JP5486751B2 - Rod-shaped indium tin oxide powder and method for producing the same - Google Patents
Rod-shaped indium tin oxide powder and method for producing the same Download PDFInfo
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- JP5486751B2 JP5486751B2 JP2009217573A JP2009217573A JP5486751B2 JP 5486751 B2 JP5486751 B2 JP 5486751B2 JP 2009217573 A JP2009217573 A JP 2009217573A JP 2009217573 A JP2009217573 A JP 2009217573A JP 5486751 B2 JP5486751 B2 JP 5486751B2
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- 239000000843 powder Substances 0.000 title claims description 86
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 239000007788 liquid Substances 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 24
- 239000002244 precipitate Substances 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 2
- 239000002245 particle Substances 0.000 description 13
- 239000010419 fine particle Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000012798 spherical particle Substances 0.000 description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 5
- 229910001887 tin oxide Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910003437 indium oxide Inorganic materials 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002472 indium compounds Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021617 Indium monochloride Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 1
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
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- Conductive Materials (AREA)
Description
本発明は、棒状微粒子からなる酸化錫インジウム粉末とその製造方法に関し、より詳しくは、熱線遮蔽材として用いたときに、優れた熱線遮蔽性を有する棒状酸化錫インジウム粉末とその製造方法に関する。 The present invention relates to an indium tin oxide powder comprising rod-shaped fine particles and a method for producing the same, and more particularly to a rod-shaped indium tin oxide powder having excellent heat ray shielding properties when used as a heat ray shielding material and a method for producing the same.
酸化錫インジウム（ＩＴＯと云う）は導電性材料として知られている。一般に球状粒子よりも針状粒子は相互に接触密度が高いので導電性を高めるうえで有利であり、酸化錫インジウム粉末についても針状微粒子とその製造方法が知られている。 Indium tin oxide (referred to as ITO) is known as a conductive material. In general, acicular particles have a higher contact density than spherical particles, which is advantageous in enhancing conductivity, and acicular fine particles and methods for producing the same are also known for indium tin oxide powders.
たとえば、特開平６−２９３５１５号公報（特許文献１）には、硝酸インジウムの高温スラリーに錫化合物を添加して錫含有針状インジウム化合物を生成させ、これを加熱分解して針状のインジウム−錫酸化物粉末を得る方法が記載されている。 For example, in JP-A-6-293515 (Patent Document 1), a tin compound is added to a high-temperature slurry of indium nitrate to produce a tin-containing acicular indium compound, which is thermally decomposed to produce acicular indium- A method for obtaining tin oxide powder is described.
さらに、特開平６−２９３５１６号公報（特許文献２）には、酸化インジウムの針状粉末を製造した後に、これに酸化錫をドープして針状の酸化錫インジウム粉末を製造する方法が記載されている。 Furthermore, Japanese Patent Application Laid-Open No. 6-293516 (Patent Document 2) describes a method of producing an acicular indium tin oxide powder by producing an indium oxide acicular powder and then doping it with tin oxide. ing.
しかし、特許文献１に記載されている方法は、酸化錫の添加量を制御するのが難しく、大量生産に向いていない。また、特許文献２の方法は、先に製造した酸化インジウムに酸化錫を固溶させるために１０００℃前後に高温加熱する必要があり、このため一次粒子が焼結して比表面積(BET)約１〜３ｍ2/ｇの粗粒になり、これを樹脂に混合して導電膜を形成したときに透明性が低下し、さらに粉末粒子が黄緑色に着色していると云う問題がある。 However, the method described in Patent Document 1 is difficult to control the amount of tin oxide added and is not suitable for mass production. In addition, the method of Patent Document 2 requires high-temperature heating to around 1000 ° C. in order to solidify tin oxide in the previously produced indium oxide. For this reason, primary particles are sintered to have a specific surface area (BET) of about becomes coarse of 1 to 3 m 2 / g, which reduces the transparency at the time of forming the conductive film by mixing the resin, further powder particles have a problem that to be colored yellowish green.
そこで、硝酸インジウム溶液を加熱濃縮してスラリーとし、これを濾過洗浄して針状インジウム化合物粉末を回収し、これを仮焼して酸化インジウム針状粉末にし、これに四塩化錫を含浸させ、メタノールを含む窒素ガス雰囲気下で還元処理を行うことによって、比表面積４〜２０ｍ2/ｇ、Ｌａｂ表色系においてＬ＝８２〜９１、ａ＝−８〜２、ｂ＝０〜１０の酸化錫インジウム針状粉末を製造する方法が提案されている（特開２００５−３２２６２６号公報：特許文献３、特開２００５−３２０５２５号公報：特許文献４）。 Therefore, the indium nitrate solution is heated and concentrated to form a slurry, which is filtered and washed to collect acicular indium compound powder, which is calcined to form indium oxide acicular powder, impregnated with tin tetrachloride, Tin oxide having a specific surface area of 4 to 20 m 2 / g and L = 82 to 91, a = −8 to 2, and b = 0 to 10 by performing a reduction treatment in a nitrogen gas atmosphere containing methanol. A method for producing indium needle-like powder has been proposed (Japanese Patent Laid-Open No. 2005-322626: Patent Document 3, Japanese Patent Laid-Open No. 2005-320525: Patent Document 4).
しかし、粉末の比表面積(BET)が２０ｍ2/ｇ以下であると、これを樹脂に混合して透明膜を形成したときに可視光透過率が低くなり、透明性が低下して塗膜が白化する現象が生じやすい。 However, when the specific surface area (BET) of the powder is 20 m 2 / g or less, when this is mixed with a resin to form a transparent film, the visible light transmittance is lowered, the transparency is lowered, and the coating film is formed. The phenomenon of whitening is likely to occur.
また、酸化錫インジウム粉末を熱線遮蔽材として用いる場合、熱線遮蔽性を高めるには、粉末の色調が、Ｌａｂ表色系において、ａ＜０およびｂ＜０であって、Ｌ値に対する(ａ・ｂ)値の比〔(ａ・ｂ)/Ｌ〕が０.３以上が好ましいことが知られている（特開２００７−１５４１５２号公報：特許文献５）。しかし、特許文献３、４の方法で製造した酸化錫インジウム粉末は、ａ値＝−８〜２、ｂ値＝０〜１０であり、上記比が小さいため熱線遮蔽性に劣る。
In the case of using indium tin oxide powder as the heat ray-shielding material, to enhance the heat ray shielding property, the color of the powder is in the Lab color system, a a <0 and b <0, for L value (a · b) It is known that the value ratio [(a · b) / L] is preferably 0.3 or more (Japanese Patent Laid-Open No. 2007-154152: Patent Document 5). However, the indium tin oxide powder produced by the methods of Patent Documents 3 and 4 has an a value = −8 to 2 and a b value = 0 to 10, and is inferior in heat ray shielding because the ratio is small.
本発明は、酸化錫インジウム粉末について、従来の上記問題を解決したものであり、従来の針状粉末より微細であって比表面積が大きく、かつ熱線遮蔽性に優れた棒状の酸化錫インジウム粉末とその製造方法に関する。 The present invention solves the above-mentioned conventional problems with indium tin oxide powder, and is a rod-shaped indium tin oxide powder that is finer than conventional acicular powder, has a large specific surface area, and is excellent in heat ray shielding properties. It relates to the manufacturing method.
本発明は以下の構成によって上記課題を解決した酸化錫インジウム粉末とその製造方法に関する。
〔１〕比表面積(BET)２９〜５５ｍ 2 /ｇ、短径２０〜２５nmおよび長径８０〜１３０nm、アスペクト比３以上であり、Ｌａｂ表色系において、Ｌが２７.６〜４３.２、ａが−１.１〜−３.８、ｂが−１０.３〜−１８.１の色調を有し、三塩化インジウム水溶液と四塩化錫水溶液とを混合し、この混合液にアルカリ水溶液を添加してｐＨ６.０〜８.０に調整し、液温１０℃〜６０℃で反応させ、生成した沈澱物を純水で洗浄し、上澄み液の電気抵抗率が５０００Ω・cm以上になるまで洗浄した後に沈殿物を固液分離して回収し、乾燥し焼成してなることを特徴とする棒状酸化錫インジウム粉末。
〔２〕三塩化インジウム水溶液と四塩化錫水溶液とを混合し、この混合液にアルカリ水溶液を添加してｐＨ６.０〜８.０に調整し、液温１０℃〜６０℃で反応させ、生成した沈澱物を純水で洗浄し、上澄み液の電気抵抗率が５０００Ω・cm以上になるまで洗浄した後に沈殿物を固液分離して回収し、乾燥し焼成することによって、比表面積(BET)２９〜５５ｍ 2 /ｇ、短径２０〜２５nmおよび長径８０〜１３０nm、アスペクト比３以上であり、Ｌａｂ表色系において、Ｌが２７.６〜４３.２、ａが−１.１〜−３.８、ｂが−１０.３〜−１８.１の色調を有する棒状酸化錫インジウム粉末を製造することを特徴とする棒状酸化錫インジウム粉末の製造方法。
〔３〕上記[２]の製造方法において、回収した沈殿物を、窒素雰囲気、またはアルコールを含有した窒素雰囲気、またはアンモニアを含有した窒素雰囲気で２５０〜８００℃で３０分〜６時間加熱して乾燥焼成する棒状酸化錫インジウム粉末の製造方法。
〔４〕上記[２]の製造方法において、回収した沈殿物を大気雰囲気下で１００℃〜１１０℃で乾燥した後、窒素雰囲気、またはアルコールを含有した窒素雰囲気、またはアンモニアを含有した窒素雰囲気で２５０〜８００℃で３０分〜６時間加熱焼成する棒状酸化錫インジウム粉末の製造方法。
The present invention relates to an indium tin oxide powder and a method for producing the same in which the above-described problems are solved by the following configuration.
[1] Specific surface area (BET) 29 to 55 m 2 / g, minor axis 20 to 25 nm and major axis 80 to 130 nm, aspect ratio 3 or more, and in the Lab color system, L is 27.6 to 43.2, a Has a color tone of -1.1 to -3.8, b is -10.3 to -18.1 , and an aqueous solution of indium trichloride and an aqueous solution of tin tetrachloride are mixed, and an aqueous alkaline solution is added to the mixture. Then, the pH is adjusted to 6.0 to 8.0, the reaction is performed at a liquid temperature of 10 ° C. to 60 ° C., the generated precipitate is washed with pure water, and washed until the supernatant has an electrical resistivity of 5000 Ω · cm or more. After that , a rod-like indium tin oxide powder is obtained by solid-liquid separation and recovery of the precipitate, and drying and firing .
[2] Indium trichloride aqueous solution and tin tetrachloride aqueous solution are mixed, alkaline aqueous solution is added to this mixed solution to adjust pH to 6.0 to 8.0, and reacted at a liquid temperature of 10 ° C to 60 ° C to form. The precipitate is washed with pure water and washed until the electrical resistivity of the supernatant reaches 5000 Ω · cm or more, and then the precipitate is solid-liquid separated and recovered, dried and fired to obtain a specific surface area (BET). 29 to 55 m 2 / g, minor axis 20 to 25 nm and major axis 80 to 130 nm, aspect ratio 3 or more, L is 27.6 to 43.2, a is −1.1 to −3 in the Lab color system A method for producing a rod-shaped indium tin oxide powder, characterized in that a rod-shaped tin indium oxide powder having a color tone of .8, b of -10.3 to -18.1 is produced.
[3] In the production method of [2] , the recovered precipitate is heated at 250 to 800 ° C. for 30 minutes to 6 hours in a nitrogen atmosphere, a nitrogen atmosphere containing alcohol, or a nitrogen atmosphere containing ammonia. A method for producing rod-shaped indium tin oxide powder to be dried and fired.
[4] In the production method of [2 ] above , the collected precipitate is dried at 100 ° C. to 110 ° C. in an air atmosphere, and then in a nitrogen atmosphere, a nitrogen atmosphere containing alcohol, or a nitrogen atmosphere containing ammonia. A method for producing a rod-like indium tin oxide powder which is heated and fired at 250 to 800 ° C. for 30 minutes to 6 hours.
本発明の酸化錫インジウム粉末は、短径５〜５０nmおよび長径３０〜１５０nm、アスペクト比３以上の棒状微粒子であるので、粉末相互の接触密度が高く、従って導電性に優れる。また、本発明の酸化錫インジウム粉末は比表面積２９〜５５ｍ 2 /ｇの微粒子であるので、樹脂に混合して導電性被膜を形成したときに、可視光透過率が高く透明性に優れ、塗膜が白化する現象を抑えた被膜を形成することができる。
The indium tin oxide powder of the present invention is a rod-shaped fine particle having a minor axis of 5 to 50 nm, a major axis of 30 to 150 nm, and an aspect ratio of 3 or more, so that the contact density between the powders is high, and therefore the conductivity is excellent. Further, since the indium tin oxide powder of the present invention is a fine particle having a specific surface area of 29 to 55 m 2 / g , when mixed with a resin to form a conductive film, it has a high visible light transmittance and excellent transparency. It is possible to form a film that suppresses the phenomenon of whitening of the film.
さらに、本発明の棒状酸化錫インジウム粉末は、窒素雰囲気またはアルコール含有窒素雰囲気またはアンモニア含有窒素雰囲気で加熱処理し、表面改質することによって、やや青緑色を帯びた色調の粉末を得ることができる。この粉末は熱線遮蔽効果に優れており、導電性も高い。 Furthermore, the rod-like indium tin oxide powder of the present invention can be heated in a nitrogen atmosphere, an alcohol-containing nitrogen atmosphere or an ammonia-containing nitrogen atmosphere, and surface-modified to obtain a slightly bluish greenish powder. . This powder is excellent in heat ray shielding effect and has high conductivity.
また、本発明の製造方法によれば、比表面積が大きく微細であって、上記棒状微粒子の割合が高い酸化錫インジウム粉末を容易に製造することができる。 Moreover, according to the production method of the present invention, it is possible to easily produce an indium tin oxide powder having a large specific surface area and a high proportion of the rod-shaped fine particles.
以下、本発明を実施例に基づいて具体的に説明する。
本発明の酸化錫インジウム粉末は、比表面積(BET)２９〜５５ｍ 2 /ｇ、短径２０〜２５nmおよび長径８０〜１３０nm、アスペクト比３以上であり、Ｌａｂ表色系において、Ｌが２７.６〜４３.２、ａが−１.１〜−３.８、ｂが−１０.３〜−１８.１の色調を有し、三塩化インジウム水溶液と四塩化錫水溶液とを混合し、この混合液にアルカリ水溶液を添加してｐＨ６.０〜８.０に調整し、液温１０℃〜６０℃で反応させ、生成した沈澱物を純水で洗浄し、上澄み液の電気抵抗率が５０００Ω・cm以上になるまで洗浄した後に沈殿物を固液分離して回収し、乾燥し焼成してなることを特徴とする棒状酸化錫インジウム粉末である。
Hereinafter, the present invention will be specifically described based on examples.
The indium tin oxide powder of the present invention has a specific surface area (BET) of 29 to 55 m 2 / g, a minor axis of 20 to 25 nm and a major axis of 80 to 130 nm, an aspect ratio of 3 or more, and in the Lab color system, L is 27.6. -43.2, a has a color tone of -1.1 to -3.8, b has a color tone of -10.3 to -18.1 , and an indium trichloride aqueous solution and a tin tetrachloride aqueous solution are mixed together. The aqueous solution was adjusted to pH 6.0 to 8.0 by adding an alkaline aqueous solution, reacted at a liquid temperature of 10 ° C. to 60 ° C., the formed precipitate was washed with pure water, and the electrical resistivity of the supernatant liquid was 5000Ω · It is a rod-shaped indium tin oxide powder characterized by being collected by solid-liquid separation after being washed until it becomes cm or more, collected, dried and fired .
〔製造方法〕
本発明の棒状酸化錫インジウム粉末は、三塩化インジウム水溶液と四塩化錫水溶液とを混合し、この混合液にアルカリ水溶液を添加してｐＨ６.０〜８.０に調整し、液温１０℃〜６０℃で反応させ、生成した沈澱物を純水で洗浄し、上澄み液の電気抵抗率が５０００Ω・cm以上になるまで洗浄した後に沈殿物を固液分離して回収し、乾燥し焼成することによって製造することができる。
〔Production method〕
The rod-shaped indium tin oxide powder of the present invention is prepared by mixing an aqueous solution of indium trichloride and an aqueous solution of tin tetrachloride, adjusting the pH to 6.0 to 8.0 by adding an alkaline aqueous solution to this mixed solution, React at 60 ° C, wash the resulting precipitate with pure water, wash until the electrical resistivity of the supernatant reaches 5000 Ω · cm or higher, then collect the precipitate by solid-liquid separation, dry it, and fire it. Can be manufactured by.
本発明の棒状酸化錫インジウム粉末は、表面改質処理することによって、導電性および熱線遮蔽効果を高めることができる。この表面改質処理によって、Ｌａｂ表色系において、Ｌが２７.６〜４３.２、ａが−１.１〜−３.８、ｂが−１０.３〜−１８.１のやや青緑色を帯びた色調の粉末を得ることができる。本発明の棒状酸化錫インジウム粉末を熱線遮蔽材として使用する場合は上記反応表面処理した粉末が好ましい。
The rod-shaped indium tin oxide powder of the present invention can enhance the conductivity and the heat ray shielding effect by subjecting it to a surface modification treatment. With this surface modification treatment, in the Lab color system, L is 27.6 to 43.2, a is -1.1 to -3.8, and b is -10.3 to -18.1. Can be obtained. When the rod-shaped indium tin oxide powder of the present invention is used as a heat ray shielding material, the above-mentioned reactive surface-treated powder is preferable.
〔In-Sn共沈殿物生成工程〕
具体的には、三塩化インジウム水溶液と四塩化錫水溶液とを混合し、この混合液に炭酸水素アンモニウム（NH4HCO3）などのアルカリ水溶液を添加してｐＨ６.０〜８.０に調整し、液温１０℃〜６０℃で反応させ、沈澱を生成させる。
[In-Sn coprecipitate production process]
Specifically, an indium trichloride aqueous solution and a tin tetrachloride aqueous solution are mixed, and an alkaline aqueous solution such as ammonium hydrogen carbonate (NH 4 HCO 3 ) is added to the mixed solution to adjust the pH to 6.0 to 8.0. The mixture is reacted at a liquid temperature of 10 ° C. to 60 ° C. to form a precipitate.
三塩化インジウム水溶液と四塩化錫水溶液とを混合し、上記ｐＨおよび液温の範囲で反応させることによって、インジウム水酸化物と錫水酸化物が共沈する。この沈殿物（In-Sn共沈殿物）を回収し大気下で焼成することによって棒状の酸化錫インジウム粉末を得ることができる。 Indium hydroxide and tin hydroxide are co-precipitated by mixing an indium trichloride aqueous solution and a tin tetrachloride aqueous solution and reacting them in the above pH and liquid temperature ranges. By collecting this precipitate (In-Sn coprecipitate) and firing it in the air, a rod-like indium tin oxide powder can be obtained.
上記In-Sn共沈殿物の生成において、混合液のｐＨと液温を調整することによって、酸化錫インジウム粉末について、棒状粒子と球状粒子の割合を制御することができる。具体的には、ｐＨ６.０〜８.０および液温液温５℃〜８０℃の範囲内で、ｐＨを低くして液温を高くしたほうが棒状粒子の生成割合が多くなる傾向がある。 In the production of the In—Sn coprecipitate, the ratio of the rod-like particles to the spherical particles can be controlled in the indium tin oxide powder by adjusting the pH and temperature of the mixed solution. Specifically, within the range of pH 6.0 to 8.0 and liquid temperature of liquid temperature 5 ° C. to 80 ° C., the proportion of rod-shaped particles tends to increase as pH is lowered and liquid temperature is increased.
例えば、上記混合液のｐＨが６のとき、液温３０℃では棒状粒子の含有割合は約４０wt％〜約６０wt％であり、ｐＨ６で液温を６０℃に上げると、球状粒子の割合が大幅に減少して棒状粒子の含有割合は約９５wt％〜約１００wt％になる。一方、ｐＨ７では液温３０℃でも棒状粒子の割合は約５wt％〜約１０wt％と低く、ｐＨ９以上では液温３０℃でも実質的に全て球状粒子になる。 For example, when the pH of the above mixed solution is 6, the content ratio of rod-shaped particles is about 40 wt% to about 60 wt% at a liquid temperature of 30 ° C, and when the liquid temperature is raised to 60 ° C at a pH of 6, the ratio of spherical particles is greatly increased. The content of the rod-like particles is reduced to about 95 wt% to about 100 wt%. On the other hand, at pH 7, the ratio of rod-like particles is as low as about 5 wt% to about 10 wt% even at a liquid temperature of 30 ° C. At pH 9 or higher, substantially all spherical particles are formed even at a liquid temperature of 30 ° C.
〔固液分離工程〕
上記In-Sn共沈殿物の生成後、該沈澱物を純水で洗浄し、上澄み液の電気抵抗率が５０００Ω・cm以上、好ましくは５００００Ω・cm以上になるまで洗浄した後に固液分離して上記沈殿物を回収する。上澄み液の電気抵抗率が５０００Ω・cmより低いと塩素等の不純物が十分に除去されておらず、高純度の酸化錫インジウム粉末を得ることができない。
[Solid-liquid separation process]
After the formation of the In-Sn coprecipitate, the precipitate is washed with pure water, washed until the supernatant has an electrical resistivity of 5000 Ω · cm or more, preferably 50000 Ω · cm or more, and then separated into solid and liquid. Collect the precipitate. If the electrical resistivity of the supernatant is lower than 5000 Ω · cm, impurities such as chlorine are not sufficiently removed, and high purity indium tin oxide powder cannot be obtained.
〔焼成工程〕
回収した上記In-Sn共沈殿物を乾燥し、大気下で焼成する。好ましくは１００〜２００℃で２〜２４時間加熱することによって乾燥した後に、２５０℃以上、好ましくは４００℃〜８００℃で、１〜６時間加熱して焼成するとよい。この焼成処理によってIn-Sn共沈殿水酸化物は酸化され、棒状粒子からなる酸化錫インジウム粉末、もしくは該棒状粒子を含有した酸化錫インジウム粉末（In-Sn酸化物）を得ることができる。
[Baking process]
The collected In-Sn coprecipitate is dried and fired in the air. Preferably, after drying by heating at 100 to 200 ° C. for 2 to 24 hours, baking is performed at 250 ° C. or higher, preferably 400 to 800 ° C. for 1 to 6 hours. By this firing treatment, the In-Sn coprecipitated hydroxide is oxidized, and indium tin oxide powder composed of rod-shaped particles or indium tin oxide powder (In-Sn oxide) containing the rod-shaped particles can be obtained.
〔表面改質工程〕
本発明の棒状酸化錫インジウム粉末は、表面処理することによって導電性が向上し、熱線遮蔽効果を高めることができる。この表面改質処理は以下のように乾燥時、焼成時の各段階で行うことができる。
[Surface modification process]
The surface of the rod-like indium tin oxide powder of the present invention is improved in conductivity, and the heat ray shielding effect can be enhanced. This surface modification treatment can be performed at each stage of drying and firing as follows.
（イ）回収した上記In-Sn共沈殿物を、大気下の乾燥焼成に代えて、窒素雰囲気、またはアルコールを含有した窒素雰囲気、またはアンモニアを含有した窒素雰囲気で２５０〜８００℃で３０分〜６時間加熱して乾燥焼成する。 (B) The recovered In-Sn coprecipitate is replaced with dry baking in the atmosphere, and a nitrogen atmosphere, a nitrogen atmosphere containing alcohol, or a nitrogen atmosphere containing ammonia at 250 to 800 ° C. for 30 minutes to Heat and dry fire for 6 hours.
（ロ）回収した上記In-Sn共沈殿物を、大気雰囲気下で、１００℃〜１１０℃で一晩乾燥した後、大気下の焼成に代えて、窒素雰囲気、またはアルコールを含有した窒素雰囲気、またはアンモニアを含有した窒素雰囲気で２５０〜８００℃で３０分〜６時間加熱焼成する。 (B) The recovered In-Sn coprecipitate is dried at 100 ° C. to 110 ° C. overnight in an air atmosphere, and then replaced with baking in the air, a nitrogen atmosphere or a nitrogen atmosphere containing alcohol, Alternatively, it is fired at 250 to 800 ° C. for 30 minutes to 6 hours in a nitrogen atmosphere containing ammonia.
なお、他の方法としては、回収した上記In-Sn共沈殿物を、乾燥後、大気下で焼成処理した後に、窒素雰囲気、またはアルコールを含有した窒素雰囲気、またはアンモニアを含有した窒素雰囲気で、２５０〜８００℃で３０分〜６時間加熱処理する。
As another method, the recovered In-Sn coprecipitate is dried and calcined in the air, and then in a nitrogen atmosphere, a nitrogen atmosphere containing alcohol, or a nitrogen atmosphere containing ammonia, Heat treatment is performed at 250 to 800 ° C. for 30 minutes to 6 hours.
〔ＩＴＯ粉末〕
上記方法によって製造されたＩＴＯ粉末は、比表面積(BET) ２９〜５５ｍ 2 /ｇであって、短径２０〜２５nmおよび長径８０〜１３０nmであり、アスペクト比３以上の棒状微粒子が沈澱生成時のｐＨおよび液温の条件に従った割合で含まれている。具体的には、ｐＨ６〜７、液温３０℃〜６０℃の条件下で、棒状粒子が約５wt％〜約１００wt％含まれている。残余は球状ないし直方体状の粒子である。この球状ないし直方体状の酸化錫インジウム粉末は、概ね、比表面積(BET)２５〜１００ｍ2/ｇ、粒子径５〜５０nm、アスペクト比３未満の粉末である。
[ITO powder]
The ITO powder produced by the above method has a specific surface area (BET) of 29 to 55 m 2 / g , a minor axis of 20 to 25 nm and a major axis of 80 to 130 nm . It is contained in proportions according to pH and liquid temperature conditions. Specifically, rod-like particles are contained in an amount of about 5 wt% to about 100 wt% under the conditions of pH 6-7 and liquid temperature 30 ° C.-60 ° C. The remainder is spherical or rectangular parallelepiped particles. This spherical or rectangular parallelepiped indium tin oxide powder is generally a powder having a specific surface area (BET) of 25 to 100 m 2 / g, a particle diameter of 5 to 50 nm, and an aspect ratio of less than 3.
また、上記表面改質処理したＩＴＯ粉末の色調は、Ｌａｂ表色系において、Ｌが２７.６〜４３.２、ａが−１.１〜−３.８、ｂが−１０.３〜−１８.１のやや青緑色を帯びた色調の粉末である。このＩＴＯ粉末は棒状粉末であり、あるいは棒状粉末を多く含むので、樹脂に混合して被膜やシートを形成したときに、球状粒子よりも少量で優れた導電性を得ることができ、また、熱線遮蔽材として用いたときに優れた熱線遮蔽効果を得ることができる。
Moreover, the color tone of the ITO powder subjected to the surface modification treatment is as follows: L is 27.6 to 43.2, a is −1.1 to −3.8, and b is −10.3 to −3 in the Lab color system. 18.1 A slightly blue-greenish-colored powder. Since this ITO powder is a rod-like powder or contains a lot of rod-like powder, when it is mixed with a resin to form a film or sheet, it can obtain superior conductivity with a smaller amount than spherical particles, When used as a shielding material, an excellent heat ray shielding effect can be obtained.
以下、本発明の実施例を比較例と共に示す。製造したＩＴＯ粉末の形状、短軸径、長軸径、比表面積、色調（Ｌａｂ値）は以下の方法によって測定した。
〔形状・短軸径・長軸径〕透過型電子顕微鏡観察（TEM）によって形状を把握し、棒状粒子の短軸径および長軸径は平均値を求めた。
〔比表面積〕BET比表面積は、柴田科学社の装置(SA-1100)を用いて測定した。
〔色調〕色調（Lａｂ値）は、スガ試験機社のカラーコンピュータ(SM-T)を用いて測定した。
Examples of the present invention are shown below together with comparative examples. The shape, minor axis diameter, major axis diameter, specific surface area, and color tone (Lab value) of the produced ITO powder were measured by the following methods.
[Shape, minor axis diameter, major axis diameter] The shape was grasped by transmission electron microscope observation (TEM), and the minor axis diameter and major axis diameter of the rod-like particles were averaged.
[Specific surface area] The BET specific surface area was measured using an apparatus (SA-1100) manufactured by Shibata Kagaku.
[Color tone] The color tone (Lab value) was measured using a color computer (SM-T) manufactured by Suga Test Instruments Co., Ltd.
〔実施例Ａ１：試料No.3〕
ＩｎＣｌ3水溶液（In金属350g含有）９００mLと５５％濃度ＳｎＣｌ4水溶液１４４ｇとを混合し、この混合水溶液に炭酸水素アンモニウム(NH4HCO3)１９００ｇを含有するアルカリ水溶液６Lを加えてｐＨ６に調整し、３０℃の液温で３０分間反応させた。生成した沈殿をイオン交換水によって繰り返し傾斜洗浄を行った。上澄み液の電気抵抗率が５００００Ω・cm以上になったところで、沈殿物(In／Sn共沈水酸化物)を濾別し、１１０℃で一晩乾燥した後、大気中５５０℃で３時間焼成し、凝集体を粉砕してほぐし、ＩＴＯ粉約４４０ｇを得た。この合成処理を２バッチ実施し、合計で約８８０ｇのＩＴＯ粉を得た。このＩＴＯ粉末の形状、短軸径、長軸径、比表面積、を表１に示した。また、この粉末の写真を図１に示した。さらに、エックス線回折にて、結晶晶系を確認したところ、立方晶系と六方晶系が確認された。
[Example A1: Sample No. 3]
900 mL of InCl 3 aqueous solution (containing 350 g of In metal) and 144 g of 55% strength SnCl 4 aqueous solution are mixed, and 6 L of alkaline aqueous solution containing 1900 g of ammonium bicarbonate (NH 4 HCO 3 ) is added to this mixed aqueous solution to adjust the pH to 6. , And reacted at a liquid temperature of 30 ° C. for 30 minutes. The generated precipitate was repeatedly washed with ion-exchange water. When the electrical resistivity of the supernatant reached 50,000 Ω · cm or more, the precipitate (In / Sn coprecipitated hydroxide) was filtered off, dried at 110 ° C. overnight, and then baked at 550 ° C. in the atmosphere for 3 hours. The aggregate was pulverized and loosened to obtain about 440 g of ITO powder. This synthesis process was performed in two batches to obtain a total of about 880 g of ITO powder. Table 1 shows the shape, minor axis diameter, major axis diameter, and specific surface area of the ITO powder. A photograph of this powder is shown in FIG. Furthermore, when the crystal system was confirmed by X-ray diffraction, a cubic system and a hexagonal system were confirmed.
上記ＩＴＯ粉４０ｇを、無水エタノールと蒸留水を混合（混合比率はエタノール９５重量部に対して蒸留水５重量部）した表面処理液に入れて含浸させた後、ガラスシャーレに入れて窒素ガス雰囲気下、３３０℃にて２時間加熱処理した。この表面処理を1回ずつ２０バッチ実施し、合計約８００ｇの表面処理ＩＴＯ粉を得た。なお、表面処理バッチ毎の特性差をなくすため、ＩＴＯ粉が良く冷えてからビニール袋に入れて表面処理したＩＴＯ粉が均一になるよう混合した。このＩＴＯ粉末の色調（Ｌ、ａ、ｂ）を表１に示した。 After impregnating 40 g of the above ITO powder in a surface treatment solution obtained by mixing absolute ethanol and distilled water (mixing ratio is 5 parts by weight of distilled water with respect to 95 parts by weight of ethanol), the glass powder is put in a glass petri dish and a nitrogen gas atmosphere Then, heat treatment was performed at 330 ° C. for 2 hours. This surface treatment was performed 20 batches at a time to obtain a total of about 800 g of surface-treated ITO powder. In addition, in order to eliminate the characteristic difference for each surface treatment batch, the ITO powder was mixed well so that the ITO powder that had been cooled and placed in a plastic bag was uniformly treated. The color tone (L, a, b) of this ITO powder is shown in Table 1.
〔実施例Ａ２：試料No.4〕
混合液の液温を６０℃にした。それ以外は実施例１と同様にしてＩＴＯ粉を得た。このＩＴＯ粉末を表１に示した。この粉末の写真を図２に示した。
[Example A2: Sample No. 4]
The liquid temperature of the mixed liquid was set to 60 ° C. Otherwise, ITO powder was obtained in the same manner as in Example 1. This ITO powder is shown in Table 1. A photograph of this powder is shown in FIG.
〔実施例Ａ３〜４：試料No.5〜6〕
アルカリ水溶液の添加量を調整して混合液のｐＨを７、液温を１０℃、３０℃にし、焼成後の表面改質処理に代えて、乾燥後焼成前にＩＴＯ粉末を実施例１と同様のアルコール液に入れて含浸させた後に、窒素ガス雰囲気下、３３０℃にて２時間加熱焼成した。それ以外は実施例１と同様にしてＩＴＯ粉を得た。このＩＴＯ粉末を表１に示した。
[Examples A3 to 4: Sample Nos. 5 to 6]
The amount of the alkaline aqueous solution was adjusted to adjust the pH of the mixture to 7, the liquid temperature to 10 ° C. and 30 ° C., and instead of the surface modification treatment after firing, the ITO powder was the same as in Example 1 after drying and before firing. After impregnating in an alcohol solution, the mixture was heated and fired at 330 ° C. for 2 hours in a nitrogen gas atmosphere. Otherwise, ITO powder was obtained in the same manner as in Example 1. This ITO powder is shown in Table 1.
〔試料No.1〜2、および試料No.7〕
原料混合液のｐＨおよび液温を表１に示すように調整し、固液分離して回収した沈殿物を実施例１と同様のアルコール液に入れて含浸させたものを、窒素ガス雰囲気下、３３０℃にて２時間加熱焼成した。それ以外は実施例１と同様にしてＩＴＯ粉を得た。このＩＴＯ粉末を表１に示した。
[Sample Nos. 1 and 2 and Sample No. 7]
The pH and liquid temperature of the raw material mixture were adjusted as shown in Table 1, and the precipitate collected by solid-liquid separation was impregnated in an alcohol liquid similar to that in Example 1, under a nitrogen gas atmosphere. Baking was performed at 330 ° C. for 2 hours. Otherwise, ITO powder was obtained in the same manner as in Example 1. This ITO powder is shown in Table 1.
〔比較例１：試料No.8〕
アルカリ水溶液の添加量を調整して混合液のｐＨを９にした以外は実施例１と同様にしてＩＴＯ粉を得た。このＩＴＯ粉末を表１に示した。この粉末の写真を図３に示した。
[Comparative Example 1: Sample No. 8]
An ITO powder was obtained in the same manner as in Example 1 except that the addition amount of the alkaline aqueous solution was adjusted to adjust the pH of the mixed solution to 9. This ITO powder is shown in Table 1. A photograph of this powder is shown in FIG.
表１に示すように、本発明の好ましい範囲の試料（No.3〜No.6）は何れも、酸化錫インジウムの棒状微粒子を含有しており、特にNo.3およびNo.4の試料には多量の棒状微粒が含まれている。また、上記試料（No.3〜No.6）の酸化錫インジウム粉末は、比表面積が２５m2/ｇ以上であり、微細な粉末であるので、樹脂に混合して被膜を形成したときに可視光透過率の高い被膜を形成することができる。
As shown in Table 1, all the samples in the preferred range of the present invention ( No. 3 to No. 6) contain rod-shaped fine particles of indium tin oxide, and in particular, No. 3 and No. 4 samples. Contains a large amount of rod-like granules. Further, the indium tin oxide powders of the above samples (No. 3 to No. 6) have a specific surface area of 25 m 2 / g or more and are fine powders, so that they are visible when mixed with a resin to form a film. A film having a high light transmittance can be formed.
また、上記試料（No.3〜No.7）の表面改質処理した粉末は、Ｌａｂ表色系において、Ｌが２７.６〜４３.２、ａが−１.１〜−３.８、ｂが−１０.３〜−１８.１のやや青緑色を帯びた色調の粉末であり、熱線遮蔽材として用いたときに優れた熱線遮蔽効果を得ることができる。
In addition, the surface-modified powders of the above samples (No. 3 to No. 7) have a Lab color system where L is 27.6 to 43.2, a is −1.1 to −3.8, b is a powder having a slightly blue-green color tone of −10.3 to −18.1 , and an excellent heat ray shielding effect can be obtained when used as a heat ray shielding material.
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