CN114507073A - Zirconium nitride powder and method for producing same - Google Patents
Zirconium nitride powder and method for producing same Download PDFInfo
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- CN114507073A CN114507073A CN202011277829.8A CN202011277829A CN114507073A CN 114507073 A CN114507073 A CN 114507073A CN 202011277829 A CN202011277829 A CN 202011277829A CN 114507073 A CN114507073 A CN 114507073A
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- zirconium nitride
- powder
- nitride powder
- dispersion
- black
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- 239000000843 powder Substances 0.000 title claims abstract description 254
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 title claims abstract description 207
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000000178 monomer Substances 0.000 claims abstract description 69
- 239000002245 particle Substances 0.000 claims abstract description 45
- 239000006185 dispersion Substances 0.000 claims abstract description 43
- 238000009826 distribution Methods 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002612 dispersion medium Substances 0.000 claims abstract description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004593 Epoxy Substances 0.000 claims abstract description 13
- 239000000049 pigment Substances 0.000 claims abstract description 13
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- 229920005989 resin Polymers 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 51
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- 230000000052 comparative effect Effects 0.000 description 27
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- 229910052749 magnesium Inorganic materials 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
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- 238000002834 transmittance Methods 0.000 description 8
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
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- 239000007788 liquid Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
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- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
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- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
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- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
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- JEYLQCXBYFQJRO-UHFFFAOYSA-N 2-[2-[2-(2-ethylbutanoyloxy)ethoxy]ethoxy]ethyl 2-ethylbutanoate Chemical compound CCC(CC)C(=O)OCCOCCOCCOC(=O)C(CC)CC JEYLQCXBYFQJRO-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
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- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
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- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/58007—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on refractory metal nitrides
- C04B35/58028—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on refractory metal nitrides based on zirconium or hafnium nitrides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/0072—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
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Abstract
The invention provides a high insulation material which can obtain high insulation and high blackness and has high insulation. The volume resistivity of the zirconium nitride powder of the present invention in a state of a green compact compacted with a pressure of 5MPa was 107A particle size distribution D of not less than Ω · cm and obtained by ultrasonic dispersion for 5 minutes in a state diluted with water or an alcohol having 2 to 5 carbon atoms90Is 10 μm or less. In addition, the above-described zirconium nitride powder may be dispersed in an acrylic monomer or an epoxy monomer to prepare a monomer dispersion. Further, the above-described zirconium nitride powder may be dispersed as a black pigment in a dispersion medium and mixed with a resin to prepare a black composition.
Description
Technical Field
The present invention relates to a zirconium nitride powder suitable for use as a black pigment having high ultraviolet transmittance and high blackness and having high insulation properties, and a method for producing the same.
Background
Heretofore, there has been disclosed a zirconium nitride powder having a specific surface area of 20m as measured by the BET method2/g~90m2(ii)/g, which has a zirconium nitride peak in an X-ray diffraction pattern but does not have a zirconium dioxide peak and a lower zirconium oxide peak (see, for example, patent document 1 (claim 1, paragraph [0016 ]])). The zirconium nitride powder has a light transmittance X at 370nm of at least 18%, a light transmittance Y at 550nm of 12% or less, and a ratio (X/Y) of the light transmittance Y at 550nm to the light transmittance X at 370nm of 2.5 or more in a transmission spectrum of a dispersion having a powder concentration of 50 ppm.
The zirconium nitride powder thus constituted had a specific surface area of 20m2More than g, so that it has the effect of inhibiting sedimentation when made into resist, and its chemical composition is formed fromAt 90m2Has a sufficient light-shielding effect because of its lower/g ratio. Further, since the dispersion has a zirconium nitride peak in an X-ray diffraction pattern, but does not have a zirconium dioxide peak, a reduced zirconium oxide peak and a reduced zirconium oxynitride peak, the dispersion has a light transmittance X of at least 18% at 370nm and a light transmittance Y of 12% or less at 550nm in a transmission spectrum of a dispersion having a powder concentration of 50ppm, and has a characteristic that X/Y is 2.5 or more. Since X/Y is 2.5 or more, it has a characteristic of transmitting more ultraviolet rays. Therefore, a high-resolution patterned film can be formed when the black patterned film is formed as a black pigment, and the formed patterned film has high light shielding performance.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2017-222559.
Disclosure of Invention
Problems to be solved by the invention
In the zirconium nitride powder disclosed in patent document 1, when the zirconium nitride coarse powder is dispersed in a dispersion medium and the dispersibility is improved by using a bead mill (medium: zirconia) or the like, although high insulation properties can be obtained, if the zirconium nitride powder is directly kneaded into a high-viscosity resin paste, the zirconium nitride coarse powder remains and the dispersibility is insufficient. Therefore, when zirconium nitride powder is used as a black pigment, the coloring power of the black paint is reduced, and the resistance value is disadvantageously reduced by the residual zirconium nitride coarse powder. Further, when the above-mentioned zirconium nitride coarse powder is forcibly pulverized by a dry pulverizer or the like, the powder diameter becomes small and an oxidation reaction is caused on the powder surface, so that there is a problem that the degree of blackness of the black paint is lowered although the insulation property is improved.
The object of the present invention 1 is to provide a zirconium nitride powder having high insulation properties and high degree of blackness while obtaining high insulation properties and a method for producing the same. The 2 nd object of the present invention is to provide a method for producing zirconium nitride powder capable of maintaining high blackness by low-temperature wet media pulverization or pulverization by a jet mill generating a small amount of heat. The 3 rd object of the present invention is to provide a method for preparing zirconium nitride powder capable of improving the insulating property of a black film by baking in an inert gas atmosphere.
Means for solving the problems
The 1 st aspect of the present invention is a zirconium nitride powder having a volume resistivity of 10 in a state of a green compact compacted with a pressure of 5MPa7A particle size distribution D of not less than Ω · cm and obtained by ultrasonic dispersion for 5 minutes in a state diluted with water or an alcohol having 2 to 5 carbon atoms90Is 10 μm or less.
The 2 nd aspect of the present invention is a method for producing a zirconium nitride powder, the method comprising: a step of forming a zirconium nitride coarse powder by a thermite method or a plasma synthesis method; a step of producing a zirconium nitride precursor powder having a particle size distribution D obtained by subjecting the zirconium nitride precursor powder to low-temperature wet medium pulverization at a dispersion medium temperature of 10 ℃ or lower or to jet mill pulverization at an air pressure of 0.3MPa or higher, the zirconium nitride precursor powder having a particle size distribution D obtained by ultrasonic dispersion for 5 minutes in a state diluted with water or an alcohol having 3 to 5 carbon atoms90Is less than 10 mu m; and a step for preparing a zirconium nitride powder having a volume resistivity of 10 in a state of a green compact compacted with a pressure of 5MPa by calcining the pulverized zirconium nitride precursor powder in an inert gas atmosphere7Omega cm or more.
The 3 rd aspect of the present invention is a monomer dispersion obtained by dispersing the zirconium nitride powder according to the 1 st aspect in an acrylic monomer or an epoxy monomer.
The 4 th aspect of the present invention is a black composition obtained by dispersing the zirconium nitride powder according to the 1 st aspect as a black pigment in a dispersion medium and mixing a resin.
The invention according to claim 5 is a method for producing a black film, comprising: a step of forming a coating film by applying the monomer dispersion according to the 3 rd aspect to a substrate, and a step of producing a black film by thermally curing or ultraviolet-curing the coating film.
The 6 th aspect of the present invention is a method for producing a black film, the method comprising: a step of forming a coating film by applying the black composition according to the 4 th aspect to a substrate, and a step of forming a black film by thermally curing or ultraviolet-curing the coating film.
ADVANTAGEOUS EFFECTS OF INVENTION
Since the zirconium nitride powder according to aspect 1 of the present invention has a volume resistivity of 10 in the state of a green compact compacted with a pressure of 5MPa7Since the thickness is not less than Ω · cm, the insulation property can be improved when a black thick film having a thickness of about 10 μm to 100 μm is produced. Further, the zirconium nitride powder has a particle size distribution D when it is dispersed by ultrasonic waves for 5 minutes in a state diluted with water or an alcohol having 2 to 5 carbon atoms90Since the particle size is 10 μm or less, a good dispersion or dispersion liquid free from the zirconium nitride coarse powder can be obtained. Thus, a black film produced from the dispersion or dispersion liquid using the zirconium nitride powder can have high insulation properties, high blackness and high insulation properties.
In the method for producing zirconium nitride powder according to aspect 2 of the present invention, when the zirconium nitride coarse powder is subjected to low-temperature wet medium pulverization at a dispersion medium temperature of 10 ℃ or lower, the amount of heat generation is small, and therefore, the surface oxidation of zirconium nitride does not proceed, and a high degree of blackness can be maintained. Further, when the zirconium nitride coarse powder is pulverized by a jet mill under an air pressure of 0.3MPa or more, the zirconium nitride coarse powder does not remain, and the insulation property of the black film can be improved. Further, the insulating property of the black film can be improved by baking the pulverized zirconium nitride precursor powder in an inert gas atmosphere.
The monomer dispersion according to aspect 3 of the present invention is obtained by dispersing the zirconium nitride powder according to aspect 1 of the present invention in an acrylic monomer or an epoxy monomer, and therefore, even if the viscosity of these monomers is high, the dispersibility of the zirconium nitride powder with respect to the above monomers can be maintained good. Thus, the black film obtained using the monomer dispersion can have high insulation properties, high degree of blackness, and high insulation properties.
Since the black composition according to the 4 th aspect of the present invention is obtained by dispersing the zirconium nitride powder according to the 1 st aspect of the present invention as a black pigment in a dispersion medium and mixing a resin, the zirconium nitride powder is uniformly dispersed in the dispersion medium. Thus, the black film obtained using the black composition has high insulation properties, high degree of blackness, and high insulation properties.
In the method for producing a black film according to aspect 5 of the present invention, after the monomer dispersion is applied onto a substrate to form a coating film, the coating film is thermally cured or ultraviolet-cured to produce a black film, and therefore the black film can have high insulation properties and high blackness and also has high insulation properties.
In the method for producing a black film according to aspect 6 of the present invention, after the black composition is applied to a substrate to form a coating film, the coating film is thermally cured or ultraviolet-cured to produce a black film, and therefore the black film has high insulation properties and high blackness and also has high insulation properties.
Detailed Description
Next, a mode for carrying out the present invention will be explained. The volume resistivity of the zirconium nitride powder of the present embodiment in a state of a green compact compacted with a pressure of 5MPa was 107Omega cm or more, preferably 108A particle size distribution D of not less than Ω · cm and obtained by ultrasonic dispersion for 5 minutes in a state diluted with water or an alcohol having 2 to 5 carbon atoms90Is 10 μm or less, preferably 8 μm or less. Here, the volume resistivity is defined as 107The reason why the value is not less than 10 Ω · cm7Omega cm, when a black thick film having a thickness of about 1 μm to 100 μm is formed using zirconium nitride powder, the insulation property is lowered. Further, the above particle size distribution D90The reason why the particle size is limited to 10 μm or less is that when it exceeds 10 μm, the coarse zirconium nitride powder remains, and a good dispersion and a black film cannot be obtained.
The bulk resistivity is measured by a four-terminal four-probe method using, for example, Loresta-GP (model: UV-3101PC), a low resistivity meter manufactured by Mitsubishi chemical corporation. The four-terminal four-probe method is a method in which 4 needle electrodes are placed on a straight line with a predetermined interval therebetween on the surface of a sample (green compact), a constant current is passed between the outer 2 needle electrodes, and the potential difference generated between the inner 2 needle electrodes is measured to determine the volume resistivity.
The zirconium nitride powder is in the form of secondary particles in which primary particles are aggregated, and has a volume-based particle size distribution measured by a laser diffraction scattering method. Here, the volume-based particle size distribution was measured by the laser diffraction scattering method as follows. First, 0.1g of zirconium nitride powder (secondary particles) was put into 20g of ion-exchanged water, and ultrasonic waves of 25kHz were irradiated for 5 minutes to disperse the zirconium nitride powder in the ion-exchanged water. Then, an appropriate amount of the obtained dispersion of zirconium nitride powder was dropped into an observation cell of a laser diffraction scattering particle size distribution measuring apparatus (trade name: LA-300, manufactured by horiba, Ltd.), and the particle size distribution was measured according to the procedure of the apparatus. The particle size distribution measured by the laser diffraction scattering method is a particle size distribution of secondary particles in which the primary particles of the zirconium nitride powder are aggregated. Instead of the ion-exchanged water, an alcohol having 2 to 5 carbon atoms may be used. 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; examples of the alcohol having 4 carbon atoms include 1-butanol, 2-butanol and the like; examples of the alcohol having 5 carbon atoms include 1-pentanol and 2-pentanol. When the number of carbon atoms is 1 or less, the volatility is high and the measured value is unstable; if the number of carbon atoms is 6 or more, the affinity may be insufficient, and the measured value may be unstable.
A method for producing the zirconium nitride powder thus constituted will be explained. First, a zirconium nitride coarse powder is produced by a thermite method or a plasma synthesis method. In the present specification, the thermit method refers to a method of mixing zirconia powder with N in the presence of magnesium metal2Gas (nitrogen) reaction and reduction. In this embodiment, zirconium dioxide (ZrO) is used as the zirconium oxide powder2) Powder or silica-coated zirconium dioxide (ZrO)2) And (3) powder. In addition, magnesium nitride (Mg) is added to the metal magnesium powder3N2) And (3) powder. These powders were used as starting materialsA material which is calcined at a specific temperature and for a specific time in a specific atmosphere to give a specific surface area of 20m as measured by the BET method2/g~90m2Per g of crude zirconium nitride powder.
[ zirconium dioxide powder ]
As the zirconia powder, for example, zirconia powders such as monoclinic zirconia, cubic zirconia, and yttrium-stabilized zirconia can be used, and monoclinic zirconia powder is preferable from the viewpoint of increasing the production rate of zirconium nitride powder. In addition, in order to obtain a specific surface area of 20m as measured by the BET method2/g~90m2The zirconium nitride raw powder/g is preferably such that the average primary particle diameter of each of the zirconium dioxide powder or the silicon dioxide-coated zirconium dioxide powder and the average primary particle diameter of the magnesium oxide powder is 500nm or less in terms of the average primary particle diameter obtained by spherical conversion from the measured value of the specific surface area, and is preferably 500nm or less and 10nm or more in terms of the average primary particle diameter from the viewpoint of easy handling of the powder.
[ silica-coated zirconium dioxide powder ]
The silica-coated zirconium dioxide powder is obtained by mixing a zirconium dioxide powder with a silicate sol-gel solution to prepare a slurry, drying the slurry, and pulverizing the dried slurry. The mixing ratio of zirconium dioxide to silicate sol-gel solution is preferably (90.0 to 99.5): (10.0 to 0.5) in terms of mass ratio of zirconium dioxide to silicate sol-gel solution. If the amount of silica is less than the lower limit, the silica coverage on the zirconia surface is too low; if the amount of silicon dioxide exceeds the upper limit, the light-shielding property may be insufficient when a patterned film is formed using the obtained zirconium nitride powder.
In order to uniformly mix zirconium dioxide into the sol-gel solution, it is preferable to add zirconium dioxide powder to a dispersion of water, alcohol, or the like, and mix the mixture, and then add the mixture to the silicate sol-gel solution. The silicate sol-gel solution is preferably a solution obtained by dissolving silicate such as methyl silicate or ethyl silicate in a solvent such as water or alcohol. The mixing ratio of zirconia and the sol-gel solution can be determined so that the solid content concentration of the slurry obtained is 10 to 50 mass% in terms of solid content. Drying the obtained slurry in the atmosphere or in a vacuum atmosphere at the temperature of 60-350 ℃ for 1-360 minutes to obtain the silicon dioxide coated zirconium dioxide powder.
By using a silica-coated zirconium dioxide powder as a starting material, grain growth can be suppressed at the time of firing, and a specific surface area of 20m as measured by the BET method can be obtained2/g~90m2Finer zirconium nitride powder per g. In this case, the zirconium nitride powder contains silicon oxide and/or silicon nitride in a proportion of 10.0 mass% or less, preferably 9.0 mass% or less. If the content exceeds 10.0 mass%, the light-shielding property may be insufficient when a patterned film is formed using the obtained zirconium nitride powder.
[ metallic magnesium powder ]
Since the reaction rapidly proceeds and the handling risk increases when the particle size of the magnesium metal powder is too small, the magnesium metal powder is preferably a granular powder having a particle size of 100 to 1000 μm, particularly 200 to 500 μm, in terms of mesh (pass) passing through the sieve. However, the metal magnesium may not be entirely within the above-mentioned particle size range, as long as 80 mass% or more, particularly 90 mass% or more thereof is within the above-mentioned range.
The amount of the metal magnesium powder added to the zirconium dioxide powder affects the reducing power of zirconium dioxide together with the amounts of ammonia and hydrogen in an atmospheric gas described later. If the amount of metallic magnesium is too small, the reduction is insufficient, and the target zirconium nitride powder is difficult to obtain; if too much, the reaction temperature is abruptly increased by the excess metallic magnesium, which may cause grain growth of the powder and become uneconomical. The magnesium metal powder is added to the zirconium dioxide powder in such a manner that the magnesium metal is 2.0-6.0 times by mole of the zirconium dioxide powder, depending on the particle size of the magnesium metal powder, and mixed. If the amount is less than 2.0 times by mol, the reduction reaction of zirconium dioxide becomes insufficient, and if the amount exceeds 6.0 times by mol, the reaction temperature may be rapidly increased by the excess metal magnesium, which may cause grain growth of the powder, and thus it becomes uneconomical.
[ magnesium nitride powder ]
The magnesium nitride powder is coated on the surface of zirconium nitride during firing, thereby moderating the reducing power of metallic magnesium to prevent sintering and grain growth of the zirconium nitride powder. The magnesium nitride powder is added to zirconium dioxide so that the magnesium nitride is in a proportion of 0.3 to 3.0 times by mole with respect to zirconium dioxide, depending on the particle size of the magnesium nitride powder. If the amount is less than 0.3 times by mol, sintering of the zirconium nitride powder cannot be prevented; if the amount exceeds 3.0 times by mole, the amount of the acidic solution used in the acid washing after the baking may be increased. Preferably 0.4 to 2.0 times by mole. The magnesium nitride powder preferably has an average primary particle diameter of 1000nm or less in terms of a sphere from a measured value of the specific surface area; from the viewpoint of easy handling of the powder, the average primary particle diameter is preferably 10nm or more and 500nm or less. Since magnesium oxide is effective not only for magnesium nitride but also for preventing sintering of zirconium nitride, magnesium nitride may be used in combination with a part of magnesium oxide.
[ reduction reaction Using metallic magnesium powder ]
The temperature of the reduction reaction by using the magnesium metal for generating the zirconium nitride coarse powder is 650-900 ℃, and preferably 700-800 ℃. 650 ℃ is the melting temperature of magnesium metal, and if the temperature is lower than this temperature, the reduction reaction of zirconium dioxide does not sufficiently occur. Even if the temperature is higher than 900 ℃, the effect is not increased, and sintering of the powder proceeds while wasting heat energy, which is not preferable. The reduction reaction time is preferably 30 to 90 minutes, and more preferably 30 to 60 minutes.
The reaction vessel in which the reduction reaction is carried out is preferably a vessel having a lid so that the raw materials and the product do not scatter during the reaction. This is because, when the metal magnesium starts to melt, the reduction reaction rapidly proceeds, and the temperature rises with the metal magnesium, and the gas inside the container expands, so that the substances inside the container may be scattered to the outside.
[ atmosphere gas in reduction reaction of metallic magnesium powder ]
The atmosphere gas is a nitrogen simple substance, or a mixed gas of nitrogen and hydrogen, or a mixed gas of nitrogen and ammonia. The reduction reaction is carried out in the gas flow of the mixed gas. The nitrogen gas in the mixed gas has the effect of preventing the metallic magnesium or the reduction product from coming into contact with oxygen, thereby preventing them from being oxidized, while allowing nitrogen to react with zirconium to form zirconium nitride. The hydrogen or ammonia in the mixed gas has the function of reducing the zirconium dioxide together with the metal magnesium. The mixed gas preferably contains 0 to 40 vol% of hydrogen, and more preferably contains 10 to 30 vol% of hydrogen. The mixed gas preferably contains 0 to 50 vol% of ammonia gas, and more preferably contains 0 to 40 vol% of ammonia gas. By using the atmosphere gas having reducing power, a zirconium nitride powder containing no lower-valent zirconia or lower-valent zirconium oxynitride can be finally prepared. On the other hand, if the ratio of hydrogen or the ratio of nitrogen is higher than this range, reduction proceeds, but the amount of nitrogen source decreases, so that low-valent zirconium oxide or low-valent zirconium oxynitride is produced, which is not preferable. In addition, it is considered that the higher proportion of ammonia gas than hydrogen gas is because ammonia has a higher gas nitriding ability than hydrogen.
On the other hand, the method for generating zirconium nitride coarse powder by using the plasma synthesis method is to introduce metal zirconium powder into a plasma nano particle preparation device, and then N is added2A method for obtaining zirconium nitride nano particles in gas atmosphere. As for the zirconium nitride synthesized by this method, 20m can be obtained2/g~90m2The zirconium nitride having a specific surface area measured by the BET method has disadvantages that the flammability of metallic zirconium as a raw material is high and the cost is high. Since the nanoparticles produced by the plasma synthesis method are coarsened by rapid surface oxidation, adhesion, agglomeration, or the like in the cooling process or the product removal process to form coarse powder, zirconium nitride produced by the plasma synthesis method is also used as the zirconium nitride coarse powder.
Then, the zirconium nitride raw powder is subjected to low-temperature wet medium grinding at a dispersion medium temperature of 10 ℃ or lower or subjected to jet mill grinding at an air pressure of 0.3MPa or higher to prepare a zirconium nitride precursor powder, which is diluted with water or an alcohol having 3 to 5 carbon atoms and subjected to ultrasonic wave spectroscopyParticle size distribution D at 5 min of dispersion90Is 10 μm or less. The zirconium nitride precursor powder had a specific surface area of 22m as measured by the BET method2/g~120m2/g。
The low-temperature wet media pulverization method is a bead mill pulverization method in which zirconium nitride coarse powder is dispersed in a dispersion medium such as ion-exchanged water or an alcohol having 2 to 5 carbon atoms, and a medium such as zirconia, alumina, glass, or a polyurethane resin having an average particle diameter of 50 to 500 μm is used while the temperature of the dispersion medium is maintained at 10 ℃ or lower. The reason why the temperature of the dispersion medium is kept at 10 ℃ or lower is that if the temperature exceeds 10 ℃, the zirconium nitride precursor powder is pulverized, and the OD value of the black film described later is lowered. In order to keep the temperature of the dispersion medium at 10 ℃ or lower, liquid nitrogen may be used as the dispersion medium, or dry ice beads may be used as the medium. Further, when the zirconium nitride coarse powder is pulverized by the low-temperature wet media pulverization method, since the amount of heat generation is small, the surface oxidation of zirconium nitride does not proceed, and a high degree of blackness can be maintained.
The jet mill pulverization with an air pressure of 0.3MPa or more means an apparatus in which high-pressure air of 0.3MPa or more, inert gas such as nitrogen, or steam ejected from a nozzle collides with the powder in the form of a super high-speed jet, and the powder is pulverized into fine powder of several μm level by the impact of the powder with each other, and the ejected air or steam reaches the sonic velocity or so. Examples of the characteristics of the jet mill include: the temperature is lowered by adiabatic expansion of the injected gas, and thus the pulverization can be performed at a low temperature; thus, oxidation can be suppressed even for a reduced substance such as zirconium nitride in the present invention. The reason why the gas pressure is limited to 0.3MPa or more is that when the gas pressure is less than 0.3MPa, the zirconium nitride coarse powder remains. When the coarse zirconium nitride powder is pulverized by the jet mill pulverization method, the coarse zirconium nitride powder does not remain, and the insulation property of the black film can be improved.
Further, by firing the pulverized zirconium nitride precursor powder in an inert gas atmosphere, a green compact having a volume resistivity of 10 in a state of being compacted with a pressure of 5MPa was prepared7Nitriding of omega cm or moreZirconium powder. As the inert gas, N can be mentioned2Gas, helium, argon, and the like. The roasting temperature is preferably within the range of 250-550 ℃, and the roasting time is preferably within the range of 1-5 hours. Here, the reason why the preferable firing temperature is limited to the range of 250 ℃ to 550 ℃ is that the increase of the resistance value is insufficient when the firing temperature is lower than 250 ℃, and the fusion of the powders is progressed when the firing temperature exceeds 550 ℃, and the coarse powder increases. 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 increase of the resistance value is insufficient, and if it exceeds 5 hours, the effect is not changed, which is uneconomical. The insulating property of the black film can be improved by baking the zirconium nitride precursor powder in an inert gas atmosphere. The detailed mechanism for improving the insulating property of the black film by firing in an inert gas atmosphere is not clear, but it is presumed that the coarse powder of zirconium nitride disappears to improve the uniformity of the powder, reduce the number of contact points, or form an extremely thin insulating layer on the surface of the black film.
The above-described zirconium nitride powder is dispersed in an acrylic monomer or an epoxy monomer to prepare a monomer dispersion. The monomer dispersion can be used for applications such as dispersing resin compositions containing inorganic powder, resin molded articles, and the like. The monomer dispersion may further contain a metal oxide powder and a plasticizer. The plasticizer is not particularly limited, and examples thereof include conventionally known plasticizers such as phosphate plasticizers such as tributyl phosphate and 2-ethylhexyl phosphate, phthalate plasticizers such as dimethyl phthalate and dibutyl phthalate, aliphatic monobasic acid ester plasticizers such as butyl oleate and glycerol monooleate, aliphatic dibasic acid ester plasticizers such as dibutyl adipate and di-2-ethylhexyl sebacate, glycol ester plasticizers such as diethylene glycol dibenzoate and triethylene glycol di-2-ethylbutyrate, and oxo acid ester plasticizers such as methyl acetylricinoleate and tributyl acetylcitrate. In addition, other monomers may be added to the monomer dispersion. The other monomers are not particularly limited, and examples thereof include conventionally known monomers such as (meth) acrylic monomers including (meth) acrylic acid and (meth) acrylic esters, styrene monomers including styrene, vinyltoluene and divinylbenzene, acetyl monomers including vinyl chloride and vinyl acetate, urethane monomers including urethane acrylate, and the above-mentioned various polyols. In consideration of the dispersibility of the zirconium nitride powder, the viscosity of the monomer dispersion is preferably set to a range of 10 to 1000 mPas (10 to 1000 mPas). The dispersion into the monomer may be carried out by a milling method using a grinding medium, similarly to the dispersion into the solvent. Although not essential, a polymeric dispersant may be used to further improve dispersibility. The molecular weight of the polymeric dispersant is effective in the range of several thousands to several tens of thousands, and examples of the functional group to be adsorbed on the pigment include secondary amines, tertiary amines, carboxylic acids, phosphoric acid esters, and the like, and particularly tertiary amines and carboxylic acids are effective. It is also effective to add a small amount of a silane coupling agent instead of the polymeric dispersant for improving dispersibility. On the other hand, a dispersion may be obtained by carrying out planetary stirring and then passing through three rolls several times. On the other hand, a black composition was prepared by dispersing zirconium nitride powder as a black pigment in a dispersion medium and mixing a resin. Examples of the dispersion medium include Propylene Glycol Monomethyl Ether Acetate (PGMEA), Methyl Ethyl Ketone (MEK), and Butyl Acetate (BA). Examples of the resin include acrylic resins and epoxy resins. In the solvent dispersion, it is effective to add a polymer dispersant as in the monomer dispersion, and it is effective to have a molecular weight of several thousands to several tens of thousands as in the monomer dispersion, and tertiary amines and carboxylic acids are effective as functional groups.
Next, a method for producing a black film using the monomer dispersion will be described. First, a photopolymerization initiator is added to a monomer dispersion, and then the monomer dispersion is coated on a substrate to form a coating film. Subsequently, the coating film is cured by heat or ultraviolet rays to produce a black film. Examples of the substrate include glass, silicone, polycarbonate, polyester, aramid, polyamideimide, and polyimide. The substrate may be subjected to a chemical treatment with a silane coupling agent or the like, a plasma treatment, ion plating, sputtering, a vapor phase reaction method, vacuum deposition, or other suitable pretreatment as needed. When the monomer dispersion is coated on a substrate, a suitable coating method such as spin coating, flow coating, roll coating, or the like can be used.
In order to thermally cure the coating film, the coating film is preferably kept at a temperature of 80 to 250 ℃ for 5 to 60 minutes in the air. Here, the reason why the heat curing temperature of the coating film is limited to the range of 80 ℃ to 250 ℃ is that the coating film is not sufficiently cured when the temperature is lower than 80 ℃, and the substrate is softened when the temperature exceeds 250 ℃. The reason why the heat 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 is not sufficiently cured, and if it exceeds 60 minutes, it takes more time than necessary, which is uneconomical. On the other hand, in order to ultraviolet-cure the coating film, a photopolymerization initiator which is cleaved by ultraviolet rays such as Irgacure 184 (BASF), Irgacure 250 (BASF), Irgacure 270 (BASF), Irgacure 369 (BASF), Irgacure 500 (BASF), Irgacure 907 (BASF), and ADEKA OPTOMER N-1919 (ADEKA) is added to the monomer dispersion in advance. Then, after the monomer dispersion to which the photopolymerization initiator is added is coated on a substrate, prebaking is performed to evaporate the solvent, thereby forming a photoresist film. Next, after the photoresist film is exposed to light through a photomask in a predetermined pattern shape, the photoresist film is developed with an alkali developing solution to dissolve and remove unexposed portions of the photoresist film, and then, after that, a predetermined black film is formed by preferably post-baking.
The thickness of the cured black film is preferably in the range of 0.1 to 100 μm. Is particularly suitable for manufacturing a black film with a thickness of 10-100 μm. The OD (Optical Density) value of the black film is an Optical Density that is an index indicating the light-shielding property (attenuation of transmittance) of the black film using the zirconium nitride powder. Specifically, the OD value is a value representing the degree of absorption of light when passing through the black film by logarithm, and is defined by the following formula (1). In the formula (1), I is the amount of transmitted light, I0Is the amount of incident light.
OD value = -log10 (I/I)0) …………(1)
In addition, in order to ensure high light-shielding property, the OD value of the black film is preferably 2.0 or more, and in order to ensure high insulation property, the volume resistivity of the black film is preferably 1 × 1013Omega cm or more.
A method for producing a black film using the black composition will be described. First, a black composition is coated on a substrate to form a coating film. Then, the coating film is cured by heat or ultraviolet rays to produce a black film. The method for producing a black film using the black composition is substantially the same as the method for producing a black film using the monomer dispersion, and therefore, redundant description is omitted.
Examples
Next, examples of the present invention will be described in detail together with comparative examples.
< example 1>
First, a zirconium nitride coarse powder was produced by a hot-melt method. Specifically, 7.3g of magnesium metal powder having an average primary particle size of 150 μm and 3.0g of magnesium nitride powder having an average primary particle size of 200nm were added to 7.4g of monoclinic zirconia powder having an average primary particle size of 50nm calculated from the specific surface area measured by the BET method, and the mixture was uniformly mixed by a reaction apparatus having a graphite boat in a quartz glass tube. In this case, the amount of magnesium metal added was 5.0 times by mol based on zirconium dioxide, and the amount of magnesium nitride added was 0.5 times by mol based on zirconium dioxide. The mixture was calcined at a temperature of 700 ℃ for 60 minutes under a nitrogen atmosphere to obtain a calcined product. Dispersing the calcined product in 1 liter of water, slowly adding 10% hydrochloric acid, washing while maintaining the pH at 1 or more and the temperature at 100 ℃ or less, adjusting the pH to 7 to 8 with 25% ammonia water, and filtering. The filtered solid was redispersed in water to 400 g/l, acid-washed again in the same manner as above, adjusted in pH with aqueous ammonia, and then filtered. After repeating the acid washing and pH adjustment with ammonia water 2 times, the filtrate was dispersed in ion-exchanged water in a solid content of 500 g/liter, heated and stirred at 60 ℃ to adjust pH7, and then filtered by a suction filtration apparatus, and further washed with an equal amount of ion-exchanged water at a set temperature: drying was carried out by a hot air dryer at 120 ℃ to obtain a zirconium nitride coarse powder.
Subsequently, 20g of the above crude zirconium nitride powder was dispersed in 5 liters of isopropyl alcohol, and wet grinding (medium: alumina) was performed at a low temperature for 60 minutes to obtain a zirconium nitride precursor powder. The temperature of the isopropyl alcohol (dispersion medium) at this time is 5 ℃ or lower. Further drying the zirconium nitride precursor powder, and then adding N2The resultant was baked at 350 ℃ for 4 hours in a gas atmosphere to obtain zirconium nitride powder. This zirconium nitride powder was used as example 1.
< examples 2 to 12 and comparative examples 1 to 10>
With respect to the zirconium nitride powders of examples 2 to 12 and comparative examples 1 to 10, coarse zirconium nitride powders were produced by the methods shown in Table 1, respectively, and then pulverized and calcined, respectively. Zirconium nitride powder was produced in the same manner as in example 1, except for the production method, the pulverization method, and the firing method shown in table 1. In the column of the method for producing zirconium nitride coarse powder in table 1, "TM" is a thermal agent method and "PZ" is a plasma method. In the column of the method for pulverizing the zirconium nitride coarse powder in table 1, "BM" is a bead mill method and "JM" is a jet mill method. In addition, in the column of firing time/gas of the zirconium nitride precursor powder of table 1, "N2"is nitrogen," He "is helium, and" Ar "is argon.
< comparative test 1>
The volume resistivity of the zirconium nitride powders of examples 1 to 12 and comparative examples 1 to 10 in a state of a green compact compacted at a pressure of 5MPa and the particle size distribution D of the zirconium nitride powder obtained in a state of dilution with water and ultrasonic dispersion for 5 minutes were measured90. These results are shown in table 1.
< comparative experiment 2>
As shown in Table 1, 40g 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, as shown in table 1, 40g of the zirconium nitride powders of example 12 and comparative example 10 were added with an amine-based dispersant, and were dispersed in 200 ml of Propylene Glycol Monomethyl Ether Acetate (PGMEA) solvent to prepare black pigment dispersions, and then acrylic resins were added and mixed to these black pigment dispersions in a mass ratio of black pigment: resin =3:7 to prepare black compositions. Then, 4g of Irgacure 500 (photopolymerization initiator: manufactured by BASF) was added to the monomer dispersion or the black composition. Next, the monomer dispersion or the black composition was spin-coated on a glass substrate so that the thickness after firing was as shown in table 1, and then prebaked to evaporate the solvent, thereby forming a photoresist film. The photoresist film is exposed to light through a photomask to form a predetermined pattern, developed with an alkali developer to dissolve and remove unexposed portions of the photoresist film, and post-baked to form black films. With respect to these black films, OD values of ultraviolet light (center wavelength of 370nm) and OD values of visible light (center wavelength of 560nm) were measured using a densitometer (densitometer) under the trade name D200 manufactured by Macbeth corporation based on the above formula (1), and the volume resistivity (Ω · cm) of the black film was also measured. These results are shown in table 1.
[ Table 1]
As is clear from Table 1, the zirconium nitride powders of comparative examples 1 and 10, that is, the zirconium nitride powders obtained by firing at 350 ℃ for 4 hours in a nitrogen atmosphere without pulverizing the zirconium nitride, although the zirconium nitride coarse powders were prepared by the hot-melt method, had bulk resistivities of 1X 10 in the state of compacts compacted at a pressure of 5MPa5Omega. cm, in a suitable range (1X 10)7Ω · cm or more) and a particle size distribution D when ultrasonically dispersed for 5 minutes in a state diluted with water90Each 30 μm, which is larger than the appropriate range (10 μm or less). The black film prepared by dispersing the zirconium nitride powder of comparative example 1 in an acrylic monomer had an OD of 1.0, which is smaller than an appropriate range (2.0 or more), and a bulk resistivity of 1 × 106Omega. cm, in a suitable range (1X 10)13The above) Small, uneven coating. The black film prepared by dispersing the zirconium nitride powder of comparative example 10 in Propylene Glycol Monomethyl Ether Acetate (PGMEA) had an OD of 1.9, which is smaller than an appropriate range (2.0 or more), and a bulk resistivity of 6 × 1012Omega. cm, in a suitable range (1X 10)13Above) are small.
The zirconium nitride powder of comparative example 3, i.e., the zirconium nitride coarse powder produced by the thermite method and pulverized by the bead mill method (low-temperature wet medium pulverization) with a dispersion medium temperature of 5 ℃ or lower, was subjected to ultrasonic dispersion in a water-diluted state for 5 minutes, and the particle size distribution D of the zirconium nitride powder obtained without firing the zirconium nitride precursor powder was found to be the particle size distribution D909 μm in an appropriate range (10 μm or less), but the volume resistivity of the green compact compacted under a pressure of 5MPa was 1X 106Omega. cm, in a suitable range (1X 10)7Ω · cm or more). 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 within an appropriate range (2.0 or more), but the bulk resistivity was 5 × 1011Omega. cm, in a suitable range (1X 10)13Above) are small.
On the other hand, the zirconium nitride powders of examples 1 and 12, i.e., the zirconium nitride coarse powders prepared by the hot-melt method, and the zirconium nitride was pulverized by the bead mill method (low-temperature wet medium pulverization) with a dispersion medium temperature of 5 ℃ or lower, and then calcined at 350 ℃ for 4 hours in a nitrogen atmosphere, had volume resistivities of 1 × 10 in the state of a green compact compacted by a pressure of 5MPa8Omega. cm, in an appropriate range (1X 10)7Ω · cm or more), particle size distribution D at 5 minutes of ultrasonic dispersion in a state of dilution with water90Each 7 μm, within an appropriate range (10 μm or less). 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 the bulk resistivity was 5 × 10 in an appropriate range (2.0 or more)13Omega. cm, in an appropriate range (1X 10)13Above). In addition, the zirconium nitride powder of example 12 was dispersed in propylene glycol monomethyl ether acetateThe OD value of the black film produced in (PGMEA) was 2.1, and the bulk resistivity was 5X 10 in an appropriate range (2.0 or more)13Omega. cm, in an appropriate range (1X 10)13Above).
The zirconium nitride powder of example 9, which was obtained by preparing a coarse powder of zirconium nitride by the thermite method, pulverizing the zirconium nitride by the bead mill method in which the dispersion medium temperature was 5 ℃ (low-temperature wet medium pulverization), and then calcining at 350 ℃ for 4 hours in a helium atmosphere, had a volume resistivity of 8 × 10 in the state of a green compact compacted at a pressure of 5MPa7Omega. cm, in an appropriate range (1X 10)7Ω · cm or more), particle size distribution D at 5 minutes of ultrasonic dispersion in a state of dilution with water90Is 7 μm and is within an appropriate range (10 μm or less). 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 the bulk resistivity was 3 × 10 in an appropriate range (2.0 or more)13Omega. cm, in an appropriate range (1X 10)13Above).
The zirconium nitride powder of example 10 was prepared by the hot-melt method, the coarse powder of zirconium nitride was pulverized by the bead mill method with a dispersion medium temperature of 5 ℃ (low-temperature wet medium pulverization), and the resultant powder was baked at 350 ℃ for 4 hours in an argon atmosphere, and the bulk resistivity of the resultant powder was 8 × 10 in the state of a green compact compacted at a pressure of 5MPa7Omega. cm, in an appropriate range (1X 10)7Ω · cm or more), particle size distribution D at 5 minutes of ultrasonic dispersion in a state of dilution with water90Is 9 μm and is within an appropriate range (10 μm or less). 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 the bulk resistivity was 3 × 10 in an appropriate range (2.0 or more)13Omega. cm, in an appropriate range (1X 10)13Above).
On the other hand, the zirconium nitride powder of comparative example 2, namely, the crude zirconium nitride powder was prepared by the plasma method, but the zirconium nitride was not pulverized, and was baked in a nitrogen atmosphere at a temperature of 350 ℃ for 4 hoursThe volume resistivity of the sintered zirconium nitride powder was 3X 10 in the state of a green compact compacted under a pressure of 5MPa4Omega. cm, in a suitable range (1X 10)7Ω · cm or more) and a particle size distribution D when ultrasonically dispersed for 5 minutes in a state diluted with water90Is 14 μm and is larger than the appropriate range (10 μm or less). The black film prepared by dispersing the zirconium nitride powder of comparative example 2 in an epoxy monomer had an OD of 1.2, which was smaller than an appropriate range (2.0 or more), and a bulk resistivity of 2 × 106Omega. cm, in a suitable range (1X 10)13Above) is small.
The zirconium nitride powder of comparative example 4, i.e., the zirconium nitride powder produced by the plasma method and the zirconium nitride coarse powder was pulverized by the bead mill method (low-temperature wet medium pulverization) with the dispersion medium temperature of 5 ℃ or lower, but the zirconium nitride powder obtained without firing the zirconium nitride precursor powder had a particle size distribution D obtained by ultrasonic dispersion for 5 minutes in a state diluted with water905 μm in an appropriate range (10 μm or less), but the volume resistivity of the green compact compacted under a pressure of 5MPa was 2X 104Omega. cm, in a suitable range (1X 10)7Ω · cm or more) is small. 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 and within an appropriate range (2.0 or more), but the bulk resistivity was 2 × 1010Omega. cm, in a suitable range (1X 10)13Above) are small.
On the other hand, the zirconium nitride powders of examples 2 and 4, which were obtained by preparing a zirconium nitride crude powder by a plasma method, pulverizing the zirconium nitride crude powder by a bead mill method (low-temperature wet medium pulverization) with a dispersion medium temperature of 5 ℃ or lower, and then calcining the same at 350 ℃ for 4 hours in a nitrogen atmosphere, had bulk resistivities of 1 × 10 in a state of a green compact compacted by a pressure of 5MPa7Omega. cm, in an appropriate range (1X 10)7Ω · cm or more), particle size distribution D at 5 minutes of ultrasonic dispersion in a state of dilution with water90Each 5 μm, within an appropriate range (10 μm or less). In addition, the zirconium nitride powder of example 2 was divided intoThe OD value of the black film prepared by dispersing the epoxy monomer in the epoxy monomer was 2.2, and the bulk resistivity was 2X 10 in an appropriate range (2.0 or more)13Omega. cm, in an appropriate range (1X 10)13Above). The OD value of the black film prepared by dispersing the zirconium nitride powder of example 4 in an acrylic monomer was 2.3, and the bulk resistivity was 1 × 10 within an appropriate range (2.0 or more)13Omega. cm, in an appropriate range (1X 10)13Above).
On the other hand, the zirconium nitride powder of comparative example 5, namely, the zirconium nitride coarse powder was produced by the hot-melt method, but the zirconium nitride coarse powder was pulverized by the bead mill method at a dispersion medium temperature of 12 ℃ higher than the appropriate dispersion medium temperature range (10 ℃ or lower) (low-temperature wet medium pulverization), and then calcined at a temperature of 350 ℃ for 4 hours in a nitrogen atmosphere, and the particle size distribution D was obtained by ultrasonic dispersion for 5 minutes in a state diluted with water9010 μm in an appropriate range (10 μm or less), and a volume resistivity of 7X 10 in a state of a green compact compacted with a pressure of 5MPa6Omega. cm, in a suitable range (1X 10)7Ω · cm or more) is small. 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 and within an appropriate range (2.0 or more), but the bulk resistivity was 4 × 1012Omega. cm, in a suitable range (1X 10)13Above) are small.
On the other hand, the zirconium nitride powder of example 5 was prepared by preparing a crude zirconium nitride powder by the hot-melt method, pulverizing the crude zirconium nitride powder by the bead mill method in which the dispersion medium temperature is 10 ℃ in an appropriate dispersion medium temperature range (10 ℃ or lower) (low-temperature wet medium pulverization), and then calcining the pulverized powder at 350 ℃ for 4 hours in a nitrogen atmosphere, and the bulk resistivity of the compacted compact compacted by a pressure of 5MPa was 8 × 107Omega. cm, in an appropriate range (1X 10)7Ω · cm or more), particle size distribution D at 5 minutes of ultrasonic dispersion in a state of dilution with water90Is 10 μm and is within a suitable range (10 μm or less). In addition, the zirconium nitride powder of example 5 was usedThe OD value of the black film prepared by dispersing the acrylic monomer in the acrylic monomer was 2.0, and the bulk resistivity was 3X 10 in an appropriate range (2.0 or more)13Omega. cm, in an appropriate range (1X 10)13Above).
On the other hand, the zirconium nitride powder of comparative example 6, i.e., the zirconium nitride coarse powder produced by the thermit method and pulverized by the bead mill method (low-temperature wet media pulverization) with the dispersion medium temperature of 5 ℃, was calcined in a nitrogen atmosphere at 200 ℃ lower than the appropriate range (250 ℃ to 550 ℃) for 4 hours with the calcination time kept within the appropriate range (1 hour to 5 hours), and the particle size distribution D was obtained by ultrasonic dispersion for 5 minutes in a state diluted with water908 μm, and a volume resistivity of 1X 10 in a state of a green compact compacted with a pressure of 5MPa within a suitable range (10 μm or less)6Omega. cm, in a suitable range (1X 10)7Ω · cm or more). 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 and within an appropriate range (2.0 or more), but the bulk resistivity was 1 × 1012Omega. cm, in a suitable range (1X 10)13Above) are small.
The zirconium nitride powder of comparative example 7 was prepared by the thermite method, and the zirconium nitride coarse powder was pulverized by the bead mill method (low-temperature wet media pulverization) with a dispersion medium temperature of 5 ℃, but the zirconium nitride powder obtained by baking at 350 ℃ in a proper range (250 ℃ to 550 ℃) for 0.5 hour shorter than the proper range (1 hour to 5 hours) in a nitrogen atmosphere with the baking temperature kept at 350 ℃ in the proper range was subjected to ultrasonic dispersion for 5 minutes in a state diluted with water, and the particle size distribution D was found to be907 μm, and a volume resistivity of 3X 10 in a state of a green compact compacted with a pressure of 5MPa within an appropriate range (10 μm or less)6Omega. cm, in a suitable range (1X 10)7Ω · cm or more). The OD value of the black film prepared by dispersing the zirconium nitride powder of comparative example 7 in the acrylic monomer was 2.0 and within an appropriate range (2.0 or more), but the bulk electric characteristics were within the appropriate rangeResistivity of 2X 1012Omega. cm, in a suitable range (1X 10)13Above) are small.
The zirconium nitride powder of comparative example 8, which was a zirconium nitride powder produced by a thermite method and pulverized by a bead mill method (low-temperature wet media pulverization) with a dispersion medium temperature of 5 ℃, was calcined in a nitrogen atmosphere at a temperature of 600 ℃ higher than the appropriate range (250 ℃ to 550 ℃) for 1 hour with a calcination time in the appropriate range (1 hour to 5 hours), and had a volume resistivity of 4 × 10 in a green compact compacted under a pressure of 5MPa6Omega. cm, in a suitable range (1X 10)7Ω · cm or more) and a particle size distribution D when ultrasonically dispersed for 5 minutes in a state diluted with water90Is 14 μm and is larger than the appropriate range (10 μm or less). The black film prepared by dispersing the zirconium nitride powder of comparative example 8 in an acrylic monomer had an OD of 1.2, which is smaller than an appropriate range (2.0 or more), and a bulk resistivity of 1 × 109Ω · cm, ratio in an appropriate range (1 × 10)13Above) are small.
On the other hand, the zirconium nitride powder of example 6 was prepared by the hot melt method, the zirconium nitride coarse powder was pulverized by the bead mill method with a dispersion medium temperature of 5 ℃ (low-temperature wet medium pulverization), and then the zirconium nitride powder was calcined in a nitrogen atmosphere at a temperature of 250 ℃ in an appropriate range (250 ℃ to 550 ℃) for 4 hours with a calcination time kept in an appropriate range (1 hour to 5 hours) at a calcination temperature of 250 ℃, and the volume resistivity was 3 × 10 in the state of a green compact compacted by a pressure of 5MPa7Omega. cm, in an appropriate range (1X 10)7Ω · cm or more), particle size distribution D at 5 minutes of ultrasonic dispersion in a state of dilution with water90Is 8 μm and is within an appropriate range (10 μm or less). 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 the bulk resistivity was 2 × 10 in an appropriate range (2.0 or more)13Omega. cm, in an appropriate range (1X 10)13Above).
Zirconium nitride powder of example 7And a zirconium nitride powder obtained by preparing a zirconium nitride coarse powder by a hot-melt method, pulverizing the zirconium nitride coarse powder by a bead mill method in which the dispersion medium temperature is 5 ℃ (low-temperature wet medium pulverization), then baking the zirconium nitride coarse powder in a nitrogen atmosphere at a baking temperature of 350 ℃ in an appropriate range (250 ℃ to 550 ℃) for 1 hour in an appropriate range (1 hour to 5 hours), wherein the volume resistivity of the zirconium nitride powder in a state of a green compact compacted by a pressure of 5MPa is 1 x 107Omega. cm, in a suitable range (1X 10)7Ω · cm or more), particle size distribution D at 5 minutes of ultrasonic dispersion in a state of dilution with water90Is 7 μm and is within an appropriate range (10 μm or less). 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 the bulk resistivity was 1 × 10 within an appropriate range (2.0 or more)13Omega. cm, in an appropriate range (1X 10)13Above).
The zirconium nitride powder of example 8 was prepared by a hot-melt method, and the zirconium nitride coarse powder was pulverized by a bead mill method with a dispersion medium temperature of 5 ℃ (low-temperature wet medium pulverization), and then calcined in a nitrogen atmosphere at 550 ℃ in an appropriate range (250 ℃ -550 ℃) for 1 hour in an appropriate range (1 hour-5 hours), and the volume resistivity of the compact compacted under a pressure of 5MPa was 1 × 108Omega. cm, in an appropriate range (1X 10)7Ω · cm or more), particle size distribution D at 5 minutes of ultrasonic dispersion in a state of dilution with water90Is 8 μm and falls within a suitable range (10 μm or less). 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 the bulk resistivity was 1 × 10 within an appropriate range (2.0 or more)14Omega. cm, in an appropriate range (1X 10)13Above).
On the other hand, the zirconium nitride powder of comparative example 9, i.e., the crude zirconium nitride powder was produced by the hot melt method, but the crude zirconium nitride powder was pulverized at a pulverizing pressure of 0.2MPa which was lower than the appropriate range (0.3MPa or more)The zirconium nitride powder obtained by pulverizing the powder by a jet mill under pressure and then calcining the powder at 350 ℃ for 4 hours in a nitrogen atmosphere had a volume resistivity of 2X 10 in the state of a green compact compacted under a pressure of 5MPa6Omega. cm, in a suitable range (1X 10)7Ω · cm or more) and a particle size distribution D when ultrasonically dispersed for 5 minutes in a state diluted with water90Is 14 μm and is larger than the appropriate range (10 μm or less). The black film prepared by dispersing the zirconium nitride powder of comparative example 9 in an epoxy monomer had an OD of 1.3, which was smaller than an appropriate range (2.0 or more), and a bulk resistivity of 1 × 1011Omega. cm, in a suitable range (1X 10)13Above) are small.
On the other hand, the zirconium nitride powder of example 3 was prepared by preparing a zirconium nitride coarse powder by a hot-melt method, pulverizing the zirconium nitride coarse powder by a jet mill under a pulverizing pressure of 0.5MPa in an appropriate range (0.3MPa or more), and then calcining the pulverized powder at 350 ℃ for 4 hours in a nitrogen atmosphere, and the bulk resistivity of the powder in a state of a green compact compacted by a pressure of 5MPa was 2 × 108Omega. cm, in an appropriate range (1X 10)7Ω · cm or more), particle size distribution D at 5 minutes of ultrasonic dispersion in a state of dilution with water90Is 6 μm and is within an appropriate range (10 μm or less). 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 the bulk resistivity was 2 × 10 in an appropriate range (2.0 or more)14Omega. cm, in an appropriate range (1X 10)13Above).
The zirconium nitride powder of example 11 was prepared by a hot-melt method, i.e., the zirconium nitride powder of example 3 was obtained by pulverizing a coarse zirconium nitride powder by a jet mill at a pulverization pressure of 0.3MPa within an appropriate range (0.3MPa or more), and then calcining the pulverized zirconium nitride powder at 350 ℃ for 4 hours in a nitrogen atmosphere, and the bulk resistivity of the compact compacted at a pressure of 5MPa was 2X 107Omega. cm, in an appropriate range (1X 10)7Omega. cm or more), dispersed by ultrasonic wave for 5 minutes in a state of being diluted with waterClock time particle size distribution D90Is 10 μm and falls within a suitable range (10 μm or less). 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 the bulk resistivity was 1 × 10 within an appropriate range (2.0 or more)13Omega. cm, in an appropriate range (1X 10)13Above).
Industrial applicability
The zirconium nitride powder of the present invention can be used as a black pigment for obtaining a black film having high insulation properties, high degree of blackness and high insulation properties.
Claims (6)
1. Zirconium nitride powder having a volume resistivity of 10 in the state of a green compact compacted with a pressure of 5MPa7A particle size distribution D of not less than Ω · cm and obtained by ultrasonic dispersion for 5 minutes in a state diluted with water or an alcohol having 2 to 5 carbon atoms90Is 10 μm or less.
2. A method of preparing zirconium nitride powder, the method comprising:
a step of forming a zirconium nitride coarse powder by a thermite method or a plasma synthesis method;
a step of producing a zirconium nitride precursor powder having a particle size distribution D obtained by subjecting the zirconium nitride precursor powder to low-temperature wet medium pulverization at a dispersion medium temperature of 10 ℃ or lower or to jet mill pulverization at an air pressure of 0.3MPa or higher, the zirconium nitride precursor powder having a particle size distribution D obtained by ultrasonic dispersion for 5 minutes in a state diluted with water or an alcohol having 2 to 5 carbon atoms90Is less than 10 μm; and
a step of preparing a zirconium nitride powder having a volume resistivity of 10 in a state of a green compact compacted with a pressure of 5MPa by calcining the pulverized zirconium nitride precursor powder in an inert gas atmosphere7Omega cm or more.
3. A monomer dispersion obtained by dispersing the zirconium nitride powder according to claim 1 in an acrylic monomer or an epoxy monomer.
4. A black composition obtained by dispersing the zirconium nitride powder according to claim 1 as a black pigment in a dispersion medium and mixing a resin.
5. The manufacturing method of the black film comprises the following steps:
a step of forming a coating film by applying the monomer dispersion according to claim 3 onto a substrate, and
and a step of producing a black film by thermally curing or ultraviolet-curing the coating film.
6. The manufacturing method of the black film comprises the following steps:
a step of forming a coating film by applying the black composition according to claim 4 onto a substrate, and
and a step of producing a black film by thermally curing or ultraviolet-curing the coating film.
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