Method for manufacturing cured-film-coated substrate, cured-film-coated substrate, and element comprising cured-film-coated substrate

Abstract

An inexpensive method is realized which does not require a pattern mask to form a patterned cured film. A method for manufacturing a cured-film-coated substrate, the method comprising, in the following order, a step of providing a coating film of a photosensitive resin composition on a substrate having a structure of recesses and protrusions on the surface, a step of drying the coating film to form a dry film, a step of exposing the dry film, a step of partially developing the dry film surface in the film thickness direction after the exposure, and a step of heating the coating film after the development to form a cured film, the method for manufacturing a cured-film-coated substrate characterized in that the attenuation ratio (B) / (A) per 1 μm of dry film thickness, which is the ratio of the total value of spectral irradiance (B) in a wavelength range of 300−450 nm of radiation light that has passed through the dry film to the total value of spectral irradiance (A) in a wavelength range of 300−450 nm of radiation light in the step of exposing the dry film, satisfies the following relational expression (I). (I) 0.001 ≤ (B) / (A) ≤ 0.2

Description

Method for manufacturing a substrate with a cured film, a substrate with a cured film, and an element including the substrate with a cured film

[0001] The present invention relates to a method for producing a cured film-coated substrate, a cured film-coated substrate using the same, and an element equipped with the cured film-coated substrate.

[0002] In recent years, the demand for higher performance displays has been increasing with the development of information terminal devices such as smartphones and tablets, and the increasing resolution of flat panel displays such as televisions. Among these, micro-LED displays, which use micro-sized LEDs, have attracted attention as high-performance displays. These displays use micro-LEDs driven by active matrix methods as light sources to produce full-color images, offering excellent contrast and color reproducibility.

[0003] This micro LED display requires the placement of a patterned cured film (partition wall) that separates the light sources and is sized to correspond to the micro LEDs that serve as the light source. Photolithography using a pattern mask is well known as a method for forming a patterned cured film (Patent Document 1). In addition, these partition walls are required to have light-blocking properties to prevent color mixing between adjacent micro LEDs, as well as reflective properties to efficiently extract light from the micro LEDs.

[0004] Furthermore, as a method for forming these patterned cured films more inexpensively and efficiently, a method has been considered in which a material with excellent flatness is applied to a substrate having an uneven structure such as a micro-LED, and then a part of the coating surface is removed (Patent Documents 2 and 3).

[0005] International Publication No. 2020-8969 Japanese Patent Application Laid-Open No. 2006-66474 Japanese Patent Application Laid-Open No. 2002-14477

[0006] However, when the material described in Patent Document 1 is used, it is difficult to selectively remove unnecessary portions of the coating film surface. Furthermore, the methods described in Patent Documents 2 and 3 require a pattern mask, making it difficult to inexpensively and efficiently form a patterned cured film.

[0007] Therefore, an object of the present invention is to form a patterned cured film by forming a coating film that flattens the convex structures on a substrate having an uneven surface, and then removing unnecessary coating film from the coating film surface to expose the surfaces of the convex structures, using an inexpensive method that does not require a pattern mask.

[0008] In order to solve the above problems, the present invention has the following configuration: [1] A method for producing a substrate with a cured film, comprising the steps of providing a coating film of a photosensitive resin composition on a substrate having a textured surface, drying the coating film to form a dry film, exposing the dried film to light, partially developing the exposed surface of the dried film in the film thickness direction, and heating the developed coating film to form a cured film, in this order, wherein the attenuation ratio (B) / (A) per μm of dry film thickness satisfies the following relationship (I): 0.001≦(B) / (A)≦0.2 (I) [2] The method for producing a substrate with a cured film according to [1], wherein the radiation in the exposing the dried film does not substantially contain light with a wavelength of 400 nm or more.

[0009] [3] The method for producing a cured film-coated substrate according to [1] or [2], wherein the radiation light used in the step of exposing the dried film includes at least light having a wavelength of 365±5 nm or 385±10 nm at which the illuminance is maximized.

[0010] [4] The method for producing a substrate with a cured film according to any one of [1] to [3], further comprising a step of post-exposing the developed coating film before heating it.

[0011] [5] The method for producing a cured film-coated substrate according to [4], wherein in the step of post-exposing the developed coating film, a sum (C) of the spectral irradiance of the radiation to which the developed coating film is post-exposed in a wavelength range of 300 nm to 450 nm and a sum (D) of the spectral irradiance of the radiation that has passed through the developed coating film in a wavelength range of 300 nm to 450 nm are such that an attenuation ratio (D) / (C) per μm of dry film thickness satisfies the following relational formula (II):

[0012] 0.05≦(D) / (C)≦0.99 (II) [6] The method for producing a substrate with a cured film according to any one of [1] to [5], wherein the photosensitive resin composition contains (E) a resin, (F) a pigment, and (G) a naphthoquinone diazide compound.

[0013] [7] The method for producing a substrate with a cured film according to [6], wherein the resin (E) is polysiloxane.

[0014] [8] The method for producing a substrate with a cured film according to [6] or [7], wherein the pigment (F) is a white pigment (F-1) having a median diameter of 0.1 to 0.6 μm.

[0015] [9] The method for producing a cured film-coated substrate according to any one of [1] to [8], wherein the substrate has a concave-convex structure on its surface, and the convex structures on the substrate have LEDs.

[0016]

[10] A substrate with a cured film produced by the method according to any one of [1] to [9].

[0017]

[11] The substrate with a cured film according to

[10] , wherein the cured film has an absorbance per 10 μm of film thickness at a wavelength of 365 nm of 1.0 to 4.0, an absorbance per 10 μm of film thickness at a wavelength of 405 nm of 0.5 to 2.0, an absorbance per 10 μm of film thickness at a wavelength of 436 nm of 0.5 to 2.0, and an absorbance per 10 μm of film thickness at a wavelength of 450 nm of 0.5 to 2.0.

[0018]

[12] The substrate with a cured film according to

[10] or

[11] , wherein the cured film has a reflectance of 20 to 80% per 10 μm of film thickness at a wavelength of 550 nm.

[0019]

[13] The substrate with a cured film according to any one of

[10] to

[12] , wherein the cured film has an arithmetic mean surface roughness of 0.005 μm to 0.1 μm.

[0020]

[14] An image display device having the substrate with the cured film according to any one of

[10] to

[13] .

[0021]

[15] A substrate having an LED and a cured film having light-shielding properties on a substrate, wherein the cured film having light-shielding properties is in contact with and integrated with the side surface of the LED without any gaps, and wherein the cured film has an absorbance per 10 μm of film thickness at a wavelength of 365 nm of 1.0 to 4.0, an absorbance per 10 μm of film thickness at a wavelength of 405 nm of 0.5 to 2.0, an absorbance per 10 μm of film thickness at a wavelength of 436 nm of 0.5 to 2.0, an absorbance per 10 μm of film thickness at a wavelength of 450 nm of 0.5 to 2.0, and a reflectance per 10 μm of film thickness at a wavelength of 550 nm of 20 to 80%.

[0022] The method for producing a cured film-coated substrate described in the Summary of the Invention makes it possible to inexpensively produce a patterned cured film that separates convex structures, such as micro-LEDs, on a textured substrate having convex structures on its surface. That is, by applying a material with excellent flatness and partially developing the coating surface, it becomes possible to form barriers that separate the micro-LEDs.

[0023] A top view of a substrate having a concave-convex structure on which a pattern is formed on a base substrate. A cross-sectional ... state in which a coated film of a photosensitive resin composition is formed on a substrate having a concave-convex structure. A cross-sectional view of a state in which a dried film of a photosensitive resin composition is formed on a substrate having a concave-convex structure. A cross-sectional view of a state in which the surface of the dried film of a photosensitive resin composition formed on a substrate having a concave-convex structure is partially developed in the film thickness direction. A cross-sectional view of a state in which a cured film of a photosensitive resin composition is formed on a substrate having a concave-convex structure.

[0024] Hereinafter, preferred embodiments of the method for producing a cured film-coated substrate according to the present invention will be specifically described. However, the present invention is not limited to the following embodiments, and can be practiced with various modifications depending on the purpose and application.

[0025] The method for producing a cured film-coated substrate of the present invention comprises the steps of providing a coating film of a photosensitive resin composition on a substrate having a textured surface, drying the coating film to form a dry film, exposing the dried film to light, partially developing the exposed dry film surface in the thickness direction, and heating the developed coating film to form a cured film, in this order, and is characterized in that the attenuation ratio (B) / (A) per μm of dry film thickness satisfies the following relationship (I): 0.001≦(B) / (A)≦0.2 (I) The substrate having a textured surface functions as a support for the cured film-coated substrate, and by providing a coating film of the photosensitive resin composition on the substrate, it is possible to form a coating film that flattens the textured structure. Subsequently, the coated film is dried to obtain a dried film with improved flatness and film thickness uniformity. In the subsequent step of exposing the dried film, the combined spectral irradiance (A) of the radiation in the wavelength range of 300 nm to 450 nm and the combined spectral irradiance (B) of the radiation transmitted through the dried film in the wavelength range of 300 nm to 450 nm are exposed so that the attenuation ratio (B) / (A) per μm of dry film thickness satisfies the above-mentioned formula (I). This allows most of the light to be absorbed on the surface of the dried film, thereby selectively reacting the photosensitizer in that area.

[0026] Furthermore, by developing the dried film after exposure, it is possible to partially develop the surface of the dried film where the photosensitizer has reacted in the film thickness direction.Finally, by heating the developed coating film to form a cured film, it is possible to further improve the film reliability such as light resistance.

[0027] <Substrate having a concave-convex structure on its surface> The concave-convex structure referred to here refers to, for example, the concave-convex structure shown in Figures 1 and 2. Figure 1 is a top view of a substrate having a concave-convex structure on its surface, and Figure 2 is a cross-sectional view taken along line A-A' in Figure 1. The pattern portions 1 are convex portions, and the openings of the pattern, i.e., the portions where the underlying substrate 2 is exposed, are concave portions.

[0028] In addition, examples of substrates having a concave-convex structure on the surface include substrates having convex structures such as micro-LEDs, wiring, and insulating films formed on a base substrate such as a silicon substrate, glass plate, resin plate, or resin film. The glass plate is preferably made of alkali-free glass. The resin plate and resin film are preferably made of polyester, (meth)acrylic polymer, transparent polyimide, polyethersulfone, or the like. The thickness of the glass plate and resin plate is preferably 1 mm or less, and more preferably 0.8 mm or less. The thickness of the resin film is preferably 100 μm or less.

[0029] <Step of Providing a Coating Film of Photosensitive Resistive Resin Composition> Examples of the step of forming a coating film of the photosensitive resin composition on a substrate having a textured surface include methods such as microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, and slit coating. Among these, spin coating and slit coating are preferred from the viewpoint of improving film flatness. Figure 3 is a schematic diagram showing a state in which a coating film of the photosensitive resin composition has been formed on a substrate having a textured surface.

[0030] <Step of drying the coated film to form a dry film> Examples of the step of drying the coated film to form a dry film include a method using a heating device such as a hot plate, a vacuum hot plate, or an oven. The drying temperature is preferably 50 to 110°C, and the drying time is preferably 30 seconds to 30 minutes. Figure 4 shows a schematic diagram of a state in which a dry film of the photosensitive resin composition has been formed on a substrate having a textured structure.

[0031] <Step of Exposing the Dried Film> In the step of exposing the dried film, the combined spectral irradiance (A) of the radiation in the wavelength range of 300 nm to 450 nm and the combined spectral irradiance (B) of the radiation transmitted through the dried film in the wavelength range of 300 nm to 450 nm are exposed so that the attenuation ratio (B) / (A) per μm of dry film thickness satisfies the above-mentioned relationship (I). From the viewpoint of decomposing the photosensitizer on the surface of the dried film with a small amount of exposure and improving mass productivity, the attenuation ratio (B) / (A) per μm of dry film thickness is preferably 0.001 or more, more preferably 0.005 or more. On the other hand, from the viewpoint of absorbing most of the light at the surface of the dried film and selectively decomposing the photosensitive material, the attenuation ratio (B) / (A) per μm of dry film thickness is preferably 0.2 or less, more preferably 0.15 or less.

[0032] The spectral irradiance of the radiation in the present invention is measured using a spectral irradiance meter. The total value (A) of the spectral irradiance of the radiation in the wavelength range of 300 nm to 450 nm in the step of exposing the dry film can be calculated by adding up the spectral irradiance of each wavelength measured with the spectral irradiance meter. Furthermore, the total value (B) of the spectral irradiance of the radiation in the wavelength range of 300 nm to 450 nm that has passed through the dry film can be calculated by measuring the radiation that has passed through the dry film in the same manner as above and adding up the spectral irradiance of each wavelength.

[0033] In the present invention, the film thickness refers to the thickness of the film in the direction perpendicular to the substrate (height direction). In the schematic diagram of the substrate with a dry film shown in Figure 4, the film thickness of the dry film is represented by the symbol H. As will be described later, the film thickness of the dry film is preferably 1 to 20 µm.

[0034] Examples of exposure devices include a stepper, a mirror projection mask aligner (MPA), a parallel light mask aligner (PLA), and an LED irradiation device. Examples of exposure light sources include a high-pressure mercury lamp, a laser, an ultraviolet LED, and a violet LED. It is preferable to use a light source that emits light with a wavelength such that the attenuation ratio of the spectral irradiance per 1 μm of film thickness in the dried film state satisfies the above-mentioned relational expression (I). Furthermore, it is preferable to control the wavelength of the emitted light by installing a wavelength-selective filter or the like that cuts off wavelengths below a specific wavelength between the exposure light source and the object to be exposed. It is more preferable that the emitted light is substantially free of light with a wavelength of 400 nm or more. "Substantially free" here means that the sum of the spectral irradiance of emitted light with wavelengths of 400 nm or more is negligibly small compared to the sum of the spectral irradiance of emitted light with wavelengths of 400 nm or less, and can be treated as non-existent. A more preferable condition is that the sum of the spectral irradiance of emitted light with wavelengths of 400 nm to 450 nm is 2.5% or less of the sum of the spectral irradiance of emitted light with wavelengths of 300 nm to 400 nm. Furthermore, a preferable condition is that the sum of the spectral irradiances of the emitted light at wavelengths of 400 nm to 450 nm is 1.0% or less of the sum of the spectral irradiances at wavelengths of 300 nm to 400 nm.

[0035] <Step of Partially Developing the Surface of the Exposed Dry Film in the Film Thickness Direction> Examples of the step of developing the exposed dried film to partially develop the surface of the dried film in the film thickness direction include development techniques such as showering, dipping, and puddling. The immersion time in the developer is preferably 5 seconds to 5 minutes. Examples of the developer include alkaline developers such as aqueous solutions containing inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates, and borates, amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine, and quaternary ammonium salts such as tetramethylammonium hydroxide and choline. After development, rinsing with water is preferred. Figure 5 shows a cross-sectional view of a state in which the surface of a dried film of a photosensitive resin composition formed on a substrate having a textured structure has been partially developed in the film thickness direction.

[0036] <Step of Post-exposing the Developed Coating Film Before Heating> In the step of post-exposing the developed coating film before heating, it is preferred to perform post-exposure so that the attenuation ratio (D) / (C) per μm of the developed coating film satisfies the relational formula (II) for the sum (C) of the spectral irradiance of radiation in the wavelength region of 300 nm to 450 nm and the sum (D) of the spectral irradiance of radiation that has passed through the developed coating film in the wavelength region of 300 nm to 450 nm.

[0037] 0.05≦(D) / (C)≦0.99 (II) In the step of post-exposing the developed coating film before heating, it is preferred that the post-exposure be carried out so that the attenuation ratio (D) / (C) per μm of film thickness of the developed coating film satisfies the above-mentioned relational expression (II) with respect to the sum (C) of the spectral irradiance of the post-exposed radiation in the wavelength region of 300 nm to 450 nm and the sum (D) of the spectral irradiance of the radiation that has passed through the developed coating film in the wavelength region of 300 nm to 450 nm. From the viewpoint of decomposing the photosensitizer in the developed coating film with a small amount of exposure and improving mass productivity, the attenuation ratio (D) / (C) per μm of film thickness of the developed coating film is preferably 0.05 or more, more preferably 0.10 or more, and even more preferably 0.15 or more. On the other hand, when the coating film is made to function as a partition wall of an LED, from the viewpoint of blocking light from the LED, the attenuation ratio (D) / (C) per 1 μm of coating film thickness is preferably 0.99 or less, and more preferably 0.70 or less.

[0038] The spectral irradiance in the present invention is measured using a spectral irradiance meter. In the step of post-exposing the developed coating film, the total value (C) of the spectral irradiance in the wavelength region of 300 nm to 450 nm of radiation can be calculated by summing the spectral irradiance of each wavelength. Furthermore, the total value (D) of the spectral irradiance in the wavelength region of 300 nm to 450 nm of radiation that has passed through the developed coating film can be calculated by measuring the spectral irradiance of each wavelength of radiation that has passed through the dried film in the same manner as above.

[0039] In the present invention, the film thickness refers to the length in the direction perpendicular to the substrate (height direction). In the cross-sectional view of the coating film after development shown in Figure 5, the film thickness of the coating film after development is represented by the symbol H. As will be described later, the film thickness of the coating film after development is preferably 1 to 20 µm.

[0040] Examples of exposure devices include a stepper, a mirror projection mask aligner (MPA), a parallel light mask aligner (PLA), and an LED irradiation device. Examples of exposure light sources include a high-pressure mercury lamp, a laser, a purple LED, and a blue LED. However, it is preferable to use a light source that emits light of a wavelength such that the attenuation ratio of the spectral irradiance per 1 μm of film thickness in the coating film state after development satisfies the above-mentioned relational formula (II). It is also preferable to install a wavelength-selective filter or the like that cuts out wavelengths other than a specific wavelength between the exposure light source and the object to be exposed, thereby controlling the wavelength of the emitted light.

[0041] <Step of Heating the Developed Coating Film to Form a Cured Film> Examples of the step of heating the developed coating film to form a cured film include methods using a hot plate, oven, etc. The heat curing temperature is preferably 60 to 230°C, and the heat curing time is preferably about 15 minutes to 2 hours. By heating the post-exposed coating film to form a cured film, the crosslinking reaction of the resin progresses, improving the reliability of the cured film. This is also preferable because the coating film flows when heated, improving the smoothness of the cured film. Figure 6 shows a cross-sectional view of a cured film of a photosensitive resin composition formed on a substrate having an uneven structure.

[0042] <Photosensitive Resin Composition> The photosensitive resin composition of the present invention preferably contains a (E) resin, a (F) pigment, and a (G) naphthoquinone diazide compound. The (E) resin has the function of improving the crack resistance and light resistance of the coating film. The (F) pigment has the function of improving the light-blocking properties of the coating film, and the (G) naphthoquinone diazide compound provides positive photosensitivity in which exposed areas are removed by a developer.

[0043] (E) Resin Examples of the (E) resin include polysiloxane, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, (meth)acrylic polymer, etc. Two or more of these may be contained. Among these, polysiloxane is preferred because of its excellent light resistance and film flatness.

[0044] The polysiloxane in the present invention is a hydrolysis / dehydration condensation product of organosilane, and in the present invention, it preferably contains a total of 20 to 60 mol % of repeating units represented by the following general formula (1): By containing a total of 20 to 60 mol % of repeating units represented by general formula (1) in the polysiloxane, the polysiloxane can be easily miscible with other components, making it possible to improve the flatness of the coating film.

[0045]

[0046] (R １ represents an aryl group having 6 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms in which all or part of the hydrogen atoms have been substituted. The content ratio of organosilane units having a repeating unit represented by general formula (1) is ２９ This can be determined by Si-NMR measurement, i.e., by calculating the ratio of the integrated value of Si derived from organosilane units having repeating units represented by general formula (1) to the integrated value of all Si derived from the organosilane.

[0047] Each repeating unit represented by the general formula (1) is derived from an alkoxysilane compound represented by the following general formula (2). That is, a polysiloxane containing a repeating unit represented by the general formula (1) can be obtained by hydrolyzing and polycondensing a plurality of alkoxysilane compounds, including an alkoxysilane compound represented by the following general formula (2). Other alkoxysilane compounds may also be used.

[0048]

[0049] In the above general formula (2), R １are R in general formula (1), respectively. １ represents the same group as ２ may be the same or different and represent a monovalent organic group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms.

[0050] Examples of organosilane compounds represented by general formula (2) include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrippropoxysilane, naphthyltrimethoxysilane, naphthyltriethoxysilane, naphthyltrippropoxysilane, etc. Two or more of these may be used.

[0051] Examples of organosilane compounds other than those represented by general formula (2) include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-(N,N-glycidyl)aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, thoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltripropoxysilane, 2-(3,4-epoxycyclohexyl)ethyltributoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltriethoxysilane, 4-(3,4-epoxycyclohexyl)butyltrimethoxysilane, 4-(3,4-epoxycyclohexyl)butyltrimethoxysilane,4-epoxycyclohexyl)butyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropylmethyldimethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, glycidoxypropylmethyldimethoxysilane, glycidoxypropylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, octadecylmethyldimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-triphenoxysilylpropylsuccinic anhydride, 3-trimethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-trimethoxysilylpropylphthalic anhydride, and the like. Two or more of these may be used.

[0052] From the viewpoint of coating properties, the weight average molecular weight (Mw) of the polysiloxane is preferably 1,000 or more, and more preferably 2,000 or more. On the other hand, from the viewpoint of developability, the Mw of the polysiloxane is preferably 50,000 or less, and more preferably 20,000 or less. Here, the Mw of the polysiloxane in the present invention refers to the polystyrene equivalent value measured by gel permeation chromatography (GPC).

[0053] In the photosensitive resin composition of the present invention, the content of polysiloxane can be set arbitrarily depending on the desired film thickness and application, but is preferably 10 to 80% by weight of the solid content of the photosensitive resin composition.

[0054] Polysiloxanes can be obtained by hydrolyzing the aforementioned organosilane compound and then subjecting the hydrolyzate to a dehydration condensation reaction in the presence or absence of a solvent. Various conditions for the hydrolysis can be set to suit the physical properties appropriate for the intended application, taking into account factors such as the reaction scale and the size and shape of the reaction vessel. Examples of the various conditions include acid concentration, reaction temperature, and reaction time. Acid catalysts that can be used for the hydrolysis reaction include hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acids or their anhydrides, and ion exchange resins. Among these, acidic aqueous solutions containing formic acid, acetic acid, and / or phosphoric acid are preferred.

[0055] When an acid catalyst is used in the hydrolysis reaction, the amount of acid catalyst added is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, relative to 100 parts by weight of the total alkoxysilane compounds used in the hydrolysis reaction, from the viewpoint of proceeding hydrolysis more rapidly. On the other hand, from the viewpoint of appropriately adjusting the progress of the hydrolysis reaction, the amount of acid catalyst added is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, relative to 100 parts by weight of the total alkoxysilane compounds. Here, the amount of all alkoxysilane compounds refers to the amount including all of the alkoxysilane compounds, their hydrolysates, and their condensates, and the same applies hereinafter.

[0056] The hydrolysis reaction can be carried out in a solvent. The solvent can be appropriately selected taking into consideration the stability, wettability, volatility, etc. of the photosensitive resin composition. Examples of the solvent include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, and diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; Examples of suitable solvents include ethers such as diethyl ether; ketones such as methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, and 2-heptanone; amides such as dimethylformamide and dimethylacetamide; acetates such as ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, and butyl lactate; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, and cyclohexane; and γ-butyrolactone, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. Two or more of these may be used.

[0057] Among these, from the viewpoint of light resistance of the cured film and the like, diacetone alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, γ-butyrolactone, and the like are preferably used.

[0058] When a solvent is produced by the hydrolysis reaction, it is also possible to carry out the hydrolysis without a solvent. After the hydrolysis reaction is completed, it is also preferable to add a solvent to adjust the concentration to an appropriate level for the photosensitive resin composition. Alternatively, after the hydrolysis, all or part of the produced alcohol, etc. can be distilled and removed by heating and / or under reduced pressure, and then a suitable solvent can be added.

[0059] When a solvent is used in the hydrolysis reaction, the amount of solvent added is preferably 50 parts by weight or more, more preferably 80 parts by weight or more, per 100 parts by weight of all alkoxysilane compounds, from the viewpoint of suppressing gel formation. On the other hand, the amount of solvent added is preferably 500 parts by weight or less, more preferably 200 parts by weight or less, per 100 parts by weight of all alkoxysilane compounds, from the viewpoint of promoting hydrolysis more rapidly. Furthermore, ion-exchanged water is preferred as the water used in the hydrolysis reaction. The amount of water can be set as desired, but is preferably 1.0 to 4.0 moles per mole of all alkoxysilane compounds.

[0060] Examples of methods for the dehydration condensation reaction include heating the silanol compound solution obtained by the hydrolysis reaction of the organosilane compound as is. The heating temperature is preferably 50°C or higher and the boiling point of the solvent or lower, and the heating time is preferably 1 to 100 hours. Furthermore, reheating or the addition of a base catalyst may be performed to increase the degree of polymerization of the polysiloxane. Depending on the purpose, after hydrolysis, an appropriate amount of the produced alcohol may be distilled and removed by heating and / or under reduced pressure, followed by the addition of a suitable solvent.

[0061] From the viewpoint of storage stability of the photosensitive resin composition, it is preferable that the polysiloxane solution after hydrolysis and dehydration condensation does not contain the catalyst, and the catalyst can be removed as necessary. From the viewpoint of ease of operation and removability, preferred catalyst removal methods include washing with water and treatment with an ion exchange resin. Water washing is a method in which the polysiloxane solution is diluted with an appropriate hydrophobic solvent, and then washed several times with water to obtain an organic layer, which is then concentrated using an evaporator or the like. Ion exchange resin treatment is a method in which the polysiloxane solution is brought into contact with an appropriate ion exchange resin.

[0062] (F) Pigment Examples of the (F) pigment include (F-1) white pigment and (F-2) black pigment, and it is preferable to contain at least one of them. By containing the (F-1) white pigment and (F-2) black pigment, the light-blocking properties of the cured film can be improved. Furthermore, by containing the (F-1) white pigment, the reflectivity of the cured film can be improved, which is more preferable.

[0063] Examples of the (F-1) white pigment include titanium dioxide, zirconium oxide, aluminum oxide, talc, mica, white carbon, magnesium oxide, zinc oxide, barium carbonate, and compounds selected from composite compounds thereof. Two or more of these may be contained. Among these, it is preferable to contain titanium dioxide, which has high reflectivity and is easy to use industrially. The crystal structure of titanium dioxide is classified into anatase type, rutile type, and brookite type. Among these, rutile type titanium oxide is preferred because of its low photocatalytic activity.

[0064] The white pigment (F-1) may be surface-treated. Surface treatment with Al, Si, and / or Zr is preferred, as this improves the dispersibility of the white pigment (F-1) in the photosensitive resin composition and further improves the light resistance of the cured film. From the viewpoint of improving reflectivity, the median diameter of the white pigment (F-1) is preferably 0.2 to 5.0 μm, more preferably 0.2 to 0.6 μm. Here, the median diameter refers to the average particle diameter of the pigment (F) calculated from the particle size distribution measured by laser diffraction.

[0065] (F-1) Titanium dioxide used as a white pigment includes, for example, R960 manufactured by DuPont (SiO ２ / Al ２ O ３ surface treatment, median diameter 0.21 μm), CR-97; Ishihara Sangyo Kaisha, Ltd. (Al ２ O ３ / ZrO ２ surface treatment, median diameter 0.25 μm), JR-405; manufactured by Teika Co., Ltd. (Al ２ O ３ Surface treatment, median diameter 0.21 μm), JR-600A; Teika Co., Ltd. (Al ２ O ３ Surface treatment, median diameter 0.25 μm), JR-603; Teika Co., Ltd. (Al ２ O ３ / ZrO ２ Examples of zirconia include 3YI-R manufactured by Toray Industries, Inc. (Al ２ O ３ surface treatment, median system 0.50 μm).

[0066] The content of the white pigment (F-1) in the photosensitive resin composition of the present invention is preferably 10% by weight or more, more preferably 20% by weight or more, of the solid content from the viewpoint of further improving the reflectance, while the content of the white pigment (F-1) in the photosensitive resin composition of the present invention is preferably 80% by weight or less, more preferably 60% by weight or less, of the solid content from the viewpoint of improving the flatness of the coating film.

[0067] Examples of black pigments (F-2) include black organic pigments, mixed-color organic pigments, and black inorganic pigments. Examples of black organic pigments include carbon black, perylene black, aniline black, and benzofuranone-based pigments. These may be coated with a resin. Examples of mixed-color organic pigments include pseudo-black pigments obtained by mixing two or more pigments, such as red, blue, green, purple, yellow, magenta, and / or cyan. Among these, a mixed pigment of a red pigment and a blue pigment is preferred from the viewpoint of achieving both a moderately high OD value and pattern processability. The weight ratio of the red pigment to the blue pigment is preferably 20 / 80 to 80 / 20, and more preferably 30 / 70 to 70 / 30. Specific examples of representative pigments, expressed by Color Index (CI) numbers, include the following: Examples of red pigments include Pigment Red (hereinafter abbreviated as PR) 9, PR48, PR97, PR122, PR123, PR144, PR149, PR166, PR168, PR177, PR179, PR180, PR192, PR209, PR215, PR216, PR217, PR220, PR223, PR224, PR226, PR227, PR228, PR240, and PR254. Two or more of these pigments may be contained. Examples of blue pigments include Pigment Blue (hereinafter abbreviated as PB) 15, PB15:3, PB15:4, PB15:6, PB22, PB60, and PB64. Two or more of these pigments may be contained. Examples of black inorganic pigments include graphite; fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, gold, platinum, and palladium; metal oxides; metal composite oxides; metal sulfides; metal nitrides; metal oxynitrides; and metal carbides. Two or more of these may be contained. Among these black pigments, titanium nitride, zirconium nitride, carbon black, palladium oxide, platinum oxide, gold oxide, silver oxide, and mixed pigments of red pigment and blue pigment in a weight ratio of 20 / 80 to 80 / 20 are preferred due to their high light-blocking properties. The content of the black pigment is preferably 0.2 wt % or more, and more preferably 0.5 wt % or more, from the viewpoint of adjusting reflectance and optical density to suppress color mixing of light in adjacent pixels.On the other hand, from the viewpoint of adjusting the reflectance and OD, the content of the black pigment is preferably 5% by weight or less, and more preferably 3% by weight or less.

[0068] (G) Naphthoquinonediazide Compounds (G) Naphthoquinonediazide compounds include, for example, compounds in which a sulfonic acid of naphthoquinonediazide is bonded to a compound having a phenolic hydroxyl group via an ester bond.

[0069] The naphthoquinone diazide compound (G) used is not particularly limited, but is preferably a compound in which a sulfonic acid of naphthoquinone diazide is bonded to a compound having a phenolic hydroxyl group via an ester bond. Examples of the compound having a phenolic hydroxyl group used herein include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (tetrakisP-DO-BPA), TrisP-HAP, TrisP-PA, BisOFP-Z, BisRS-2P, BisPG-26X, and BisRS. -3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T-OCHP, methylenetrith-FR-CR, BisRS-26X, BisRS-OCHP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (all trade names, manufactured by Asahi Organic Chemicals Industry Co., Ltd.), 4,4'-sulfonyldiphenol (manufactured by Wako Pure Chemical Industries Co., Ltd.), BPFL (trade name, manufactured by JFE Chemical Corporation).

[0070] Of these, preferred examples of compounds having a phenolic hydroxyl group include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F. Among these, particularly preferred compounds having a phenolic hydroxyl group include, for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR-BIPC-F, 4,4'-sulfonyldiphenol, and BPFL. Preferred examples include compounds having a phenolic hydroxyl group to which 4-naphthoquinone diazide sulfonic acid has been introduced via an ester bond, but other compounds can also be used.

[0071] The molecular weight of the naphthoquinone diazide compound (G) is preferably 300 to 1500, more preferably 350 to 1200. By setting the molecular weight to 300 or more, the effect of inhibiting dissolution of unexposed areas can be obtained. Furthermore, by setting the molecular weight to 1500 or less, a good relief pattern free of scum and the like can be obtained.

[0072] These (G) naphthoquinone diazide compounds may be used alone or in combination of two or more. The content of these (G) naphthoquinone diazide compounds is preferably 1 to 30 parts by weight relative to the (E) resin. By using 1 part by weight or more, processing can be performed with practical sensitivity. Furthermore, by using 30 parts by weight or less, a photosensitive resin composition with excellent light resistance can be obtained. Furthermore, when a (G) naphthoquinone diazide compound is added, unreacted photosensitizer may remain in the unexposed area, which may cause discoloration of the film after heat curing. In order to obtain a cured film with little discoloration, it is preferable to irradiate the developed coating film with ultraviolet light and then heat it.

[0073] The photosensitive resin composition of the present invention may further contain, as necessary, a crosslinking agent, an adhesion improver, a solvent, a surfactant, a dissolution inhibitor, a stabilizer, an antifoaming agent, etc. By including a crosslinking agent in the photosensitive resin composition of the present invention, crosslinking of the polysiloxane is promoted during thermal curing, resulting in a high degree of crosslinking in the cured film. Examples of curing agents include nitrogen-containing organic compounds, silicone resin curing agents, isocyanate compounds and polymers thereof, methylolated melamine derivatives, methylolated urea derivatives, various metal alcoholates, various metal chelate compounds, thermal acid generators, and photoacid generators. Two or more of these may be contained. Among these, methylolated melamine derivatives and methylolated urea derivatives are preferably used from the viewpoint of curing agent stability, etc.

[0074] By including an adhesion improver in the photosensitive resin composition of the present invention, adhesion to the substrate can be improved, and a highly reliable cured film can be obtained. Examples of adhesion improvers include alicyclic epoxy compounds and silane coupling agents. Among these, silane coupling agents are preferred because they have high heat resistance and can further suppress color change after heating.

[0075] Examples of silane coupling agents include (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltripropoxysilane, 2-(3,4-epoxycyclohexyl)ethyltributoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltriethoxysilane, 4-(3,4-epoxycyclohexyl)butyltrimethoxysilane, and 4-(3,4-epoxycyclohexyl)butyltriethoxysilane. Two or more of these may be used.

[0076] The content of the adhesion promoter in the photosensitive resin composition of the present invention is preferably 0.1 wt % or more, more preferably 1 wt % or more, of the solid content from the viewpoint of further improving adhesion to the substrate, while the content of the adhesion promoter is preferably 20 wt % or less, more preferably 10 wt % or less, of the solid content from the viewpoint of further suppressing color change due to heating.

[0077] By including a solvent in the photosensitive resin composition of the present invention, the viscosity can be easily adjusted to a level suitable for application, thereby improving the uniformity of the coating film. It is preferable to combine a solvent having a boiling point of more than 150°C and not more than 250°C at atmospheric pressure with a solvent having a boiling point of 150°C or less. By including a solvent having a boiling point of more than 150°C and not more than 250°C, the solvent volatilizes appropriately during application, allowing the coating film to dry more rapidly, thereby preventing coating unevenness and improving film thickness uniformity. Furthermore, by including a solvent having a boiling point of not more than 150°C at atmospheric pressure, the solvent can be prevented from remaining in the cured film of the present invention, as described below. From the viewpoint of preventing the solvent from remaining in the cured film and improving chemical resistance and adhesion over a long period of time, it is preferable to include a solvent having a boiling point of not more than 150°C at atmospheric pressure in an amount of 50% by weight or more of the total solvent.

[0078] Examples of solvents having a boiling point of 150°C or less under atmospheric pressure include ethanol, isopropyl alcohol, 1-propyl alcohol, 1-butanol, 2-butanol, isopentyl alcohol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, methoxymethyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, 1-methoxypropyl-2-acetate, acetol, acetylacetone, methyl isobutyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl lactate, toluene, cyclopentanone, cyclohexane, normal heptane, benzene, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, and 5-hydroxy-2-pentanone. Two or more of these may be used.

[0079] Examples of solvents having a boiling point under atmospheric pressure of more than 150 ° C. and not more than 250 ° C. include ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-tert-butyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, 2-ethoxyethyl acetate, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, 3-ethoxyethyl propionate, propylene glycol monomethyl ether propionate, dipropylene glycol methyl ether, diisobutyl ketone, diacetone alcohol, ethyl lactate, butyl lactate, dimethylformamide, dimethylacetamide, γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, cycloheptanone, diethylene glycol monobutyl ether, and ethylene glycol dibutyl ether. Two or more of these may be used.

[0080] The content of the solvent can be set arbitrarily depending on the application method, etc. For example, when forming a film by spin coating, the content of the solvent in the photosensitive resin composition is generally set to 50% by weight or more and 95% by weight or less.

[0081] By including a surfactant in the photosensitive resin composition of the present invention, flow properties during application can be improved. Examples of surfactants include fluorine-based surfactants such as "Megafac" (registered trademark) F142D, F172, F173, F183, F445, F470, F475, and F477 (all trade names, manufactured by Dainippon Ink and Chemicals, Inc.), and NBX-15 and FTX-218 (all trade names, manufactured by Neos Corporation); silicone-based surfactants such as "Disperbyk" (registered trademark) 333, 301, 331, 345, and 207 (all trade names, manufactured by BYK-Chemie Co., Ltd.); polyalkylene oxide-based surfactants; and poly(meth)acrylate-based surfactants. Two or more of these surfactants may be included.

[0082] The solid content concentration of the photosensitive resin composition of the present invention can be set arbitrarily depending on the application method, etc. For example, when forming a film by spin coating as described below, the solid content concentration is generally set to 5 wt % or more and 50 wt % or less.

[0083] Next, a method for producing the photosensitive resin composition of the present invention will be described. The photosensitive resin composition of the present invention can be obtained by mixing the above-mentioned components (E) to (G) and, if necessary, other components. More specifically, for example, a method can be used in which the (E) resin, the (G) naphthoquinone diazide compound, and, if necessary, other additives are added to an arbitrary solvent and dissolved by stirring, and then the (F) pigment is added, and the mixture is further stirred for 20 minutes to 3 hours, and the resulting solution is filtered.

[0084] Next, the dry film of the present invention will be described. The dry film of the present invention is formed by drying a coating film of the photosensitive resin composition of the present invention described above. The film thickness of the dry film of the present invention is preferably 1 to 20 μm. By making the film thickness of the dry film 1 μm or more, the film flatness of the uneven structure can be improved, which is preferable. Furthermore, by making the film thickness of the dry film 20 μm or less, the film uniformity of the dry film can be improved, which is preferable.

[0085] Next, the cured film of the present invention will be described. The cured film of the present invention is composed of a cured product of the photosensitive resin composition of the present invention described above. The film thickness of the cured film is preferably 1 to 20 μm. Furthermore, the absorbance per 10 μm of the cured film at a wavelength of 365 nm is preferably 1.0 to 4.0, the absorbance per 10 μm of the cured film at a wavelength of 405 nm is preferably 0.5 to 2.0, the absorbance per 10 μm of the cured film at a wavelength of 436 nm is preferably 0.5 to 2.0, and the absorbance per 10 μm of the cured film at a wavelength of 450 nm is preferably 0.5 to 2.0. Setting the absorbance of the cured film within the above range is preferable because it allows the manufacturing method of the cured film-coated substrate of the present invention to be applied. Furthermore, when the cured film of the present invention is used as a partition wall of a micro-LED, it is necessary to sufficiently block the emitted color of adjacent micro-LEDs and avoid color mixing. Setting the absorbance within the above range is preferable because it allows for good light-blocking properties to be obtained. When the cured film of the present invention is used as a partition wall of a micro LED, a reflectance of 20% or more is preferable, since it enables the cured film to reflect light emitted from the micro LED and improve the light extraction efficiency, and a reflectance of 50% or more is more preferable, and a reflectance of 60% or more is even more preferable. On the other hand, a reflectance of 80% or less is preferable, since it enables the efficient use of light irradiated when post-exposing the coating film after development, and a reflectance of 70% or less is more preferable.

[0086] Furthermore, the arithmetic mean surface roughness of the cured film is preferably 0.005 μm to 0.1 μm. By making the arithmetic mean surface roughness of the cured film 0.005 μm or more, it is possible to improve the adhesion between the cured film of the present invention and an upper layer film formed in a later step, which is preferable. Furthermore, by making the arithmetic mean surface roughness of the cured film 0.1 μm or less, it is possible to uniformly and easily form an upper layer film on the cured film of the present invention in a later step, which is preferable. An arithmetic mean surface roughness of 0.02 μm or less is preferable, more preferably 0.015 μm or less, and most preferably 0.010 μm or less.

[0087] Next, the image display device of the present invention will be described. The image display device of the present invention can be produced by combining a substrate on which driving wiring electrodes are formed, micro LED cells are arranged, and a cured film is tightly contacted with the side surfaces of the micro LEDs to integrate them, with a driving IC driver, etc. By tightly contacting and integrating the micro LEDs with the cured film, the side surfaces of the micro LEDs are not exposed to the air, which is preferable because it improves the stability over time of the micro LED characteristics. Here, "without a gap" means that the distance between the micro LEDs and the cured film is preferably 0.5 μm or less, more preferably 0.1 μm or less.

[0088] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Among the compounds used in the synthesis examples and examples, the abbreviations used are as follows: PGMEA: propylene glycol monomethyl ether acetate DAA: diacetone alcohol.

[0089] The solids concentration of the polysiloxane solution and acrylic resin solution in Synthesis Examples 1 and 2 was determined by the following method. 1.5 g of the polysiloxane solution or acrylic resin solution was weighed into an aluminum cup and heated on a hot plate at 250°C for 30 minutes to evaporate the liquid. The weight of the solids remaining in the aluminum cup after heating was weighed, and the solids concentration of the polysiloxane solution or acrylic resin solution was determined from the ratio to the weight before heating.

[0090] The weight-average molecular weights of the polysiloxane and acrylic resin solutions in Synthesis Examples 1 and 2 were determined by the following method: GPC analysis was performed using a GPC analyzer (HLC-8220; manufactured by Tosoh Corporation) and tetrahydrofuran as a fluidized bed in accordance with JIS K7252-3 (established on March 20, 2008) to measure the weight-average molecular weights in terms of polystyrene.

[0091] The content ratio of each organosilane unit in the polysiloxane in Synthesis Example 1 was determined by the following method: The polysiloxane solution was poured into a 10 mm diameter Teflon (registered trademark) NMR sample tube. ２９ Si-NMR measurement was carried out, and the content ratio of each organosilane unit was calculated from the ratio of the integrated value of Si derived from a specific organosilane unit to the integrated value of the entire Si derived from organosilanes. ２９ The Si-NMR measurement conditions are as follows: Apparatus: Nuclear magnetic resonance apparatus (JNM-GX270; manufactured by JEOL Ltd.) Measurement method: Gated decoupling method Measurement nuclear frequency: 53.6693 MHz ( ２９ Si nucleus) Spectral width: 20,000 Hz Pulse width: 12 μs (45° pulse) Pulse repetition time: 30.0 seconds Solvent: acetone-d6 Reference substance: tetramethylsilane Measurement temperature: 23° C. Sample rotation speed: 0.0 Hz.

[0092] Synthesis Example 1 Polysiloxane (E-1) Solution A 500 ml three-neck flask was charged with 99.15 g (0.500 mol) of phenyltrimethoxysilane, 24.64 g (0.100 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 54.48 g (0.400 mol) of methyltrimethoxysilane, and 103.44 g of PGMEA, and an aqueous phosphoric acid solution prepared by dissolving 0.768 g of phosphoric acid (0.50 wt% based on the charged monomers) in 54.00 g of water was added over 30 minutes with stirring at room temperature. The three-neck flask was then immersed in a 70°C oil bath and stirred for 90 minutes, after which the oil bath was heated to 115°C over 30 minutes. One hour after the start of the temperature increase, the internal temperature (solution temperature) of the three-neck flask reached 100°C, and the mixture was then heated and stirred for 2 hours (internal temperature: 100-110°C) to obtain a polysiloxane solution. During the temperature increase and heating and stirring, nitrogen was flowed at 0.05 liters / minute. During the reaction, a total of 123.00 g of by-products, methanol and water, was distilled off. PGMEA was added to the obtained polysiloxane solution so that the solids concentration was 40% by weight, to obtain a polysiloxane (E-1) solution. The weight-average molecular weight of the obtained polysiloxane (E-1) was 4,100 (polystyrene equivalent). Furthermore, ２９ The results of Si-NMR measurement showed that the molar ratios of repeating units derived from phenyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and methyltrimethoxysilane in polysiloxane (E-1) were 50 mol %, 10 mol %, and 40 mol %, respectively.

[0093] Synthesis Example 2 Acrylic Resin (e-1) Solution 3 g of 2,2'-azobis(isobutyronitrile) and 50 g of PGMEA were placed in a 500 ml three-neck flask. Then, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and tricyclo[5.2.1.0 ２，６35 g of decane-8-yl methacrylate was added and stirred at room temperature for a while. The atmosphere in the flask was replaced with nitrogen, and the mixture was heated and stirred at 70°C for 5 hours to obtain an acrylic resin solution. PGMEA was added to the obtained acrylic resin solution so that the solids concentration was 40 wt %, to obtain an acrylic resin (e) solution. The weight-average molecular weight of the acrylic resin (e) was 10,000 (polystyrene equivalent).

[0094] Preparation Example 1 Photosensitive Resin Composition (P-1) (F-1) Titanium dioxide (R-960; manufactured by DuPont Co., Ltd.) was used as a white pigment. ２ / Al ２ O ３ 50.00 g of the polysiloxane (E-1) solution obtained in Synthesis Example 1 (surface-treated, median diameter 0.21 μm) was mixed with 50.00 g of the polysiloxane (E-1), and the resulting mixture was dispersed using a mill-type disperser filled with zirconia beads to obtain a pigment dispersion (MW-1).

[0095] Next, 32.00 g of pigment dispersion liquid (MW-1), 34.925 g of polysiloxane (E-1) solution, 2.000 g of TP5-280M (manufactured by Toyo Gosei Co., Ltd.) as a naphthoquinone dioxide compound (G), 0.800 g of a melamine resin compound ("Nicalac" (registered trademark) MX-270 (trade name), manufactured by Sanwa Kasei Co., Ltd.) as a curing agent, 2-(3,4-epoxycyclohexyl) 0.800 g of ethyltrimethoxysilane (KBM-303 (trade name), manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.300 g (corresponding to a concentration of 300 ppm) of a 10 wt % PGMEA diluted solution of a fluorine-based surfactant ("Megafac" (registered trademark) F-477 (trade name), manufactured by DIC Corporation) as a surfactant were dissolved in a mixed solvent of 3.000 g of DAA and 26.175 g of PGMEA and stirred. Next, the mixture was filtered through a 5.0 μm filter to obtain a photosensitive resin composition (P-1).

[0096] Preparation Example 2 Photosensitive Resin Composition (P-2) The same procedure as in Preparation Example 1 was carried out except that the acrylic resin (e-1) solution was used instead of the polysiloxane (E-1) solution, to obtain a photosensitive resin composition (P-2).

[0097] Preparation Example 3 Photosensitive Resin Composition (P-3) (F-2) As a black pigment, 50.00 g of titanium nitride (manufactured by Wako Pure Chemical Industries, Ltd.; particle size: 50 nm, titanium content: 74.3 wt%, nitrogen content: 20.3 wt%, oxygen content: 2.94 wt%) was mixed with 50.00 g of a polysiloxane (E-1) solution as an (E) resin, and dispersed using a mill-type disperser filled with zirconia beads to obtain a pigment dispersion (MW-2). The same procedure as in Preparation Example 1 was carried out, except that the amount of polysiloxane (E-1) solution added was changed to 34.645 g, the amount of PGMEA mixed solvent was changed to 26.343 g, and 0.112 g of the pigment dispersion (MW-2) was added to the pigment dispersion (MW-1). A photosensitive resin composition (P-3) was obtained.

[0098] Preparation Example 4 Photosensitive Resin Composition (P-4) The same procedure as in Preparation Example 1 was carried out, except that the amount of polysiloxane (E-1) solution added was changed to 62.925 g, the amount of PGMEA in the mixed solvent was changed to 14.175 g, and the amount of pigment dispersion (MW-1) added was changed to 16.000 g, to obtain a photosensitive resin composition (P-4).

[0099] Preparation Example 5 Photosensitive Resin Composition (P-5) The same procedure as in Preparation Example 1 was carried out except that the amount of polysiloxane (E-1) solution added was changed to 35.925 g, the amount of PGMEA in the mixed solvent was changed to 25.575 g, and the amount of TP5-280M added as the (G) naphthoquinone dioxide compound was changed to 1.600 g, thereby obtaining a photosensitive resin composition (P-5).

[0100] Preparation Example 6 Photosensitive Resin Composition (P-6) The same procedure as in Preparation Example 1 was carried out except that the amount of polysiloxane (E-1) solution added was changed to 33.925 g, the amount of PGMEA in the mixed solvent was changed to 26.775 g, and the amount of TP5-280M added as the (G) naphthoquinone dioxide compound was changed to 2.400 g, to obtain a photosensitive resin composition (P-6).

[0101] Preparation Example 7 Photosensitive Resin Composition (P-7) (F-1) As a white pigment, zirconia (3YI-R; manufactured by Toray Industries, Inc. (Al ２ O ３ A photosensitive resin composition (P-7) was obtained in the same manner as in Preparation Example 1, except that the surface treatment, median diameter 0.50 μm) was used.

[0102] Preparation Example 8 Photosensitive Resin Composition (P-8) The same procedure as in Preparation Example 1 was carried out except that the amount of polysiloxane (E-1) solution added was changed to 39.925 g, the amount of PGMEA in the mixed solvent was changed to 23.175 g, and TP5-280M was not added as the naphthoquinone dioxide compound (G), to obtain a photosensitive resin composition (P-8).

[0103] Preparation Example 9 Photosensitive Resin Composition (P-9) The same procedure as in Preparation Example 1 was carried out except that the amount of polysiloxane (E-1) solution added was changed to 90.925 g, the amount of PGMEA in the mixed solvent was changed to 2.175 g, and the pigment dispersion liquid (MW-1) was not added, to obtain a photosensitive resin composition (P-9).

[0104] The compositions of Preparation Examples 1 to 9 are shown in Table 1.

[0105]

[0106] <Preparation of Glass Substrate with Textured Structure> Under a dry nitrogen stream, 15.9 g (0.043 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF, manufactured by Central Glass Co., Ltd.) and 0.62 g (0.0025 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (SiDA) were dissolved in 200 g of N-methylpyrrolidone (NMP). To this solution, 15.5 g (0.05 mol) of 3,3',4,4'-diphenylethertetracarboxylic acid dianhydride (ODPA, manufactured by Manac Corporation) was added along with 50 g of N-methylpyrrolidone (NMP), and the mixture was stirred at 40°C for 2 hours. Subsequently, 1.17 g (0.01 mol) of 4-ethynylaniline (Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 40°C for 2 hours. Furthermore, a solution prepared by diluting 3.57 g (0.03 mol) of dimethylformamide dimethyl acetal (DFA, manufactured by Mitsubishi Rayon Co., Ltd.) with 5 g of N-methylpyrrolidone (NMP) was added dropwise over 10 minutes, and after the dropwise addition, stirring was continued for 2 hours at 40°C. After stirring was completed, the solution was poured into 2 L of water, and the precipitate of a polymer solid was collected by filtration. The solution was further washed three times with 2 L of water, and the collected polymer solid was dried in a vacuum dryer at 50°C for 72 hours to obtain a polyamic acid ester.

[0107] 10.00 g (100 parts by weight) of polyamic acid ester, 3.00 g (30 parts by weight) of naphthoquinone diazide compound TP5-280M (manufactured by Toyo Gosei Co., Ltd.), 0.01 g (0.1 parts by weight) of diphenyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-202SS), 0.50 g (0.5 parts by weight) of 1,1,1-tris(4-hydroxyphenyl)ethane (manufactured by Honshu Chemical Industry Co., Ltd., TrisP-HAP) as a compound having a phenolic hydroxyl group, and an amount (52.04 g) of γ-butyrolactone (GBL) as a solvent such that the solids concentration of the composition was 20% by weight were mixed and stirred under yellow light to obtain a homogeneous solution, and then filtered through a 0.20 μm filter to prepare a positive photosensitive polyamide precursor resin composition.

[0108] The positive photosensitive precursor resin composition was spin-coated (product name 1H-360S, manufactured by Mikasa Co., Ltd.) onto a 10 cm square alkali-free glass substrate (manufactured by AGC Technoglass Co., Ltd., film thickness 0.7 mm), and dried at a temperature of 100°C for 2 minutes using a hot plate (product name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.) to produce a dry film. The produced dry film was then irradiated with a parallel light mask aligner (product name PLA-501F, manufactured by Canon Inc.) using an ultra-high pressure mercury lamp as a light source, with a photomask on one side of the glass substrate and without a photomask on the other side, at an exposure dose of 200 mJ / cm. ２ The film was exposed to 1000 kJ / cm² (equivalent to i-line radiation). The film was then shower-developed with a 2.38 wt % aqueous solution of tetramethylammonium hydroxide for 120 seconds using an automatic developing apparatus ("AD-2000 (trade name)" manufactured by Takizawa Sangyo Co., Ltd.) and then rinsed with water for 30 seconds. The film was then cured at 230°C for 30 minutes using an oven (DN43HI manufactured by Yamato Scientific) to obtain a glass substrate having a concave-convex structure on one side of the substrate. The obtained glass substrate having a concave-convex structure had a pattern formed on one side of the substrate, with convex structures measuring 20 μm in length and width and a film thickness of 5 μm, and the spacing between adjacent convex structures was 80 μm.

[0109] The evaluation methods used in each example and comparative example are as follows. <Evaluation of film flatness of photosensitive resin composition on glass substrate having concavo-convex structure> The photosensitive resin composition used in each example and comparative example was spin-coated onto the glass substrate having the above-mentioned concavo-convex structure (product name 1H-360S, manufactured by Mikasa Co., Ltd.), and then heated and dried at a temperature of 100°C for 2 minutes using a hot plate (product name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.). The appearance of the substrate with the obtained dried film was visually inspected, and the flatness of the photosensitive resin composition on the substrate with concavo-convex structure was evaluated according to the following criteria. A: The concavo-convex structure was flattened, and the dried film appeared to be formed uniformly without any unevenness in film thickness.

[0110] B: The concave-convex structure is flattened, but the dried film appears to have uneven thickness. C: The concave-convex structure is not flattened, and some of the convex structures remain unflattened, making the dried film appear to have uneven thickness.

[0111] <Measurement of Spectral Irradiance of Radiant Light in the Step of Exposing a Dry Film> The spectral irradiance of the radiant light emitted from the exposure machine used in each of the Examples and Comparative Examples in the step of exposing a dry film was measured at a wavelength resolution of 1 nm using a spectral irradiance meter (trade name USR45DA, manufactured by Ushio Inc.). Subsequently, the spectral irradiance for each wavelength in the wavelength range of 300 nm to 450 nm was added together to calculate the total spectral irradiance (A) of the radiant light in the wavelength range of 300 nm to 450 nm in the step of exposing a dry film.

[0112] <Measurement of Spectral Irradiance of Radiant Light Passing Through a Dried Film> The photosensitive resin composition used in each of the Examples and Comparative Examples was spin-coated onto a glass substrate (product name 1H-360S, manufactured by Mikasa Co., Ltd.), and dried by heating at a temperature of 100°C for 2 minutes using a hot plate (product name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.) to form a dried film having a film thickness of 1 μm. Radiant light from an exposure machine used in the step of exposing the dried film used in each of the Examples and Comparative Examples was irradiated from the side of the dried film having a film thickness of 1 μm, and the value of the spectral irradiance after passing through the dried film was measured on the glass substrate side using an irradiance meter (product name USR45DA, manufactured by Ushio Inc.) with a wavelength resolution of 1 nm. Next, the spectral irradiance for each wavelength in the wavelength range of 300 nm to 450 nm was added together to calculate the sum (B) of the spectral irradiance of the emitted light that passed through the dry film in the wavelength range of 300 nm to 450 nm when the film thickness was 1 μm.

[0113] <Flatness of a Photosensitive Resin Composition on a Glass Substrate Having a Concave-Convex Structure After Development> The photosensitive resin composition used in each Example and Comparative Example was spin-coated onto the glass substrate having the concave-convex structure described above (product name 1H-360S, manufactured by Mikasa Co., Ltd.), and dried for 2 minutes at a temperature of 100°C using a hot plate (product name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.) to form a dried film with a thickness of 10 μm. The substrate with the dried film was exposed without a photomask using the specified exposure device and exposure amount set for each Example and Comparative Example. Thereafter, using an automatic developing apparatus ("AD-2000 (product name)" manufactured by Takizawa Sangyo Co., Ltd.), the film was shower-developed for 60 seconds with a 2.38 wt % aqueous solution of tetramethylammonium hydroxide, followed by rinsing with water for 30 seconds, and a portion of the upper layer of the dried film corresponding to a thickness of 5 μm was developed and removed. After development, the thickness of the coating film of the photosensitive resin composition on the substrate was 5 μm, the same as the thickness of the convex structures. The developed substrate was visually inspected for appearance and the developed coating film was magnified using a microscope adjusted to 20x magnification to observe the flatness of the photosensitive resin composition on the substrate having a concave-convex structure after development, and the flatness was evaluated according to the following criteria: A: The film thickness of the convex structures and the film thickness of the coating film after development appear to be approximately the same. B: The film thickness of the convex structures and the film thickness of the coating film after development appear to be approximately the same, but unevenness in the film thickness of the coating film after development is observed. C: There are parts where the developed film remains on the tops of the convex structures, and many parts are observed where the film thickness of the convex structures and the film thickness of the coating film after development are different.

[0114] <Calculation of the Change in Film Thickness of the Coating Film in the Step of Developing the Dried Film After Exposure> The photosensitive resin composition used in each of the Examples and Comparative Examples was spin-coated (product name 1H-360S, manufactured by Mikasa Co., Ltd.) onto a glass substrate having the aforementioned uneven structure, and then dried at a temperature of 100°C for 2 minutes using a hot plate (product name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.) to form a dried film with a film thickness of 10 μm. The film thickness of the dried film in the pattern-free region on one half of the glass substrate was measured using a Surfcom stylus film thickness measuring device, and the value at the center of the film was then measured under the same conditions as in each of the Examples and Comparative Examples. The film thickness of the developed coating film was measured using a Surfcom stylus film thickness measuring device, and the change in film thickness before and after development was calculated. The above-mentioned calculation of the change in film thickness was also performed at five points, top, bottom, left, and right, including the center of the pattern-free region on one half of the glass substrate, to determine the maximum and minimum film thickness changes. Furthermore, the variation in film thickness change during the development step was evaluated from the difference between the maximum and minimum values. It is preferable that this difference be 1.0 μm or less.

[0115] <Measurement of Spectral Irradiance of Radiant Light in the Step of Post-Exposing the Developed Coating Film> The spectral irradiance of the radiant light used in each of the Examples and Comparative Examples in the step of post-exposing the developed coating film was measured at a wavelength resolution of 1 nm using a spectrophotometer (trade name USR45DA, manufactured by Ushio Inc.). Subsequently, the spectral irradiance for each wavelength in the wavelength range of 300 nm to 450 nm was added together to calculate the sum (C) of the spectral irradiance of the radiant light in the wavelength range of 300 nm to 450 nm in the step of post-exposing the developed coating film.

[0116] <Measurement of Spectral Irradiance of Radiant Light Passing Through Developed Coating Film> The photosensitive resin composition used in each Example and Comparative Example was spin-coated onto a glass substrate (product name 1H-360S, manufactured by Mikasa Co., Ltd.), and dried by heating at a temperature of 100°C for 2 minutes using a hot plate (product name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.). Except for changing the film thickness, processing was performed under the same conditions as in each Example and Comparative Example, so that the developed coating film had a film thickness of 1 μm. Radiant light from an exposure machine used in the step of post-exposing the developed coating film used in each Example and Comparative Example was irradiated from the side of the developed coating film with a film thickness of 1 μm, and the value of the spectral irradiance after passing through the developed coating film was measured on the glass substrate side using a radiant meter (product name USR45DA, manufactured by Ushio Inc.) with a wavelength resolution of 1 nm. Next, the spectral irradiance for each wavelength in the wavelength region of 300 nm to 450 nm was added together to calculate the sum (D) of the spectral irradiance of the radiation in the wavelength region of 300 nm to 450 nm that had passed through the coating film after development in the case of a film thickness of 1 μm.

[0117] <Reflectance> The photosensitive resin composition used in each Example and Comparative Example was processed in the same manner as in each Example and Comparative Example, except that the film thickness was changed, to produce a 10 μm cured film on a flat glass substrate. The obtained cured film was used as a model of the cured film formed on a substrate having a textured structure in each Example and Comparative Example, and the reflectance at a wavelength of 550 nm was measured in SCI mode from the cured film side using a spectrophotometer (product name CM-2600d, manufactured by Konica Minolta, Inc.). Note that evaluation was not performed on samples in which the amount of developed coating film during development was too large, making it difficult to form a cured film.

[0118] <Absorbance (OD value)> The photosensitive resin composition used in each Example and Comparative Example was processed in the same manner as in each Example and Comparative Example, except that the film thickness was changed, to produce a 10 μm cured film on a flat glass substrate. The obtained cured film was used as a model of the cured film formed on a substrate having a concavo-convex structure in each Example and Comparative Example, and the intensities of incident light and transmitted light were measured from the top surface using an optical densitometer (U-4100, manufactured by Hitachi High-Tech Science), and the absorbance (OD value) was calculated using the following formula (III). Note that evaluation was not performed on samples in which the amount of developed coating film during development was large and it was determined that it was difficult to form a cured film.

[0119] OD value=log10(I0 / I) Formula (III) I0: incident light intensity I: transmitted light intensity.

[0120] <Arithmetic mean surface roughness> The photosensitive resin composition used in each Example and Comparative Example was processed in the same manner as in each Example and Comparative Example, except that the film thickness of the resulting cured film was changed, and a substrate with a 10 μm solid cured film was produced on a flat glass substrate. The obtained cured film was used as a model of the cured film of the cured film-coated substrate formed on a substrate with a concave-convex structure formed in each Example and Comparative Example, and the arithmetic mean surface roughness was determined using a Surfcom stylus film thickness measuring device. Note that evaluation was not performed on samples where the amount of developed dry film during development was too large and it was determined that it was difficult to form a 10 μm cured film.

[0121] <Median diameter of pigment> For the photosensitive resin compositions used in each of the Examples and Comparative Examples, the pigment dispersion used as a raw material was placed in a quartz cell, and the particle size distribution of the pigment was measured by a laser diffraction method using a submicron particle size distribution analyzer (N4-PLUS; manufactured by Beckman Coulter, Inc.), and the median diameter was calculated.

[0122] Example 1 The photosensitive resin composition of Preparation Example 1 was spin-coated (product name 1H-360S, manufactured by Mikasa Co., Ltd.) onto a glass substrate having the aforementioned uneven structure, and a coating film was formed using a hot plate (product name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.). The coating was then dried at a temperature of 100°C for 2 minutes to form a dried film with a film thickness of 10 μm. A parallel light mask aligner (product name PLA-501F, manufactured by Canon Inc.) was used as the exposure machine for the step of exposing the substrate with the dried film. An ultra-high pressure mercury lamp was used as the light source, and an optical filter (product name HB-365, manufactured by Asahi Spectroscopy Co., Ltd.) that passes light near the i-line (365 nm) was placed between the exposure light source and the object to be exposed, so that light near the i-line was selectively emitted. At this time, the total spectral irradiance at wavelengths of 400 nm to 450 nm was 0.05 mW / cm. 2 The total spectral irradiance at wavelengths of 300 nm to 400 nm is 32.2 mW / cm 2The total spectral irradiance at wavelengths of 400 nm to 450 nm was 0.16% of the total spectral irradiance at wavelengths of 300 nm to 400 nm, and exposure was performed with radiation that did not substantially contain light with a wavelength of 400 nm or more. The substrate with the dry film was exposed to an exposure dose of 80 mJ (calculated from the spectral irradiance at a wavelength of 365 nm) using the above-mentioned exposure machine without using a photomask. Thereafter, the exposed substrate with the dry film was shower-developed with a 2.38 wt % aqueous solution of tetramethylammonium hydroxide for 60 seconds using an automatic developing apparatus ("AD-2000 (trade name)" manufactured by Takizawa Sangyo Co., Ltd.), and then rinsed with water for 30 seconds. For the developed substrate, a parallel light mask aligner (trade name PLA-501F, manufactured by Canon Inc.) was used. An ultra-high pressure mercury lamp was used as the light source, and an optical filter (trade name LU0400, manufactured by Asahi Spectroscopy Co., Ltd.) that passes light of 400 nm or longer was placed between the exposure light source and the object to be exposed, so that light of 400 nm or longer was selectively irradiated. The developed coated substrate was post-exposed to 100 mJ (calculated from the irradiance at a wavelength of 405 nm) without using a photomask. Thereafter, using an oven (trade name IHPS-222, manufactured by Espec Corp.), the substrate was heated in air at a temperature of 170°C for 30 minutes, producing a cured film-coated substrate having a 5 μm thick cured film on a glass substrate having an uneven structure. That is, by exposure and development under the above conditions, the 10 μm thick dried film was partially developed by about 5 μm, and then cured to form a cured film with a thickness of 5 μm. In the following examples and comparative examples, the exposure dose before development is determined after similarly calculating the exposure dose required for development of about 5 μm.

[0123] Example 2 Processing was carried out in the same manner as in Example 1, except that P-2 was used as the photosensitive resin composition and the exposure dose before development was 80 mJ.

[0124] Example 3 Processing was carried out in the same manner as in Example 1, except that P-3 was used as the photosensitive resin composition and the exposure dose before development was 100 mJ.

[0125] Example 4 Processing was carried out in the same manner as in Example 1, except that P-4 was used as the photosensitive resin composition and the exposure dose before development was 40 mJ.

[0126] Example 5 Processing was carried out in the same manner as in Example 1, except that P-5 was used as the photosensitive resin composition and the exposure dose before development was set to 60 mJ.

[0127] Example 6 Processing was carried out in the same manner as in Example 1, except that P-6 was used as the photosensitive resin composition and the exposure dose before development was 100 mJ.

[0128] Example 7 The photosensitive resin composition of Preparation Example 1 was spin-coated (product name 1H-360S, manufactured by Mikasa Co., Ltd.) onto a glass substrate having the aforementioned uneven structure, and a coating film was formed using a hot plate (product name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.). The coating was then dried at a temperature of 100°C for 2 minutes to form a dried film with a film thickness of 10 μm. A parallel light mask aligner (product name PLA-501F, manufactured by Canon Inc.) was used as the exposure machine for the step of exposing the substrate with the dried film, and an ultra-high pressure mercury lamp was used as the light source. No optical filter for selecting wavelengths was placed between the exposure light source and the object to be exposed. The substrate with the dried film was exposed to light using the aforementioned exposure machine without using a photomask, at an exposure dose of 30 mJ (calculated from the spectral irradiance at a wavelength of 365 nm). At this time, the total spectral irradiance at wavelengths of 400 nm to 450 nm was 43.8 mW / cm. 2 The total spectral irradiance at wavelengths of 300 nm to 400 nm is 46.8 mW / cm 2 The subsequent processing of developing the substrate with the dried film after exposure was carried out in the same manner as in Example 1.

[0129] Example 8 The photosensitive resin composition of Preparation Example 1 was spin-coated (product name 1H-360S, manufactured by Mikasa Co., Ltd.) onto a glass substrate having the aforementioned uneven structure, and a coating film was formed using a hot plate (product name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.). The coating was then dried at a temperature of 100°C for 2 minutes to form a dried film with a film thickness of 10 μm. A parallel light mask aligner (product name PLA-501F, manufactured by Canon Inc.) was used as the exposure machine for the step of exposing the substrate with the dried film. An ultra-high pressure mercury lamp was used as the light source, and an optical filter (product name LU0400, manufactured by Asahi Spectroscopy Co., Ltd.) that transmits light of 400 nm or more was placed between the exposure light source and the object to be exposed, so that light of 400 nm or more was selectively irradiated. The substrate with the dried film was exposed using the exposure machine described above without a photomask, at an exposure dose of 25 mJ (calculated from the spectral irradiance at a wavelength of 405 nm). At this time, the total spectral irradiance at wavelengths of 400 nm to 450 nm is 40.2 mW / cm 2 The total spectral irradiance at wavelengths of 300 nm to 400 nm is 0.65 mW / cm 2 The subsequent processing of developing the substrate with the dried film after exposure was carried out in the same manner as in Example 1.

[0130] Example 9 The photosensitive resin composition of Preparation Example 1 was spin-coated (product name 1H-360S, manufactured by Mikasa Co., Ltd.) onto a glass substrate having the aforementioned uneven structure, and a coating film was formed using a hot plate (product name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.). The coating was then dried at a temperature of 100°C for 2 minutes to form a dried film with a film thickness of 10 μm. As an exposure machine for the step of exposing the substrate with the dried film, a parallel light mask aligner (product name PLA-501F, manufactured by Canon Inc.) was used, and an ultra-high pressure mercury lamp was used as the light source. An optical filter (product name SH0400, manufactured by Asahi Spectroscopy Co., Ltd.) that transmits light of 400 nm or less was placed between the exposure light source and the object to be exposed, so that light of 400 nm or less was selectively irradiated. The substrate with the dried film was exposed using the exposure machine described above without using a photomask, with an exposure dose of 70 mJ (calculated from the spectral irradiance at a wavelength of 365 nm). The subsequent processing of developing the substrate with the dried film after exposure was carried out in the same manner as in Example 1. At this time, the total value of the spectral irradiance at wavelengths of 400 nm to 450 nm was 0.97 mW / cm 2 The total spectral irradiance at wavelengths of 300 nm to 400 nm is 44.9 mW / cm 2 The total spectral irradiance at wavelengths of 400 nm to 450 nm was 2.2% of the total spectral irradiance at wavelengths of 300 nm to 400 nm, and exposure was performed with radiation that did not substantially contain light with a wavelength of 400 nm or more. The subsequent processing, in which the substrate with the dried film after exposure was developed, was performed in the same manner as in Example 1.

[0131] Comparative Example 1 Processing was carried out in the same manner as in Example 1, except that P-7 was used as the photosensitive resin composition and the exposure dose before development was 15 mJ.

[0132] Comparative Example 2 Processing was carried out in the same manner as in Example 1, except that P-8 was used as the photosensitive resin composition and exposure before development was not carried out.

[0133] Comparative Example 3: Processing was carried out in the same manner as in Example 1, except that P-9 was used as the photosensitive resin composition and the exposure dose before development was 10 mJ. The configurations and evaluation results of each example and comparative example are shown in Tables 2 and 3.

[0134]

[0135]

[0136] 1: Pattern portion 2: Base substrate 3: Coating film of photosensitive resin composition 4: Dried film of photosensitive resin composition 5: Coating film of photosensitive resin composition after development 6: Cured film of photosensitive resin composition H: Film thickness

Claims

1. A method for producing a cured film-coated substrate, the method comprising the steps of: providing a coating film of a photosensitive resin composition on a substrate having an uneven surface; drying the coating film to form a dry film; exposing the dried film to light; partially developing the exposed surface of the dried film in the film thickness direction; and heating the developed coating film to form a cured film, in this order; wherein, in the step of exposing the dried film, a total value (A) of spectral irradiance of radiation in the wavelength range of 300 nm to 450 nm is used; and, in the step of exposing the dried film, a total value (B ... that has passed through the dried film in the wavelength range of 300 nm to 450 nm is used; the attenuation ratio (B) / (A) of the spectral irradiance per μm of film thickness of the dried film satisfies the following relational formula (I): 0.001≦(B) / (A)≦0.2...(I)

2. 2. The method for producing a substrate with a cured film according to claim 1, wherein the radiation in the step of exposing the dried film does not substantially contain light with a wavelength of 400 nm or more.

3. 3. The method for producing a cured film-coated substrate according to claim 1, wherein the radiation light used in the step of exposing the dried film includes at least light having a wavelength of 365±5 nm or 385±10 nm at which the illuminance is maximized.

4. The method for producing a substrate with a cured film according to claim 1 or 2, further comprising a step of post-exposing the developed coating film before heating it.

5. 5. The method for producing a cured film-coated substrate according to claim 4, wherein, in the step of post-exposing the developed coating film, a sum (C) of spectral irradiances of radiation with which the developed coating film is post-exposed in a wavelength region of 300 nm to 450 nm and a sum (D) of spectral irradiances of radiation with which the developed coating film is post-exposed in a wavelength region of 300 nm to 450 nm are passed through the developed coating film, and an attenuation ratio (D) / (C) per μm of dry film thickness satisfies the following relational formula (II): 0.05≦(D) / (C)≦0.99 (II)

6. 3. The method for producing a substrate with a cured film according to claim 1, wherein the photosensitive resin composition contains (E) a resin, (F) a pigment, and (G) a naphthoquinone diazide compound.

7. A method for manufacturing a substrate with a cured film as described in Claim 6, wherein the (F) pigment contains at least one of a white pigment or a black pigment.

8. The method for producing a substrate with a cured film according to claim 6, wherein the resin (E) is a polysiloxane.

9. 7. The method for producing a substrate with a cured film according to claim 6, wherein the pigment (F) is a white pigment (F-1) having a median diameter of 0.1 to 0.6 μm.

10. The method for producing a cured film-coated substrate according to claim 1 or 2, wherein the substrate has a concave-convex structure on its surface, and the convex structures on the substrate include LEDs.

11. A substrate with a cured film produced by the method of claim 1 or 2.

12. The cured film-coated substrate according to claim 11, wherein the cured film has an absorbance per 10 μm of film thickness at a wavelength of 365 nm of 1.0 to 4.0, an absorbance per 10 μm of film thickness at a wavelength of 405 nm of 0.5 to 2.0, an absorbance per 10 μm of film thickness at a wavelength of 436 nm of 0.5 to 2.0, and an absorbance per 10 μm of film thickness at a wavelength of 450 nm of 0.5 to 2.

0.

13. The substrate with a cured film according to claim 11, wherein the cured film has a reflectance of 20 to 80% per 10 μm of film thickness at a wavelength of 550 nm.

14. The substrate with a cured film according to claim 11, wherein the cured film has an arithmetic mean surface roughness of 0.005 μm to 0.1 μm.

15. An image display device comprising the substrate with the cured film according to claim 11.

16. A method for manufacturing a substrate with a cured film, comprising the steps of: manufacturing a substrate with a cured film by the manufacturing method of claim 1 or 2, which has an LED and a cured film having light-blocking properties on a substrate, the cured film having light-blocking properties in contact with and integrated with the side surface of the LED without any gaps; and the cured film having an absorbance of 1.0 to 4.0 per 10 μm film thickness at a wavelength of 365 nm, an absorbance of 0.5 to 2.0 per 10 μm film thickness at a wavelength of 405 nm, an absorbance of 0.5 to 2.0 per 10 μm film thickness at a wavelength of 436 nm, an absorbance of 0.5 to 2.0 per 10 μm film thickness at a wavelength of 450 nm, and a reflectance of 20 to 80% per 10 μm film thickness at a wavelength of 550 nm.