Zirconium nitride-containing powder and black uv-curable organic composition

Abstract

The composition of the zirconium nitride-containing powder is represented by the following general formula (I). General formula (I): (Zr, X, Y) (N, O), wherein, in the above general formula (I), X represents at least one element selected from the group consisting of Dy, Er, Gd, Ho, Lu, Nd, Pr, Sc, Sm, Tb, and Tm, Y represents the element symbol of yttrium, the content of Y is 0 mol or more relative to the total content of Zr, X, and Y of 1 mol, N represents nitrogen, O represents oxygen, and the content of oxygen is 0 mol or more relative to the total content of nitrogen and oxygen of 1 mol.

Description

TECHNICAL FIELD

[0001] The present application relates to a zirconium nitride-containing powder and a black ultraviolet-curable organic composition.

[0002] This application is based on Japanese Patent Application No. 2020-183603 filed on November 2, 2020, and the content thereof is incorporated herein by reference. BACKGROUND

[0003] Insulating black pigments are utilized, for example, as a material for a black matrix that constitutes a color filter for a display or a black pattern that is a light-shielding material in a CMOS camera module. As a method for forming a black pattern, a photolithography method using a black photosensitive composition containing an ultraviolet-curable organic substance and an insulating black pigment is known. In the photolithography method, a black photosensitive composition is applied to a substrate to form a photoresist film. Next, a pattern composed of a cured portion that is cured by exposure and an uncured portion that is not exposed is produced by exposing ultraviolet light in a pattern shape on the photoresist film. Then, the uncured portion is removed to form a black pattern. The insulating black pigment used when a black pattern is formed by the photolithography method needs to transmit ultraviolet light that cures the photoresist film, that is, needs to have ultraviolet light transmittance.

[0004] As an insulating black pigment having ultraviolet light transmittance, a zirconium nitride powder is known. In order to improve the ultraviolet light transmittance of the zirconium nitride powder, a method of adding magnesium and / or aluminum to the zirconium nitride has been studied (Patent Document 1).

[0005] In recent years, with the high resolution of displays and the miniaturization of CMOS camera modules, high fineness of black patterns is required. Improving the ultraviolet light transmittance of a black pigment, particularly the transmittance of ultraviolet light of a wavelength of 365 nm (i-line) that is commonly used in an ultraviolet exposure device, has an effect on forming a high-fineness black pattern using a photolithography method. However, if the ultraviolet light transmittance of the black pigment is improved, the visible light shielding property can possibly decrease.

[0006] Patent Document 1: Japanese Patent Application Publication No. 2019-112275 SUMMARY

[0007] The present application was completed in view of the above circumstances, and an object thereof is to provide a powder excellent in ultraviolet light transmittance and visible light shielding property.

[0008] In order to solve the above problem, the composition of the zirconium nitride-containing powder according to the first aspect of the present application is represented by the following general formula (I).

[0009] (Zr, X, Y) (N, O) (I)

[0010] wherein, in the above general formula (I), X represents at least one element selected from the group consisting of Dy, Er, Gd, Ho, Lu, Nd, Pr, Sc, Sm, Tb, and Tm, Y represents the element symbol of yttrium, the content of Y is 0 mol or more relative to the total content of Zr, X, and Y, which is 1 mol, N represents nitrogen, and O represents oxygen, the content of oxygen being 0 mol or more relative to the total content of nitrogen and oxygen, which is 1 mol.

[0011] The zirconium nitride-containing powder thus configured has a composition represented by the above general formula (I), and thus the wavelength at which the maximum peak of the extinction coefficient in the visible light region is represented is set to a range of 540 nm or more and 600 nm or less. Therefore, visible light from the short wavelength side (for example, a wavelength of 400 nm) to the long wavelength side (for example, a wavelength of 800 nm) can be shielded. Thus, the zirconium nitride-containing powder thus configured is excellent in ultraviolet light transmittance and visible light shielding property.

[0012] Here, the average particle diameter of the zirconium nitride-containing powder according to the first aspect of the present application is preferably in a range of 10 nm or more and 70 nm or less.

[0013] In this case, the average particle diameter of the zirconium nitride-containing powder is fine within the above range, and thus plasmon vibration of the zirconium nitride particles caused by visible light is less likely to attenuate. Therefore, the visible light shielding property is further improved. Also, since the particle size is sufficiently small relative to the wavelength of light, light scattering is less likely to occur, and thus the transmittance of ultraviolet light having a wavelength of 365 nm is improved.

[0014] Also, in the zirconium nitride-containing powder according to the first aspect of the present application, the ratio of the extinction coefficient of visible light having a wavelength of 550 nm to the extinction coefficient of ultraviolet light having a wavelength of 365 nm in the extinction coefficient measured by the following method is preferably in a range of 1.4 or more and 100 or less.

[0015] (Measurement method of extinction coefficient)

[0016] A dispersion liquid containing 50 ppm of the zirconium nitride-containing powder in terms of mass concentration is placed in a cuvette having an optical path length d (unit: m). Light is irradiated to the cuvette containing the dispersion liquid, and the transmitted light intensity of the light transmitted through the cuvette is measured. The optical path length d, the incident light intensity I0 of the light irradiated to the cuvette, and the transmitted light intensity I of the light transmitted through the cuvette are substituted into the following formula (1), and a is calculated as the extinction coefficient of the light irradiated to the cuvette.

[0017] I = I0exp(-a x d) (1)

[0018] In this case, the ratio of the extinction coefficient of visible light of wavelength 550 nm to the extinction coefficient of ultraviolet light of wavelength 365 nm is in the range of 1.4 or more and 100 or less, and thus the ultraviolet light transmittance and the visible light shielding property are balanced and improved. Therefore, by using the zirconium nitride-containing powder having the above-described configuration, a black pattern having high fineness and excellent visible light shielding property can be formed.

[0019] Further, the zirconium nitride-containing powder according to the first aspect of the present application preferably has an extinction coefficient of visible light of wavelength 550 nm of 600 m -1 or more.

[0020] In this case, the extinction coefficient of visible light of wavelength 550 nm is 600 m -1 or more, and thus the visible light shielding property is further improved. Therefore, the black pattern formed using the zirconium nitride-containing powder having the above-described configuration is useful as a black matrix of a color filter of a display or a light shielding material in a CMOS camera module.

[0021] Further, the zirconium nitride-containing powder according to the second aspect of the present application has an average particle diameter in the range of 10 nm or more and 70 nm or less, and in the extinction coefficient measured by the following method, the ratio of the extinction coefficient of visible light of wavelength 550 nm to the extinction coefficient of ultraviolet light of wavelength 365 nm is in the range of 1.4 or more and 100 or less.

[0022] (Measurement method of extinction coefficient)

[0023] A dispersion liquid containing 50 ppm of the zirconium nitride-containing powder in terms of mass concentration is put in a cuvette having an optical path length d (unit: m). Light is irradiated to the cuvette containing the dispersion liquid, and the transmitted light intensity of the light transmitted through the cuvette is measured. The optical path length d, the incident light intensity I0 of the light irradiated to the cuvette, and the transmitted light intensity I of the light transmitted through the cuvette are substituted into the following formula (1), and a is calculated as the extinction coefficient of the light irradiated to the cuvette.

[0024] I = I0exp(-a x d) (1)

[0025] According to the zirconium nitride-containing powder configured as described above, the average particle diameter is fine within the range described above, and thus plasma vibration of the zirconium nitride-containing powder particles caused by visible light is likely to be attenuated. Therefore, the visible light shielding property is likely to be improved. Also, since the particle size is sufficiently small relative to the wavelength of light, light scattering is unlikely to occur, and thus the ultraviolet light transmittance at a wavelength of 365 nm is likely to be improved. Further, the ratio of the extinction coefficient of visible light at a wavelength of 550 nm to the extinction coefficient of ultraviolet light at a wavelength of 365 nm, which is measured by the method described above, is within a range of 1.4 or more and 100 or less, and thus the ultraviolet light transmittance and the visible light shielding property are likely to be improved in balance. Therefore, by using the zirconium nitride-containing powder configured as described above, a black pattern that is high in precision and excellent in visible light shielding property can be formed.

[0026] The black ultraviolet-curable organic composition according to the third aspect of the present application contains an ultraviolet-curable organic substance and a black pigment dispersed in the ultraviolet-curable organic substance, the black pigment being the zirconium nitride-containing powder according to the first aspect or the second aspect of the present application.

[0027] In the black ultraviolet-curable organic composition according to the third aspect of the present application, the ultraviolet-curable organic substance is preferably at least one organic substance selected from the group consisting of an acrylic acid monomer, an acrylic acid oligomer, an epoxy monomer, and an epoxy oligomer.

[0028] According to the first aspect and the second aspect of the present application, a powder excellent in ultraviolet light transmittance and visible light shielding property can be provided.

[0029] According to the third aspect of the present application, a black ultraviolet-curable organic composition excellent in ultraviolet light transmittance and visible light shielding property can be provided. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 is a wavelength-extinction coefficient curve of each of five kinds of zirconium nitride powders having an average particle diameter of 20 nm, 40 nm, 60 nm, 80 nm, and 100 nm calculated in Test Example 1.

[0031] Figure 2 is a wavelength-extinction coefficient curve of each of zirconium nitride-containing powders in which Dy, Er, Gd, Ho, Lu, Nd, Pr, Sc, Sm, Tb, Tm, or Y+Dy is substituted, calculated in Test Example 2.

[0032] Figure 3 is a graph showing the particle diameter and the extinction coefficient a of visible light at a wavelength of 550 nm in each of the zirconium nitride powders assumed in Test Example 1 and the zirconium nitride-containing powders in which Dy, Er, Ho, Tb, Tm, or Y+Dy is substituted, assumed in Test Example 2. 550 is a graph showing the particle diameter and the extinction coefficient a of ultraviolet light at a wavelength of 365 nm in each of the zirconium nitride powders assumed in Test Example 1 and the zirconium nitride-containing powders in which Dy, Er, Ho, Tb, Tm, or Y+Dy is substituted, assumed in Test Example 2. 365ratio (a 550 / a 365 ) of the peak position of the extinction coefficient in the visible light region and the peak position of the extinction coefficient in the ultraviolet light region. DETAILED DESCRIPTION

[0033] An embodiment of the present application relates to a zirconium-containing nitride powder.

[0034] The zirconium-containing nitride powder according to the present embodiment is, for example, a black powder used as a material for a black pattern, which constitutes a black matrix of a color filter of a display or a light shielding material in a CMOS camera module. The black pattern is formed, for example, by a photolithography method using a black ultraviolet-curable organic composition containing the zirconium-containing nitride powder according to the present embodiment and an ultraviolet-curable organic substance.

[0035] (Zirconium-containing nitride powder)

[0036] The average particle diameter of the zirconium-containing nitride powder according to the present embodiment is in a range of 10 nm or more and 70 nm or less. The zirconium-containing nitride powder is fine in the range, and thus plasmon vibration of the zirconium-containing nitride particles caused by visible light is less likely to attenuate. Therefore, the visible light shielding property is improved. Also, since the particle size is sufficiently small relative to the wavelength of light, light scattering is less likely to occur, and thus the transmittance of ultraviolet light (i-line) having a wavelength of 365 nm, which is commonly used in an ultraviolet light exposure device, is high. However, if the average particle diameter of the zirconium-containing nitride powder is too small, the wavelength of plasmon resonance is too short, and the peak position of the extinction coefficient in the visible light region is sometimes excessively shifted to the short wavelength side. If the peak position of the extinction coefficient in the visible light region is excessively shifted to the short wavelength side, the extinction coefficient of visible light on the long wavelength side decreases, and this can result in a decrease in the visible light shielding property on the long wavelength side. Therefore, the average particle diameter of the zirconium-containing nitride powder according to the present embodiment is set in a range of 10 nm or more and 70 nm or less. The average particle diameter of the zirconium-containing nitride powder is preferably in a range of 20 nm or more and 70 nm or less, and particularly preferably in a range of 30 nm or more and 60 nm or less.

[0037] The average particle diameter of the zirconium-containing nitride powder refers to the BET diameter, which is measured by the following method.

[0038] Nitrogen molecules are adsorbed on the surface of the particles of the zirconium-containing nitride powder at the temperature of liquid nitrogen, and the adsorption isotherm (adsorption amount) is measured. The BET graph is plotted, and the monolayer adsorption amount of the nitrogen molecules is calculated using the BET formula. Then, the specific surface area of the particles of the zirconium-containing nitride powder is calculated from the monolayer adsorption amount of the nitrogen molecules. Assuming that the particles of the zirconium-containing nitride powder are spherical, the BET diameter is calculated from the specific surface area (BET specific surface area) measured by the BET single-point method using the following equation.

[0039] BET diameter = 6 / (density x BET specific surface area)

[0040] The BET diameter in the present specification was measured using Macsorb HM model-1210 manufactured by MOUNTECH Co., Ltd.

[0041] The composition of the zirconium-containing nitride powder of the present embodiment is represented by the following general formula (I).

[0042] (Zr, X, Y) (N, O) (I)

[0043] In the above general formula (I), X represents at least one element selected from the group consisting of Dy, Er, Gd, Ho, Lu, Nd, Pr, Sc, Sm, Tb, and Tm. Y represents the element symbol of yttrium, and the content of Y is 0 mol or more relative to the total content of Zr, X, and Y, which is 1 mol. N represents nitrogen, and O represents oxygen, and the content of oxygen is 0 mol or more relative to the total content of nitrogen and oxygen, which is 1 mol. The total number of moles of Zr, X, and Y is the same as the total number of moles of N and O in 1 mol of the zirconium-containing nitride powder.

[0044] The general formula (I) represents the overall composition of the zirconium-containing nitride powder, and the zirconium-containing nitride powder can be a single phase of a nitride or an oxynitride, or any one of a mixture of a nitride and an oxide, a mixture of an oxynitride and an oxide, a mixture of a nitride and an oxynitride, and a mixture of a nitride, an oxynitride, and an oxide.

[0045] In the above general formula (I), the elements represented by X are all Group 3 elements. The elements represented by X have the effect of moving the wavelength at which the maximum peak of the extinction coefficient of the zirconium-containing nitride powder in the visible light region is represented toward the long wavelength side. The elements represented by X can be used singly or in combination of two or more. Among the elements represented by X, Dy, Er, Ho, and Tm are preferable. When the total content of zirconium, the elements represented by X, and yttrium is set to 1 mol, the content of the elements represented by X is preferably in the range of 0.05 mol or more and 0.30 mol or less. When the content of the elements represented by X is in this range, it is possible to maintain the wavelength at which the maximum peak of the extinction coefficient in the visible light region is represented in the range of 540 nm or more and 600 nm or less. The content of the elements represented by X is more preferably in the range of 0.07 mol or more and 0.25 mol or less, and particularly preferably in the range of 0.10 mol or more and 0.20 mol or less.

[0046] In the case where yttrium is not contained, the composition of the zirconium-containing nitride powder of the present embodiment is preferably represented by the following general formula (II).

[0047] Zr 1-a X a N1-c O c (II)

[0048] wherein, in the above general formula (II), X is the same as in the above general formula (I). a represents a number in the range of 0.05 or more and 0.30 or less. a is more preferably in the range of 0.07 or more and 0.25 or less, and particularly preferably in the range of 0.10 or more and 0.20 or less.

[0049] c is preferably in the range of 0 or more and 0.5 or less, more preferably in the range of 0 or more and 0.45 or less, and particularly preferably in the range of 0 or more and 0.4 or less.

[0050] The amount of the metal elements (including Y described later) in the zirconium-containing nitride powder is measured by X-ray photoelectron spectroscopy. The amount of nitrogen in the zirconium-containing nitride powder is measured by inert gas fusion-thermal conductivity method. The amount of oxygen (c in general formula (II)) in the zirconium-containing nitride powder is measured by a method conforming to JIS Z2613 "General rules for oxygen determination in metallic materials".

[0051] The zirconium-containing nitride powder of the present embodiment can also contain Y (yttrium). In this case, the composition of the zirconium-containing nitride powder is preferably represented by the following general formula (III).

[0052] Zr 1-a-b X a Y b N 1-c O c (III)

[0053] When the total content of zirconium, the element represented by X, and Y is set to 1 mole, the content of Y (b in general formula (III)) is preferably in the range of 0.05 moles or more and 0.30 moles or less, more preferably in the range of 0.07 moles or more and 0.25 moles or less, and particularly preferably in the range of 0.10 moles or more and 0.20 moles or less. The numerical ranges of a and c in general formula (III) are the same as those of a and c in general formula (II).

[0054] The ratio (a 550 The ratio (a 365 of the extinction coefficient a 550 of the zirconium-containing nitride powder of the present embodiment for visible light of wavelength 550 nm to the extinction coefficient a 365 of the zirconium-containing nitride powder of the present embodiment for ultraviolet light of wavelength 365 nm is in the range of 1.4 or more and 100 or less. Since the ratio (a 550 / a 365 ) is in this range, both the ultraviolet light transmittance and the visible light shielding property are improved in balance. The ratio (a 550 / a 365) more preferably in a range of 2 or more and 80 or less, and particularly preferably in a range of 2.5 or more and 60 or less.

[0055] Extinction coefficient a of visible light having a wavelength of 550 nm 550 Preferably 600 m -1 More preferably 700 m or more above -1 Particularly preferably 750 m or more above -1 Extinction coefficient a of visible light having a wavelength of 550 nm 550 Can be 1000 m or more above -1 Extinction coefficient a of visible light having a wavelength of 550 nm

[0056] Extinction coefficient a of ultraviolet light having a wavelength of 365 nm 365 Preferably 300 m or more above -1 More preferably 250 m or more above -1 Particularly preferably 200 m or more above -1 Extinction coefficient a of ultraviolet light having a wavelength of 365 nm 365 Can be 1 m or more above -1 Extinction coefficient a of ultraviolet light having a wavelength of 365 nm

[0057] The extinction coefficient is a proportion in which the intensity of light transmitted through a dispersion liquid containing a zirconium-containing nitride powder is attenuated with distance by scattering and absorption of the zirconium-containing nitride particles in the dispersion liquid. In the present embodiment, the extinction coefficient of the zirconium-containing nitride powder is a value measured by the following method.

[0058] A dispersion liquid containing 50 ppm of a zirconium-containing nitride powder in terms of mass concentration is placed in a cuvette having an optical path length d (unit: m). Light is irradiated to the cuvette containing the dispersion liquid, and the transmitted light intensity of the light transmitted through the cuvette is measured. The optical path length d, the incident light intensity I0 of the light irradiated to the cuvette, and the transmitted light intensity I of the light transmitted through the cuvette are substituted into the following formula (1), and a is calculated as the extinction coefficient of the light irradiated to the cuvette.

[0059] I = I0exp(-a x d) (1)

[0060] The zirconium-containing nitride powder of the present embodiment can be manufactured, for example, by the following first manufacturing method and second manufacturing method.

[0061] <First manufacturing method>

[0062] First, a zirconia powder containing an X element oxide and a Y oxide (raw material oxide powder) is prepared, which contains an oxide powder of an element represented by X (X element) in General Formula (I), an oxide powder of yttrium, and a zirconia (Zr02) powder.

[0063] As the zirconium dioxide powder, for example, a monoclinic zirconium dioxide powder, a cubic zirconium dioxide powder, a yttrium-stabilized zirconium dioxide powder, or the like can be used. Among these zirconium dioxide powders, the monoclinic zirconium dioxide powder is preferable from the viewpoint of increasing the generation rate of the zirconium nitride powder. The average primary particle diameter of the zirconium dioxide powder is preferably in the range of 10 nm or more and 500 nm or less. The preferable average primary particle diameter of the zirconium dioxide powder is set in the above range for the following reason. If less than 10 nm, the particle diameter of the zirconium nitride-containing compound obtained by the reaction is too small, which can result in a decrease in visible light shielding property. On the other hand, if more than 500 nm, the particle diameter of the zirconium nitride-containing compound obtained by the reaction is too large, which can result in a decrease in visible light shielding property.

[0064] The average primary particle diameter of the X element oxide powder is preferably 10 nm or more and 500 nm or less. The preferable average primary particle diameter of the X element oxide powder is set in the above range for the following reason. If less than 10 nm, the particle diameter of the zirconium nitride-containing compound obtained by the reaction is too small, which can result in a decrease in visible light shielding property. On the other hand, if more than 500 nm, the particle diameter of the zirconium nitride-containing compound obtained by the reaction is too large, which can result in a decrease in visible light shielding property.

[0065] As the yttrium oxide powder, a yttrium-stabilized zirconium dioxide powder, a yttrium oxide (Y2O3) powder can be used. The yttrium-stabilized zirconium dioxide can be the aforementioned zirconium dioxide powder. The average primary particle diameter of the yttrium oxide powder is preferably 1000 nm or less, and more preferably 10 nm or more and 500 nm or less from the viewpoint of ease of handling of the powder.

[0066] In the case where the zirconium nitride-containing compound does not contain yttrium, the yttrium oxide powder is not added.

[0067] In addition, the average primary particle diameters of the zirconium dioxide powder, the X element oxide powder, and the yttrium oxide powder are values (BET diameters) calculated from the measured values of the specific surface areas measured by the BET method, by spherical conversion.

[0068] The zirconium dioxide powder containing the X element oxide and the Y oxide (raw material oxide powder) can be obtained, for example, by mixing the X element oxide powder, the yttrium oxide powder, and the zirconium dioxide powder. Also, the zirconium dioxide powder containing the X element oxide and the Y oxide can be obtained by the following method. An aqueous solution of an inorganic salt or an organic salt containing zirconium, an inorganic salt or an organic salt of the X element, and an inorganic salt or an organic salt of yttrium is made alkaline, and a hydroxide of the X element, yttrium hydroxide, and zirconium hydroxide are co-precipitated. The obtained co-precipitated product is recovered, and dried and calcined.

[0069] Next, one or both of the zirconia powder containing the oxide of the element X and the oxide of Y (raw material oxide powder) and the magnesium oxide powder or the magnesium nitride powder described above and the magnesium powder are mixed in a nitrogen-containing gas atmosphere to prepare a mixed powder. As the nitrogen-containing gas, for example, N2gas, a mixed gas of N2and Ar, a mixed gas of N2and H2, or a mixed gas of N2and NH3may be used.

[0070] The magnesium oxide powder and the magnesium nitride powder have an effect of preventing sintering of the zirconium nitride generated by firing of the mixed powder. The average primary particle diameter of the magnesium oxide powder and the magnesium nitride powder is preferably 1000 nm or less, and from the viewpoint of ease of powder handling, the average primary particle diameter is particularly preferably 500 nm or less and 10 nm or more. In addition, the average primary particle diameter is a converted value calculated by spherical conversion from a measured value of the specific surface area measured by the BET method. The total amount of magnesium atoms in the magnesium oxide and the magnesium nitride, relative to 1 mole of the total of zirconium, the element X, and yttrium, is preferably an amount in a range of 0.3 times or more and 3.0 times or less, and more preferably an amount in a range of 0.4 times or more and 2.0 times or less. The preferable total amount of magnesium atoms in the magnesium oxide and the magnesium nitride is set in the above range for the following reasons. If less than 0.3 times, it can be possible that the effect of preventing sintering of the zirconium nitride powder becomes insufficient. On the other hand, if more than 3.0 times, the amount of the acid solution required at the time of pickling after firing can possibly increase.

[0071] The magnesium metal powder has an effect of promoting reduction of the X element oxide, the yttrium oxide, and the zirconia to easily generate the zirconium nitride-containing powder. If the particle diameter of the magnesium metal powder is too small, the reaction will proceed sharply, and the danger in handling will increase. Therefore, with respect to the magnesium metal powder, it is preferable to use a sieve to sieve so that the particle diameter is 100 μm or more and 1000 μm or less, and it is particularly preferable that the particle diameter is 200 μm or more and 500 μm or less. However, even if the particle diameter of the magnesium metal is not all within the above range, as long as the particle diameter of 80% by mass or more, particularly 90% by mass or more of the particles is within the above range. If the addition amount of the magnesium metal is too small, it can be difficult to obtain the zirconium nitride powder as the target product due to insufficient reduction. On the other hand, if it is too much, the reaction temperature can sharply increase due to the excess magnesium metal, and the particle growth of the powder can occur, and it is not economical. The addition amount of the magnesium metal powder with respect to 1 mole of the total of the zirconium, the X element, and the yttrium is preferably an amount within a range of 2.0 times or more and 6.0 times or less, and further preferably an amount within a range of 3.0 times or more and 5.0 times or less. The preferable addition amount of the magnesium metal is set within the above range for the following reasons. If it is less than 2.0 times, the reduction power of the zirconia can be insufficient. On the other hand, if it exceeds 6.0 times, the reaction temperature can sharply increase due to the excess magnesium metal, and the particle growth of the powder can occur, and it is not economical.

[0072] Next, the X element oxide, the yttrium oxide, and the zirconia are reduced and a nitriding reaction is performed by firing the above mixed powder in a nitrogen-containing gas atmosphere, and thereby a zirconium nitride-containing powder is manufactured.

[0073] As the nitrogen-containing gas, for example, N2 gas, a mixed gas of N2 and Ar, a mixed gas of N2 and H2, or a mixed gas of N2 and NH3 can be used. The N2 gas has the following effects: reacting with the X element oxide, the yttrium oxide, and the zirconium dioxide to produce the zirconium nitride-containing powder; and preventing contact between the metallic magnesium or the zirconium nitride-containing powder and oxygen, thereby suppressing oxidation thereof. Further, the H2 gas or the NH3 gas, together with the metallic magnesium, has the effect of reducing the zirconium dioxide. The concentration of the H2 gas in the mixed gas of N2 and H2 is preferably in the range of more than 0 vol% and 40 vol% or less, and further preferably in the range of 10 vol% or more and 30 vol% or less. Further, the concentration of the NH3 gas in the mixed gas of N2 and NH3 is preferably in the range of more than 0 vol% and 50 vol% or less, and further preferably in the range of 0 vol% or more and 40 vol% or less. By using the nitrogen-containing gas having such a reducing power, it is finally possible to produce the zirconium nitride (zirconium nitride-containing) powder that does not contain the low-stage zirconium oxide or the low-stage zirconium oxynitride. On the other hand, if the concentration of the H2 gas in the mixed gas of N2 and H2 and the concentration of the NH3 gas in the mixed gas of N2 and NH3 are too high, although reduction is performed, it is possible to produce the low-stage zirconium oxide or the low-stage zirconium oxynitride due to a decrease in the nitrogen source. Further, the maximum concentration (upper limit value of the preferable concentration range) of the NH3 gas is higher than that of the H2 gas because the NH3 gas contains nitrogen and has a higher ability to make the X element oxide and the zirconium dioxide into nitrides than the H2 gas.

[0074] The sintering temperature of the mixed powder is preferably in the range of 650°C or higher and 900°C or lower, and further preferably in the range of 700°C or higher and 800°C or lower. The preferable sintering temperature of the mixed powder is set in the above range for the following reasons. 650°C is the melting temperature of the metallic magnesium, and thus if the sintering temperature is lower than 650°C, it is possible that reduction of the X element oxide, the yttrium oxide, and the zirconium dioxide does not sufficiently occur. On the other hand, even if the sintering temperature is higher than 900°C, the effect does not increase, but rather, heat energy can be wasted, and sintering of the produced zirconium nitride particles can occur.

[0075] Further, the sintering time of the mixed powder is preferably in the range of 30 minutes or more and 90 minutes or less, and further preferably in the range of 30 minutes or more and 60 minutes or less. Further, the reaction container in which the mixed powder is sintered is preferably a container with a lid so that the raw materials or the products do not scatter during the reaction. This is because, if melting of the metallic magnesium starts, reduction of the X element oxide, the yttrium oxide, and the zirconium dioxide rapidly occurs, and the temperature rises, and thus the gas in the container expands, and the substances in the container can scatter to the outside.

[0076] Next, the zirconium-containing nitride powder obtained in the above nitriding reaction is washed with an acid solution, and then neutralized. Specifically, the zirconium-containing nitride powder obtained in the above nitriding reaction is taken out of the reaction vessel, and finally cooled to room temperature. Next, it is washed with an acid solution such as an aqueous hydrochloric acid solution. By this, magnesium oxide produced by oxidation of the magnesium metal, and magnesium nitride and magnesium oxide contained in the reaction from the beginning in order to prevent sintering of the product are removed. As for this acid washing, it is preferable to be performed under conditions that the pH of the acid solution is 0.5 or more, particularly 1.0 or more, and the temperature of the acid solution is 90°C or less. This is because, if the acidity of the acid solution is too strong or the liquid temperature is too high, even the zirconium, X element, and yttrium in the zirconium-containing nitride powder can be dissolved out. Then, after this acid washing, the pH is adjusted to 5 to 6 with ammonia water or the like, and a black slurry is obtained. Further, the solid component is separated from this black slurry and dried, and thereby a black material is obtained. Specifically, the solid component is separated by filtering or centrifuging the black slurry. By drying and then pulverizing this solid component, a black material (black pigment, zirconium-containing nitride powder) can be obtained.

[0077] <Second Production Method>

[0078] This production method is a method of producing a zirconium-containing nitride powder (black material) by a thermal plasma method. As a device for carrying out the above thermal plasma method, for example, a thermal plasma device such as a high-frequency induction thermal plasma nanoparticle synthesizer (manufactured by JEOL Ltd., TP40020NPS) can be given. This thermal plasma device is provided with: a raw material supply machine that supplies a raw material to a plasma torch; a plasma torch that is connected to the raw material supply machine and causes the raw material to undergo a synthesis nitriding reaction by a thermal plasma method; an induction coil that is wound around the outer periphery of the plasma torch; a high-frequency power source that is electrically connected to the induction coil and supplies high-frequency electric power to the induction coil; a chamber that is connected to the plasma torch and has a cooling gas such as N2 gas or Ar gas flowing therein; and a bag filter that is connected to the chamber and recovers a zirconium-containing nitride powder.

[0079] When the above thermal plasma device is used to produce a zirconium-containing nitride powder, first, a raw material, that is, a raw material metal powder containing a metal zirconium powder, a metal powder of an X element, and a metal yttrium powder is supplied to the raw material supply machine.

[0080] In addition, in the case of producing a zirconium-containing nitride that does not contain yttrium, a raw material metal powder that does not contain a metal yttrium powder is used.

[0081] As for the metal zirconium powder, the purity is preferably 98% or more, and the average primary particle diameter is preferably 30 μm or less. The average primary particle diameter of the metal zirconium powder is set to 30 μm or less because it is easy to obtain a high-purity zirconium nitride-containing powder. On the other hand, if the average primary particle diameter exceeds 30 μm, the dissolution and vaporization of the metal zirconium powder become insufficient, and the metal zirconium powder is recovered in a state where it is not nitrided, and it can be impossible to obtain a zirconium nitride-containing powder exhibiting sufficient characteristics.

[0082] Also, as for the metal powder of the X element, the purity is preferably 98% or more, and the average primary particle diameter is preferably 1000 μm or less. Here, the purity of the metal powder of the X element is set to 98% or more because if the purity is less than 98%, the purity of the obtained zirconium nitride-containing powder decreases, and it can be impossible to obtain sufficient characteristics. Also, the average primary particle diameter of the metal powder of the X element is set to 1000 μm or less because if the average primary particle diameter exceeds 1000 μm, it can be difficult to obtain a zirconium nitride-containing powder of uniform composition.

[0083] As for the metal yttrium powder, the purity is preferably 98% or more, and the average primary particle diameter is preferably 1 μm or more and 1000 μm or less. If the average primary particle diameter of the metal yttrium powder exceeds 1000 μm, it can be difficult to obtain a zirconium nitride-containing powder of uniform composition.

[0084] In addition, the average primary particle diameter of the metal zirconium powder, the metal powder of the X element, and the metal yttrium powder is the particle diameter (median particle diameter (D50) on a volume basis) measured using a laser diffraction / scattering particle size distribution measuring device (manufactured by HORIBA, Ltd., LA-950), and is the average primary particle diameter on a volume basis.

[0085] Next, the above raw material metal powder supplied to the raw material supply machine is introduced into the plasma torch together with a carrier gas such as N2 gas or Ar gas. The inside of the plasma torch can be an N2 gas atmosphere, an N2 and H2 mixed gas atmosphere, an N2 and Ar mixed gas atmosphere, or an N2 and NH3 mixed gas atmosphere. These N2-containing gases generate a hot plasma of N2 gas, a hot plasma of N2 and H2 mixed gas, a hot plasma of N2 and Ar mixed gas, or a hot plasma of N2 and NH3 mixed gas (plasma flame) by supplying high-frequency electric power from a high-frequency power source to the induction coil. Then, the raw material metal powder introduced into the plasma torch is volatilized and vaporized by the high-temperature N2 gas hot plasma or the like generated in the plasma torch. That is, the synthesis nitriding reaction is performed by the hot plasma method. Next, the above vaporized raw material metal is rapidly cooled in a chamber in which a cooling gas such as N2 gas or Ar gas flows. That is, the raw material metal is instantaneously cooled and condensed by the cooling gas such as N2 gas or Ar gas in the chamber below the plasma torch. Thus, a zirconium-containing nitride powder is generated. The generated zirconium-containing nitride powder is recovered by a bag filter. In this way, a zirconium-containing nitride powder is obtained. The zirconium-containing nitride powder obtained by the above method can be a black material of nanometer size having an average primary particle diameter in the range of 10 nm or more and 50 nm or less.

[0086] In addition, the average primary particle diameter of the black material (black pigment, zirconium-containing nitride powder) is a converted value (BET diameter) calculated from the measured value of the specific surface area measured by the BET method.

[0087] According to the zirconium-containing nitride powder of the present embodiment configured as described above, having a composition represented by the above general formula (I) and containing a specific third group element represented by X, it is possible to set the wavelength at which the maximum peak of the extinction coefficient in the visible light region is represented to be in the range of 540 nm or more and 600 nm or less. Thus, it is possible to shield the visible light from the short wavelength side (for example, wavelength 400 nm) to the long wavelength side (for example, wavelength 800 nm). Thus, the ultraviolet light transmittance and the visible light shielding property of the zirconium-containing nitride powder of the present embodiment are excellent. Also, in the case where the average particle diameter of the zirconium-containing nitride powder of the present embodiment is in the range of 10 nm or more and 70 nm or less, the plasmon vibration of the zirconium-containing nitride particles caused by visible light will be difficult to attenuate. Thus, the visible light shielding property will further improve. Also, since the particle size is sufficiently small with respect to the wavelength of light, light scattering will be difficult to occur, and thus the transmittance of ultraviolet light of wavelength 365 nm will improve.

[0088] Also, in the case of the zirconium-containing nitride powder of the present embodiment, in the extinction coefficient measured by the above method, the extinction coefficient a 550extinction coefficient a of ultraviolet light with respect to wavelength 365 nm 365 the ratio (a 550 / a 365 ) is in the range of 1.4 or more and 100 or less, the ultraviolet light transmittance and the visible light shielding property are balancedly improved. Therefore, by using the zirconium-containing nitride powder of the present embodiment, a black pattern with high fineness and excellent visible light shielding property can be formed. Further, in the case of the zirconium-containing nitride powder of the present embodiment, in the case where the extinction coefficient of visible light with wavelength 550 nm is 600 m -1 or more, the visible light shielding property is further improved. Therefore, the black pattern formed using the zirconium-containing nitride powder of the present embodiment is useful as a black matrix of a color filter of a display or a light shielding material in a CMOS camera module.

[0089] In addition, in the case of the zirconium-containing nitride powder of the present embodiment, in the case where the above ratio (a 550 / a 365 ) is in the range of 1.4 or more and 100 or less, the composition does not necessarily have to be the composition represented by the above general formula (I).

[0090] (Black ultraviolet-curable organic composition)

[0091] For example, as a black matrix of an image forming element or a light shielding material in a CMOS camera module, a black pattern is used. As a raw material of the black ultraviolet-curable organic composition for forming the black pattern, the above zirconium-containing nitride powder can be used.

[0092] The black ultraviolet-curable organic composition contains an ultraviolet-curable organic substance and a black pigment dispersed in the ultraviolet-curable organic substance. As the black pigment, the above zirconium-containing nitride powder can be used.

[0093] As the ultraviolet-curable organic substance, for example, an acrylate, a methacrylate, a glycidyl ether, a glycidyl amine, a glycidyl ester, or the like can be used. Also, as the ultraviolet-curable organic substance, a monomer or an oligomer that polymerizes to form a polymer by ultraviolet irradiation can be used. As examples thereof, an acrylic acid monomer, an acrylic acid oligomer, an epoxy monomer, an epoxy oligomer can be given. These organic substances can be used alone or in combination with two or more.

[0094] The acrylic monomer is a monomer having a (meth)acryloyl group. The (meth)acryloyl group includes an acryloyl group and a methacryloyl group. The acrylic monomer can be a monofunctional acrylic monomer having one (meth)acrylic acid group in one molecule, or a multifunctional acrylic monomer having two or more (meth)acrylic acid groups in one molecule. As the monofunctional (meth)acrylic monomer, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, isoamyl acrylate, tetrahydrofurfuryl methacrylate, isobornyl (meth)acrylate, and the like can be given. As the difunctional (meth)acrylic monomer, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, oxirane-modified bisphenol A di(meth)acrylate, neopentyl glycol triethylene glycol di(meth)acrylate, and the like can be given. As the multifunctional (meth)acrylic monomer, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, and the like can be given.

[0095] The acrylic oligomer is a low-molecular-weight polymer of the acrylic monomer. Acrylic ester, urethane acrylate, epoxy acrylate, polyester acrylate, and the like can be given. The molecular weight of the acrylic oligomer can be, for example, in the range of 1000 or more and 10000 or less in terms of number average molecular weight. These (meth)acrylate monomers and oligomers can be used alone or in combination of two or more. Furthermore, the (meth)acrylic monomer and oligomer are not limited to the above-described substances, and commonly available (meth)acrylic monomers and oligomers can be used.

[0096] The epoxy monomer is a substance having an epoxy group. The epoxy monomer can be a monofunctional epoxy monomer having one epoxy group in one molecule, or a multifunctional epoxy monomer having two or more epoxy groups in one molecule. As the epoxy monomer, glycidyl ether, alicyclic epoxy resin, and the like can be given.

[0097] The epoxy oligomer is a low-molecular-weight polymer of the epoxy monomer. The molecular weight of the epoxy oligomer can be, for example, in the range of 1000 or more and 10000 or less in terms of number average molecular weight.

[0098] The black ultraviolet-curable organic composition can also contain other ultraviolet-curable organic substances. As the other ultraviolet-curable organic substances, for example, a styrene-based monomer, a vinyl-based monomer, a cationically curable monomer, and the like can be used. As examples of the styrene-based monomer, styrene, vinyltoluene, divinylbenzene can be given. As examples of the vinyl-based monomer, vinyl chloride, vinyl acetate can be given. As examples of the cationically curable monomer, oxetane can be given.

[0099] The black ultraviolet-curable organic composition can also contain a photopolymerization initiator. The photopolymerization initiator is preferably a compound capable of absorbing ultraviolet rays (specifically, light of a wavelength of 100 to 400 nm) and initiating a polymerization reaction. As the photopolymerization initiator, for example, benzophenone, azobisisobutyl ether, benzoyl peroxide, bis(4-tert-butylphenyl) iodonium hexafluorophosphate, triphenylsulfonium tetrafluoroborate, tri-p-tolylsulfonium trifluoromethanesulfonate, and the like can be used.

[0100] The content of the ultraviolet-curable organic substance is preferably in the range of 50% by mass or more and 90% by mass or less with respect to the solid content of the black ultraviolet-curable organic composition. With the content of the ultraviolet-curable organic substance in this range, there is a tendency that the shielding property of the obtained black pattern is improved. The content of the ultraviolet-curable organic substance is more preferably in the range of 55% by mass or more and 85% by mass or less, and particularly preferably in the range of 60% by mass or more and 80% by mass or less.

[0101] The content of the photopolymerization initiator is preferably in the range of 0.5% by mass or more and 15% by mass or less with respect to the ultraviolet-curable organic substance.

[0102] The content of the zirconium-containing nitride powder is preferably in the range of 0.1% by mass or more and 50% by mass or less with respect to the solid content of the black ultraviolet-curable organic composition. With the content of the zirconium-containing nitride powder in this range, it is possible to improve both the ultraviolet light transmittance and the visible light shielding property in balance. The content of the zirconium-containing nitride powder is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 20% by mass or more. The content of the zirconium-containing nitride powder is preferably 45% by mass or less, and more preferably 40% by mass or less.

[0103] The black ultraviolet-curable organic composition can contain a solvent. As the solvent, for example, propylene glycol monomethyl ether acetate (PGM-Ac), ethanol, toluene, water, or the like can be used. The content of the solvent with respect to the black ultraviolet-curable organic composition is preferably in a range of 0 mass% or more and 60 mass% or less. Since the content of the solvent is in this range, the coatability of the black ultraviolet-curable organic composition is improved, and there is a tendency that the film thickness of the photoresist film formed on the substrate becomes uniform. The content of the solvent is more preferably in a range of 5 mass% or more and 50 mass% or less, and particularly preferably in a range of 10 mass% or more and 40 mass% or less.

[0104] The black ultraviolet-curable organic composition can be prepared, for example, by mixing the zirconium-containing nitride powder, the ultraviolet-curable organic substance, and the solvent. As for the order of mixing, the zirconium-containing nitride powder, the ultraviolet-curable organic substance, and the solvent can be mixed at the same time, or the zirconium-containing nitride powder and the ultraviolet-curable organic substance can be mixed first, and then the solvent can be added and mixed, or the zirconium-containing nitride powder and the solvent can be mixed first, and then the ultraviolet-curable organic substance can be added and mixed, or the ultraviolet-curable organic substance and the solvent can be mixed first, and then the zirconium-containing nitride powder can be added and mixed.

[0105] The black ultraviolet-curable organic composition configured as described above contains the zirconium-containing nitride powder of the present embodiment, and thus has excellent ultraviolet light transmittance and visible light shielding properties. Therefore, by using the above-described black ultraviolet-curable organic composition, a high-fineness black pattern can be formed by photolithography using ultraviolet light. Then, the obtained black pattern has excellent visible light shielding properties.

[0106] (Method for forming black pattern)

[0107] As the method for forming a black pattern using the above-described black ultraviolet-curable organic composition, photolithography using ultraviolet light can be employed. The method for forming a black pattern by photolithography includes, for example, a coating step, an exposure step, a cleaning step, and a heating step.

[0108] The coating step is a step of coating the black ultraviolet-curable organic composition on a substrate to form a photoresist film. In the case where the black ultraviolet-curable organic composition contains a solvent, the black ultraviolet-curable organic composition is coated, followed by heating to remove the solvent. As the substrate, for example, glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamide-imide, polyimide, or the like can be used. Furthermore, as needed, a chemical agent treatment such as a silane coupling agent, a plasma treatment, ion plating, sputtering, a vapor reaction method, vacuum evaporation, or the like can be performed on the substrate as appropriate. The coating method of the black ultraviolet-curable organic composition can use a spin coating method, a flow coating method, a roll coating method, a dipping method, or the like. The thickness of the photoresist film is usually in the range of 0.1 μm or more and 10 μm or less, preferably in the range of 0.2 μm or more and 7.0 μm or less, and particularly preferably in the range of 0.5 μm or more and 6.0 μm or less.

[0109] The exposure step is a step of generating a pattern composed of a cured portion exposed to light and an uncured portion not exposed to light by exposing ultraviolet light to the photoresist film in a pattern. As the method of exposing ultraviolet light in a pattern, a method using a photomask, a method of emitting ultraviolet light in a pattern can be adopted. As the ultraviolet light, ultraviolet light (i-line) having a wavelength of 365 nm can be used.

[0110] The cleaning step is a step of removing the uncured portion not exposed to light using a cleaning liquid. As the cleaning liquid, an aqueous alkaline solution can be used. As the cleaning method, for example, a dipping method, a spray cleaning, a mist cleaning, an ultrasonic cleaning can be used.

[0111] The heating step is a step of further curing the cured portion by heating the cured portion after drying after the cleaning step. The heating temperature is, for example, in the range of 100°C or more and 300°C or less. In addition, in the case where the cured portion formed by the exposure step has sufficient hardness, the heating step can be omitted.

[0112] The black pattern forming method configured as described above uses a black material containing the zirconium nitride-containing powder of the present embodiment, and thus a high-fineness black pattern can be formed. Then, the obtained black pattern is excellent in visible light shielding property.

[0113] Example

[0114] [Experimental Example 1]

[0115] As to the zirconium nitride (ZrN) powder, five samples having a particle diameter of 20 nm, 40 nm, 60 nm, 80 nm, and 100 nm were assumed. First principle calculation was performed on each of the assumed zirconium nitride powders to calculate a dielectric constant. Using the obtained dielectric constant, Mie scattering calculation of each of the zirconium nitride powders was performed to calculate extinction efficiency Q of one particleext Then, the wavelength-absorbance coefficient curve of the dispersion liquid containing each zirconium nitride powder at 50 mass ppm was calculated. The results are shown in FIG. 2. Figure 1 And, the absorbance coefficient a of the visible light of wavelength 550 nm is shown in Table 1 below 550 The absorbance coefficient a of the ultraviolet light of wavelength 365 nm 365 The ratio (a 550 / a 365 ) of the absorbance coefficient a of the visible light of wavelength 550 nm to the absorbance coefficient a of the ultraviolet light of wavelength 365 nm.

[0116] [Table 1]

[0117]

[0118] From the wavelength-absorbance coefficient curve of Figure 1 , it is known that as the particle diameter of the zirconium nitride powder decreases from 100 nm to 40 nm, the maximum absorbance coefficient value in the visible light region becomes large, and the maximum absorbance coefficient value in the visible light region is approximately equal at the particle diameters of 40 nm and 20 nm. And, it is known that as the particle diameter decreases, the wavelength of the maximum peak value indicating the absorbance coefficient in the visible light region becomes shorter, and the absorbance coefficient of the visible light on the long wavelength side decreases. This is because as the particle diameter decreases, the wavelength of the plasmon resonance becomes shorter.

[0119] [Experiment Example 2]

[0120] A zirconium-containing nitride (Zr 0.875 X 0.125 N) particle in which 8 / 1 of the Zr atoms of zirconium nitride (ZrN) is substituted with another element X is assumed. The element X is Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Ti, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, Sb, Bi, S, Se, Te, Po, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu. And, a zirconium-containing nitride (Zr 0.875 Y 0.0625 Dy 0.0625 N) particle in which a part of the Zr atoms of zirconium nitride (ZrN) is substituted with Y and Dy is assumed. The particle diameter of the zirconium-containing nitride particle is set to five kinds of 20 nm, 40 nm, 60 nm, 80 nm, 100 nm.

[0121] For each of the envisioned zirconium nitride particles, wavelength-extinction coefficient curves were calculated in the same manner as in Experimental Example 1. The results showed that Group III elements, namely Dy, Er, Gd, Ho, Lu, Nd, Pr, Sc, Sm, Tb, Tm, and Y+Dy, have the effect of shifting the wavelength representing the maximum peak value of the extinction coefficient in the visible light region to the longer wavelength side. Wavelength-extinction coefficient curves for zirconium nitrides (particle size: 100 nm) with a portion of Zr replaced by Dy, Er, Gd, Ho, Lu, Nd, Pr, Sc, Sm, Tb, Tm, or Y+Dy are shown below. Figure 2 .

[0122] from Figure 2 The wavelength-extinction coefficient curves show that the wavelengths of the maximum peak extinction coefficient in the visible light region of zirconium nitrides, which replace a portion of Zr with Dy, Er, Gd, Ho, Lu, Nd, Pr, Sc, Sm, Tb, Tm or Y+Dy, are all above 580 nm. Compared with zirconium nitride, the wavelength of the maximum peak extinction coefficient in the visible light region is shifted to the longer wavelength side.

[0123] The results of Experiment 1 and Experiment 2 above show that by reducing the average particle size of zirconium nitride powder and further replacing a portion of Zr with Group III elements such as Dy, Er, Gd, Ho, Lu, Nd, Pr, Sc, Sm, Tb, Tm or Y+Dy, zirconium nitride powder with excellent ultraviolet light transmittance and visible light shielding can be obtained.

[0124] [Experimental Example 3]

[0125] For the zirconium nitride particles (particle sizes: 20 nm, 40 nm, 60 nm, 80 nm, 100 nm) hypothesized in Experimental Example 2, calculate the extinction coefficient α of visible light at a wavelength of 550 nm. 550 Extinction coefficient α relative to ultraviolet light with a wavelength of 365 nm 365 The ratio (α) 550 / α 365 The particle size and ratio (α) of the zirconium nitride particles were determined. 550 / α 365 The relationship between the two is shown together with the results obtained from the zirconium nitride (ZrN) powder in Experimental Example 1. Figure 3 .

[0126] exist Figure 3 In the chart, the horizontal axis represents particle size, and the vertical axis represents the ratio (α). 550 / α 365 ).from Figure 3 The results show that if the particle size is below 70 nm, the ratio of zirconium nitride powder (α) 550 / α 365 The ratio of α to zirconium nitride powder550 / α 365 ) becomes larger.

[0127] [Inventive Example 1]

[0128] Zirconium dioxide powder and dysprosium oxide powder were weighed in a manner such that the molar ratio of zirconium to dysprosium was 0.875:0.125 and the total mass was 10 g. The weighed zirconium dioxide powder and dysprosium oxide powder were uniformly mixed using a blender. The obtained zirconium oxide powder containing dysprosium oxide powder 7.86 g, magnesium metal powder 5.83 g, and magnesium oxide powder 3.39 g were mixed in a nitrogen atmosphere, thereby preparing a mixed powder. In the obtained mixed powder, the content of the magnesium metal powder was 4.0 times the molar amount based on the mass of the metal atoms in the zirconium oxide powder containing dysprosium oxide. Also, the content of the magnesium atoms in the magnesium oxide powder was 1.4 times the molar amount based on the mass of the metal atoms in the zirconium oxide powder containing dysprosium oxide. The above mixed powder was fired at a temperature of 700°C for 60 minutes under a nitrogen atmosphere, and a fired product was obtained. The obtained fired product was dispersed in 1 L of water, and 17.5% hydrochloric acid was slowly added, and washing was performed under conditions where the pH was 1 or more and the temperature was maintained at 100°C or less. Subsequently, the pH was adjusted to 7 to 8 with 25% ammonia water, and filtration was performed. The filtered solid component was again dispersed in water at 400 g / L, and the pH was adjusted with acid and ammonia water in the same manner as described above. Subsequently, filtration was performed. The pH adjustment with acid and ammonia water was repeated twice in this manner. Subsequently, the filtrate was dispersed in ion exchange water at 500 g / L in terms of the solid component, and heating and stirring were performed at 60°C while adjusting the pH to 7. Subsequently, filtration was performed using a suction filtration device, and the same amount of ion exchange water was used for washing, and drying was performed using a hot air dryer with a set temperature of 120°C. The obtained dried powder was subjected to X-ray diffraction pattern measurement, and elemental analysis was performed using X-ray Photoelectron Spectroscopy (XPS). Also, the oxygen content was measured using a method in accordance with JIS Z2613 "General Rules for Oxygen Quantification in Metal Materials". The nitrogen content was measured by inert gas fusion-thermal conductivity method. As a result, it was confirmed that the obtained dried powder was a zirconium-containing nitride powder containing dysprosium represented by general formula (II). The average particle diameter of the obtained zirconium-containing nitride powder was 50 nm.

[0129] [Inventive Example 2]

[0130] A zirconium-containing nitride powder was produced in the same manner as in Inventive Example 1, except that erbium oxide powder, gadolinium oxide powder, holmium oxide powder, lutetium oxide powder, neodymium oxide powder, praseodymium oxide powder, scandium oxide powder, samarium oxide powder, terbium oxide powder, and thulium oxide powder were used instead of dysprosium oxide powder. The obtained zirconium-containing nitride powder contained the respective Group III elements.

[0131] Industrial applicability

[0132] The zirconium nitride-containing powder of the present embodiment is excellent in ultraviolet light transmittance and visible light shielding property. Therefore, the zirconium nitride-containing powder of the present embodiment is suitable as a material for a black matrix constituting a color filter for a display or a black pattern of a light shielding material in a CMOS camera module.

Claims

1. A zirconium-containing nitride powder, a composition of the zirconium-containing nitride powder being represented by the following general formula (I), (Zr, X, Y) (N, O) (I) wherein X represents at least one element selected from the group consisting of Dy, Er, Gd, Ho, Lu, Nd, Pr, Sc, Sm, Tb, and Tm, Y represents an element symbol of yttrium, the content of Y is 0 mol or more relative to the total content of Zr, X, and Y of 1 mol, N represents nitrogen, O represents oxygen, and the content of oxygen is 0 mol or more and 0.4 mol or less relative to the total content of nitrogen and oxygen of 1 mol.

2. The zirconium-containing nitride powder according to claim 1, wherein the average particle diameter of the zirconium-containing nitride powder is in the range of 10 nm or more and 70 nm or less. wherein 3. The zirconium-containing nitride powder according to claim 1 or 2, wherein the ratio of the extinction coefficient of visible light at a wavelength of 550 nm to the extinction coefficient of ultraviolet light at a wavelength of 365 nm is in the range of 1.4 or more and 100 or less in the extinction coefficient determined by the following method.

4. The zirconium-containing nitride powder according to claim 3, wherein the zirconium-containing nitride powder has a particle diameter distribution in which the content of particles having a particle diameter of 10 nm or more and 70 nm or less is 50% or more.

5. A black ultraviolet-curable organic composition containing an ultraviolet-curable organic substance and a black pigment dispersed in the ultraviolet-curable organic substance, the black pigment being the zirconium-containing nitride powder according to any one of claims 1 to 4.

6. The black ultraviolet-curable organic composition according to claim 5, wherein the ultraviolet-curable organic substance is at least one organic substance selected from the group consisting of an acrylic acid monomer, an acrylic acid oligomer, an epoxy monomer, and an epoxy oligomer. ​ ​ ​ ​ ​ The extinction coefficient of the zirconium nitride-containing powder for visible light having a wavelength of 550 nm is 600 m -1 The above. ​ ​ ​ ​

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