JP5186090B2 - Conductive tin oxide particles and method for producing the same - Google Patents
Conductive tin oxide particles and method for producing the same Download PDFInfo
- Publication number
- JP5186090B2 JP5186090B2 JP2006164321A JP2006164321A JP5186090B2 JP 5186090 B2 JP5186090 B2 JP 5186090B2 JP 2006164321 A JP2006164321 A JP 2006164321A JP 2006164321 A JP2006164321 A JP 2006164321A JP 5186090 B2 JP5186090 B2 JP 5186090B2
- Authority
- JP
- Japan
- Prior art keywords
- tin oxide
- tin
- xps
- sno
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
- Paints Or Removers (AREA)
Description
本発明は、導電性に優れ、且つアンチモンを含有しない酸化スズ粒子及びその製造方法に関し、詳しくは液晶ディスプレイやプラズマディスプレイの透明帯電防止膜などの機能性フィルムや、塗料・インキ・プラスチック・コーティング剤等へ配合し塗装することで得られる導電性塗膜や、トナーや感光ドラムなどの電荷調整剤などに使用できる酸化スズ粒子及びその製造方法に関する。 The present invention relates to tin oxide particles having excellent conductivity and not containing antimony and a method for producing the same, and more specifically, functional films such as transparent antistatic films for liquid crystal displays and plasma displays, paints, inks, plastics and coating agents. The present invention relates to a tin oxide particle that can be used for a conductive coating film obtained by blending and coating the toner, a charge control agent such as a toner or a photosensitive drum, and a method for producing the same.
液晶ディスプレイやプラズマディスプレイの透明帯電防止膜などで使用されている酸化スズはアンチモンドープ酸化スズ（以下ＡＴＯ）であり、酸化スズ結晶中の一部のＳｎ４＋をＳｂ５＋で置換したものである。ＡＴＯの特徴は、塗膜にしたときの表面抵抗率が低く導電性に優れる、塗膜にしたときの透明性が高い、塗膜にしたときやや黒味を帯びる、アンチモンを含有するなどが挙げられるが、安全性や環境負荷軽減の面から、アンチモンを含有しない導電性材料が望まれており、これまで様々な検討が行われた。 Tin oxide used in transparent antistatic films of liquid crystal displays and plasma displays is antimony-doped tin oxide (hereinafter referred to as ATO), and a part of Sn 4+ in the tin oxide crystal is substituted with Sb 5+ . The characteristics of ATO are low surface resistivity when made into a coating film, excellent conductivity, high transparency when made into a coating film, slightly blackish when made into a coating film, and containing antimony. However, from the viewpoint of safety and reduction of environmental burden, a conductive material not containing antimony is desired, and various studies have been conducted so far.
アンチモンを含有しない導電性酸化スズとしては結晶中に酸素欠陥を導入した酸化スズがあり、製造方法としては（ｉ）第二スズ塩を含有するアルカリ性溶液又は酸性溶液とその中和剤をｐＨ２〜１２となるよう同時に添加し反応させ、そのスラリーを固液分離処理して沈殿物を回収し、乾燥し、その後不活性又は弱還元性雰囲気中、３００〜８００℃で焼成する（特許文献１）などが知られている。 As the conductive tin oxide not containing antimony, there is tin oxide in which oxygen defects are introduced into the crystal. As a manufacturing method, (i) an alkaline solution or acidic solution containing a stannic salt and a neutralizer thereof having a pH of 2 to 2 are used. At the same time, the slurry is added and reacted so that the slurry is subjected to solid-liquid separation treatment to collect a precipitate, dried, and then fired at 300 to 800 ° C. in an inert or weakly reducing atmosphere (Patent Document 1). Etc. are known.
一方、アンチモン以外の元素をドープすることで導電性を付与した酸化スズも知られており、特にリンをドープした酸化スズについては種々の検討がなされている。例えば、（ii）塩化スズ溶液にリンを溶解し、アルカリ水溶液中に添加し沈澱を得、それを洗浄乾燥後、空気中３５０〜７００℃で焼成する方法（特許文献２）や、（iii）リン含有含水酸化スズ沈殿を８００〜１３００℃の温度で焼成し、粉砕して、酸化スズを主成分とし、リンをＰ／Ｓｎ原子比で２．７×１０−２〜１．４×１０−１の割合で含み、比表面積が１０ｍ２／ｇ以上であり、かつ粉体抵抗値が５００Ω・ｃｍ以下である導電性微粉末を製造する方法（特許文献３）などが知られている。 On the other hand, tin oxide imparted with conductivity by doping with an element other than antimony is also known, and in particular, various studies have been made on tin oxide doped with phosphorus. For example, (ii) a method in which phosphorus is dissolved in a tin chloride solution and added to an alkaline aqueous solution to obtain a precipitate, which is washed and dried, and then fired at 350 to 700 ° C. in air (Patent Document 2), (iii) The phosphorus-containing hydrous tin oxide precipitate is calcined at a temperature of 800 to 1300 ° C., pulverized, tin oxide as a main component, and phosphorus in a P / Sn atomic ratio of 2.7 × 10 −2 to 1.4 × 10 −. There is known a method (Patent Document 3) for producing a conductive fine powder having a ratio of 1 , a specific surface area of 10 m 2 / g or more, and a powder resistance value of 500 Ω · cm or less.
導電性材料は塗料中に分散し、ディスプレイパネルなどの被塗物表面に塗布することで、被塗物表面に導電性を付与する。従来使用されているＡＴＯは毒性が懸念されているアンチモンを含有しているため、アンチモンフリーの導電性を有した酸化スズが市場において望まれ種々検討されている。 The conductive material is dispersed in the paint and applied to the surface of the object to be coated such as a display panel, thereby imparting conductivity to the surface of the object to be coated. Conventionally used ATO contains antimony which is feared to be toxic, so antimony-free conductive tin oxide is desired in the market and various studies have been made.
また、従来導電性材料として使用されているＡＴＯは、粉体色が青黒色のためＬａｂ表色系で示されるＬ値が低く、塗料化し塗装した時の全光線透過率が低い。 In addition, ATO, which has been used as a conductive material in the past, has a low L value indicated by the Lab color system because the powder color is blue-black, and has a low total light transmittance when painted and painted.
そこで、アンチモンを含有することなく導電性を有し、粉体色Ｌ値が高く、塗装したときにＡＴＯよりも高い透明性が得られる酸化スズの製造方法を検討した。 Then, the manufacturing method of the tin oxide which has electroconductivity without containing antimony, has high powder color L value, and can obtain transparency higher than ATO when it applied is examined.
従来の方法で得られるアンチモン非含有酸化スズの内、（ｉ）で示される酸素欠陥型酸化スズの製法では粉体色が濃褐色のためＬ値が低く、（ii）及び（iii）で示されるリンドープ型酸化スズの製法ではアンチモンドープよりは緩和されるもののまだ粉体色が青灰色を呈するためＬ値が低くなるという問題があった。 Among the antimony-free tin oxides obtained by conventional methods, the oxygen defect type tin oxide production method shown in (i) has a low L value because the powder color is dark brown, as shown in (ii) and (iii) In the method of manufacturing phosphorus-doped tin oxide, which is relaxed as compared with antimony dope, the powder color still exhibits a blue-gray color, so that the L value is low.
本発明は上記従来法の問題点を解決し、粉体色Ｌ値が高く、塗膜に配合した場合にＡＴＯ並みの表面抵抗率でありながら、高い全光線透過率が得られる、アンチモン非含有の酸化スズ結晶超微粒子を提供するものである。 The present invention solves the above-mentioned problems of the conventional method, has a high powder color L value, and has a high total light transmittance when it is blended in a coating film while having a surface resistivity equivalent to that of ATO. The present invention provides ultrafine particles of tin oxide crystals.
上記課題を解決すべく鋭意検討を行った結果、リンドープ型酸化スズでは十分な導電性が得られるレベルまでリンをドープすると粉体色L値が低下する傾向にあるため、酸素欠陥型酸化スズの酸素欠陥量の最適条件を検討した。その結果、ＸＰＳ（Ｘ線光電子分光分析）で検出される酸素とスズの原子比Ｏ／Ｓｎを１．７５〜１．９５にコントロールすることで、粉体色が向上することを見出した。 As a result of intensive studies to solve the above problems, phosphorus-doped tin oxide tends to lower the powder color L value when phosphorus is doped to a level where sufficient conductivity is obtained. The optimum conditions for the amount of oxygen defects were investigated. As a result, it was found that the powder color was improved by controlling the atomic ratio O / Sn of oxygen and tin detected by XPS (X-ray photoelectron spectroscopy) to 1.75 to 1.95.
酸素欠陥型酸化スズは窒素ガス雰囲気などの非酸化性雰囲気下で焼成することで製造することができるが、このような条件では酸素欠陥量が多すぎて、ＸＰＳで検出される酸素とスズの原子比Ｏ／Ｓｎが１．７５以下となり粉体色L値が低下する。 Oxygen-deficient tin oxide can be produced by firing in a non-oxidizing atmosphere such as a nitrogen gas atmosphere, but under these conditions, the amount of oxygen defects is too large, and oxygen and tin detected by XPS The atomic ratio O / Sn becomes 1.75 or less, and the powder color L value decreases.
そこで、金属酸化物を大気下で焼成し急冷すると酸素欠陥が生成することに着目し、さらに酸素欠陥量を増やすために、酸化スズ表面への酸素の供給を抑制する方法を種々検討した。その結果、酸化スズ表面にリンをコーティングすると窒素が固定化され、ＸＰＳで検出される酸素とスズの原子比Ｏ／Ｓｎを１．７５〜１．９５にコントロールすることができ、粉体色Ｌ値を大幅に向上することができた。 Therefore, focusing on the fact that oxygen defects are generated when metal oxides are fired in the atmosphere and rapidly cooled, various methods for suppressing the supply of oxygen to the surface of tin oxide were studied in order to further increase the amount of oxygen defects. As a result, when phosphorus is coated on the surface of tin oxide, nitrogen is fixed, and the atomic ratio O / Sn of oxygen and tin detected by XPS can be controlled to 1.75 to 1.95. The value could be greatly improved.
リンは表面にコーティングされることが重要であるため、ＸＰＳにより測定される粒子最表面のＰ原子がＸＲＦ（蛍光Ｘ線分析）により測定された粒子全体中のＰ原子より多くなるように最適な製造方法を見出した。また、このときリンの含有量が多すぎると、酸化スズ粒子同士の接触が阻害され導電性が低下することを考慮し、最適なリン含有量が存在することを見出した。 Since it is important that phosphorus is coated on the surface, it is optimal that the number of P atoms on the outermost surface of the particle measured by XPS is larger than the number of P atoms in the entire particle measured by XRF (fluorescence X-ray analysis). A manufacturing method was found. In addition, it has been found that there is an optimal phosphorus content in consideration of the fact that if the phosphorus content is too high, the contact between the tin oxide particles is hindered and the conductivity decreases.
即ち、本発明の酸化スズ結晶超微粒子は粉体色Ｌ値が６５〜９０で体積抵抗率が０．１〜５００Ω・ｃｍである。 That is, the tin oxide crystal ultrafine particles of the present invention have a powder color L value of 65 to 90 and a volume resistivity of 0.1 to 500 Ω · cm.
また、本発明は、一般式ＳｎＯ（２−ｘ）（ただし、０＜ｘ＜１）で表される酸素欠陥型酸化スズよりなり、ＸＰＳ（Ｘ線光電子分光分析）で検出される酸素とスズの原子比Ｏ／Ｓｎが１．７５〜１．９５であり、結晶子径が３〜１５ｎｍである酸化スズ結晶超微粒子である。また、Ｐ原子をＳｎＯ２に換算したＳｎＯ（２−ｘ）に対して０．０１〜０．８質量％含有し、ＸＰＳにより測定された粒子最表面のＰ原子とＸＲＦ（蛍光Ｘ線分析）により測定された粒子全体中のＰ原子の組成比が１より大であり、Ｌａｂ表色系における粉体色Ｌ値が６５〜９０である酸化スズ結晶超微粒子である。 Further, the present invention comprises oxygen-deficient tin oxide represented by the general formula SnO (2-x) (where 0 <x <1), and oxygen and tin detected by XPS (X-ray photoelectron spectroscopy). These are tin oxide crystal ultrafine particles having an atomic ratio O / Sn of 1.75 to 1.95 and a crystallite diameter of 3 to 15 nm. Further, P atoms and XRF (fluorescence X-ray analysis) on the outermost surface of the particles containing 0.01 to 0.8% by mass with respect to SnO 2 (2-x) converted to SnO 2 and measured by XPS. The tin oxide crystal ultrafine particles in which the composition ratio of P atoms in the whole particle measured by the above is greater than 1 and the powder color L value in the Lab color system is 65 to 90.
また、本発明の酸化スズを分散体、塗料組成物またはフィルム組成物として使用する方法に関するものである。 Moreover, it is related with the method of using the tin oxide of this invention as a dispersion, a coating composition, or a film composition.
また、本発明は３０〜５０℃の温水へ、水溶性スズ化合物とその中和剤の水溶液をｐＨ７〜１０を保ちながら滴下し含水酸化スズ沈殿を生成させ、この反応の後にリン化合物を添加し、含水酸化スズ表面に吸着させ、この沈澱を洗浄および乾燥後、大気中４００〜１２００℃の温度で焼成することを特徴とする酸化スズ結晶超微粒子の製造方法に関するものである。 In the present invention, an aqueous solution of a water-soluble tin compound and its neutralizing agent is added dropwise to warm water of 30 to 50 ° C. while maintaining pH 7 to 10 to form a hydrous tin oxide precipitate, and a phosphorus compound is added after this reaction. The present invention relates to a method for producing ultrafine tin oxide crystals characterized by adsorbing on a surface of hydrous tin oxide, washing and drying the precipitate, and firing at 400 to 1200 ° C. in the atmosphere.
本発明の酸化スズ粒子は、毒性を危惧されるアンチモンを含有することなく、ＡＴＯと同等の体積抵抗率、結晶子径を得ることができる。そのため、塗料・インキ・プラスチック・コーティング剤などに配合することで導電性（表面抵抗率）を付与でき、トナーや感光ドラムなどの電荷調整剤などに使用できる。また、アンチモンを結晶中に含まないため、ＡＴＯ特有の黒味がなく、結晶子径がＡＴＯと同等でありながら、同等以上の透明性が得られる。よって、アンチモンフリー導電性材料として使用可能である。 The tin oxide particles of the present invention can obtain a volume resistivity and crystallite size equivalent to those of ATO without containing antimony that is toxic. Therefore, by adding it to paints, inks, plastics, coating agents, etc., conductivity (surface resistivity) can be imparted, and it can be used for charge control agents such as toner and photosensitive drums. Further, since antimony is not included in the crystal, there is no blackness peculiar to ATO, and the crystallite diameter is equivalent to that of ATO, but transparency equal to or higher than that can be obtained. Therefore, it can be used as an antimony-free conductive material.
本発明の酸化スズ結晶超微粒子は、一般式ＳｎＯ（２−ｘ）（ただし、０＜ｘ＜１）で表される酸素欠陥型酸化スズよりなり、ＸＰＳ（Ｘ線光電子分光分析）で検出される酸素とスズの原子比Ｏ／Ｓｎが１．７５〜１．９５であり、結晶子径が３〜１５ｎｍである。また、Ｐ原子をＳｎＯ２に換算したＳｎＯ（２−ｘ）に対して０．０１〜０．８質量％含有し、ＸＰＳにより測定された粒子最表面のＰ原子とＸＲＦ（蛍光Ｘ線分析）により測定された粒子全体中のＰ原子の組成比が１より大である。 The tin oxide crystal ultrafine particles of the present invention are made of oxygen-deficient tin oxide represented by the general formula SnO (2-x) (where 0 <x <1), and are detected by XPS (X-ray photoelectron spectroscopy). The oxygen to tin atomic ratio O / Sn is 1.75 to 1.95, and the crystallite diameter is 3 to 15 nm. Further, P atoms and XRF (fluorescence X-ray analysis) on the outermost surface of the particles containing 0.01 to 0.8% by mass with respect to SnO 2 (2-x) converted to SnO 2 and measured by XPS. The composition ratio of P atoms in the whole particle measured by the above is greater than 1.
このような酸化スズ粒子は結晶子径が小さく、体積抵抗率が低いため、例えば塗料中に配合し、塗膜を作製した場合、樹脂成分１に対しこの酸化スズを１〜8、好ましくは２〜４配合することで、可視光透過率が高く、表面抵抗率が１０4〜１０13Ω／□となる機能性を有している。 Since such tin oxide particles have a small crystallite size and low volume resistivity, for example, when blended in a paint and a coating film is produced, the tin oxide is added to the resin component 1 in an amount of 1 to 8, preferably 2 By adding ~ 4, the visible light transmittance is high, and the surface resistivity is 10 4 to 10 13 Ω / □.
結晶子径が３ｎｍを下回ると塗料中での分散が困難となる傾向にあり、１５ｎｍを超えると高い可視光透過率と低い表面抵抗率の両立が困難となる傾向にある。 If the crystallite diameter is less than 3 nm, dispersion in the paint tends to be difficult, and if it exceeds 15 nm, it is difficult to achieve both high visible light transmittance and low surface resistivity.
本発明の酸化スズ粒子はＳｎＯ（２−ｘ）で表されるが、ＸＰＳで検出される酸素とスズの原子比Ｏ／Ｓｎが１．７５を下回ると一般的に粉体色Ｌ値が６５以下になる傾向にある。また、ＸＰＳで検出される酸素とスズの原子比Ｏ／Ｓｎが１．９５を上回ると一般的に粉体色Ｌ値は高くなる傾向にあるが、酸素欠陥量が十分ではなくなり体積抵抗率が高くなる傾向にある。また、毒性のあるアンチモン以外の元素、例えばリンをドープ剤として使用する方法では、アンチモンドープに比べると粉体色は高くなるものの、粉体色Ｌ値は６５以下になる傾向にある。 The tin oxide particles of the present invention are represented by SnO 2 (2-x). When the oxygen / tin atomic ratio O / Sn detected by XPS is less than 1.75, the powder color L value is generally 65. It tends to be below. Further, when the atomic ratio O / Sn of oxygen and tin detected by XPS exceeds 1.95, the powder color L value generally tends to increase, but the amount of oxygen defects becomes insufficient and the volume resistivity increases. It tends to be higher. Further, in the method using an element other than toxic antimony, such as phosphorus, as a dopant, the powder color L value tends to be 65 or less, although the powder color is higher than that of antimony dope.
粉体色Ｌ値が６５〜９０で体積抵抗率が０．１〜５００Ω・ｃｍの酸化スズ結晶超微粒子を得るためには、ＸＰＳで検出される酸素とスズの原子比Ｏ／Ｓｎが１．７５〜１．９５に調整すると好適である。また、このような酸化スズ結晶超微粒子を得るためには、Ｐ原子をＳｎＯ２に換算したＳｎＯ（２−ｘ）に対して０．０１〜０．８質量％含有し、ＸＰＳにより測定された粒子最表面のＰ原子とＸＲＦにより測定された粒子全体中のＰ原子の組成比が１より大であるものが好適である。 In order to obtain tin oxide crystal ultrafine particles having a powder color L value of 65 to 90 and a volume resistivity of 0.1 to 500 Ω · cm, the atomic ratio O / Sn of oxygen and tin detected by XPS is 1. It is preferable to adjust to 75 to 1.95. In addition, in order to obtain such tin oxide crystal ultrafine particles, 0.01 to 0.8% by mass of P atom was contained with respect to SnO 2 (2-x) converted to SnO 2 and measured by XPS. It is preferable that the composition ratio of P atoms in the whole particle measured by XRF and P atoms on the outermost surface of the particle is larger than 1.
Ｐの含有量はＳｎＯ２に対して０．０１質量％を下回ると酸素欠陥量が十分でなくなり導電性が得られにくい傾向にあり、ＳｎＯ２に対して０．８質量％を超えると酸化スズ粒子の表面を被覆する割合が増すため、塗膜中で酸化スズ粒子同士の接触が妨げられ導電性を低下させる傾向にある。Ｐの含有量はリン化合物の添加量によって調節することができる。 The content of P is in the less likely that the conductive oxygen defect amount is below 0.01 mass% relative to the SnO 2 is not sufficient to obtain a tin oxide with respect to SnO 2 exceeds 0.8 wt% Since the ratio which coat | covers the surface of particle | grains increases, it exists in the tendency for the contact of tin oxide particles to be prevented in a coating film and to reduce electroconductivity. The content of P can be adjusted by adding the phosphorus compound.
このような酸化スズ粒子の製造方法は、スズ化合物溶液と、酸またはアルカリ性水溶液とを混合し、この反応の後にリン化合物を添加し沈殿物を生成し、この沈殿物を洗浄、乾燥、粉砕した後、大気下で焼成し、粉砕することを特徴としている。 In such a method for producing tin oxide particles, a tin compound solution and an acid or alkaline aqueous solution are mixed, and after this reaction, a phosphorus compound is added to form a precipitate, and this precipitate is washed, dried, and pulverized. After that, it is characterized by firing in the atmosphere and pulverization.
以下に限定されないが、本発明において原料として使用されるスズ化合物溶液としては、塩化第二スズ、塩化第一スズ、スズ酸カリウム、スズ酸ナトリウムなどが挙げられる。また、リン化合物としては、オルトリン酸、リン酸ナトリウム、リン酸アンモニウム、亜リン酸などが挙げられ、これらのうちの一種或いは二種以上の化合物を使用することができる。中和剤として使用するアルカリ性水溶液としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウムなどのアルカリ金属の水酸化物、炭酸塩やアンモニアなどが挙げられ、酸性水溶液としては硫酸、塩酸、硝酸などが挙げられる。 Although not limited to the following, examples of the tin compound solution used as a raw material in the present invention include stannic chloride, stannous chloride, potassium stannate, sodium stannate and the like. Examples of the phosphorus compound include orthophosphoric acid, sodium phosphate, ammonium phosphate, phosphorous acid, and the like, and one or more of these compounds can be used. Examples of the alkaline aqueous solution used as the neutralizing agent include hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, carbonates and ammonia, and acidic aqueous solutions include sulfuric acid, hydrochloric acid, Examples include nitric acid.
本発明の酸化スズ粒子の製造方法では、３０〜５０℃、好ましくは３５〜４５℃の温水中にスズ化合物溶液と酸性又はアルカリ性水溶液をｐＨ７〜１０、好ましくはｐＨ７．５〜９．５に保ちながら反応させ、この反応の後にリン化合物を添加し、リン含有含水酸化スズを生成する。温水温度は６０℃を上回る及び／又はｐＨ６を下回ると、リン含有酸化スズ水和物の凝集体が大きく、凝集の度合いも強くなり、個々の酸化スズ粒子表面が非酸化性ガスに晒されないため、酸素欠陥が十分に生成されず、導電性が低下する傾向にあり好適でない。 In the method for producing tin oxide particles of the present invention, the tin compound solution and the acidic or alkaline aqueous solution are kept at a pH of 7 to 10, preferably a pH of 7.5 to 9.5 in warm water of 30 to 50 ° C., preferably 35 to 45 ° C. The phosphorus compound is added after this reaction to produce phosphorus-containing hydrous tin oxide. When the hot water temperature is higher than 60 ° C. and / or lower than pH 6, the aggregates of phosphorus-containing tin oxide hydrate are large and the degree of aggregation is strong, and the surface of individual tin oxide particles is not exposed to non-oxidizing gas. , Oxygen defects are not sufficiently generated, and the conductivity tends to decrease.
上記のリン含有酸化スズ水和物は十分洗浄した後、１００〜２００℃で乾燥し、粉砕した後、大気下４００〜１２００℃で３０分〜６時間焼成し、粉砕するのが好ましい。焼成温度は、４００℃を下回ると所望の導電性が得られにくく、１２００℃を上回ると結晶子径が１５ｎｍを超えて粒子成長してしまうため好適でない。また、焼成時間は３０分以内だと所望の導電性が得られにくく、６時間を超えて焼成することは経済性の点で好ましくない。 The phosphorus-containing tin oxide hydrate is preferably thoroughly washed, dried at 100 to 200 ° C., pulverized, then calcined at 400 to 1200 ° C. for 30 minutes to 6 hours, and pulverized. If the firing temperature is less than 400 ° C., it is difficult to obtain desired conductivity, and if it exceeds 1200 ° C., the crystallite diameter exceeds 15 nm and particle growth is not suitable. Further, if the firing time is within 30 minutes, it is difficult to obtain desired conductivity, and firing for more than 6 hours is not preferable in terms of economy.
このようにして得られる本発明の酸化スズ粒子は、例えば塗料・インキ・プラスチック・コーティング剤等へ配合し塗装することで、これらの組成物に導電性を付与することができる。また、トナーや感光ドラム等の電荷調整剤としても使用することができる。酸化スズの配合比率は任意に変えることができるが、塗料・インキ・プラスチック・トナーや感光ドラム、それぞれの組成物中で本発明の酸化スズの配合量が下限を下回った場合、導電性を有していても、配合比率の低下に伴い効果は小さくなる。配合量が上限を上回ると、導電性を有していても、それぞれの組成物としての特性を損なう。 The tin oxide particles of the present invention thus obtained can be imparted with conductivity to these compositions by, for example, blending and painting in paints, inks, plastics, coating agents and the like. It can also be used as a charge control agent for toner, photosensitive drums and the like. The tin oxide compounding ratio can be changed arbitrarily, but if the tin oxide content of the present invention falls below the lower limit in the paint, ink, plastic, toner, photosensitive drum, or other composition, it has conductivity. Even if it does, an effect becomes small with the fall of a compounding ratio. If the blending amount exceeds the upper limit, the properties as the respective compositions are impaired even if they have electrical conductivity.
本発明の酸化スズ粒子を塗料・インキの用途に用いる場合、酸化スズ粒子の配合比率は樹脂成分１に対して酸化スズ粒子を１〜８配合することが好ましい。本発明の酸化スズを塗料・インキの用途に用いる場合、配合比率は樹脂の使用目的などに応じて任意に変えることができるが、樹脂１あたり、酸化スズ１〜８が望ましい。酸化スズとの配合に使用する樹脂は、アクリルメラミン、常乾アクリル、アクリルウレタン、ポリエステルメラミン、アルキドメラミン、ポリウレタン、ニトロセルロース、フッ素樹脂、塩化ビニル／酢酸ビニル共重合樹脂などが挙げられ、紫外線反応性オリゴマー、紫外線反応性モノマー及び光重合開始剤から少なくともなる紫外線硬化型インキなども挙げられる。 When the tin oxide particles of the present invention are used for paints and inks, it is preferable that the tin oxide particles are mixed at 1 to 8 tin oxide particles with respect to the resin component 1. When the tin oxide of the present invention is used for paints and inks, the blending ratio can be arbitrarily changed according to the purpose of use of the resin, but tin oxides 1 to 8 are desirable per resin. Resins used for blending with tin oxide include acrylic melamine, normally dried acrylic, acrylic urethane, polyester melamine, alkyd melamine, polyurethane, nitrocellulose, fluororesin, vinyl chloride / vinyl acetate copolymer resin, etc. And an ultraviolet curable ink comprising at least a reactive oligomer, an ultraviolet-reactive monomer, and a photopolymerization initiator.
上記樹脂組成物に酸化スズを配合する際には、まず有機溶剤または水に溶解混合し、分散と塗装に適した粘度に調整する。有機溶剤としては、炭化水素系、アルコール系、エーテルアルコール及びエーテル系、エステル及びエステルアルコール系、ケトン系の中から任意に分散性、塗装性に適したものを用いればよい。そして、ペイントコンディショナー、ディスパー、サンドグラインドミルなど使用目的に応じて分散・攪拌に適した装置を用いて本発明の酸化スズを分散する。 When blending tin oxide into the resin composition, first, it is dissolved and mixed in an organic solvent or water, and adjusted to a viscosity suitable for dispersion and coating. As the organic solvent, a hydrocarbon solvent, an alcohol solvent, an ether alcohol and an ether solvent, an ester and an ester alcohol solvent, and a ketone solvent that are arbitrarily suitable for dispersibility and paintability may be used. And the tin oxide of this invention is disperse | distributed using the apparatus suitable for dispersion | distribution and stirring according to the intended purpose, such as a paint conditioner, a disper, and a sand grind mill.
作製した塗料は金属又はプラスチック製の被塗物に、バーコーター、刷毛、エアスプレー、静電塗装、スピナー法、ディッピング法などにより塗装することができる。膜厚は目的により適宜変えることができる。なお、使用する樹脂によっては、１１０〜１８０℃の温度で１０〜４０分間程度乾燥する又は紫外線照射などにより硬化させる必要がある。 The prepared paint can be applied to an object made of metal or plastic by a bar coater, brush, air spray, electrostatic coating, spinner method, dipping method or the like. The film thickness can be appropriately changed depending on the purpose. Depending on the resin used, it is necessary to dry at a temperature of 110 to 180 ° C. for about 10 to 40 minutes or to cure by ultraviolet irradiation or the like.
以下実施例及び比較例に基づいて本発明を説明するが、本発明はかかる実施例のみに限定されたものではない。 EXAMPLES Hereinafter, although this invention is demonstrated based on an Example and a comparative example, this invention is not limited only to this Example.
実施例１
市水１０００ｇを４０℃に加熱し、そこへＳｎＯ２として１００ｇ分のＳｎＣｌ４溶液とアンモニア水溶液をｐＨ７．５〜８．５の範囲を維持しながら定量ポンプにて２０分間で同時に滴下し含水酸化スズの沈殿を生成し、その後ＳｎＯ２に対してＰ原子換算で０．４質量％分のリン（Ｈ３ＰＯ３使用）を添加し、その後ｐＨ２．５に調整後、ろ過、洗浄し、リン添加含水酸化スズを得た。得られたリン添加含水酸化スズは１２０℃で１２時間乾燥し、この乾燥物を流体エネルギーミルで粉砕した。この粉砕物を大気下８００℃で２時間焼成し、この焼成物を流体エネルギーミルで粉砕し酸化スズ粒子を得た。上記の方法で得られた酸化スズ粒子の評価結果を表１に示した。
Example 1
1000 g of city water is heated to 40 ° C., and SnO 2 as SnO 2 and 100 g of SnCl 4 solution and aqueous ammonia solution are simultaneously added dropwise over 20 minutes with a metering pump while maintaining a pH range of 7.5 to 8.5. A tin precipitate is formed, and then 0.4 mass% phosphorus (using H 3 PO 3 ) in terms of P atom is added to SnO 2 , and then adjusted to pH 2.5, filtered, washed, phosphorus Addition hydrous tin oxide was obtained. The obtained phosphorus-added hydrous tin oxide was dried at 120 ° C. for 12 hours, and the dried product was pulverized by a fluid energy mill. The pulverized product was calcined at 800 ° C. for 2 hours in the air, and the calcined product was pulverized with a fluid energy mill to obtain tin oxide particles. The evaluation results of the tin oxide particles obtained by the above method are shown in Table 1.
実施例２
実施例１においてＰの添加量がＳｎＯ２に対して０．２質量％（Ｈ３ＰＯ３使用）であること以外は実施例１と同様にして酸化スズ粒子を得た。上記の方法で得られた酸化スズ粒子の評価結果を表１に示した。
Example 2
Tin oxide particles were obtained in the same manner as in Example 1 except that the amount of P added in Example 1 was 0.2% by mass (using H 3 PO 3 ) with respect to SnO 2 . The evaluation results of the tin oxide particles obtained by the above method are shown in Table 1.
比較例１
実施例１において焼成を窒素雰囲気下８００℃で２時間焼成すること以外は実施例１と同様にして酸化スズ粒子を得た。上記の方法で得られた酸化スズ粒子の評価結果を表１に示した。
Comparative Example 1
In Example 1, tin oxide particles were obtained in the same manner as in Example 1 except that baking was performed at 800 ° C. for 2 hours in a nitrogen atmosphere. The evaluation results of the tin oxide particles obtained by the above method are shown in Table 1.
比較例２
市水１０００ｇを５０℃に加熱し、そこへ３Ｎ塩酸１００ｍｌとＳｎＯ２として４３ｇ分のＳｎＣｌ４溶液及びＳｎＯ２に対してＰ原子換算で１．０質量％分のリン（ＰＣｌ３使用）を溶解した溶液と水酸化ナトリウム水溶液とを、ｐＨ７．０〜７．５の範囲に維持しながら定量ポンプにて２０分間で同時に滴下しリン含有含水酸化スズの沈殿を生成した。その後ｐＨ２．５に調整後、ろ過、洗浄し、リン含有含水酸化スズを得た。得られたリン含有含水酸化スズは１２０℃で１２時間乾燥し、この乾燥物を流体エネルギーミルで粉砕した。この粉砕物を大気下１０００℃で１時間焼成し、この焼成物を流体エネルギーミルで粉砕し酸化スズ粒子を得た。上記の方法で得られた酸化スズ粒子の評価結果を表１に示した。
Comparative Example 2
City water 1000g was heated to 50 ° C., dissolved in 1.0 wt% fraction of phosphorus (PCl 3 used) in the P atom in terms relative to the SnCl 4 solution and SnO 2 of 43g content as 3N hydrochloric acid 100ml and SnO 2 thereto The solution and the aqueous sodium hydroxide solution were simultaneously added dropwise over 20 minutes with a metering pump while maintaining the pH in the range of 7.0 to 7.5 to produce a precipitate of phosphorus-containing tin hydroxide. Thereafter, the pH was adjusted to 2.5, followed by filtration and washing to obtain phosphorus-containing hydrous tin oxide. The obtained phosphorus-containing hydrous tin oxide was dried at 120 ° C. for 12 hours, and the dried product was pulverized by a fluid energy mill. The pulverized product was calcined at 1000 ° C. for 1 hour in the atmosphere, and the calcined product was pulverized with a fluid energy mill to obtain tin oxide particles. The evaluation results of the tin oxide particles obtained by the above method are shown in Table 1.
上記の方法で得られた酸化スズ粒子について、体積抵抗率、結晶子径、粉体色、ＸＰＳ（Ｘ線光電子分光分析）によるＯ／Ｓｎ比、及び、リンのＸＰＳ値／ＸＲＦ値（蛍光Ｘ線分析値）を測定した。各測定の方法については以下に示した。 About the tin oxide particles obtained by the above method, volume resistivity, crystallite diameter, powder color, O / Sn ratio by XPS (X-ray photoelectron spectroscopy), and XPS value / XRF value of phosphorus (fluorescence X Line analysis value) was measured. Each measurement method is shown below.
（１）体積抵抗率の測定
酸化スズ粉末を１００ｋｇ／ｃｍ２の圧力で加圧成形し試料片を作製し、加圧した状態で試料片の上下間の抵抗値を測定し、同時に試験片の厚みを測定した。測定された抵抗値及び試験片の厚さ及び断面積から体積抵抗率を算出した。
(1) Measurement of volume resistivity A tin oxide powder was pressure-molded at a pressure of 100 kg / cm 2 to prepare a sample piece, and the resistance value between the upper and lower sides of the sample piece was measured in a pressurized state. The thickness was measured. The volume resistivity was calculated from the measured resistance value and the thickness and cross-sectional area of the test piece.
（２）結晶子径の測定
酸化スズ粉末をスペクトリス社製Ｘ線回折装置Ｘ‘Ｐｅｒｔ ＰＲＯにより、ＣｕＫα線を使用して印加電圧４５ｋＶ、印加電流４０ｍＡの条件にて、θ−２θ法でＸ線回折分析を行った。次に正方晶系ＳｎＯ２の（１１０）面のピークの半価幅を求め、Ｓｈｅｒｒｅｒの式から結晶子径を求めた。
(2) Measurement of crystallite diameter X-rays of tin oxide powder by the X-ray diffractometer X'Pert PRO manufactured by Spectris Co. Diffraction analysis was performed. Next, the half width of the peak of the (110) plane of tetragonal SnO 2 was determined, and the crystallite diameter was determined from the Serrer equation.
（３）粉体色の測定
酸化スズ粉末を粉体測定セルに入れて５０回タッピングし、日本電色工業社製測色色差計ＺＥ ２０００にて粉体色Ｌ値を測定した。
(3) Measurement of powder color A tin oxide powder was put in a powder measurement cell and tapped 50 times, and a powder color L value was measured with a colorimetric color difference meter ZE 2000 manufactured by Nippon Denshoku Industries Co., Ltd.
（４）Ｏ／Ｓｎの測定
酸化スズ粉末を島津製作所社製Ｘ線光電子分光装置ＥＳＣＡ−３４００にて原子比Ｏ／Ｓｎ測定した。
(4) Measurement of O / Sn The atomic ratio O / Sn of the tin oxide powder was measured with an X-ray photoelectron spectrometer ESCA-3400 manufactured by Shimadzu Corporation.
（５）リンのＸＰＳ量／ＸＲＦ量の測定
酸化スズ中のＰ換算リン全含有量（ＸＲＦ量）は島津製作所社製エネルギー分散型蛍光X線分析装置ＥＤＸ−７００にて測定した。また、島津製作所社製Ｘ線光電子分光装置ＥＳＣＡ−３４００より測定した値を最表面のＰ換算リン含有量（ＸＰＳ量）として測定した。それぞれの測定値より原子比でリンのＸＰＳ量／ＸＲＦ量を算出した。
(5) Measurement of phosphorus XPS amount / XRF amount The total P-converted phosphorus content (XRF amount) in tin oxide was measured with an energy dispersive X-ray fluorescence spectrometer EDX-700 manufactured by Shimadzu Corporation. Moreover, the value measured by Shimadzu Corporation X-ray photoelectron spectrometer ESCA-3400 was measured as P conversion phosphorus content (XPS amount) on the outermost surface. From the respective measured values, the XPS amount / XRF amount of phosphorus was calculated by atomic ratio.
Claims (12)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006164321A JP5186090B2 (en) | 2006-06-14 | 2006-06-14 | Conductive tin oxide particles and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006164321A JP5186090B2 (en) | 2006-06-14 | 2006-06-14 | Conductive tin oxide particles and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007331966A JP2007331966A (en) | 2007-12-27 |
| JP5186090B2 true JP5186090B2 (en) | 2013-04-17 |
Family
ID=38931796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006164321A Expired - Fee Related JP5186090B2 (en) | 2006-06-14 | 2006-06-14 | Conductive tin oxide particles and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5186090B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5158537B2 (en) * | 2007-07-13 | 2013-03-06 | 三菱マテリアル株式会社 | Conductive tin oxide powder, production method and use thereof |
| JP2010123302A (en) * | 2008-11-17 | 2010-06-03 | Mitsubishi Materials Corp | Surface-modified white conductive powder, and method of manufacturing the same |
| DE102010052889A1 (en) | 2010-12-01 | 2012-06-06 | Merck Patent Gmbh | Semiconductive dielectric coatings and articles |
| JP6071360B2 (en) | 2012-09-14 | 2017-02-01 | 三井金属鉱業株式会社 | Conductive particles |
| CN103318951B (en) * | 2013-07-10 | 2015-05-20 | 赵宝勤 | Preparation method of ATO (Antimony doped Tin Oxide) nanopowder |
| JP6453533B2 (en) * | 2013-09-19 | 2019-01-16 | チタン工業株式会社 | Fluorine-doped phosphorus-doped conductive tin oxide powder, process for producing the same, and film composition using the same |
| CN115201241A (en) * | 2022-07-18 | 2022-10-18 | 吉林大学 | SnBi regulated and controlled by high-voltage technology 2 Te 4 Method for detecting Sn atom defect |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0232213B2 (en) * | 1984-06-05 | 1990-07-19 | Mitsubishi Metal Corp | TEIDENKITEIKOSANKASUZUBIFUNMATSUNOSEIZOHO |
| JP3365821B2 (en) * | 1992-06-11 | 2003-01-14 | 石原産業株式会社 | Conductive tin oxide fine powder and method for producing the same |
| JP3456540B2 (en) * | 1993-06-14 | 2003-10-14 | 三井金属鉱業株式会社 | Method for producing conductive ultrafine tin dioxide |
| JP3822284B2 (en) * | 1996-08-02 | 2006-09-13 | 石原産業株式会社 | Conductive tin oxide powder, method for producing the same, conductive suspension composition using the same, conductive coating composition, and antistatic material |
| JP4904575B2 (en) * | 2004-07-23 | 2012-03-28 | 三菱マテリアル株式会社 | Surface-modified transparent conductive tin oxide fine powder, production method thereof and dispersion thereof |
-
2006
- 2006-06-14 JP JP2006164321A patent/JP5186090B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007331966A (en) | 2007-12-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5186090B2 (en) | Conductive tin oxide particles and method for producing the same | |
| WO2012057053A1 (en) | Indium tin oxide powder, method for producing same, dispersion, paint, and functional thin film | |
| EP2510060A1 (en) | Metal effect pigments coated with sio2, method for producing said metal effect pigments and use | |
| CN110402237B (en) | Near-infrared reflection black pigment and preparation method thereof | |
| JP4801617B2 (en) | Conductive zinc oxide particles and method for producing the same | |
| EP3252115B1 (en) | Near-infrared ray absorbing microparticle dispersion solution and production method thereof | |
| JP2004349167A (en) | White conductive powder and its application | |
| Ding et al. | V-doped LaPO4 new solar heat-reflective pigments and its improvement on the aging resistance of poly-methyl methacrylate | |
| US7157024B2 (en) | Metal oxide particle and process for producing same | |
| JP5292809B2 (en) | Ultrafine barium sulfate, aqueous coating composition and aqueous ink composition | |
| JP2006172916A (en) | Conductive tin oxide particle | |
| DE60129524T2 (en) | Electrically conductive oxide particles and process for their preparation | |
| KR101878846B1 (en) | Spherical magnesium hydroxide particles and magnesium oxide particles having a large specific surface area, as well as method for producing same | |
| DE10051872C2 (en) | Electrically conductive pigments and processes for their production | |
| EP0639625B1 (en) | Stabilized conductive pigment | |
| JP2015160759A (en) | Transparent electroconductive compound oxide fine powder, production method thereof, and transparent electroconductive film | |
| DE10148055B4 (en) | Electrically conductive pigment | |
| DE4333673A1 (en) | Substrate-free, conductive pigments | |
| JP5706797B2 (en) | Tin-doped indium oxide particles | |
| JP3976484B2 (en) | Conductive powder organic solvent dispersion and conductive paint | |
| JP5977603B2 (en) | White conductive powder, dispersion thereof, paint, and film | |
| JP4848672B2 (en) | Highly dispersible conductive fine powder and its application | |
| EP2512650A2 (en) | Method for producing encapsulated metal colloids as inorganic pigments | |
| JP2005008515A (en) | Metal oxide particle and its manufacturing method | |
| JP4438925B2 (en) | Modified carbon black particle powder and method for producing the same, paint and resin composition containing the modified carbon black particle powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20081030 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100630 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120207 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120327 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120821 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120907 |
|
| 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: 20130115 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130121 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160125 Year of fee payment: 3 |
|
| LAPS | Cancellation because of no payment of annual fees |