JP5954082B2 - ITO powder and method for producing the same - Google Patents
ITO powder and method for producing the same Download PDFInfo
- Publication number
- JP5954082B2 JP5954082B2 JP2012213756A JP2012213756A JP5954082B2 JP 5954082 B2 JP5954082 B2 JP 5954082B2 JP 2012213756 A JP2012213756 A JP 2012213756A JP 2012213756 A JP2012213756 A JP 2012213756A JP 5954082 B2 JP5954082 B2 JP 5954082B2
- Authority
- JP
- Japan
- Prior art keywords
- slurry
- mass
- range
- ito powder
- indium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/90—Other properties not specified above
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
- Paints Or Removers (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
Description
本発明は、低い圧力で圧粉体にしたときに高い導電性を示す表面改質したＩＴＯ粉末及びその製造方法に関するものである。本明細書において、ＩＴＯとはインジウム錫酸化物(Indium Tin Oxide)をいう。 The present invention relates to a surface-modified ITO powder that exhibits high conductivity when formed into a green compact at a low pressure and a method for producing the same. In this specification, ITO refers to indium tin oxide.
ＩＴＯは、Ｉｎ２Ｏ３に錫(Ｓｎ)をドープした化合物であり、１０２０〜１０２１ｃｍ−３の高いキャリア濃度を有し、スパッタリング法等の気相法で成膜したＩＴＯ膜では、１×１０−４Ωｃｍ程度の低い抵抗率が得られる。このＩＴＯから作られたＩＴＯ膜は、可視光領域で高い透明性を有している（例えば、特許文献１参照。）。このためＩＴＯ膜は、液晶ディスプレーの透明電極（例えば、特許文献２参照。）や、熱線遮断効果の高い熱線遮蔽材料（例えば、特許文献３参照。）などの優れた光学特性を求められる分野に多く用いられている。このＩＴＯ膜の成膜方法として、コストが高い真空蒸着法やスパッタリング法などの物理的成膜法に代わって、簡便な塗布による成膜法が検討されている（例えば、特許文献４参照。）。 ITO is a compound in which tin (Sn) is doped into In 2 O 3 , has a high carrier concentration of 10 20 to 10 21 cm −3 , and an ITO film formed by a vapor phase method such as a sputtering method, A resistivity as low as 1 × 10 −4 Ωcm is obtained. The ITO film made from this ITO has high transparency in the visible light region (see, for example, Patent Document 1). Therefore, the ITO film is used in fields where excellent optical properties such as a transparent electrode of a liquid crystal display (for example, see Patent Document 2) and a heat ray shielding material having a high heat ray shielding effect (for example, see Patent Document 3) are required. Many are used. As a method for forming the ITO film, a simple film-forming method is being considered in place of the costly physical film-forming methods such as vacuum deposition and sputtering (see, for example, Patent Document 4). .
ＩＴＯ膜を成膜する方法として塗布型の成膜方法は、材料の利用効率及び生産性が高く、屈曲性に優れ、塗布する基板に制限が少ない利点を有する。しかしその反面、物理型成膜方法に比べて、粒子自体の導電性が低く、粒子同士の接触抵抗が高いために、導電性が低い欠点があった。 As a method for forming an ITO film, a coating-type film forming method has advantages in that the material utilization efficiency and productivity are high, the flexibility is excellent, and the substrate to be applied is less restricted. On the other hand, however, the conductivity of the particles themselves is low and the contact resistance between the particles is high as compared with the physical film-forming method, so that the conductivity is low.
本発明の目的は、塗布型でＩＴＯ膜を成膜したときの抵抗率を低くして高い導電性を得ることができるＩＴＯ粉末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 an ITO powder capable of obtaining a high conductivity by reducing a resistivity when an ITO film is formed by a coating type, and a method for producing the same.
本発明の第１の観点は、３価インジウム化合物と２価錫化合物の混合水溶液にアルカリ水溶液を混合して、インジウムと錫の共沈水酸化物を生成し、前記沈殿物を上澄み液の抵抗率が少なくとも５０００Ω・ｃｍになるまで純水又はイオン交換水で洗浄し、前記沈殿物の上澄み液を捨ててインジウム錫水酸化物粒子が分散したスラリーを調製し、前記水酸化物粒子の濃度が１０〜３０質量％の範囲になるように前記上澄み液を捨てたスラリーを水で希釈し、パルミチルジメチルエチルアンモニウムエチルサルフェート、ポリビニルアルコール又はオクチルジメチルエチルアンモニウムエチルサルフェートである有機保護剤を前記スラリーに前記水酸化物粒子１００質量％に対して０．１〜５質量％の範囲で撹拌しながら添加し、前記有機保護剤が表面に吸着したインジウム錫水酸化物を乾燥した後、大気中２５０〜８００℃の範囲で０．５〜６時間焼成炉にて焼成し、焼成したＩＴＯ粉末の凝集体を粉砕し、この粉砕されたＩＴＯ粉末を５０〜９５質量％の無水エタノールと５〜５０質量％の蒸留水を混合した表面処理液に含浸し、続いて窒素ガス雰囲気下、２００〜４００℃の範囲で０．５〜５時間加熱することにより表面改質されたＩＴＯ粉末であって、前記ＩＴＯ粉末からなる圧粉体に０．９８ＭＰａ（１０ｋｇｆ／ｃｍ2）の圧力を加えたときの前記圧粉体の体積抵抗率が０．５０Ωｃｍ以下であり、前記圧粉体に０．１９６〜２９．４２ＭＰａ（２〜３００ｋｇｆ／ｃｍ2）の圧力を加えたときの前記圧粉体の体積抵抗率をＹとし前記圧力をＸとする場合、前記圧力と前記体積抵抗率の関係が、最小二乗法により、下記の式（１）で近似され、この式（１）においてａが５．００以下であり、かつｎが−０．５００以下であることを特徴とするＩＴＯ粉末である。
Ｙ＝ａＸn （１）
According to a first aspect of the present invention, a mixed aqueous solution of a trivalent indium compound and a divalent tin compound is mixed with an alkaline aqueous solution to form a coprecipitated hydroxide of indium and tin, and the precipitate is filtered with the resistivity of the supernatant. Is washed with pure water or ion-exchanged water until it becomes at least 5000 Ω · cm, the supernatant liquid of the precipitate is discarded, and a slurry in which indium tin hydroxide particles are dispersed is prepared, and the concentration of the hydroxide particles is 10 The slurry from which the supernatant was discarded so as to be in the range of ˜30% by mass was diluted with water, and the organic protective agent which was palmityldimethylethylammonium ethyl sulfate, polyvinyl alcohol or octyldimethylethylammonium ethyl sulfate was added to the slurry. Add with stirring in the range of 0.1-5% by mass with respect to 100% by mass of hydroxide particles, the organic protection After the indium tin hydroxide adsorbed on the surface is dried, it is baked in a baking furnace in the range of 250 to 800 ° C. for 0.5 to 6 hours in the atmosphere, and the aggregate of the baked ITO powder is pulverized. The ITO powder thus prepared was impregnated in a surface treatment liquid in which 50 to 95% by mass of absolute ethanol and 5 to 50% by mass of distilled water were mixed, and then in a nitrogen gas atmosphere at a temperature of 200 to 400 ° C. in the range of 0.5 to a ITO powder surface-reformed by heating for 5 hours, the volume resistivity of the powder compact at the time of a pressure of 0.98MPa (10kgf / cm 2) in green compact made of the ITO powder Is 0.50 Ωcm or less, and Y represents the volume resistivity of the green compact when a pressure of 0.196 to 29.42 MPa ( 2 to 300 kgf / cm 2 ) is applied to the green compact. And the pressure and the The relationship between the volume resistivity is approximated by the following equation (1) by the least square method, and in this equation (1), a is 5.00 or less and n is −0.500 or less. ITO powder.
Y = aX n (1)
また本発明の第２の観点は、３価インジウム化合物と２価錫化合物の混合水溶液にアルカリ水溶液を混合して、インジウムと錫の共沈水酸化物を生成する工程と、前記沈殿物を純水又はイオン交換水で洗浄する工程と、前記沈殿物の上澄み液を捨ててインジウム錫水酸化物粒子が分散したスラリーを調製する工程と、前記スラリーを乾燥する工程と、前記乾燥したインジウム水錫酸化物を焼成してインジウム錫酸化物を得る工程とを含むＩＴＯ粉末を製造する方法の改良である。その特徴ある点は、前記洗浄工程で、前記上澄み液の抵抗率が少なくとも５０００Ω・ｃｍになるまで洗浄し、前記スラリーの調製工程で、前記水酸化物粒子の濃度が１０〜３０質量％の範囲になるように前記上澄み液を捨てたスラリーを水で希釈した後、パルミチルジメチルエチルアンモニウムエチルサルフェート、ポリビニルアルコール又はオクチルジメチルエチルアンモニウムエチルサルフェートである有機保護剤を前記スラリーに前記水酸化物粒子１００質量％に対して０．１〜５質量％の範囲で撹拌しながら添加し、前記有機保護剤が表面に吸着したインジウム錫水酸化物を乾燥した後、前記焼成工程で、大気中２５０〜８００℃の範囲で０．５〜６時間焼成炉にて焼成し、前記焼成工程の後で、焼成したＩＴＯ粉末の凝集体を粉砕し、この粉砕されたＩＴＯ粉末を５０〜９５質量％の無水エタノールと５〜５０質量％の蒸留水を混合した表面処理液に含浸した後、窒素ガス雰囲気下、２００〜４００℃の範囲で０．５〜５時間加熱することにある。
本発明の第３の観点は、３価インジウム化合物と２価錫化合物の混合水溶液にアルカリ水溶液を混合して、インジウムと錫の共沈水酸化物を生成し、前記沈殿物を上澄み液の抵抗率が少なくとも５０００Ω・ｃｍになるまで純水又はイオン交換水で洗浄し、前記沈殿物の上澄み液を捨ててインジウム錫水酸化物粒子が分散したスラリーを調製し、前記水酸化物粒子の濃度が１０〜３０質量％の範囲になるように前記上澄み液を捨てたスラリーを水で希釈し、パルミチルジメチルエチルアンモニウムエチルサルフェート、ポリビニルアルコール又はオクチルジメチルエチルアンモニウムエチルサルフェートである有機保護剤を前記スラリーに前記水酸化物粒子１００質量％に対して０．１〜５質量％の範囲で撹拌しながら添加し、前記有機保護剤を添加したインジウム錫水酸化物が分散したスラリーを乾燥した後、大気中で２．４５ＧＨｚ〜２８ＧＨｚのマイクロ波で２５０〜８００℃の範囲で、１０分以内で目的温度に達する速度で昇温し、続いて前記目的温度で５〜１２０分の範囲保持することにより加熱焼成し、焼成したＩＴＯ粉末の凝集体を粉砕し、この粉砕されたＩＴＯ粉末を５０〜９５質量％の無水エタノールと５〜５０質量％の蒸留水を混合した表面処理液に含浸した後、窒素ガス雰囲気下、２００〜４００℃の範囲で０．５〜５時間加熱することにより表面改質されたＩＴＯ粉末であって、前記ＩＴＯ粉末からなる圧粉体に０．９８ＭＰａの圧力を加えたときの前記圧粉体の体積抵抗率が０．５０Ωｃｍ以下であり、前記圧粉体に０．１９６〜２９．４２ＭＰａの圧力を加えたときの前記圧粉体の体積抵抗率をＹとし前記圧力をＸとする場合、前記圧力と前記体積抵抗率の関係が、最小二乗法により、下記の式（１）で近似され、この式（１）においてａが５．００以下であり、かつｎが−０．５００以下であることを特徴とするＩＴＯ粉末。
Ｙ＝ａＸ n （１）
The second aspect of the present invention, a trivalent indium compound and a mixture of an aqueous alkali solution to a mixed aqueous solution of divalent tin compound, pure water and generating a co-precipitated hydroxide of indium and tin, the precipitate Alternatively, the step of washing with ion-exchanged water, the step of throwing away the supernatant of the precipitate and preparing a slurry in which indium tin hydroxide particles are dispersed, the step of drying the slurry, and the dried indium water tin oxidation Improvement of a method for producing an ITO powder including a step of firing an object to obtain indium tin oxide. The characteristic point is that in the washing step, the supernatant is washed until the resistivity becomes at least 5000 Ω · cm, and in the slurry preparation step, the concentration of the hydroxide particles ranges from 10 to 30% by mass. The slurry from which the supernatant was discarded was diluted with water, and an organic protective agent such as palmityldimethylethylammonium ethyl sulfate, polyvinyl alcohol, or octyldimethylethylammonium ethyl sulfate was added to the slurry. It is added while stirring in the range of 0.1 to 5% by mass with respect to mass%, and after drying the indium tin hydroxide adsorbed on the surface of the organic protective agent, in the firing step, 250 to 800 in the atmosphere. and calcined at 0.5 to 6 hours calcination furnace in the range of ° C., after the firing step, the powder aggregates of fired ITO powder And, after impregnation the ground ITO powder to the surface treatment solution obtained by mixing 50-95 wt% of absolute ethanol and 5 to 50 wt% of distilled water, under a nitrogen gas atmosphere, in the range of 0 200 to 400 ° C. It is to heat for 5 to 5 hours.
According to a third aspect of the present invention, an alkaline aqueous solution is mixed with a mixed aqueous solution of a trivalent indium compound and a divalent tin compound to form a coprecipitated hydroxide of indium and tin, and the precipitate is filtered to have a resistivity of the supernatant. Is washed with pure water or ion-exchanged water until it becomes at least 5000 Ω · cm, the supernatant liquid of the precipitate is discarded, and a slurry in which indium tin hydroxide particles are dispersed is prepared, and the concentration of the hydroxide particles is 10 The slurry from which the supernatant was discarded so as to be in the range of ˜30% by mass was diluted with water, and the organic protective agent which was palmityldimethylethylammonium ethyl sulfate, polyvinyl alcohol or octyldimethylethylammonium ethyl sulfate was added to the slurry. Add with stirring in the range of 0.1-5% by mass with respect to 100% by mass of hydroxide particles, the organic protection After drying the slurry in which the indium tin hydroxide added has been dispersed, the temperature is raised in the atmosphere at a rate of reaching the target temperature within 10 minutes in the range of 250 to 800 ° C. with a microwave of 2.45 GHz to 28 GHz. Subsequently, the mixture is heated and fired at the target temperature for 5 to 120 minutes, and the aggregate of the fired ITO powder is pulverized. The crushed ITO powder is mixed with 50 to 95% by mass of absolute ethanol and 5 to 5%. After impregnating the surface treatment liquid mixed with 50% by mass of distilled water, the ITO powder is surface-modified by heating in a nitrogen gas atmosphere at a temperature of 200 to 400 ° C. for 0.5 to 5 hours, A volume resistivity of the green compact when a pressure of 0.98 MPa is applied to the green compact made of the ITO powder is 0.50 Ωcm or less, and a pressure of 0.196 to 29.42 MPa is applied to the green compact. When the volume resistivity of the green compact is Y and the pressure is X, the relationship between the pressure and the volume resistivity is approximated by the following equation (1) by the least square method: In this formula (1), ITO is characterized in that a is 5.00 or less and n is -0.500 or less.
Y = aX n (1)
また本発明の第４の観点は、３価インジウム化合物と２価錫化合物の混合水溶液にアルカリ水溶液を混合して、インジウムと錫の共沈水酸化物を生成する工程と、前記沈殿物を純水又はイオン交換水で洗浄する工程と、前記沈殿物の上澄み液を捨ててインジウム錫水酸化物粒子が分散したスラリーを調製する工程と、前記スラリーを乾燥する工程と、前記乾燥したインジウム水錫酸化物を焼成してインジウム錫酸化物を得る工程とを含むＩＴＯ粉末を製造する方法の改良である。その特徴ある点は、前記洗浄工程で、前記上澄み液の抵抗率が少なくとも５０００Ω・ｃｍになるまで洗浄し、前記スラリーの調製工程で、前記水酸化物粒子の濃度が１０〜３０質量％の範囲になるように前記上澄み液を捨てたスラリーを水で希釈した後、パルミチルジメチルエチルアンモニウムエチルサルフェート、ポリビニルアルコール又はオクチルジメチルエチルアンモニウムエチルサルフェートである有機保護剤を前記スラリーに前記水酸化物粒子１００質量％に対して０．１〜５質量％の範囲で撹拌しながら添加し、前記乾燥工程で、前記有機保護剤を添加したインジウム錫水酸化物が分散したスラリーを乾燥し、前記焼成工程で、大気中で２．４５ＧＨｚ〜２８ＧＨｚのマイクロ波で２５０〜８００℃の範囲で、１０分以内で目的温度に達する速度で昇温した後、前記目的温度で５〜１２０分の範囲保持することにより加熱焼成し、前記焼成工程の後で、焼成したＩＴＯ粉末の凝集体を粉砕し、この粉砕されたＩＴＯ粉末を５０〜９５質量％の無水エタノールと５〜５０質量％の蒸留水を混合した表面処理液に含浸した後、窒素ガス雰囲気下、２００〜４００℃の範囲で０．５〜５時間加熱することにある。
本発明の第５の観点は、３価インジウム化合物と２価錫化合物の混合水溶液にアルカリ水溶液を混合して、インジウムと錫の共沈水酸化物を生成し、前記沈殿物を上澄み液の抵抗率が少なくとも５０００Ω・ｃｍになるまで純水又はイオン交換水で洗浄し、前記沈殿物の上澄み液を捨ててインジウム錫水酸化物粒子が分散したスラリーを調製し、前記水酸化物粒子の濃度が１〜５質量％の範囲になるように前記上澄み液を捨てたスラリーをアルコールで希釈し、パルミチルジメチルエチルアンモニウムエチルサルフェート、ポリビニルアルコール又はオクチルジメチルエチルアンモニウムエチルサルフェートである有機保護剤を前記スラリーに前記水酸化物粒子１００質量％に対して０．１〜５質量％の範囲で撹拌しながら添加し、前記アルコールで希釈され前記有機保護剤を添加したインジウム錫水酸化物粒子が分散したスラリーを２５０〜８００℃の範囲に加熱した管状炉の内部に、窒素ガスを線速度０．５〜５ｍ／ｓの範囲で流通させている状態で、噴霧してインジウム錫水酸化物粒子を前記管状炉内で熱分解して焼成することにより表面改質されたＩＴＯ粉末であって、前記ＩＴＯ粉末からなる圧粉体に０．９８ＭＰａの圧力を加えたときの前記圧粉体の体積抵抗率が０．５０Ωｃｍ以下であり、前記圧粉体に０．１９６〜２９．４２ＭＰａの圧力を加えたときの前記圧粉体の体積抵抗率をＹとし前記圧力をＸとする場合、前記圧力と前記体積抵抗率の関係が、最小二乗法により、下記の式（１）で近似され、この式（１）においてａが５．００以下であり、かつｎが−０．５００以下であることを特徴とするＩＴＯ粉末。
Ｙ＝ａＸ n （１）
The fourth aspect of the present invention, a trivalent indium compound and a mixture of an aqueous alkali solution to a mixed aqueous solution of divalent tin compound, pure water and generating a co-precipitated hydroxide of indium and tin, the precipitate Alternatively, the step of washing with ion-exchanged water, the step of throwing away the supernatant of the precipitate and preparing a slurry in which indium tin hydroxide particles are dispersed, the step of drying the slurry, and the dried indium water tin oxidation Improvement of a method for producing an ITO powder including a step of firing an object to obtain indium tin oxide. The characteristic point is that in the washing step, the supernatant is washed until the resistivity becomes at least 5000 Ω · cm, and in the slurry preparation step, the concentration of the hydroxide particles ranges from 10 to 30% by mass. The slurry from which the supernatant was discarded was diluted with water, and an organic protective agent such as palmityldimethylethylammonium ethyl sulfate, polyvinyl alcohol, or octyldimethylethylammonium ethyl sulfate was added to the slurry. It is added with stirring in the range of 0.1 to 5% by mass with respect to mass%, and in the drying step, the slurry in which the indium tin hydroxide added with the organic protective agent is dispersed is dried, and in the baking step , in the range of 250~800 ℃ in the microwave 2.45GHz~28GHz in the air, eyes in less than 10 minutes After heating at a rate which reaches a temperature, the heated baking by maintaining range target temperature of 5 to 120 minutes, after the baking step, pulverizing the aggregates of the fired ITO powder it was the crushed After impregnating the ITO powder with a surface treatment liquid in which 50 to 95% by mass of absolute ethanol and 5 to 50% by mass of distilled water are mixed, the mixture is heated in a nitrogen gas atmosphere at 200 to 400 ° C. for 0.5 to 5 hours. There is to do.
According to a fifth aspect of the present invention, an alkaline aqueous solution is mixed with a mixed aqueous solution of a trivalent indium compound and a divalent tin compound to produce a coprecipitated hydroxide of indium and tin, and the precipitate is resisted by a supernatant. Is washed with pure water or ion-exchanged water until it becomes at least 5000 Ω · cm, the supernatant liquid of the precipitate is discarded, and a slurry in which indium tin hydroxide particles are dispersed is prepared, and the concentration of the hydroxide particles is 1 The slurry from which the supernatant was discarded so as to be in the range of ˜5% by mass was diluted with alcohol, and an organic protective agent that was palmityldimethylethylammonium ethylsulfate, polyvinyl alcohol or octyldimethylethylammonium ethylsulfate was added to the slurry. While stirring in the range of 0.1 to 5% by mass with respect to 100% by mass of hydroxide particles, In a tubular furnace heated to a temperature in the range of 250 to 800 ° C., a slurry in which indium tin hydroxide particles diluted with a slurry and added with the above organic protective agent are dispersed is introduced with nitrogen gas at a linear velocity of 0.5 to 5 m / s. The ITO powder is surface-modified by spraying and thermally decomposing and firing the indium tin hydroxide particles in the tubular furnace in a state of being distributed in the range of the pressure of the ITO powder. The volume resistivity of the green compact when a pressure of 0.98 MPa is applied to the powder is 0.50 Ωcm or less, and the pressure when a pressure of 0.196 to 29.42 MPa is applied to the green compact When the volume resistivity of the powder is Y and the pressure is X, the relationship between the pressure and the volume resistivity is approximated by the following equation (1) by the least square method. In this equation (1), a Is 5.00 or less, and n is -0. ITO powder characterized by being 500 or less.
Y = aX n (1)
また本発明の第６の観点は、３価インジウム化合物と２価錫化合物の混合水溶液にアルカリ水溶液を混合して、インジウムと錫の共沈水酸化物を生成する工程と、前記沈殿物を純水又はイオン交換水で洗浄する工程と、前記沈殿物の上澄み液を捨ててインジウム錫水酸化物粒子が分散したスラリーを調製する工程と、前記インジウム水錫酸化物が分散したスラリーを焼成してインジウム錫酸化物を得る工程とを含むＩＴＯ粉末を製造する方法の改良である。その特徴ある点は、前記洗浄工程で、前記上澄み液の抵抗率が少なくとも５０００Ω・ｃｍになるまで洗浄し、前記スラリーの調製工程で、前記水酸化物粒子の濃度が１〜５質量％の範囲になるように前記上澄み液を捨てたスラリーをアルコールで希釈した後、パルミチルジメチルエチルアンモニウムエチルサルフェート、ポリビニルアルコール又はオクチルジメチルエチルアンモニウムエチルサルフェートである有機保護剤を前記スラリーに前記水酸化物粒子１００質量％に対して０．１〜５質量％の範囲で撹拌しながら添加し、前記前記焼成工程で、前記アルコールで希釈され前記有機保護剤を添加したインジウム錫水酸化物粒子が分散したスラリーを２５０〜８００℃の範囲に加熱した管状炉の内部に、窒素ガスを線速度０．５〜５ｍ／ｓの範囲で流通させている状態で、噴霧することによりインジウム錫水酸化物粒子を前記管状炉内で熱分解して焼成しインジウム錫酸化物粒子を得ることにある。
本発明の第７の観点は、第５又は第６の観点に基づく発明であって、前記アルコールがエタノール、メタノール又はプロパノールであるＩＴＯ粉末の製造方法である。
また本発明の第８の観点は、第１、第３又は第５の観点のＩＴＯ粉末又は第２、第４又は第６の方法により製造されたＩＴＯ粉末を溶媒に分散させて分散液を製造する方法である。
更に本発明の第９の観点は、第８の観点の分散液からＩＴＯ膜を製造する方法である。
The sixth aspect of the present invention, a trivalent indium compound and a mixture of an aqueous alkali solution to a mixed aqueous solution of divalent tin compound, pure water and generating a co-precipitated hydroxide of indium and tin, the precipitate or a step of washing with deionized water, a step of indium tin hydroxide particles to prepare a dispersion slurry discarded the supernatant of the precipitate, indium by firing the slurry the indium aqueous tin oxide are dispersed Improvement of the method of manufacturing ITO powder including the process of obtaining a tin oxide. The characteristic point is that in the washing step, the supernatant is washed until the resistivity is at least 5000 Ω · cm, and in the slurry preparation step, the concentration of the hydroxide particles is in the range of 1 to 5% by mass. The slurry from which the supernatant was discarded was diluted with alcohol, and an organic protective agent such as palmityldimethylethylammonium ethyl sulfate, polyvinyl alcohol, or octyldimethylethylammonium ethyl sulfate was added to the slurry. A slurry in which indium tin hydroxide particles diluted with the alcohol and added with the organic protective agent are dispersed in the baking step with stirring in a range of 0.1 to 5% by mass with respect to mass%. Inside the tubular furnace heated to a range of 250 to 800 ° C., nitrogen gas is fed at a linear velocity of 0.5 to 5 m. In a state in which is circulated in the range of s, is to obtain the indium tin hydroxide particles and firing the thermally decomposed in the tube furnace indium tin oxide particles by spraying.
Seventh aspect of the present invention is an invention based on the fifth or sixth aspect, wherein the alcohol is ethanol, the production method of the ITO powder is methanol or propanol.
Further, an eighth aspect of the present invention is to produce a dispersion by dispersing the ITO powder of the first , third or fifth aspect or the ITO powder produced by the second , fourth or sixth method in a solvent. It is a method to do.
Furthermore, a ninth aspect of the present invention is a method for producing an ITO film from the dispersion liquid according to the eighth aspect.
本発明の第１の観点のＩＴＯ粉末は、０．９８ＭＰａ（１０ｋｇｆ／ｃｍ２）の圧力を加えたときのＩＴＯ粉末の圧粉体の体積抵抗率が０．５０Ωｃｍ以下であり、圧粉体に０．１９６〜２９．４２ＭＰａ（２〜３００ｋｇｆ／ｃｍ２）の圧力を加えたときの前記圧粉体の体積抵抗率をＹとし前記圧力をＸとする場合に、上記式（１）に近似し、式（１）におけるａが５．００以下であってｎが−０．５００以下であるため、このＩＴＯ粉末を用いて塗布型でＩＴＯ膜を成膜したときの抵抗率を低くして高い導電性を得ることができる。 The ITO powder of the first aspect of the present invention has a volume resistivity of 0.50 Ωcm or less when a pressure of 0.98 MPa (10 kgf / cm 2 ) is applied, When the volume resistivity of the green compact when applying a pressure of 0.196 to 29.42 MPa ( 2 to 300 kgf / cm 2 ) is Y and the pressure is X, it approximates the above equation (1). In the formula (1), a is 5.00 or less and n is −0.500 or less. Therefore, the resistivity when the ITO film is formed in a coating type using this ITO powder is lowered and increased. Conductivity can be obtained.
また本発明の第２の観点のＩＴＯ粉末の製造方法では、洗浄工程で、上澄み液の抵抗率が少なくとも５０００Ω・ｃｍになるまで洗浄し、スラリーの調製工程で、水酸化物粒子の濃度が１０〜３０質量％の範囲になるように上澄み液を捨てたスラリーを水で希釈した後、有機保護剤を前記スラリーに前記水酸化物粒子１００質量％に対して０．１〜５質量％の範囲で撹拌しながら添加し、焼成工程の後で、焼成したＩＴＯ粉末の凝集体を粉砕し、この粉砕されたＩＴＯ粉末を表面処理液に含浸した後、窒素ガス雰囲気下、２００〜４００℃の範囲で０．５〜５時間加熱する。水酸化物粒子が分解温度の比較的高い有機保護剤で被包されるため、焼成過程でＩＴＯ粒子同士の接触が阻止され粒成長しにくくなる。この有機保護剤は焼成により最終的に熱分解する。これによりＩＴＯ粉末の表面が改質され、このＩＴＯ粉末を用いて塗布型でＩＴＯ膜を成膜したときの抵抗率を低くして高い導電性を得ることができる。 In the method for producing ITO powder according to the second aspect of the present invention, the washing process is performed until the supernatant has a resistivity of at least 5000 Ω · cm, and the concentration of hydroxide particles is 10 in the slurry preparation process. After diluting the slurry in which the supernatant was discarded so as to be in the range of ˜30 mass% with water, the organic protective agent was added to the slurry in the range of 0.1 to 5 mass% with respect to 100 mass% of the hydroxide particles. After the firing step, the aggregate of the fired ITO powder is pulverized, and the pulverized ITO powder is impregnated in the surface treatment liquid, and then in the range of 200 to 400 ° C. in a nitrogen gas atmosphere. For 0.5 to 5 hours. Since the hydroxide particles are encapsulated with an organic protective agent having a relatively high decomposition temperature, the ITO particles are prevented from coming into contact with each other during the baking process, and the grain growth becomes difficult. This organic protective agent is finally thermally decomposed by firing. As a result, the surface of the ITO powder is modified, and a high conductivity can be obtained by lowering the resistivity when an ITO film is formed by a coating type using the ITO powder.
また本発明の第４の観点のＩＴＯ粉末の製造方法では、洗浄工程で、上澄み液の抵抗率が少なくとも５０００Ω・ｃｍになるまで洗浄し、スラリーの調製工程で、水酸化物粒子の濃度が１０〜３０質量％の範囲になるように上澄み液を捨てたスラリーを水で希釈した後、有機保護剤を前記スラリーに前記水酸化物粒子１００質量％に対して０．１〜５質量％の範囲で撹拌しながら添加し、乾燥工程で、有機保護剤を添加したインジウム錫水酸化物が分散したスラリーを乾燥し、焼成工程で、大気中で２．４５ＧＨｚ〜２８ＧＨｚのマイクロ波で加熱焼成し、焼成工程の後で、焼成したＩＴＯ粉末の凝集体を粉砕し、この粉砕されたＩＴＯ粉末を表面処理液に含浸した後、窒素ガス雰囲気下、２００〜４００℃の範囲で０．５〜５時間加熱する。水酸化物粒子が分解温度の比較的高い有機保護剤で被包されるため、焼成過程でＩＴＯ粒子同士の接触が阻止され粒成長しにくくなる。この有機保護剤は焼成により最終的に熱分解する。これによりＩＴＯ粉末の表面が改質され、このＩＴＯ粉末を用いて塗布型でＩＴＯ膜を成膜したときの抵抗率を低くして高い導電性を得ることができる。 Moreover, in the manufacturing method of the ITO powder of the 4th viewpoint of this invention, it wash | cleans until the resistivity of a supernatant liquid will be at least 5000 ohm * cm at a washing | cleaning process, and the density | concentration of hydroxide particle | grains is 10 at the slurry preparation process. After diluting the slurry in which the supernatant was discarded so as to be in the range of ˜30 mass% with water, the organic protective agent was added to the slurry in the range of 0.1 to 5 mass% with respect to 100 mass% of the hydroxide particles. In the drying step, the slurry in which the indium tin hydroxide added with the organic protective agent is dispersed is dried in the drying step. In the firing step, the slurry is heated and fired in the atmosphere with a microwave of 2.45 GHz to 28 GHz. After the firing step, the aggregate of the fired ITO powder is pulverized, and the pulverized ITO powder is impregnated with the surface treatment liquid, and then, in a nitrogen gas atmosphere, in the range of 200 to 400 ° C. for 0.5 to 5 hours. To heatSince the hydroxide particles are encapsulated with an organic protective agent having a relatively high decomposition temperature, the ITO particles are prevented from coming into contact with each other during the baking process, and the grain growth becomes difficult. This organic protective agent is finally thermally decomposed by firing. As a result, the surface of the ITO powder is modified, and a high conductivity can be obtained by lowering the resistivity when an ITO film is formed by a coating type using the ITO powder.
更に本発明の第６の観点のＩＴＯ粉末の製造方法では、洗浄工程で、上澄み液の抵抗率が少なくとも５０００Ω・ｃｍになるまで洗浄し、スラリーの調製工程で、水酸化物粒子の濃度が１〜５質量％の範囲になるように上澄み液を捨てたスラリーをアルコールで希釈した後、有機保護剤を前記スラリーに水酸化物粒子１００質量％に対して０．１〜５質量％の範囲で撹拌しながら添加し、前記焼成工程で、アルコールで希釈され有機保護剤を添加したインジウム錫水酸化物粒子が分散したスラリーを２５０〜８００℃の範囲に加熱した管状炉の内部に、窒素ガスを線速度０．５〜５ｍ／ｓの範囲で流通させている状態で、噴霧することによりインジウム錫水酸化物粒子を管状炉内で熱分解して焼成しインジウム錫酸化物粒子を得る。水酸化物粒子が分解温度の比較的高い有機保護剤で被包されるため、焼成過程でＩＴＯ粒子同士の接触が阻止され粒成長しにくくなる。この有機保護剤は焼成により最終的に熱分解する。これによりＩＴＯ粉末の表面が改質され、このＩＴＯ粉末を用いて塗布型でＩＴＯ膜を成膜したときの抵抗率を低くして高い導電性を得ることができる。 Furthermore, in the method for producing ITO powder according to the sixth aspect of the present invention, in the washing step, the supernatant is washed until the resistivity becomes at least 5000 Ω · cm, and in the slurry preparation step, the hydroxide particle concentration is 1 After diluting the slurry in which the supernatant was discarded so as to be in the range of ˜5 mass% with alcohol, the organic protective agent was added to the slurry in the range of 0.1 to 5 mass% with respect to 100 mass% of the hydroxide particles. Nitrogen gas was added to the inside of the tubular furnace heated to a temperature of 250 to 800 ° C., in which the slurry in which indium tin hydroxide particles diluted with alcohol and added with an organic protective agent were dispersed in the firing step was added while stirring. Indium tin hydroxide particles are thermally decomposed and fired in a tubular furnace by spraying in a state where the linear velocity is in the range of 0.5 to 5 m / s to obtain indium tin oxide particles. Since the hydroxide particles are encapsulated with an organic protective agent having a relatively high decomposition temperature, the ITO particles are prevented from coming into contact with each other during the baking process, and the grain growth becomes difficult. This organic protective agent is finally thermally decomposed by firing. As a result, the surface of the ITO powder is modified, and a high conductivity can be obtained by lowering the resistivity when an ITO film is formed by a coating type using the ITO powder.
次に本発明を実施するための形態を説明する。
ＩＴＯ粉末の抵抗率は、このＩＴＯ粉末から作られるＩＴＯ膜の特性を評価するうえで重要な指標である。特にＩＴＯ膜を導電性シートや電極として使用する場合には、高い導電性、即ち低い抵抗率が求められる。このＩＴＯ粉末の抵抗率は、ＩＴＯ粉末を圧粉体の形態にしたうえで、その体積抵抗率を測定することにより求められる。一方、圧粉体の体積抵抗率は印加する圧力によって変化する。従って、ある決められた圧力における圧粉体の体積抵抗率は一応の目安にはなるけれども、ＩＴＯ粉末の形状、比表面積によっては、低い圧力から高い圧力に変化させた状態で、体積抵抗率を求めて、それをＩＴＯ粉末の抵抗率とすれば、より精度良いＩＴＯ粉末の抵抗率が求められる。本発明はこうした知見に基づいてなされたものである。
Next, the form for implementing this invention is demonstrated.
The resistivity of the ITO powder is an important index for evaluating the characteristics of the ITO film made from the ITO powder. In particular, when an ITO film is used as a conductive sheet or electrode, high conductivity, that is, low resistivity is required. The resistivity of the ITO powder can be obtained by measuring the volume resistivity after making the ITO powder into a green compact. On the other hand, the volume resistivity of the green compact varies depending on the applied pressure. Therefore, although the volume resistivity of the green compact at a certain pressure is a tentative measure, depending on the shape and specific surface area of the ITO powder, the volume resistivity can be changed with the pressure changed from a low pressure to a high pressure. If it is obtained and used as the resistivity of the ITO powder, a more accurate resistivity of the ITO powder is obtained. The present invention has been made based on these findings.
本発明のＩＴＯ粉末は、表面改質したＩＴＯ粉末であって、このＩＴＯ粉末からなる圧粉体に０．９８ＭＰａ（１０ｋｇｆ／ｃｍ2）の圧力を加えたときの圧粉体の体積抵抗率が０．５０Ωｃｍ以下であり、圧粉体に０．１９６〜２９．４２ＭＰａ（２〜３００ｋｇｆ／ｃｍ2）の圧力を加えたときの圧粉体の体積抵抗率をＹとし圧力をＸとする場合、圧力と体積抵抗率の関係が、最小二乗法により、下記の式（１）で近似される。ここで式（１）のａは５．００以下であり、かつｎは−０．５００以下である。
Ｙ＝ａＸn （１）
The ITO powder of the present invention is a surface-modified ITO powder, and the volume resistivity of the green compact when a pressure of 0.98 MPa (10 kgf / cm 2 ) is applied to the green compact made of this ITO powder. When the volume resistivity of the green compact is Y and the pressure is X when a pressure of 0.196 to 29.42 MPa ( 2 to 300 kgf / cm 2 ) is applied to the green compact. The relationship between pressure and volume resistivity is approximated by the following equation (1) by the least square method . Here, a in the formula (1) is 5.00 or less, and n is −0.500 or less.
Y = aX n (1)
この式は、表面改質した体積抵抗率が低いＩＴＯ粉末を圧粉体の状態で測定した結果に基づいて、導き出したものである。上記ａが５．００が超えたり、ｎが−０．５００を超えたりすると、粉末への印加圧力を大きく、つまり、粒子同士の接触を強くしても、導電性が向上しにくい傾向があって不具合がある。 This formula is derived based on the result of measuring the surface-modified ITO powder having a low volume resistivity in a green compact state. When the above a exceeds 5.00 or n exceeds −0.500, there is a tendency that even if the pressure applied to the powder is increased, that is, the contact between particles is increased, the conductivity is difficult to improve. There is a problem.
本発明のＩＴＯ膜の製造に用いられるＩＴＯ粉末は、以下の３つの方法で製造された表面改質処理したＩＴＯ粉末である。表面改質処理することによってこのＩＴＯ粉末を用いて製造されたＩＴＯ膜の導電性を上げることができる。 The ITO powder used for the production of the ITO film of the present invention is a surface-modified ITO powder produced by the following three methods. By conducting the surface modification treatment, the conductivity of the ITO film produced using this ITO powder can be increased.
（１）第１の製造方法
ＩＴＯ粉末は、３価インジウム化合物と２価錫化合物の混合水溶液にアルカリ水溶液を混合して、インジウムと錫の共沈水酸化物を生成し、この沈澱を乾燥し、焼成した後、得られたインジウム錫酸化物を粉砕することにより得られる。３価インジウム化合物としては３塩化インジウム（ＩｎＣｌ３）、硝酸インジウム(Ｉｎ(ＮＯ３)３)、酢酸インジウム(Ｉｎ(ＣＨ３ＣＯＯ)３)などが挙げられ、２価錫化合物としては、２塩化錫（ＳｎＣｌ２・２Ｈ２Ｏ）、硫酸錫(ＳｎＳＯ4)、臭化スズ(ＳｎＢｒ２)などが挙げられる。アルカリ水溶液としてはアンモニア（ＮＨ３）水、炭酸水素アンモニウム（ＮＨ４ＨＣＯ３）水などが挙げられる。インジウムと錫の水酸化物を共沈させるときの反応液の最終ｐＨを３．５〜９．３、好ましくはｐＨ５．０〜８．０、液温を５℃以上、好ましくは液温１０℃〜８０℃に調整することによって、インジウム錫の共沈水酸化物を沈澱させることができる。アルカリ水溶液の混合は、上記混合水溶液にアルカリ水溶液を滴下し、上記ｐＨ範囲に調整しながら行われるか、或いは上記混合水溶液とアルカリ水溶液とを同時に水に滴下し、上記ｐＨ範囲に調整しながら行われる。
(1) 1st manufacturing method ITO powder mixes alkaline aqueous solution with the mixed aqueous solution of a trivalent indium compound and a bivalent tin compound, produces | generates the coprecipitated hydroxide of indium and tin, and dries this precipitate, After firing, the obtained indium tin oxide is obtained by pulverization. Examples of the trivalent indium compound include indium trichloride (InCl 3 ), indium nitrate (In (NO 3 ) 3 ), indium acetate (In (CH 3 COO) 3 ), and the divalent tin compound includes dichloride. Examples thereof include tin (SnCl 2 .2H 2 O), tin sulfate (SnSO 4 ), tin bromide (SnBr 2 ), and the like. Examples of the alkaline aqueous solution include ammonia (NH 3 ) water and ammonium hydrogen carbonate (NH 4 HCO 3 ) water. The final pH of the reaction solution when coprecipitating indium and tin hydroxide is 3.5 to 9.3, preferably pH 5.0 to 8.0, and the solution temperature is 5 ° C. or more, preferably 10 ° C. By adjusting to ˜80 ° C., a coprecipitated hydroxide of indium tin can be precipitated. The mixing of the alkaline aqueous solution is performed while dropping the alkaline aqueous solution into the mixed aqueous solution and adjusting it to the pH range, or simultaneously dropping the mixed aqueous solution and the alkaline aqueous solution into water and adjusting the pH range. Is called.
上記共沈インジウム錫水酸化物の生成後、この沈殿物を純水又はイオン交換水で洗浄し、上澄み液の抵抗率が少なくとも５０００Ω・ｃｍ、好ましくは少なくとも５００００Ω・ｃｍになるまで洗浄する。上澄み液の抵抗率が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、高純度のインジウム錫酸化物粉末を得ることができない。抵抗率が５０００Ω・ｃｍ以上となった上記沈殿物の上澄み液を捨て、インジウム錫水酸化物粒子が分散した粘度の高いスラリーを得る。水酸化物粒子の濃度が１０〜３０質量％、好ましくは１５〜２５質量％の範囲になるようにこのスラリーを純水又はイオン交換水で希釈した後、水酸化物粒子表面に吸着してこの粒子の分散性を向上させるための有機保護剤をスラリーに撹拌しながら添加する。上記希釈範囲が下限値未満ではスラリーの乾燥に時間がかかる不具合があり、上限値を超えるとスラリーの粘度が高い状態で有機保護剤を混合することになり有機保護剤の混合が不十分になる不具合がある。この有機保護剤の添加量は、水酸化物粒子１００質量％に対して０．１〜５質量％の範囲である。この有機保護剤は、熱分解後のＩＴＯ粉末の焼結を抑制する観点から、有機保護剤の分解温度が２５０〜５００℃の範囲にあることが好ましい。この有機保護剤としては、パルミチルジメチルエチルアンモニウムエチルサルフェート、ポリビニルアルコール又はオクチルジメチルエチルアンモニウムエチルサルフェートなどが挙げられる。有機保護剤の添加量が上記範囲の下限値未満では水酸化物粒子表面の保護が十分に行われず、粒子の分散性に劣る。また上限値を超えると、有機物の一部や有機物由来の炭素分が残留する不具合を生じる。 After the coprecipitated indium tin hydroxide is formed, the precipitate is washed with pure water or ion-exchanged water and washed until the supernatant has a resistivity of at least 5000 Ω · cm, preferably at least 50000 Ω · cm. If the resistivity of the supernatant liquid is lower than 5000 Ω · cm, impurities such as chlorine are not sufficiently removed, and high-purity indium tin oxide powder cannot be obtained. The supernatant liquid of the precipitate having a resistivity of 5000 Ω · cm or more is discarded to obtain a highly viscous slurry in which indium tin hydroxide particles are dispersed. The slurry is diluted with pure water or ion-exchanged water so that the concentration of hydroxide particles is in the range of 10 to 30% by mass, preferably 15 to 25% by mass, and then adsorbed on the surface of the hydroxide particles. An organic protective agent for improving the dispersibility of the particles is added to the slurry with stirring. When the dilution range is less than the lower limit, there is a problem that it takes time to dry the slurry. When the upper limit is exceeded, the organic protective agent is mixed with the slurry having a high viscosity, and the organic protective agent is not sufficiently mixed. There is a bug. The addition amount of the organic protective agent is in the range of 0.1 to 5% by mass with respect to 100% by mass of the hydroxide particles. The organic protective agent preferably has a decomposition temperature in the range of 250 to 500 ° C. from the viewpoint of suppressing sintering of the ITO powder after thermal decomposition. Examples of the organic protective agent include palmityl dimethyl ethyl ammonium ethyl sulfate, polyvinyl alcohol, octyl dimethyl ethyl ammonium ethyl sulfate, and the like. If the addition amount of the organic protective agent is less than the lower limit of the above range, the surface of the hydroxide particles is not sufficiently protected and the dispersibility of the particles is poor. On the other hand, when the upper limit value is exceeded, there is a problem that a part of the organic matter or carbon derived from the organic matter remains.
有機保護剤が表面に吸着したインジウム錫水酸化物を、大気中、好ましくは窒素やアルゴンなどの不活性ガス雰囲気下、１００〜２００℃の範囲で２〜２４時間乾燥した後、大気中２５０〜８００℃の範囲で０．５〜６時間焼成炉にて焼成する。この焼成により形成された凝集体をハンマーミルやボールミルなどを用いて粉砕してほぐし、ＩＴＯ粉末を得る。このＩＴＯ粉末を５０〜９５質量％の無水エタノールと５〜５０質量％の蒸留水を混合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、２００〜４００℃の範囲で０．５〜５時間加熱すると、表面改質処理したＩＴＯ粉末が得られる。 The indium tin hydroxide adsorbed on the surface of the organic protective agent is dried in the atmosphere, preferably in the range of 100 to 200 ° C. in an inert gas atmosphere such as nitrogen or argon, for 2 to 24 hours, and then in the atmosphere 250 to Baking in a baking furnace at 800 ° C. for 0.5 to 6 hours. Aggregates formed by this firing are pulverized using a hammer mill, ball mill, or the like, and ITO powder is obtained. The ITO powder was impregnated with a surface treatment liquid in which 50 to 95% by mass of absolute ethanol and 5 to 50% by mass of distilled water were mixed, and then placed in a glass petri dish under a nitrogen gas atmosphere at 200 to 400 ° C. When heated in the range for 0.5 to 5 hours, ITO powder subjected to surface modification treatment is obtained.
（２）第２の製造方法
第１の製造方法とはスラリーの固液分離方法と加熱焼成方法が異なる。先ず、第１の製造方法で得られた有機保護剤を添加したインジウム錫水酸化物が分散したスラリーを乾燥する。この乾燥方法の一例として、スラリーを加圧ポンプでフィルタープレス内に圧入して水酸化物のスラッジケーキを得、このケーキを乾燥する。次いで乾燥物を、大気中で２．４５ＧＨｚ〜２８ＧＨｚのマイクロ波で加熱焼成する。このマイクロ波加熱処理は、例えば上記ケーキをシーエムシー技術開発株式会社製の電子レンジに充填し、四国計測工業製のμ−reactorの２．４５ＧＨｚのマイクロ波加熱処理を用いて行う。
(2) Second production method The first production method is different from the solid-liquid separation method of the slurry and the heating and firing method. First, the slurry in which the indium tin hydroxide added with the organic protective agent obtained by the first production method is dispersed is dried. As an example of this drying method, the slurry is pressed into a filter press with a pressure pump to obtain a hydroxide sludge cake, and the cake is dried. Next, the dried product is heated and fired in the atmosphere with microwaves of 2.45 GHz to 28 GHz. This microwave heat treatment is performed by, for example, filling the cake in a microwave oven manufactured by CMC Technology Development Co., Ltd. and using a 2.45 GHz microwave heat treatment of μ-reactor manufactured by Shikoku Keiki Kogyo.
マイクロ波加熱は２５０〜８００℃、好ましくは３５０〜６００℃の範囲で、１０分以内で目的温度に達する速度で昇温して行われ、焼成は目的温度で５〜１２０分、好ましくは１０〜６０分の範囲保持することにより行われる。加熱温度が下限値未満では水酸化物が酸化物に分解し切らない不具合があり、上限値を超えるとＩＴＯ粒子が粗大化する不具合がある。目的温度までの昇温時間が１０分を超えると急速昇温の効果が消える不具合がある。目的温度での保持時間が下限値未満では水酸化物が酸化物に分解し切らない不具合があり、上限値を超えるとＩＴＯ粒子が粗大化する不具合がある。焼成物をハンマーミルやボールミルなどを用いて粉砕してほぐし、ＩＴＯ粉末を得る。以下、第１の製造方法と同様にして、表面改質処理したＩＴＯ粉末を得る。 Microwave heating is performed at a temperature that reaches a target temperature within 10 minutes in a range of 250 to 800 ° C., preferably 350 to 600 ° C., and firing is performed at a target temperature for 5 to 120 minutes, preferably 10 to 10 minutes. This is done by holding the range for 60 minutes. If the heating temperature is less than the lower limit, there is a problem that the hydroxide is not decomposed into oxides, and if it exceeds the upper limit, there is a problem that the ITO particles become coarse. If the temperature rise time to the target temperature exceeds 10 minutes, there is a problem that the effect of rapid temperature rise disappears. If the holding time at the target temperature is less than the lower limit, there is a problem that the hydroxide is not completely decomposed into an oxide, and if the upper limit is exceeded, there is a problem that the ITO particles become coarse. The fired product is pulverized using a hammer mill, ball mill, or the like to obtain ITO powder. Thereafter, an ITO powder subjected to surface modification treatment is obtained in the same manner as in the first production method.
（３）第３の製造方法
第１及び第２の製造方法とはインジウム錫水酸化物を焼成した後にインジウム錫酸化物の粉砕を要しない点で異なる。
第１の製造方法で得られたインジウム錫水酸化物粒子が分散した粘度の高いスラリーを水酸化物粒子の濃度が１〜５質量％、好ましくは１〜３質量％の範囲になるようにアルコールで希釈し、水酸化物粒子表面に吸着してこの粒子の分散性を向上させるための有機保護剤をスラリーに撹拌しながら添加する。この有機保護剤の添加量は、水酸化物粒子１００質量％に対して０．１〜５質量％の範囲である。上記希釈範囲及び上記有機保護剤の添加量範囲の各下限値及び各上限値を規定した理由は、第１の製造方法と同じである。この有機保護剤は、熱分解後のＩＴＯ粉末の焼結を抑制する観点から、有機保護剤の分解温度が２５０〜５００℃の範囲にあることが好ましい。このアルコールとしては、エタノール、プロパノール又はメタノールなどが挙げられ、有機保護剤としては、パルミチルジメチルエチルアンモニウムエチルサルフェート、ポリビニルアルコール又はオクチルジメチルエチルアンモニウムエチルサルフェートなどが挙げられる。
(3) Third Manufacturing Method The third manufacturing method is different from the first and second manufacturing methods in that the indium tin oxide is not pulverized after the indium tin hydroxide is fired.
The high-viscosity slurry in which the indium tin hydroxide particles obtained by the first production method are dispersed is alcohol so that the concentration of hydroxide particles is in the range of 1 to 5% by mass, preferably 1 to 3% by mass. Then, an organic protective agent for improving the dispersibility of the particles by adsorbing on the surface of the hydroxide particles is added to the slurry with stirring. The addition amount of the organic protective agent is in the range of 0.1 to 5% by mass with respect to 100% by mass of the hydroxide particles. The reason why the lower limit value and the upper limit value of the dilution range and the addition amount range of the organic protective agent are specified is the same as in the first production method. The organic protective agent preferably has a decomposition temperature in the range of 250 to 500 ° C. from the viewpoint of suppressing sintering of the ITO powder after thermal decomposition. Examples of the alcohol include ethanol, propanol, and methanol, and examples of the organic protective agent include palmityl dimethyl ethyl ammonium ethyl sulfate, polyvinyl alcohol, octyl dimethyl ethyl ammonium ethyl sulfate, and the like.
アルコールで希釈され有機保護剤を添加したインジウム錫水酸化物粒子が分散したスラリーを、管の長手方向を鉛直にして配置した、２５０〜８００℃の範囲に加熱した管状炉の内部に、キャリアガスである窒素ガスを線速度０．５〜５ｍ／ｓ、好ましくは１〜３ｍ／ｓの範囲で流通させている状態で、二流体ノズルを用いて、噴霧し、窒素ガスとともに管状路内に導入する。線速度が下限値未満ではＩＴＯ粉末の収量が少なくなり、上限値を超えると噴霧されたスラリーが十分に加熱されない。これによりインジウム錫水酸化物粒子が管状炉内で熱分解して焼成され管状炉の排出口より表面改質処理したＩＴＯ粉末が得られる。 A slurry in which indium tin hydroxide particles diluted with alcohol and added with an organic protective agent are dispersed in a tubular furnace heated to a temperature in the range of 250 to 800 ° C. in which the longitudinal direction of the tube is arranged vertically is placed in a carrier gas. In a state where the nitrogen gas is circulated at a linear velocity of 0.5 to 5 m / s, preferably 1 to 3 m / s, it is sprayed using a two-fluid nozzle and introduced into the tubular passage together with the nitrogen gas. To do. If the linear velocity is less than the lower limit value, the yield of ITO powder decreases, and if the linear velocity exceeds the upper limit value, the sprayed slurry is not sufficiently heated. As a result, indium tin hydroxide particles are thermally decomposed and fired in a tubular furnace, and an ITO powder whose surface is modified from the outlet of the tubular furnace is obtained.
次に本発明の実施例を比較例とともに詳しく説明する。 Next, examples of the present invention will be described in detail together with comparative examples.
＜実施例１＞
〔表面改質処理したＩＴＯ粉末の製法〕
Ｉｎ金属濃度が２４質量％の塩化インジウム（ＩｎＣｌ３）水溶液１６３ｇに、二塩化錫粉末（ＳｎＣｌ２・２Ｈ２Ｏ粉末）４ｇを添加混合し、二塩化錫粉末が全て溶けるまで攪拌した後、全量を１０００ｍｌの純水に加え、原料液とした。この原料液に２５質量％のアンモニア（ＮＨ３）水溶液を９０分かけて滴下した。このとき反応温度を８０℃、最終の反応液のｐＨを８．０に調整した。生成したインジウム錫共沈水酸化物である沈殿物をイオン交換水によって繰り返し傾斜洗浄を行った。上澄み液の抵抗率が５０００Ω・ｃｍ以上になったところで、上記沈殿物の上澄み液を捨て、インジウム錫水酸化物粒子が分散した粘度の高いスラリーを得た。
<Example 1>
[Production of surface-modified ITO powder]
After adding 163 g of indium chloride (InCl 3 ) aqueous solution having an In metal concentration of 24% by mass to 4 g of tin dichloride powder (SnCl 2 .2H 2 O powder) and stirring until all the tin dichloride powder is dissolved, the total amount Was added to 1000 ml of pure water to obtain a raw material solution. A 25% by mass aqueous ammonia (NH 3 ) solution was dropped into this raw material solution over 90 minutes. At this time, the reaction temperature was adjusted to 80 ° C., and the pH of the final reaction solution was adjusted to 8.0. The generated precipitate of indium tin coprecipitated hydroxide was repeatedly washed with ion-exchanged water using an inclined exchange. When the resistivity of the supernatant liquid became 5000 Ω · cm or more, the supernatant liquid of the precipitate was discarded, and a highly viscous slurry in which indium tin hydroxide particles were dispersed was obtained.
このスラリーを撹拌しながら、水酸化物粒子の濃度が２０質量％になるようにこのスラリーを純水で希釈した後、有機保護剤であるポリビニルアルコール１．３ｇを添加した。この有機保護剤の添加量は、インジウム錫水酸化物に対して１.０質量％であった。このスラリーを、大気中、１１０℃で１０時間乾燥した後、大気中７００℃で２時間焼成し、凝集体を粉砕してほぐし、ＩＴＯ粉末約７０ｇを得た。このＩＴＯ粉末７０ｇを無水エタノールと蒸留水を混合した表面処理液(混合比率はエタノール９５質量％に対して蒸留水５質量％)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時間加熱して表面改質処理したＩＴＯ粉末を得た。 While stirring the slurry, the slurry was diluted with pure water so that the concentration of hydroxide particles was 20% by mass, and then 1.3 g of polyvinyl alcohol as an organic protective agent was added. The addition amount of this organic protective agent was 1.0 mass% with respect to indium tin hydroxide. The slurry was dried in the atmosphere at 110 ° C. for 10 hours and then calcined in the atmosphere at 700 ° C. for 2 hours. The aggregate was crushed and loosened to obtain about 70 g of ITO powder. After impregnating 70 g of this ITO powder in a surface treatment liquid (mixing ratio of 5% by mass of distilled water with respect to 95% by mass of ethanol) mixed with absolute ethanol and distilled water, it was placed in a glass petri dish and placed under a nitrogen gas atmosphere. The ITO powder which was heated at 330 ° C. for 2 hours and surface-modified was obtained.
〔ＩＴＯ膜の製造〕
この表面改質処理したＩＴＯ粉末２０ｇを、蒸留水（０．０２０ｇ）、トリエチレングリコール−ジ−２−エチルヘキサノエート[３Ｇ]（２３．８ｇ）、無水エタノール（２．１ｇ）、リン酸ポリエステル（１．０ｇ）、２−エチルヘキサン酸（２．０ｇ）、２，４−ペンタンジオン（０．５ｇ）の混合液に入れて分散させた。調製した分散液を無水エタノールで固形分であるＩＴＯ粉末の含有量が１０質量％になるまで希釈した。この希釈した分散液をスピンコーティングにより石英ガラス板に塗布して成膜し、厚さ０．２μｍのＩＴＯ膜を得た。
[Production of ITO film]
20 g of this surface-modified ITO powder was added to distilled water (0.020 g), triethylene glycol-di-2-ethylhexanoate [3G] (23.8 g), absolute ethanol (2.1 g), phosphoric acid The mixture was dispersed in a mixed solution of polyester (1.0 g), 2-ethylhexanoic acid (2.0 g), and 2,4-pentanedione (0.5 g). The prepared dispersion was diluted with absolute ethanol until the content of ITO powder as a solid content was 10% by mass. This diluted dispersion was applied to a quartz glass plate by spin coating to form a film, and an ITO film having a thickness of 0.2 μm was obtained.
＜実施例２＞
Ｉｎ金属濃度が２４質量％の塩化インジウム（ＩｎＣｌ３）水溶液１３５ｇに、二塩化錫粉末（ＳｎＣｌ２・２Ｈ２Ｏ粉末）１６ｇを添加混合し、二塩化錫粉末が全て溶けるまで攪拌した後、全量を１０００ｍｌの純水に加え、原料液とした。この原料液に２５質量％のアンモニア（ＮＨ３）水溶液を９０分かけて滴下した。このとき反応温度を６０℃、最終の反応液のｐＨを５．０に調整した。生成したインジウム錫共沈水酸化物である沈殿物をイオン交換水によって繰り返し傾斜洗浄を行った。上澄み液の抵抗率が５０００Ω・ｃｍ以上になったところで、上記沈殿物の上澄み液を捨て、インジウム錫水酸化物粒子が分散した粘度の高いスラリーを得た。このスラリーを撹拌しながら、水酸化物粒子の濃度が１５質量％になるようにこのスラリーを純水で希釈した後、有機保護剤であるパルミチルジメチルエチルアンモニウムエチルサルフェート（７０質量％）４．５ｇを添加した。この有機保護剤の添加量は、インジウム錫水酸化物に対して３.０質量％であった。
<Example 2>
16 g of tin dichloride powder (SnCl 2 .2H 2 O powder) was added to and mixed with 135 g of an indium chloride (InCl 3 ) aqueous solution having an In metal concentration of 24% by mass and stirred until all of the tin dichloride powder was dissolved. Was added to 1000 ml of pure water to obtain a raw material solution. A 25% by mass aqueous ammonia (NH 3 ) solution was dropped into this raw material solution over 90 minutes. At this time, the reaction temperature was adjusted to 60 ° C., and the pH of the final reaction solution was adjusted to 5.0. The generated precipitate of indium tin coprecipitated hydroxide was repeatedly washed with ion-exchanged water using an inclined exchange. When the resistivity of the supernatant liquid became 5000 Ω · cm or more, the supernatant liquid of the precipitate was discarded, and a highly viscous slurry in which indium tin hydroxide particles were dispersed was obtained. While stirring the slurry, the slurry was diluted with pure water so that the concentration of hydroxide particles was 15% by mass, and then an organic protective agent palmityldimethylethylammonium ethyl sulfate (70% by mass) 4. 5 g was added. The addition amount of this organic protective agent was 3.0 mass% with respect to indium tin hydroxide.
このスラリーを、大気中、１１０℃で１０時間乾燥した後、大気中８００℃で３時間焼成し、凝集体を粉砕してほぐし、ＩＴＯ粉末約７５ｇを得た。このＩＴＯ粉末７５ｇを無水エタノールと蒸留水を混合した表面処理液(混合比率はエタノール９５質量％に対して蒸留水５質量％)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時間加熱して表面改質処理したＩＴＯ粉末を得た。またこのＩＴＯ粉末を用いて、実施例１と同様にしてＩＴＯ膜を作製した。 The slurry was dried at 110 ° C. for 10 hours in the air, and then calcined at 800 ° C. for 3 hours in the air. The aggregate was pulverized and loosened to obtain about 75 g of ITO powder. 75 g of this ITO powder was impregnated in a surface treatment liquid (mixing ratio of 5% by mass of distilled water to 95% by mass of ethanol) mixed with absolute ethanol and distilled water, and then placed in a glass petri dish under a nitrogen gas atmosphere. The ITO powder which was heated at 330 ° C. for 2 hours and surface-modified was obtained. Further, an ITO film was produced in the same manner as in Example 1 using this ITO powder.
＜実施例３＞
Ｉｎ金属濃度が２４質量％の塩化インジウム（ＩｎＣｌ３）水溶液１５４ｇに、二塩化錫粉末（ＳｎＣｌ２・２Ｈ２Ｏ粉末）８ｇを添加混合し、二塩化錫粉末が全て溶けるまで攪拌した後、全量を１０００ｍｌの純水に加え、原料液とした。この原料液に２５質量％のアンモニア（ＮＨ３）水溶液を９０分かけて滴下した。このとき反応温度を２０℃、最終の反応液のｐＨを７．０に調整した。生成したインジウム錫共沈水酸化物である沈殿物をイオン交換水によって繰り返し傾斜洗浄を行った。上澄み液の抵抗率が５０００Ω・ｃｍ以上になったところで、上記沈殿物の上澄み液を捨て、インジウム錫水酸化物粒子が分散した粘度の高いスラリーを得た。このスラリーを撹拌しながら、水酸化物粒子の濃度が１．０質量％になるようにこのスラリーをエタノールで希釈した後、有機保護剤であるオクチルジメチルエチルアンモニウムエチルサルフェート(５０質量％)１０ｇを添加した。この有機保護剤の添加量は、インジウム錫水酸化物に対して５．０質量％であった。
<Example 3>
To 154 g of indium chloride (InCl 3 ) aqueous solution having an In metal concentration of 24% by mass, 8 g of tin dichloride powder (SnCl 2 .2H 2 O powder) was added and mixed, and stirred until all the tin dichloride powder was dissolved. Was added to 1000 ml of pure water to obtain a raw material solution. A 25% by mass aqueous ammonia (NH 3 ) solution was dropped into this raw material solution over 90 minutes. At this time, the reaction temperature was adjusted to 20 ° C., and the pH of the final reaction solution was adjusted to 7.0. The generated precipitate of indium tin coprecipitated hydroxide was repeatedly washed with ion-exchanged water using an inclined exchange. When the resistivity of the supernatant liquid became 5000 Ω · cm or more, the supernatant liquid of the precipitate was discarded, and a highly viscous slurry in which indium tin hydroxide particles were dispersed was obtained. While stirring the slurry, the slurry was diluted with ethanol so that the concentration of hydroxide particles was 1.0% by mass, and then 10 g of octyldimethylethylammonium ethyl sulfate (50% by mass) as an organic protective agent was added. Added. The addition amount of this organic protective agent was 5.0 mass% with respect to indium tin hydroxide.
このスラリーを管の長手方向を鉛直にして配置した、５００℃に加熱した管状炉の内部に、キャリアガスである窒素ガスを線速度１ｍ／ｓの範囲で流通させている状態で、二流体ノズルを用いて、噴霧し、窒素ガスとともに管状路内に導入した。これによりインジウム錫水酸化物粒子が管状炉内で熱分解して焼成され管状炉の排出口より表面改質処理したＩＴＯ粉末を得た。またこのＩＴＯ粉末を用いて、実施例１と同様にしてＩＴＯ膜を作製した。 A two-fluid nozzle in which nitrogen gas as a carrier gas is circulated in a range of a linear velocity of 1 m / s in a tubular furnace heated to 500 ° C. in which the longitudinal direction of the pipe is arranged vertically. Was sprayed and introduced into the tubular channel together with nitrogen gas. As a result, indium tin hydroxide particles were thermally decomposed and fired in a tubular furnace, and ITO powder subjected to surface modification treatment from the outlet of the tubular furnace was obtained. Further, an ITO film was produced in the same manner as in Example 1 using this ITO powder.
＜比較例１＞
Ｉｎ金属濃度が２４質量％の塩化インジウム（ＩｎＣｌ３）水溶液２４５ｇに、濃度５５質量％の四塩化錫（ＳｎＣｌ４）水溶液１１．５ｇを添加混合し、ＩｎＣｌ３−ＳｎＣｌ４混合溶液を調製した。次に、炭酸水素アンモニウム（ＮＨ４ＨＣＯ３）水５００ｇをイオン交換水に溶解し、全量１０００ｍｌで温度７０℃に調製した。この水溶液に上記ＩｎＣｌ３−ＳｎＣｌ４混合溶液の全量を約２０分間攪拌しながら滴下してインジウム錫共沈水酸化物を生成した。更にそのまま３０分間攪拌した。このときの反応液の最終ｐＨは９．０であった。沈澱物であるインジウム錫水酸化物を回収し、遠心分離機で脱水した後、イオン交換水を加えて洗浄しながら遠心濾過を行い、濾液の抵抗率が５０００Ωｃｍ以上に達したところで遠心濾過を終了した。次いでこの沈殿物を１００℃で一晩乾燥した後、６００℃で３時間焼成し、凝集体を粉砕してほぐし、ＩＴＯ粉末７５ｇを得た。
<Comparative Example 1>
To 245 g of an indium chloride (InCl 3 ) aqueous solution having an In metal concentration of 24% by mass, 11.5 g of a tin tetrachloride (SnCl 4 ) aqueous solution having a concentration of 55% by mass was added and mixed to prepare an InCl 3 —SnCl 4 mixed solution. Next, 500 g of ammonium hydrogen carbonate (NH 4 HCO 3 ) water was dissolved in ion-exchanged water, and the total amount was 1000 ml, and the temperature was adjusted to 70 ° C. The total amount of the InCl 3 —SnCl 4 mixed solution was added dropwise to this aqueous solution while stirring for about 20 minutes to produce indium tin coprecipitated hydroxide. The mixture was further stirred for 30 minutes. The final pH of the reaction solution at this time was 9.0. The precipitate, indium tin hydroxide, is collected and dehydrated with a centrifuge, and then subjected to centrifugal filtration while washing with ion-exchanged water. When the resistivity of the filtrate reaches 5000 Ωcm or more, the centrifugal filtration is terminated. did. Next, the precipitate was dried at 100 ° C. overnight and then calcined at 600 ° C. for 3 hours. The aggregate was pulverized and loosened to obtain 75 g of ITO powder.
このＩＴＯ粉末７５ｇを無水エタノールと蒸留水を混合した表面処理液(混合比率はエタノール９５質量％に対して蒸留水５質量％)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３時間加熱して表面改質処理したＩＴＯ粉末を得た。またこのＩＴＯ粉末を用いて、実施例１と同様にしてＩＴＯ膜を作製した。 75 g of this ITO powder was impregnated in a surface treatment liquid (mixing ratio of 5% by mass of distilled water to 95% by mass of ethanol) mixed with absolute ethanol and distilled water, and then placed in a glass petri dish under a nitrogen gas atmosphere. The ITO powder was obtained by heating at 330 ° C. for 3 hours to perform surface modification treatment. Further, an ITO film was produced in the same manner as in Example 1 using this ITO powder.
＜比較試験＞
〔ＩＴＯ粉末の評価〕
実施例１〜３及び比較例１で得られた各ＩＴＯ粉末からなる圧粉体に０．９８ＭＰａ（１０ｋｇｆ／ｃｍ２）の圧力を加えたときのこの圧粉体の体積抵抗率を次の表１に示す。この実施例１〜３及び比較例１で得られた各ＩＴＯ粉末の体積抵抗率は図１に示す測定装置（三菱化学アナリティック製 MCP-PD51）を用いて測定した。具体的には、図１に示す、内径φが２５ｍｍのシリンダー１にＩＴＯ粉末２．００ｇを充填し、０．１９６〜２９．４２ＭＰａ（２〜３００ｋｇｆ／ｃｍ２）の範囲で圧力を変えて、実施例１〜３及び比較例１で得られたＩＴＯ粉末１０点以上の抵抗率と試料厚を同時にそれぞれ測定した。圧力は図示しない圧力センサにより、抵抗率は直流４端子法で測定した。図１において、２はＩＴＯ粉末の圧粉体である。
<Comparison test>
[Evaluation of ITO powder]
The volume resistivity of the green compact when a pressure of 0.98 MPa (10 kgf / cm 2 ) is applied to the green compact made of each ITO powder obtained in Examples 1 to 3 and Comparative Example 1 is shown in the following table. It is shown in 1. The volume resistivity of each ITO powder obtained in Examples 1 to 3 and Comparative Example 1 was measured using a measuring apparatus (MCP-PD51 manufactured by Mitsubishi Chemical Analytic) shown in FIG. Specifically, the
図２に試料粉末に加えた単位面積当りに力に換算した圧力（よこ軸）とＩＴＯ粉末の圧粉体の体積抵抗率（たて軸）との関係を示す。この関係は、最小二乗法により、次の累乗の式（１）に近似する。なお、粉末の体積抵抗率は測定された値に、測定システム付属の補正係数を掛けることで算出される。表１に実施例１〜３及び比較例１で得られた近似式（１）のａ及びｎの値を示す。
Ｙ＝ａＸｎ （１）
実施例１〜３及び比較例１で得られた各ＩＴＯ膜の表面抵抗率（Ω／□）を抵抗率測定装置（三菱油化社製 ＭＣＰ-Ｔ４００）により測定した。その結果を表１に示す。
FIG. 2 shows the relationship between the pressure converted into force per unit area applied to the sample powder (horizontal axis) and the volume resistivity (vertical axis) of the green compact of ITO powder. This relationship is approximated to the following power expression (1) by the method of least squares. The volume resistivity of the powder is calculated by multiplying the measured value by a correction coefficient attached to the measurement system. Table 1 shows the values of a and n in the approximate expression (1) obtained in Examples 1 to 3 and Comparative Example 1.
Y = aX n (1)
The surface resistivity (Ω / □) of each ITO film obtained in Examples 1 to 3 and Comparative Example 1 was measured with a resistivity measuring device (MCP-T400 manufactured by Mitsubishi Yuka Co., Ltd.). The results are shown in Table 1.
＜評価＞
表１から明らかなように、式（１）のａが５．００以下であり、しかもｎが−０．５００以下の実施例１〜３のＩＴＯ粉末からなる圧粉体に０．９８ＭＰａ（１０ｋｇｆ／ｃｍ２）の圧力を加えたときのこの圧粉体の体積抵抗率は０．５００Ωｃｍ以下であった。またこれらのＩＴＯ粉末から作られたＩＴＯ膜の表面抵抗率は１．０×１０６Ω／□以下であった。これに対して式（１）のａが５．００以下であるけれども、ｎが−０．５００を超える比較例１のＩＴＯ粉末からなる圧粉体に０．９８ＭＰａ（１０ｋｇｆ／ｃｍ２）の圧力を加えたときのこの圧粉体の体積抵抗率は０．５Ωｃｍを超えていた。また比較例１のＩＴＯ粉末からＩＴＯ膜の表面抵抗率は１．０×１０６Ω／□を超えていた。以上のことから、式（１）に近似した関係を有する実施例１〜３は塗布型でＩＴＯ膜を成膜したときの抵抗率を低くして高い導電性を得ることが立証された。
<Evaluation>
As is apparent from Table 1, 0.98 MPa (10 kgf) is applied to the green compact made of the ITO powder of Examples 1 to 3 in which a in the formula (1) is 5.00 or less and n is −0.500 or less. The volume resistivity of the green compact when a pressure of / cm 2 ) was applied was 0.500 Ωcm or less. Moreover, the surface resistivity of the ITO film made from these ITO powders was 1.0 × 10 6 Ω / □ or less. On the other hand, a pressure of 0.98 MPa (10 kgf / cm 2 ) is applied to the green compact made of the ITO powder of Comparative Example 1 where a in Formula (1) is 5.00 or less but n exceeds −0.500. The volume resistivity of the green compact when added was over 0.5 Ωcm. Further, the surface resistivity of the ITO film from the ITO powder of Comparative Example 1 exceeded 1.0 × 10 6 Ω / □. From the above, it was proved that Examples 1 to 3 having a relationship approximate to the equation (1) obtain high conductivity by lowering the resistivity when an ITO film is formed by a coating type.
Claims (9)
Ｙ＝ａＸn （１） A mixed aqueous solution of a trivalent indium compound and a divalent tin compound is mixed with an alkaline aqueous solution to form a coprecipitated hydroxide of indium and tin, and the precipitate is purified until the supernatant has a resistivity of at least 5000 Ω · cm. Wash with water or ion-exchanged water, discard the supernatant of the precipitate and prepare a slurry in which indium tin hydroxide particles are dispersed, so that the concentration of the hydroxide particles is in the range of 10 to 30% by mass. The slurry from which the supernatant was discarded was diluted with water, and an organic protective agent, which was palmityldimethylethylammonium ethyl sulfate, polyvinyl alcohol or octyldimethylethylammonium ethyl sulfate, was added to the slurry with respect to 100% by mass of the hydroxide particles. In the case where the organic protective agent is adsorbed on the surface. After the um-tin hydroxide is dried, it is baked in a baking furnace in the range of 250 to 800 ° C. for 0.5 to 6 hours in the atmosphere, and the aggregate of the baked ITO powder is pulverized. Impregnation into a surface treatment liquid in which 50 to 95% by weight of absolute ethanol and 5 to 50% by weight of distilled water are mixed, followed by heating in the range of 200 to 400 ° C. for 0.5 to 5 hours in a nitrogen gas atmosphere. surface modification a quality has been ITO powder, the powder compact volume resistivity when applying a pressure of 0.98MPa to green compact made of the ITO powder is less 0.50Omucm, the dust by When the volume resistivity of the green compact when a pressure of 0.196 to 29.42 MPa is applied to the body is Y and the pressure is X, the relationship between the pressure and the volume resistivity is determined by the least square method. It is approximated by the following equation (1), the formula ( ITO powder wherein a a is 5.00 or less, and n is -0.500 or less in).
Y = aX n (1)
前記洗浄工程で、前記上澄み液の抵抗率が少なくとも５０００Ω・ｃｍになるまで洗浄し、
前記スラリーの調製工程で、前記水酸化物粒子の濃度が１０〜３０質量％の範囲になるように前記上澄み液を捨てたスラリーを水で希釈した後、パルミチルジメチルエチルアンモニウムエチルサルフェート、ポリビニルアルコール又はオクチルジメチルエチルアンモニウムエチルサルフェートである有機保護剤を前記スラリーに前記水酸化物粒子１００質量％に対して０．１〜５質量％の範囲で撹拌しながら添加し、
前記有機保護剤が表面に吸着したインジウム錫水酸化物を乾燥した後、前記焼成工程で、大気中２５０〜８００℃の範囲で０．５〜６時間焼成炉にて焼成し、
前記焼成工程の後で、焼成したＩＴＯ粉末の凝集体を粉砕し、この粉砕されたＩＴＯ粉末を５０〜９５質量％の無水エタノールと５〜５０質量％の蒸留水を混合した表面処理液に含浸した後、窒素ガス雰囲気下、２００〜４００℃の範囲で０．５〜５時間加熱する
ことを特徴とする請求項１記載のＩＴＯ粉末の製造方法。 Mixing an alkaline aqueous solution with a mixed aqueous solution of a trivalent indium compound and a divalent tin compound to produce a coprecipitated hydroxide of indium and tin, washing the precipitate with pure water or ion-exchanged water, Discarding the supernatant of the precipitate to prepare a slurry in which indium tin hydroxide particles are dispersed; drying the slurry; and firing the dried indium tin oxide to form indium tin oxide. A method of producing an ITO powder comprising the steps of:
In the washing step, washing until the supernatant has a resistivity of at least 5000 Ω · cm,
In the slurry preparation step, the slurry in which the supernatant is discarded so that the concentration of the hydroxide particles is in the range of 10 to 30% by mass is diluted with water, and then palmityldimethylethylammonium ethyl sulfate, polyvinyl alcohol Alternatively, an organic protective agent that is octyldimethylethylammonium ethyl sulfate is added to the slurry with stirring in a range of 0.1 to 5% by mass with respect to 100% by mass of the hydroxide particles,
After drying the indium tin hydroxide adsorbed on the surface of the organic protective agent, in the firing step, firing in a firing furnace in the range of 250 to 800 ° C. in the atmosphere for 0.5 to 6 hours,
After the firing step, the aggregate of the fired ITO powder is pulverized, and the pulverized ITO powder is impregnated in a surface treatment liquid in which 50 to 95% by mass of absolute ethanol and 5 to 50% by mass of distilled water are mixed. After that, the ITO powder is heated in the range of 200 to 400 ° C. for 0.5 to 5 hours in a nitrogen gas atmosphere. The method for producing ITO powder according to claim 1.
Ｙ＝ａＸY = aX nn （１）(1)
前記洗浄工程で、前記上澄み液の抵抗率が少なくとも５０００Ω・ｃｍになるまで洗浄し、
前記スラリーの調製工程で、前記水酸化物粒子の濃度が１０〜３０質量％の範囲になるように前記上澄み液を捨てたスラリーを水で希釈した後、パルミチルジメチルエチルアンモニウムエチルサルフェート、ポリビニルアルコール又はオクチルジメチルエチルアンモニウムエチルサルフェートである有機保護剤を前記スラリーに前記水酸化物粒子１００質量％に対して０．１〜５質量％の範囲で撹拌しながら添加し、
前記乾燥工程で、前記有機保護剤を添加したインジウム錫水酸化物が分散したスラリーを乾燥し、
前記焼成工程で、大気中で２．４５ＧＨｚ〜２８ＧＨｚのマイクロ波で２５０〜８００℃の範囲で、１０分以内で目的温度に達する速度で昇温した後、前記目的温度で５〜１２０分の範囲保持することにより加熱焼成し、
前記焼成工程の後で、焼成したＩＴＯ粉末の凝集体を粉砕し、この粉砕されたＩＴＯ粉末を５０〜９５質量％の無水エタノールと５〜５０質量％の蒸留水を混合した表面処理液に含浸した後、窒素ガス雰囲気下、２００〜４００℃の範囲で０．５〜５時間加熱する
ことを特徴とする請求項３記載のＩＴＯ粉末の製造方法。 Mixing an alkaline aqueous solution with a mixed aqueous solution of a trivalent indium compound and a divalent tin compound to produce a coprecipitated hydroxide of indium and tin, washing the precipitate with pure water or ion-exchanged water, Discarding the supernatant of the precipitate to prepare a slurry in which indium tin hydroxide particles are dispersed; drying the slurry; and firing the dried indium tin oxide to form indium tin oxide. A method of producing an ITO powder comprising the steps of:
In the washing step, washing until the supernatant has a resistivity of at least 5000 Ω · cm,
In the slurry preparation step, the slurry in which the supernatant is discarded so that the concentration of the hydroxide particles is in the range of 10 to 30% by mass is diluted with water, and then palmityldimethylethylammonium ethyl sulfate, polyvinyl alcohol Alternatively, an organic protective agent that is octyldimethylethylammonium ethyl sulfate is added to the slurry with stirring in a range of 0.1 to 5% by mass with respect to 100% by mass of the hydroxide particles,
In the drying step, the slurry in which the indium tin hydroxide added with the organic protective agent is dispersed is dried,
In the firing step, the temperature is raised at a rate of reaching the target temperature within 10 minutes in the range of 250 to 800 ° C. with microwaves of 2.45 GHz to 28 GHz in the atmosphere, and then in the range of 5 to 120 minutes at the target temperature. It is heated and fired by holding ,
After the firing step, the aggregate of the fired ITO powder is pulverized, and the pulverized ITO powder is impregnated in a surface treatment liquid in which 50 to 95% by mass of absolute ethanol and 5 to 50% by mass of distilled water are mixed. After that, the ITO powder is heated in the range of 200 to 400 ° C. for 0.5 to 5 hours in a nitrogen gas atmosphere. The method for producing ITO powder according to claim 3 .
Ｙ＝ａＸY = aX nn （１）(1)
前記洗浄工程で、前記上澄み液の抵抗率が少なくとも５０００Ω・ｃｍになるまで洗浄し、
前記スラリーの調製工程で、前記水酸化物粒子の濃度が１〜５質量％の範囲になるように前記上澄み液を捨てたスラリーをアルコールで希釈した後、パルミチルジメチルエチルアンモニウムエチルサルフェート、ポリビニルアルコール又はオクチルジメチルエチルアンモニウムエチルサルフェートである有機保護剤を前記スラリーに前記水酸化物粒子１００質量％に対して０．１〜５質量％の範囲で撹拌しながら添加し、
前記焼成工程で、前記アルコールで希釈され前記有機保護剤を添加したインジウム錫水酸化物粒子が分散したスラリーを２５０〜８００℃の範囲に加熱した管状炉の内部に、窒素ガスを線速度０．５〜５ｍ／ｓの範囲で流通させている状態で、噴霧することによりインジウム錫水酸化物粒子を前記管状炉内で熱分解して焼成しインジウム錫酸化物粒子を得る
ことを特徴とする請求項５記載のＩＴＯ粉末の製造方法。 Mixing an alkaline aqueous solution with a mixed aqueous solution of a trivalent indium compound and a divalent tin compound to produce a coprecipitated hydroxide of indium and tin, washing the precipitate with pure water or ion-exchanged water, ITO containing a step of indium tin hydroxide particles to prepare a dispersion slurry discarded the supernatant of the precipitate, and a step in which the indium aqueous tin oxide to obtain an indium tin oxide by firing the dispersed slurry In a method for producing a powder,
In the washing step, washing until the supernatant has a resistivity of at least 5000 Ω · cm,
In the slurry preparation step, the slurry in which the supernatant liquid is discarded so that the concentration of the hydroxide particles is in the range of 1 to 5% by mass is diluted with alcohol, and then palmityldimethylethylammonium ethyl sulfate, polyvinyl alcohol. Alternatively, an organic protective agent that is octyldimethylethylammonium ethyl sulfate is added to the slurry with stirring in a range of 0.1 to 5% by mass with respect to 100% by mass of the hydroxide particles,
Before Symbol Firing step, the linear velocity inside the nitrogen gas tube furnace indium tin hydroxide particles which are diluted in the alcohol was added the organic protective agent is heated dispersed slurry in the range of 250 to 800 ° C. The indium tin hydroxide particles are thermally decomposed and fired in the tubular furnace by spraying in a state of flowing in the range of 0.5 to 5 m / s to obtain indium tin oxide particles. The method for producing ITO powder according to claim 5 .
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012213756A JP5954082B2 (en) | 2012-09-27 | 2012-09-27 | ITO powder and method for producing the same |
| CN201310287607.8A CN103693678B (en) | 2012-09-27 | 2013-07-10 | Ito powder and the manufacture method of manufacture method and dispersion liquid and ito film thereof |
| KR1020130095585A KR101729365B1 (en) | 2012-09-27 | 2013-08-12 | Ito powder and method of producing same |
| TW102129796A TWI568675B (en) | 2012-09-27 | 2013-08-20 | ITO powder and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012213756A JP5954082B2 (en) | 2012-09-27 | 2012-09-27 | ITO powder and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2014065643A JP2014065643A (en) | 2014-04-17 |
| JP5954082B2 true JP5954082B2 (en) | 2016-07-20 |
Family
ID=50355375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012213756A Active JP5954082B2 (en) | 2012-09-27 | 2012-09-27 | ITO powder and method for producing the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5954082B2 (en) |
| KR (1) | KR101729365B1 (en) |
| CN (1) | CN103693678B (en) |
| TW (1) | TWI568675B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108109722A (en) * | 2017-12-14 | 2018-06-01 | 湖南兴威新材料有限公司 | Ito thin film preparation method |
| KR102454200B1 (en) * | 2017-12-14 | 2022-10-14 | 엘티메탈 주식회사 | Manufacturing method of Indium-Tin-Oxide powder and Indium-Tin-Oxide powder using it |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2585032B2 (en) * | 1987-11-30 | 1997-02-26 | 株式会社資生堂 | Detergent composition |
| JP3355733B2 (en) * | 1992-12-28 | 2002-12-09 | 三菱マテリアル株式会社 | Low resistance conductive pigment and method for producing the same |
| ATE330908T1 (en) * | 1998-09-06 | 2006-07-15 | Leibniz Inst Neue Materialien | METHOD FOR PRODUCING SUSPENSIONS AND POWDERS BASED ON INDIUM TIN OXIDE AND THEIR USE |
| JP4389368B2 (en) * | 1999-12-02 | 2009-12-24 | 三菱マテリアル株式会社 | Conductive pigment powder and transparent conductive film made using the same |
| JP2004123523A (en) | 2002-09-11 | 2004-04-22 | Sumitomo Chem Co Ltd | Method for producing indium oxide-tin oxide powder |
| GB0411949D0 (en) * | 2004-05-28 | 2004-06-30 | Ici Plc | Mixed metal oxides |
| KR100787635B1 (en) | 2007-01-22 | 2007-12-21 | 삼성코닝 주식회사 | Indium tin oxide target, method of manufacturing the same and transparent electrode manufactured by using the same |
| EP1967495B1 (en) * | 2007-02-21 | 2012-08-01 | Sumitomo Metal Mining Co., Ltd. | Manufacturing method for antimony-containing tin oxide fine particles for forming solar radiation shielding body, dispersion for forming solar radiation shielding body, solar radiation sheilding body, and solar radiation shielding base material |
| EP2116513B1 (en) * | 2008-05-06 | 2017-07-05 | Evonik Degussa GmbH | Process for preparing a surface modified indium tin oxide agglomerate, the agglomerate obtained by the said process and a coating composition comprising said agglomerate. |
| JP2010059040A (en) * | 2008-08-07 | 2010-03-18 | Idemitsu Kosan Co Ltd | Method for producing microparticle and heat-ray-shielding microparticle obtained thereby |
| JP5726728B2 (en) * | 2009-05-12 | 2015-06-03 | Ｄｏｗａエレクトロニクス株式会社 | ITO powder, ITO paint, and transparent conductive film formed using ITO paint |
| JP2011246305A (en) * | 2010-05-26 | 2011-12-08 | Hiroshima Univ | Method for producing powder by solid phase reaction |
| JP5754580B2 (en) * | 2010-10-26 | 2015-07-29 | 三菱マテリアル電子化成株式会社 | Indium tin oxide powder |
-
2012
- 2012-09-27 JP JP2012213756A patent/JP5954082B2/en active Active
-
2013
- 2013-07-10 CN CN201310287607.8A patent/CN103693678B/en active Active
- 2013-08-12 KR KR1020130095585A patent/KR101729365B1/en active IP Right Grant
- 2013-08-20 TW TW102129796A patent/TWI568675B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103693678B (en) | 2016-10-05 |
| TWI568675B (en) | 2017-02-01 |
| KR101729365B1 (en) | 2017-04-24 |
| TW201422533A (en) | 2014-06-16 |
| KR20140041329A (en) | 2014-04-04 |
| JP2014065643A (en) | 2014-04-17 |
| CN103693678A (en) | 2014-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20130093123A (en) | Indium tin oxide powder, method for producing same, dispersion, paint, and functional thin film | |
| JP2013139589A (en) | Silver fine particles, method for producing the same, and conductive paste, conductive film, and electronic device containing the silver fine particles | |
| JP5924214B2 (en) | ITO powder and method for producing the same | |
| CN109326401B (en) | Preparation process of nano zinc oxide composite powder varistor | |
| JP4617499B2 (en) | ITO powder and manufacturing method thereof, coating material for transparent conductive material, and transparent conductive film | |
| KR100444142B1 (en) | ITO fine powder and method for producing the same | |
| JP5954082B2 (en) | ITO powder and method for producing the same | |
| Wang et al. | A cost-effective co-precipitation method for synthesizing indium tin oxide nanoparticles without chlorine contamination | |
| KR20200038742A (en) | Silver powder manufacturing method | |
| JP2012176859A (en) | Indium tin oxide particle and method for producing the same | |
| TWI568676B (en) | ITO powder and its manufacturing method | |
| KR101157460B1 (en) | Aluminium doped zinc oxide particle and manufacturing method of producing the same using spray pyrolysis | |
| JP5285412B2 (en) | Tin-doped indium oxide particles and method for producing the same | |
| KR102302205B1 (en) | Silver powder manufacturing method | |
| CN105347377A (en) | Preparation method for high-purity flaky alumina | |
| CN101830694B (en) | High-purity stannic oxide electrode ceramic material and preparation method thereof | |
| JP2013256425A (en) | Tin oxide powder for ito sputtering target, method of manufacturing mixed powder of tin oxide and indium oxide for ito sputtering target, and sintered body for ito sputtering target | |
| JP2012216550A (en) | Fluid dispersion for forming transparent conductive film, transparent conductive film and method for manufacturing transparent conductive film | |
| JP5885507B2 (en) | Indium tin oxide powder and method for producing the same | |
| KR101403371B1 (en) | Manufacturing method of metal particle and metal particle using thereof, and conductive paste and shielding electromagnetic wave containing the same | |
| JP2010040397A (en) | Conductive particulate and its manufacturing method | |
| JP2010135227A (en) | Conductive zinc oxide particultes, its dispersion solution, paint, and its manufacturing method | |
| JP2011111351A (en) | Method for producing high conductivity indium tin oxide fine particle | |
| CN116178006A (en) | High-conductivity titanium oxide target and preparation method thereof | |
| JP4629849B2 (en) | Conductive tin oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150324 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20160118 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160126 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160215 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20160517 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160530 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5954082 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |