JP2006182627A - Blackish titanium oxynitride - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide blackish titanium oxynitride which has excellent blackness, is fine and contains little content of aggregated particles. <P>SOLUTION: The titanium oxynitride has a composition expressed by compositional formula: TiNxOy-nSiO<SB>2</SB>, contains nitrogen (expressed by N) in an amount of 10-20 wt.%, and has crystallite diameters of ≥7 nm and <17 nm, measured by using an X-ray diffractometer. In the compositional formula, Ti, N, O and Si express a titanium atom, nitrogen atom, oxygen atom and silicon atom, respectively; x expresses the ratio of a nitrogen atom to titanium atom; y expresses the ratio of the oxygen atom to titanium atom; x and y each has a real number of >0 and <2; n expresses the molar ratio of SiO<SB>2</SB>to TiNxOy; and n is a real number of ≥0.05 and ≤0.15. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to black titanium oxynitride.

Titanium oxynitride is a compound mainly composed of titanium-oxygen-nitrogen, generally represented by TiNxOy, and is also called titanium black, and since it has a black color and conductivity, a black pigment such as resin, paint, ink, It is blended in cosmetics or the like, or blended in a film, fiber, toner, magnetic recording medium or the like as a conductivity imparting agent. As such titanium oxynitride, for example, in Patent Document 1, titanium dioxide powder is heated at a temperature of 550 to 950 ° C. under a flow of ammonia gas, and oxygen is 4 to 30 wt%, nitrogen is 5 to 20 wt% (O / N titanium oxynitride pigment powder having an N weight ratio of 6 to 0.2 and an L value of 14 to 8 is disclosed.
On the other hand, as a titanium compound used as a black pigment, titanium nitride containing titanium-nitrogen as a main component and generally represented by TiN is also known. For example, Patent Document 2 discloses titanium tetrachloride at a temperature of 700 to 1500 ° C. A TiN powder is produced by reacting a gas and ammonia gas, and then a nitrogen-oxygen mixed gas is flowed to oxidize the surface layer portion to titanium oxynitride. A titanium nitride black powder containing 30% by weight is disclosed.

JP 60-65069 A JP-A 64-37408

  In order to use titanium oxynitride or titanium nitride as a black pigment, improvements in pigment properties such as blackness, coloring power, concealability (light shielding properties), light resistance, durability, dispersibility, and the like are required. ing. In relation to the blackness, Patent Document 1 describes titanium oxynitride exhibiting blackness with an L value of 8 to 14, and commercially available titanium black is about 8 to 9, and Patent Document 2 describes titanium nitride having an L value of about 10, but a higher blackness is desired. Moreover, although the surface layer part of TiN powder is partially oxidized to form titanium oxynitride in the above-mentioned Patent Document 2, the pigment properties are not stable because oxidation in air gradually proceeds. There's a problem.

  As a result of intensive studies to solve these problems, the present inventors have made titanium oxynitride produced by reacting titanium dioxide or the like with ammonia gas or the like, and the amount of nitrogen contained is 10 to 20% by weight. In addition, by reducing the size of the crystallites constituting the titanium oxynitride particles to be in the range of 7 nm or more and less than 17 nm, the size effect has been found to produce titanium oxynitride with high blackness, and the present invention has been completed. did.

That is, the present invention has a composition formula: TiNxOy · nSiO ₂ (in the composition formula, Ti represents a titanium atom, N represents a nitrogen atom, O represents an oxygen atom, Si represents a silicon atom, and x represents a ratio of the nitrogen atom to the titanium atom). , Y represents the ratio of oxygen atoms to titanium atoms, and x and y can each be a real number greater than 0 and less than 2. n represents the molar ratio of SiO _{2 to} TiNxOy, and n is 0.05 ≦ n ≦ 0. .15 and a crystallite diameter of 7 nm including a nitrogen atom represented by N in a range of 10 to 20% by weight and measured using an X-ray diffractometer. This is a black titanium oxynitride characterized by being less than 17 nm.

  Since the titanium oxynitride of the present invention has excellent blackness, it is blended in a resin, paint, ink or the like as a black pigment and used for various applications. In addition, since the titanium oxynitride of the present invention is fine and has few aggregated particles, it can be made black and transparent when adjusted in its blending amount and visible. As a member for reducing the amount of transmitted light, for example, it can be used by blending it with glass, a lens, a film or the like. Moreover, since the titanium oxynitride of this invention has electroconductivity, utilization expansion can be aimed at also as an electroconductivity imparting agent.

(1) titanium oxynitride having the composition present invention titanium oxynitride includes a silicon oxide represented by titanium oxynitride and SiO ₂ represented by TiNxOy, composition formula: represented by TiNxOy · nSiO _2. In the composition formula, Ti represents a titanium atom, N represents a nitrogen atom, O represents an oxygen atom, Si represents a silicon atom, x represents a ratio of the nitrogen atom to the titanium atom, y represents a ratio of the oxygen atom to the titanium atom, n Represents the molar ratio of SiO _{2 to} TiNxOy. x and y can each be a real number greater than 0 and less than 2, but in order to obtain a desired value, the ratio y / x between x and y is preferably 0.65 or more, more preferably 0.70 or more. preferable. Silicon oxide may form a mixture with titanium oxynitride or may adhere to the surface of titanium oxynitride particles, or may form a solid solution inside the titanium oxynitride particles even if it forms a composite with titanium oxynitride. You may do it. Silicon oxide is an anhydrous silicon oxide because of its anti-sintering action during the production of titanium oxynitride, nitriding acceleration action, dispersion effect when titanium oxynitride is dispersed in resin and solvent, and dispersion stability in paint. However, it may be silicon oxide that has adsorbed moisture, or may be in the form of hydrous silicon oxide, and when used to produce titanium oxynitride at a high temperature, it tends to be anhydrous silicon oxide. Silicon oxide is thought to exist in the state of SiO ₂ , but when titanium oxynitride is produced, if it is fired at high temperature with ammonia gas, amine gas, etc., part of silicon oxide is nitrided to produce oxynitride or nitride In some cases, silicon oxynitride or silicon nitride may be present in the present invention. The molar ratio n of the silicon oxide contained can take a real number in the range of 0.05 ≦ n ≦ 0.15, but is preferably in the range of 0.075 ≦ n ≦ 0.14, and 0.10 ≦ n ≦ 0.13. The range of is more preferable.
Titanium atoms and silicon atoms are analyzed by ICP emission spectrometry, and nitrogen atoms are analyzed by a carbon / hydrogen / nitrogen analyzer, and x and n are calculated from these values. Oxygen atoms are analyzed using an inert gas-carrying melting infrared absorption method. When silicon atoms are present, the oxygen atoms are analyzed by assuming that silicon atoms are bonded to oxygen atoms to form silicon oxide SiO _2. The value obtained by subtracting the oxygen atom portion that is bonded to the silicon atom and becomes SiO ₂ from the value is the value of the oxygen atom in TiNxOy, and y is calculated from the value.

(2) Nitrogen content and oxygen content of titanium oxynitride It is important for the TiNxOy · nSiO ₂ that the nitrogen content represented by N is in the range of 10 to 20% by weight. The range is more preferable, and the range of 12 to 18% by weight is still more preferable. Even if the nitrogen content is less than 10% by weight or more than 20% by weight, the blackness is lowered, which is not preferable.
On the other hand, the oxygen content represented by O in TiNxOy is preferably in the range of about 3 to 25% by weight because oxidation hardly proceeds with time and is stable, and is preferably about 5 to 20% by weight. The range is more preferable, the range of about 10 to 20% by weight is further preferable, and the range of about 15 to 20% by weight is further preferable.

(3) X-ray diffraction of titanium oxynitride In the X-ray diffraction of titanium oxynitride (using Cuα rays), the main (first) peak is 2θ between 40 and 45 °, and the second is between 35 and 40 °. A peak can be observed, and when the nitrogen content is increased, the angle of the first peak gradually shifts to a smaller side. For example, if the nitrogen content is about 15% by weight, 2θ is about 43.1 ° and about 20% by weight. If so, the main (first) peak is confirmed in the range of 43.0 ° to 43.5 ° in the titanium oxynitride of the present invention. 6), the titanium oxynitride of the present invention is different from titanium nitride or a partially oxidized surface thereof. Titanium oxynitride is obtained by heating and baking titanium oxide such as titanium dioxide, hydrous titanium oxide, titanium hydroxide, low-order titanium oxide such as TiO, Ti ₂ O ₃ , Ti ₃ O ₅ with ammonia gas, amine gas, etc. Therefore, when the titanium oxide used as a starting material remains, an X-ray diffraction peak derived from titanium dioxide or the like can be confirmed, but in the present invention, it is reduced to the extent that titanium dioxide or the like that is an impurity does not exist. preferable. On the other hand, the X-ray diffraction peak of silicon oxide cannot be confirmed even when a considerable amount thereof exists.
The size of the crystallites constituting the titanium oxynitride particles can be determined from the half width of the X-ray diffraction main (first) peak of titanium oxynitride using the Scherrer formula of Formula 1. Commercially available titanium black has a crystallite diameter of 26 nm, but it is important for the titanium oxynitride of the present invention to have a crystallite diameter in the range of 7 nm to less than 17 nm. Is preferable because it has relatively high blackness, more preferably in the range of 8 to 16.5 nm, still more preferably in the range of 9 to 16 nm, and most preferably in the range of 10 to 16 nm.
Formula 1: D = 0.9λ / (β _1/2 × cos θ)
(In formula 1, D is the calculated crystallite diameter (Å), λ is the X-ray wavelength, and 1.54α of the Cu α-ray wavelength is used. Β _1/2 is the half width of the main (first) peak (In radians, θ represents the reflection angle.)

(4) Titanium oxynitride blackness Titanium oxynitride has a blackish color and has a bluish black, purplish black, reddish black, and brownishness in addition to pure black Other colors besides black, such as black, may be exhibited. As for the brightness and hue of titanium oxynitride, 1.5 g of a sample was placed in a glass round cell (Nippon Denshoku, part No. 1483), and a color difference meter (Nippon Denshoku Color Meter ZE2000) was used from the bottom of the cell. Obtained by the Lab color system. The blackness is represented by the lightness index L value of the Lab color system. The smaller the L value, the stronger the blackness. In the titanium oxynitride of the present invention, for example, the L value has a blackness of about 2 to 14. Preferably about 3-8.
In addition, the Lab color system a value and b value obtained in the same manner as the L value are indices representing hue saturation, and the redness increases as the a value increases toward the positive side and the greenness increases as the value increases toward the negative side. It shows that it is strong, yellow value is so strong that b value becomes large on the positive side, and blue color is so strong that it becomes large on the negative side. The titanium oxynitride of the present invention can have a hue having an a value of about -3 to 2 and a b value of about -5 to -1.

(5) Visible light absorptivity of titanium oxynitride Since titanium oxynitride has a black color, it has a large absorption over the entire wavelength range of visible light. The visible light absorptance can be easily obtained from (100-reflectance) (%), and the visible light reflectivity is oxynitrided using an ultraviolet-visible spectrophotometer (V-570 manufactured by JASCO Corporation). It can be obtained by packing 0.3 g of titanium powder in a cylindrical cell (diameter 16 mm, JASCO PSH-001 type) and measuring the reflection spectrum of visible light (using barium sulfate powder as a comparative sample). Since the titanium oxynitride of the present invention has a high degree of nitridation and a small crystallite diameter, the size effect reduces the reflectance of visible light. For example, the reflectance at a wavelength of 650 nm is about 12% or less. It is preferably about 11% or less, more preferably about 11% or less for a reflectance at a wavelength of 550 nm, and preferably about 12% or less for a reflectance at a wavelength of 450 nm.

(6) Particle diameter of titanium oxynitride The particles of TiNxOy · nSiO ₂ are preferably observed when observed with an electron microscope and the particle diameter is in the range of about 0.005 to 0.25 μm. A range of about 0.005 to 0.15 μm is more preferable, a range of about 0.005 to 0.05 μm is more preferable, and a range of about 0.01 to 0.03 μm is most preferable. When silicon oxide is included, its presence cannot be confirmed with an electron microscope, but it is assumed that silicon oxide is attached to the surface of the titanium oxynitride particles, and the particle diameter is not measured.

(7) Specific surface area of titanium oxynitride The specific surface area of titanium oxynitride is preferably in the range of about 30 to ²⁰⁰ m ² / g, as measured by the BET method, because the blackness increases, and the dispersibility in the resin binder is also preferable. more preferably in the range 50~150m about ² / g of when considering, even more preferably in the range of from about 50 to 100 m ² / g, and most preferably in the range of about 60～90M ² / g.
In addition, from the specific surface area value measured by the BET method, the particle diameter assuming that the titanium oxynitride particles are spherical can be calculated using the following formula 2. If the specific surface area is in the range of 50 to 150 m ² / g, the particle diameter is 8 ˜24 nm.
Formula 2: d = 6 × 10 ³ / (SSA × ρ)
(In Formula 2, d is the calculated particle diameter (nm), SSA is the specific surface area value (m ² / g), ρ is the density (g / cm ³ ) of titanium nitride, and here it is 4.9. (6 is the spherical shape factor.)
The ratio obtained by dividing the particle diameter calculated from the specific surface area value measured by the BET method by the crystallite diameter measured using the X-ray diffractometer is a small value in the present invention. Usually, since the titanium oxynitride particles are aggregated to some extent, the ratio of the particle diameter calculated from the specific surface area value to the crystallite diameter measured with an X-ray diffractometer is about 2 to 6, but in the present invention it is preferably 0. It is in the range of about .9 to 1.5, more preferably in the range of about 1.0 to 1.4, and it can be said that almost no aggregated particles are present.

  The titanium oxynitride of the present invention can be produced by raising the temperature of an apparatus loaded with titanium oxide in the presence of a nitrogen-containing reducing agent to a temperature in the range of about 600 to 1200 ° C. and baking it. It can be produced by coating the surface of the particles with silicon oxide. The heating and baking temperature is preferably in the range of about 800 to 1100 ° C, more preferably about 850 to 1050 ° C. When the heating and baking temperature is lower than the above range, nitriding is difficult to proceed and it is difficult to obtain desired titanium oxynitride, and when it is higher than the above range, sintering is advanced and it is difficult to obtain fine particles. The heating and firing time varies depending on the amount of the titanium oxide and the nitrogen-containing reducing agent, and is appropriately set. However, about 1 to 20 hours is appropriate for operation, and about 3 to 10 hours is preferable. Moreover, after performing heat baking, it may cool, and heat baking may be repeated repeatedly after that. As the heating and baking apparatus, a known apparatus such as a fluidized bed apparatus, a rotary kiln, or a tunnel kiln can be used, and a rotary kiln is particularly preferable. As the nitrogen-containing reducing agent, for example, ammonia, alkylamines such as methylamine and dimethylamine, hydrazine and hydrazine-based compounds such as hydrazine sulfate and hydrazine hydrochloride, and the like can be used. You may mix and use. Among these, ammonia and alkylamine are preferable because they can be made into a gaseous state and brought into contact with the titanium oxide and easily reacted uniformly. Furthermore, it is preferable to add a small amount of nitrogen, hydrogen, or hydrocarbon to these nitrogen-containing reducing agents because nitriding can be promoted. In particular, a hydrocarbon is preferable because it reacts with oxygen in the titanium oxide to become carbon dioxide, and generation of water that suppresses the nitriding reaction can be suppressed.

The titanium oxide referred to in the present invention is not only a normal rutile type (R type) or anatase type (A type) titanium dioxide, but also hydrated titanium oxide, hydrous titanium oxide, titanium hydroxide, TiO, Ti ₂ O. ₃ and a compound including low-order titanium oxide such as Ti ₃ O ₅ . Titanium dioxide is obtained, for example, by heating and baking hydrous titanium oxide (or titanium hydroxide) at a temperature of about 800 to 1000 ° C. in an atmosphere of air or oxygen-containing gas or in an inert gas atmosphere such as nitrogen or argon. It is done. In addition, hydrous titanium oxide is obtained by, for example, grinding titanium-containing ores such as illuminite ore and titanium slag as necessary, and reacting the titanium component and sulfuric acid while dissolving with sulfuric acid to produce titanyl sulfate (TiOSO ₄ ). It is obtained by standing, classifying and filtering, and then hydrolyzing titanyl sulfate with heating. In the nitriding reaction in which titanium oxide is heated and fired in the presence of a nitrogen-containing reducing agent, it is difficult to proceed with nitriding in the presence of water. Anatase type titanium dioxide is more preferable than rutile type because it is more easily nitrided. In the present invention, the crystallite diameter of the titanium oxide calculated from the half width of the X-ray diffraction main (first) peak of the titanium oxide using the Scherrer formula of Formula 1 is preferably in the range of about 5 to 50 nm. The range of about 10-40 nm is more preferable, the range of about 10-30 nm is still more preferable, and the range of about 10-20 nm is the most preferable. Moreover, the range which the particle diameter observes with an electron microscope is about 0.005-0.25 micrometer is preferable, The range which is about 0.005-0.15 micrometer is more preferable, The range which is about 0.005-0.1 micrometer is preferable. More preferably, the range of about 0.005 to 0.05 μm is most preferable. Further, preferably in the range of about 20 to 200 m ² / g in specific surface area of titanium oxide as measured by the BET method, and more preferably in the range of about 30 to 150 m ² / g, still in the range of about 40 to 100 m ² / g A range of about 50 to 90 m ² / g is most preferable.

  In the present invention, when silicon oxide is coated on the surface of titanium oxide particles and then heated and fired, the particles are difficult to sinter even at a high temperature within the above range, and further, rutile titanium dioxide is not easily generated in the reaction process. Therefore, nitriding is easy to proceed, and fine titanium oxynitride is more easily obtained, which is preferable. Silicon oxide may be coated as porous silicon oxide or dense silicon oxide, but coating as dense silicon oxide is preferable because an effect of suppressing sintering can be easily obtained. The coating amount of silicon oxide may be an amount that is in a range of 0.05 ≦ n ≦ 0.15 in terms of a molar ratio n to TiNxOy obtained by heating and firing, and 0.075 ≦ n ≦ 0.15. The range is preferable, and the range of 0.01 ≦ n ≦ 0.14 is more preferable. If the coating amount of silicon oxide is less than the above range, it is difficult to obtain a desired sintering suppressing effect, and if it is too large, nitriding is difficult to proceed, which is not preferable.

  As a method for coating the dense silicon oxide, a known method as described in JP-A-53-33228, JP-A-7-8971, or the like can be used. The method described in JP-A-53-33228 preferably adjusts the pH of the slurry to a range of 9 to 10.5 while maintaining the titanium oxide slurry at a temperature in the range of 80 to 100 ° C. After the rapid addition of sodium silicate, it is neutralized at a pH in the range of 9 to 10.5 and then maintained at a temperature in the range of 80 to 100 ° C. for 50 to 60 minutes. In the method described in JP-A-7-8971, after adjusting the pH of the slurry of titanium oxide to the range of 9.5 to 11, it is 60 ° C or higher, preferably 70 ° C or higher, more preferably 90 ° C or higher. Under temperature, the silicate is gradually added over 30 to 120 minutes, then neutralized, and then maintained for 60 to 120 minutes while maintaining the slurry temperature. As the silicate, sodium silicate, potassium silicate and the like can be used. As the neutralizing agent, an inorganic compound such as sulfuric acid and hydrochloric acid, and an acidic compound such as organic acid such as acetic acid and formic acid can be used. it can. After coating with silicon oxide, it is preferably dehydrated and washed, and then subjected to a heating and firing step.

  After producing the titanium oxynitride, if necessary, dry pulverization may be performed by a known method, or after slurrying, wet pulverization, dehydration, drying, and dry pulverization may be performed. For wet grinding, vertical sand mill, horizontal sand mill, etc., for drying, band type heater, batch type heater, etc., for dry grinding, hammer mill, pin mill etc. impact crusher, crusher etc. grinding crusher, jet An airflow crusher such as a mill or a snail mill, or a device such as a spray dryer can be used.

  The surface of the titanium oxynitride particles of the present invention may be coated with at least one selected from an inorganic compound and an organic compound for the purpose of improving affinity with a resin binder or improving productivity. Good. Examples of the inorganic compound include an aluminum compound, a silicon compound, a zirconium compound, a tin compound, a titanium compound, an antimony compound, and the like. They can also be used in combination, for example, by mixing and coating the above inorganic compounds. More preferably, these inorganic compounds are at least one selected from oxides, hydroxides, hydrated oxides, and phosphates. Examples of organic compounds include polyhydric alcohols, alkanolamines or derivatives thereof, organosilicon compounds, higher fatty acids or metal salts thereof, and organometallic compounds. Specifically, for example, (1) polyhydric alcohol includes trimethylolethane, trimethylolpropane, tripropanolethane, pentaerythritol and the like. (2) Examples of the alkanolamine include triethanolamine and tripropanolamine. (3) Examples of organosilicon compounds include: (a) polysiloxanes (dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, dimethylpolysiloxanediol, alkyl-modified silicone oil, alkylaralkyl-modified silicone oil, amino-modified silicone) Oil, both-end amino-modified silicone oil, epoxy-modified silicone oil, both-end epoxy-modified silicone oil, fluorine-modified silicone oil, etc.), (b) organosilanes (n-butyltriethoxysilane, isobutyltrimethoxysilane, n-hexyl) Trimethoxysilane, n-hexyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, n-octadecyltrimeth Non-reactive silanes such as silane, alkylsilanes such as n-octadecylmethyldimethoxysilane, phenylsilanes such as phenyltriethoxysilane, fluorosilanes such as trifluoropropyltrimethoxysilane, aminopropyltriethoxysilane, N -(Β-aminoethyl) -γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, γ-glycidoxypropyltrimethoxy And silane coupling agents such as silane, methacryloxypropyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane). (4) Examples of higher fatty acids include stearic acid and lauric acid, and examples of metal salts thereof include magnesium salts and zinc salts. (5) Examples of organometallic compounds include isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyro) Phosphate) oxyacetate titanate, titanium coupling agent such as bis (dioctylpyrophosphate) ethylene titanate, aluminum coupling agent such as acetoalkoxyaluminum diisopropylate, zirconium tributoxyacetylacetonate, zirconium tributoxy systemate, etc. Zirconium compounds and the like can be mentioned. These can be coated alone or in combination of two or more. The coating amount can be appropriately set, but is preferably in the range of about 0.01 to 30% by weight, more preferably in the range of about 0.05 to 10% by weight, and 0.1 to 5% by weight with respect to titanium oxynitride. A range of about is more preferred. When the surface of titanium oxynitride is coated with an inorganic compound or an organic compound, a known method can be used when titanium oxynitride is dry pulverized, slurried or wet pulverized.

  The black titanium oxynitride of the present invention is a resin composition utilizing its excellent black performance or conductive performance when blended with a resin such as paint, ink or film, as a black pigment or as a conductivity imparting agent. It can be. In this resin composition, the black titanium oxynitride of the present invention is blended in an arbitrary amount, preferably 20% by weight or more, and in addition, a composition forming material used in each field is blended. You may mix | blend an additive. In the case of paints and inks, coating film forming materials or ink film forming materials, solvents, dispersants, pigments, fillers, thickeners, flow control agents, leveling agents, curing agents, crosslinking agents, curing catalysts Etc. Examples of coating film forming materials include organic components such as acrylic resins, alkyd resins, urethane resins, polyester resins, and amino resins, and inorganic components such as organosilicates and organotitanates. In this case, urethane resin, acrylic resin, polyamide resin, vinyl acetate resin, chlorinated propylene resin and the like can be used. Various materials such as thermosetting resin, room temperature curable resin, and ultraviolet curable resin can be used for these coating film forming material and ink film forming material. When a resin is used, a photopolymerization initiator or photosensitizer is blended, and UV light is applied and cured after application, a coating with excellent hardness and adhesion can be obtained without applying a thermal load to the substrate. Therefore, it is preferable. In the case of plastic moldings, the black type of the present invention can be used for plastics, pigments, dyes, dispersants, lubricants, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, flame retardants, bactericides, and the like. It is kneaded with titanium oxynitride and formed into an arbitrary shape such as a film. Plastics include thermoplastic resins such as polyolefin resin, polystyrene resin, polyester resin, acrylic resin, polycarbonate resin, fluororesin, polyamide resin, cellulose resin, and polylactic acid resin, and thermosetting resins such as phenol resin and urethane resin. Can be used.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Example 1
1. Coating titanium dioxide with silicon oxide 300 g of hydrous titanium dioxide is suspended in 1 liter of water as TiO ₂ to make a slurry, the pH of the slurry is adjusted to 10 with an aqueous sodium hydroxide solution, and the slurry temperature is then raised to 70 ° C. After warming, an aqueous sodium silicate solution was added dropwise for 2 hours. Subsequently, after heating the slurry temperature to 90 ° C., dilute sulfuric acid was added dropwise for 2 hours to neutralize the pH to 5, and the mixture was further maintained for 30 minutes. Thereafter, it was dehydrated and washed, and further baked in air at 850 ° C. for 5 hours to obtain titanium dioxide coated with dense silicon oxide (9% by weight as SiO ₂ ). The obtained titanium dioxide was anatase type.
The obtained titanium dioxide coated with dense silicon oxide had a particle diameter of 0.020 μm, a crystallite diameter of 19 nm, and a specific surface area of 79.7 m ² / g.
2. Next, titanium dioxide coated with this silicon oxide was charged into a quartz tube having an inner diameter of 7.5 cm, and the quartz tube was heated to 900 ° C. while aeration of ammonia gas at a flow rate of 10 liters / minute. For 3 hours. Next, the obtained product was cooled to 100 ° C. under the same atmosphere, and further allowed to cool to room temperature in the air to obtain titanium oxynitride (sample A) of the present invention.

Example 2
In Example 1, the titanium oxynitride (sample B) of the present invention was obtained in the same manner as in Example 1 except that the reduction firing temperature of 900 ° C. was 980 ° C.

Comparative Example 1
Titanium dioxide not coated with silicon oxide was charged into a quartz tube having an inner diameter of 7.5 cm, and the quartz tube was heated at 980 ° C. for 3 hours while supplying ammonia gas at a flow rate of 10 liters / minute. Next, the obtained product was cooled to 100 ° C. under the same atmosphere, and further allowed to cool to room temperature in the air to obtain titanium oxynitride (sample C) of the present invention.
The particle diameter of titanium dioxide not coated with silicon oxide is 0.15 to 0.40 μm, the crystallite diameter is 56 nm, the specific surface area is 4.4 m ² / g, and the water content used in Example 1 Titanium dioxide was obtained by firing in air at 850 ° C. for 5 hours.

Comparative Example 2
Commercially available titanium black (Mitsubishi Materials, 13M-C) was used as Comparative Sample D.

  Table 1 shows the compositions and characteristics of Samples A to D obtained in Examples and Comparative Examples. Since the titanium oxynitride of the present invention has a small crystallite diameter, it can be seen that the L value is small, the blackness is high, and the visible light reflectance is low. Further, it can be seen that the ratio of the particle diameter calculated from the specific surface area with respect to the crystallite diameter is small, and there are few aggregated particles.

  Since the titanium oxynitride of the present invention has excellent blackness, it is blended in a resin, paint, ink or the like as a black pigment and used for various applications. In addition, since the titanium oxynitride of the present invention is fine and has few aggregated particles, it can be made black and transparent when adjusted in its blending amount and visible. As a member for reducing the amount of transmitted light, for example, it can be used by blending it with glass, a lens, a film or the like. In addition, the titanium oxynitride of the present invention is used as a conductivity-imparting agent by blending it into a film, fiber, toner, magnetic recording medium or the like.

2 is a graph showing a visible light reflection spectrum of Sample A obtained in Example 1. FIG. 6 is a graph showing a visible light reflection spectrum of Sample B obtained in Example 2. 6 is a graph showing a visible light reflection spectrum of Sample C obtained in Comparative Example 1. 6 is a graph showing a visible light reflection spectrum of Sample D obtained in Comparative Example 2.

Claims (4)

Composition formula: TiNxOy · nSiO ₂ (in the composition formula, Ti represents a titanium atom, N represents a nitrogen atom, O represents an oxygen atom, Si represents a silicon atom, x represents a ratio of a nitrogen atom to a titanium atom, and y represents a titanium atom) Represents the ratio of oxygen atoms, x and y can each be a real number greater than 0 and less than 2. n represents the molar ratio of SiO _{2 to} TiNxOy, and n is a real number in the range of 0.05 ≦ n ≦ 0.15 And a nitrogen atom represented by N is included in the range of 10 to 20% by weight, and the crystallite diameter measured using an X-ray diffractometer is 7 nm or more and less than 17 nm. This is a black titanium oxynitride. 2. The black titanium oxynitride according to claim 1, wherein the specific surface area of TiNxOy · nSiO ₂ is in the range of 50 to 100 m ² / g. The ratio of the particle diameter calculated by the following formula 1 from the specific surface area value measured by the BET method to the crystallite diameter measured using an X-ray diffractometer is in the range of 0.9 to 1.5. The black titanium oxynitride according to claim 1.
Formula 1: d = 6 × 10 ³ / (SSA × ρ)
(In Formula 1, d is the calculated particle diameter (nm), SSA is the specific surface area value (m ² / g), and ρ is the density (g / cm ³ ) of titanium oxynitride. 9 is used, and 6 is a spherical shape factor.) The black titanium oxynitride according to claim 1, wherein the particle surface is coated with an inorganic compound and / or an organic compound in the range of 0.01 to 30% by weight.

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