparticles |
| CN102744421A (en) * | 2012-07-16 | 2012-10-24 | 浙江师范大学 | Method for preparing large-scale Ag nanowires in aqueous solution |
| CN103203468B (en) * | 2013-04-17 | 2016-05-25 | 苏州冷石纳米材料科技有限公司 | A kind of preparation method of nano silver wire |
| CN104109909B (en) | 2013-04-18 | 2018-09-04 | 财团法人工业技术研究院 | nano metal wire and manufacturing method thereof |
| CN103752850B (en) * | 2014-02-18 | 2015-08-26 | 南京瑞盈环保科技有限公司 | A kind of method utilizing alumina formwork to prepare nano silver wire |
| JP2015209555A (en) * | 2014-04-24 | 2015-11-24 | 株式会社ノリタケカンパニーリミテド | Silver nanowire and manufacturing method therefor |
| CN104014805B (en) * | 2014-05-20 | 2016-04-20 | 苏州明动新材料科技有限公司 | A kind of preparation method of nano silver wire |
| KR20190092397A (en) * | 2016-10-25 | 2019-08-07 | 도와 일렉트로닉스 가부시키가이샤 | Manufacturing method of silver nanowire |
| EP4079772A4 (en) * | 2019-12-20 | 2023-12-27 | Resonac Corporation | Production method for polymer composition |
| CN111992735A (en) * | 2020-08-24 | 2020-11-27 | 深圳先进电子材料国际创新研究院 | Silver nanowire and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2003068674A1 (en) * | 2002-02-15 | 2005-06-02 | 独立行政法人科学技術振興機構 | Noble metal nanowire structure and manufacturing method thereof |
| JP2006161102A (en) * | 2004-12-07 | 2006-06-22 | Mitsuboshi Belting Ltd | Method for producing metal nanostructure |
| JP2009299162A (en) * | 2008-06-16 | 2009-12-24 | Fujifilm Corp | Silver nanowire, method for producing the same, water base dispersion product and transparent conductor |
-
2009
- 2009-05-11 JP JP2009114671A patent/JP5467252B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010261090A (en) | 2010-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5467252B2 (en) | Silver nanowire manufacturing method and silver nanowire | |
| Niu et al. | Seed-mediated growth of noble metal nanocrystals: crystal growth and shape control | |
| Alavi et al. | Syntheses and characterization of Mg (OH) 2 and MgO nanostructures by ultrasonic method | |
| Sui et al. | Low temperature synthesis of Cu2O crystals: shape evolution and growth mechanism | |
| Xie et al. | Morphological control in solvothermal synthesis of titanium oxide | |
| Wang et al. | Hydrothermal synthesis and characterization of KNbO 3 nanorods | |
| Zhang et al. | Controlling the synthesis of CoO nanocrystals with various morphologies | |
| CN105397103A (en) | Nano-silver/graphene composite material and preparation method thereof | |
| US10099191B1 (en) | Method of making colloidal metal nanoparticles | |
| Yang et al. | Templated high-yield synthesis of Pt nanorods enclosed by high-index {311} facets for methanol selective oxidation | |
| Hong et al. | Graphene oxide stabilized Cu 2 O for shape selective nanocatalysis | |
| Morgan et al. | Alkaline hydrothermal kinetics in titanate nanostructure formation | |
| Tao et al. | Synthesis of corundum-type In 2 O 3 porous spheres and their photocatalytic properties | |
| KR20130059333A (en) | Process for preparing anisotropic metal nanoparticles | |
| KR101286108B1 (en) | Manufacturing method of Te and bismuth telluride nano wire by solvothermal synthesis | |
| Hou et al. | Solution-phase synthesis of single-crystalline Bi 12 TiO 20 nanowires with photocatalytic properties | |
| CN113151856A (en) | Preparation of high-entropy alloy phosphide nanoparticle catalyst and application of high-entropy alloy phosphide nanoparticle catalyst in hydrogen production by water electrolysis | |
| KR20080057102A (en) | Method for manufacturing titanate nanotube | |
| JP2007290887A (en) | Bismuth titanate-based nanoparticle, piezoelectric ceramic using the same, and methods for producing them | |
| Gao et al. | One‐Pot Hydrothermal Synthesis of Thin Tellurene Nanosheet and Its Formation Mechanism | |
| Hu et al. | A facile solution route for the synthesis of PbSe–Au nanocomposites with different morphologies | |
| Xu et al. | A growth model of single crystalline hollow spheres: oriented attachment of Cu2O nanoparticles to the single crystalline shell wall | |
| Hakuta et al. | Hydrothermal synthesis of photocatalyst potassium hexatitanate nanowires under supercritical conditions. | |
| JP2008024968A (en) | Method for manufacturing noble-metal nanomaterial | |
| JP5678437B2 (en) | Synthesis method of nanocrystalline alloys |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120507 |
|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20121024 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20121024 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20131101 |
|
| 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: 20131119 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20131219 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |