阅读说明：本技术 黑色遮光膜形成用粉末及其制备方法 (Powder for forming black light-shielding film and method for producing same ) 是由 小西隆史 影山谦介 于 2018-10-25 设计创作，主要内容包括：一种黑色遮光膜形成用粉末,该粉末通过BET法测定的比表面积为20～90m<Sup>2</Sup>/g,以氮化锆作为主要成分,且含有镁和/或铝。在含有镁时,相对于100质量%的黑色遮光膜形成用粉末,镁的含有比例为0.01～1.0质量%,在含有铝时,相对于100质量%的黑色遮光膜形成用粉末,铝的含有比例为0.01～1.0质量%。(A powder for forming a black light-shielding film, which has a specific surface area of 20 to 90m as measured by the BET method 2 In terms of/g, ofZirconium nitride is used as a main component, and magnesium and/or aluminum are contained. When magnesium is contained, the content of magnesium is 0.01-1.0% by mass relative to 100% by mass of the black light-shielding film-forming powder, and when aluminum is contained, the content of aluminum is 0.01-1.0% by mass relative to 100% by mass of the black light-shielding film-forming powder.)

1. A black light-shielding film-forming powder characterized by: the specific surface area is 20-90 m measured by a BET method²(ii)/g of a black light-shielding film-forming powder containing zirconium nitride as a main component and magnesium and/or aluminum,

wherein, when the magnesium is contained, the content ratio of the magnesium is 0.01-1.0% by mass relative to 100% by mass of the black light-shielding film-forming powder, and when the aluminum is contained, the content ratio of the aluminum is 0.01-1.0% by mass relative to 100% by mass of the black light-shielding film-forming powder.

2. A method for producing a black light-shielding film-forming powder, which comprises mixing 25 to 150 mass% of magnesium metal with respect to 100 mass% of zirconium dioxide, 15 to 500 mass% of magnesium oxide with respect to 100 mass% of zirconium dioxide, and 0.02 to 5.0 mass% of aluminum oxide or aluminum nitride with respect to 100 mass% of zirconium dioxide, and calcining the obtained mixed powder at 650 to 900 ℃ in a nitrogen-free atmosphere, a mixed gas atmosphere of nitrogen and hydrogen, a mixed gas atmosphere of nitrogen and ammonia, or a nitrogen and inert gas atmosphere, thereby reducing the mixed powder to produce a black light-shielding film-forming powder.

3. A black photosensitive composition comprising the powder for forming a black light-shielding film according to claim 1 or the powder for forming a black light-shielding film produced by the method according to claim 2 as a black pigment.

4. A method for forming a black light-shielding film using the black photosensitive composition according to claim 3.

Technical Field

The present invention relates to a powder for forming a black light-shielding film containing zirconium nitride as a main component, which is suitable for use as an insulating black pigment, and a method for producing the same. More particularly, the present invention relates to a powder for forming a black light-shielding film, which is excellent in ultraviolet light transmittance and has high-resolution patterning characteristics, and which forms a black light-shielding film having high light-shielding performance and high weather resistance as a black pigment, and a method for producing the same. It should be noted that, the international application claims priority from japanese patent application No. 248647 (japanese patent application 2017 plus 248647) applied on 26/12/2017, and the entire contents of the japanese patent application 2017 plus 248647 are incorporated into the international application.

Background

Such a black pigment is dispersed in a photosensitive resin to prepare a black photosensitive composition, the composition is applied onto a substrate to form a photoresist film, and the photoresist film is exposed to light by photolithography to form a black light-shielding film (hereinafter, also referred to as a patterned film) having patterning characteristics, and thus the black pigment is used for a black matrix of an image forming device such as a color filter of a liquid crystal display. Carbon black, which is a conventional black pigment, is not suitable for applications requiring insulation properties because it has conductivity.

Conventionally, as a black pigment having high insulation properties, there has been disclosed a high-resistance black powder containing: a black powder composed of titanium oxynitride of a specific composition, also called titanium black; and from Y₂O₃、ZrO₂、Al₂O₃、SiO₂、TiO₂、V₂O₅An insulating powder having at least one of the above constitutions (see, for example, patent document 1). The black powder is considered to be suitable as a color filter because it has a high resistance value and excellent light-shielding properties when a black film is formedA black matrix.

Also disclosed is a black resin composition containing titanium nitride particles as a light-shielding material, wherein when CuK α radiation is used as an X-ray source, the diffraction angle 2 of the peak originating from the (200) plane of at least one of the titanium nitride particles is 2θIs 42.5 ° or more and 42.8 ° or less, and has a crystallite size of 10nm or more and 20nm or less as determined from the half width of the X-ray diffraction peak derived from the (200) plane of the titanium nitride particles (see, for example, patent document 2). Although the black resin composition is not colored, a resin black matrix having a high OD value and a high resistance value can be obtained, and it is considered that a color filter which can realize black display of black image can be provided when used in a liquid crystal display device.

Further, disclosed is a blue-shielding black powder characterized by: the black powder is composed of one or two kinds of oxynitride of vanadium or niobium, has an oxygen content of 16wt% or less and a nitrogen content of 10wt% or more, and has a transmittance X at 450nm of 10.0% or less in a transmission spectrum of a dispersion having a powder concentration of 50ppm, wherein a ratio (X/Y) of the transmittance X at 450nm to the transmittance Y at 550nm is 2.0 or less, and/or a ratio (X/Z) of the transmittance X at 450nm to the transmittance Z at 650nm is 1.5 or less (see, for example, patent document 3). The blue shielding black powder has a high degree of blackness and excellent light shielding properties against blue light, and preferably has high insulating properties.

Further, as an insulating black pigment and also containing zirconium nitride, there is disclosed a fine particulate zirconium suboxide/zirconium nitride composite characterized in that: has a peak of low-valence zirconia and a peak of zirconium nitride in an X-ray diffraction profile (X-ray diffraction profile), and has a specific surface area of 10 to 60m²(see, for example, patent document 4). The particulate zirconium suboxide/zirconium nitride composite is prepared by calcining zirconium dioxide or a mixture of zirconium hydroxide, magnesium oxide and magnesium metal in a nitrogen gas or an inert gas stream containing nitrogen gas at 650-800 ℃. The fine-particle low-valent zirconia/zirconium nitride composite is considered to be useful as a fine-particle material having low conductivity and being of black type, and is also considered to be useful as a fine-particle black pigment having lower conductivity for televisions and the like using carbon black or the likeIn a black matrix for a display or the like, it is considered that the above fine particulate zirconium suboxide/zirconium nitride composite can be produced (mass-produced) on an industrial scale according to the above production method.

Disclosure of Invention

Problems to be solved by the invention

However, with regard to the black powder called titanium black shown in patent document 1, the black resin composition containing titanium nitride particles shown in patent document 2, the black powder composed of vanadium or niobium oxynitride shown in patent document 3, and the fine-particle zirconium suboxide/zirconium nitride composite shown in patent document 4, when the black pigment is used, a black photosensitive composition is prepared by increasing the pigment concentration to obtain higher light-shielding properties, and the black photosensitive composition is applied to a substrate to form a photoresist film, and the photoresist film is exposed to light by photolithography to form a black patterned film, the black pigment in the photoresist film also shields i-rays (wavelength 365nm) as ultraviolet rays, causing ultraviolet rays not to reach the bottom of the photoresist film, undercutting (underrout) occurs at the bottom, and there is a problem that a high-resolution patterned film cannot be formed.

Further, the fine particulate zirconium suboxide/zirconium nitride composite shown in patent document 4 has a problem that when the particle diameter is made smaller, the oxidation resistance becomes weak, and the degree of blackness in the moisture resistance and heat resistance test is lowered, that is, the weather resistance is lowered.

An object of the present invention is to provide a powder for forming a black light-shielding film, which forms a black light-shielding film having excellent ultraviolet transmittance and high-resolution patterning characteristics as a black pigment, and which forms a black light-shielding film having high light-shielding performance and high weather resistance, and a method for producing the same.

Means for solving the problems

The present inventors have focused on: when magnesium and/or aluminum is contained in the powder for forming a black light-shielding film containing zirconium nitride as a main component, an oxide coating layer or a nitride coating layer of aluminum or magnesium is formed on the outermost layer of the nano-particulate zirconium nitride particles, and the black light-shielding film formed using the powder as a black pigment exhibits high light-shielding performance and can obtain high light resistance, thereby achieving the present invention.

The invention according to 1 aspect relates to a powder for forming a black light-shielding film, comprising: the powder for forming a black light-shielding film has a specific surface area of 20 to 90m as measured by the BET method²And/or magnesium and/or aluminum, wherein when the magnesium is contained, the content of the magnesium is 0.01 to 1.0 mass% relative to 100 mass% of the black light-shielding film-forming powder, and when the aluminum is contained, the content of the aluminum is 0.01 to 1.0 mass% relative to 100 mass% of the black light-shielding film-forming powder.

The invention of claim 2 relates to a method for producing a black light-shielding film-forming powder by mixing a zirconium dioxide powder, a metallic magnesium powder, a magnesium oxide powder, and an aluminum oxide powder or an aluminum nitride powder at the following respective ratios, specifically, the metal magnesium accounts for 25 to 150 mass% of the zirconium dioxide based on 100 mass%, the magnesium oxide accounts for 15 to 500 mass% of the zirconium dioxide based on 100 mass%, and the aluminum oxide or the aluminum nitride accounts for 0.02 to 5.0 mass% of the zirconium dioxide based on 100 mass%, and the obtained mixed powder is calcined at a temperature of 650 to 900 ℃ in a nitrogen gas monomer environment, a nitrogen gas and hydrogen gas mixed gas environment, a nitrogen gas and ammonia gas mixed gas environment, or a nitrogen gas and inert gas environment, so that the mixed powder is reduced to prepare the black light-shielding film-forming powder.

An aspect 3 of the present invention relates to a black photosensitive composition comprising the powder for forming a black light-shielding film according to aspect 1 or the powder for forming a black light-shielding film prepared by the method according to aspect 2 as a black pigment.

The 4 th aspect of the present invention relates to a method for forming a black light-shielding film using the black photosensitive composition of the 3 rd aspect.

Effects of the invention

The black light-shielding film-forming powder according to claim 1 of the present invention has a specific surface area of 20m²(ii)/g or more, so that the resist composition has an effect of inhibiting precipitation (sedimentation) when used as a resist, and has a specific surface area of 90m²Has an effect of sufficient light-shielding properties because of its concentration of water or less. Zirconium nitride has a characteristic of further transmitting ultraviolet rays by being used as a main component. As a result, a high-resolution patterned film can be formed as a black pigment, and the formed patterned film has high light-shielding properties. Further, by containing 0.01 to 1.0 mass% of aluminum, the light-shielding performance of the black light-shielding film formed when the black light-shielding film is formed as a black pigment is not lowered, and the weather resistance thereof can be remarkably improved. Further, by further containing magnesium in an amount of 0.01 to 1.0 mass%, the black light-shielding film has an effect of improving weather resistance without deteriorating light-shielding performance.

In the method for producing a powder for forming a black light-shielding film according to claim 2 of the present invention, a powder for forming a black light-shielding film containing 0.01 to 1.0 mass% of magnesium and 0.01 to 1.0 mass% of aluminum is produced by calcining a zirconium dioxide powder, a metallic magnesium powder, a magnesium oxide powder, and an aluminum oxide powder or an aluminum nitride powder at a predetermined ratio. Further, the reduction reaction is further promoted by firing in a predetermined gas atmosphere, so that the reaction efficiency is further improved, and the black light-shielding film-forming powder mainly composed of zirconium nitride can be produced even with a smaller amount of metal magnesium.

According to the black photosensitive composition of aspect 3 of the present invention, since the black photosensitive composition mainly contains zirconium nitride powder as a black pigment, if a black patterned film is formed using the composition, a patterned film with high resolution can be formed, the formed patterned film has high light-shielding performance, and the formed patterned film has high weather resistance because the zirconium nitride powder further contains aluminum.

According to the method for forming a black light-shielding film of viewpoint 4 of the present invention, a black light-shielding film having high-resolution patterning characteristics can be formed, and the formed black light-shielding film has high light-shielding performance and high weather resistance.

Detailed Description

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

[ through ZrO₂Metal Mg, MgO, Al₂O₃The method for preparing a black light-shielding film-forming powder by calcination]

In the present embodiment, zirconium dioxide (ZrO) is used₂) Magnesium metal (metal Mg), magnesium oxide (MgO) and aluminum oxide (Al)₂O₃) The respective powders of (a) are used as starting materials, and are calcined at a predetermined temperature and for a predetermined time in a predetermined environment to prepare a black light-shielding film-forming powder mainly composed of zirconium nitride (ZrN). Aluminum nitride (AlN) powder may be used instead of the alumina powder.

[ zirconium dioxide powder ]

As the zirconia powder of the present embodiment, 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 improving the yield of zirconium nitride powder.

[ metallic magnesium powder ]

The metal magnesium powder of the present embodiment preferably has a particle size of 100 to 1000 after sieving because the reaction proceeds vigorously and the operational risk increases if the particle size is too smallμm is preferably 100 to 500 in particularμm is a granular powder. However, even if the metallic magnesium is not entirely within the above-mentioned particle size range, it is sufficient if 80 mass% or more, particularly 90 mass% or more thereof is within the above-mentioned range.

The amount of the metallic magnesium powder added to the zirconium dioxide powder affects the reducing power of zirconium dioxide. If the amount of metallic magnesium is too small, the reduction is insufficient and the target zirconium nitride powder is not easily obtained, and if the amount of metallic magnesium is too large, the reaction temperature rapidly increases due to the excessive metallic magnesium, which may cause particle growth of the powder and is not economical. The magnesium metal powder is added to zirconium dioxide powder according to the particle size, and mixed so that the ratio of magnesium metal to 100 mass% of zirconium dioxide is 25 to 150 mass%. If the amount is less than 25% by mass, the reducing power of zirconium dioxide is insufficient, and if it exceeds 150% by mass, the reaction temperature is rapidly increased by excessive magnesium metal, which may cause particle growth of the powder and is uneconomical. Preferably 40 to 100 mass%.

[ magnesium oxide powder ]

The magnesium oxide powder of the present embodiment relieves the reducing power of metallic magnesium during calcination, and prevents sintering and grain growth of zirconium nitride powder. The magnesium oxide powder is added to zirconium dioxide according to the particle size thereof and mixed so that the ratio of magnesium oxide to 100 mass% of zirconium dioxide is 15 to 500 mass%. If the amount is less than 15% by mass, sintering of the zirconium nitride powder cannot be prevented, and if the amount exceeds 500% by mass, the amount of the acidic solution used in the acid washing after calcination increases, which is uneconomical. Preferably 25 to 400 mass%. The magnesium oxide powder preferably has an average primary particle diameter of 1000nm or less in terms of sphere from the measured value of the specific surface area, and preferably has an average primary particle diameter of 500nm or less and 10nm or more in view of ease of handling of the powder. Since magnesium nitride is effective for preventing sintering of zirconium nitride in addition to magnesium oxide, magnesium oxide may be used in combination with a part of magnesium nitride. The content of magnesium in the black light-shielding film-forming powder described later is 0.01 to 1.0 mass% based on the above amounts of magnesium metal and magnesium oxide.

[ alumina powder or aluminum nitride powder ]

The alumina powder of the present embodiment improves the weather resistance of the black light-shielding film when the black light-shielding film is formed using the black light-shielding film-forming powder containing the alumina powder as a black pigment. In addition, the reducing power of the metal magnesium is relieved during the calcination, and the sintering and particle growth of the zirconium nitride powder are prevented. Alumina powder is added to zirconia depending on the particle size thereof and mixed so that the proportion of alumina to 100 mass% zirconia is 0.02 to 5.0 mass%. If the content is less than 0.02 mass%, the weatherability of the black light-shielding film is not improved, and if the content exceeds 5.0 mass%, the light-shielding performance of the black light-shielding film is lowered. Preferably 0.05 to 1.0 mass%. The alumina powder preferably has an average primary particle size of 1000nm or less in terms of spheres obtained from the measured value of the specific surface area, and preferably has an average primary particle size of 500nm or less and 10nm or more in terms of ease of handling of the powder. The aluminum nitride powder can be used in place of the alumina powder because it improves the weather resistance of the black light-shielding film even when the black light-shielding film is formed using the black light-shielding film-forming powder containing the aluminum nitride powder as a black pigment. The aluminum nitride powder is added in the same proportion as the aluminum oxide powder. The aluminum content in the black light-shielding film-forming powder described later is 0.01 to 1.0 mass% based on the amount of the aluminum oxide powder or the aluminum nitride powder added.

[ reduction reaction Using metallic magnesium powder ]

The temperature of the reduction reaction with magnesium metal for producing zirconium nitride powder according to the present embodiment is 650 to 900 ℃, preferably 700 to 800 ℃. 650 ℃ is the melting temperature of magnesium metal, and if the temperature is lower than this value, the reduction reaction of zirconium dioxide does not sufficiently occur. Further, even if the temperature is higher than 900 ℃, the effect is not increased, and sintering of particles is not performed while heat energy is wasted. The reduction reaction time is preferably 10 to 90 minutes, and more preferably 15 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 or products do not scatter during the reaction. This is because, when the metal magnesium starts to melt, the reduction reaction proceeds rapidly, and the gas inside the container expands with an increase in temperature, and thus, there is a possibility that the substances inside the container may be scattered to the outside.

[ atmosphere gas in reduction reaction Using metallic magnesium powder ]

The atmosphere in the reduction reaction in the present embodiment is a nitrogen gas atmosphere, a mixed gas atmosphere of nitrogen gas and hydrogen gas, a mixed gas atmosphere of nitrogen gas and ammonia gas, or a nitrogen gas and inert gas atmosphere. Examples of the inert gas include argon, helium, neon, krypton, and xenon. Among these, argon is most preferable. In the case of the mixed gas, in addition to the method of using nitrogen and hydrogen in combination, or using nitrogen and ammonia in combination, or using nitrogen and an inert gas in combination in the above-mentioned reduction reaction, the reduction reaction may be initially carried out in a hydrogen atmosphere, an ammonia atmosphere, or an inert gas atmosphere, and then the reduction reaction may be carried out in an atmosphere of a nitrogen monomer. The reduction reaction is carried out in the gas flow of the mixed gas. The mixed gas has the following functions: preventing the metallic magnesium or reduction products from contacting oxygen, preventing their oxidation, while reacting nitrogen with zirconium to form zirconium nitride.

[ treatment of the calcined reaction product ]

The reaction product obtained by calcining a mixture of zirconium dioxide powder, metallic magnesium powder, magnesium oxide powder, and aluminum oxide powder or aluminum nitride powder in the atmosphere of the above-mentioned mixed gas or nitrogen gas, or in the atmosphere of hydrogen gas, ammonia gas, or inert gas and in the atmosphere of nitrogen gas alone is taken out from the reaction vessel, finally cooled to room temperature, and then washed with an acid solution such as a hydrochloric acid aqueous solution, and magnesium oxide, aluminum oxide, or aluminum nitride contained from the beginning of the reaction is removed in order to prevent sintering of magnesium oxide or a product generated by oxidation of metallic magnesium. Here, the amount of magnesium remaining can be adjusted to 0.01 to 1.0 mass% which is the range of the present invention by adjusting the washing time and the washing pH. The acid washing is preferably carried out at a pH of 0.5 or more, particularly at a pH of 0.7 or more, and at a temperature of 90 ℃ or less. This is due to: if the acidity is too high or the temperature is too high, zirconium nitride may be oxidized. Subsequently, after the acid washing, the pH is adjusted to 5 to 6 with ammonia water or the like, and then the solid is separated by filtration or centrifugal separation, dried and pulverized to obtain a black light-shielding film-forming powder mainly composed of zirconium nitride.

The finally obtained black light-shielding film-forming powder contains magnesium and/or aluminum depending on the amounts of the metallic magnesium powder, the magnesium oxide powder, and the aluminum oxide powder or aluminum nitride powder added. That is, if the amount of each of the metallic magnesium powder and the magnesium oxide powder is large, the black light-shielding film-forming powder contains 0.01 to 1.0 mass% of magnesium. On the other hand, if the respective amounts of the metallic magnesium powder and/or the magnesium oxide powder added are small, the black light-shielding film-forming powder contains no magnesium. Similarly, if the amount of each of the alumina powder and the aluminum nitride powder added is large, the black light-shielding film-forming powder contains 0.01 to 1.0 mass% of aluminum. On the other hand, if the amount of the aluminum oxide powder or the aluminum nitride powder added is small, the black light-shielding film-forming powder contains no aluminum.

< Properties of the obtained black light-shielding film-forming powder >

The black light-shielding film-forming powder obtained in the present embodiment contains zirconium nitride as a main component and magnesium and aluminum. The powder for forming a black light-shielding film has a specific surface area of 20 to 90m as measured by the BET value²(ii) in terms of/g. If the specific surface area of the black light-shielding film-forming powder is less than 20m²When the black resist is formed, the pigment precipitates during long-term storage, and when the concentration exceeds 90m²When a patterned film is formed as a black pigment,/g, the light-shielding property is insufficient. More preferably 25 to 80m²The average particle diameter considered to be spherical can be calculated from the above specific surface area value by the following formula (1). the average particle diameter calculated from the BET specific surface area value is preferably 10 to 50nm in formula (1), L is the average particle diameter: (A), (B), (C), (μm)，ρIs powder density (g/cm)³) S is the specific surface area value (m) of the powder²/g)。

L=6/(ρ×S)　　　　　(1)

The content of magnesium in the case of magnesium is 0.01 to 1.0 mass%, preferably 0.05 to 0.5 mass%, based on 100 mass% of the black light-shielding film-forming powder, and the content of aluminum in the case of aluminum is 0.01 to 1 mass%, preferably 0.05 to 0.5 mass%, based on 100 mass% of the black light-shielding film-forming powder. If the content of magnesium is less than 0.01% by mass, the weather resistance of the black light-shielding film formed when the black light-shielding film is formed as a black pigment cannot be improved, and if it exceeds 1.0% by mass, the content of zirconium nitride decreases, and the light-shielding property is lowered. If the content of aluminum is less than 0.01 mass%, the weather resistance of the black light-shielding film formed when the black light-shielding film is formed as a black pigment cannot be improved, and if it exceeds 1.0 mass%, the light-shielding performance of the black light-shielding film is lowered.

[ method for Forming a patterned film Using Black light-Shielding film-Forming powder as Black pigment ]

A method of forming a patterned film represented by a black matrix using the black light-shielding film-forming powder as a black pigment will be described. First, the black photosensitive composition is prepared by dispersing the black light-shielding film-forming powder in a photosensitive resin. Then, the black photosensitive composition was applied onto a substrate, and then prebaked to evaporate the solvent, thereby forming a photoresist film. Next, the photoresist film is exposed to light through a photomask to form a predetermined pattern shape, and then developed with an alkaline developer to dissolve and remove unexposed portions of the photoresist film, and then post-baked, preferably, to form a predetermined black patterned film, that is, a black light-shielding film.

As an index indicating the light-shielding property (attenuation of transmittance) of the formed patterned film (black light-shielding film), an optical density, that is, an od (optical density) value is known. The patterned film formed using the black light-shielding film-forming powder of the present embodiment has a high OD value. Here, the OD value is a value obtained by logarithmically expressing the degree of absorption of light when passing through the patterned film, and is defined by the following formula (2). In the formula (2), I is the transmitted light amount, and I0 is the incident light amount.

OD value = -log 10(I/I0) (2)

Examples of the substrate include: glass, silicon, polycarbonate, polyester, aramid, polyamideimide, polyimide, and the like. The substrate may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, vapor phase reaction, or vacuum deposition, as desired. Applying a black photosensitive composition to a substrateIn the case of a plate, an appropriate coating method such as spin coating, flow coating, roll coating, etc. can be used. The coating thickness is usually 0.1 to 10% in terms of the film thickness after dryingμm, preferably 0.2 to 7.0μm, more preferably 0.5 to 6.0μAnd m is selected. As the radiation used for forming the patterned film, in the present embodiment, radiation having a wavelength in the range of 250 to 370nm is preferable. The irradiation energy of the radiation is preferably 10 to 10,000J/m². In addition, the alkali developer is preferably sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1, 8-diazabicyclo- [5.4.0]-7-undecene, 1, 5-diazabicyclo- [4.3.0]The development method may be a spray development method, an immersion (immersion) development method, a paddle (liquid-filled) development method, or the like, and the development conditions are preferably 5 to 300 seconds at normal temperature, and the patterned film formed in this manner is suitably used for highly fine liquid crystals, black matrix materials for organic E L, light-shielding materials for image sensors, light-shielding materials for optical parts, light-shielding filters, IR cut-off filters, and the like.