JP2011026172A - Tin oxide particle and method for producing tin oxide sol - Google Patents
Tin oxide particle and method for producing tin oxide sol Download PDFInfo
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- JP2011026172A JP2011026172A JP2009174028A JP2009174028A JP2011026172A JP 2011026172 A JP2011026172 A JP 2011026172A JP 2009174028 A JP2009174028 A JP 2009174028A JP 2009174028 A JP2009174028 A JP 2009174028A JP 2011026172 A JP2011026172 A JP 2011026172A
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 138
- 239000002245 particle Substances 0.000 title claims abstract description 104
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 143
- 239000007788 liquid Substances 0.000 claims abstract description 43
- 239000007864 aqueous solution Substances 0.000 claims abstract description 31
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 239000002019 doping agent Substances 0.000 claims abstract description 17
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 14
- 230000001590 oxidative effect Effects 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 32
- 239000000843 powder Substances 0.000 description 24
- 238000005406 washing Methods 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- 238000010298 pulverizing process Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 229910052787 antimony Inorganic materials 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 150000004679 hydroxides Chemical class 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- DWZBSOVYCROKJR-UHFFFAOYSA-N 4-(2-methylphenyl)butan-1-ol Chemical compound CC1=CC=CC=C1CCCCO DWZBSOVYCROKJR-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009125 cardiac resynchronization therapy Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QBWXYICYWNSGPT-UHFFFAOYSA-L dichlorotin pentahydrate Chemical compound O.O.O.O.O.Cl[Sn]Cl QBWXYICYWNSGPT-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- SYRHIZPPCHMRIT-UHFFFAOYSA-N tin(4+) Chemical compound [Sn+4] SYRHIZPPCHMRIT-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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- Chemical & Material Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
Description
本発明は酸化スズ粒子に関する。また本発明は、酸化スズゾルの製造方法に関する。 The present invention relates to tin oxide particles. The present invention also relates to a method for producing a tin oxide sol.
非導電性材料、例えばプラスチックに導電性を付与する方法として、プラスチックに導電性粉末を添加する方法が知られている。導電性粉末としては、例えば、金属粉末、カーボンブラック、アンチモン等をドープした酸化スズ等が知られている。しかし、金属粉末やカーボンブラックをプラスチックに添加すると得られるプラスチックが黒色になり、プラスチックの用途が限定されることがある。一方、アンチモン等をドープした酸化スズをプラスチックに添加すると、プラスチックが青黒色になり、カーボンブラック等と同様にやはりプラスチックの用途が限定されることがある。またアンチモンの使用に起因する環境負荷の問題もある。そこで、アンチモン等のドーパントを含まない酸化スズについての検討が種々行われている。 As a method for imparting conductivity to a non-conductive material such as plastic, a method of adding conductive powder to the plastic is known. As the conductive powder, for example, tin powder doped with metal powder, carbon black, antimony or the like is known. However, when metal powder or carbon black is added to the plastic, the resulting plastic becomes black, which may limit the use of the plastic. On the other hand, when tin oxide doped with antimony or the like is added to the plastic, the plastic becomes blue-black, and the use of the plastic may be limited as in the case of carbon black. There is also a problem of environmental load caused by the use of antimony. Therefore, various studies have been made on tin oxide not containing a dopant such as antimony.
例えば特許文献１には、水酸化テトラメチルアンモニウムをＮＨ3／ＳｎＯ2モル比０．０１〜０．３の範囲で含有してなる粒子径３０ｎｍ以下のアルカリ安定型酸化スズゾルが記載されている。この酸化スズゾルは、酸化スズ濃度がＳｎＯ2として１５質量％以下のアルカリ型酸化スズゾルに水酸化テトラメチルアンモニウムを添加し、濃縮を行うことで製造される。 For example, Patent Document 1 describes an alkali-stable tin oxide sol having a particle diameter of 30 nm or less and containing tetramethylammonium hydroxide in a NH 3 / SnO 2 molar ratio in the range of 0.01 to 0.3. This tin oxide sol is produced by adding tetramethylammonium hydroxide to an alkali-type tin oxide sol having a tin oxide concentration of SnO 2 of 15% by mass or less and concentrating.
酸化スズゾルの製造方法の別法として、特許文献２には、０．１〜８規定の塩酸にスズをＨＣｌ／Ｓｎ（モル比）＝０．５〜１となるように添加し、この液に過酸化水素水を添加する方法が提案されている。同文献によれば、この方法で得られる酸化スズ粒子の平均粒子径は５〜１００ｎｍになるとされている。 As another method for producing a tin oxide sol, in Patent Document 2, tin is added to 0.1 to 8 N hydrochloric acid so that HCl / Sn (molar ratio) = 0.5 to 1, and this solution is added to this liquid. A method of adding hydrogen peroxide water has been proposed. According to this document, the average particle diameter of tin oxide particles obtained by this method is supposed to be 5 to 100 nm.
しかし、上述の技術によって製造された酸化スズ粒子は、これを膜にしたときの透明性や導電性が十分なものとは言えない。 However, the tin oxide particles produced by the above-described technology cannot be said to have sufficient transparency and conductivity when they are used as a film.
また、二価及び四価のスズを含む化合物に関して特許文献３及び特許文献４に記載の技術が知られている。特許文献３においては、二価及び四価のスズ並びにスズと複合酸化物を形成しうる第２元素を含む複合酸化スズ粉末が提案されている。特許文献４においては、二価及び四価のスズを含む二酸化スズ前駆体粒子が提案されている。特許文献３に記載の複合酸化スズ粉末は、スズ以外の元素を含むものであり、経済性や環境負荷の点から有利とは言えない。また特許文献４に記載の二酸化スズ前駆体粒子は、同文献全体の記載から見て水酸化物であると考えられ、酸化物ではない。更に、この前駆体粒子から製造される二酸化スズは、四価のスズのみを含むと考えられる。 Moreover, the technique of patent document 3 and patent document 4 is known regarding the compound containing bivalent and tetravalent tin. Patent Document 3 proposes a composite tin oxide powder containing divalent and tetravalent tin and a second element capable of forming a composite oxide with tin. Patent Document 4 proposes tin dioxide precursor particles containing divalent and tetravalent tin. The composite tin oxide powder described in Patent Document 3 contains elements other than tin, and is not advantageous from the viewpoints of economy and environmental burden. Further, the tin dioxide precursor particles described in Patent Document 4 are considered to be hydroxides from the description of the entire document, and are not oxides. Furthermore, the tin dioxide produced from this precursor particle is considered to contain only tetravalent tin.
特許文献５には、導電性フィラーとして用いられるスズ系酸化物が提案されている。そのスズ系酸化物は、ＳｎＯ2-xで表され、スズの平均価数は四価以下になっている。しかし、このことはスズが複数の価数を有していることを意味するものではなく、スズの価数としては四価のみの単一のものである。 Patent Document 5 proposes a tin-based oxide used as a conductive filler. The tin-based oxide is represented by SnO 2-x , and the average valence of tin is less than tetravalent. However, this does not mean that tin has a plurality of valences, and the valence of tin is a single valence of only four.
発明の目的は、前述した従来技術が有する種々の欠点を解消し得る酸化スズ粒子及びその製造方法を提供することにある。 An object of the present invention is to provide tin oxide particles and a method for producing the same that can eliminate the various disadvantages of the above-described prior art.
本発明は、２価〜４価の範囲で価数が異なる複数種のスズを含み、ドーパント元素を実質的に含んでおらず、かつ導電性を有することを特徴とする酸化スズ粒子を提供するものである。 The present invention provides a tin oxide particle comprising a plurality of types of tin having different valences in the range of divalent to tetravalent, substantially not including a dopant element, and having conductivity. Is.
また本発明は、前記の酸化スズ粒子の好ましい製造方法として、
２価のスズを含む水溶液とアルカリとを混合し、２価のスズの水酸化物を液中に生成させ、
生成した２価のスズの水酸化物を液中で酸化して、２価のスズの一部を２価超４価以下のスズに酸化することを特徴とする酸化スズゾルの製造方法であって、
２価のスズを含む水溶液とアルカリとを混合した液のｐＨが１〜７となるように、該アルカリを混合する酸化スズゾルの製造方法を提供するものである。
In addition, the present invention provides a preferable method for producing the tin oxide particles as described above.
An aqueous solution containing divalent tin and an alkali are mixed to produce a divalent tin hydroxide in the liquid,
A method for producing a tin oxide sol, wherein the produced divalent tin hydroxide is oxidized in a liquid to oxidize a part of the divalent tin to a divalent to higher than tetravalent tin. ,
The present invention provides a method for producing a tin oxide sol in which an alkali is mixed so that the pH of a solution obtained by mixing an aqueous solution containing divalent tin and an alkali becomes 1 to 7.
本発明によれば、膜にしたときの導電性や透明性が高い酸化スズ粒子が提供される。 According to the present invention, tin oxide particles having high conductivity and transparency when formed into a film are provided.
以下本発明を、その好ましい実施形態に基づき説明する。本発明の酸化スズ粒子は、価数が２価から４価までの範囲で価数が異なる複数種のスズを含んでいる点に特徴の一つを有する。従来知られている導電性酸化スズは、一般に４価のスズに、アンチモン、ニオブ、タンタル等のドーパント元素をドープして導電性を高めていたところ、本発明においてはｎ型半導体である２価の酸化スズに、ドーパント元素として２価超４価以下のスズをドープする構成を採用している。この構成を採用することによって、従来用いられてきたドーパント元素が有する不都合、例えば経済的に不利であることや、環境負荷が大きいこと等を克服しつつ、酸化スズ粒子の導電性を高めることが可能となった。２価のスズのみからなる酸化物は黒色となり、透明性が要求される用途、例えば透明導電膜等に利用することができない。一方、４価のスズのみからなる酸化物は、２価のスズのみからなる酸化物に比べて導電性を高くすることができない。２価超４価以下のスズの具体例には、４価のスズ（ＳｎＯ2）や３価のスズ（Ｓｎ2Ｏ3）等がある。 Hereinafter, the present invention will be described based on preferred embodiments thereof. The tin oxide particles of the present invention are characterized in that they contain a plurality of types of tin having different valences in the range of valences from 2 to 4. Conventionally known conductive tin oxide is generally a tetravalent tin doped with a dopant element such as antimony, niobium, tantalum, etc., to improve conductivity. In the present invention, a divalent which is an n-type semiconductor is used. In this case, the tin oxide is doped with tin that is more than bivalent and less than tetravalent as a dopant element. By adopting this configuration, it is possible to improve the conductivity of tin oxide particles while overcoming the disadvantages of conventionally used dopant elements, such as being economically disadvantageous and having a large environmental load. It has become possible. An oxide composed only of divalent tin is black and cannot be used for applications requiring transparency, such as a transparent conductive film. On the other hand, an oxide made of only tetravalent tin cannot have higher conductivity than an oxide made of only divalent tin. Specific examples of tin that is more than bivalent and less than tetravalent include tetravalent tin (SnO 2 ) and trivalent tin (Sn 2 O 3 ).
２価から４価までの範囲で価数が異なる複数種のスズが酸化スズ粒子中に存在することは、例えば酸化スズ粒子のＸＲＤ測定によって確認することができる。具体的には、酸化スズ粒子は、スズの価数に応じてＸＲＤの回折ピークが異なるので、この回折ピークを測定することで、酸化スズ粒子を構成するスズの価数を知ることができる。また、価数が異なる複数種のスズが存在することは、粉末の色によって確認することもできる。すなわち、酸化スズ（II）粒子の粉末は黒色であり、一方酸化スズ（IV）粒子の粉末は白色ないし透明である。これに対し、２価から４価までの範囲で価数が異なる複数種のスズを含む酸化スズ粒子の粉末は、それぞれの価数のスズの存在割合に応じて、黄色みがかった色に着色されている。したがって、かかる色に着色されている酸化スズには、２価から４価までの範囲で価数が異なる複数種のスズが含まれていると判断する。 The presence of plural types of tin having different valences in the range from divalent to tetravalent in the tin oxide particles can be confirmed, for example, by XRD measurement of the tin oxide particles. Specifically, since tin oxide particles have different XRD diffraction peaks depending on the valence of tin, the valence of tin constituting the tin oxide particles can be known by measuring this diffraction peak. The presence of multiple types of tin with different valences can also be confirmed by the color of the powder. That is, the powder of tin (II) oxide particles is black, while the powder of tin (IV) particles is white or transparent. On the other hand, the powder of tin oxide particles containing a plurality of types of tin having different valences in the range from divalent to tetravalent is colored in a yellowish color according to the proportion of tin of each valence. Has been. Therefore, it is determined that the tin oxide colored in such a color includes a plurality of types of tin having different valences in the range from divalent to tetravalent.
本発明の酸化スズ粒子は、金属としてスズのみを有し、ドーパント元素を実質的に含有しない、いわゆるノンドープのものである。酸化スズ粒子がノンドープのものであることによって、高価であり経済性に劣るか又は環境負荷の大きい元素である各種のドーパント元素を用いることなく、導電性の高い酸化スズ粒子を得ることができる。ドーパント元素としては、酸化スズの導電性を向上させるための元素として当該技術分野において従来用いられてきたものが挙げられる。そのような元素としては、例えばＮｂ、Ｔａ、Ｓｂ、Ｗ、Ｐ、Ｎ、Ｂｉが挙げられる。なお「実質的に含有しない」とは、意図的にドーパント元素を添加することを除外することを意図するものであり、酸化スズ粒子の製造過程において不可避的に微量のドーパント元素が混入することは許容される趣旨である。 The tin oxide particles of the present invention are so-called non-doped particles having only tin as a metal and substantially not containing a dopant element. When the tin oxide particles are non-doped, highly conductive tin oxide particles can be obtained without using various dopant elements which are expensive and inferior in economic efficiency or have a large environmental load. As a dopant element, what has been conventionally used in the said technical field as an element for improving the electroconductivity of tin oxide is mentioned. Examples of such elements include Nb, Ta, Sb, W, P, N, and Bi. In addition, “substantially does not contain” is intended to exclude intentionally adding a dopant element, and a small amount of dopant element is inevitably mixed in the production process of tin oxide particles. This is an acceptable purpose.
本発明の酸化スズ粒子における２価のスズと、２価超４価以下のスズとの割合は、モル比で表して前者：後者＝１：９〜９：１、特に２：８〜５：５であることが好ましい。この比率は、ＸＲＤ測定装置によって測定される。 In the tin oxide particles of the present invention, the ratio of divalent tin and divalent to tetravalent or lower tin is expressed by molar ratio: former: latter = 1: 9 to 9: 1, particularly 2: 8 to 5: 5 is preferable. This ratio is measured by an XRD measuring device.
本発明の酸化スズ粒子は微粒のものであることによっても特徴付けられる。具体的には、透過型電子顕微鏡（ＴＥＭ）で観察された一次粒子の平均粒径が１〜２０ｎｍ、特に２〜１０ｎｍという微粒のものである。 The tin oxide particles of the present invention are also characterized by being fine particles. Specifically, the primary particles observed with a transmission electron microscope (TEM) have an average particle diameter of 1 to 20 nm, particularly 2 to 10 nm.
微粒であることに加えて、本発明の酸化スズ粒子は導電性の高いものである。具体的には、５００ｋｇｆ下での圧粉体積抵抗率が１０7Ω・ｃｍ以下、特に１０5Ω・ｃｍ以下という低抵抗のものである。圧粉体積抵抗率は例えば三菱化学株式会社製ロレスタＰＡＰＤ−４１を用い、四端子法に従い測定される。 In addition to being fine particles, the tin oxide particles of the present invention are highly conductive. Specifically, the powder has a low volume resistivity of 10 7 Ω · cm or less, particularly 10 5 Ω · cm or less under 500 kgf. The powder volume resistivity is measured according to a four-terminal method using, for example, Loresta PAPD-41 manufactured by Mitsubishi Chemical Corporation.
更に本発明の酸化スズ粒子は、これを膜状に成形した場合に、透明性の高いものである。例えば厚さ２〜３μｍで、酸化スズ粒子の含有量が３０〜８０％の膜を製造した場合、この膜の可視光の全光線透過率は８５％以上、特に９０％以上という透明性の高いものとなる。 Furthermore, the tin oxide particles of the present invention are highly transparent when formed into a film. For example, when a film having a thickness of 2 to 3 μm and a tin oxide particle content of 30 to 80% is manufactured, the total light transmittance of the visible light of the film is 85% or more, particularly 90% or more. It will be a thing.
次に本発明の酸化スズ粒子の好ましい製造方法について説明する。本製造方法においては、２価のスズを原料として用い、これを用いて２価のスズの水酸化物を得、該水酸化物を酸化して、２価〜４価の範囲で価数が異なる複数種のスズを含む酸化スズ粒子を得る。以下、具体的な工程について説明する。 Next, the preferable manufacturing method of the tin oxide particle of this invention is demonstrated. In this production method, divalent tin is used as a raw material, and a divalent tin hydroxide is obtained using the divalent tin, and the hydroxide is oxidized to have a valence in the range of divalent to tetravalent. Tin oxide particles containing different types of tin are obtained. Hereinafter, specific steps will be described.
先ず原料として２価のスズを含む水溶液を用意する。この水溶液を調製するために、例えば２価のスズの塩、例えば二塩化スズ（II）を用いることができる。水溶液中における２価のスズのイオンの濃度は０．０１〜０．３５ｍｏｌ／Ｌとすることかできる。二塩化スズ（II）の水への溶解を促進させるために、濃塩酸又は希塩酸を併用してもよい。なお、原料として四価のスズを用いることも考えられるが、２価のスズと４価のスズとでは、２価のスズの方が４価のスズよりも酸化物になりやすいことが本発明者らの検討の結果判明したことから、本製造方法では２価のスズを原料として用いている。 First, an aqueous solution containing divalent tin is prepared as a raw material. In order to prepare this aqueous solution, for example, a divalent tin salt such as tin (II) dichloride can be used. The concentration of divalent tin ions in the aqueous solution can be 0.01 to 0.35 mol / L. In order to promote dissolution of tin (II) dichloride in water, concentrated hydrochloric acid or dilute hydrochloric acid may be used in combination. Although tetravalent tin may be used as a raw material, in the case of divalent tin and tetravalent tin, the present invention shows that divalent tin is more likely to be an oxide than tetravalent tin. Since it became clear as a result of examination of those, in this manufacturing method, bivalent tin is used as a raw material.
このようにして２価のスズを含む水溶液が調製できたら、この水溶液をアルカリ（塩基性物質）の水溶液中に添加する。この操作によって液中に２価のスズの水酸化物が生成する。アルカリとしては、例えば水酸化ナトリウムや水酸化カリウム等のアルカリ金属の水酸化物、水酸化マグネシウム等のアルカリ土類金属の水酸化物、アンモニア等が挙げられる。両者の混合は室温において行うこともでき、又は加熱下に行うこともできる。両者の混合時に加熱を行う場合も行わない場合も、アルカリの水溶液のｐＨは７〜１３、特に１１〜１３であることが好ましい。ｐＨがこの範囲内であれば、十分に反応速度が高いので、微粒子が得られるからである。なお、２価のスズの水溶液中にアルカリを添加することも可能であるが、この操作よりも、上述したようにアルカリの水溶液中に２価のスズの水溶液を添加する方が、微粒子を得る観点から有利である。 When an aqueous solution containing divalent tin can be prepared in this way, this aqueous solution is added to an aqueous solution of an alkali (basic substance). By this operation, a divalent tin hydroxide is generated in the liquid. Examples of the alkali include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide, and ammonia. The mixing of both can be performed at room temperature or under heating. Whether the heating is performed or not when the two are mixed, the pH of the alkaline aqueous solution is preferably 7 to 13, particularly 11 to 13. This is because if the pH is within this range, the reaction rate is sufficiently high, and fine particles can be obtained. Although it is possible to add alkali to the divalent tin aqueous solution, fine particles are obtained by adding the divalent tin aqueous solution to the alkaline aqueous solution as described above rather than this operation. It is advantageous from the viewpoint.
２価のスズの水溶液をアルカリの水溶液中に添加する際、添加のしかたによっては、２価のスズの水酸化物が生成せずに、直接に酸化スズが生成することがあるので注意を要する。直接に酸化スズが生成することを防止するためには、２価のスズの水溶液をアルカリの水溶液中に添加する際に、激しく攪拌を行って２価のスズの濃度が局所的に高くなることを防止するようにすればよい。２価のスズを含む水溶液から直接酸化スズを生成させず、２価のスズの水酸化物の生成を経由して酸化スズを生成させる理由は、後述する易解粒性の凝集体からなる酸化スズ粒子を容易に生成させるためである。易解粒性の酸化スズ粒子を生成させることの利点については後述する When adding a divalent tin aqueous solution to an alkaline aqueous solution, depending on how it is added, care must be taken because divalent tin hydroxide may not be generated and tin oxide may be generated directly. . In order to prevent the formation of tin oxide directly, when adding an aqueous solution of divalent tin to the aqueous solution of alkali, the concentration of divalent tin is locally increased by vigorous stirring. Can be prevented. The reason why tin oxide is not generated directly from an aqueous solution containing divalent tin but through the formation of a divalent tin hydroxide is that oxidation consisting of easily disaggregated aggregates, which will be described later. This is because tin particles are easily generated. The advantages of producing easily disaggregated tin oxide particles will be described later.
２価の水酸化スズの生成よって、反応系内には該水酸化スズからなる易解粒性の凝集体が生成する。この凝集体を構成する水酸化スズの粒径は、最終目的物である酸化スズ粒子の粒径に影響を及ぼす。この凝集体を構成する水酸化スズの粒径は、温度、時間及びｐＨなどの反応条件をコントロールすることによって制御することができる。また、この凝集体自体の平均粒径は、０．１〜１０μｍ程度である。２価のスズの水酸化物の生成時に易解粒性の凝集体が生成するメカニズムは、一次径が微粒であることによる強い凝集性に起因していると、本発明者らは推測している。 Due to the production of divalent tin hydroxide, an easily disaggregated aggregate composed of the tin hydroxide is produced in the reaction system. The particle size of tin hydroxide constituting the aggregate affects the particle size of tin oxide particles that are the final target. The particle size of tin hydroxide constituting the aggregate can be controlled by controlling reaction conditions such as temperature, time and pH. Moreover, the average particle diameter of this aggregate itself is about 0.1-10 micrometers. The present inventors speculate that the mechanism by which the easily disaggregated aggregates are formed during the formation of the divalent tin hydroxide is due to the strong agglomeration due to the fine primary diameter. Yes.
本明細書において「易解粒性」とは、メディアミルを用い、直径０．３ｍｍのジルコニアビーズを５０ｃｃの樹脂容器に充填率６０％となるように仕込み、１時間にわたり解粒操作を行なったときに、解砕前の凝集体の個数が１０％以下まで減少する程度に容易に解粒させやすいことをいう。 In this specification, “easily pulverizing” means that a media mill was used and zirconia beads having a diameter of 0.3 mm were charged in a 50 cc resin container so that the filling rate was 60%, and the pulverization operation was performed for 1 hour. Sometimes it is easy to be pulverized to such an extent that the number of aggregates before pulverization is reduced to 10% or less.
本製造方法において２価のスズの水酸化物を生成させる場合、これを易解粒性の凝集体の形態で生成させる理由は、後工程における酸化スズ粒子の洗浄を容易にするためである。酸化スズ粒子が生成した時点で、この酸化スズ粒子が高分散性の微粒である場合には、効率のよい洗浄を行うことができず、不純物がゾル中に残存してしまう。不純物がゾル中に残存すると、ゾルに着色が生じてしまう。その結果、本製造方法によって得られた酸化スズ粒子を用いて膜を形成した場合、当該膜の透明性を低下させる一因となることがある。 In the case of producing a divalent tin hydroxide in the present production method, the reason for producing it in the form of an easily disaggregated aggregate is to facilitate washing of the tin oxide particles in the subsequent step. When the tin oxide particles are generated, if the tin oxide particles are highly dispersible fine particles, efficient cleaning cannot be performed, and impurities remain in the sol. If the impurities remain in the sol, the sol is colored. As a result, when a film is formed using the tin oxide particles obtained by this production method, it may contribute to a decrease in the transparency of the film.
２価のスズの水酸化物が生成したら、これを液中で酸化する。酸化には各種の酸化剤を用いることができる。具体的には、例えば過酸化水素の液への添加、酸素ガスの液中への吹き込みなどを用いることができる。また、過酸化水素以外の過酸化物、ハロゲン、ペルオキソ酸、酸素酸、高価数の金属塩、オゾン等を酸化剤として用いることもできる。この酸化によって、２価のスズのうちの一部を、２価超４価以下のスズに酸化するとともに、２価〜４価の範囲で価数が異なる複数種のスズを含む酸化スズ粒子が得られる。この酸化スズ粒子は易解粒性酸化スズ粒子の凝集体の形態で液中に生成する。 When a divalent tin hydroxide is formed, it is oxidized in a liquid. Various oxidizing agents can be used for the oxidation. Specifically, for example, addition of hydrogen peroxide to the liquid, blowing of oxygen gas into the liquid, or the like can be used. In addition, peroxides other than hydrogen peroxide, halogens, peroxo acids, oxyacids, expensive metal salts, ozone, and the like can also be used as oxidizing agents. By this oxidation, a part of the divalent tin is oxidized to a divalent to higher than tetravalent tin and tin oxide particles containing a plurality of types of tin having different valences in the divalent to tetravalent range. can get. The tin oxide particles are generated in the liquid in the form of aggregates of easily defatted tin oxide particles.
本製造方法においては、酸化剤の種類やその添加量を適切に制御することによって、酸化スズ中に含まれる各種の価数を有するスズの割合をコントロールすることができる。詳細には、酸化性の強い環境で２価のスズの水酸化物の酸化を行うと、ほとんどすべての２価のスズが４価のスズまで酸化されてしまうところ、酸化の環境を調節することで、２価のスズのうちの一部のみを２価超４価以下のスズに酸化させることが可能になる。 In this production method, the proportion of tin having various valences contained in the tin oxide can be controlled by appropriately controlling the type of oxidant and the amount added. Specifically, when oxidizing divalent tin hydroxide in a highly oxidative environment, almost all divalent tin is oxidized to tetravalent tin. Thus, it becomes possible to oxidize only a part of the divalent tin to tin of more than 2 valences and less than 4 valences.
２価のスズのうちの一部のみを２価超４価以下のスズに酸化させるための条件としては、例えば酸化剤として過酸化水素を用いる場合には、過酸化水素を添加する前の状態において、液中に含まれる２価のスズ１モルに対して、１〜１３モル、特に３〜１２モルの過酸化水素を添加することが好ましい。この場合、過酸化水素は一括添加でもよく、あるいは逐次添加でもよい。スズ（II）の局所的な酸化が生じるのを防止する観点からは、所定の時間にわたって逐次添加することが好ましい。 As conditions for oxidizing only a part of the divalent tin to tin of more than 2 valences and less than 4 valences, for example, when hydrogen peroxide is used as an oxidizing agent, the state before adding hydrogen peroxide In addition, it is preferable to add 1-13 mol, especially 3-12 mol hydrogen peroxide with respect to 1 mol of bivalent tin contained in a liquid. In this case, hydrogen peroxide may be added all at once or sequentially. From the viewpoint of preventing local oxidation of tin (II), it is preferable to sequentially add over a predetermined time.
一方、酸化剤として酸素ガスを用いる場合には、１Ｌの液に対して、酸素ガスを０．０１〜１Ｌ／ｍｉｎ、特に０．０５〜０．１Ｌ／ｍｉｎの割合で吹き込めばよい。 On the other hand, when oxygen gas is used as the oxidizing agent, oxygen gas may be blown at a rate of 0.01 to 1 L / min, particularly 0.05 to 0.1 L / min, with respect to 1 L of liquid.
２価のスズのうちの一部のみを２価超４価以下のスズに酸化させる場合、液中に存在する不純物の濃度も影響を及ぼすことが本発明者らの検討の結果判明した。詳細には、２価のスズの原料として二塩化スズ（II）を用いる場合、これを水に溶解させるために塩酸（例えば濃塩酸）を併用すると、水溶液中には、二塩化スズ（II）の化学量論比よりも過剰の塩化物イオンが存在することになる。この過剰の塩化物イオンが、２価のスズがそれ以上の酸化数のスズへの酸化を妨げることが本発明者らの検討の結果判明した。この観点から、酸化反応前の状態において、液中に存在する２価のスズ１モルに対して、塩化物イオンを０．１〜５モル、特に１．５〜３．５モル存在させることが好ましい。 As a result of the examination by the present inventors, when only a part of divalent tin is oxidized to tin of more than 2 valences and less than 4 valences, the concentration of impurities present in the liquid also affects. Specifically, when tin (II) dichloride is used as a raw material for divalent tin, if hydrochloric acid (for example, concentrated hydrochloric acid) is used in combination with water to dissolve it in water, tin (II) dichloride is contained in the aqueous solution. There will be an excess of chloride ions than the stoichiometric ratio. As a result of the examination by the present inventors, it was found that this excessive chloride ion hinders the oxidation of divalent tin to tin having a higher oxidation number. From this point of view, in the state before the oxidation reaction, 0.1 to 5 mol, particularly 1.5 to 3.5 mol of chloride ion may be present with respect to 1 mol of divalent tin present in the liquid. preferable.
２価のスズのうちの一部のみを２価超４価以下のスズに酸化させる場合、２価のスズの水酸化物を生成させるときのアルカリの濃度も影響を及ぼすことが本発明者らの検討の結果判明した。詳細には、アルカリの濃度が高い場合よりも低い場合の方が、２価超の価数を有するスズが生成しやすくなる。より具体的に説明すると、２価のスズを含む水溶液とアルカリとを混合した液のｐＨが１〜７、好ましくは２〜６となるように、該アルカリを混合すると、２価超の価数を有するスズが生成しやすくなる。 In the case where only a part of divalent tin is oxidized to tin that is more than 2 valences or less than 4 valences, the inventors also have an influence on the alkali concentration when producing a hydroxide of divalent tin. It became clear as a result of examination. Specifically, tin having a valence of more than two is more likely to be produced when the alkali concentration is lower than when the alkali concentration is high. More specifically, when the alkali is mixed such that the pH of the solution obtained by mixing the aqueous solution containing divalent tin and the alkali is 1 to 7, preferably 2 to 6, the valence of more than 2 valences. It becomes easy to produce tin having.
２価のスズを酸化させるときの温度及びそれに先立つ２価のスズの水酸化物を生成させるときの温度は、２価のスズのうちの一部のみを２価超４価以下のスズに酸化させることに影響を及ぼす場合がある。具体的には、両温度を低めに設定すると２価超４価以下のスズが生成しやすく、両温度を高めに設定すると２価超４価以下のスズが生成しづらい。中間の温度に設定することで、２価〜４価の範囲で価数が異なる複数種のスズを適切な割合で生成させることができる。より具体的には、両温度を２〜１００℃、特に４０〜１００℃、とりわけ５０〜９０℃とすることが好ましい。 The temperature at which bivalent tin is oxidized and the temperature at which bivalent tin hydroxide is generated prior to oxidation of the divalent tin is oxidized only to a part of divalent tin that is more than divalent and less than tetravalent. May have an effect. Specifically, when both temperatures are set to be low, tin with a valence of more than 2 and less than 4 is easily generated, and when both temperatures are set to be higher, it is difficult to generate a tin with a valence of more than 2 and less than 4 valences. By setting to an intermediate temperature, it is possible to generate a plurality of types of tin having different valences in an appropriate ratio in the range of divalent to tetravalent. More specifically, it is preferable that both temperatures be 2 to 100 ° C., particularly 40 to 100 ° C., particularly 50 to 90 ° C.
以上の（イ）塩化物イオンの濃度、（ロ）２価のスズの水酸化物を生成させるときのアルカリの濃度、（ハ）２価のスズを酸化させるときの温度及び２価のスズの水酸化物を生成させるときの温度を適切に設定することで、価数の異なる複数種のスズの組成を所望のものとすることができる。 (B) Concentration of chloride ion, (b) Concentration of alkali when producing divalent tin hydroxide, (c) Temperature when oxidizing divalent tin and divalent tin By appropriately setting the temperature at which the hydroxide is generated, it is possible to obtain a desired composition of a plurality of types of tin having different valences.
生成した酸化スズ粒子は、その原料である水酸化スズにおける易解粒性の凝集体の形態を引き継ぎ、易解粒性の凝集体の形態となっている。酸化スズ粒子を易解粒性の凝集体の形態として生成させるための条件としては、水酸化スズ生成後、液の組成を変えずに、酸化することが挙げられる。 The produced tin oxide particles take over the form of easily disaggregated aggregates in the raw material tin hydroxide and are in the form of easily disaggregated aggregates. As conditions for producing the tin oxide particles in the form of easily flocculated aggregates, oxidation is performed without changing the composition of the liquid after the production of tin hydroxide.
酸化スズ粒子が易解粒性の凝集体であることによって、次工程における酸化スズ粒子の洗浄を容易にすることが可能となる。具体的には、易解粒性の凝集体からなる酸化スズ粒子は、例えばリパルプ洗浄を行うことで、不純物の容易な除去が可能である。洗浄は、分散媒である水の導電率が５００μＳ以下、特に１００μＳ以下になるまで行うことが、不純物の十分な除去の点から好ましい。特に液中の塩化物イオンの濃度が０．５〜１．０重量％になるまで洗浄を行うことが好ましい。 When the tin oxide particles are easily flocculated aggregates, it is possible to facilitate the cleaning of the tin oxide particles in the next step. Specifically, the tin oxide particles made of easily flocculated aggregates can be easily removed by, for example, repulp washing. Washing is preferably performed until the conductivity of water as a dispersion medium is 500 μS or less, particularly 100 μS or less, from the viewpoint of sufficient removal of impurities. In particular, washing is preferably performed until the concentration of chloride ions in the solution is 0.5 to 1.0% by weight.
リパルプ洗浄によって所定の導電率まで洗浄された易解粒性酸化スズ粒子の分散液は、解粒操作に付される。それによって、酸化スズゾルが得られる。解粒操作には、例えばビーズミル等のメディアミルを用いることができる。この場合、各種のｐＨ調整剤を液に添加して解粒操作を行うことで、酸化スズ粒子を単分散状態に近づけやすくなる。ｐＨ調整剤としては、液のｐＨを２〜１２に調整できるものを用いることが好ましい。そのようなｐＨ調整剤としては、例えばトリエタノールアミン等のアミン類や、水酸化テトラメチルアンモニウム等の四級アンモニウム化合物が挙げられる。 The dispersion liquid of easily disaggregated tin oxide particles washed to a predetermined conductivity by repulp washing is subjected to a granulation operation. Thereby, a tin oxide sol is obtained. For the granulation operation, for example, a media mill such as a bead mill can be used. In this case, tin oxide particles can be easily brought close to a monodispersed state by adding various pH adjusters to the liquid and performing a granulation operation. As the pH adjuster, it is preferable to use one that can adjust the pH of the liquid to 2 to 12. Examples of such pH adjusters include amines such as triethanolamine and quaternary ammonium compounds such as tetramethylammonium hydroxide.
以上の操作によって、水を分散媒とする酸化スズゾルが得られる。この酸化スズゾルにおける酸化スズ粒子の濃度は０．１〜３０重量％、特に１０〜２０重量％とすることが好ましい。この酸化スズゾルにおいては、酸化スズ粒子が高度に分散しており、長時間保存しても沈殿の生成等は認められない。 By the above operation, a tin oxide sol using water as a dispersion medium is obtained. The concentration of the tin oxide particles in the tin oxide sol is preferably 0.1 to 30% by weight, particularly 10 to 20% by weight. In this tin oxide sol, tin oxide particles are highly dispersed, and no precipitates are formed even when stored for a long time.
以上の方法によれば、液中（水中）でスズの酸化物を生成させるので、焼成によって得られた酸化スズを粉砕した後にゾル化する従来の方法に比べて、凝集が少なく分散性の高い酸化スズゾルを容易に得ることができる。 According to the above method, since the oxide of tin is generated in the liquid (in water), there is less aggregation and high dispersibility compared to the conventional method in which the tin oxide obtained by firing is pulverized and then solated. A tin oxide sol can be easily obtained.
このようにして得られた酸化スズ粒子は、例えばその高い導電性を利用して、プリンタや複写機関連の帯電ローラー、感光ドラム、トナー、静電ブラシ等の分野、フラットパネルディスプレイ、ＣＲＴ、ブラウン管等の分野、塗料、インク、エマルジョンの分野等など、幅広い用途に適用できる。 The tin oxide particles obtained in this way can be used, for example, in the fields of printers and copier-related charging rollers, photosensitive drums, toners, electrostatic brushes, flat panel displays, CRTs, Can be applied to a wide range of applications such as paints, inks, and emulsions.
以下、実施例により本発明を更に詳細に説明する。しかしながら本発明の範囲は、かかる実施例に制限されない。特に断らない限り、「％」は「重量％」を意味する。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to such examples. Unless otherwise specified, “%” means “% by weight”.
〔実施例１〕
８０ｇの二塩化スズ（II）・五水和物を２０００ｍｌの純水に溶解させ、スズ（II）を含む水溶液を得た。溶解させる際、１２０ｍｌの濃塩酸を用いた。この水溶液とは別に、１％水酸化ナトリウム水溶液２０００ｍｌを用意した。水酸化ナトリウム水溶液中に、２価のスズを含む水溶液を３３ｍｌ／ｍｉｎの添加速度で逐次添加し、ｐＨを３．０とした。このときの混合液の温度は２５℃であった。この添加によって、液中に２価のスズの水酸化物からなる黄色の沈殿が生じた。この沈殿は、易解粒性の凝集体から構成されていた。
[Example 1]
80 g of tin (II) dichloride pentahydrate was dissolved in 2000 ml of pure water to obtain an aqueous solution containing tin (II). When dissolved, 120 ml of concentrated hydrochloric acid was used. Apart from this aqueous solution, 2000 ml of 1% aqueous sodium hydroxide solution was prepared. An aqueous solution containing divalent tin was sequentially added to an aqueous sodium hydroxide solution at an addition rate of 33 ml / min to adjust the pH to 3.0. The temperature of the liquid mixture at this time was 25 degreeC. This addition produced a yellow precipitate consisting of divalent tin hydroxide in the liquid. This precipitate was composed of easily disaggregated aggregates.
次に、液中に２００ｍｌの過酸化水素水（３０％）を、２０ｍｌ／ｍｉｎの添加速度で逐次添加し、２価のスズの水酸化物の酸化を行った。過酸化水素の全添加量は２００ｍｌであった。酸化は２５℃で行った。過酸化水素の添加によって、液中に存在する２価のスズの一部を４価のスズに酸化させるとともに、易解粒性の凝集体からなる酸化スズ粒子を液中に生成させた。凝集体の大きさをマイクロトラックＵＰＡ（商品名）で測定したところ、平均して１０ｎｍ程度であった。マイクロトラックＵＰＡによる測定の手順は以下の次のとおりである。すなわち、分散液を原液のままセル内に入れ、レーザーを照射して粒径を測定する。 Next, 200 ml of hydrogen peroxide (30%) was sequentially added to the solution at an addition rate of 20 ml / min to oxidize divalent tin hydroxide. The total amount of hydrogen peroxide added was 200 ml. The oxidation was performed at 25 ° C. By adding hydrogen peroxide, a part of the divalent tin present in the liquid was oxidized to tetravalent tin, and tin oxide particles composed of easily disaggregated aggregates were generated in the liquid. When the size of the aggregate was measured by Microtrac UPA (trade name), it was about 10 nm on average. The measurement procedure using Microtrack UPA is as follows. That is, the dispersion is put into the cell as a stock solution, and laser is irradiated to measure the particle size.
次に、６０℃の温水を用いて液のリパルプ洗浄を行った。洗浄は、液の導電率が１００μＳになるまで行った。この時点での液中の塩化物イオンの濃度は、イオンクロマト法を用いた測定の結果０．４％であった。洗浄完了後、易解粒性酸化スズ粒子の解粒を行った。解粒には、０．１ｍｍφのジルコニアビーズを用いたペイントシェーカを使用した。解粒においては、ｐＨ調整剤として水酸化テトラメチルアンモニウムを液に添加し、液のｐＨを１１に調整した。解粒は１時間行った。最後に液を０．２μｍのメンブランフィルターに通し粗粒を除去して、目的とする酸化スズ粒子のゾルを得た。このゾルにおける酸化スズ粒子の濃度は２０％であった。ＴＥＭによって測定された酸化スズ粒子の平均粒径は５ｎｍであった。また、この酸化スズ粒子のゾル及び粉末は薄黄色を呈していた。この粉末についてＸＲＤ測定を行ったところ、２価のスズの酸化物と４価のスズの酸化物のパターンが混在していた。ＸＲＤの測定結果を図１に示す。図１に示すＸＲＤ測定図においては、ブロードなピークが４価の酸化スズのピークであり、シャープなピークが２価の酸化スズのピークである。この結果から、この酸化スズは２価のスズ及び４価のスズを含むものであることが確認された。２価のスズと４価のスズの比率は、２価の酸化スズのピーク面積及び４価の酸化スズのピーク面積から算出した。その結果、２価のスズ：４価のスズ＝５：５であった。また、この酸化スズ粒子はドーパント元素を実質的に含んでいなかった。この酸化スズ粒子のＴＥＭ像を図２に示す。同図から明らかなように、得られた酸化スズ粒子はその直径は数ｎｍの微粒のものである。 Next, the repulp washing | cleaning of the liquid was performed using 60 degreeC warm water. Washing was performed until the conductivity of the liquid reached 100 μS. The concentration of chloride ions in the liquid at this time was 0.4% as a result of measurement using ion chromatography. After the cleaning was completed, the easy-definable tin oxide particles were pulverized. For the pulverization, a paint shaker using 0.1 mmφ zirconia beads was used. In pulverization, tetramethylammonium hydroxide was added to the liquid as a pH adjuster, and the pH of the liquid was adjusted to 11. The pulverization was performed for 1 hour. Finally, the liquid was passed through a 0.2 μm membrane filter to remove coarse particles to obtain a target sol of tin oxide particles. The concentration of tin oxide particles in this sol was 20%. The average particle diameter of the tin oxide particles measured by TEM was 5 nm. Further, the sol and powder of the tin oxide particles had a light yellow color. When XRD measurement was performed on this powder, a divalent tin oxide pattern and a tetravalent tin oxide pattern were mixed. The measurement result of XRD is shown in FIG. In the XRD measurement diagram shown in FIG. 1, a broad peak is a tetravalent tin oxide peak, and a sharp peak is a divalent tin oxide peak. From this result, it was confirmed that this tin oxide contains divalent tin and tetravalent tin. The ratio of divalent tin to tetravalent tin was calculated from the peak area of divalent tin oxide and the peak area of tetravalent tin oxide. As a result, divalent tin: tetravalent tin = 5: 5. The tin oxide particles did not substantially contain a dopant element. A TEM image of the tin oxide particles is shown in FIG. As can be seen from the figure, the obtained tin oxide particles have a diameter of several nanometers.
この酸化スズ粒子の圧粉体積抵抗率（５００ｋｇｆ下）を、三菱化学株式会社製ロレスタＰＡＰＤ−４１を用い、四端子法に従い測定したところ、２．１×１０5Ω・ｃｍであった。また、この酸化スズ粒子を市販のアクリル樹脂とともにトルエン−ブタノール混合溶液に添加し、ペイントシェーカを用いてビーズ分散して分散液を調製した。この分散液をＰＥＴフィルムに塗布し、１時間風乾して透明薄膜を形成した。この薄膜について、可視光の全光線透過率を測定したところ９０％であった。 The dust volume resistivity (under 500 kgf) of the tin oxide particles was measured according to a four-terminal method using Loresta PAPD-41 manufactured by Mitsubishi Chemical Corporation, and found to be 2.1 × 10 5 Ω · cm. The tin oxide particles were added to a toluene-butanol mixed solution together with a commercially available acrylic resin, and the beads were dispersed using a paint shaker to prepare a dispersion. This dispersion was applied to a PET film and air-dried for 1 hour to form a transparent thin film. With respect to this thin film, the total light transmittance of visible light was measured and found to be 90%.
〔実施例２〕
２価のスズを含む水溶液を添加する際のｐＨを２．０とした以外は、実施例１と同様に反応を行い、２価のスズの水酸化物の沈殿を得た。この水酸化物は黄色の沈殿であった。この沈殿は、易解粒性の凝集体から構成されていた。次に、実施例１と同様の条件で液中に過酸化水素水（３０％）を添加し、２価のスズの水酸化物の酸化を行った。過酸化水素の添加によって、液中に存在する２価のスズの一部を４価のスズに酸化させるとともに、易解粒性の凝集体からなる酸化スズ粒子を液中に生成させた。凝集体の大きさをマイクロトラックＵＰＡ（商品名）で測定したところ、平均して１０ｎｍ程度であった。
[Example 2]
The reaction was carried out in the same manner as in Example 1 except that the pH at the time of adding the aqueous solution containing divalent tin was 2.0, to obtain a precipitate of divalent tin hydroxide. This hydroxide was a yellow precipitate. This precipitate was composed of easily disaggregated aggregates. Next, hydrogen peroxide (30%) was added to the solution under the same conditions as in Example 1 to oxidize divalent tin hydroxide. By adding hydrogen peroxide, a part of the divalent tin present in the liquid was oxidized to tetravalent tin, and tin oxide particles composed of easily disaggregated aggregates were generated in the liquid. When the size of the aggregate was measured by Microtrac UPA (trade name), it was about 10 nm on average.
次に、実施例１と同様の条件でリパルプ洗浄及び易解粒性酸化スズ粒子の解粒を行った。洗浄後の易解粒性酸化スズ粒子の大きさをマイクロトラックＵＰＡ（商品名）で測定したところ、平均して１０ｎｍ程度であった。また、解粒後の酸化スズ粒子をＴＥＭで測定したところ、平均粒径は５ｎｍであった。この酸化スズ粒子のゾル及び粉末は黄色を呈していた。この粉末についてＸＲＤ測定を行ったところ、２価のスズの酸化物と４価のスズの酸化物のパターンが混在していた。この結果から、この酸化スズは２価のスズ及び４価のスズを含むものであることが確認された。２価のスズと４価のスズの比率は、２価のスズ：４価のスズ＝４：６であった。また、この酸化スズ粒子はドーパント元素を実質的に含んでいなかった。この酸化スズについて、実施例１と同様に圧粉体積抵抗率及び全光線透過率を測定した。結果を以下の表１に示す。 Next, repulp washing and easy pulverizing tin oxide particles were pulverized under the same conditions as in Example 1. When the size of the easily disaggregated tin oxide particles after washing was measured with Microtrac UPA (trade name), it was about 10 nm on average. Moreover, when the tin oxide particle | grains after pulverization were measured by TEM, the average particle diameter was 5 nm. The sol and powder of the tin oxide particles had a yellow color. When XRD measurement was performed on this powder, a divalent tin oxide pattern and a tetravalent tin oxide pattern were mixed. From this result, it was confirmed that this tin oxide contains divalent tin and tetravalent tin. The ratio of divalent tin to tetravalent tin was divalent tin: tetravalent tin = 4: 6. The tin oxide particles did not substantially contain a dopant element. About this tin oxide, the dust volume resistivity and the total light transmittance were measured in the same manner as in Example 1. The results are shown in Table 1 below.
〔実施例３〕
２価のスズを含む水溶液を添加する際のｐＨを６．０とし、かつ２価のスズの水酸化物を生成させるときの温度を５０℃とした以外は、実施例１と同様に反応を行い、２価のスズの水酸化物を得た。この水酸化物は白色の沈殿であった。この沈殿は、易解粒性の凝集体から構成されていた。次に、温度を５０℃とした以外は実施例１と同様の条件で液中に過酸化水素水（３０％）を添加し、２価のスズの水酸化物の酸化を行った。過酸化水素の添加によって、液中に存在する２価のスズの一部を４価のスズに酸化させるとともに、易解粒性の凝集体からなる酸化スズ粒子を液中に生成させた。凝集体の大きさをマイクロトラックＵＰＡ（商品名）で測定したところ、平均して１０ｎｍ程度であった。
Example 3
The reaction was carried out in the same manner as in Example 1 except that the pH at the time of adding the aqueous solution containing divalent tin was 6.0 and the temperature at which divalent tin hydroxide was formed was 50 ° C. Then, a divalent tin hydroxide was obtained. This hydroxide was a white precipitate. This precipitate was composed of easily disaggregated aggregates. Next, hydrogen peroxide (30%) was added to the solution under the same conditions as in Example 1 except that the temperature was 50 ° C., and bivalent tin hydroxide was oxidized. By adding hydrogen peroxide, a part of the divalent tin present in the liquid was oxidized to tetravalent tin, and tin oxide particles composed of easily disaggregated aggregates were generated in the liquid. When the size of the aggregate was measured by Microtrac UPA (trade name), it was about 10 nm on average.
次に、実施例１と同様の条件でリパルプ洗浄及び易解粒性酸化スズ粒子の解粒を行った。洗浄後の易解粒性酸化スズ粒子の大きさをマイクロトラックＵＰＡ（商品名）で測定したところ、平均して１０ｎｍ程度であった。また、解粒後の酸化スズ粒子をＴＥＭで測定したところ、平均粒径は５ｎｍであった。この酸化スズ粒子のゾル及び粉末は白色を呈していた。この粉末についてＸＲＤ測定を行ったところ、２価のスズの酸化物と４価のスズの酸化物のパターンが混在していた。この結果から、この酸化スズは２価のスズ及び４価のスズを含むものであることが確認された。２価のスズと４価のスズの比率は、２価のスズ：４価のスズ＝２：８であった。また、この酸化スズ粒子はドーパント元素を実質的に含んでいなかった。この酸化スズについて、実施例１と同様に圧粉体積抵抗率及び全光線透過率を測定した。結果を以下の表１に示す。 Next, repulp washing and easy pulverizing tin oxide particles were pulverized under the same conditions as in Example 1. When the size of the easily disaggregated tin oxide particles after washing was measured with Microtrac UPA (trade name), it was about 10 nm on average. Moreover, when the tin oxide particle | grains after pulverization were measured by TEM, the average particle diameter was 5 nm. The sol and powder of the tin oxide particles had a white color. When XRD measurement was performed on this powder, a divalent tin oxide pattern and a tetravalent tin oxide pattern were mixed. From this result, it was confirmed that this tin oxide contains divalent tin and tetravalent tin. The ratio of divalent tin to tetravalent tin was divalent tin: tetravalent tin = 2: 8. The tin oxide particles did not substantially contain a dopant element. About this tin oxide, the dust volume resistivity and the total light transmittance were measured in the same manner as in Example 1. The results are shown in Table 1 below.
〔実施例４〕
実施例１で用いた１％水酸化ナトリウム水溶液に代えて１％アンモニア水溶液を用い、２価のスズを含む水溶液を添加する際のｐＨを６．０とし、かつ２価のスズの水酸化物を生成させるときの温度を５０℃とした以外は、実施例１と同様に反応を行い、２価のスズの水酸化物を得た。この水酸化物は黄色の沈殿であった。この沈殿は、易解粒性の凝集体から構成されていた。次に、温度を５０℃とした以外は実施例１と同様の条件で液中に過酸化水素水（３０％）を添加し、２価のスズの水酸化物の酸化を行った。過酸化水素の添加によって、液中に存在する２価のスズの一部を４価のスズに酸化させるとともに、易解粒性の凝集体からなる酸化スズ粒子を液中に生成させた。凝集体の大きさをマイクロトラックＵＰＡ（商品名）で測定したところ、平均して１０ｎｍ程度であった。
Example 4
A 1% aqueous ammonia solution was used in place of the 1% aqueous sodium hydroxide solution used in Example 1, the pH when adding an aqueous solution containing divalent tin was 6.0, and a divalent tin hydroxide was added. The reaction was carried out in the same manner as in Example 1 except that the temperature when generating was changed to 50 ° C. to obtain a divalent tin hydroxide. This hydroxide was a yellow precipitate. This precipitate was composed of easily disaggregated aggregates. Next, hydrogen peroxide (30%) was added to the solution under the same conditions as in Example 1 except that the temperature was 50 ° C., and bivalent tin hydroxide was oxidized. By adding hydrogen peroxide, a part of the divalent tin present in the liquid was oxidized to tetravalent tin, and tin oxide particles composed of easily disaggregated aggregates were generated in the liquid. When the size of the aggregate was measured by Microtrac UPA (trade name), it was about 10 nm on average.
次に、実施例１と同様の条件でリパルプ洗浄及び易解粒性酸化スズ粒子の解粒を行った。洗浄後の易解粒性酸化スズ粒子の大きさをマイクロトラックＵＰＡ（商品名）で測定したところ、平均して１０ｎｍ程度であった。また、解粒後の酸化スズ粒子をＴＥＭで測定したところ、平均粒径は５ｎｍであった。この酸化スズ粒子のゾル及び粉末は黄色を呈していた。この粉末についてＸＲＤ測定を行ったところ、２価のスズの酸化物と４価のスズの酸化物のパターンが混在していた。この結果から、この酸化スズは２価のスズ及び４価のスズを含むものであることが確認された。２価のスズと４価のスズの比率は、２価のスズ：４価のスズ＝４：６であった。また、この酸化スズ粒子はドーパント元素を実質的に含んでいなかった。この酸化スズについて、実施例１と同様に圧粉体積抵抗率及び全光線透過率を測定した。結果を以下の表１に示す。 Next, repulp washing and easy pulverizing tin oxide particles were pulverized under the same conditions as in Example 1. When the size of the easily disaggregated tin oxide particles after washing was measured with Microtrac UPA (trade name), it was about 10 nm on average. Moreover, when the tin oxide particle | grains after pulverization were measured by TEM, the average particle diameter was 5 nm. The sol and powder of the tin oxide particles had a yellow color. When XRD measurement was performed on this powder, a divalent tin oxide pattern and a tetravalent tin oxide pattern were mixed. From this result, it was confirmed that this tin oxide contains divalent tin and tetravalent tin. The ratio of divalent tin to tetravalent tin was divalent tin: tetravalent tin = 4: 6. The tin oxide particles did not substantially contain a dopant element. About this tin oxide, the dust volume resistivity and the total light transmittance were measured in the same manner as in Example 1. The results are shown in Table 1 below.
〔比較例１〕
２価のスズを含む水溶液を添加する際のｐＨを８．０とし、かつ２価のスズの水酸化物を生成させるときの温度を９０℃とした以外は、実施例１と同様に反応を行い、２価のスズの水酸化物を得た。この水酸化物は黒色の沈殿であった。次に、温度を９０℃とした以外は実施例１と同様の条件で液中に過酸化水素水（３０％）を添加し、２価のスズの水酸化物の酸化を行い酸化スズ（II）粒子を液中に生成させた。
[Comparative Example 1]
The reaction was performed in the same manner as in Example 1 except that the pH when adding the aqueous solution containing divalent tin was 8.0, and the temperature when generating the divalent tin hydroxide was 90 ° C. Then, a divalent tin hydroxide was obtained. This hydroxide was a black precipitate. Next, hydrogen peroxide (30%) was added to the solution under the same conditions as in Example 1 except that the temperature was 90 ° C., and the divalent tin hydroxide was oxidized to produce tin oxide (II ) Particles were generated in the liquid.
次に、実施例１と同様の条件でリパルプ洗浄を行った。この酸化スズ粒子のゾル及び粉末は黒色を呈していた。この粉末についてＸＲＤ測定を行ったところ、スズ（II）の酸化物のパターンであることが確認された。また、この酸化スズ粒子はドーパント元素を実質的に含んでいなかった。この酸化スズについて、実施例１と同様に圧粉体積抵抗率及び全光線透過率を測定した。結果を以下の表１に示す。 Next, repulp washing was performed under the same conditions as in Example 1. The sol and powder of the tin oxide particles were black. When XRD measurement was performed on this powder, it was confirmed that it was a tin (II) oxide pattern. The tin oxide particles did not substantially contain a dopant element. About this tin oxide, the dust volume resistivity and the total light transmittance were measured in the same manner as in Example 1. The results are shown in Table 1 below.
〔比較例２〕
２価のスズを含む水溶液を添加する際のｐＨを７．０とした以外は、実施例１と同様に反応を行い、２価のスズの水酸化物を得た。この水酸化物は白色の沈殿であった。次に、実施例１と同様の条件で液中に過酸化水素水（３０％）を２０ｍｌ／ｍｉｎの添加速度で逐次添加し、２価のスズの水酸化物の酸化を行った。過酸化水素の全添加量は４００ｍｌであった。過酸化水素の過剰添加によって、液中に存在する２価のスズのすべてを４価のスズに酸化させ、酸化スズ粒子を液中に生成させた。
[Comparative Example 2]
The reaction was carried out in the same manner as in Example 1 except that the pH at the time of adding the aqueous solution containing divalent tin was 7.0, to obtain a divalent tin hydroxide. This hydroxide was a white precipitate. Next, hydrogen peroxide (30%) was sequentially added to the solution at the rate of 20 ml / min under the same conditions as in Example 1 to oxidize divalent tin hydroxide. The total amount of hydrogen peroxide added was 400 ml. By the excessive addition of hydrogen peroxide, all of the divalent tin present in the liquid was oxidized to tetravalent tin, and tin oxide particles were generated in the liquid.
次に、実施例１と同様の条件でリパルプ洗浄を行った。この酸化スズ粒子のゾル及び粉末は黒色を呈していた。この粉末についてＸＲＤ測定を行ったところ、スズ（IV）の酸化物のパターンであることが確認された。この酸化スズについて、実施例１と同様に圧粉体積抵抗率及び全光線透過率を測定した。結果を以下の表１に示す。 Next, repulp washing was performed under the same conditions as in Example 1. The sol and powder of the tin oxide particles were black. When XRD measurement was performed on this powder, it was confirmed that it was a tin (IV) oxide pattern. About this tin oxide, the dust volume resistivity and the total light transmittance were measured in the same manner as in Example 1. The results are shown in Table 1 below.
表１に示す結果から明らかなとおり、各実施例で得られた酸化スズは、高透明性を有し、かつ低抵抗のものであることが判る。これに対し、比較例１で得られた酸化スズは、抵抗は低いものの透明性に劣ることが判る。比較例２で得られた酸化スズは、逆に透明性は良好なものの高抵抗であることが判る。 As is clear from the results shown in Table 1, it can be seen that the tin oxide obtained in each example has high transparency and low resistance. In contrast, the tin oxide obtained in Comparative Example 1 has low resistance but poor transparency. On the contrary, it can be seen that the tin oxide obtained in Comparative Example 2 has high resistance but good transparency.
Claims (3)
生成した２価のスズの水酸化物を液中で酸化して、２価のスズの一部を２価超４価以下のスズに酸化することを特徴とする酸化スズゾルの製造方法であって、
２価のスズを含む水溶液とアルカリとを混合した液のｐＨが１〜７となるように、該アルカリを混合する酸化スズゾルの製造方法。 An aqueous solution containing divalent tin and an alkali are mixed to produce a divalent tin hydroxide in the liquid,
A method for producing a tin oxide sol, wherein the produced divalent tin hydroxide is oxidized in a liquid to oxidize a part of the divalent tin to a divalent to higher than tetravalent tin. ,
The manufacturing method of the tin oxide sol which mixes this alkali so that the pH of the liquid which mixed the aqueous solution containing divalent tin and the alkali may become 1-7.
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| KR1020100069415A KR20110011548A (en) | 2009-07-27 | 2010-07-19 | Method of manufacturing tin oxide particles and tin oxide sol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012098948A1 (en) * | 2011-01-19 | 2012-07-26 | 三井金属鉱業株式会社 | Tin oxide particles and method for producing same |
| JP2014018849A (en) * | 2012-07-23 | 2014-02-03 | Fuji Kihan:Kk | Method for strengthening welding tip, and welding tip |
| WO2016133017A1 (en) * | 2015-02-16 | 2016-08-25 | 三菱マテリアル株式会社 | Stannous oxide powder and method for producing stannous oxide powder |
| JP2017003806A (en) * | 2015-06-11 | 2017-01-05 | 株式会社リコー | Electrochromic display element, display device, information equipment, manufacturing method of electrochromic display element, electrochromic lighting control lens |
| JP2018027874A (en) * | 2016-08-19 | 2018-02-22 | ヒロセホールディングス株式会社 | Method for manufacturing metal oxide nanoparticle |
| CN110171842A (en) * | 2019-04-17 | 2019-08-27 | 华中科技大学 | A kind of preparation method and application of mixed valence tin-based oxide semiconductor material |
| US10392262B2 (en) | 2015-02-16 | 2019-08-27 | Mitsubishi Materials Corporation | Stannous oxide powder and method for producing stannous oxide powder |
| DE112021002332T5 (en) | 2020-06-09 | 2023-01-26 | Mitsui Mining & Smelting Co., Ltd. | COMPOSITION FOR FORMING A PRIMER COAT, A PRIMER COAT, AN EMISSION CONTROL CATALYST AND AN EMISSION CONTROL DEVICE INCLUDING PRIMER COAT |
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| CN103787405A (en) * | 2014-02-27 | 2014-05-14 | 东华大学 | Preparation method of rutile-phase tin dioxide sol |
| KR20190142797A (en) * | 2018-06-18 | 2019-12-30 | 삼성디스플레이 주식회사 | Display device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012098948A1 (en) * | 2011-01-19 | 2012-07-26 | 三井金属鉱業株式会社 | Tin oxide particles and method for producing same |
| US8916070B2 (en) | 2011-01-19 | 2014-12-23 | Mitsui Mining & Smelting Co., Ltd. | Tin oxide particles and method for producing same |
| JP2014018849A (en) * | 2012-07-23 | 2014-02-03 | Fuji Kihan:Kk | Method for strengthening welding tip, and welding tip |
| WO2016133017A1 (en) * | 2015-02-16 | 2016-08-25 | 三菱マテリアル株式会社 | Stannous oxide powder and method for producing stannous oxide powder |
| US10392262B2 (en) | 2015-02-16 | 2019-08-27 | Mitsubishi Materials Corporation | Stannous oxide powder and method for producing stannous oxide powder |
| JP2017003806A (en) * | 2015-06-11 | 2017-01-05 | 株式会社リコー | Electrochromic display element, display device, information equipment, manufacturing method of electrochromic display element, electrochromic lighting control lens |
| JP2018027874A (en) * | 2016-08-19 | 2018-02-22 | ヒロセホールディングス株式会社 | Method for manufacturing metal oxide nanoparticle |
| CN110171842A (en) * | 2019-04-17 | 2019-08-27 | 华中科技大学 | A kind of preparation method and application of mixed valence tin-based oxide semiconductor material |
| DE112021002332T5 (en) | 2020-06-09 | 2023-01-26 | Mitsui Mining & Smelting Co., Ltd. | COMPOSITION FOR FORMING A PRIMER COAT, A PRIMER COAT, AN EMISSION CONTROL CATALYST AND AN EMISSION CONTROL DEVICE INCLUDING PRIMER COAT |
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