JP6949604B2 - Method for producing mixed powder for forming a black film - Google Patents

Description

The present invention relates to a method for producing a mixed powder for forming a black film, which is suitably used as an insulating black pigment. More specifically, when a black patterning film is formed as a black pigment, a high-resolution patterning film that transmits light having a wavelength of 365 nm to 410 nm is formed, and light having a wavelength of 500 nm to 1200 nm is blocked to have high light-shielding performance. The present invention relates to a method for producing a mixed powder for forming a black film for forming a patterning film.

This type of black pigment is dispersed in a photosensitive resin to prepare a black photosensitive composition, and this composition is applied to a substrate to form a photoresist film, and the photoresist film is irradiated with ultraviolet rays by a photolithography method. By exposing the photoresist film to form a patterning film, it is used as a black matrix for an image forming element such as a color filter of a liquid crystal display. Since carbon black as a conventional black pigment has conductivity, it is not suitable for applications requiring insulation. Further, since carbon black shields ultraviolet rays, it is difficult to form a high-resolution patterning film, and the light-shielding property is inferior in the wavelength region of visible light to near-infrared light.

Conventionally, as a black pigment having high insulating properties, a black powder made of titanium oxynitride, which is also called titanium black having a specific composition, and Y ₂ O ₃ , ZrO ₂ , Al ₂ O ₃ , SiO ₂ , TiO ₂ , V A high-resistance black powder containing an insulating powder consisting of at least one of ₂ O _{5 is disclosed (see, for example, Patent Document 1).} According to this black powder, when it is formed into a black film, it has a high resistance value and excellent light-shielding property, and is therefore considered to be suitable as a black matrix for a color filter. In Patent Document 1, the high-resistance black powder containing the titanium oxynitride powder and the insulating powder is subjected to a nitride reduction treatment by adding an insulating powder to the raw material titanium oxide, or is insulated after the titanium oxide nitride reduction treatment. It is produced by adding powder, and the nitride reduction treatment of titanium oxide can be performed by heating the titanium oxide powder as a raw material to 700 to 1000 ° C. in an atmosphere of a reducing gas such as ammonia. Have been described.

Further, in a black resin composition which is an insulating black pigment containing titanium nitride and is composed of at least a light-shielding material, a resin and a solvent and contains titanium nitride particles as the light-shielding material, CuKα ray is used as an X-ray source. The diffraction angle 2θ of the peak derived from the (200) plane of at least one kind of titanium nitride particles is 42.5 ° or more and 42.8 ° or less, and on the (200) plane of the titanium nitride particles. A black resin composition characterized in that the crystallite size determined from the half-value width of the derived X-ray diffraction peak is 10 nm or more and 20 nm or less is disclosed (see, for example, Patent Document 2). According to this black resin composition, it is possible to form a black matrix having a high OD value and a high resistance value while being achromatic. By using such a black resin composition, the resin black matrix has low reflectance over all wavelengths and has a small wavelength dependence of reflectance, that is, so-called neutral black, and even a thin film has an OD value. Has a high resistance value. Therefore, it becomes possible to provide a color filter capable of displaying blackish black when used in a liquid crystal display device.

Further, an insulating black pigment containing vanadium oxynitride or niobium nitride, which is a black powder composed of one or two oxynitrides of vanadium or niobium, having an oxygen content of 16 wt% or less and a nitrogen content. A blue shielding black powder characterized in that the amount is 10 wt% or more and the transmittance X at 450 nm is 10.0% or less in a dispersion liquid transmission spectrum having a powder concentration of 50 ppm is disclosed (for example, Patent Document 3). reference.). This blue-shielding black powder has excellent shielding properties against blue light, has an oxygen content of 16 wt% or less and a nitrogen content of 10 wt% or more, and has a transmittance X of 450 nm in a dispersion liquid transmission spectrum having a powder concentration of 50 ppm. It is 0% or less. The conventional titanium oxynitride (titanium black) has a nitrogen content of 20 wt% and the transmittance X is about 10%, but the black powder of the present invention has a transmittance X of 10% or less even if the nitrogen content is 10 wt%. It is possible to obtain a powder having excellent shielding property against blue light.

Furthermore, as an insulating black pigment containing zirconium nitride, it has a low-order zirconium oxide peak and a zirconium nitride peak in the X-ray diffraction profile, and has a specific surface area of 10 to 60 m ² / g. A fine particle low-order zirconium oxide / zirconium nitride composite is disclosed (see, for example, Patent Document 4). This fine particle low-order zirconium oxide / zirconium nitride composite is a mixture of zirconium dioxide or zirconium hydroxide, magnesium oxide, and metallic magnesium at 650 to 800 ° C. in an inert gas stream containing nitrogen gas or nitrogen gas. Manufactured through a firing process. The fine particle low-order zirconium oxide / zirconium nitride composite can be used as a black-based fine particle material having low electrical conductivity, and has higher electrical conductivity to a black matrix for a display such as a television in which carbon black or the like is used. It is said that it can be used as a fine-grained black pigment with a low content, and that the fine-grained low-order zirconium oxide / zirconium nitride composite can be manufactured (mass-produced) on an industrial scale according to the above-mentioned production method. ..

JP-A-2008-266045 (Claim 1, Claim 5, paragraph [0002], paragraph [0010], paragraph [0020], paragraph [0021]) JP-A-2009-058946 (Claim 1, paragraph [0007]) Japanese Unexamined Patent Publication No. 2012-096945 (Claim 1, Claim 5, Paragraph [0011]) JP-A-2009-091205 (Claim 1, Claim 2, paragraph [0015], paragraph [0016])

However, a black powder called titanium black shown in Patent Document 1, a black resin composition containing titanium nitride particles shown in Patent Document 2, and one or two types of vanadium or niobium shown in Patent Document 3. When the black powder made of oxynitride and the fine particle low-order zirconium oxide / zirconium nitride composite shown in Patent Document 4 are used as a black pigment, the pigment concentration is increased to obtain higher light-shielding property, and the black photosensitive property is obtained. When a composition is prepared, the composition is applied to a substrate to form a photoresist film, and the photoresist film is exposed by a photoresist method to form a black patterning film, the black pigment in the photoresist film is exposed to ultraviolet rays. Since the i-line (wavelength 365 nm) and h-line (405 nm) are blocked, the ultraviolet rays do not reach the bottom of the photoresist film, undercut occurs at the bottom, and a high-resolution patterning film may be formed. There was a problem I couldn't do. In particular, since h-line has lower energy than i-line, it is advantageous to reduce running cost if patterning can be performed with h-line, but it has been regarded as a problem that there is no material having both high visible light shading property and h-line transparency. ..

An object of the present invention is to form a high-resolution patterning film that transmits light having a wavelength of 365 nm to 410 nm when forming a black patterning film as a black pigment, and to block light having a wavelength of 500 nm to 1200 nm to provide high light-shielding performance. It is an object of the present invention to provide a method for producing a mixed powder for forming a black film for forming a patterning film having the above.

In the X-ray diffraction profile, when a peak of zirconium dioxide, low-order zirconium oxide, or low-order zirconium nitride is present even in a trace amount, the present inventors use this powder as a black pigment to form a black patterning film in the visible light region. It was found that the light-shielding property of Zirconium dioxide was significantly reduced. On the other hand, when the present inventors prepare a black photosensitive composition by increasing the pigment concentration in order to obtain higher light-shielding property, the performance of transmitting i-ray (wavelength 365 nm) light is significantly deteriorated. It was found that when a black patterning film was formed using powder as a black pigment, a high-resolution patterning film could not be formed, and the light-shielding performance of the formed patterning film was deteriorated. On the other hand, as described above, titanium black shields i-line (wavelength 365 nm) and h-line (wavelength 405 nm) light, but pays attention to the fact that light in the vicinity of wavelength 450 nm is transmitted. Furthermore, the inventor has to black patterned film where the mixed powder of zirconium nitride and titanium nitride emissions obtained by nitriding a mixture of zirconium oxide titanium oxide formed as a black pigment has a high resolution and high light-shielding performance Focusing on it, we arrived at the present invention.

The first aspect of the present invention is to mix zirconium dioxide powder and titanium oxide powder to obtain a first mixture, and then add metal magnesium powder and magnesium oxide powder to the first mixture, and metal magnesium is said to be the same. A second mixture is prepared by mixing the first mixture in a proportion of 1 to 10 times the molar amount and magnesium oxide in a proportion of 0 to 10 times the molar amount of the first mixture, and then the second mixture. the mixture under a nitrogen atmosphere and baked at a temperature of 200 to 1500 ° C., by reducing the zirconium dioxide powder and the titanium oxide powder, mixed powder of zirconium nitride powder (a) and titanium nitride powder (B) to prepare a mass ratio of zirconium and titanium before Symbol mixed powder prepared (Zr: Ti) is (40:60) - (95: 5) powder mixing black film formed, which is a range of It is a manufacturing method of.

The second aspect of the present invention is the method for producing a mixed powder for forming a black film according to the first aspect, in which light having a wavelength of 365 nm is obtained in a dispersion liquid spectrum in which the mixed powder is dispersed in the dispersion liquid at a concentration of 50 ppm. When the transmittance is X, the light transmittance at a wavelength of 550 nm is Y, and the light transmittance at a wavelength of 1200 nm is Z, X> 8%, Y <8%, Z <25%, and X / Y is 1. It is 0.00 or more and Z / Y is 4.0 or less.

A third aspect of the present invention is a method for producing a black photosensitive composition by dispersing the mixed powder for forming a black film produced by the method of the first aspect or the second aspect in a photosensitive resin.

A fourth aspect of the present invention is a method of forming a black patterning film using the black photosensitive composition produced by the method of the third aspect.

In a first aspect the black film-forming mixture method of producing a powder of the present invention, per to prepare a mixed powder of zirconium nitride powder (A) and the titanium nitride Powder (B), zirconium nitride and titanium nitride that have already been nitrided Since the raw materials are mixed before nitriding, the optical spectrum of the obtained nitride is significantly improved as compared with the method of preparing a mixture with.

Furthermore, per to prepare a mixed powder of zirconium nitride powder (A) and the titanium nitride Powder (B), can proceed the reaction in a nitrogen gas alone, a mixed gas of a mixture of nitrogen gas and hydrogen gas, nitrogen gas and ammonia By firing in an atmosphere of a mixed gas of gas or a mixed gas of nitrogen gas and argon gas, the reduction reaction is further promoted, the reaction efficiency is further increased, and even with a smaller amount of metallic magnesium, zirconium dioxide and lower zirconium oxide are used. and low without following zirconium oxynitride, can be produced only mixed powder of powder zirconium nitride powder and titanium nitride powder.

Fabricated zirconium nitride powder (A) and the titanium nitride powder powder and (B), zirconium and titanium content ratio (Zr: Ti) at (40:60) - (95: 5) to the mixing be so Therefore, if a black patterning film is formed by using this mixed powder as a black pigment, it is possible to form a high-resolution patterning film by further transmitting ultraviolet rays, and the formed patterning film has high light-shielding performance. ..

According to the method for producing a mixed powder for forming a black film according to the second aspect of the present invention, the mixed powder has a light transmittance of X at a wavelength of 365 nm and a wavelength of 550 nm in the dispersion liquid spectrum dispersed in the dispersion liquid at a concentration of 50 ppm. When the light transmittance of is Y and the light transmittance at a wavelength of 1200 nm is Z, X> 8%, Y <8%, Z <25%, and X / Y is 1.00 or more, Z / It has a characteristic that Y is 4.0 or less. Since X, Y, Z, X / Y and Z / Y are in the above range, if a black patterning film is formed as a black pigment, ultraviolet rays can be further transmitted to form a high-resolution patterning film. Moreover, the formed patterning film has high light-shielding performance.

According to the method for producing a black photosensitive composition according to the third aspect of the present invention, the zirconium nitride powder (A) constituting the mixed powder as a black pigment contains zirconium dioxide, low-order zirconium oxide and low-order zirconium oxynitride. without the addition the mass ratio of the zirconium and titanium of zirconium nitride powder (a) and the titanium nitride powder (B) in order to contain in the range of:: (5 95), ( Zr Ti) is (40:60) - If a black patterning film is formed using the method for producing this composition, a high-resolution patterning film can be formed, and the formed patterning film has high light-shielding performance.

According to the method for forming a black patterning film according to the fourth aspect of the present invention, a high-resolution patterning film can be formed, and the formed patterning film has high light-shielding performance.

It is an X-ray diffraction profile of the zirconium nitride powder obtained in Example 1 of this invention. It is an X-ray diffraction profile of the zirconium nitride powder obtained in Comparative Example 6 of the present invention. It is a spectroscopic curve which shows the light transmittance in the dispersion liquid which diluted the powder obtained in Examples 1 and 2 of this invention and Comparative Example 1 and 2 to a powder concentration of 50 ppm.

Next, a mode for carrying out the present invention will be described.

[Mixed powder for forming a black film]
Black film forming mixed powder of the present embodiment includes a zirconium nitride powder (A) and the titanium nitride Powder (B), zirconium and titanium in the zirconium nitride powder (A), the titanium nitride Powder (B) The content ratio (Zr: Ti) is (Zr: Ti) and is in the range of (40:60) to (95: 5), preferably in the range of (45: 55-80: 20). If the zirconium and titanium content ratio (Zr: Ti) in the mixed powder exceeds (95: 5) and the zirconium content is excessive, when a black film is formed from this mixed powder, the black film is formed. The light-shielding property at a wavelength of 1200 nm becomes inferior. Further, when the zirconium and titanium content ratio (Zr: Ti) exceeds (40:60) and the titanium content becomes excessive, when a black film is formed from this mixed powder, light at a wavelength of 365 nm of the black film is formed. The permeability is poor, and a high-resolution patterning film cannot be obtained.

Further, the zirconium nitride powder (A) constituting the mixed powder for forming a black film has a zirconium nitride peak in the X-ray diffraction profile, while the zirconium dioxide peak, the lower zirconium oxide peak and the lower zirconium oxynitride peak. It has the characteristic of not having a peak. The zirconium nitride powder preferably has a specific surface area of 10 to 90 m ² / g as measured by the BET method. If the specific surface area of the zirconium nitride powder ^{is less than 10 m 2} / g, it tends to settle during long-term storage when it is made into a black resist, and if it ^{exceeds 90 m 2} / g, it has a light-shielding property when a patterning film is formed as a black pigment. This is because it is easy to run short. It is preferably 30 to 60 m ² / g.

The powder of titanium nitride powder constituting a mixed powder for a black film formed (B) is that the specific surface area measured by the BET method is 10~90m ² / g is prevent settling during prolonged storage, as a black pigment It is preferable to obtain sufficient light-shielding property when the patterning film is formed. The powder (B) has, TiN is Ru consists of 100% of the powder.

Further, the mixed powder for forming a black film has a light transmittance of X at a wavelength of 365 nm, a light transmittance of Y at a wavelength of 550 nm, and a light transmittance of 1200 nm in a dispersion spectrum obtained by dispersing the mixed powder in a dispersion at a concentration of 50 ppm. When is Z, X> 8%, Y <8%, Z <25%, X / Y is 1.00 or more, and Z / Y is 4.0 or less. .. When X is 8% or less, the light transmittance at a wavelength of 365 nm is too low, and when forming a patterning film as a black pigment, the bottom of the photoresist film is not exposed, undercutting of the patterning film occurs, and high-resolution patterning occurs. No film can be obtained. When Y is 8% or more, the light transmittance at a wavelength of 550 nm is too high, and when Z is 25% or more, the light transmittance at a wavelength of 1200 nm is too high, and both are inferior in light-shielding property. Preferably, X> 10%, Y <5%, Z <15%, and X / Y of 1.25 or more has an effect of transmitting ultraviolet rays and does not cause undercut of the patterning film. When Z / Y is 2.0 or less, there is an effect of shielding visible light. Preferably, X / Y is 2 or more and Z / Y is 2 or less.

Hereinafter, the starting raw materials for the mixed powder for forming a black film of the present embodiment will be described for each raw material.

[Zirconium dioxide powder]
As the zirconium dioxide powder used for producing the mixed powder for forming a black film, for example, any of zirconium dioxide powders such as monoclinic zirconium dioxide, cubic zirconium dioxide, and yttrium-stabilized zirconium dioxide can be used. However, monoclinic zirconium dioxide powder is preferable from the viewpoint of increasing the production rate of zirconium nitride powder. The zirconium dioxide powder, that an average primary particle diameter as sphere converted from the measured values of the specific surface area is 500nm or less, zirconium nitride powder of the measured specific surface area 20~90m 2 / ^g by BET method (A) It is preferable to obtain it, and it is more preferable that the average primary particle size is 10 nm or more and 500 nm or less from the viewpoint of easy handling of the powder.

[Titanium dioxide powder]
Examples of the titanium dioxide powder used for producing the mixed powder for forming a black film include tetragonal (antase type, rutile type) titanium dioxide and oblique (brookite type) titanium dioxide powder. However, tetragonal titanium dioxide powder is preferable from the viewpoint of increasing the production rate of titanium nitride powder. The titanium dioxide powder may be at 70nm or less in average primary particle diameter as sphere converted from the measured values of the specific surface area, specific surface area measured by BET method 10~90m ² / g titanium nitride Powder (B) It is preferable to obtain the powder, and it is more preferable that the average primary particle size is 10 nm or more and 60 nm or less from the viewpoint of easy handling of the powder.

[Metallic magnesium powder]
If the particle size of the metallic magnesium powder used to prepare the mixed powder for forming a black film is too small, the reaction will proceed rapidly and the operational risk will increase. Therefore, the particle size is 100 with a mesh path of a sieve. Granules of ~ 1000 μm are preferable, and granular ones of 200 to 500 μm are particularly preferable. However, even if all the metallic magnesium is not within the above particle size range, 80% by mass or more, particularly 90% by mass or more of the metallic magnesium may be within the above range.

The amount of the metal magnesium powder added to the zirconium dioxide powder and the titanium oxide powder (first mixture) affects the reducing power of zirconium dioxide together with the amounts of ammonia gas and hydrogen gas in the atmospheric gas described later. If the amount of metallic magnesium is too small, it will be difficult to obtain the desired zirconium nitride powder due to insufficient reduction, and if it is too large, the reaction temperature will rise sharply due to excess metallic magnesium, which may cause grain growth of the powder. It becomes uneconomical with. The metallic magnesium powder is mixed by adding the metallic magnesium powder to the first mixture so that the metallic magnesium has a ratio of 1.0 to 10.0 times the molar amount of the first mixture depending on the size of the particle size. If it is less than 1.0 times the mole, the reducing power of zirconium dioxide and titanium oxide is insufficient, and if it exceeds 10.0 times the mole, the reaction temperature rises sharply due to excess metallic magnesium, which may cause powder grain growth. At the same time, it becomes uneconomical. It is preferably 3 to 5 times the molar amount.

[Magnesium oxide powder]
The magnesium oxide powder used for producing the mixed powder for forming a black film coats the surface of zirconium nitride or the surface of titanium nitride at the time of firing to relax the reducing power of metallic magnesium, and the zirconium nitride powder or titanium nitride powder. Prevents sintering and grain growth. Magnesium oxide powder is added to and mixed with the first mixture so that magnesium nitride has a proportion of 0 to 10 times the molar amount of the first mixture, depending on the size of the particle size. If it exceeds 10 times the mole, there is a problem that the amount of the acidic solution required for acid cleaning after firing increases. It is preferably 1 to 2 times the molar amount. The magnesium oxide powder preferably has an average primary particle size of 1000 nm or less in terms of sphere from the measured value of the specific surface area, and preferably has an average primary particle size of 10 nm or more and 500 nm or less from the viewpoint of ease of handling of the powder. Since not only magnesium oxide but also magnesium nitride is effective in preventing the sintering of zirconium nitride, it is possible to use magnesium oxide mixed with a part of magnesium nitride.

[Manufacturing method of mixed powder for forming a black film]
In the method for producing a mixed powder for forming a black film of the present embodiment, a zirconium dioxide powder and a titanium oxide powder are uniformly mixed at the above-mentioned mass ratio to obtain a first mixture, and then the first mixture is mixed with a metallic magnesium powder. and magnesium oxide powder were uniformly mixed at a weight ratio described above, by sintering, a method for producing a mixed powder of zirconium nitride powder (a) and the titanium nitride powder (B).

[Reduction reaction with metallic magnesium powder]
The temperature during the reduction reaction with metallic magnesium for producing a mixed powder for forming a black film is 200 to 1500 ° C, preferably 500 to 800 ° C. If the temperature is lower than 200 ° C., the reduction reaction of zirconium dioxide does not sufficiently occur. Further, even if the temperature is higher than 1500 ° C., the effect does not increase, heat energy is wasted, and the sintering of particles proceeds, which is not preferable. The reduction reaction time is preferably 10 to 120 minutes, more preferably 30 to 60 minutes.

The reaction vessel for carrying out the reduction reaction is preferably one having a lid so that the raw materials and products do not scatter during the reaction. This is because when the melting of metallic magnesium is started, the reduction reaction proceeds rapidly, and the temperature rises accordingly, and the gas inside the container expands, thereby scattering the things inside the container to the outside. This is because there is a risk.

[Atmospheric gas during reduction reaction with metallic magnesium powder]
The atmospheric gas during the reduction reaction with the metallic magnesium powder is either a nitrogen gas alone, a mixed gas of nitrogen gas and hydrogen gas, a mixed gas of nitrogen gas and ammonia gas, or a mixed gas of nitrogen gas and argon gas. The reduction reaction is carried out in a stream of the nitrogen gas or the mixed gas. Nitrogen gas in the mixed gas is to prevent contact between the metallic magnesium and the reduction product and oxygen, while preventing their oxidation, nitrogen is reacted with zirconium and titanium, it serves to produce a zirconium nitride and titanium nitride Powder Have. Hydrogen gas, ammonia gas and argon gas in the mixed gas have a role of reducing zirconium dioxide and titanium dioxide together with metallic magnesium. The hydrogen gas and the argon gas are preferably contained in the mixed gas in an amount of 0 to 90% by volume, more preferably 20 to 70% by volume. By using this reducing atmospheric gas, a zirconium nitride powder containing no lower zirconium oxide and lower zirconium oxynitride can be finally produced. On the other hand, if the proportion of components other than nitrogen gas is higher than this range, reduction proceeds but the nitrogen source is reduced, so that low-order zirconium oxide or low-order zirconium oxynitride is generated, which is not desirable.

[Treatment of reactants after firing]
The reaction product obtained by firing a mixture of zirconium dioxide powder, titanium oxide powder, metallic magnesium powder, and magnesium oxide powder in the atmosphere of the mixed gas is taken out from the reaction vessel and finally at room temperature. After cooling to, it is washed with an acid solution such as an aqueous hydrochloric acid solution to remove magnesium oxide generated by oxidation of metallic magnesium and magnesium oxide contained from the beginning of the reaction to prevent sintering of the product. The acid cleaning is preferably carried out at pH 3.0 or lower, particularly pH 1.0 to 2.0, and a temperature of 80 ° C. or lower. Then, after the acid cleaning, the pH is adjusted to 5 to 6 with aqueous ammonia or the like, the solid content is separated by filtration or centrifugation, the solid content is dried, and then pulverized to form zirconium nitride powder and titanium nitride powder. obtaining a mixed powder youngest.

In the present embodiment, the zirconium nitride powder mainly using metallic magnesium is described, but this zirconium nitride powder can also be produced by the nanoparticle plasma synthesis method. Specifically introducing metallic zirconium powder into the plasma nanoparticle production apparatus, a method for obtaining a zirconium nitride nanoparticles at an N ₂ gas atmosphere. ^{Zirconium nitride synthesized by this method can also obtain a powder having a specific surface area of 20 to 90 m 2} / g measured by the BET method as in the embodiment of the present application, but the raw material zirconium nitride is highly combustible and dangerous. There is a demerit that the cost is high.

[Method of forming a patterning film using mixed powder as a black pigment]
A method for forming a patterning film typified by a black matrix using the obtained mixed powder as a black pigment will be described. First, the mixed powder is dispersed in a photosensitive resin to prepare a black photosensitive composition. Next, after applying this black photosensitive composition on the substrate, prebaking is performed to evaporate the solvent to form a photoresist film. Next, the photoresist film is exposed to a predetermined pattern shape via a photomask, and then developed with an alkaline developer to dissolve and remove the unexposed portion of the photoresist film, and then post-baking is preferably performed. As a result, a predetermined black patterning film is formed.

The optical density, that is, the OD (Optical Density) value is known as an index showing the light-shielding property (attenuation of the transmittance) of the formed patterning film. The patterning film formed by using the mixed powder of the present embodiment has a high OD value. Here, the OD value is a logarithmic representation of the degree to which light is absorbed when passing through the patterning film, and is defined by the following equation (1). In the formula (1), I is the amount of transmitted light and I ₀ is the amount of incident light.
OD value = -log ₁₀ (I / I ₀ ) (1)

Examples of the substrate include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamide-imide, and polyimide. Further, if desired, the substrate may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction method, vacuum deposition and the like. When the black photosensitive composition is applied to the substrate, an appropriate coating method such as rotary coating, cast coating, roll coating or the like can be adopted. The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 7.0 μm, and more preferably 0.5 to 6.0 μm as the film thickness after drying. As the radiation used for forming the patterning film, in the present embodiment, radiation having a wavelength in the range of 250 to 410 nm is preferable. The amount of radiation energy is preferably 10 to 10,000 J / m ² . Examples of the alkaline developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, and 1,5. An aqueous solution of −diazabicyclo- [4.3.0] -5-nonene or the like is preferable. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. After alkaline development, it is usually washed with water. As the developing method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid filling) developing method and the like can be applied, and the developing conditions are preferably 5 to 300 seconds at room temperature. The patterning film thus formed is a high-definition liquid crystal display, a black matrix material for organic EL, and a light-shielding material for an image sensor. It is suitably used for light-shielding materials for optical members, light-shielding filters, IR cut filters, black coverlay films, and the like.

Next, examples of the present invention will be described in detail together with comparative examples.

<Example 1>
5.5 g of monoclinic zirconium dioxide powder having an average primary particle size of 50 nm calculated from the specific surface area measured by the BET method and an average primary particle size of 30 nm calculated from the specific surface area measured by the BET method. 1.9 g of titanium dioxide powder was uniformly mixed in a glass container to prepare a first mixture. At this time, the ratio of the zirconium dioxide powder to the titanium dioxide powder was 75:25 in terms of mass ratio. Next, 8.3 g of metal magnesium powder having an average primary particle size of 150 μm and 3.8 g of magnesium oxide powder having an average primary particle size of 200 nm were added and mixed uniformly with the first mixture to prepare a second mixture. The amount of metallic magnesium added to the second mixture was 5.0 times the molar amount of the first mixture, and the amount of magnesium oxide added was 1.4 times the molar amount of the first mixture. This second mixture was calcined at a temperature of 700 ° C. for 60 minutes in an atmosphere of nitrogen gas to obtain a calcined product. This fired product was dispersed in 100 mL of water, 5% hydrochloric acid was gradually added, and the mixture was washed with a pH of 3 or less and a temperature of 90 ° C. or less, and then with 2.5% aqueous ammonia for pH 6 to. It was adjusted to 7 and filtered. The filtered solid content was redistributed in water at 40 g / liter, again acid-washed and pH-adjusted with ammonia water in the same manner as described above, filtered with a suction filtration device, and further washed with 100 mL of ion-exchanged water. , Set temperature: A mixed powder of zirconium nitride powder (A) and titanium nitride powder (B) was prepared by drying in a hot air dryer at 120 ° C.

<Example 2>
Zirconium nitride powder (A) and titanium nitride powder (B) were used in the same manner as in Example 1 using the same raw materials as in Example 1 except that the mass ratio of the zirconium nitride powder to the titanium dioxide powder was changed to 40:60. ) Was prepared.

<Example 3>
The zirconium nitride powder (A) and the titanium nitride powder (B) were used in the same manner as in Example 1 using the same raw materials as in Example 1 except that the mass ratio of the zirconium nitride powder and the titanium dioxide powder was changed to 50:50. ) Was prepared.

<Example 4>
Zirconium nitride powder (A) and titanium nitride powder (B) were used in the same manner as in Example 1 using the same raw materials as in Example 1 except that the mass ratio of the zirconium nitride powder to the titanium dioxide powder was changed to 95: 5. ) Was prepared.

<Example 5>
Zirconium nitride powder (A) and titanium nitride powder (B) were used in the same manner as in Example 1 using the same raw materials as in Example 1 except that the amount of metallic magnesium added was changed to 4.0 times the molar amount of the first mixture. ) Was prepared.

<Example 6>
Zirconium nitride powder (A) and titanium nitride powder (B) were used in the same manner as in Example 2 using the same raw materials as in Example 2 except that the amount of metallic magnesium added was changed to 4.0 times the molar amount of the first mixture. ) Was prepared.

<Example 7>
Zirconium nitride powder (A) and titanium nitride powder (B) were used in the same manner as in Example 4 using the same raw materials as in Example 4 except that the amount of metallic magnesium added was changed to 6.0 times the molar amount of the first mixture. ) Was prepared.

<Example 8>
Zirconium nitride powder (A) and titanium nitride powder (B) were used in the same manner as in Example 2 using the same raw materials as in Example 2 except that the amount of metallic magnesium added was changed to 1.0 times the molar amount of the first mixture. ) Was prepared.

<Example 9>
Zirconium nitride powder (A) and titanium nitride powder (B) were used in the same manner as in Example 4 using the same raw materials as in Example 4 except that the amount of metallic magnesium added was changed to 10.0 times the molar amount of the first mixture. ) Was prepared.

<Example 10>
Zirconium nitride powder (A) and titanium nitride powder (B) were used in the same manner as in Example 1 using the same raw materials as in Example 1 except that the amount of magnesium oxide added was changed to 10.0 times the molar amount of the first mixture. ) Was prepared.

<Example 11>
Using the same raw materials as in Example 4 except that the amount of magnesium oxide added was changed to 0 times the molar amount of the first mixture, the zirconium nitride powder (A) and titanium nitride powder (B) were prepared in the same manner as in Example 4. A mixed powder was prepared.

<Comparative example 1>
The titanium black black powder shown in Example 1 of Patent Document 1 was prepared. That is, titanium oxide powder having an average primary particle size of 160 nm is calcined at a temperature of 850 ° C. for 180 minutes in an atmosphere of ammonia gas _{to obtain a titanium oxynitride of 70 nm (TiO 0.3} N _0.9 ), and then this _{5.0 parts by mass of titanium oxynitride and an insulating powder made of Al 2} O ₃ having an average primary particle size of 10 nm were added to 100 parts by mass of titanium oxynitride and mixed to prepare a black powder.

<Comparative example 2>
The average primary particle size is 7.4 g of monoclinic zirconium dioxide powder with an average primary particle size of 50 nm calculated from the specific surface area measured by the BET method, and 7.3 g of metallic magnesium powder with an average primary particle size of 150 μm. 3.4 g of 200 nm magnesium oxide powder was added and mixed uniformly in a glass container. At this time, the amount of metallic magnesium added was 5.0 times the molar amount of zirconium dioxide, and the amount of magnesium oxide added was 1.4 times the molar amount of zirconium dioxide. This mixture was calcined at a temperature of 700 ° C. for 60 minutes in an atmosphere of nitrogen gas to obtain a calcined product. This fired product was dispersed in 100 mL of water, 5% hydrochloric acid was gradually added, and the mixture was washed with a pH of 3 or less and a temperature of 90 ° C. or less, and then with 2.5% aqueous ammonia for pH 6 to. It was adjusted to 7 and filtered. The filtered solid content was redistributed in water at 40 g / liter, again acid-washed and pH-adjusted with ammonia water in the same manner as described above, filtered with a suction filtration device, and further washed with 100 mL of ion-exchanged water. , Set temperature; The zirconium nitride powder (A) was prepared by drying in a hot air dryer at 120 ° C.

<Comparative example 3>
Zirconium nitride powder (A) and titanium nitride powder (B) were used in the same manner as in Example 1 using the same raw materials as in Example 1 except that the mass ratio of the zirconium nitride powder to the titanium dioxide powder was changed to 98: 2. ) Was prepared.

<Comparative example 4>
The zirconium nitride powder (A) and the titanium nitride powder (B) were used in the same manner as in Example 1 using the same raw materials as in Example 1 except that the mass ratio of the zirconium nitride powder and the titanium dioxide powder was changed to 20:80. ) Was prepared.

<Comparative example 5>
The zirconium nitride powder (A) and the titanium nitride powder (B) were used in the same manner as in Example 1 using the same raw materials as in Example 1 except that the mass ratio of the zirconium nitride powder to the titanium dioxide powder was changed to 5:95. ) Was prepared.

<Comparative Example 6>
Using the same raw materials as in Example 1, except that the mass ratio of zirconium nitride powder to titanium dioxide powder was changed to 30:70 and the amount of metallic magnesium added was changed to 0.9 times the molar amount of the first mixture. Zirconium nitride powder (A) was prepared in the same manner as in Example 1.

<Comparative Example 7>
A zirconium nitride powder (A) was prepared in the same manner as in Comparative Example 4 using the same raw materials as in Comparative Example 4 except that the amount of metallic magnesium added was changed to 11.0 times the molar amount of the first mixture.

<Comparative Example 8>
A zirconium nitride powder (A) was prepared in the same manner as in Comparative Example 5 using the same raw materials as in Comparative Example 5 except that the amount of magnesium oxide added was changed to 11.0 times the molar amount of the first mixture.

Each production method of Examples 1 to 11 and Comparative Examples 1 to 8, the molar ratio of zirconium dioxide to the addition amount of metallic magnesium and magnesium nitride or magnesium oxide (hereinafter referred to as Mg source), and the type of reaction gas which is an atmospheric gas. Table 1 shows the ratio of the metal and its volume%, the firing temperature and the firing time.

<Comparative test and evaluation 1>
Examples 1 to 11, the mixed powder of the powder (A) and the powder (B) obtained in Comparative Examples 3 to 8, the powder of only the powder (B) obtained in Comparative Example 1, and the powder obtained in Comparative Example 2. Using the powder of powder (A) only as a sample, (1) X-ray diffraction profile, (2) spectroscopic curve in a dispersion with a powder concentration of 50 ppm, and (3) light transmittance X of 365 nm, by the method described in detail below. The light transmittance Y at 550 nm, the light transmittance Z at 1200 nm, and (4) X / Y and Z / Y were measured or calculated. Table 2 shows each measurement result or calculation result. In Table 2, "TiN" means titanium nitride.

(1) X-ray diffraction profile: For the sample of Example 1, the θ-2θ method was performed using an X-ray diffractometer (manufactured by Rigaku Co., Ltd., model number MiniflexII) under the conditions of an applied voltage of 45 kV and an applied current of 40 mA using CuKα rays. X-ray diffraction analysis was performed from the X-ray diffraction profile. From the X-ray diffraction profile, zirconium nitride peak (2θ = 34.0 °, 39.3 °), zirconium dioxide peak (2θ = 30.2 °), low-order zirconium oxide peak and low-order zirconium oxynitride peak. The presence or absence of the peak (2θ = 30.5 °, 35.3 °) and the peak of titanium nitride (2θ = 36.7 °, 42.6 °) were examined. FIG. 1 shows an X-ray diffraction profile. In Figure 1, the "ZrN" is zirconium nitride, _"Zr 2 _{N 2} O" as the low order zirconium oxynitride, "TiN" means titanium nitride, respectively.

(2) Spectral curve in a dispersion with a powder concentration of 50 ppm: For each sample of Examples 1 to 11 and Comparative Examples 1 to 8, an amine-based dispersant was added and in a propylene glycol monomethyl ether acetate (PGM-AC) solvent. The distributed processing was performed in. The obtained 19 kinds of dispersions were diluted 100,000 times to adjust the powder concentration to 50 ppm. The light transmittance of each sample in this diluted dispersion was measured using Hitachi High-Tech Fielding Co., Ltd. (UH-4150) in the wavelength range of 240 nm to 1300 nm, and the i-line (365 nm) wavelength was 365 nm and the wavelength was 550 nm. And each light transmittance (%) at a wavelength of 1200 nm was determined. FIG. 2 shows four spectral curves of Example 1, Example 2, and Comparative Examples 1 and 2.

(3) Light transmittance X at 365 nm, light transmittance Y at 550 nm and light transmittance Z at 1200 nm: From the spectral curves of each sample of Examples 1 to 11 and Comparative Examples 1 to 8, the respective light transmittance X, Y and Z were read.

(4) X / Y: X / Y from the light transmittance X and the light transmittance Y read from the spectral curves of each sample of Examples 1 to 11 and Comparative Examples 1 to 8, and the light transmittance Z and the light transmittance. Z / Y was calculated from the rate Y, respectively.

From the X-ray diffraction profile of FIG. 1 (b), the sample of Comparative Example 6 has not only the peak of zirconium nitride (2θ = 33.95 °, 39.3 °) but also the peak of low-order zirconium nitride (2θ = 30). It had .5 ° and 35.3 °). On the other hand, the samples of Examples 1 to 5 have a zirconium nitride peak in the X-ray diffraction profile, as represented by the X-ray diffraction profile of Example 1 of FIG. 1 (a), while zirconium dioxide. It did not have a peak of zirconium oxide, a peak of low-order zirconium oxide, or a peak of low-order zirconium nitride.

As is clear from FIGS. 2 and 2, the samples of Comparative Examples 1 and 4 to 8 have a transmittance X of 365 nm in the spectral transmission curve in the range of 6.0 to 9.4%, and a transmittance Y of 550 nm. Was in the range of 6.4 to 10.5%. The transmittance Z at 1200 nm was in the range of 12.5 to 20.5%. Z / Y, which is the ratio of the light transmittance Y to the light transmittance Z of each sample, is in the range of 1.9 to 2.2 and satisfies the requirement of 4.0 or less of the present invention, but the light transmittance X. The ratio of light transmittance Y to X / Y was in the range of 0.8 to 0.9 and did not satisfy the requirement of the present invention of 1.00 or more.

Further, X / Y, which is the ratio of the light transmittance Y to the light transmittance X of the samples of Comparative Examples 2 and 3, is 3.7 and 3.9, respectively, which satisfies the requirement of 1.00 or more of the present invention. Z / Y, which is the ratio of the light transmittance Y to the light transmittance Z, was 4.5 and 4.7, respectively, which did not satisfy the requirement of 4.0 or less of the present invention.

On the other hand, the transmittance X at 365 nm in the spectral transmission curves of the samples of Examples 1 to 11 is in the range of 8.4 to 18.7%, and the transmittance Y at 550 nm is 4.1 to 7.0. It was in the range of%. The transmittance Z at 1200 nm was in the range of 12.9 to 20.6%. X / Y, which is the ratio of the light transmittance Y to the light transmittance X of the samples of Examples 1 to 11, is in the range of 1.3 to 4.5 and satisfies the requirement of the present invention of 1.00 or more. Z / Y, which is the ratio of the light transmittance Y to the light transmittance Z, was in the range of 1.9 to 3.5 and satisfied 4.0 or less, which is the requirement of the present invention.

<Comparative test and evaluation 2>
Acrylic resin was added to the dispersion of the samples obtained in Examples 1 to 11 and Comparative Examples 1 to 8 for measuring the light transmittance, and mixed by adding a black pigment: resin = 5: 5 by mass ratio. To prepare a black photosensitive composition. This composition was spin-coated on a glass substrate so that the film thickness after firing was 1 μm, and fired at a temperature of 250 ° C. for 60 minutes to form a film. The OD values of ultraviolet rays (center wavelength 370 nm) and visible light (center wavelength 650 nm) of this film were measured based on the above-mentioned formula (1) using a densitometer of product name D200 manufactured by Macbeth. The results are shown in Table 2. In Table 2, as a measure of the transparency of ultraviolet rays, an OD value of ultraviolet rays (UV) at 370 nm of 2.0 or less is regarded as “excellent”, and a value of more than 2.0 and 2.5 or less is regarded as “good”. A case exceeding 5 was regarded as "defective". As a measure of the light blocking effect of visible light, when the OD value of visible light at 650 nm exceeds 3.0, it is regarded as "excellent", when it is 2.5 or more and 3.0 or less, it is regarded as "good", and when it is less than 2.5. It was considered "bad".

As is clear from Table 2, regarding the OD value as a measure of the transparency of ultraviolet rays and the light blocking property of visible light, the sample of Comparative Example 1 does not contain the zirconium nitride powder (A), so that the 365 nm OD value of UV is high. It was "bad". The sample of Comparative Example 2 because it does not contain titanium nitride Powder a (B), 1200nmOD value near infrared was lower "bad". The samples of Comparative Examples 4 to 8 have a mass ratio (Zr: Ti) of zirconium to titanium of (4: 96) to (35:65), and the mass of zirconium nitride (A) and titanium nitride powder (B). Since the content ratio of the powder (A) was too low in the ratio, the 365 nm OD value of UV was high and was “poor”. Further, in the sample of Comparative Example 3, the mass ratio (Zr: Ti) of zirconium to titanium was (98: 2), and the content ratio of the powder (B) was too low in the mass ratio of the powder (A) to the powder (B). Therefore, the OD value at 1200 nm in the near infrared was low and was “defective”.

Further, the sample of Comparative Example 6 was prepared by mixing metallic magnesium in an amount of 0.9 times the molar amount of a mixture of zirconium dioxide and titanium oxide in an excessively small proportion, so that the 550 nm OD value of visible light was low and was “poor”.

On the other hand, since the samples of Examples 1 to 11 satisfy the requirements of the present invention, the 365 nm OD value of ultraviolet rays (UV) is “excellent” or “good”, and the OD of 550 nm of visible light. The value was also "excellent" or "good". From this, it was found that the samples of Examples 1 to 11 are advantageous for patterning because they transmit ultraviolet rays in addition to having high light-shielding performance of visible light.

The mixed powder for forming a black film of the present invention is used for high-definition liquid crystal displays, black matrix materials for organic EL, light-shielding materials for image sensors, light-shielding materials for optical members, light-shielding filters, IR cut filters, black coverlay films, and the like. be able to.

Claims (4)

After mixing zirconium dioxide powder and titanium oxide powder to obtain a first mixture, metal magnesium powder and magnesium oxide powder are added to the first mixture, and metal magnesium is 1 to 10 times the molar amount of the first mixture. A second mixture is prepared by mixing the mixture so as to have a ratio of 0 to 10 times that of the first mixture, and then the second mixture is mixed in a nitrogen gas atmosphere from 200 to 200. by calcining at a temperature of 1500 ° C., by reducing the zirconium dioxide powder and the titanium oxide powder to prepare a mixed powder of zirconium nitride powder (a) and titanium nitride powder (B),
A method for producing a mixed powder for forming a black film, wherein the mass ratio (Zr: Ti) of zirconium to titanium in the produced mixed powder is in the range of (40:60) to (95: 5). The mixed powder is X when the light transmittance at a wavelength of 365 nm is X, the light transmittance at a wavelength of 550 nm is Y, and the light transmittance at a wavelength of 1200 nm is Z in the dispersion liquid spectrum dispersed in the dispersion liquid at a concentration of 50 ppm. The mixed powder for forming a black film according to claim 1, wherein> 8%, Y <8%, Z <25%, X / Y is 1.00 or more, and Z / Y is 4.0 or less. Production method. A method for producing a black photosensitive composition by dispersing the mixed powder for forming a black film produced by the method according to claim 1 or 2 in a photosensitive resin. A method for forming a black patterning film using the black photosensitive composition produced by the method according to claim 3.

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