JP5747475B2 - Blue shielding black powder and its production method and use - Google Patents
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本発明は、高い黒色度と青色光に対する優れた遮光性を有し、さらに好ましくは高い絶縁性を有する黒色粉末に関する。 The present invention relates to a black powder having a high blackness and an excellent light shielding property against blue light, and more preferably a high insulating property.
黒色粉末として、カーボンブラック、酸化鉄、低次酸化チタン、酸窒化チタン粉末などが知られている。カーボンブラックは黒色度、着色度とも優れており高い導電性を有しているが、嵩が大きいため取り扱いが難しく、また樹脂との馴染みが良くない。また極微量ではあるが原料起因の発ガン性物質である３，４−ベンズピレンを伴うため、その安全性が問題となっている。 As black powder, carbon black, iron oxide, low-order titanium oxide, titanium oxynitride powder, and the like are known. Carbon black is excellent in both blackness and coloration and has high conductivity, but it is bulky and difficult to handle, and is not well adapted to resin. Moreover, since it is accompanied by 3, 4- benzpyrene which is a carcinogenic substance derived from a raw material although it is a trace amount, the safety | security is a problem.
酸化鉄は磁性による凝集があり、分散性に劣る。耐熱性も低く、大気中１５０℃付近で茶色のγ−Ｆｅ2Ｏ3に酸化される。低次酸化チタンは二酸化チタン粉末をＴｉ粉末または水素ガスによって１０００℃以上の温度で還元して得られる粉末であり、Ｔｉ3Ｏ5およびＴｉ2Ｏ3等の多種の構造を持つ低次酸化チタンの混合物である。低次酸化チタンは高温での還元反応を行うために焼結による粒子成長が著しく、顔料用としては不適な粗大粒子（１.０ミクロン以上）となってしまう。 Iron oxide has agglomeration due to magnetism and is inferior in dispersibility. It has low heat resistance and is oxidized to brown γ-Fe 2 O 3 at about 150 ° C. in the atmosphere. Low-order titanium oxide is obtained by reducing titanium dioxide powder with Ti powder or hydrogen gas at a temperature of 1000 ° C. or higher, and low-order titanium oxide having various structures such as Ti 3 O 5 and Ti 2 O 3. It is a mixture of Since low-order titanium oxide undergoes a reduction reaction at a high temperature, particle growth due to sintering is remarkable, resulting in coarse particles (1.0 microns or more) that are unsuitable for pigments.
特許１７５８３４４号公報に記載されている黒色顔料である酸窒化チタン(チタンブラック)は二酸化チタンをアンモニアによって還元して得られる粉末であり、半導電性を示す青みを帯びた特徴のある黒色を示す黒色顔料粉末である。酸窒化チタンは有害物質を含まないため、飲食品用プラスチックス、化粧品の原料として最適である。また近年、黒色顔料を樹脂に分散させ、フォトリソ法などでパターニングすることによって液晶カラーフィルター等画像形成素子のブラックマトリックス（以下樹脂ＢＭ）に用いられている。酸窒化チタンは高い隠蔽性や高絶縁性等のブラックマトリックス用黒色顔料としての優れた性質を有している。 Titanium oxynitride (titanium black), which is a black pigment described in Japanese Patent No. 1758344, is a powder obtained by reducing titanium dioxide with ammonia and exhibits a bluish characteristic black color indicating semiconductivity. Black pigment powder. Since titanium oxynitride does not contain harmful substances, it is optimal as a raw material for plastics for foods and beverages and cosmetics. In recent years, a black pigment is dispersed in a resin and patterned by a photolithography method or the like, and used for a black matrix (hereinafter, resin BM) of an image forming element such as a liquid crystal color filter. Titanium oxynitride has excellent properties as a black pigment for black matrix, such as high concealability and high insulation.
酸化チタンを還元処理した低次酸化チタンや酸窒素化チタンは青みを有する黒色あるいは青色を有する粉末であり、可視光の低波長側、具体的には４５０ｎｍ付近の青色波長域における遮蔽性が低く、青色光を十分に遮蔽することが出来ないと云う問題があった。 Low-order titanium oxide or titanium oxynitride obtained by reduction treatment of titanium oxide is a bluish black or blue powder, and has low shielding properties on the low wavelength side of visible light, specifically in the blue wavelength region around 450 nm. There was a problem that the blue light could not be sufficiently shielded.
青色光に対する遮蔽性を高めるために、低次酸化チタン粉末や酸窒化チタン粉末にカーボンブラックを混合することも提案されているが、カーボンは導電性があるためにブラックマトリックスとして要求される絶縁性が低下し、またカーボンと混ぜることによって凝集が起こり、均一な色味を出すことが困難になると云う問題を生じる。 In order to improve the shielding against blue light, it is also proposed to mix carbon black with low-order titanium oxide powder or titanium oxynitride powder, but because carbon is conductive, the insulation required as a black matrix In addition, there is a problem that agglomeration occurs when mixed with carbon and it becomes difficult to produce a uniform color.
本発明は、従来用いられているチタン（４Ａ族元素）に代えて、バナジウムおよびニオブ（５族元素）の酸窒化物を検討し、これらの酸窒化物は黒色度が高く、かつ青色光の遮蔽性が従来の酸窒化チタンよりも格段に高いことを見出した。その中でもバナジウム酸窒化物は３００ｎｍから８００ｎｍの広い波長域において優れた遮蔽性を有することを見出した。本発明は上記知見に基づくものであり、高い黒色度と青色光に対する優れた遮光性を有し、さらに好ましくは高い絶縁性を有する黒色粉末を提供する。 The present invention examined oxynitrides of vanadium and niobium (group 5 element) instead of conventionally used titanium (group 4A element). These oxynitrides have high blackness and blue light. It has been found that the shielding properties are much higher than conventional titanium oxynitride. Among them, it was found that vanadium oxynitride has excellent shielding properties in a wide wavelength range of 300 nm to 800 nm. The present invention is based on the above findings, and provides a black powder having high blackness and excellent light shielding properties against blue light, and more preferably having high insulating properties.
本発明によれば、以下の構成からなる青色遮蔽黒色粉末が提供される。
〔１〕酸窒化バナジウムまたは酸窒化ニオブからなる黒色粉末であり、酸窒化バナジウムは酸素含有量１６wt％以下および窒素含有量１０wt％以上であって粉末濃度５０ppmの分散液透過スペクトルにおいて４５０nmの透過率Ｘが１０.０％以下であり、酸窒化ニオブはシリカまたはアルミナがコーティングされていて酸素含有量８.５〜９.３wt％および窒素含有量１０〜１２wt％であって粉末濃度５０ppmの分散液透過スペクトルにおいて４５０nmの透過率Ｘが８.２〜８.４％であることを特徴とする青色遮蔽黒色粉末。
〔２〕酸窒化バナジウムはシリカまたはアルミナがコーティングされていて酸素含有量１２〜１６wt％および窒素含有量１３〜１４wt％であって粉末濃度５０ppmの分散液透過スペクトルにおいて４５０nmの透過率Ｘが８.３〜８.９％である上記[１]に記載する青色遮蔽黒色粉末。
〔３〕４５０nmの透過率Ｘと５５０nmの透過率Ｙの比（Ｘ／Ｙ）が２.０以下であり、および/または４５０nmの透過率Ｘと６５０nmの透過率Ｚの比（Ｘ／Ｚ）が１.５以下である上記[１]または上記[２]に記載する青色遮蔽黒色粉末。
〔４〕黒色度のＬ値が１６.５以下であり、比表面積が１０ｍ２/ｇ以上である上記[１]〜上記[３]の何れかに記載する青色遮蔽黒色粉末。
According to this invention, the blue shielding black powder which consists of the following structures is provided.
[1] Black powder composed of vanadium oxynitride or niobium oxynitride, and vanadium oxynitride having an oxygen content of 16 wt% or less and a nitrogen content of 10 wt% or more and having a transmittance of 450 nm in a dispersion transmission spectrum having a powder concentration of 50 ppm A dispersion in which X is 10.0% or less, niobium oxynitride is coated with silica or alumina, has an oxygen content of 8.5 to 9.3 wt%, a nitrogen content of 10 to 12 wt%, and a powder concentration of 50 ppm A blue-shielding black powder having a transmittance X of 450 nm in the transmission spectrum of 8.2 to 8.4% .
[2] Vanadium oxynitride is coated with silica or alumina, has an oxygen content of 12 to 16 wt%, a nitrogen content of 13 to 14 wt%, and a transmittance X at 450 nm of 8. The blue shielding black powder described in [1] above, which is 3 to 8.9% .
[3] The ratio (X / Y) between the transmittance X at 450 nm and the transmittance Y at 550 nm is 2.0 or less, and / or the ratio between the transmittance X at 450 nm and the transmittance Z at 650 nm (X / Z) The blue shielding black powder as described in [1] or [2] above, wherein is 1.5 or less.
[4] The blue shielding black powder described in any one of [1] to [3] above, wherein the L value of blackness is 16.5 or less and the specific surface area is 10 m 2 / g or more.
本発明によれば、以下の構成からなる青色遮蔽黒色粉末の製造方法および用途が提供される。
〔５〕バナジウムまたはニオブの金属酸化物または金属水酸化物を、バナジウムについては酸素含有量１６wt％以下および窒素含有量１０wt％以上になるように８００℃まで昇温してアンモニアガスを用いて還元処理することによって粉末濃度５０ppmの分散液透過スペクトルにおいて４５０nmの透過率Ｘが１０.０％以下になるようにし、ニオブについてはシリカまたはアルミナをコーティングした後に酸素含有量８.５〜９.３wt％および窒素含有量１０〜１２wt％になるように８００℃まで昇温してアンモニアガスを用いて還元処理することによって粉末濃度５０ppmの分散液透過スペクトルにおいて４５０nmの透過率Ｘが８.２〜８.４％になるようにする青色遮蔽黒色粉末を製造する方法。
〔６〕上記[５]に記載する製造方法において、バナジウムまたはニオブを含む塩化物、硝酸塩、硫酸塩、またはアンモニウム塩を水で溶解し、酸または塩基によって中和処理した後に乾燥した水酸化物原料を用いる青色遮蔽黒色粉末の製造方法。
〔７〕上記[１]〜上記[４]の何れかに記載する青色遮蔽黒色粉末を含有する黒色ペースト、黒色塗料、黒色樹脂フィルム、または黒色被膜。
According to this invention, the manufacturing method and use of blue shielding black powder which consist of the following structures are provided.
[5] The vanadium or niobium metal oxide or metal hydroxide, for vanadium using an oxygen content of 16 wt% or less and a nitrogen content of 10 wt% or more so as to warm to ammonia gas to 800 ° C. reduction By performing the treatment, the transmittance X at 450 nm in the dispersion spectrum with a powder concentration of 50 ppm is reduced to 10.0% or less . For niobium, the oxygen content is 8.5 to 9.3 wt% after coating silica or alumina. Further, by increasing the temperature to 800 ° C. so that the nitrogen content is 10 to 12 wt% and reducing with ammonia gas, the transmittance X at 450 nm in the dispersion liquid transmission spectrum with a powder concentration of 50 ppm is 8.2 to 8. A method for producing a blue shielding black powder to be 4% .
[6] A hydroxide obtained by dissolving a chloride, nitrate, sulfate, or ammonium salt containing vanadium or niobium in water, neutralizing with an acid or a base, and then drying in the production method described in [5] above A method for producing a blue shielding black powder using raw materials.
[7] A black paste, black paint, black resin film, or black film containing the blue shielding black powder described in any one of [1] to [4].
本発明の青色遮蔽黒色粉末は青色光に対する遮蔽性に優れており、酸素含有量１６wt％以下および窒素含有量１０wt％以上であって、粉末濃度５０ppmの分散液透過スペクトルにおいて４５０nmの透過率Ｘが１０.０％以下である。従来の酸窒化チタン(チタンブラック)は窒素含有量が２０wt％で上記透過率Ｘが１０％程度であるが、本発明の黒色粉末は窒素含有量が１０wt％でも上記透過率Ｘが１０％以下の青色光に対する遮蔽性に優れた粉末を得ることができる。 The blue shielding black powder of the present invention is excellent in shielding against blue light, has an oxygen content of 16 wt% or less and a nitrogen content of 10 wt% or more, and has a transmittance X of 450 nm in a dispersion transmission spectrum having a powder concentration of 50 ppm. It is 10.0% or less. Conventional titanium oxynitride (titanium black) has a nitrogen content of 20 wt% and the transmittance X is about 10%. However, the black powder of the present invention has a transmittance X of 10% or less even if the nitrogen content is 10 wt%. It is possible to obtain a powder excellent in shielding property against blue light.
本発明の黒色粉末において、酸素含有量が少なく、かつ窒素含有量が多いものは、さらに遮光性に優れている。具体的には、酸素含有量６.５wt％以下であって窒素含有量１４wt％以上に調整することによって、粉末濃度５０ppmの分散液透過スペクトルにおいて４５０nm〜５５０nmの透過率が７％以下の青色光に対する遮蔽性が格段に優れた粉末を得ることができる。 In the black powder of the present invention, those having a low oxygen content and a high nitrogen content are further excellent in light shielding properties. Specifically, by adjusting the oxygen content to 6.5 wt% or less and the nitrogen content to 14 wt% or more, blue light having a transmittance of 450 nm to 550 nm of 7% or less in a dispersion liquid transmission spectrum having a powder concentration of 50 ppm. Can be obtained.
従来のチタンブラックは、波長域４５０nm〜５５０nmにおける透過率は概ね９％〜１０％であるので、本発明によれば、酸素含有量６.５wt％以下であって窒素含有量１４wt％以上に調整することによって、青色光の透過率がチタンブラックの約２/３以下、好ましくは１/２である青色波長域の遮蔽性が格段に高い黒色粉末を得ることができる。 Conventional titanium black has a transmittance in the wavelength range of 450 nm to 550 nm of approximately 9% to 10%. Therefore, according to the present invention, the oxygen content is adjusted to 6.5 wt% or less and the nitrogen content is adjusted to 14 wt% or more. By doing so, it is possible to obtain a black powder having a remarkably high shielding property in the blue wavelength region, in which the transmittance of blue light is about 2/3 or less, preferably 1/2, of titanium black.
本発明の黒色粉末は、粉末濃度５０ppmの分散液透過スペクトルにおいて、４５０nmの透過率Ｘが１０.０％以下であり、４５０nmの透過率Ｘと５５０nmの透過率Ｙの比(Ｘ／Ｙ)が２.０以下、および/または４５０nmの透過率Ｘと６５０nmの透過率Ｚの比(Ｘ／Ｚ)が１.５以下である。 The black powder of the present invention has a transmittance X at 450 nm of 10.0% or less and a ratio (X / Y) of the transmittance X at 450 nm and the transmittance Y at 550 nm in the dispersion transmission spectrum with a powder concentration of 50 ppm. And / or the ratio of the transmittance X at 450 nm to the transmittance Z at 650 nm (X / Z) is 1.5 or less.
従来のチタンブラックは、４５０ｎｍの透過率Ｘと５５０ｎｍの透過率Ｙの比（Ｘ／Ｙ）は概ね２.３以上であり、４５０ｎｍの透過率Ｘと６５０ｎｍの透過率Ｚの比（Ｘ／Ｚ）は６.０以上であるが、本発明の黒色粉末はＸ／Ｙ比およびＸ／Ｚ比が格段に小さく、４５０ｎｍ〜６５０ｎｍの広い波長域において透過率の変化が小さく安定である。 Conventional titanium black has a ratio (X / Y) of the transmittance X of 450 nm to the transmittance Y of 550 nm (X / Y) is approximately 2.3 or more, and the ratio of the transmittance X of 450 nm to the transmittance Z of 650 nm (X / Z ) Is 6.0 or more, but the black powder of the present invention has a very small X / Y ratio and X / Z ratio, and is stable with a small change in transmittance in a wide wavelength range of 450 nm to 650 nm.
以下、本発明を実施形態に基づいて具体的に説明する。
本発明の黒色粉末は、酸窒化バナジウムまたは酸窒化ニオブからなる黒色粉末であり、酸窒化バナジウムは酸素含有量１６wt％以下および窒素含有量１０wt％以上であって粉末濃度５０ppmの分散液透過スペクトルにおいて４５０nmの透過率Ｘが１０.０％以下であり、酸窒化ニオブはシリカまたはアルミナがコーティングされていて酸素含有量８.５〜９.３wt％および窒素含有量１０〜１２wt％であって粉末濃度５０ppmの分散液透過スペクトルにおいて４５０nmの透過率Ｘが８.２〜８.４％であることを特徴とする青色遮蔽黒色粉末である。
Hereinafter, the present invention will be specifically described based on embodiments.
The black powder of the present invention is a black powder made of vanadium oxynitride or niobium oxynitride , and the vanadium oxynitride has an oxygen content of 16 wt% or less and a nitrogen content of 10 wt% or more in a dispersion transmission spectrum having a powder concentration of 50 ppm. 450 nm transmittance X is 10.0% or less, niobium oxynitride is coated with silica or alumina, oxygen content is 8.5 to 9.3 wt%, nitrogen content is 10 to 12 wt%, powder concentration It is a blue shielding black powder characterized by having a transmittance X at 450 nm of 8.2 to 8.4% in a 50 ppm dispersion transmission spectrum .
〔バナジウムまたはニオブの酸窒化物〕
本発明の黒色粉末は酸窒化バナジウムまたは酸窒化ニオブからなる黒色粉末である。酸窒化バナジウムまたは酸窒化ニオブは、バナジウムまたはニオブの金属酸化物または金属水酸化物を、高温下でアンモニアガスを用いて還元処理することによって得ることができる。
[ Vanadium or niobium oxynitride]
The black powder of the present invention is a black powder made of vanadium oxynitride or niobium oxynitride. Vanadium oxynitride or niobium oxynitride can be obtained by reducing a metal oxide or metal hydroxide of vanadium or niobium with ammonia gas at a high temperature.
バナジウムの金属酸化物または金属水酸化物を、酸素含有量１６wt％以下および窒素含有量１０wt％以上になるように８００℃まで昇温してアンモニアガスを用いて還元処理することによって、黒色度のＬ値が１６.５以下であって、粉末濃度５０ppmの分散液透過スペクトルにおいて４５０ｎｍの透過率Ｘが１０.０％以下の青色遮蔽黒色粉末を製造することができ、また、ニオブの金属酸化物または金属水酸化物をシリカまたはアルミナをコーティングした後に、酸素含有量８.５〜９.３wt％および窒素含有量１０〜１２wt％になるように８００℃まで昇温してアンモニアガスを用いて還元処理することによって、粉末濃度５０ppmの分散液透過スペクトルにおいて４５０nmの透過率Ｘが８.２〜８.４％の青色遮蔽黒色粉末を製造することができる。
By reducing the metal oxide or metal hydroxide of vanadium to 800 ° C. so as to have an oxygen content of 16 wt% or less and a nitrogen content of 10 wt% or more, reduction treatment using ammonia gas is performed. A blue shielding black powder having an L value of 16.5 or less and a transmittance X at 450 nm of 10.0% or less in a dispersion transmission spectrum having a powder concentration of 50 ppm can be produced . Alternatively, after coating the metal hydroxide with silica or alumina, the temperature is raised to 800 ° C. so that the oxygen content is 8.5 to 9.3 wt% and the nitrogen content is 10 to 12 wt%, and reduced using ammonia gas. By processing, a blue shielding black powder having a transmittance X at 450 nm of 8.2 to 8.4% in a dispersion transmission spectrum having a powder concentration of 50 ppm can be produced.
酸窒化バナジウムまたは酸窒化ニオブにおいて、窒素含有量が１０wt％未満であると黒色度が低下する。黒色度はＬ、ａ、ｂ表色系のＬ値であり、Ｌ値が小さいほど黒色度が高い。また、酸窒化バナジウムまたは酸窒化ニオブにおいて、窒素含有量が１０wt％未満であると４５０ｎｍの透過率Ｘが１０.０％より高くなる傾向があり、青色光に対する遮蔽性が低下する。
In oxynitride vanadium or acid niobium, blackness decreases the nitrogen content is less than 10 wt%. The blackness is an L value of the L, a, b color system, and the blackness is higher as the L value is smaller. In addition, in vanadium oxynitride or niobium oxynitride , if the nitrogen content is less than 10 wt%, the transmittance X at 450 nm tends to be higher than 10.0%, and the shielding property against blue light is lowered.
本発明の黒色粉末は、粉末濃度５０ppmの分散液透過スペクトルにおいて、４５０nmの透過率Ｘが１０.０％以下であって、４５０nmの透過率Ｘと５５０nmの透過率Ｙの比(Ｘ／Ｙ)が２.０以下であるもの、あるいは４５０nmの透過率Ｘと６５０nmの透過率Ｚの比(Ｘ／Ｚ)が１.５以下であるもの、あるいはＸ／Ｙ＝２.０以下であってＸ／Ｚ＝１.５以下である。 The black powder of the present invention has a transmittance X at 450 nm of 10.0% or less in a dispersion spectrum having a powder concentration of 50 ppm, and the ratio of the transmittance X at 450 nm to the transmittance Y at 550 nm (X / Y) Is less than 2.0, or the ratio of the transmittance X at 450 nm to the transmittance Z at 650 nm (X / Z) is 1.5 or less, or X / Y = 2.0 or less and X /Z=1.5 or less.
Ｘ／Ｙ＝２.０以下、および/またはＸ／Ｚ＝１.５以下の酸窒化バナジウムまたは酸窒化ニオブは４５０nm〜６５０nmの広い波長域において透過率の変化が小さく安定である。
Vanadium oxynitride or niobium oxynitride having X / Y = 2.0 or less and / or X / Z = 1.5 or less is stable with a small change in transmittance in a wide wavelength range of 450 nm to 650 nm.
本発明の黒色粉末は、好ましくは、黒色度のＬ値が１６.５以下であって、比表面積１０ｍ２/ｇ以上の粉末である。
The black powder of the present invention is preferably a powder having a blackness L value of 16.5 or less and a specific surface area of 10 m 2 / g or more.
〔製造方法〕
バナジウムまたはニオブの金属酸化物または金属水酸化物を、バナジウムについては酸素含有量１６wt％以下、および窒素含有量１０wt％以上（実施例１、２では酸素含有量６.０wt％、６.４wt％、窒素含有量１４wt％、１９wt％、実施例５、６では酸素含有量１２ｗｔ％、１６wt％、窒素含有量１３wt％、１４wt％）になるように８００℃まで昇温してアンモニアガスを用いて還元処理することにより、粉末濃度５０ppmの分散液透過スペクトルにおいて４５０nmの透過率Ｘが１０.０％以下の酸窒化バナジウムを製造することができ、ニオブについてはシリカまたはアルミナをコーティングした後に、酸素含有量８.５〜９.３wt％および窒素含有量１０〜１２wt％になるように８００℃まで昇温してアンモニアガスを用いて還元処理することによって、粉末濃度５０ppmの分散液透過スペクトルにおいて４５０nmの透過率Ｘが８.２〜８.４％の酸窒化ニオブを製造することができる。
〔Production method〕
The vanadium or niobium metal oxide or metal hydroxide is an oxygen content of 16 wt% or less and a nitrogen content of 10 wt% or more for vanadium (in Examples 1 and 2, the oxygen content is 6.0 wt% and 6.4 wt%). The nitrogen content was 14 wt%, 19 wt%, and in Examples 5 and 6 , the oxygen content was 12 wt%, 16 wt%, the nitrogen content was 13 wt%, 14 wt%) and the temperature was raised to 800 ° C. using ammonia gas. By performing the reduction treatment, it is possible to produce vanadium oxynitride having a transmittance X at 450 nm of 10.0% or less in a dispersion spectrum having a powder concentration of 50 ppm. Niobium is coated with silica or alumina and then contains oxygen. By heating to 800 ° C. and reducing with ammonia gas so that the amount is 8.5 to 9.3 wt% and the nitrogen content is 10 to 12 wt%. 450nm transmittance X of the dispersion transmission spectrum of the powder concentration 50ppm can be produced from 8.2 to 8.4% acid niobium.
酸化バナジウムや酸化ニオブを原料として用いることができる。また、バナジウムまたはニオブの塩化物、硝酸塩、硫酸塩などを水に溶解した後に、デカンテーションにより不純物を除去し、酸または塩基によって中和処理した後に乾燥して回収した水酸化物を原料に用いてもよい。これらの原料は比表面積１０ｍ2/ｇ以上の粉末が好ましい。 Vanadium oxide or niobium oxide can be used as a raw material. In addition, after dissolving vanadium or niobium chloride, nitrate, sulfate, etc. in water, impurities are removed by decantation, neutralized with acid or base, dried and recovered hydroxide is used as raw material May be. These raw materials are preferably powders having a specific surface area of 10 m 2 / g or more.
バナジウムまたはニオブの酸化物または水酸化物を効率よく還元して窒化反応を進めるにはアンモニアガスによる還元が適している。目的の窒素含有量になるように、反応温度、ガス流量を調整し、所定の黒色度になるまで反応を継続する。黒色度は酸素濃度、窒素濃度により確認できる。酸素濃度１７％以上、窒素濃度１０％未満では還元反応が不十分であり、目標とする遮光性能が得られない。 In order to efficiently reduce the vanadium or niobium oxide or hydroxide to advance the nitriding reaction, reduction with ammonia gas is suitable. The reaction temperature and gas flow rate are adjusted so as to achieve the target nitrogen content, and the reaction is continued until a predetermined blackness is achieved. Blackness can be confirmed by oxygen concentration and nitrogen concentration. When the oxygen concentration is 17% or more and the nitrogen concentration is less than 10%, the reduction reaction is insufficient and the target light shielding performance cannot be obtained.
本発明の黒色粉末の絶縁性を向上させるために、シリカ、アルミナ、ジルコニア、イットリアなどをコーティングしても良い。その際、原料粉末にコーティングしてもよいが、還元後の粉末にコーティングを行ってもよい。コーティングは乾式、湿式いずれの方法でも効果がある。 In order to improve the insulation of the black powder of the present invention, silica, alumina, zirconia, yttria, or the like may be coated. At that time, the raw material powder may be coated, or the reduced powder may be coated. The coating is effective by both dry and wet methods.
本発明の青色遮蔽黒色粉末は、黒色ペースト、黒色塗料、黒色樹脂フィルム、または黒色被膜の黒色顔料として好適である。 The blue shielding black powder of the present invention is suitable as a black pigment, black paint, black resin film, or black pigment for black coating.
以下、本発明の実施例を比較例と共に示す。
Ｌ値は規格ＪＩＳＺ８７２２に従って測定した。
比表面積は規格ＪＩＳＺ８８３０に従って測定した。
酸素濃度および窒素濃度は不活性ガス雰囲気溶解ガスクロマトグラフ法により測定した。
透過率は規格ＪＩＳＲ３１０６に従って測定した。
Examples of the present invention are shown below together with comparative examples.
The L value was measured according to the standard JISZ8722.
The specific surface area was measured according to the standard JISZ8830.
The oxygen concentration and nitrogen concentration were measured by an inert gas atmosphere dissolved gas chromatograph method.
The transmittance was measured according to the standard JIS R3106.
〔実施例１〜２、比較例１〕
酸化バナジウム粉末（比表面積１〜１０ｍ2/ｇ）を、窒素雰囲気下、７℃/minで８００℃まで昇温後、アンモニアガスを流し、表１に示す黒色度(Ｌ値)、酸素含有量および窒素含有量になるように窒化還元を行った。得られた黒色粉末を循環式横型ビーズミル（メディア：ジルコニア）を使用し、アミン系分散剤を使用しＰＧＭ−Ａｃ溶剤中で分散処理を行った後、作製した分散液を１０万倍に希釈し（粉末濃度５０ppm）、透過率を測定した。測定結果を表１および図１に示した。
[Examples 1 and 2, Comparative Example 1]
Vanadium oxide powder (specific surface area of 1 to 10 m 2 / g) was heated to 800 ° C. at 7 ° C./min in a nitrogen atmosphere, then ammonia gas was flown, and the blackness (L value) and oxygen content shown in Table 1 And nitriding reduction was performed so as to obtain a nitrogen content. The resulting black powder was subjected to a dispersion treatment in a PGM-Ac solvent using a circulating horizontal bead mill (media: zirconia) and an amine dispersant, and then the prepared dispersion was diluted 100,000 times. (Powder concentration 50 ppm), transmittance was measured. The measurement results are shown in Table 1 and FIG.
〔参考例３〜４、比較例２〜３〕
酸化ニオブ粉末または酸化チタン粉末（比表面積８ｍ２/ｇ、９ｍ２/ｇ）を用いた以外は実施例１〜２と同様にして、黒色粉末を製造し、該黒色粉末を用いて分散液を調製し、透過率を測定した。測定結果を表１に示した。
[ Reference Examples 3-4, Comparative Examples 2-3]
A black powder was produced in the same manner as in Examples 1 and 2 except that niobium oxide powder or titanium oxide powder (specific surface area 8 m 2 / g, 9 m 2 / g) was used, and a dispersion liquid was prepared using the black powder. Prepared and measured transmittance. The measurement results are shown in Table 1.
表１の結果に示すように、実施例１〜２の黒色粉末（酸窒化バナジウム）および参考例３〜４の黒色粉末（酸窒化ニオブ）は、４５０nm〜５００nmにおける透過率が７％以下であって青色光に対する遮光性が高く、また４５０nm〜６５０nmの広い波長域における透過率も低く、高い遮光性を有している。具体的には、実施例１〜２、参考例３〜４の黒色粉末は４５０nmの透過率Ｘと５５０nmの透過率Ｙの比(Ｘ／Ｙ)が２.０以下であり、さらに４５０nmの透過率Ｘと６５０nmの透過率Ｚの比(Ｘ／Ｚ)が１.５以下である。
As shown in the results of Table 1, the black powder of Example 1-2 (vanadium oxynitride) and the black powder of Reference Examples 3-4 (niobium oxynitride) had a transmittance of 7% or less at 450 nm to 500 nm. Therefore, it has a high light blocking property against blue light, and also has a low transmittance in a wide wavelength range of 450 nm to 650 nm, and has a high light blocking property. Specifically, the black powders of Examples 1 and 2 and Reference Examples 3 to 4 have a ratio (X / Y) of 450 nm transmittance X to 550 nm transmittance Y of 2.0 or less, and further 450 nm transmittance. The ratio (X / Z) between the rate X and the transmittance Z at 650 nm is 1.5 or less.
一方、窒素含有量が１０wt％未満の比較例１および比較例２の黒色粉末は、４５０ｎｍの透過率が１０％より高く、実施例１〜２、実施例の黒色粉末よりも遮光性が低い。また、表１および図１に示すように、従来の酸窒化チタン粉末（比較例３）は５５０nm〜６５０nmの透過率は低いが、４５０nmの透過率が１０％であり、青色光に対する遮光性が低い。また、比較例３の黒色粉末はＸ／Ｙ比が２.０よりも高く、Ｘ／Ｚ比が１.５よりも大幅に高い。 On the other hand, the black powders of Comparative Example 1 and Comparative Example 2 having a nitrogen content of less than 10 wt% have a transmittance of 450 nm higher than 10% and lower light blocking properties than the black powders of Examples 1-2 and Examples. Further, as shown in Table 1 and FIG. 1, the conventional titanium oxynitride powder (Comparative Example 3) has a low transmittance of 550 nm to 650 nm, but a transmittance of 450 nm is 10%, and has a light blocking property against blue light. Low. Further, the black powder of Comparative Example 3 has an X / Y ratio higher than 2.0 and an X / Z ratio significantly higher than 1.5.
〔実施例５〜８〕
酸化ニオブ粉末または酸化バナジウム粉末（比表面積１〜１０ｍ２/ｇ）について、おのおの粉末表面にシリカまたはアルミナをコーティング（コーティング量は粉末量の４wt％）した後に、実施例１〜２と同様にして、黒色粉末を製造し、該黒色粉末を用いて分散液を調製し、透過率を測定した。測定結果を表２に示した。
[Examples 5 to 8]
For niobium oxide powder or vanadium oxide powder (specific surface area 1 to 10 m 2 / g), silica or alumina was coated on each powder surface (the coating amount was 4 wt% of the powder amount), and then the same as in Examples 1 and 2. A black powder was produced, a dispersion was prepared using the black powder, and the transmittance was measured. The measurement results are shown in Table 2.
表２に示すように、実施例５〜８の黒色粉末は４５０nmの透過率Ｘと５５０nmの透過率Ｙの比(Ｘ／Ｙ)が２.０以下であって、また４５０nmの透過率Ｘと６５０nmの透過率Ｚの比(Ｘ／Ｚ)が１.５以下であり、４５０nm〜６５０nmの広い波長域において透過率の変化が小さく、安定である。 As shown in Table 2, the black powders of Examples 5 to 8 had a ratio (X / Y) of 450 nm transmittance X to 550 nm transmittance Y of 2.0 or less, and 450 nm transmittance X The ratio (X / Z) of the transmittance Z at 650 nm is 1.5 or less, and the change in transmittance is small and stable in a wide wavelength range of 450 nm to 650 nm.
実施例５〜８の黒色粉末について、圧粉体積抵抗値を測定することにより絶縁性を測定した。圧粉体積抵抗値は粉末を円筒状の治具に充填後、上下を金属製電極ではさみ、油圧プレスにより５０kg/cm2の圧力を印加、上下の電極間の抵抗値をデジタルマルチメーター（アドバンテスト社製）により測定した。その結果、実施例５〜８の粉末については、いずれも１.０ｘ１０5Ω・ｃｍ以上の高い絶縁性を有していた。 About the black powder of Examples 5-8, insulation was measured by measuring a compact volume resistance value. The powder volume resistance value is filled with powder in a cylindrical jig, and the upper and lower sides are sandwiched between metal electrodes, a pressure of 50 kg / cm 2 is applied by a hydraulic press, and the resistance value between the upper and lower electrodes is digital multimeter (Advantest ). As a result, the powders of Examples 5 to 8 all had high insulation properties of 1.0 × 10 5 Ω · cm or more.
〔実施例９〕
実施例１の黒色粉末について、透過率の測定に用いた分散液にアクリル樹脂を添加し、黒色顔料：樹脂＝６：４となるように黒色塗料を作製した。作製した塗料をガラス基板上に膜厚１μmになるようにスピンコート成膜し、２５０℃、一時間焼成して被膜を形成した。この被膜のＯＤ値を測定したところ、Ｒ（620nm）、Ｇ（530nm）、Ｂ（440nm）のＯＤ値はそれぞれ５.６４、５.４６、５.６５であり、ＢＭ膜として使用するための充分な特性を有することが確認され、いずれの波長でも高い数値が得られた。実施例２〜８の黒色粉末についても同様の傾向を示した。
[ Example 9 ]
About the black powder of Example 1, an acrylic resin was added to the dispersion used for the measurement of transmittance, and a black paint was prepared so that black pigment: resin = 6: 4. The prepared paint was spin-coated on a glass substrate to a film thickness of 1 μm and baked at 250 ° C. for 1 hour to form a film. When the OD value of this film was measured, the OD values of R (620 nm), G (530 nm), and B (440 nm) were 5.64, 5.46, and 5.65, respectively, for use as a BM film. It was confirmed that it had sufficient characteristics, and a high numerical value was obtained at any wavelength. The same tendency was shown also about the black powder of Examples 2-8.
〔比較例４〕
比較例３の黒色粉末（酸窒化チタン粉末）について、透過率の測定に用いた分散液にアクリル樹脂を添加し、黒色顔料：樹脂＝６：４となるように黒色塗料を作製した。作製した塗料をガラス基板上に膜厚１μmになるようにスピンコート成膜し、２５０℃、一時間焼成して被膜を形成した。この被膜のＯＤ値を測定したところ、Ｒ（620nm）、Ｇ(530nm)、Ｂ(440nm)のＯＤ値はそれぞれ４.５９、３.３０、３.１５であり、ＢＭ膜として使用することは可能だが、Ｂの波長でやや低い数値となった。
[Comparative Example 4]
About the black powder (titanium oxynitride powder) of the comparative example 3, the acrylic resin was added to the dispersion liquid used for the transmittance | permeability measurement, and the black coating material was produced so that it might become black pigment: resin = 6: 4. The prepared paint was spin-coated on a glass substrate to a film thickness of 1 μm and baked at 250 ° C. for 1 hour to form a film. When the OD value of this film was measured, the OD values of R (620 nm), G (530 nm), and B (440 nm) were 4.59, 3.30, and 3.15, respectively. Possible, but slightly lower at B wavelength.
Claims (7)
A black paste, a black paint, a black resin film, or a black coating containing the blue shielding black powder according to any one of claims 1 to 4.
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