TW202216586A

TW202216586A - Zirconium nitride powder and production method thereof dispersing the zirconium nitride powder in an acrylic monomer or epoxy monomer to prepare a monomer dispersoid

Info

Publication number: TW202216586A
Application number: TW109137782A
Authority: TW
Inventors: 影山謙介; 史; 幸
Original assignee: 日商三菱綜合材料電子化成股份有限公司
Priority date: 2020-10-30
Filing date: 2020-10-30
Publication date: 2022-05-01

Abstract

The task is to achieve a high insulating property while achieving a high insulating property and a high blackness degree. A means for completing the task is that a zirconium nitride powder in this invention has a volume resistivity of 107[Omega].cm or above in a state of a compacted powder obtained by compacting at the pressure of 5 Mpa and the particle size distribution D90 of 10[mu]m or below when being ultrasonically distributed for 5 min in a state that the powder is diluted with alcohol in which water or carbon ranges from 2 to 5. Moreover, the zirconium nitride powder is dispersed in an acrylic monomer or epoxy monomer to prepare a monomer dispersoid. Furthermore, the zirconium nitride powder used as a black pigment is dispersed in a dispersion medium and is further mixed with resin to prepare a black composition.

Description

氮化鋯粉末及其製造方法Zirconium nitride powder and method for producing the same

本發明為關於適合作為具有高的紫外線穿透率及高的黑色度，進而具有高的絕緣性的黑色顏料來使用的氮化鋯粉末及其製造方法。The present invention relates to a zirconium nitride powder suitable for use as a black pigment having high ultraviolet transmittance and high blackness, and further having high insulating properties, and a method for producing the same.

以往，揭示著一種氮化鋯粉末，以BET法測定的比表面積為20m ²/g~90m ²/g，在X射線繞射圖譜中，具有氮化鋯的波峰，但不具有二氧化鋯的波峰及低次氧化鋯(lower zirconium oxide)的波峰(參考例如專利文獻1(請求項1、段落[0016]))。該氮化鋯粉末，在該粉末濃度50ppm的分散液的穿透頻譜圖中，370nm的光線穿透率X至少為18%，550nm的光線穿透率Y為12%以下，且550nm的光線穿透率Y對370nm的光線穿透率X(X/Y)為2.5以上。 In the past, a zirconium nitride powder has been disclosed, which has a specific surface area of 20 m ² /g to 90 m ² /g measured by the BET method, and has peaks of zirconium nitride but not of zirconium dioxide in the X-ray diffraction pattern. Peaks and peaks of lower zirconium oxide (refer to, for example, Patent Document 1 (claim 1, paragraph [0016])). The zirconium nitride powder, in the transmission spectrum diagram of the dispersion liquid with a powder concentration of 50ppm, the light transmittance X of 370nm is at least 18%, the light transmittance Y of 550nm is 12% or less, and the light transmittance of 550nm The transmittance Y to the light transmittance X (X/Y) of 370 nm is 2.5 or more.

由於如此般構成的氮化鋯粉末的比表面積為20m ²/g以上，故在製成阻劑(resist)之情形時具有抑制沈降之效果，又，由於為90m ²/g以下，故具有充分遮光性之效果。又，在X射線繞射圖譜中，具有氮化鋯的波峰，但不具有二氧化鋯的波峰、低次氧化鋯的波峰及低次氮氧化鋯(lower zirconium oxynitride)的波峰，因而在粉末濃度50ppm的分散液的穿透頻譜圖中，具有370nm的光線穿透率X至少為18%、且550nm的光線穿透率Y為12%以下的特徵，又，具有X/Y為2.5以上的特徵。藉由使X/Y成為2.5以上，具有可更進一步使紫外線穿透之優點。其結果，在作為黑色顏料來形成黑色圖型膜時，能夠得到高解析度的圖型膜，且所形成的圖型膜變得具有高的遮光性能。 [先前技術文獻] [專利文獻] Since the specific surface area of the zirconium nitride powder thus constituted is 20 m ² /g or more, it has the effect of suppressing sedimentation when it is used as a resist, and since it is 90 m ² /g or less, it has sufficient shading effect. In addition, in the X-ray diffraction spectrum, the peak of zirconium nitride is present, but the peak of zirconium dioxide, the peak of lower zirconium oxide, and the peak of lower zirconium oxynitride are not present, so the powder concentration In the transmission spectrum of the dispersion at 50 ppm, the light transmittance X at 370 nm is at least 18% and the light transmittance Y at 550 nm is 12% or less, and X/Y is 2.5 or more. . By making X/Y 2.5 or more, there is an advantage that ultraviolet rays can be further penetrated. As a result, when a black patterned film is formed as a black pigment, a high-resolution patterned film can be obtained, and the formed patterned film has high light-shielding performance. [Prior Art Literature] [Patent Literature]

[專利文獻1]日本特開2017-222559號公報[Patent Document 1] Japanese Patent Application Laid-Open No. 2017-222559

[發明所欲解決之課題][The problem to be solved by the invention]

如上述專利文獻1所示的氮化鋯粉末，若使氮化鋯粗粉末分散於分散媒中並使用珠磨機(bead mill)(介質(media)：氧化鋯)等來提高分散性時，雖然可得到高的絕緣性，但若將該氮化鋯粉末直接混煉入高黏度的樹脂糊(resin paste)中時，氮化鋯粗粉末會殘留，而分散性為不足。因此，將氮化鋯粉末作為黑色顏料來使用時，黑色塗料的著色力會降低之同時，由於氮化鋯粗粉末的殘留，而會有電阻值變低之不良。又，若將上述氮化鋯粗粉末強制使用乾式粉碎機等進行粉碎時，粉末徑會變小、且會引起粉末表面的氧化反應，因而具有雖然絕緣性為提昇，但黑色塗料的黑色度為降低之問題點。As in the zirconium nitride powder described in the above-mentioned Patent Document 1, when the coarse zirconium nitride powder is dispersed in a dispersion medium and the dispersibility is improved using a bead mill (media: zirconia) or the like, Although high insulating properties can be obtained, when the zirconium nitride powder is directly kneaded into a high-viscosity resin paste, the coarse zirconium nitride powder remains and the dispersibility is insufficient. Therefore, when the zirconium nitride powder is used as a black pigment, the coloring power of the black paint is lowered, and the resistance value is lowered due to the residue of the coarse zirconium nitride powder. In addition, when the above-mentioned coarse zirconium nitride powder is forcibly pulverized using a dry pulverizer or the like, the diameter of the powder will be reduced, and an oxidation reaction on the surface of the powder will occur, so that although the insulating properties are improved, the blackness of the black paint is The problem of lowering.

本發明的第一目的為提供一種能夠得到高絕緣性及高黑色度之同時，具有高的絕緣性的氮化鋯粉末及其製造方法。本發明的第二目的為提供一種在藉由低溫濕式介質粉碎或以發熱量較少的噴射磨機(jet mill)的粉碎時，能夠維持高的黑色度的氮化鋯粉末之製造方法。本發明的第三目的為提供一種以在惰性氣體環境中的燒成而能夠提昇黑色膜的絕緣性的氮化鋯粉末之製造方法。 [解決課題之手段] A first object of the present invention is to provide a zirconium nitride powder having high insulating properties and a method for producing the same, while obtaining high insulating properties and high blackness. The second object of the present invention is to provide a method for producing zirconium nitride powder that can maintain a high blackness during pulverization by a low-temperature wet medium or a jet mill with a small calorific value. The third object of the present invention is to provide a method for producing a zirconium nitride powder capable of improving the insulating properties of a black film by firing in an inert gas atmosphere. [Means of Solving Problems]

本發明的第一觀點為一種氮化鋯粉末，在以5MPa的壓力進行壓實而得的壓粉體之狀態下，體積電阻率為10 ⁷Ω・cm以上，且以水或碳數位於2~5的範圍內的醇進行稀釋之狀態下，進行5分鐘超音波分散時的粒度分布D ₉₀為10μm以下。 A first aspect of the present invention is a zirconium nitride powder having a volume resistivity of 10 ⁷ Ω·cm or more in the state of a powder compact obtained by compaction at a pressure of 5 MPa, and having water or carbon number within 2 The particle size distribution D ₉₀ at the time of ultrasonic dispersion for 5 minutes in a state where the alcohol in the range of ~5 was diluted was 10 μm or less.

本發明的第二觀點為一種氮化鋯粉末之製造方法，包含下述之步驟：藉由鋁熱法(Thermite method)或電漿合成法來生成氮化鋯粗粉末之步驟；將該氮化鋯粗粉末藉由以10℃以下的分散媒溫度進行低溫濕式介質粉碎或以0.3MPa以上的氣壓進行噴射磨機粉碎，來製作以水或碳數位於3~5的範圍內的醇進行稀釋之狀態下，進行5分鐘超音波分散時的粒度分布D ₉₀為10μm以下的氮化鋯前驅物粉末之步驟；藉由將該經粉碎的氮化鋯前驅物粉末在惰性氣體環境中燒成，來製造在以5MPa的壓力進行壓實而得的壓粉體之狀態下，體積電阻率為10 ⁷Ω・cm以上的氮化鋯粉末之步驟。 A second aspect of the present invention is a method for producing zirconium nitride powder, comprising the following steps: a step of generating coarse zirconium nitride powder by thermite method or plasma synthesis method; Coarse zirconium powder is prepared and diluted with water or alcohol having a carbon number in the range of 3 to 5 by pulverizing in a low-temperature wet medium at a dispersion medium temperature of 10°C or lower or by jet mill pulverization at an air pressure of 0.3 MPa or more. Under the condition of 5 minutes, the particle size distribution D ₉₀ of ultrasonic dispersion is 10 μm or less of zirconium nitride precursor powder; By firing the pulverized zirconium nitride precursor powder in an inert gas environment, The process of producing a zirconium nitride powder having a volume resistivity of 10 ⁷ Ω·cm or more in the state of a green powder compacted at a pressure of 5 MPa.

本發明的第三觀點為一種單體分散體，其係將第一觀點記載的氮化鋯粉末分散於丙烯酸單體或環氧單體中來得到。A third aspect of the present invention is a monomer dispersion obtained by dispersing the zirconium nitride powder described in the first aspect in an acrylic monomer or an epoxy monomer.

本發明的第四觀點為一種黑色組成物，其係將第一觀點記載的氮化鋯粉末作為黑色顏料分散於分散媒中並進一步混合樹脂來得到。A fourth aspect of the present invention is a black composition obtained by dispersing the zirconium nitride powder described in the first aspect in a dispersion medium as a black pigment and further mixing a resin.

本發明的第五觀點為一種黑色膜之製作方法，包含下述之步驟：將第三觀點記載的單體分散體塗布於基板上來形成塗膜之步驟；將該塗膜熱硬化或紫外線硬化來製作黑色膜之步驟。A fifth aspect of the present invention is a method for producing a black film, comprising the steps of: applying the monomer dispersion described in the third aspect on a substrate to form a coating film; The steps of making black film.

本發明的第六觀點為一種黑色膜之製作方法，包含下述之步驟：將第四觀點記載的黑色組成物塗布於基板上來形成塗膜之步驟；將該塗膜熱硬化或紫外線硬化來製作黑色膜之步驟。 [發明的效果] A sixth aspect of the present invention is a method for producing a black film, comprising the steps of: applying the black composition described in the fourth aspect on a substrate to form a coating film; and producing the coating film by thermosetting or ultraviolet curing Steps of black film. [Effect of invention]

本發明的第一觀點的氮化鋯粉末，由於在以5MPa的壓力進行壓實而得的壓粉體之狀態下，體積電阻率為10 ⁷Ω・cm以上，故能夠提昇在製作厚度10μm~100μm左右的黑色厚膜時的絕緣性。又，由於氮化鋯粉末以水或碳數位於2~5的範圍內的醇進行稀釋之狀態下，進行5分鐘超音波分散時的粒度分布D ₉₀為10μm以下，故不存在氮化鋯粗粉末，將能夠得到良好的分散體或分散液。其結果，藉由使用上述氮化鋯粉末而得的分散體或分散液來製作的黑色膜，將能夠得到高絕緣性及高黑色度之同時，具有高的絕緣性。 The zirconium nitride powder according to the first aspect of the present invention has a volume resistivity of 10 ⁷ Ω·cm or more in the state of a powder compact obtained by compaction at a pressure of 5 MPa, so that the production thickness of 10 μm to 10 μm can be improved. Insulation properties for black thick films of about 100 μm. In addition, since the particle size distribution _D90 of the zirconium nitride powder when ultrasonically dispersed for 5 minutes in a state of being diluted with water or an alcohol having a carbon number in the range of 2 to 5 is 10 μm or less, there is no coarse zirconium nitride. powder, will be able to get a good dispersion or dispersion. As a result, the black film produced by using the dispersion or dispersion liquid of the zirconium nitride powder described above can obtain high insulating properties and high blackness, and also have high insulating properties.

本發明的第二觀點的氮化鋯粉末之製造方法當中，若將氮化鋯粗粉末以10℃以下的分散媒溫度進行低溫濕式介質粉碎時，由於發熱量少，故不會進行氮化鋯的表面氧化，而能夠維持高的黑色度。又，若將氮化鋯粗粉末以0.3MPa以上的氣壓進行噴射磨機粉碎，將不會殘留氮化鋯粗粉末，而能夠提昇黑色膜的絕緣性。進而，藉由將上述經粉碎的氮化鋯前驅物粉末在惰性氣體環境中燒成，將能夠提昇黑色膜的絕緣性。In the method for producing zirconium nitride powder according to the second aspect of the present invention, when the coarse zirconium nitride powder is pulverized in a low-temperature wet medium at a dispersion medium temperature of 10° C. or lower, nitriding is not performed because of a small amount of heat generated. The surface of zirconium is oxidized to maintain high blackness. In addition, when the zirconium nitride coarse powder is pulverized by a jet mill at an air pressure of 0.3 MPa or more, the zirconium nitride coarse powder does not remain, and the insulating properties of the black film can be improved. Furthermore, the insulating properties of the black film can be improved by firing the pulverized zirconium nitride precursor powder in an inert gas atmosphere.

本發明的第三觀點的單體分散體，係將本發明的第一觀點的氮化鋯粉末分散於丙烯酸單體或環氧單體中，因此，即便是該等的單體的黏度相對為高，但氮化鋯粉末對於上述單體仍可保持良好的分散性。其結果，使用單體分散體而得到的黑色膜，將能夠得到高絕緣性及高黑色度之同時，具有高的絕緣性。The monomer dispersion according to the third aspect of the present invention disperses the zirconium nitride powder according to the first aspect of the present invention in an acrylic monomer or an epoxy monomer. Therefore, even if the viscosity of these monomers is relatively high, but the zirconium nitride powder can still maintain good dispersibility for the above monomers. As a result, the black film obtained by using the monomer dispersion can obtain high insulating properties and high blackness, and also have high insulating properties.

本發明的第四觀點的黑色組成物，係將本發明的第一觀點的氮化鋯粉末作為黑色顏料分散於分散媒中並進一步混合樹脂，因此，氮化鋯粉末均勻地分散於分散媒中。其結果，使用黑色組成物而得到的黑色膜，將能夠得到高絕緣性及高黑色度之同時，具有高的絕緣性。The black composition of the fourth aspect of the present invention disperses the zirconium nitride powder of the first aspect of the present invention as a black pigment in a dispersion medium and further mixes a resin, so that the zirconium nitride powder is uniformly dispersed in the dispersion medium . As a result, the black film obtained by using the black composition can obtain high insulating properties and high blackness, and also have high insulating properties.

本發明的第五觀點的黑色膜之製作方法當中，將上述單體分散體塗布於基板上來形成塗膜後，將該塗膜熱硬化或紫外線硬化來製作黑色膜，因此，黑色膜係能夠得到高絕緣性及高黑色度之同時，具有高的絕緣性。In the method for producing a black film according to the fifth aspect of the present invention, the above-mentioned monomer dispersion is applied on a substrate to form a coating film, and then the coating film is thermally cured or UV-cured to prepare a black film. Therefore, a black film system can be obtained. In addition to high insulation and high blackness, it has high insulation.

本發明的第六觀點的黑色膜之製作方法當中，將上述黑色組成物塗布於基板上來形成塗膜後，將該塗膜熱硬化或紫外線硬化來製作黑色膜，因此，黑色膜係能夠得到高絕緣性及高黑色度之同時，具有高的絕緣性。In the method for producing a black film according to the sixth aspect of the present invention, after applying the above-mentioned black composition on a substrate to form a coating film, the coating film is thermally cured or cured with ultraviolet rays to prepare a black film, so that the black film system can obtain high Insulation and high blackness, as well as high insulation.

[實施發明之最佳形態][The best form of implementing the invention]

接下來，對於用來實施本發明之形態進行說明。本實施形態的氮化鋯粉末，在以5MPa的壓力進行壓實而得的壓粉體之狀態下，體積電阻率為10 ⁷Ω・cm以上(較佳為10 ⁸Ω・cm以上)，且以水或碳數位於2~5的範圍內的醇進行稀釋之狀態下，進行5分鐘超音波分散時的粒度分布D ₉₀為10μm以下(較佳為8μm以下)。在此，之所以要將上述體積電阻率限定為10 ⁷Ω・cm以上，是由於若未滿10 ⁷Ω・cm的話，使用氮化鋯粉末來製作厚度1μm~100μm左右的黑色厚膜時，絕緣性會降低之緣故。又，之所以要將上述粒度分布D ₉₀限定為10μm以下，是由於若超過10μm的話，會殘留氮化鋯粗粉末，而無法得到良好的分散體或黑色膜之緣故。 Next, the form for implementing this invention is demonstrated. The zirconium nitride powder of the present embodiment has a volume resistivity of 10 ⁷ Ω·cm or more (preferably 10 ⁸ Ω·cm or more) in the state of a compact powder compacted at a pressure of 5 MPa, and The particle size distribution D ₉₀ when ultrasonically dispersed for 5 minutes in a state of dilution with water or an alcohol having a carbon number in the range of 2 to 5 is 10 μm or less (preferably 8 μm or less). Here, the reason why the above-mentioned volume resistivity is limited to 10 ⁷ Ω·cm or more is that if it is less than 10 ⁷ Ω·cm, when a black thick film with a thickness of about 1 μm to 100 μm is produced using zirconium nitride powder, Insulation performance will be reduced. In addition, the reason why the particle size distribution D ₉₀ is limited to 10 μm or less is because if it exceeds 10 μm, coarse zirconium nitride powder remains, and a good dispersion or black film cannot be obtained.

可使用例如三菱化學公司製的低電阻率計ROLESTAR-GP(型式：UV-3101PC)，以四端子四探針法來測定上述體積電阻率。該四端子四探針法為如下述之方法：在試料(壓粉體)的表面將4根針狀電極隔開指定的間隔並放置在一直線上，使外側的2根針狀電極之間流通一定的電流，藉由測定在內側的2根針狀電極之間所產生的電位差，來求出體積電阻率。The volume resistivity can be measured by a four-terminal four-probe method using, for example, a low-resistivity meter ROLESTAR-GP (type: UV-3101PC) manufactured by Mitsubishi Chemical Corporation. The four-terminal four-probe method is a method in which four needle-shaped electrodes are placed in a straight line at a predetermined interval on the surface of a sample (powder compact), and flow is made between the two outer needle-shaped electrodes. The volume resistivity was obtained by measuring the potential difference generated between the two needle electrodes on the inside at a constant current.

又，氮化鋯粉末為一次粒子凝集而成的二次粒子之狀態，氮化鋯粉末藉由雷射繞射散射法來測定體積基準的粒度分布，在此，如下述般來進行藉由雷射繞射散射法來測定體積基準的粒度分布。首先，將氮化鋯粉末(二次粒子)0.1g投入至離子交換水20g中，施予25kHz的超音波5分鐘，來將氮化鋯粉末分散於離子交換水中。接下來，將適量的得到的氮化鋯粉末的分散液滴下至雷射繞射散射式粒度分布測定裝置(堀場製作所製商品名：LA-300)的觀察單元中，並依據該裝置之程序來測定粒度分布。藉由該雷射繞射散射法測定的粒度分布為一次粒子凝集而成的二次粒子的粒度分布。尚，亦可使用碳數位於2~5的範圍內的醇來代替離子交換水。作為碳數2的醇，可舉出乙醇，作為碳數3的醇，可舉出1-丙醇、2-丙醇等，作為碳數4的醇，可舉出1-丁醇、2-丁醇等，作為碳數5的醇，可舉出1-戊醇、2-戊醇等。尚，碳數1以下的醇，具有所謂的揮發性高、而測定值不穩定之不良；碳數6以上的醇，具有所謂的親和性不足、而測定值不穩定之不良。In addition, the zirconium nitride powder is in the state of secondary particles formed by agglomeration of primary particles, and the particle size distribution on a volume basis of the zirconium nitride powder is measured by a laser diffraction scattering method. Diffraction scattering method to determine volume-based particle size distribution. First, 0.1 g of zirconium nitride powder (secondary particles) was put into 20 g of ion-exchanged water, and ultrasonic waves of 25 kHz were applied for 5 minutes to disperse the zirconium nitride powder in the ion-exchanged water. Next, drop an appropriate amount of the obtained dispersion of zirconium nitride powder into the observation unit of a laser diffraction scattering particle size distribution measuring device (trade name: LA-300, manufactured by Horiba, Ltd.), and follow the procedures of the device to measure The particle size distribution is determined. The particle size distribution measured by this laser diffraction scattering method is the particle size distribution of the secondary particles in which the primary particles are aggregated. Furthermore, an alcohol having a carbon number in the range of 2 to 5 can also be used instead of ion-exchanged water. Examples of the alcohol having 2 carbon atoms include ethanol, examples of the alcohol having 3 carbon atoms include 1-propanol, 2-propanol, and the like, and examples of the alcohol having 4 carbon atoms include 1-butanol, 2-propanol, and the like. Butanol etc., 1-pentanol, 2-pentanol etc. are mentioned as a C5 alcohol. In addition, alcohols with 1 or less carbon atoms have so-called high volatility and unstable measured values, and alcohols with 6 or more carbon atoms have so-called insufficient affinity and unstable measured values.

對於如此般構成的氮化鋯粉末之製造方法進行說明。首先，藉由鋁熱法或電漿合成法來生成氮化鋯粗粉末。本說明書中，鋁熱法係指在金屬鎂的存在下使氧化鋯粉末與N ₂氣體(氮氣)反應，來進行還原之方法。該實施形態當中，作為氧化鋯粉末為使用二氧化鋯(ZrO ₂)粉末或塗布有二氧化矽的二氧化鋯(ZrO ₂)粉末。又，金屬鎂粉末中添加有氮化鎂(Mg ₃N ₂)粉末。將該等的粉末作為起始原料，藉由在特定的環境下、以特定的溫度與時間來進行燒成，而生成以BET法測定的比表面積為20m ²/g~90m ²/g的氮化鋯粗粉末。 The manufacturing method of the zirconium nitride powder comprised in this way is demonstrated. First, coarse powder of zirconium nitride is produced by the thermite method or the plasma synthesis method. In this specification, the aluminothermic method refers to a method in which reduction is performed by reacting zirconia powder with N ₂ gas (nitrogen gas) in the presence of metallic magnesium. In this embodiment, zirconium dioxide (ZrO ₂ ) powder or zirconium dioxide (ZrO ₂ ) powder coated with silicon dioxide is used as the zirconium oxide powder. In addition, magnesium nitride (Mg ₃ N ₂ ) powder is added to the metallic magnesium powder. These powders are used as starting materials, and are fired in a specific environment at a specific temperature and time to generate nitrogen with a specific surface area of 20 m ² /g to 90 m ² /g measured by the BET method. Coarse zirconium powder.

[二氧化鋯粉末] 作為二氧化鋯粉末，例如單斜晶系二氧化鋯、立方晶系二氧化鋯、釔穩定化二氧化鋯等的二氧化鋯粉末皆可使用，就提高氮化鋯粉末的生成率之觀點而言，較佳為單斜晶系二氧化鋯粉末。又，關於二氧化鋯粉末或塗布有二氧化矽的二氧化鋯粉末的各平均一次粒徑、及氧化鎂粉末的平均一次粒徑，為了得到以BET法測定的比表面積為20m ²/g~90m ²/g的氮化鋯粗粉末，由比表面積的測定值換算成球形的平均一次粒徑較佳為500nm以下，就粉末的處理容易性而言，平均一次粒徑較佳為500nm以下且10nm以上。 [Zirconium dioxide powder] As the zirconium dioxide powder, for example, any zirconium dioxide powder such as monoclinic zirconium dioxide, cubic zirconium dioxide, and yttrium-stabilized zirconium dioxide can be used. From the viewpoint of the generation rate of , the monoclinic zirconium dioxide powder is preferred. In addition, regarding the average primary particle size of each of the zirconium dioxide powder or the silica-coated zirconium dioxide powder, and the average primary particle size of the magnesium oxide powder, the specific surface area measured by the BET method is 20 m ² /g~ The zirconium nitride coarse powder of 90 m ² /g preferably has an average primary particle size of 500 nm or less in terms of spherical average primary particle size converted from the measured value of specific surface area, and the average primary particle size is preferably 500 nm or less and 10 nm in terms of ease of powder handling above.

[塗布有二氧化矽的二氧化鋯粉末] 塗布有二氧化矽的二氧化鋯粉末為如下述般來得到：將二氧化鋯粉末與矽酸酯溶膠凝膠液混合來調製漿料，將該漿料進行乾燥、粉碎而得到。二氧化鋯與矽酸酯溶膠凝膠液的混合比例，以質量比計，二氧化鋯：矽酸酯溶膠凝膠液的二氧化矽成分較佳為(90.0~99.5)：(10.0~0.5)。若二氧化矽成分未滿下限值的話，二氧化鋯表面的二氧化矽被覆率會過低，若二氧化矽成分超出上限值的話，使用得到的氮化鋯粉末來形成圖型膜時，會有遮光性不足之不良。 [Zirconium dioxide powder coated with silicon dioxide] The zirconium dioxide powder coated with silicon dioxide is obtained by mixing the zirconium dioxide powder and the silicate sol-gel liquid to prepare a slurry, and drying and pulverizing the slurry. The mixing ratio of zirconium dioxide and silicate sol-gel solution, in terms of mass ratio, the silica content of zirconium dioxide:silicate sol-gel solution is preferably (90.0~99.5):(10.0~0.5) . If the silicon dioxide content is less than the lower limit, the silicon dioxide coverage on the zirconium dioxide surface will be too low. If the silicon dioxide content exceeds the upper limit, the resulting zirconium nitride powder will be used to form a patterned film. , there will be insufficient shading.

為了使二氧化鋯均勻地混合至溶膠凝膠液中，較佳為將二氧化鋯粉末加入至水、醇等的分散液中混合後，再將該混合液添加並混合至矽酸酯溶膠凝膠液中。矽酸酯溶膠凝膠液較佳為將矽酸甲酯、矽酸乙酯等的矽酸酯溶解至水、醇等的溶劑中而成的液體。使得到的漿料的固體成分濃度以固體成分計為10質量%~50質量%之方式，來決定二氧化鋯與溶膠凝膠液的混合比例。將得到的漿料在大氣中或真空環境下，以60℃~350℃的溫度來乾燥1分鐘~360分鐘，而得到塗布有二氧化矽的二氧化鋯粉末。In order to uniformly mix the zirconium dioxide into the sol-gel liquid, it is preferable to add the zirconium dioxide powder to a dispersion liquid of water, alcohol, etc. and mix it, and then add and mix the mixed liquid until the silicate sol gels. in the glue. The silicate sol-gel liquid is preferably a liquid obtained by dissolving silicate esters such as methyl silicate and ethyl silicate in a solvent such as water and alcohol. The mixing ratio of zirconium dioxide and the sol-gel liquid is determined so that the solid content concentration of the obtained slurry is 10 mass % to 50 mass % in terms of solid content. The obtained slurry is dried at a temperature of 60° C. to 350° C. for 1 minute to 360 minutes in the air or in a vacuum environment to obtain a zirconium dioxide powder coated with silicon dioxide.

藉由使用塗布有二氧化矽的二氧化鋯粉末來作為起始原料，燒成時可抑制晶粒成長，而能夠得到以BET法測定的比表面積為20m ²/g~90m ²/g的更細微的氮化鋯粉末。此時，氮化鋯粉末以10.0質量%以下(較佳為9.0質量%以下)之比例來含有氧化矽及/或氮化矽。若超過10.0質量%的話，使用得到的氮化鋯粉末來形成圖型膜時，會有遮光性不足之不良。 By using zirconium ^dioxide powder coated with silicon ^dioxide as the starting material, the growth of crystal grains can be suppressed during firing, and the specific surface area measured by the BET method can be obtained. Fine zirconium nitride powder. At this time, the zirconium nitride powder contains silicon oxide and/or silicon nitride in a ratio of 10.0 mass % or less (preferably 9.0 mass % or less). When it exceeds 10.0 mass %, when a patterned film is formed using the obtained zirconium nitride powder, there is a defect that the light-shielding property is insufficient.

[金屬鎂粉末] 若金屬鎂粉末的粒徑過小的話，反應會劇烈地進行，而操作上的危險性會增加，因此，以通過的篩目計粒徑為100μm~1000μm的粒狀金屬鎂為較佳，特佳為200μm~ 500μm的粒狀金屬鎂。但是，即便全部的金屬鎂不是在上述粒徑範圍內，只要其80質量%以上(特別是90質量%以上)為上述範圍內即可。 [Metal magnesium powder] If the particle size of the magnesium metal powder is too small, the reaction will proceed violently, and the risk in operation will increase. Therefore, granular metal magnesium with a particle size of 100 μm to 1000 μm in terms of the passing mesh is preferred, particularly preferred. It is granular metal magnesium of 200μm~500μm. However, even if all the metallic magnesium is not within the above-mentioned particle size range, 80 mass % or more (especially 90 mass % or more) may be within the above-mentioned range.

金屬鎂粉末對二氧化鋯粉末的添加量的多寡，會與後述的環境氣體中的氨氣及氫氣的量一起來影響二氧化鋯的還原力。若金屬鎂的量過少的話，由於還原不足，而難以得到目標的氮化鋯粉末，若過多的話，由於過量的金屬鎂會使得反應溫度急劇地上昇，而有可能引起粉末的晶粒成長，同時是不經濟的。金屬鎂粉末根據其粒徑的大小，以金屬鎂成為二氧化鋯的2.0倍莫耳~6.0倍莫耳之比例之方式，來將金屬鎂粉末添加並混合於二氧化鋯粉末中。若未滿2.0倍莫耳的話，二氧化鋯的還原反應會不足，若超過6.0倍莫耳的話，由於過量的金屬鎂會使得反應溫度急劇地上昇，而有可能引起粉末的晶粒成長，同時是不經濟的。The addition amount of the magnesium metal powder to the zirconium dioxide powder affects the reducing power of the zirconium dioxide together with the amounts of ammonia gas and hydrogen gas in the ambient gas to be described later. If the amount of metallic magnesium is too small, it will be difficult to obtain the target zirconium nitride powder due to insufficient reduction. If the amount is too large, the reaction temperature will rise rapidly due to the excess metallic magnesium, which may cause grain growth of the powder, and at the same time is uneconomical. The magnesium metal powder is added and mixed into the zirconium dioxide powder according to the size of its particle size, in such a way that the metal magnesium becomes 2.0 times moles to 6.0 times moles of the zirconium dioxide. If it is less than 2.0 times mol, the reduction reaction of zirconium dioxide will be insufficient, and if it exceeds 6.0 times mol, the reaction temperature will rise rapidly due to excessive metal magnesium, which may cause grain growth of the powder, and at the same time is uneconomical.

[氮化鎂粉末] 氮化鎂粉末在燒成時塗布於氮化鋯表面，而緩和金屬鎂的還原力，並防止氮化鋯粉末的燒結及晶粒成長。氮化鎂粉末根據其粒徑的大小，以氮化鎂成為二氧化鋯的0.3倍莫耳~3.0倍莫耳之比例之方式，來添加並混合於二氧化鋯中。若未滿0.3倍莫耳的話，則不能防止氮化鋯粉末的燒結，若超過3.0倍莫耳的話，則會有燒成後的酸洗淨時所需要的酸性溶液的使用量增加之不良。較佳為0.4倍莫耳~2.0倍莫耳。氮化鎂粉末，由比表面積的測定值換算成球形的平均一次粒徑較佳為1000nm以下，就粉末的處理容易性而言，平均一次粒徑較佳為10nm以上且500nm以下。尚且，不僅是氮化鎂，氧化鎂對於預防氮化鋯的燒結亦為有效，因此，可在氮化鎂中混合一部分的氧化鎂來使用。 [Magnesium Nitride Powder] The magnesium nitride powder is coated on the surface of the zirconium nitride during firing, so as to reduce the reducing power of the metal magnesium and prevent the sintering and grain growth of the zirconium nitride powder. Magnesium nitride powder is added and mixed into zirconium dioxide in a ratio of 0.3 times moles to 3.0 times moles of zirconium dioxide according to the size of its particle size. If it is less than 0.3 moles, the sintering of the zirconium nitride powder cannot be prevented, and if it exceeds 3.0 moles, the usage amount of the acidic solution required for acid cleaning after firing may increase. Preferably, it is 0.4 times mol to 2.0 times mol. The magnesium nitride powder preferably has a spherical average primary particle size of 1000 nm or less in terms of the measured value of the specific surface area, and the average primary particle size is preferably 10 nm or more and 500 nm or less in view of the ease of powder handling. Furthermore, not only magnesium nitride but also magnesium oxide is effective in preventing sintering of zirconium nitride, so it is possible to use a part of magnesium oxide mixed with magnesium nitride.

[藉由金屬鎂粉末的還原反應] 用來生成氮化鋯粗粉末的藉由金屬鎂的還原反應時的溫度為650~900℃，較佳為700~800℃。650℃為金屬鎂的熔融溫度，若溫度比其低的話，二氧化鋯的還原反應會不足。又，即使溫度高於900℃，其效果也不增加，浪費熱能之同時，粉末會發生燒結，故不佳。又，還原反應時間較佳為30~90分鐘，更佳為30~60分鐘。 [Reduction by metal magnesium powder] The temperature at the time of the reduction reaction by metallic magnesium for generating the coarse zirconium nitride powder is 650 to 900°C, preferably 700 to 800°C. 650°C is the melting temperature of metallic magnesium, and if the temperature is lower than that, the reduction reaction of zirconium dioxide will be insufficient. In addition, even if the temperature is higher than 900°C, the effect does not increase, and the powder is sintered while wasting heat energy, which is not good. In addition, the reduction reaction time is preferably 30 to 90 minutes, more preferably 30 to 60 minutes.

進行上述還原反應之際的反應容器，為了使反應時原料或生成物不會飛濺，較佳為具有蓋子。此係由於，如果金屬鎂開始熔融時，還原反應會急劇進行，伴隨於此溫度會上昇，而容器內部的氣體會膨脹，因此，容器內部之物質有可能飛濺到外部之緣故。It is preferable that the reaction container when the above-mentioned reduction reaction is carried out has a lid in order to prevent the raw materials and products from splashing during the reaction. This is because when the metal magnesium begins to melt, the reduction reaction will proceed rapidly, and the temperature will rise along with this, and the gas inside the container will expand, so the material inside the container may splash to the outside.

[藉由金屬鎂粉末的還原反應時的環境氣體] 環境氣體可以是氮氣單獨，或是氮氣與氫氣的混合氣體，或是氮氣與氨氣的混合氣體。上述還原反應在上述混合氣體的氣流中進行。混合氣體中的氮氣具有下述之作用：防止金屬鎂或還原生成物與氧之接觸，防止該等的氧化之同時，使氮與鋯反應來生成氮化鋯。混合氣體中的氫氣或氨氣具有下述之作用：與金屬鎂一起來還原二氧化鋯。上述混合氣體中，較佳為包含0體積%~40體積%的氫氣，更佳為包含10體積%~30體積%的氫氣。又，上述混合氣體中，較佳為包含0體積%~50體積%的氨氣，更佳為包含0體積%~40體積%的氨氣。藉由使用該具有還原力的環境氣體，最終能夠製造出不含有低次氧化鋯及低次氮氧化鋯的氮化鋯粉末。另一方面，若氫氣之比例或氨氣之比例高於該範圍時，雖然還原可以進行，但是氮源減少，因此會生成低次氧化鋯或低次氮氧化鋯，故不宜。又，氨氣之比例高於氫氣之比例，係認為是在氣體的氮化能力方面氨比氫高之緣故。 [Ambient gas at the time of reduction reaction by metal magnesium powder] The ambient gas can be nitrogen alone, or a mixture of nitrogen and hydrogen, or a mixture of nitrogen and ammonia. The above-mentioned reduction reaction is carried out in the gas flow of the above-mentioned mixed gas. Nitrogen in the mixed gas has the following functions: to prevent the contact of metal magnesium or reduction products with oxygen, and to prevent the oxidation of these, nitrogen and zirconium are reacted to generate zirconium nitride. The hydrogen or ammonia in the mixed gas has the following function: reducing zirconium dioxide together with metal magnesium. In the above-mentioned mixed gas, it is preferable to contain 0% to 40% by volume of hydrogen, and it is more preferable to contain 10% to 30% of hydrogen by volume. Moreover, in the said mixed gas, it is preferable to contain the ammonia gas of 0 to 50 volume %, and it is more preferable to contain the ammonia gas of 0 to 40 volume %. By using the atmospheric gas having the reducing power, zirconium nitride powder containing no lower-order zirconium oxide and lower-order zirconium oxynitride can finally be produced. On the other hand, if the ratio of hydrogen gas or the ratio of ammonia gas is higher than this range, although the reduction can be carried out, the nitrogen source is reduced, so that lower-order zirconium oxide or lower-order zirconium oxynitride is formed, which is not suitable. In addition, the reason why the ratio of ammonia gas is higher than that of hydrogen gas is considered to be because ammonia is higher than hydrogen in terms of gas nitriding ability.

另一方面，藉由電漿合成法的氮化鋯粗粉末的生成方法為下述之方法：將金屬鋯粉末導入至電漿奈米粒子製造裝置中，以N ₂氣體環境來得到氮化鋯奈米粒子。藉由該方法來合成的氮化鋯，能夠得到以BET法測定的比表面積為20m ²/g~90m ²/g的氮化鋯，但具有下述之缺點：原料的金屬鋯的燃燒性高而危險、及成本提高。尚，藉由電漿合成法所生成的奈米粒子，在冷卻過程、製品取出過程中由於劇烈的表面氧化、附著、凝集等而粗大化，而具有粗粉末的氮化鋯，故亦將藉由電漿合成法所生成的氮化鋯設定為氮化鋯粗粉末。 On the other hand, a method for generating coarse zirconium nitride powder by plasma synthesis is a method of introducing metal zirconium powder into a plasma nanoparticle manufacturing apparatus, and obtaining zirconium nitride in an N ₂ gas atmosphere Nanoparticles. Zirconium nitride synthesized by this method can obtain zirconium nitride with a specific surface area of 20 m ² /g to 90 m ² /g measured by the BET method, but has the following disadvantage: the metal zirconium as the raw material has high flammability Dangerous and costly. However, the nanoparticles generated by the plasma synthesis method are coarsened due to severe surface oxidation, adhesion, agglomeration, etc. during the cooling process and the product extraction process, and have coarse powder of zirconium nitride, so it will also be used. The zirconium nitride produced by the plasma synthesis method was set as a zirconium nitride coarse powder.

接下來，將該氮化鋯粗粉末藉由以10℃以下的分散媒溫度進行低溫濕式介質粉碎或以0.3MPa以上的氣壓進行噴射磨機粉碎，來製作以水或碳數位於3~5的範圍內的醇進行稀釋之狀態下，進行5分鐘超音波分散時的粒度分布D ₉₀為10μm以下的氮化鋯前驅物粉末。尚，該氮化鋯前驅物粉末以BET法測定的比表面積為22m ²/g~120m ²/g。 Next, the zirconium nitride coarse powder is pulverized in a low-temperature wet medium at a dispersion medium temperature of 10° C. or lower, or by jet mill pulverization at an air pressure of 0.3 MPa or higher, to prepare water or carbon numbers of 3 to 5. A zirconium nitride precursor powder with a particle size distribution D ₉₀ of 10 μm or less when ultrasonically dispersed for 5 minutes in a state of being diluted with alcohol within the range of . Furthermore, the specific surface area of the zirconium nitride precursor powder measured by the BET method is 22m ² /g~120m ² /g.

上述低溫濕式介質粉碎法，係指將氮化鋯粗粉末分散於離子交換水或碳數2~5的醇等的分散媒中，並將分散媒溫度以保持在10℃以下之狀態下，使用平均粒徑50μm~500μm的氧化鋯、氧化鋁、玻璃、胺基甲酸酯樹脂等的介質來進行的珠磨機粉碎法。在此，之所以要將分散媒溫度保持在10℃以下，是由於若超過10℃的話，會發生氮化鋯前驅物粉末的粉碎，而使得後述的黑色膜的OD值降低之緣故。尚，為了將分散媒溫度保持在10℃以下，可使用液體氮來作為分散媒，或可使用乾冰珠粒來作為介質。又，若將氮化鋯粗粉末以上述低溫濕式介質粉碎法來進行粉碎的話，由於發熱量少，故不會進行氮化鋯的表面氧化，而能夠維持高的黑色度。The above-mentioned low-temperature wet medium pulverization method refers to dispersing the coarse powder of zirconium nitride in a dispersing medium such as ion-exchanged water or an alcohol having 2 to 5 carbon atoms, and keeping the temperature of the dispersing medium in a state of below 10°C, A bead mill pulverization method using media such as zirconia, alumina, glass, urethane resin, and the like with an average particle diameter of 50 μm to 500 μm. Here, the reason why the temperature of the dispersion medium is kept below 10°C is that if it exceeds 10°C, the zirconium nitride precursor powder is pulverized and the OD value of the black film described later is lowered. Furthermore, in order to keep the temperature of the dispersion medium below 10°C, liquid nitrogen may be used as the dispersion medium, or dry ice beads may be used as the medium. In addition, when the zirconium nitride coarse powder is pulverized by the above-mentioned low-temperature wet medium pulverization method, the surface oxidation of the zirconium nitride is not carried out because of a small amount of heat generation, and a high blackness can be maintained.

又，氣壓0.3MPa以上的噴射磨機粉碎，係指下述之裝置：將作為超高速噴流的來自噴嘴所噴射的0.3MPa以上的高壓的空氣、氮等的惰性氣體、或蒸氣碰撞於粉末，藉由粉末彼此之撞擊來進行粉碎至數μm等級的微粉末之裝置，所噴射的空氣或蒸氣為達到音速左右。作為噴射磨機之特徵，可舉出所噴射的氣體因為絕熱膨脹而溫度會降低，故可以低溫來進行粉碎，即便是如本發明中的氮化鋯般的還原性物質，亦能抑制該氧化。在此，之所以要將上述氣壓限定在0.3MPa以上，是由於若未滿0.3MPa的話，會殘留氮化鋯粗粉末之緣故。尚，若將氮化鋯粗粉末以上述噴射磨機粉碎法來進行粉碎的話，將不會殘留氮化鋯粗粉末，而能夠提昇黑色膜的絕緣性。In addition, pulverization by a jet mill with a pressure of 0.3 MPa or more refers to a device that collides with a powder, an inert gas such as high-pressure air, nitrogen, etc., or vapor of a high pressure of 0.3 MPa or more sprayed from a nozzle as an ultra-high-speed jet flow, A device that pulverizes micro-powders of several μm level by the collision of powders with each other, and the ejected air or steam reaches about the speed of sound. As a feature of the jet mill, the temperature of the jetted gas decreases due to adiabatic expansion, so it can be pulverized at a low temperature, and even a reducing substance such as zirconium nitride in the present invention can suppress the oxidation. . Here, the reason why the above-mentioned gas pressure is limited to 0.3 MPa or more is because if it is less than 0.3 MPa, the coarse powder of zirconium nitride will remain. Furthermore, if the coarse zirconium nitride powder is pulverized by the above-mentioned jet mill pulverization method, the coarse zirconium nitride powder will not remain, and the insulating properties of the black film can be improved.

進而，藉由將該經粉碎的氮化鋯前驅物粉末在惰性氣體環境中燒成，來製造在以5MPa的壓力進行壓實而得的壓粉體之狀態下，體積電阻率為10 ⁷Ω・cm以上的氮化鋯粉末。作為惰性氣體，可舉出N ₂氣體、氦氣、氬氣等。上述燒成溫度較佳為在250℃~550℃的範圍內，燒成時間較佳為在1小時~5小時的範圍內。在此，之所以要將較佳的燒成溫度限定在250℃~550℃的範圍內，是由於若未滿250℃的話，電阻值的上昇會不足，若超過550℃的話，會發生粉末彼此的熔接，而使得粗粉末增加之緣故。又，之所以要將較佳的燒成時間限定在1小時~5小時的範圍內，是由於若未滿1小時的話，電阻值的上昇會不足，即便是超過5小時，效果亦不會變化，而不經濟之緣故。尚，藉由將氮化鋯前驅物粉末在惰性氣體環境中進行燒成，將能夠提昇黑色膜的絕緣性。藉由在惰性氣體環境中的燒成而能夠提昇黑色膜的絕緣性之詳細機制尚不明確，但可推測是起因於氮化鋯的粗粉末的消失而使得粉末的均勻性變得良好、或接觸點的減少、或於黑色膜的表面形成了極薄的絕緣層所致。 Furthermore, by sintering the pulverized zirconium nitride precursor powder in an inert gas atmosphere, a compacted powder compacted at a pressure of 5 MPa was produced, and the volume resistivity was 10 ⁷ Ω・Zirconium nitride powder over cm. As an inert gas, N ₂ gas, helium gas, argon gas, etc. are mentioned. The above-mentioned firing temperature is preferably in the range of 250° C. to 550° C., and the firing time is preferably in the range of 1 hour to 5 hours. Here, the reason why the preferable firing temperature is limited to the range of 250°C to 550°C is that if the temperature is less than 250°C, the increase in the resistance value will be insufficient, and if it exceeds 550°C, the powders will interact with each other. The welding, which makes the coarse powder increase. In addition, the reason why the preferable firing time is limited to the range of 1 hour to 5 hours is that if it is less than 1 hour, the rise of the resistance value will be insufficient, and even if it exceeds 5 hours, the effect will not change. , not for economic reasons. Furthermore, by firing the zirconium nitride precursor powder in an inert gas environment, the insulating properties of the black film can be improved. The detailed mechanism by which the insulating properties of the black film can be improved by firing in an inert gas atmosphere is not clear, but it is presumed that the uniformity of the powder is improved due to the disappearance of the coarse powder of zirconium nitride, or The reduction of contact points or the formation of an extremely thin insulating layer on the surface of the black film.

將上述氮化鋯粉末分散於丙烯酸單體或環氧單體中，來調製單體分散體。該單體分散體係對於使無機粉末分散並含有該無機粉末的樹脂組成物、樹脂成形體等之用途為有用的。又，上述單體分散體能夠進一步包含金屬氧化物粉末，並能夠進一步含有可塑劑。作為可塑劑並未特別限定，可舉例如：磷酸三丁酯、磷酸2-乙基己酯等的磷酸酯系可塑劑、鄰苯二甲酸二甲酯、鄰苯二甲酸二丁酯等的鄰苯二甲酸酯系可塑劑、油酸丁酯、甘油單油酸酯等的脂肪族-鹼性酯系可塑劑、己二酸酸二丁酯、癸二酸二-2-乙基己酯等的脂肪族二元酸酯系可塑劑；二乙二醇二苯甲酸酯、三乙二醇二-2-乙基丁酸酯等的二價醇酯系可塑劑；乙醯蓖麻油酸甲酯、乙醯檸檬酸三丁酯等含氧酸酯系可塑劑等的以往周知的可塑劑。進而，單體分散體中能夠進一步添加其他的單體。作為其他的單體並未特別限定，可舉例如：(甲基)丙烯酸、(甲基)丙烯酸酯等的(甲基)丙烯酸系單體；苯乙烯、乙烯基甲苯、二乙烯基苯等的苯乙烯系單體；氯乙烯、乙酸乙烯酯等的乙烯基系單體；胺基甲酸酯丙烯酸酯等的胺基甲酸酯系單體；上述各種多元醇類等的以往周知的單體。尚，考量氮化鋯粉末的分散性，單體分散體的黏度較佳設定在10Pa･s~1000mPa･s的範圍內。對於單體之分散，亦可與對於溶劑之分散為相同地，採用使用粉碎介質的磨機方式。又，雖然不為必須成分，但為了更提昇分散性，亦可使用高分子分散劑。高分子分散劑係以分子量為數千~數萬為有效的，又，作為吸附於顏料的官能基，可舉出二級胺、三級胺、羧酸、磷酸、磷酸酯等，特別以三級胺、羧酸為有效。亦可添加少量的矽烷偶合劑來取代高分子分散劑，對於分散性的提昇為有效的。另一方面，在實施行星式攪拌後通過三軸輥數次，亦可得到分散液。另一方面，將氮化鋯粉末作為黑色顏料分散於分散媒中並進一步混合樹脂來調製黑色組成物。作為該上述分散媒，可舉出丙二醇單甲基醚乙酸酯(PGMEA)、甲基乙基酮(MEK)、乙酸丁酯(BA)等。又，作為上述樹脂，可舉出丙烯酸樹脂、環氧樹脂等。關於溶劑系分散，係與單體分散為相同地，高分子分散劑的添加為有效的，亦與單體分散為相同地，以分子量為數千至數萬為有效的，作為官能基，以三級胺、羧酸為有效的。The above-mentioned zirconium nitride powder is dispersed in an acrylic monomer or an epoxy monomer to prepare a monomer dispersion. The monomer dispersion system is useful for use in resin compositions, resin moldings, and the like that disperse inorganic powders and contain the inorganic powders. Moreover, the said monomer dispersion can further contain a metal oxide powder, and can further contain a plasticizer. The plasticizer is not particularly limited, and examples thereof include phosphate-based plasticizers such as tributyl phosphate and 2-ethylhexyl phosphate, and orthophthalic plasticizers such as dimethyl phthalate and dibutyl phthalate. Phthalate-based plasticizers, aliphatic-basic ester-based plasticizers such as butyl oleate and glycerol monooleate, dibutyl adipate, di-2-ethylhexyl sebacate Aliphatic dibasic acid ester plasticizers such as diethylene glycol dibenzoate, divalent alcohol ester plasticizers such as triethylene glycol di-2-ethyl butyrate, etc.; acetyl ricinoleic acid Conventionally known plasticizers such as oxoester-based plasticizers such as methyl ester and acetonitrile tributyl citrate. Furthermore, other monomers can be further added to the monomer dispersion. It does not specifically limit as another monomer, For example, (meth)acrylic-type monomers, such as (meth)acrylic acid, (meth)acrylate, etc.; styrene, vinyltoluene, divinylbenzene, etc. are mentioned. Styrene-based monomers; vinyl-based monomers such as vinyl chloride and vinyl acetate; urethane-based monomers such as urethane acrylates; conventionally known monomers such as the aforementioned various polyols . Furthermore, considering the dispersibility of the zirconium nitride powder, the viscosity of the monomer dispersion is preferably set in the range of 10Pa･s~1000mPa･s. For the dispersion of the monomer, a mill method using a pulverizing medium may be employed in the same manner as for the dispersion of the solvent. Moreover, although it is not an essential component, in order to further improve dispersibility, you may use a polymeric dispersing agent. The polymer dispersant is effective with a molecular weight of several thousands to tens of thousands, and as the functional group adsorbed on the pigment, secondary amines, tertiary amines, carboxylic acids, phosphoric acid, phosphoric acid esters, etc. Grade amines and carboxylic acids are effective. A small amount of silane coupling agent can also be added to replace the polymer dispersant, which is effective for improving the dispersibility. On the other hand, after carrying out planetary stirring, a dispersion liquid can also be obtained by passing through a three-axis roll several times. On the other hand, zirconium nitride powder is dispersed in a dispersion medium as a black pigment, and a resin is further mixed to prepare a black composition. As the said dispersing medium, propylene glycol monomethyl ether acetate (PGMEA), methyl ethyl ketone (MEK), butyl acetate (BA), etc. are mentioned. Moreover, as said resin, an acrylic resin, an epoxy resin, etc. are mentioned. With regard to solvent-based dispersion, the addition of a polymer dispersant is the same as that of monomer dispersion, and the addition of a polymer dispersant is also effective as for monomer dispersion, and the molecular weight is thousands to tens of thousands. Tertiary amines and carboxylic acids are effective.

接下來，對於使用上述單體分散體來製作黑色膜之方法進行說明。首先，將光聚合起始劑添加於單體分散體中後，將該單體分散體塗布於基板上來形成塗膜。接下來，將該塗膜熱硬化或紫外線硬化來製作黑色膜。作為上述基板，可舉例如玻璃、矽、聚碳酸酯、聚酯、芳族聚醯胺、聚醯胺醯亞胺、聚醯亞胺等。又，依所希望，亦可對於上述基板施予藉由矽烷偶合劑等的藥劑處理、電漿處理、離子被覆、濺鍍、氣相反應法、真空蒸鍍等的適當的前處理。在將單體分散體塗布於基板之際，能夠採用旋轉塗布、澆鑄塗布、輥塗布等的適當的塗布法。Next, a method for producing a black film using the above-mentioned monomer dispersion will be described. First, after adding a photopolymerization initiator to the monomer dispersion, the monomer dispersion is applied on a substrate to form a coating film. Next, the coating film is thermally cured or cured with ultraviolet rays to prepare a black film. As said board|substrate, glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamide imide, polyimide, etc. are mentioned, for example. Further, as desired, appropriate pretreatments such as chemical treatment with a silane coupling agent, plasma treatment, ion coating, sputtering, gas phase reaction method, and vacuum vapor deposition may be given to the substrate. When applying the monomer dispersion to the substrate, an appropriate coating method such as spin coating, cast coating, and roll coating can be employed.

為了使上述塗膜熱硬化，較佳為在大氣中以80℃~250℃的溫度來保持5分鐘~60分鐘。在此，之所以要將塗膜的熱硬化溫度限定在80℃~250℃的範圍內，是由於若未滿80℃的話，塗膜會無法充分地硬化，若超過250℃的話，基板會軟化之緣故。又，之所以要將塗膜的熱硬化時間限定在5分鐘~60分鐘的範圍內，是由於若未滿5分鐘的話，塗膜會無法充分地硬化，若超過60分鐘的話，會花費較所需之時間為更多的時間，故不經濟。另一方面，為了使上述塗膜紫外線硬化，事先將Irgacure 184(BASF公司製)、Irgacure 250(BASF公司製)、Irgacure 270(BASF公司製)、Irgacure 369(BASF公司製)、Irgacure 500(BASF公司製)、Irgacure 907(BASF公司製)、Adeka Optomer N-1919(ADEKA公司製)等的以紫外線進行裂解的光聚合起始劑添加至單體分散體中。然後，將添加有該光聚合起始劑的單體分散體塗布於基板上後，進行預烘烤來使溶劑蒸發，而形成光阻膜。之後，隔著光罩，對於該光阻膜進行指定的圖型形狀的曝光後，使用鹼顯影液進行顯影，來將光阻膜的未曝光部予以溶解去除，之後，較佳為進行後烘烤，藉此來形成指定的黑色膜。In order to thermoset the said coating film, it is preferable to hold|maintain for 5 minutes - 60 minutes at the temperature of 80 degreeC - 250 degreeC in the air. Here, the reason why the thermal curing temperature of the coating film is limited to the range of 80°C to 250°C is that if it is less than 80°C, the coating film will not be sufficiently cured, and if it exceeds 250°C, the substrate will be softened the reason. In addition, the reason why the thermal curing time of the coating film is limited to the range of 5 minutes to 60 minutes is that if it is less than 5 minutes, the coating film will not be fully cured, and if it exceeds 60 minutes, it will take a lot of time. The time required is more time, so it is not economical. On the other hand, Irgacure 184 (manufactured by BASF), Irgacure 250 (manufactured by BASF), Irgacure 270 (manufactured by BASF), Irgacure 369 (manufactured by BASF), and Irgacure 500 (manufactured by BASF) were previously prepared in order to cure the above-mentioned coating film by ultraviolet rays. Co., Ltd.), Irgacure 907 (manufactured by BASF), and Adeka Optomer N-1919 (manufactured by ADEKA), a photopolymerization initiator that is cleaved by ultraviolet rays is added to the monomer dispersion. Then, after apply|coating the monomer dispersion which added this photoinitiator to a board|substrate, prebaking is performed to evaporate a solvent, and a photoresist film is formed. After that, the photoresist film is exposed to a predetermined pattern shape through a photomask, and then developed using an alkali developer to dissolve and remove the unexposed portion of the photoresist film, and then, preferably, post-baking is performed. Bake, thereby forming the designated black film.

硬化後的黑色膜的膜厚較佳為0.1μm~100μm的範圍內。特別是適合於製作所謂的膜厚為10μm~100μm的厚的黑色膜。又，黑色膜的OD值(Optical Density值)，係指作為表示使用氮化鋯粉末而成的黑色膜的遮光性(穿透率的衰減)的指標的光學濃度。具體而言，OD值是以對數表示的光通過黑色膜之際被吸收的程度的值，以下述式(1)來定義。式(1)中，I為穿透光量，I ₀為入射光量。

進而，為了確保高遮光性，上述黑色膜的OD值較佳為2.0以上，為了確保高的絕緣性，黑色膜的體積電阻率較佳為1×10 ¹³Ω・cm以上。 It is preferable that the film thickness of the black film after hardening exists in the range of 0.1 micrometer - 100 micrometers. In particular, it is suitable for the production of a so-called black film having a thickness of 10 μm to 100 μm. In addition, the OD value (Optical Density value) of a black film means the optical density as an index which shows the light-shielding property (attenuation of transmittance) of the black film formed using zirconium nitride powder. Specifically, the OD value is a logarithmic value of the degree to which light is absorbed when passing through a black film, and is defined by the following formula (1). In formula (1), I is the amount of transmitted light, and I ₀ is the amount of incident light.

Furthermore, in order to ensure high light-shielding properties, the OD value of the black film is preferably 2.0 or more, and the volume resistivity of the black film is preferably 1×10 ¹³ Ω·cm or more in order to ensure high insulating properties.

對於使用上述黑色組成物來製作黑色膜之方法進行說明。首先，將黑色組成物塗布於基板上來形成塗膜。接下來，將該塗膜熱硬化或紫外線硬化來製作黑色膜。使用該黑色組成物的黑色膜之製作方法，係與上述使用單體分散體的黑色膜之製作方法略為相同，故省略重複之說明。 [實施例] A method of producing a black film using the above-mentioned black composition will be described. First, a black composition is applied on a substrate to form a coating film. Next, the coating film is thermally cured or cured with ultraviolet rays to prepare a black film. The production method of the black film using this black composition is almost the same as the above-mentioned production method of the black film using the monomer dispersion, so the repeated description is omitted. [Example]

接下來，將本發明的實施例與比較例一併進行詳細的說明。Next, the Example of this invention is demonstrated in detail together with a comparative example.

＜實施例1＞首先，藉由鋁熱法來製作氮化鋯粗粉末。具體而言，對於以BET法測定的比表面積所算出的平均一次粒徑為50nm的單斜晶系二氧化鋯粉末7.4g，添加平均一次粒徑為150μm的金屬鎂粉末7.3g及平均一次粒徑為200nm的氮化鎂粉末3.0g，利用在石英製玻璃管中內裝有石墨舟的反應裝置來進行均勻混合。此時的金屬鎂的添加量為二氧化鋯的5.0倍莫耳，氮化鎂的添加量為二氧化鋯的0.5倍莫耳。將該混合物在氮氣環境下、以700℃的溫度燒成60分鐘，而得到燒成物。將該燒成物分散於1升的水中，緩慢添加10%鹽酸，使pH成為1以上，使溫度保持在100℃以下之同時進行洗淨後，利用25%氨水調整至pH7~pH8，並進行過濾。將該過濾的固體成分以400g/升再分散於水中，再次與上述相同地進行酸洗淨、利用氨水進行的pH調整後，進行過濾。如此般地將酸洗淨-利用氨水的pH調整重複2次後，將過濾物分散於離子交換水中，使換算為固體成分為500g/升，再進行60℃的加熱攪拌與調整至pH7後，利用吸引過濾裝置過濾，進一步利用等量的離子交換水進行洗淨，以設定溫度：120℃的熱風乾燥機來進行乾燥，而得到氮化鋯粗粉末。 <Example 1> First, zirconium nitride coarse powder is produced by the aluminothermic method. Specifically, to 7.4 g of monoclinic zirconium dioxide powder having an average primary particle diameter of 50 nm calculated from the specific surface area measured by the BET method, 7.3 g of magnesium metal powder having an average primary particle diameter of 150 μm and an average primary particle diameter of 7.3 g were added. 3.0 g of magnesium nitride powder having a diameter of 200 nm was uniformly mixed using a reaction apparatus equipped with a graphite boat in a glass tube made of quartz. The addition amount of metallic magnesium at this time was 5.0 times the mole of zirconium dioxide, and the addition amount of magnesium nitride was 0.5 times the mole of zirconium dioxide. The mixture was fired at a temperature of 700° C. for 60 minutes under a nitrogen atmosphere to obtain a fired product. The calcined product was dispersed in 1 liter of water, 10% hydrochloric acid was gradually added to make pH 1 or higher, and the temperature was kept at 100°C or lower while washing, and then adjusted to pH 7 to pH 8 with 25% ammonia water, and carried out filter. The filtered solid content was redispersed in water at 400 g/liter, acid washing and pH adjustment with ammonia water were performed again in the same manner as above, followed by filtration. After repeating the acid washing and pH adjustment with ammonia water twice in this way, the filtrate was dispersed in ion-exchanged water so that the solid content was 500 g/liter, and the pH was adjusted to 7 by heating and stirring at 60°C. It filtered with a suction filter, washed with an equal amount of ion-exchanged water, and dried with a hot-air dryer with a set temperature of 120° C. to obtain a coarse powder of zirconium nitride.

接下來，將上述氮化鋯粗粉末20g分散於異丙醇5升中，進行低溫濕式介質粉碎(介質：氧化鋁)60分鐘，而得到氮化鋯前驅物粉末。此時的異丙醇(分散媒)的溫度為5℃以下。進而，使上述氮化鋯前驅物粉末乾燥後，在N ₂氣體環境中以350℃的溫度保持4小時來進行燒成，而得到氮化鋯粉末。將該氮化鋯粉末設定為實施例1。 Next, 20 g of the above-mentioned zirconium nitride coarse powder was dispersed in 5 liters of isopropanol, and subjected to low-temperature wet medium pulverization (medium: alumina) for 60 minutes to obtain a zirconium nitride precursor powder. The temperature of the isopropyl alcohol (dispersion medium) at this time is 5°C or lower. Furthermore, after drying the said zirconium nitride precursor powder, it sintered at the temperature of 350 degreeC in _N2 gas atmosphere for 4 hours, and obtained the zirconium nitride powder. This zirconium nitride powder was set as Example 1.

＜實施例2~12及比較例1~10＞實施例2~12及比較例1~10的氮化鋯粉末為利用表1所示之方法，分別生成氮化鋯粗粉末，並將該等分別進行粉碎、進而將該等分別進行燒成。尚，除了表1所示之生成方法、粉碎方法及燒成方法以外，其餘係與實施例1相同地來製作氮化鋯粉末。尚，表1的氮化鋯粗粉末的生成方法之欄位中，「TM」表示鋁熱法，「PZ」表示電漿法。又，表1的氮化鋯粗粉末的粉碎方法之欄位中，「BM」表示珠磨機法，「JM」表示噴射磨機法。進而，表1的氮化鋯前驅物粉末的燒成時間/氣體之欄位中，「N ₂」表示氮氣，「He」表示氦氣，「Ar」表示氬氣。 <Examples 2 to 12 and Comparative Examples 1 to 10> The zirconium nitride powders of Examples 2 to 12 and Comparative Examples 1 to 10 were prepared as coarse zirconium nitride powders by the methods shown in Table 1, respectively, and these The pulverization is performed separately, and these are further fired separately. Furthermore, except for the production method, pulverization method, and firing method shown in Table 1, zirconium nitride powder was produced in the same manner as in Example 1. In addition, in the column of the production method of the zirconium nitride coarse powder in Table 1, "TM" represents the thermite method, and "PZ" represents the plasma method. In addition, in the column of the grinding method of the zirconium nitride coarse powder in Table 1, "BM" represents the bead mill method, and "JM" represents the jet mill method. Furthermore, in the column of firing time/gas of the zirconium nitride precursor powder in Table 1, "N ₂ " means nitrogen gas, "He" means helium gas, and "Ar" means argon gas.

＜比較試驗1＞對於實施例1~12及比較例1~10的氮化鋯粉末，分別測定以5MPa的壓力進行壓實而得的壓粉體之狀態下的體積電阻率、及以水進行稀釋之狀態下並進行5分鐘超音波分散時的粒度分布D ₉₀。將該等的結果表示於表1。 <Comparative Test 1> With respect to the zirconium nitride powders of Examples 1 to 12 and Comparative Examples 1 to 10, the volume resistivity in the state of the compacted powder compacted with a pressure of 5 MPa, and the volume resistivity of the powder compacted with water were measured, respectively. Particle size distribution D ₉₀ in the state of dilution and ultrasonic dispersion for 5 minutes. These results are shown in Table 1.

＜比較試驗2＞關於實施例1~11及比較例1~9的氮化鋯粉末40g，如表1所示般，分散於200毫升的丙烯酸單體或環氧單體中，來調製單體分散體。另一方面，關於實施例12及比較例10的氮化鋯粉末40g，如表1所示般，添加胺系分散劑，在200毫升的丙二醇單甲基醚乙酸酯(PGMEA)溶劑中進行分散處理，來調製黑色顏料分散液後，對於該等的黑色顏料分散液，以質量比記為黑色顏料：樹脂＝3：7之比例來添加丙烯酸樹脂，混合後調製成黑色組成物。然後，對於上述單體分散體或黑色組成物添加Irgacure 500(光聚合起始劑：BASF公司製)4g。接下來，以燒成後的膜厚成為表1所示之厚度之方式，將上述單體分散體或黑色組成物旋轉塗布於玻璃基板上後，進行預烘烤來使溶劑蒸發，而形成光阻膜。進而，隔著光罩，對於該光阻膜進行指定的圖型形狀的曝光後，使用鹼顯影液進行顯影，來將光阻膜的未曝光部予以溶解去除，之後，藉由進行後烘烤，而分別形成黑色膜。對於該等的黑色膜，使用Macbeth公司製的品名D200的濃度計(densitometer)，依據前述式(1)，分別測定紫外線(中心波長370nm)及可視光(中心波長560nm)的OD值，同時亦測定分別的黑色膜的體積電阻率(Ω・cm)。將該等的結果表示於表1。 <Comparative test 2> As shown in Table 1, 40 g of the zirconium nitride powders of Examples 1 to 11 and Comparative Examples 1 to 9 were dispersed in 200 ml of an acrylic monomer or an epoxy monomer to prepare a monomer dispersion. On the other hand, about 40 g of zirconium nitride powders of Example 12 and Comparative Example 10, as shown in Table 1, an amine-based dispersant was added, and the test was carried out in 200 ml of a propylene glycol monomethyl ether acetate (PGMEA) solvent. After dispersion treatment to prepare a black pigment dispersion liquid, an acrylic resin was added to these black pigment dispersion liquids at a mass ratio of black pigment:resin=3:7, and mixed to prepare a black composition. Then, 4 g of Irgacure 500 (photopolymerization initiator: manufactured by BASF Corporation) was added to the above-mentioned monomer dispersion or black composition. Next, after the above-mentioned monomer dispersion or black composition was spin-coated on a glass substrate so that the film thickness after firing became the thickness shown in Table 1, prebaking was performed to evaporate the solvent to form a light barrier film. Furthermore, after exposing the photoresist film in a predetermined pattern shape through a photomask, it is developed using an alkali developer to dissolve and remove the unexposed portion of the photoresist film, and then post-baking is performed. , and black films were formed, respectively. For these black films, the OD values of ultraviolet (central wavelength 370 nm) and visible light (central wavelength 560 nm) were measured according to the aforementioned formula (1) using a densitometer (densitometer) manufactured by Macbeth, Inc. The volume resistivity (Ω·cm) of each black film was measured. These results are shown in Table 1.

由表1可明確得知般，比較例1及10的氮化鋯粉末，即，雖然是藉由鋁熱法來製作氮化鋯粗粉末，但未將該氮化鋯粉碎，在氮氣環境中以350℃的溫度保持4小時來進行燒成而得的氮化鋯粉末，在以5MPa的壓力進行壓實而得的壓粉體之狀態下的體積電阻率為分別1×10 ⁵Ω・cm，而較適宜的範圍(1×10 ⁷Ω・cm以上)為小，以水進行稀釋之狀態下並進行5分鐘超音波分散時的粒度分布D ₉₀分別為30μm，而較適宜的範圍(10μm以下)為大。又，將比較例1的氮化鋯粉末分散於丙烯酸單體中來製作黑色膜的OD值為1.0，而較適宜的範圍(2.0以上)為小，體積電阻率為1×10 ⁶Ω・cm，而較適宜的範圍(1×10 ¹³以上)為小，無法成為均勻的塗膜。更，將比較例10的氮化鋯粉末分散於丙二醇單甲基醚乙酸酯(PGMEA)中來製作黑色膜的OD值為1.9，而較適宜的範圍(2.0以上)為小，體積電阻率為6×10 ¹²Ω・cm，而較適宜的範圍(1×10 ¹³以上)為小。 As is clear from Table 1, the zirconium nitride powders of Comparative Examples 1 and 10, that is, although the zirconium nitride coarse powder was produced by the aluminothermic method, the zirconium nitride was not pulverized, and the zirconium nitride powder was placed in a nitrogen atmosphere. The volume resistivity of the zirconium nitride powder obtained by sintering at 350°C for 4 hours and the compacted powder at a pressure of 5MPa is 1×10 ⁵ Ω·cm, respectively. , and the more suitable range (above 1×10 ⁷ Ω·cm) is small, the particle size distribution D ₉₀ in the state of dilution with water and ultrasonic dispersion for 5 minutes is 30 μm, and the more suitable range (10 μm below) is larger. In addition, the OD value of the black film produced by dispersing the zirconium nitride powder of Comparative Example 1 in an acrylic monomer was 1.0, and the preferred range (2.0 or more) was small, and the volume resistivity was 1×10 ⁶ Ω·cm , and the more suitable range (1×10 ¹³ or more) is small, and a uniform coating film cannot be obtained. Furthermore, the OD value of the black film produced by dispersing the zirconium nitride powder of Comparative Example 10 in propylene glycol monomethyl ether acetate (PGMEA) was 1.9, and the suitable range (2.0 or more) was small, and the volume resistivity was small. is 6×10 ¹² Ω·cm, and the suitable range (1×10 ¹³ or more) is small.

比較例3的氮化鋯粉末，即，雖然是藉由鋁熱法來製作氮化鋯粗粉末，並將該氮化鋯粗粉末以分散媒溫度5℃以下的珠磨機法來進行粉碎(低溫濕式介質粉碎)，但未將氮化鋯前驅物粉末進行燒成而得的氮化鋯粉末，以水進行稀釋之狀態下並進行5分鐘超音波分散時的粒度分布D ₉₀為9μm，雖然是在適宜的範圍(10μm以下)內，但在以5MPa的壓力進行壓實而得的壓粉體之狀態下的體積電阻率為1×10 ⁶Ω・cm，而較適宜的範圍(1×10 ⁷Ω・cm以上)為小。又，將比較例3的氮化鋯粉末分散於丙烯酸單體中來製作的黑色膜的OD值為2.1，雖然是在適宜的範圍(2.0以上)內，但體積電阻率為5×10 ¹¹Ω・cm，而較適宜的範圍(1×10 ¹³以上)為小。 The zirconium nitride powder of Comparative Example 3, that is, the zirconium nitride coarse powder was produced by the aluminothermic method, and the zirconium nitride coarse powder was pulverized by the bead mill method with a dispersion medium temperature of 5°C or lower ( Low-temperature wet medium pulverization), but the zirconium nitride powder obtained by not sintering the zirconium nitride precursor powder, the particle size distribution _D90 of the zirconium nitride powder when it is diluted with water and subjected to ultrasonic dispersion for 5 minutes is 9 μm, Although it is within a suitable range (10 μm or less), the volume resistivity in the state of the compacted powder compacted at a pressure of 5 MPa is 1×10 ⁶ Ω·cm, which is a suitable range (1 ×10 ⁷ Ω·cm or more) is small. In addition, the OD value of the black film prepared by dispersing the zirconium nitride powder of Comparative Example 3 in an acrylic monomer was 2.1, which was within a suitable range (2.0 or more), but the volume resistivity was 5×10 ¹¹ Ω・cm, and a suitable range (1×10 ¹³ or more) is small.

相較於該等，實施例1及12的氮化鋯粉末，即，藉由鋁熱法來製作氮化鋯粗粉末，並將該氮化鋯以分散媒溫度5℃以下的珠磨機法來進行粉碎(低溫濕式介質粉碎)後，在氮氣環境中以350℃的溫度保持4小時來進行燒成而得的氮化鋯粉末，在以5MPa的壓力進行壓實而得的壓粉體之狀態下的體積電阻率分別為1×10 ⁸Ω・cm，而在適宜的範圍(1×10 ⁷Ω・cm以上)內，以水進行稀釋之狀態下並進行5分鐘超音波分散時的粒度分布D ₉₀分別為7μm，而在適宜的範圍(10μm以下)內。又，將實施例1的氮化鋯粉末分散於丙烯酸單體中來製作的黑色膜的OD值為2.1，而在適宜的範圍(2.0以上)內，體積電阻率為5×10 ¹³Ω・cm，而在適宜的範圍(1×10 ¹³以上)。更，將實施例12的氮化鋯粉末分散於丙二醇單甲基醚乙酸酯(PGMEA)中來製作的黑色膜的OD值為2.1，而在適宜的範圍(2.0以上)內，體積電阻率為5×10 ¹³Ω・cm，而在適宜的範圍(1×10 ¹³以上)內。 In contrast to these, the zirconium nitride powders of Examples 1 and 12, that is, the zirconium nitride coarse powder was produced by the aluminothermic method, and the zirconium nitride was subjected to a bead mill method in which the dispersion medium temperature was 5°C or lower. Zirconium nitride powder obtained by pulverization (low-temperature wet medium pulverization), sintered at a temperature of 350° C. in a nitrogen atmosphere for 4 hours, and compacted at a pressure of 5 MPa The volume resistivity in the state was 1 × 10 ⁸ Ω·cm, respectively, and within the appropriate range (1 × 10 ⁷ Ω·cm or more), when diluted with water and ultrasonically dispersed for 5 minutes The particle size distribution D ₉₀ was 7 μm, respectively, and was within a suitable range (10 μm or less). In addition, the OD value of the black film prepared by dispersing the zirconium nitride powder of Example 1 in an acrylic monomer was 2.1, and within a suitable range (2.0 or more), the volume resistivity was 5×10 ¹³ Ω·cm , and in a suitable range (1×10 ¹³ or more). Furthermore, the OD value of the black film prepared by dispersing the zirconium nitride powder of Example 12 in propylene glycol monomethyl ether acetate (PGMEA) was 2.1, and within a suitable range (2.0 or more), the volume resistivity is 5×10 ¹³ Ω·cm, which is within a suitable range (1×10 ¹³ or more).

實施例9的氮化鋯粉末，即，藉由鋁熱法來製作氮化鋯粗粉末，並將該氮化鋯以分散媒溫度5℃的珠磨機法來進行粉碎(低溫濕式介質粉碎)後，在氦氣環境中以350℃的溫度保持4小時來進行燒成而得的氮化鋯粉末，在以5MPa的壓力進行壓實而得的壓粉體之狀態下的體積電阻率為8×10 ⁷Ω・cm，而在適宜的範圍(1×10 ⁷Ω・cm以上)內，以水進行稀釋之狀態下並進行5分鐘超音波分散時的粒度分布D ₉₀為7μm，而在適宜的範圍(10μm以下)內。又，將實施例9的氮化鋯粉末分散於丙烯酸單體中來製作的黑色膜的OD值為2.2，而在適宜的範圍(2.0以上)內，體積電阻率為3×10 ¹³Ω・cm，而在適宜的範圍(1×10 ¹³以上)內。 The zirconium nitride powder of Example 9, that is, a coarse powder of zirconium nitride was produced by the aluminothermic method, and the zirconium nitride was pulverized by a bead mill method with a dispersion medium temperature of 5°C (low temperature wet medium pulverization). ), the zirconium nitride powder obtained by firing at a temperature of 350° C. for 4 hours in a helium atmosphere, and the volume resistivity of the powder compacted at a pressure of 5 MPa 8 × 10 ⁷ Ω·cm, and within a suitable range (above 1 × 10 ⁷ Ω·cm), the particle size distribution D ₉₀ when diluted with water and subjected to ultrasonic dispersion for 5 minutes is 7 μm, while in within a suitable range (10 μm or less). In addition, the OD value of the black film prepared by dispersing the zirconium nitride powder of Example 9 in an acrylic monomer was 2.2, and within a suitable range (2.0 or more), the volume resistivity was 3×10 ¹³ Ω·cm , and within a suitable range (1×10 ¹³ or more).

實施例10的氮化鋯粉末，即，藉由鋁熱法來製作氮化鋯粗粉末，並將該氮化鋯以分散媒溫度5℃的珠磨機法來進行粉碎(低溫濕式介質粉碎)後，在氬氣環境中以350℃的溫度保持4小時來進行燒成而得的氮化鋯粉末，在以5MPa的壓力進行壓實而得的壓粉體之狀態下的體積電阻率為8×10 ⁷Ω・cm，而在適宜的範圍(1×10 ⁷Ω・cm以上)內，以水進行稀釋之狀態下並進行5分鐘超音波分散時的粒度分布D ₉₀為9μm，而在適宜的範圍(10μm以下)內。又，將實施例10的氮化鋯粉末分散於丙烯酸單體中來製作的黑色膜的OD值為2.2，而在適宜的範圍(2.0以上)內，體積電阻率為3×10 ¹³Ω・cm，而在適宜的範圍(1×10 ¹³以上)內。 The zirconium nitride powder of Example 10, that is, a coarse zirconium nitride powder was produced by the aluminothermic method, and the zirconium nitride was pulverized by a bead mill method with a dispersion medium temperature of 5°C (low temperature wet medium pulverization). ), the volume resistivity of the zirconium nitride powder obtained by sintering at 350°C for 4 hours in an argon atmosphere in the state of the compacted powder compacted at a pressure of 5 MPa 8 × 10 ⁷ Ω·cm, and within a suitable range (above 1 × 10 ⁷ Ω·cm), the particle size distribution D ₉₀ in the state of dilution with water and ultrasonic dispersion for 5 minutes is 9 μm, while in within a suitable range (10 μm or less). In addition, the OD value of the black film prepared by dispersing the zirconium nitride powder of Example 10 in an acrylic monomer was 2.2, and within a suitable range (2.0 or more), the volume resistivity was 3×10 ¹³ Ω·cm , and within a suitable range (1×10 ¹³ or more).

另一方面，比較例2的氮化鋯粉末，即，雖然是藉由電漿法來製作氮化鋯粗粉末，但未將該氮化鋯粉碎，在氮氣環境中以350℃的溫度保持4小時來進行燒成而得的氮化鋯粉末，在以5MPa的壓力進行壓實而得的壓粉體之狀態下的體積電阻率為3×10 ⁴Ω・cm，而較適宜的範圍(1×10 ⁷Ω・cm以上)為小，以水進行稀釋之狀態下並進行5分鐘超音波分散時的粒度分布D ₉₀為14μm，而較適宜的範圍(10μm以下)為大。又，將比較例2的氮化鋯粉末分散於環氧單體中來製作的黑色膜的OD值為1.2，而較適宜的範圍(2.0以上)為小，體積電阻率為2×10 ⁶Ω・cm，而較適宜的範圍(1×10 ¹³以上)為小。 On the other hand, the zirconium nitride powder of Comparative Example 2, that is, the zirconium nitride coarse powder was produced by the plasma method, but the zirconium nitride was not pulverized, and was kept at a temperature of 350° C. in a nitrogen atmosphere for 4 The volume resistivity of the zirconium nitride powder obtained by sintering at a pressure of 5 MPa in the state of the powder compact is 3×10 ⁴ Ω·cm, and a suitable range (1 ×10 ⁷ Ω·cm or more) is small, and the particle size distribution D ₉₀ when ultrasonically dispersed for 5 minutes in a state of dilution with water is 14 μm, and a suitable range (10 μm or less) is large. In addition, the OD value of the black film prepared by dispersing the zirconium nitride powder of Comparative Example 2 in an epoxy monomer was 1.2, and the suitable range (2.0 or more) was small, and the volume resistivity was 2×10 ⁶ Ω・cm, and a suitable range (1×10 ¹³ or more) is small.

比較例4的氮化鋯粉末，即，雖然是藉由電漿法來製作氮化鋯粗粉末，並將該氮化鋯粗粉末以分散媒溫度5℃以下的珠磨機法來進行粉碎(低溫濕式介質粉碎)，但未將氮化鋯前驅物粉末進行燒成而得的氮化鋯粉末，以水進行稀釋之狀態下並進行5分鐘超音波分散時的粒度分布D ₉₀為5μm，雖然是在適宜的範圍(10μm以下)內，但在以5MPa的壓力進行壓實而得的壓粉體之狀態下的體積電阻率為2×10 ⁴Ω・cm，而較適宜的範圍(1×10 ⁷Ω・cm以上)為小。又，將比較例4的氮化鋯粉末分散於環氧單體中來製作的黑色膜的OD值為2.0，雖然是在適宜的範圍(2.0以上)內，但體積電阻率為2×10 ¹⁰Ω・cm，而較適宜的範圍(1×10 ¹³以上)為小。 The zirconium nitride powder of Comparative Example 4, that is, the zirconium nitride coarse powder was produced by the plasma method, and the zirconium nitride coarse powder was pulverized by the bead mill method with a dispersion medium temperature of 5°C or lower ( Low-temperature wet medium pulverization), but the zirconium nitride powder obtained by not sintering the zirconium nitride precursor powder, the particle size distribution _D90 of the zirconium nitride powder when it is diluted with water and subjected to ultrasonic dispersion for 5 minutes is 5 μm, Although it is within a suitable range (10 μm or less), the volume resistivity in the state of the compacted powder compacted at a pressure of 5 MPa is 2×10 ⁴ Ω·cm, which is a suitable range (1 ×10 ⁷ Ω·cm or more) is small. In addition, the OD value of the black film prepared by dispersing the zirconium nitride powder of Comparative Example 4 in an epoxy monomer was 2.0, which was within a suitable range (2.0 or more), but the volume resistivity was 2×10 ¹⁰ Ω·cm, and the more suitable range (1×10 ¹³ or more) is small.

相較於該等，實施例2及4的氮化鋯粉末，即，藉由電漿法來製作氮化鋯粗粉末，並將該氮化鋯粗粉末以分散媒溫度5℃以下的珠磨機法來進行粉碎(低溫濕式介質粉碎)後，在氮氣環境中以350℃的溫度保持4小時來進行燒成而得的氮化鋯粉末，在以5MPa的壓力進行壓實而得的壓粉體之狀態下的體積電阻率分別為1×10 ⁷Ω・cm，而在適宜的範圍(1×10 ⁷Ω・cm以上)內，以水進行稀釋之狀態下並進行5分鐘超音波分散時的粒度分布D ₉₀分別為5μm，而在適宜的範圍(10μm以下)內。又，將實施例2的氮化鋯粉末分散於環氧單體中來製作的黑色膜的OD值為2.2，而在適宜的範圍(2.0以上)內，體積電阻率為2×10 ¹³Ω・cm，而在適宜的範圍(1×10 ¹³以上)內。更，將實施例4的氮化鋯粉末分散於丙烯酸單體中來製作的黑色膜的OD值為2.3，而在適宜的範圍(2.0以上)內，體積電阻率為1×10 ¹³Ω・cm，而在適宜的範圍(1×10 ¹³以上)內。 In contrast to these, the zirconium nitride powders of Examples 2 and 4, that is, the zirconium nitride coarse powders were produced by the plasma method, and the zirconium nitride coarse powders were bead milled with a dispersion medium temperature of 5°C or lower. The zirconium nitride powder obtained by sintering at a temperature of 350° C. for 4 hours in a nitrogen atmosphere after being pulverized by a mechanical method (low-temperature wet medium pulverization) was compacted at a pressure of 5 MPa. The volume resistivity in the powder state is 1 × 10 ⁷ Ω·cm, respectively, and within the appropriate range (1 × 10 ⁷ Ω·cm or more), it is diluted with water and ultrasonically dispersed for 5 minutes. The particle size distribution D ₉₀ at 5 μm, respectively, was within a suitable range (10 μm or less). In addition, the OD value of the black film prepared by dispersing the zirconium nitride powder of Example 2 in an epoxy monomer was 2.2, and within a suitable range (2.0 or more), the volume resistivity was 2×10 ¹³ Ω· cm, and within the appropriate range (1×10 ¹³ or more). Furthermore, the OD value of the black film prepared by dispersing the zirconium nitride powder of Example 4 in acrylic monomer was 2.3, and within a suitable range (2.0 or more), the volume resistivity was 1×10 ¹³ Ω·cm , and within a suitable range (1×10 ¹³ or more).

另一方面，比較例5的氮化鋯粉末，即，藉由鋁熱法來製作氮化鋯粗粉末，但將該氮化鋯粗粉末以較適宜的分散媒溫度範圍(10℃以下)為高的分散媒溫度12℃的珠磨機法來進行粉碎(低溫濕式介質粉碎)後，在氮氣環境中以350℃的溫度保持4小時來進行燒成而得的氮化鋯粉末，以水進行稀釋之狀態下並進行5分鐘超音波分散時的粒度分布D ₉₀為10μm，雖然是在適宜的範圍(10μm以下)內，但在以5MPa的壓力進行壓實而得的壓粉體之狀態下的體積電阻率為7×10 ⁶Ω・cm，而較適宜的範圍(1×10 ⁷Ω・cm以上)為小。又，將比較例5的氮化鋯粉末分散於丙烯酸單體中來製作的黑色膜的OD值為2.0，雖然是在適宜的範圍(2.0以上)內，但體積電阻率為4×10 ¹²Ω・cm，而較適宜的範圍(1×10 ¹³以上)為小。 On the other hand, the zirconium nitride powder of Comparative Example 5, that is, the zirconium nitride coarse powder was produced by the aluminothermic method, but the zirconium nitride coarse powder was in a suitable dispersion medium temperature range (10°C or lower) as Zirconium nitride powder obtained by pulverizing with a bead mill method at a high dispersion medium temperature of 12°C (low-temperature wet medium pulverization), and holding it at a temperature of 350°C for 4 hours in a nitrogen atmosphere, was mixed with water. The particle size distribution D ₉₀ when ultrasonically dispersed for 5 minutes in the diluted state is 10 μm, which is within a suitable range (10 μm or less), but in the state of the compacted powder compacted at a pressure of 5 MPa The volume resistivity at 7×10 6 Ω·cm is 7×10 ⁶ Ω·cm, and the suitable range (1×10 ⁷ Ω·cm or more) is small. In addition, the OD value of the black film prepared by dispersing the zirconium nitride powder of Comparative Example 5 in an acrylic monomer was 2.0, which was within a suitable range (2.0 or more), but the volume resistivity was 4×10 ¹² Ω・cm, and a suitable range (1×10 ¹³ or more) is small.

相對於此，實施例5的氮化鋯粉末，即，藉由鋁熱法來製作氮化鋯粗粉末，但將該氮化鋯粗粉末以適宜的分散媒溫度範圍(10℃以下)內的分散媒溫度10℃的珠磨機法來進行粉碎(低溫濕式介質粉碎)後，在氮氣環境中以350℃的溫度保持4小時來進行燒成而得的氮化鋯粉末，在以5MPa的壓力進行壓實而得的壓粉體之狀態下的體積電阻率為8×10 ⁷Ω・cm，而在適宜的範圍(1×10 ⁷Ω・cm以上)內，以水進行稀釋之狀態下並進行5分鐘超音波分散時的粒度分布D ₉₀為10μm，而在適宜的範圍(10μm以下)內。又，將實施例5的氮化鋯粉末分散於丙烯酸單體中來製作的黑色膜的OD值為2.0，而在適宜的範圍(2.0以上)內，體積電阻率為3×10 ¹³Ω・cm，而在適宜的範圍(1×10 ¹³以上)內。 On the other hand, the zirconium nitride powder of Example 5, that is, the zirconium nitride coarse powder was produced by the aluminothermic method, but the zirconium nitride coarse powder was heated in a suitable dispersion medium temperature range (10° C. or less). The zirconium nitride powder obtained by pulverizing by the bead mill method at a dispersion medium temperature of 10°C (low-temperature wet medium pulverization), held at a temperature of 350°C for 4 hours in a nitrogen atmosphere, was calcined at a temperature of 5MPa. The volume resistivity of the powder compacted under pressure is 8 × 10 ⁷ Ω·cm, and it is within a suitable range (1 × 10 ⁷ Ω·cm or more) when diluted with water. The particle size distribution D ₉₀ when ultrasonic dispersion was carried out for 5 minutes was 10 μm, which was within a suitable range (10 μm or less). In addition, the OD value of the black film prepared by dispersing the zirconium nitride powder of Example 5 in an acrylic monomer was 2.0, and within a suitable range (2.0 or more), the volume resistivity was 3×10 ¹³ Ω·cm , and within a suitable range (1×10 ¹³ or more).

另一方面，比較例6的氮化鋯粉末，即，藉由鋁熱法來製作氮化鋯粗粉末，並將該氮化鋯粗粉末以分散媒溫度5℃的珠磨機法來進行粉碎(低溫濕式介質粉碎)後，但在氮氣環境中以低於適宜的燒成溫度範圍(250℃~550℃)的200℃的溫度，保持在適宜的燒成時間範圍(1小時~5小時)內的4小時來進行燒成而得的氮化鋯粉末，以水進行稀釋之狀態下並進行5分鐘超音波分散時的粒度分布D ₉₀為8μm，雖然是在適宜的範圍(10μm以下)內，但在以5MPa的壓力進行壓實而得的壓粉體之狀態下的體積電阻率為1×10 ⁶Ω・cm，而較適宜的範圍(1×10 ⁷Ω・cm以上)為小。又，將比較例6的氮化鋯粉末分散於丙烯酸單體中來製作的黑色膜的OD值為2.0，雖然是在適宜的範圍(2.0以上)內，但體積電阻率為1×10 ¹²Ω・cm，而較適宜的範圍(1×10 ¹³以上)為小。 On the other hand, the zirconium nitride powder of Comparative Example 6, that is, the zirconium nitride coarse powder was produced by the aluminothermic method, and the zirconium nitride coarse powder was pulverized by the bead mill method at a dispersion medium temperature of 5°C After (low temperature wet medium pulverization), but in a nitrogen atmosphere at a temperature of 200 °C lower than the appropriate firing temperature range (250 °C ~ 550 °C), keep it in the appropriate firing time range (1 hour ~ 5 hours) The zirconium nitride powder obtained by sintering for 4 hours within ), the particle size distribution D ₉₀ when ultrasonically dispersed for 5 minutes in the state of dilution with water is 8 μm, although it is in a suitable range (10 μm or less) However, the volume resistivity in the state of the compact powder compacted at a pressure of 5 MPa is 1×10 ⁶ Ω·cm, and the suitable range (1×10 ⁷ Ω·cm or more) is as small as 1×10 6 Ω·cm. . In addition, the OD value of the black film prepared by dispersing the zirconium nitride powder of Comparative Example 6 in an acrylic monomer was 2.0, which was within a suitable range (2.0 or more), but the volume resistivity was 1×10 ¹² Ω・cm, and a suitable range (1×10 ¹³ or more) is small.

比較例7的氮化鋯粉末，即，藉由鋁熱法來製作氮化鋯粗粉末，並將該氮化鋯粗粉末以分散媒溫度5℃的珠磨機法來進行粉碎(低溫濕式介質粉碎)後，但在氮氣環境中以適宜的燒成溫度範圍(250℃~550℃)內的350℃的溫度，保持在短於適宜的燒成溫度範圍(1小時~5小時)的0.5小時來進行燒成而得的氮化鋯粉末，以水進行稀釋之狀態下並進行5分鐘超音波分散時的粒度分布D ₉₀為7μm，雖然是在適宜的範圍(10μm以下)內，但在以5MPa的壓力進行壓實而得的壓粉體之狀態下的體積電阻率為3×10 ⁶Ω・cm，而較適宜的範圍(1×10 ⁷Ω・cm以上)為小。又，將比較例7的氮化鋯粉末分散於丙烯酸單體中來製作的黑色膜的OD值為2.0，雖然是在適宜的範圍(2.0以上)內，但體積電阻率為2×10 ¹²Ω・cm，而較適宜的範圍(1×10 ¹³以上)為小。 The zirconium nitride powder of Comparative Example 7, that is, a zirconium nitride coarse powder was produced by the aluminothermic method, and the zirconium nitride coarse powder was pulverized by a bead mill method with a dispersion medium temperature of 5°C (low temperature wet method). After the medium is crushed), but in a nitrogen atmosphere at a temperature of 350 °C within the appropriate firing temperature range (250 °C ~ 550 °C), it is kept at a temperature of 0.5°C shorter than the appropriate firing temperature range (1 hour ~ 5 hours). The particle size distribution D ₉₀ of the zirconium nitride powder obtained by sintering for 5 minutes in the state of being diluted with water and ultrasonically dispersed for 5 minutes is 7 μm, which is within a suitable range (10 μm or less), but in The volume resistivity in the state of the compacted powder compacted at a pressure of 5 MPa is 3×10 ⁶ Ω·cm, and a suitable range (1×10 ⁷ Ω·cm or more) is small. In addition, the OD value of the black film prepared by dispersing the zirconium nitride powder of Comparative Example 7 in an acrylic monomer was 2.0, which was within a suitable range (2.0 or more), but the volume resistivity was 2×10 ¹² Ω・cm, and a suitable range (1×10 ¹³ or more) is small.

比較例8的氮化鋯粉末，即，藉由鋁熱法來製作氮化鋯粗粉末，並將該氮化鋯粗粉末以分散媒溫度5℃的珠磨機法來進行粉碎(低溫濕式介質粉碎)後，但在氮氣環境中以高於適宜的燒成溫度範圍(250℃~550℃)的600℃的溫度，保持在適宜的燒成時間範圍(1小時~5小時)內的1小時來進行燒成而得的氮化鋯粉末，在以5MPa的壓力進行壓實而得的壓粉體之狀態下的體積電阻率為4×10 ⁶Ω・cm，而較適宜的範圍(1×10 ⁷Ω・cm以上)為小，以水進行稀釋之狀態下並進行5分鐘超音波分散時的粒度分布D ₉₀為14μm，而較適宜的範圍(10μm以下)為大。又，將比較例8的氮化鋯粉末分散於丙烯酸單體中來製作的黑色膜的OD值為1.2，而較適宜的範圍(2.0以上)為，體積電阻率為1×10 ⁹Ω・cm，而較適宜的範圍(1×10 ¹³以上)為小。 The zirconium nitride powder of Comparative Example 8, that is, a zirconium nitride coarse powder was produced by the aluminothermic method, and the zirconium nitride coarse powder was pulverized by a bead mill method with a dispersion medium temperature of 5°C (low temperature wet method). After the medium is crushed), but in a nitrogen atmosphere at a temperature of 600 °C higher than the appropriate firing temperature range (250 °C ~ 550 °C), it is maintained within the appropriate firing time range (1 hour ~ 5 hours) within 1 hour. The volume resistivity of the zirconium nitride powder obtained by sintering at a pressure of 5 MPa in the state of the powder compact is 4×10 ⁶ Ω·cm, which is a suitable range (1 ×10 ⁷ Ω·cm or more) is small, and the particle size distribution D ₉₀ when ultrasonically dispersed for 5 minutes in a state of dilution with water is 14 μm, and a suitable range (10 μm or less) is large. In addition, the OD value of the black film prepared by dispersing the zirconium nitride powder of Comparative Example 8 in an acrylic monomer was 1.2, and a suitable range (2.0 or more) was that the volume resistivity was 1×10 ⁹ Ω·cm , and the more suitable range (more than 1×10 ¹³ ) is small.

相較於該等，實施例6的氮化鋯粉末，即，藉由鋁熱法來製作氮化鋯粗粉末，並將該氮化鋯粗粉末以分散媒溫度5℃的珠磨機法來進行粉碎(低溫濕式介質粉碎)後，在氮氣環境中以適宜的燒成溫度範圍(250℃~550℃)內的250℃的溫度，保持在適宜的燒成時間範圍(1小時~5小時)內的4小時來進行燒成而得的氮化鋯粉末，在以5MPa的壓力進行壓實而得的壓粉體之狀態下的體積電阻率為3×10 ⁷Ω・cm，而在適宜的範圍(1×10 ⁷Ω・cm以上)內，以水進行稀釋之狀態下並進行5分鐘超音波分散時的粒度分布D ₉₀為8μm，而在適宜的範圍(10μm以下)內。又，將實施例6的氮化鋯粉末分散於丙烯酸單體中來製作的黑色膜的OD值為2.0，而在適宜的範圍(2.0以上)內，體積電阻率為2×10 ¹³Ω・cm，而在適宜的範圍(1×10 ¹³以上)內。 In contrast to these, the zirconium nitride powder of Example 6, that is, the zirconium nitride coarse powder was produced by the aluminothermic method, and the zirconium nitride coarse powder was subjected to a bead mill method with a dispersion medium temperature of 5°C. After pulverization (low-temperature wet medium pulverization), in a nitrogen atmosphere at a temperature of 250°C within a suitable firing temperature range (250°C to 550°C), keep it within a suitable firing time range (1 hour to 5 hours). The zirconium nitride powder obtained by firing for 4 hours within ) has a volume resistivity of 3×10 ⁷ Ω·cm in the state of the powder compact obtained by pressing at a pressure of 5 MPa, and it is suitable for Within the range of 1×10 ⁷ Ω·cm or more, the particle size distribution D ₉₀ in the state of dilution with water and ultrasonic dispersion for 5 minutes is 8 μm, which is within the appropriate range (10 μm or less). In addition, the OD value of the black film prepared by dispersing the zirconium nitride powder of Example 6 in an acrylic monomer was 2.0, and within a suitable range (2.0 or more), the volume resistivity was 2×10 ¹³ Ω·cm , and within a suitable range (1×10 ¹³ or more).

實施例7的氮化鋯粉末，即，藉由鋁熱法來製作氮化鋯粗粉末，並將該氮化鋯粗粉末以分散媒溫度5℃的珠磨機法來進行粉碎(低溫濕式介質粉碎)後，在氮氣環境中以適宜的燒成溫度範圍(250℃~550℃)內的350℃的溫度，保持在適宜的燒成時間範圍(1小時~5小時)內的1小時來進行燒成而得的氮化鋯粉末，在以5MPa的壓力進行壓實而得的壓粉體之狀態下的體積電阻率為1×10 ⁷Ω・cm，而在適宜的範圍(1×10 ⁷Ω・cm以上)內，以水進行稀釋之狀態下並進行5分鐘超音波分散時的粒度分布D ₉₀為7μm，而在適宜的範圍(10μm以下)內。又，將實施例7的氮化鋯粉末分散於丙烯酸單體中來製作的黑色膜的OD值為2.0，而在適宜的範圍(2.0以上)內，體積電阻率為1×10 ¹³Ω・cm，而在適宜的範圍(1×10 ¹³以上)內。 The zirconium nitride powder of Example 7, that is, the zirconium nitride coarse powder was produced by the aluminothermic method, and the zirconium nitride coarse powder was pulverized by the bead mill method with a dispersion medium temperature of 5°C (low temperature wet method). After the medium is crushed), in a nitrogen atmosphere at a temperature of 350 °C within the appropriate firing temperature range (250 °C ~ 550 °C), it is maintained for 1 hour within the appropriate firing time range (1 hour ~ 5 hours). The zirconium nitride powder obtained by firing has a volume resistivity of 1 × 10 ⁷ Ω·cm in the state of the powder compact obtained by pressing at a pressure of 5 MPa, which is within a suitable range (1 × 10 Ω·cm). ⁷ Ω·cm or more), the particle size distribution D ₉₀ when diluted with water and subjected to ultrasonic dispersion for 5 minutes is 7 μm, which is within a suitable range (10 μm or less). In addition, the OD value of the black film prepared by dispersing the zirconium nitride powder of Example 7 in an acrylic monomer was 2.0, and within a suitable range (2.0 or more), the volume resistivity was 1×10 ¹³ Ω·cm , and within a suitable range (1×10 ¹³ or more).

實施例8的氮化鋯粉末，即，藉由鋁熱法來製作氮化鋯粗粉末，並將該氮化鋯粗粉末以分散媒溫度5℃的珠磨機法來進行粉碎(低溫濕式介質粉碎)後，在氮氣環境中以適宜的燒成溫度範圍(250℃~550℃)內的550℃的溫度，保持在適宜的燒成時間範圍(1小時~5小時)內的1小時來進行燒成而得的氮化鋯粉末，在以5MPa的壓力進行壓實而得的壓粉體之狀態下的體積電阻率為1×10 ⁸Ω・cm，而在適宜的範圍(1×10 ⁷Ω・cm以上)內，以水進行稀釋之狀態下並進行5分鐘超音波分散時的粒度分布D ₉₀為8μm，而在適宜的範圍(10μm以下)內。又，將實施例8的氮化鋯粉末分散於丙烯酸單體中來製作的黑色膜的OD值為2.4，而在適宜的範圍(2.0以上)內，體積電阻率為1×10 ¹⁴Ω・cm，而在適宜的範圍(1×10 ¹³以上)內。 The zirconium nitride powder of Example 8, that is, a zirconium nitride coarse powder was produced by the aluminothermic method, and the zirconium nitride coarse powder was pulverized by a bead mill method with a dispersion medium temperature of 5°C (low temperature wet method). After the medium is crushed), in a nitrogen atmosphere at a temperature of 550 °C within the appropriate firing temperature range (250 °C ~ 550 °C), it is maintained for 1 hour within the appropriate firing time range (1 hour ~ 5 hours). The zirconium nitride powder obtained by sintering has a volume resistivity of 1×10 ⁸ Ω·cm in the state of the powder compact obtained by pressing at a pressure of 5 MPa, which is within a suitable range (1×10 Ω·cm). ⁷ Ω·cm or more), the particle size distribution D ₉₀ when diluted with water and ultrasonically dispersed for 5 minutes is 8 μm, which is within a suitable range (10 μm or less). In addition, the OD value of the black film prepared by dispersing the zirconium nitride powder of Example 8 in an acrylic monomer was 2.4, and within a suitable range (2.0 or more), the volume resistivity was 1×10 ¹⁴ Ω·cm , and within a suitable range (1×10 ¹³ or more).

另一方面，比較例9的氮化鋯粉末，即，雖然是藉由鋁熱法來製作氮化鋯粗粉末，但將該氮化鋯粗粉末以小於適宜的粉碎壓力範圍(0.3MPa以上)的0.2MPa的粉碎壓力來進行噴射磨機粉碎後，在氮氣環境中以350℃的溫度保持4小時來進行燒成而得的氮化鋯粉末，在以5MPa的壓力進行壓實而得的壓粉體之狀態下的體積電阻率為2×10 ⁶Ω・cm，而較適宜的範圍(1×10 ⁷Ω・cm以上)為小，以水進行稀釋之狀態下並進行5分鐘超音波分散時的粒度分布D ₉₀為14μm，而較適宜的範圍(10μm以下)為大。又，將比較例9的氮化鋯粉末分散於環氧單體中來製作的黑色膜的OD值為1.3，而較適宜的範圍(2.0以上)為小，體積電阻率為1×10 ¹¹Ω・cm，而較適宜的範圍(1×10 ¹³以上)為小。 On the other hand, the zirconium nitride powder of Comparative Example 9, that is, the zirconium nitride coarse powder was produced by the aluminothermic method, but the zirconium nitride coarse powder was crushed at a pressure lower than the suitable pulverization pressure range (0.3 MPa or more). The zirconium nitride powder obtained by sintering at a temperature of 350°C for 4 hours in a nitrogen atmosphere after being pulverized by a jet mill at a pulverization pressure of 0.2 MPa, was compressed at a pressure of 5 MPa. The volume resistivity in the state of powder is 2×10 ⁶ Ω·cm, and the suitable range (more than 1×10 ⁷ Ω·cm) is small, and it is diluted with water and ultrasonically dispersed for 5 minutes. The particle size distribution D ₉₀ at this time was 14 μm, and the preferable range (10 μm or less) was large. In addition, the OD value of the black film prepared by dispersing the zirconium nitride powder of Comparative Example 9 in an epoxy monomer was 1.3, and the suitable range (2.0 or more) was small, and the volume resistivity was 1×10 ¹¹ Ω・cm, and a suitable range (1×10 ¹³ or more) is small.

相對於此，實施例3的氮化鋯粉末，即，藉由鋁熱法來製作氮化鋯粗粉末，並將該氮化鋯粗粉末以適宜的粉碎壓力範圍(0.3MPa以上)內的0.5MPa的粉碎壓力來進行噴射磨機粉碎後，在氮氣環境中以350℃的溫度保持4小時來進行燒成而得的氮化鋯粉末，在以5MPa的壓力進行壓實而得的壓粉體之狀態下的體積電阻率為2×10 ⁸Ω・cm，而在適宜的範圍(1×10 ⁷Ω・cm以上)內，以水進行稀釋之狀態下並進行5分鐘超音波分散時的粒度分布D ₉₀為6μm，而在適宜的範圍(10μm以下)內。又，將實施例3的氮化鋯粉末分散於環氧單體中來製作的黑色膜的OD值為2.2，而在適宜的範圍(2.0以上)內，體積電阻率為2×10 ¹⁴Ω・cm，而在適宜的範圍(1×10 ¹³以上)內。 On the other hand, the zirconium nitride powder of Example 3, that is, the zirconium nitride coarse powder was produced by the aluminothermic method, and the zirconium nitride coarse powder was pulverized at 0.5 within a suitable pulverization pressure range (0.3 MPa or more). Zirconium nitride powder obtained by sintering at 350°C for 4 hours in a nitrogen atmosphere after being pulverized by a jet mill at a pulverization pressure of MPa, and compacted at a pressure of 5MPa ^The volume ^resistivity in the state of The distribution D ₉₀ is 6 μm, which is within a suitable range (10 μm or less). In addition, the OD value of the black film prepared by dispersing the zirconium nitride powder of Example 3 in an epoxy monomer was 2.2, and within a suitable range (2.0 or more), the volume resistivity was 2×10 ¹⁴ Ω· cm, and within the appropriate range (1×10 ¹³ or more).

實施例11的氮化鋯粉末，即，藉由鋁熱法來製作氮化鋯粗粉末，並將該氮化鋯粗粉末以適宜的粉碎壓力範圍(0.3MPa以上)內的0.3MPa的粉碎壓力來進行噴射磨機粉碎後，在氮氣環境中以350℃的溫度保持4小時來進行燒成而得的實施例3的氮化鋯粉末，在以5MPa的壓力進行壓實而得的壓粉體之狀態下的體積電阻率為2×10 ⁷Ω・cm，而在適宜的範圍(1×10 ⁷Ω・cm以上)內，以水進行稀釋之狀態下並進行5分鐘超音波分散時的粒度分布D ₉₀為10μm，而在適宜的範圍(10μm以下)內。又，將實施例11的氮化鋯粉末分散於環氧單體中來製作的黑色膜的OD值為2.4，而在適宜的範圍(2.0以上)內，體積電阻率為1×10 ¹³Ω・cm，而在適宜的範圍(1×10 ¹³以上)內。 [產業利用性] The zirconium nitride powder of Example 11, that is, the zirconium nitride coarse powder was produced by the aluminothermic method, and the zirconium nitride coarse powder was pulverized at a pulverizing pressure of 0.3 MPa within a suitable pulverizing pressure range (0.3 MPa or more). The zirconium nitride powder of Example 3 obtained by sintering at a temperature of 350° C. in a nitrogen atmosphere after being pulverized by a jet mill for 4 hours was compacted at a pressure of 5 MPa. ^The volume ^resistivity in the state of The distribution D ₉₀ is 10 μm, which is within a suitable range (10 μm or less). In addition, the OD value of the black film prepared by dispersing the zirconium nitride powder of Example 11 in an epoxy monomer was 2.4, and within a suitable range (2.0 or more), the volume resistivity was 1×10 ¹³ Ω· cm, and within the appropriate range (1×10 ¹³ or more). [industrial availability]

本發明的氮化鋯粉末，能夠作為用來得到高絕緣性、具有高黑色度及高絕緣性的黑色膜的黑色顏料使用。The zirconium nitride powder of the present invention can be used as a black pigment for obtaining a black film having high insulating properties, high blackness, and high insulating properties.

Claims

一種氮化鋯粉末，在以5MPa的壓力進行壓實而得的壓粉體之狀態下，體積電阻率為10 ⁷Ω・cm以上，且以水或碳數位於2~5的範圍內的醇進行稀釋之狀態下，進行5分鐘超音波分散時的粒度分布D ₉₀為10μm以下。 A zirconium nitride powder having a volume resistivity of 10 ⁷ Ω·cm or more in the state of a powder compact obtained by compaction at a pressure of 5 MPa, and an alcohol with water or carbon number in the range of 2 to 5 In the diluted state, the particle size distribution D ₉₀ at the time of ultrasonic dispersion for 5 minutes was 10 μm or less.

一種氮化鋯粉末之製造方法，包含下述之步驟：藉由鋁熱法或電漿合成法來生成氮化鋯粗粉末之步驟；將該氮化鋯粗粉末藉由以10℃以下的分散媒溫度進行低溫濕式介質粉碎或以0.3MPa以上的氣壓進行噴射磨機粉碎，來製作以水或碳數位於2~5的範圍內的醇進行稀釋之狀態下，進行5分鐘超音波分散時的粒度分布D ₉₀為10μm以下的氮化鋯前驅物粉末之步驟；藉由將前述經粉碎的氮化鋯前驅物粉末在惰性氣體環境中燒成，來製作在以5MPa的壓力進行壓實而得的壓粉體之狀態下，體積電阻率為10 ⁷Ω・cm以上的氮化鋯粉末之步驟。 A method for producing zirconium nitride powder, comprising the following steps: generating a coarse zirconium nitride powder by aluminothermic method or plasma synthesis method; dispersing the coarse zirconium nitride powder at a temperature below 10° C. When the medium temperature is low-temperature wet medium pulverization or the jet mill pulverization is carried out with an air pressure of 0.3MPa or more, and the preparation is carried out in a state of dilution with water or an alcohol whose carbon number is in the range of 2 to 5, and ultrasonic dispersion is carried out for 5 minutes. The step of zirconium nitride precursor powder with a particle size distribution D ₉₀ of 10 μm or less; by sintering the aforementioned pulverized zirconium nitride precursor powder in an inert gas environment, to produce a zirconium nitride precursor powder that is compacted at a pressure of 5 MPa. A step of obtaining a zirconium nitride powder with a volume resistivity of 10 ⁷ Ω·cm or more in the state of the obtained compact.

一種單體分散體，其係將請求項1之氮化鋯粉末分散於丙烯酸單體或環氧單體中來得到。A monomer dispersion obtained by dispersing the zirconium nitride powder of claim 1 in an acrylic monomer or an epoxy monomer.

一種黑色組成物，其係將請求項1之氮化鋯粉末作為黑色顏料分散於分散媒中並進一步混合樹脂來得到。A black composition obtained by dispersing the zirconium nitride powder of claim 1 in a dispersion medium as a black pigment and further mixing a resin.

一種黑色膜之製作方法，包含下述之步驟：將請求項3之單體分散體塗布於基板上來形成塗膜之步驟；將前述塗膜熱硬化或紫外線硬化來製作黑色膜之步驟。 A method of making a black film, comprising the following steps: The step of coating the monomer dispersion of claim 3 on a substrate to form a coating film; The step of making the black film by thermal curing or ultraviolet curing of the coating film.

一種黑色膜之製作方法，包含下述之步驟：將請求項4之黑色組成物塗布於基板上來形成塗膜之步驟；將前述塗膜熱硬化或紫外線硬化來製作黑色膜之步驟。 A method of making a black film, comprising the following steps: The step of coating the black composition of claim 4 on a substrate to form a coating film; The step of making the black film by thermal curing or ultraviolet curing of the coating film.