WO2023054046A1

WO2023054046A1 - Method for manufacturing cured-film-coated substrate, cured-film-coated substrate, and element comprising cured-film-coated substrate

Info

Publication number: WO2023054046A1
Application number: PCT/JP2022/034903
Authority: WO
Inventors: 小林秀行; 谷野貴広; 諏訪充史
Original assignee: 東レ株式会社
Priority date: 2021-09-29
Filing date: 2022-09-20
Publication date: 2023-04-06
Also published as: CN117859097A; TW202323396A

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

Cured film-coated substrate manufacturing method, cured film-coated substrate, and device provided with cured film-coated substrate

The present invention relates to a method for manufacturing a cured film-coated substrate, a cured film-coated substrate using the same, and an element having a cured film-coated substrate.

In recent years, with the development of information terminal devices such as smartphones and tablets, and the high definition of flat panel displays such as televisions, the demand for higher performance displays has increased further. Among them, as a high-performance display, a micro-LED display using micro-sized LEDs is attracting attention. This display uses micro LEDs driven by an active matrix method or the like as a light source to display in full color, and is excellent in contrast and color reproducibility.

In this micro LED display, it is necessary to arrange a patterned cured film (partition wall) that separates the light source with a size corresponding to the micro LED that is the light source. As a method for forming a patterned cured film, a photolithography method using a pattern mask is well known (Patent Document 1). In addition, these barrier ribs are required to have a light-shielding property to prevent color mixing between adjacent micro-LEDs and a reflective property to efficiently extract light from the micro-LEDs.

Furthermore, as a method of forming these patterned cured films more inexpensively and efficiently, a material with excellent flatness is applied to a substrate having an uneven structure such as a micro LED, and a part of the coating film surface is covered. Techniques such as removal (Patent Documents 2 and 3) are being considered.

International Publication No. 2020-8969 JP 2006-66474 A JP-A-2002-14477

However, when the material described in Patent Document 1 is used, it is difficult to selectively remove unnecessary portions of the coating film surface. In addition, since the methods described in

Patent Documents

2 and 3 require a pattern mask, it is difficult to form a patterned cured film efficiently and inexpensively.

Therefore, in the present invention, after forming a coating film for flattening the convex structures on a substrate having an uneven structure on the surface, unnecessary coating film on the surface of the coating film is removed to expose the surface of the convex structures. Accordingly, an object of the present invention is to realize a patterned cured film by an inexpensive method that does not require a pattern mask.

In order to solve the above problems, the present invention has the following configurations.
[1] A step of providing a coating film of a photosensitive resin composition on a substrate having an uneven structure on its surface, a step of drying the coating film to form a dry film, a step of exposing the dry film, and after the exposure. A method for producing a cured film-coated substrate having, in this order, a step of partially developing the dry film surface in the film thickness direction, and a step of heating the developed coating film to form a cured film, wherein the dry film is About the total value (A) of the spectral irradiance in the wavelength range of 300 nm to 450 nm of the radiant light in the exposure process and the total value (B) of the spectral irradiance in the wavelength range of 300 nm to 450 nm of the radiant light that has passed through the dry film , the attenuation ratio (B)/(A) per 1 μm of dry film thickness satisfies the following relational expression (I).
0.001≦(B)/(A)≦0.2 (I)

[2] The method for producing a cured film-coated substrate according to [1], wherein the emitted light in the step of exposing the dry film does not substantially contain light having a wavelength of 400 nm or more.

[3] The radiant light in the step of exposing the dry film includes at least light having a wavelength of 365±5 nm or 385±10 nm with maximum illuminance. A method for producing a substrate with a cured film.

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

[5] 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 the radiation light post-exposed to the developed coating film, and the post-development For the total value (D) of the spectral irradiance in the wavelength range of 300 nm to 450 nm of the radiant light that has passed through the coating film, the attenuation ratio (D) / (C) per 1 μm of the dry film thickness is given by the following relational expression (II). The method for producing a cured film-coated substrate according to [4], wherein

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

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

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

[9] The method for producing a cured film-coated substrate according to any one of [1] to [8], wherein the substrate having an uneven structure on its surface has an LED as the convex structure on the substrate.

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

[11] The cured film has an absorbance of 1.0 to 4.0 per 10 μm thickness at a wavelength of 365 nm, an absorbance of 0.5 to 2.0 per 10 μm thickness at a wavelength of 405 nm, and a thickness of 10 μm at a wavelength of 436 nm. The substrate with a cured film according to [10], which has an absorbance of 0.5 to 2.0 per 10 μm film thickness at a wavelength of 450 nm.

[12] The cured film-coated substrate according to [10] or [11], wherein the cured film has a reflectance of 20 to 80% per 10 µm film thickness at a wavelength of 550 nm.

[13] The cured film-coated substrate 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.

An image display device having the cured film-coated substrate according to any one of [14][10]-[13].

[15] An LED and a cured film having a light-shielding property are provided on a substrate, and the cured film having a light-shielding property is in contact with and integrated with the side surface of the LED, and the cured film has a thickness of 10 μm at a wavelength of 365 nm. A film with an absorbance of 1.0 to 4.0, 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, and a film at a wavelength of 450 nm. A substrate with a cured film having an absorbance of 0.5 to 2.0 per 10 μm thickness and a reflectance of 20 to 80% per 10 μm thickness at a wavelength of 550 nm.

According to the method for manufacturing a cured film-coated substrate described in the means for solving the problems, a patterned cured film that separates the convex structures can be inexpensively formed on a concave-convex substrate having convex structures such as micro LEDs on the surface. It becomes possible to manufacture by the method.
That is, by applying a material with excellent flatness and partially developing the surface of the coating film, it is possible to form partitions separating the micro LEDs.

A top view of a substrate having an uneven structure in which a pattern is formed on a base substrate Cross-sectional view of a substrate having an uneven structure in which a pattern is formed on a base substrate Sectional view of a state in which a coating film of a photosensitive resin composition is formed on a substrate having an uneven structure. Sectional view of a state in which a dry film of a photosensitive resin composition is formed on a substrate having an uneven structure. FIG. 4 is a cross-sectional view of a state in which the surface of a dry film of a photosensitive resin composition formed on a substrate having an uneven structure is partially developed in the film thickness direction. FIG. 2 is a cross-sectional view showing a state in which a cured film of a photosensitive resin composition is formed on a substrate having an uneven structure;

Preferred embodiments of the method for producing a cured film-coated substrate according to the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and various can be implemented by changing to

The method for producing a cured film-coated substrate of the present invention includes the steps of providing a coating film of a photosensitive resin composition on a substrate having an uneven structure on its surface, drying the coating film to form a dry film, and and a step of partially developing the dry film surface after the exposure in the film thickness direction, and a step of heating the developed coating film to form a cured film, in this order. In the manufacturing method, the total value (A) of the spectral irradiance in the wavelength range of 300 nm to 450 nm of the radiation light in the step of exposing the dry film, and the spectrum in the wavelength range of 300 nm to 450 nm of the radiation light that has passed through the dry film The attenuation ratio (B)/(A) per 1 μm of dry film thickness for the total value (B) of irradiance satisfies the following relational expression (I).
0.001≦(B)/(A)≦0.2 (I)
A substrate having an uneven structure on its surface functions as a support for a substrate with a cured film. can be formed. Subsequently, by drying the coating film, it is possible to obtain a dry film with improved flatness and film thickness uniformity. After that, in the step of exposing the dry film, the total value (A) of the spectral irradiance in the wavelength range of 300 nm to 450 nm of the radiant light, and the spectral irradiance in the wavelength range of 300 nm to 450 nm of the radiant light that has passed through the dry film. Regarding the total value (B), most of the light is absorbed on the surface of the dry film by exposing so that the attenuation ratio (B)/(A) per 1 μm of the dry film thickness satisfies the relational expression (I), It becomes possible to selectively react the photosensitive agent in that portion.

Furthermore, by developing the dry film after the exposure, it becomes possible to partially develop the dry film surface on which the photosensitive agent is reacting in the film thickness direction. Finally, by heating the developed coating film to form a cured film, it is possible to further improve film reliability such as light resistance.

<Substrate having uneven structure on its surface>
The concave-convex structure here means, for example, a concave-convex structure as shown in FIGS. 1 and 2 . FIG. 1 is a top view of a substrate having an uneven structure on its surface, and FIG. 2 is a cross-sectional view taken along line AA' of FIG. The pattern portion 1 is a convex portion, and the opening portion of the pattern, that is, the portion where the underlying substrate 2 is exposed, is a concave portion.

Further, as a substrate having an uneven structure on its surface, for example, there is a substrate in which convex structures such as micro LEDs, wiring, and insulating films are formed on a base substrate such as a silicon substrate, a glass plate, a resin plate, or a resin film. mentioned. Non-alkali glass is preferable as the material of the glass plate. Polyester, (meth)acrylic polymer, transparent polyimide, polyethersulfone and the like are preferable as materials for the resin plate and the resin film. The film thickness of the glass plate and the resin plate is preferably 1 mm or less, more preferably 0.8 mm or less. The film thickness of the resin film is preferably 100 μm or less.

<Step of providing a coating film of a photosensitive resin composition>
Examples of the step of forming a coating film of a photosensitive resin composition on a substrate having an uneven structure on its surface include methods such as microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, and slit coating. The one using is mentioned. Among them, spin coating and slit coating are preferable from the viewpoint of improving film flatness. FIG. 3 shows a schematic diagram of a state in which a coating film of a photosensitive resin composition is formed on a substrate having an uneven structure on its surface.

<Step of drying the coating film to form a dry film>
Examples of the step of drying the coating 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. FIG. 4 shows a schematic diagram of a state in which a dry film of a photosensitive resin composition is formed on a substrate having an uneven structure.

<Step of exposing dry film>
In the step of exposing the dry film, the total value (A) of the spectral irradiance in the wavelength range of 300 nm to 450 nm of the radiant light and the sum of the spectral irradiance in the wavelength range of 300 nm to 450 nm of the radiant light that has passed through the dry film. As for the value (B), the exposure is performed so that the attenuation ratio (B)/(A) per 1 μm of the dry film thickness satisfies the relational expression (I). From the viewpoint of decomposing the photosensitive agent on the dry film surface with a small amount of exposure and improving mass productivity, the attenuation ratio (B)/(A) per 1 μm of the dry film thickness is preferably 0.001 or more, and 0.005 or more. more preferred. On the other hand, from the viewpoint of selectively decomposing the photosensitive material by absorbing most of the light on the surface of the dry film, the attenuation ratio (B)/(A) per 1 μm of the dry film thickness is preferably 0.2 or less, and 0 0.15 or less is more preferred.

The spectral irradiance of radiated light in the present invention is measured using a spectral irradiance meter. The total value (A) of the spectral irradiance in the wavelength range of 300 nm to 450 nm of the radiant light in the step of exposing the dry film is calculated by summing the spectral irradiance of each wavelength measured by the spectral irradiance meter. can be done. In addition, for the total value (B) of the spectral irradiance in the wavelength range of 300 nm to 450 nm of the radiant light that has passed through the dry film, the radiant light that has passed through the dry film is measured in the same manner as above, and the spectrum of each wavelength is The irradiance can be summed and calculated.

The film thickness in the present invention refers to the thickness of the film in the vertical direction (height direction) with respect to the substrate. In the case of the schematic diagram of the substrate with the dry film shown in FIG. As will be described later, the thickness of the dry film is preferably 1 to 20 μm.

As an exposure machine, for example, a stepper, a mirror projection mask aligner (MPA), a parallel light mask aligner (PLA), an LED irradiation device, etc. can be used. Examples of the exposure light source include a high-pressure mercury lamp, a laser, an ultraviolet LED, and a violet LED. It is good to use what is released. In addition, it is preferable to install a wavelength selection filter or the like that cuts off a specific wavelength or more between the exposure light source and the exposure object to control the wavelength of the radiated light, and substantially does not include light with a wavelength of 400 nm or more. more preferred. The term “substantially not included” here means that the total value of the spectral irradiance of synchrotron radiation of 400 nm or more is so small that it can be ignored compared to the total value of the spectral irradiance of synchrotron radiation of 400 nm or less, and is treated as non-existent. Means if you can. A better condition is that the sum of spectral irradiances at wavelengths of 400 nm to 450 nm of radiated light is 2.5% or less of the sum of spectral irradiances at wavelengths of 300 nm to 400 nm. Furthermore, as a preferable condition, the total value of spectral irradiance at wavelengths of 400 nm to 450 nm of radiated light is 1.0% or less of the total value of spectral irradiances at wavelengths of 300 nm to 400 nm.

<Step of partially developing the dry film surface after the exposure in the film thickness direction>
Examples of the step of developing the dry film after the exposure and partially developing the surface of the dry film in the film thickness direction include developing techniques such as showering, dipping, and puddle. The immersion time in the developer is preferably 5 seconds to 5 minutes. Examples of the developer include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates; amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine; Alkaline developers such as aqueous solutions containing quaternary ammonium salts such as ammonium hydroxide and choline are included. Rinsing with water is preferred after development. FIG. 5 shows a cross-sectional view of a state in which the surface of a dry film of a photosensitive resin composition formed on a substrate having an uneven structure is partially developed in the film thickness direction.

<Step of post-exposure before heating the developed coating film>
In the step of post-exposure before heating the developed coating film, the total value (C) of the spectral irradiance in the wavelength range of 300 nm to 450 nm of radiant light, and the radiant light that has passed through the developed coating film For the total value (D) of the spectral irradiance in the wavelength range of 300 nm to 450 nm, post-exposure so that the attenuation ratio (D) / (C) per 1 μm of the coated film after the development satisfies the relational expression (II) is preferred.

0.05≦(D)/(C)≦0.99 (II)
In the step of post-exposure before heating the developed coating film, the total value (C) of the spectral irradiance in the region of the wavelength of 300 nm to 450 nm of the radiation light to be post-exposed, and the developed coating film For the total value (D) of the spectral irradiance in the wavelength range of 300 nm to 450 nm of the radiated light, the attenuation ratio (D)/(C) per 1 μm of the coating film thickness after the development is given by the relational expression (II) It is preferable to perform post-exposure so as to satisfy From the viewpoint of decomposing the photosensitive agent in the coating film after development with a small amount of exposure and improving mass productivity, the attenuation ratio (D)/(C) per 1 μm of the coating film thickness after development is 0.05. 0.10 or more is more preferable, and 0.15 or more is even more preferable. On the other hand, when the coating film functions as a partition wall of the LED, the attenuation ratio (D) / (C) per 1 μm of the coating film thickness is preferably 0.99 or less from the viewpoint of blocking the light of the LED. It is more preferably 0.70 or less.

The spectral irradiance in the present invention is measured using a spectral irradiance meter. In the step of post-exposure of the developed coating film, the total value (C) of the spectral irradiance in the wavelength region of radiant light of 300 nm to 450 nm can be calculated by summing the spectral irradiance of each wavelength. can. In addition, for the total value (D) of the spectral irradiance in the wavelength range of 300 nm to 450 nm of the radiant light that passed through the developed coating film, the radiant light that passed through the dry film was calculated for each wavelength in the same manner as described above. Spectral irradiance can be measured and calculated.

The film thickness in the present invention refers to the length in the vertical direction (height direction) with respect to the substrate. In the case of the cross-sectional view of the coating film after the development shown in FIG. As will be described later, the thickness of the coating film after the development is preferably 1 to 20 μm.

As an exposure machine, for example, a stepper, a mirror projection mask aligner (MPA), a parallel light mask aligner (PLA), an LED irradiation device, etc. can be used. Examples of the exposure light source include high-pressure mercury lamps, lasers, violet LEDs, and blue LEDs. It is preferable to use one that emits light of a wavelength that satisfies the requirements. It is also preferable to install a wavelength selection filter or the like that cuts off wavelengths other than a specific wavelength between the exposure light source and the exposure object to control the wavelength of the radiated light.

<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 such as a hot plate and an oven. 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 coating film after the post-exposure to form a cured film, the cross-linking reaction of the resin proceeds and the reliability of the cured film is improved. In addition, it is preferable because the smoothness of the cured film is improved by allowing the coating film to flow when heated. FIG. 6 shows a cross-sectional view of a state in which a cured film of a photosensitive resin composition is formed on a substrate having an uneven structure.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention preferably contains (E) a resin, (F) a pigment and (G) a naphthoquinonediazide compound. (E) The resin has the function of improving the crack resistance and light resistance of the coating film. The pigment (F) has a function of improving the light-shielding property of the coating film, and by including the naphthoquinone diazide compound (G), exhibits positive photosensitivity in which the exposed area is removed with a developer.

(E) Resin Examples of resin (E) include polysiloxane, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and (meth)acrylic polymer. You may contain 2 or more types of these. Among these, polysiloxane is preferable because it is excellent in light resistance and film flatness.

The polysiloxane in the present invention is a hydrolysis/dehydration condensate of organosilane, and in the present invention, preferably contains 20 to 60 mol % of repeating units represented by the following general formula (1). By containing a total of 20 to 60 mol% of the repeating unit represented by the general formula (1) in the polysiloxane, the polysiloxane can be easily compatible with other components, so that the coating film It is possible to improve the flatness of

(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 hydrogen is substituted.)
The content ratio of organosilane units having repeating units represented by general formula (1) can be determined by ²⁹ Si-NMR measurement. That is, it can be obtained by calculating the ratio of the integrated value of Si derived from the organosilane unit having the repeating unit represented by the general formula (1) to the integrated value of all Si derived from the organosilane.

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

In general formula (2) above, each R ¹ represents the same group as R ¹ in general formula (1). R ² , which may be the same or different, represents a monovalent organic group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms.

Examples of organosilane compounds represented by general formula (2) include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, naphthyltrimethoxysilane, naphthyltriethoxysilane, naphthyltripropoxysilane, and the like. be done. You may use 2 or more types of these.

Examples of organosilane compounds other than the general formula (2) include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, and 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, (3,4 -epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltripropoxysilane, 2-(3,4-epoxycyclohexyl)ethyltributoxysilane Silane, 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-epoxy cyclohexyl)butyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropylmethyldimethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-(2-aminoethyl )-3-aminopropylmethyldimethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, ethoxysilane, cyclohexylmethyldimethoxysilane, octadecylmethyldimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-triphenoxysilylpropylsuccinic anhydride, 3-tri methoxysilylpropylcyclohexyldicarboxylic anhydride, 3-trimethoxysilylpropylphthalic anhydride, and the like. You may use 2 or more types of these.

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

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

Polysiloxane 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 hydrolysis can be set according to physical properties suitable for the intended use, taking into consideration the reaction scale, the size and shape of the reaction vessel, and the like. Various conditions include, for example, acid concentration, reaction temperature, and reaction time. Acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acids and their anhydrides, and ion exchange resins can be used for the hydrolysis reaction. Among these, acidic aqueous solutions containing formic acid, acetic acid and/or phosphoric acid are preferred.

When an acid catalyst is used for the hydrolysis reaction, the amount of the acid catalyst added is 0.05 parts by weight with respect to 100 parts by weight of all the alkoxysilane compounds used in the hydrolysis reaction, from the viewpoint of making the hydrolysis proceed more rapidly. part or more is preferable, and 0.1 part by weight or more is more preferable. On the other hand, from the viewpoint of appropriately adjusting the progress of the hydrolysis reaction, the amount of the acid catalyst to be added is preferably 20 parts by weight or less, more preferably 10 parts by weight or less with respect to 100 parts by weight of all the alkoxysilane compounds. Here, the total amount of alkoxysilane compound means the amount including all of the alkoxysilane compound, its hydrolyzate and its condensate, and the same shall apply hereinafter.

The hydrolysis reaction can be carried out in a solvent. The solvent can be appropriately selected in consideration of the stability, wettability, volatility, etc. of the photosensitive resin composition. Examples of solvents include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy -Alcohols such as 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 Ethers such as , propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethyl ether; methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone , diisobutyl ketone, cyclopentanone, 2-heptanone and other ketones; dimethylformamide, dimethylacetamide and other amides; 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, butyl lactate and other acetates; toluene, xylene, hexane, cyclohexane and other aromatic or aliphatic hydrocarbons; γ-butyrolactone , N-methyl-2-pyrrolidone, dimethylsulfoxide and the like. You may use 2 or more types of these.

Among them, 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.

When a solvent is generated by the hydrolysis reaction, it is possible to perform the hydrolysis without a solvent. After the hydrolysis reaction is completed, it is also preferable to adjust the concentration to be suitable for the photosensitive resin composition by further adding a solvent. It is also possible to distill off and remove all or part of the alcohol produced by heating and/or under reduced pressure after hydrolysis, and then add a suitable solvent.

When a solvent is used for the hydrolysis reaction, the amount of the solvent to be added is preferably 50 parts by weight or more, more preferably 80 parts by weight or more, based on 100 parts by weight of all the alkoxysilane compounds, from the viewpoint of suppressing gel formation. . On the other hand, the amount of the solvent to be added is preferably 500 parts by weight or less, more preferably 200 parts by weight or less with respect to 100 parts by weight of all the alkoxysilane compounds, from the viewpoint of accelerating the hydrolysis.
Moreover, ion-exchanged water is preferable as the water used for the hydrolysis reaction. Although the amount of water can be set arbitrarily, it is preferably 1.0 to 4.0 mol with respect to 1 mol of all alkoxysilane compounds.

As a method for the dehydration condensation reaction, for example, there is a method of heating the silanol compound solution obtained by the hydrolysis reaction of the organosilane compound as it 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. Further, reheating or addition of a base catalyst may be performed in order to increase the degree of polymerization of polysiloxane. Also, depending on the purpose, after hydrolysis, an appropriate amount of the alcohol produced may be distilled off under heating and/or under reduced pressure, and then a suitable solvent may be added.

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. As the method for removing the catalyst, washing with water, treatment with an ion-exchange resin, and the like are preferable from the viewpoint of ease of operation and removability. Washing with water is a method of diluting a polysiloxane solution with a suitable hydrophobic solvent, washing with water several times, and concentrating the obtained organic layer with an evaporator or the like. Ion exchange resin treatment is a method of contacting a polysiloxane solution with a suitable ion exchange resin.

(F) Pigment Examples of (F) pigment include (F-1) white pigment and (F-2) black pigment, and at least one of them is preferably contained. By containing (F-1) a white pigment and (F-2) a black pigment, the light shielding property of the cured film can be improved. In addition, (F-1) containing a white pigment is more preferable because the reflectivity of the cured film can be improved.

Examples of (F-1) white pigments include compounds selected from titanium dioxide, zirconium oxide, aluminum oxide, talc, mica, white carbon, magnesium oxide, zinc oxide, barium carbonate, and composite compounds thereof. be done. You may contain 2 or more types of these. Among these, it is preferable to contain titanium dioxide because of its high reflectivity and easy industrial use. The crystal structure of titanium dioxide is classified into an anatase type, rutile type, and brookite type. Among these, rutile-type titanium oxide is preferable because of its low photocatalytic activity.

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

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

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

(F-2) Black pigments include, for example, 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 pigments. These may be coated with a resin. Mixed organic pigments include, for example, 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 preferable from the viewpoint of achieving both a moderately high OD value and pattern workability. The weight ratio of the red pigment and the blue pigment is preferably 20/80 to 80/20, more preferably 30/70 to 70/30. Specific examples of representative pigments are shown below by color index (CI) number. 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, and PR220. , PR223, PR224, PR226, PR227, PR228, PR240, PR254, and the like. You may contain 2 or more types of these. Examples of blue pigments include Pigment Blue (hereinafter abbreviated as PB) 15, PB15:3, PB15:4, PB15:6, PB22, PB60 and PB64. You may contain 2 or more types of these. Black inorganic pigments include, for example, 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; metal carbides and the like. You may contain 2 or more types of these. Among the above black pigments, titanium nitride, zirconium nitride, carbon black, palladium oxide, platinum oxide, gold oxide, silver oxide, and a weight ratio of red pigment to blue pigment of 20/80 to 80 are used because of their high light-shielding properties. /20 mixed pigments are preferred. The content of the black pigment is preferably 0.2% by weight or more, more preferably 0.5% by weight or more, from the viewpoint of adjusting the reflectance and OD to suppress color mixture 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, more preferably 3% by weight or less.

(G) Naphthoquinonediazide compound The (G) naphthoquinonediazide compound includes, for example, a compound in which a sulfonic acid of naphthoquinonediazide is bonded to a compound having a phenolic hydroxyl group via an ester.

The (G) naphthoquinonediazide compound to be used is not particularly limited, but a compound in which the sulfonic acid of naphthoquinonediazide is ester-bonded to a compound having a phenolic hydroxyl group is preferable. Examples of compounds having a phenolic hydroxyl group used here include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, and BisP-MZ. , BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (tetrakis P-DO-BPA), TrisP -HAP, TrisP-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T-OCHP, methylene tris- FR-CR, BisRS-26X, BisRS-OCHP (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC- F, 4PC, BIR-BIPC-F, TEP-BIP-A (trade names, manufactured by Asahi Organic Chemicals Industry Co., Ltd.), 4,4'-sulfonyldiphenol (manufactured by Wako Pure Chemical Industries, Ltd.), BPFL (trade name, manufactured by JFE Chemical Co., Ltd.) can be mentioned.

Among these, preferred compounds having a phenolic hydroxyl group include, for example, 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, BIR-BIPC-F etc. 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, BPFL. A preferred example is a compound having a phenolic hydroxyl group into which 4-naphthoquinonediazide sulfonic acid is introduced via an ester bond, but compounds other than this can also be used.

(G) The naphthoquinonediazide compound preferably has a molecular weight of 300 to 1,500, more preferably 350 to 1,200. By setting the molecular weight to 300 or more, an effect of inhibiting dissolution of unexposed areas can be obtained. Also, by setting the molecular weight to 1500 or less, a good relief pattern without scum or the like can be obtained.

These (G) naphthoquinonediazide compounds may be used alone or in combination of two or more. The content of these (G) naphthoquinonediazide compounds is preferably 1 to 30 parts by weight relative to the (E) resin. By making it 1 part by weight or more, processing can be performed with practical sensitivity. Moreover, by making it 30 weight part or less, the photosensitive resin composition excellent in light resistance is obtained.
Further, when (G) a naphthoquinonediazide compound is added, unreacted photosensitive agent remains in unexposed areas, which may cause coloration of the film after heat curing. In order to obtain a cured film with little coloration, it is preferable to heat the developed coating film after irradiating it with ultraviolet rays.

The photosensitive resin composition of the present invention may further contain a cross-linking agent, an adhesion improver, a solvent, a surfactant, a dissolution inhibitor, a stabilizer, an antifoaming agent and the like, if necessary.
By including a cross-linking agent in the photosensitive resin composition of the present invention, the cross-linking of polysiloxane is promoted during heat curing, and the degree of cross-linking of the cured film is increased. Curing agents include, for example, nitrogen-containing organic substances, silicone resin curing agents, isocyanate compounds and their polymers, methylolated melamine derivatives, methylolated urea derivatives, various metal alcoholates, various metal chelate compounds, thermal acid generators, photoacid generation material, and the like. You may contain 2 or more types of these. Among these, methylolated melamine derivatives and methylolated urea derivatives are preferably used from the viewpoint of the stability of the curing agent.

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

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)butyltri methoxysilane, 4-(3,4-epoxycyclohexyl)butyltriethoxysilane and the like. You may contain 2 or more types of these.

The content of the adhesion improver in the photosensitive resin composition of the present invention is preferably 0.1% by weight or more, more preferably 1% by weight or more, based on the solid content, from the viewpoint of further improving the adhesion to the substrate. . On the other hand, the content of the adhesion improver is preferably 20% by weight or less, more preferably 10% by weight or less, based on the solid content, from the viewpoint of further suppressing color change due to heating.

By including a solvent in the photosensitive resin composition of the present invention, it is possible to easily adjust the viscosity suitable for coating and improve the uniformity of the coating film. It is preferable to combine a solvent having a boiling point of more than 150° C. and 250° C. or less under atmospheric pressure with a solvent having a boiling point of 150° C. or less. By containing a solvent having a boiling point of more than 150° C. and not more than 250° C., the solvent is volatilized appropriately during coating, and the coating film dries, thereby suppressing uneven coating and improving the uniformity of the film thickness. can be done. Furthermore, by containing a solvent having a boiling point of 150° C. or less under atmospheric pressure, it is possible to suppress the solvent from remaining in the cured film of the present invention, which will be described later. From the viewpoint of suppressing the solvent remaining in the cured film and improving chemical resistance and adhesion over a long period of time, a solvent having a boiling point of 150° C. or lower under atmospheric pressure should be contained in an amount of 50% by weight or more of the total solvent. is preferred.

Solvents having a boiling point of 150° C. or less under atmospheric pressure include, for example, ethanol, isopropyl alcohol, 1-propyl alcohol, 1-butanol, 2-butanol, isopentyl alcohol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol mono Ethyl 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, n-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, 5-hydroxy-2-pentanone. You may use 2 or more types of these.

Solvents having a boiling point of more than 150° C. and 250° C. or less under atmospheric pressure include, for example, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-tert-butyl ether, propylene glycol mono-n-butyl ether, and 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-ethoxypropionic acid Ethyl, 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, carbonic acid Propylene, N-methylpyrrolidone, cyclohexanone, cycloheptanone, diethylene glycol monobutyl ether, ethylene glycol dibutyl ether. You may use 2 or more types of these.

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

By including a surfactant in the photosensitive resin composition of the present invention, it is possible to improve flowability during application. Surfactants include, for example, "Megafac" (registered trademark) F142D, F172, F173, F183, F445, F470, F475, F477 (trade names, manufactured by Dainippon Ink & Chemicals, Inc.), NBX- 15, fluorine-based surfactants such as FTX-218 (trade name, manufactured by Neos Co., Ltd.); )), polyalkylene oxide surfactants, poly(meth)acrylate surfactants, and the like. You may contain 2 or more types of these.

The solid content concentration of the photosensitive resin composition of the present invention can be arbitrarily set according to the coating method and the like. For example, when forming a film by spin coating as described later, it is common to set the solid content concentration to 5% by weight or more and 50% by weight or less.

Next, the method for producing the photosensitive resin composition of the present invention will be explained. The photosensitive resin composition of the present invention can be obtained by mixing the aforementioned components (E) to (G) and, if necessary, other components. More specifically, for example, (E) a resin, (G) a naphthoquinone diazide compound and, if necessary, other additives are added to an arbitrary solvent and stirred to dissolve, then (F) a pigment is added, A method of further stirring for 20 minutes to 3 hours and filtering the resulting solution may be used.

Next, the dry film of the present invention will be explained. The dry film of the present invention is obtained by drying the coating film of the aforementioned photosensitive resin composition of the present invention. Moreover, the film thickness of the dry film of the present invention is preferably 1 to 20 μm. It is preferable to set the film thickness of the dry film to 1 μm or more because the film flatness of the uneven structure can be improved. Further, by setting the film thickness of the dry film to 20 μm or less, the film uniformity of the dry film can be improved, which is preferable.

Next, the cured film of the present invention will be described. The cured film of the present invention comprises a cured product of the aforementioned photosensitive resin composition of the present invention. The thickness of the cured film is preferably 1 to 20 μm. In addition, the absorbance per 10 μm of film thickness at a wavelength of 365 nm of the cured film is 1.0 to 4.0, the absorbance per 10 μm of film thickness at a wavelength of 405 nm is 0.5 to 2.0, and the absorbance per 10 μm of film thickness at a wavelength of 436 nm. is preferably 0.5 to 2.0, and the absorbance per 10 μm film thickness at a wavelength of 450 nm is preferably 0.5 to 2.0. By setting the absorbance of the cured film within the above range, the method for producing a cured film-coated substrate of the present invention can be applied, which is preferable. In addition, when the cured film of the present invention is used as a partition wall for micro LEDs, it is necessary to sufficiently shield the colors of light emitted from adjacent micro LEDs to avoid color mixture. By setting the absorbance within the above range, it is possible to obtain good light shielding properties, which is preferable.
When the cured film of the present invention is used as a partition wall of a micro LED, by setting the reflectance to 20% or more, the light emitted from the micro LED can be reflected by the cured film, improving the light extraction efficiency. 50% or more is more preferable, and 60% or more is even more preferable. On the other hand, a reflectance of 80% or less is preferable, and more preferably 70% or less, because it is possible to efficiently utilize the light irradiated when post-exposure is applied to the developed coating film.

Furthermore, the arithmetic mean surface roughness of the cured film is preferably 0.005 μm to 0.1 μm. By setting the arithmetic mean surface roughness of the cured film to 0.005 μm or more, it is possible to improve the adhesion between the upper layer film formed in the post-process and the cured film of the present invention, which is preferable. In addition, by setting the arithmetic mean surface roughness of the cured film to 0.1 m or less, it is possible to uniformly and easily form an upper layer film on the cured film of the present invention in a post-process, so it is preferable, 0.02 μm or less is preferable, 0.015 μm or less is more preferable, and 0.010 μm or less is most preferable.

Next, the image display device of the present invention will be explained. The image display device of the present invention comprises a substrate in which wiring electrodes for driving are formed on a substrate, micro LED cells are arranged, a cured film is brought into contact with the side surfaces of the micro LEDs without gaps, and the substrate is integrated; can be created by combining the IC drivers, etc. By integrating the micro LED and the cured film by contacting them without gaps, the sides of the micro LED do not come into contact with the air. The term "no gap" as used herein means that the distance between the micro LED and the cured film is preferably 0.5 μm or less, more preferably 0.1 μm or less.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Among the compounds used in Synthesis Examples and Examples, abbreviations are used, and the details thereof are shown below.
PGMEA: propylene glycol monomethyl ether acetate DAA: diacetone alcohol.

The solid content concentrations of the polysiloxane solutions and acrylic resin solutions in Synthesis Examples 1 and 2 were determined by the following method. 1.5 g of polysiloxane solution or acrylic resin solution was put into an aluminum cup and heated at 250° C. for 30 minutes using a hot plate to evaporate the liquid component. The weight of the solid content remaining in the aluminum cup after heating was weighed, and the solid content concentration of the polysiloxane solution or acrylic resin solution was obtained from the ratio to the weight before heating.

The polysiloxane and acrylic resin solution weight average molecular weights in Synthesis Examples 1 and 2 were determined by the following method. Using a GPC analyzer (HLC-8220; manufactured by Tosoh Corporation) and using tetrahydrofuran as a fluidized bed, GPC analysis was performed based on "JIS K7252-3 (enacted date = 2008/03/20)", A polystyrene equivalent weight average molecular weight was measured.

The content ratio of each organosilane unit in polysiloxane in Synthesis Example 1 was obtained by the following method. A polysiloxane solution is injected into a “Teflon” (registered trademark) NMR sample tube with a diameter of 10 mm and ²⁹ Si-NMR measurement is performed. The content ratio of each organosilane unit was calculated from the ratio of the integrated value of Si. ²⁹ Si-NMR measurement conditions are shown below.
Apparatus: Nuclear magnetic resonance apparatus (JNM-GX270; manufactured by JEOL Ltd.)
Measurement method: Gated decoupling method Measurement nucleus frequency: 53.6693 MHz ( ²⁹ Si nuclei)
Spectrum width: 20000Hz
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.

Synthesis Example 1 Polysiloxane (E-1) solution In a 500 ml three-necked flask, 99.15 g (0.500 mol) of phenyltrimethoxysilane and 24.64 g (0.500 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane were added. 0.100 mol), 54.48 g (0.400 mol) of methyltrimethoxysilane, and 103.44 g of PGMEA were charged, and while stirring at room temperature, 0.768 g of phosphoric acid was added to 54.00 g of water (0.50 wt. %) was added over 30 minutes. After that, the three-necked flask was immersed in an oil bath at 70° C. and stirred for 90 minutes, and then the oil bath was heated to 115° C. over 30 minutes. After 1 hour from the start of heating, the internal temperature (solution temperature) of the three-necked flask reached 100° C., and the mixture was heated and stirred for 2 hours (internal temperature: 100 to 110° C.) to obtain a polysiloxane solution. In addition, 0.05 liter/minute of nitrogen was flowed during the temperature rise and heating and stirring. A total of 123.00 g of methanol and water, which are by-products, were distilled during the reaction. PGMEA was added to the obtained polysiloxane solution so that the solid content 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 (converted to polystyrene). In addition, from ^{the 29} Si-NMR measurement results, repeating units derived from phenyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and methyltrimethoxysilane in polysiloxane (E-1) The molar ratios were 50 mol %, 10 mol % and 40 mol %, respectively.

Synthesis Example 2 Acrylic Resin (e-1) Solution A 500 ml three-necked flask was charged with 3 g of 2,2′-azobis(isobutyronitrile) and 50 g of PGMEA. After that, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo[5.2.1.0 ^2,6 ]decan-8-yl methacrylate were charged, stirred at room temperature for a while, and after replacing the inside of the flask with nitrogen, The mixture was heated and stirred at °C for 5 hours to obtain an acrylic resin solution. PGMEA was added to the obtained acrylic resin solution so that the solid content concentration was 40% by weight to obtain an acrylic resin (e) solution. The acrylic resin (e) had a weight average molecular weight of 10,000 (converted to polystyrene).

Preparation Example 1 Photosensitive resin composition (P-1)
(F-1) As a white pigment, 50.00 g of titanium dioxide (R-960; DuPont Co., Ltd. (SiO ₂ /Al ₂ O ₃ surface treatment, median diameter 0.21 μm)), (E-1) poly As siloxane, 50.00 g of the polysiloxane (E-1) solution obtained in Synthesis Example 1 was mixed and dispersed using a mill-type disperser filled with zirconia beads to obtain a pigment dispersion (MW-1). .

Next, 32.00 g of a pigment dispersion (MW-1), 34.925 g of a polysiloxane (E-1) solution, (G) 2.000 g of TP5-280M (manufactured by Toyo Gosei Co., Ltd.) as a naphthoquinone dido compound, 0.800 g of a melamine resin compound (“Nikalac” (registered trademark) MX-270 (trade name), manufactured by Sanwa Kasei Co., Ltd.) as a curing agent, and 2-(3,4-epoxycyclohexyl) as an adhesion improver. Ethyltrimethoxysilane (KBM-303 (trade name), manufactured by Shin-Etsu Chemical Co., Ltd.) 0.800 g; , DIC Corporation) was dissolved in a mixed solvent of 3.000 g of DAA and 26.175 g of PGMEA and stirred. Then, filtration was performed with a 5.0 μm filter to obtain a photosensitive resin composition (P-1).

Preparation Example 2 Photosensitive resin composition (P-2)
A photosensitive resin composition (P-2) was obtained in the same manner as in Preparation Example 1 except that the acrylic resin (e-1) solution was used instead of the polysiloxane (E-1) solution.

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

Preparation Example 4 Photosensitive resin composition (P-4)
The addition amount of the polysiloxane (E-1) solution was changed to 62.925 g, the mixed solvent PGMEA was changed to 14.175 g, and the addition amount of the pigment dispersion (MW-1) was changed to 16.000 g. was carried out in the same manner as in Preparation Example 1 to obtain a photosensitive resin composition (P-4).

Preparation Example 5 Photosensitive resin composition (P-5)
The added amount of the polysiloxane (E-1) solution was changed to 35.925 g, the mixed solvent PGMEA was changed to 25.575 g, and the added amount of TP5-280M as the (G) naphthoquinone dido compound was changed to 1.600 g. A photosensitive resin composition (P-5) was obtained in the same manner as in Preparation Example 1 except for the changes.

Preparation Example 6 Photosensitive resin composition (P-6)
The added amount of the polysiloxane (E-1) solution was changed to 33.925 g, the mixed solvent PGMEA was changed to 26.775 g, and the added amount of TP5-280M as the (G) naphthoquinone dide compound was changed to 2.400 g. A photosensitive resin composition (P-6) was obtained in the same manner as in Preparation Example 1 except for the changes.

Preparation Example 7 Photosensitive resin composition (P-7)
(F-1) Preparation example except that zirconia oxide (3YI-R; manufactured by Toray Industries, Inc. (Al ₂ O ₃ surface treatment, median system 0.50 μm)) was used instead of R-960 as the white pigment. 1 to obtain a photosensitive resin composition (P-7).

Preparation Example 8 Photosensitive resin composition (P-8)
The amount of polysiloxane (E-1) solution added was changed to 39.925 g, the mixed solvent PGMEA was changed to 23.175 g, and TP5-280M was not added as (G) naphthoquinone dide compound. A photosensitive resin composition (P-8) was obtained in the same manner as in Example 1.

Preparation Example 9 Photosensitive resin composition (P-9)
Same as Preparation Example 1 except that the amount of polysiloxane (E-1) solution added was changed to 90.925 g, the mixed solvent PGMEA was changed to 2.175 g, and the pigment dispersion (MW-1) was not added. to obtain a photosensitive resin composition (P-9).

The compositions of Preparation Examples 1 to 9 are summarized in Table 1.

<Creation of a glass substrate having an uneven structure>
Under a stream of dry nitrogen, 15.9 g (0.043 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (manufactured by Central Glass Co., Ltd., BAHF), 1,3-bis(3 -aminopropyl)tetramethyldisiloxane (SiDA) 0.62 g (0.0025 mol) was dissolved in 200 g N-methylpyrrolidone (NMP). 15.5 g (0.05 mol) of 3,3′,4,4′-diphenylethertetracarboxylic dianhydride (manac manufactured by Manac Co., Ltd., ODPA) was added together with 50 g of N-methylpyrrolidone (NMP), Stir at 40° C. for 2 hours. After that, 1.17 g (0.01 mol) of 4-ethynylaniline (manufactured by Tokyo Kasei Co., Ltd.) was added and stirred at 40° C. for 2 hours. Furthermore, a solution obtained 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. Stirring was continued at 40° C. for 2 hours. After stirring was completed, the solution was poured into 2 L of water, and polymer solid precipitates were collected by filtration. Furthermore, it was washed with 2 L of water three times, and the collected polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a polyamic acid ester.

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

The positive photosensitive precursor resin composition is spin-coated on a 10 cm square non-alkali glass substrate (manufactured by AGC Techno Glass Co., Ltd., film thickness 0.7 mm) (trade name 1H-360S, manufactured by Mikasa Co., Ltd.). ) and dried at a temperature of 100° C. for 2 minutes using a hot plate (trade name: SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.) to prepare a dry film. For the prepared dried film, a parallel light mask aligner (trade name: PLA-501F, manufactured by Canon Inc.) was used, and an ultra-high pressure mercury lamp was used as a light source. The portion was exposed with an exposure amount of 200 mJ/cm ² (i-ray conversion value) without a photomask. After that, using an automatic developing device ("AD-2000 (trade name)" manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 120 seconds, and then rinsed with water for 30 seconds. . After that, it was cured at 230° C. for 30 minutes using an oven (DN43HI manufactured by Yamato Scientific Co., Ltd.) to obtain a glass substrate having an uneven structure on one half of the substrate. The obtained glass substrate having the concave-convex structure has, on one half of the substrate, convex structures each having a length and a width of 20 μm and a film thickness of 5 μm, and the distance between the adjacent convex structures is 80 μm. are patterned as follows.

Evaluation methods in each example and comparative example are shown below.
<Evaluation of Film Flatness Performance of Photosensitive Resin Composition for Glass Substrate Having Concavo-convex Structure>
The photosensitive resin composition used in each example and comparative example was spin-coated (trade name 1H-360S, manufactured by Mikasa Co., Ltd.) on the glass substrate having the uneven structure described above, and a hot plate (trade name SCW- 636, manufactured by Dainippon Screen Mfg. Co., Ltd.), and dried by heating at a temperature of 100° C. for 2 minutes. The appearance of the obtained substrate with the dry film was visually inspected, and the flatness of the photosensitive resin composition with respect to the substrate with the concave-convex structure was evaluated according to the following criteria.
A: It seems that the uneven structure is flattened and the dry film is uniformly formed without unevenness in thickness.

B: The concave-convex structure is flattened, but the dry film appears to have thickness unevenness.
C: The uneven structure was not flattened, and part of the convex structure remained without being flattened, and the dry film appeared uneven.

<Spectral irradiance measurement of radiant light in the process of exposing a dry film>
The spectral irradiance of the light emitted from the exposure machine in the step of exposing the dry film used in each of the examples and comparative examples was measured at 1 nm using a spectral irradiance meter (trade name USR45DA, manufactured by Ushio Inc.). was measured with a wavelength resolution of . Subsequently, by adding up the spectral irradiance for each wavelength in the wavelength range of 300 nm to 450 nm, the total value (A) of the spectral irradiance in the wavelength range of 300 nm to 450 nm of the radiant light in the step of exposing the dry film is obtained. Calculated.

<Spectral irradiance measurement of radiant light passing through dry film>
The photosensitive resin composition used in each example and comparative example was spin-coated on a glass substrate (trade name 1H-360S, manufactured by Mikasa Co., Ltd.), and a hot plate (trade name SCW-636, Dainippon Screen Mfg. Co., Ltd.) was applied. (manufactured by Co., Ltd.), and dried by heating at a temperature of 100° C. for 2 minutes to form a dry film having a thickness of 1 μm. Value of spectral irradiance after passing through the dry film after irradiating the radiant light from the exposure machine in the step of exposing the dry film from the dry film surface side with a film thickness of 1 μm used in each example and comparative example was measured on the glass substrate side with a wavelength resolution of 1 nm using an irradiance meter (trade name USR45DA, manufactured by Ushio Inc.). Subsequently, by summing the spectral irradiance for each wavelength in the wavelength range of 300 nm to 450 nm, the spectral irradiance in the wavelength range of 300 nm to 450 nm of the radiant light that has passed through the dry film when the film thickness is 1 μm is summed. Value (B) was calculated.

<Flatness after development of the photosensitive resin composition on a glass substrate having an uneven structure>
The photosensitive resin composition used in each example and comparative example was spin-coated (trade name 1H-360S, manufactured by Mikasa Co., Ltd.) on the glass substrate having the uneven structure described above, and a hot plate (trade name SCW- 636, manufactured by Dainippon Screen Mfg. Co., Ltd.), and dried at a temperature of 100° C. for 2 minutes to form a dry film having a thickness of 10 μm. The substrate with the dry film was exposed without a photomask using a predetermined exposure machine and exposure amount set for each example and comparative example. Thereafter, using an automatic developing device ("AD-2000 (trade name)" manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds, followed by rinsing with water for 30 seconds. , a portion corresponding to a film thickness of 5 μm on the dry film upper layer was removed by development. With respect to the substrate after development, the film thickness of the coating film of the photosensitive resin composition was 5 μm, which was the same as the film thickness of the convex structures. For the obtained substrate after development, the coating film after development was enlarged using a visual inspection of the appearance and a microscope adjusted to a magnification of 20 times, and the photosensitive resin composition for the substrate having an uneven structure according to the following criteria. Flatness after development was evaluated.
A: It appears that the film thickness of the convex structure and the film thickness of the coating film after development are approximately the same.
B: The film thickness of the convex structure and the film thickness of the coating film after development appear to be approximately the same, but the film thickness of the coating film after development is observed to be uneven.
C: There is a portion where the developed film remains on the top of the convex structure, and many portions where the film thickness of the convex structure and the film thickness of the coating film after development are different are observed.

<Calculation of film thickness change amount of the coating film in the step of developing the dry film after the exposure>
The photosensitive resin composition used in each example and comparative example was spin-coated (trade name 1H-360S, manufactured by Mikasa Co., Ltd.) on the glass substrate having the uneven structure described above, and a hot plate (trade name SCW- 636, manufactured by Dainippon Screen Mfg. Co., Ltd.), and dried at a temperature of 100° C. for 2 minutes to form a dry film having a thickness of 10 μm. Regarding the film thickness, the value of the central part of the dry film in the pattern-free region on the half surface of the glass substrate was measured using a surfcom stylus type film thickness measuring device. After that, exposure and development were performed under the same conditions as in each example and comparative example. The film thickness of the coating film after development was measured using a Surfcom stylus film thickness measuring device, and the amount of change in film thickness before and after development was calculated. In addition, the above-mentioned film thickness change amount was calculated at five points on the top, bottom, left, and right including the central portion of the pattern-free region on the half surface of the glass substrate, and the maximum and minimum film thickness change amounts were obtained. Furthermore, the variation in film thickness variation in the developing process was evaluated from the difference between the maximum value and the minimum value. This difference is preferably 1.0 μm or less.

<Spectral irradiance measurement of radiant light in the step of post-exposure of the coating film after development>
The spectral irradiance of the radiant light in the step of post-exposure of the developed coating film used in each example and comparative example was measured at 1 nm using a spectral irradiance meter (trade name USR45DA, manufactured by Ushio Inc.). was measured with a wavelength resolution of . Subsequently, by adding the spectral irradiance for each wavelength in the wavelength range of 300 nm to 450 nm, the total value of the spectral irradiance in the wavelength range of 300 nm to 450 nm of the radiated light in the process of post-exposing the coating film after development. (C) was calculated.

<Spectral irradiance measurement of radiant light passing through the coating film after development>
The photosensitive resin composition used in each example and comparative example was spin-coated on a glass substrate (trade name 1H-360S, manufactured by Mikasa Co., Ltd.), and a hot plate (trade name SCW-636, Dainippon Screen Mfg. Co., Ltd.) was applied. (manufactured by Co., Ltd.) was heated at a temperature of 100 ° C. for 2 minutes and dried, except that the film thickness was changed, processing was performed under the same conditions as in each example and comparative example, and the film thickness of the coating film after development. was processed to be 1 μm. The radiant light from the exposure machine in the step of post-exposure of the developed coating film used in each example and comparative example was irradiated from the side of the developed coating film having a thickness of 1 μm, and the developed coating film The value of the spectral irradiance after passing through was measured on the glass substrate side with an irradiance meter (trade name USR45DA, manufactured by Ushio Inc.) with a wavelength resolution of 1 nm. Subsequently, by summing the spectral irradiance for each wavelength in the wavelength region of 300 nm to 450 nm, the spectral irradiance in the wavelength region of 300 nm to 450 nm of the emitted light that has passed through the coating film after development when the film thickness is 1 μm. A total value (D) of illuminance was calculated.

<Reflectance>
The photosensitive resin composition used in each example and comparative example was processed in the same manner as the processing conditions in each example and comparative example except that the film thickness was changed, and cured to 10 μm on a flat glass substrate. A membrane was prepared. The obtained cured film was used as a model of the cured film of the cured film-attached substrate formed on the substrate having the concave-convex structure formed in each example and comparative example. (manufactured by Konica Minolta, Inc.) was used to measure the reflectance at a wavelength of 550 nm in the SCI mode from the cured film side. In addition, evaluation was not carried out for those judged to be difficult to form a cured film because the amount of the coating film developed during development was too large.

<Absorbance (OD value)>
The photosensitive resin composition used in each example and comparative example was processed in the same manner as the processing conditions in each example and comparative example except that the film thickness was changed, and cured to 10 μm on a flat glass substrate. A membrane was prepared. The obtained cured film was used as a model of the cured film of the substrate with the cured film formed on the substrate having the concave-convex structure formed in each example and comparative example, and an optical densitometer (U -4100) was used to measure the intensity of incident light and transmitted light, and the absorbance (OD value) was calculated from the following formula (III). In addition, evaluation was not carried out for those judged to be difficult to form a cured film due to a large amount of coating film developed during development.

OD value = log10(I0/I) ... formula (III)
I0: Incident light intensity I: Transmitted light intensity.

<Arithmetic mean surface roughness>
The photosensitive resin composition used in each example and comparative example was processed in the same manner as in the processing conditions in each example and comparative example, except that the thickness of the resulting cured film was changed, and a flat glass substrate A substrate with a solid cured film of 10 μm was prepared thereon. The obtained cured film was used as a model of the cured film of the substrate with the cured film formed on the substrate having the uneven structure, which was formed in each example and comparative example. , the arithmetic mean surface roughness was obtained. In addition, evaluation was not carried out for those judged to be difficult to form a cured film of 10 μm because the amount of dry film developed during development was too large.

<Median diameter of pigment>
For the photosensitive resin composition used in each example and comparative example, the pigment dispersion used as a raw material was placed in a quartz cell, and a submicron particle size distribution measuring device (N4-PLUS; manufactured by Beckman Coulter, Inc.) was measured. was used to measure the particle size distribution of the pigment by a laser diffraction method, and the median diameter was calculated.

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

(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 amount before development was changed to 80 mJ.

(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 amount before development was changed to 100 mJ.

(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 amount before development was changed to 40 mJ.

(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 amount before development was changed to 60 mJ.

(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 amount before development was changed to 100 mJ.

(Example 7)
The photosensitive resin composition of Preparation Example 1 was spin-coated (trade name 1H-360S, manufactured by Mikasa Co., Ltd.) on the glass substrate having the uneven structure described above, and a hot plate (trade name SCW-636, Dainippon Screen Mfg. Co., Ltd.) was applied. (manufactured by Co., Ltd.) was used to form a coating film. After that, it was dried at a temperature of 100° C. for 2 minutes to form a dry film having a thickness of 10 μm. A parallel light mask aligner (trade name: PLA-501F, manufactured by Canon Inc.) is used as an exposure machine in the step of exposing a substrate with a dry film, and an ultra-high pressure mercury lamp is used as a light source. , no wavelength-selective optical filter was placed. The dry film-coated substrate was exposed with an exposure dose of 30 mJ (converted from the spectral irradiance at a wavelength of 365 nm) using the above-described exposure device without using a photomask. At this time, the sum of spectral irradiances at wavelengths of 400 nm to 450 nm was 43.8 mW/cm ² , and the sum of spectral irradiances at wavelengths of 300 nm to 400 nm was 46.8 mW/cm ² . The same method as in Example 1 was used for the subsequent processing of developing the substrate with the dried film after exposure.

(Example 8)
The photosensitive resin composition of Preparation Example 1 was spin-coated (trade name 1H-360S, manufactured by Mikasa Co., Ltd.) on the glass substrate having the uneven structure described above, and a hot plate (trade name SCW-636, Dainippon Screen Mfg. Co., Ltd.) was applied. (manufactured by Co., Ltd.) was used to form a coating film. After that, it was dried at a temperature of 100° C. for 2 minutes to form a dry film having a thickness of 10 μm. A parallel light mask aligner (trade name: PLA-501F, manufactured by Canon Inc.) is used as an exposure machine in the step of exposing a substrate with a dry film, and an ultra-high pressure mercury lamp is used as a light source. , an optical filter (trade name: LU0400, manufactured by Asahi Spectrosco Co., Ltd.) that passes light of 400 nm or longer was arranged so that light of 400 nm or longer was selectively irradiated. The dry film-coated substrate was exposed with an exposure amount of 25 mJ (converted from the spectral irradiance at a wavelength of 405 nm) using the aforementioned exposure machine without using a photomask. At this time, the sum of spectral irradiances at wavelengths of 400 nm to 450 nm was 40.2 mW/cm ² , and the sum of spectral irradiances at wavelengths of 300 nm to 400 nm was 0.65 mW/cm ² . The same method as in Example 1 was used for the subsequent processing of developing the substrate with the dried film after exposure.

(Example 9)
The photosensitive resin composition of Preparation Example 1 was spin-coated (trade name 1H-360S, manufactured by Mikasa Co., Ltd.) on the glass substrate having the uneven structure described above, and a hot plate (trade name SCW-636, Dainippon Screen Mfg. Co., Ltd.) was applied. (manufactured by Co., Ltd.) was used to form a coating film. After that, it was dried at a temperature of 100° C. for 2 minutes to form a dry film having a thickness of 10 μm. A parallel light mask aligner (trade name: PLA-501F, manufactured by Canon Inc.) is used as an exposure machine in the step of exposing a substrate with a dry film, and an ultra-high pressure mercury lamp is used as a light source. , an optical filter (trade name SH0400, manufactured by Asahi Spectrosco Co., Ltd.) that passes light of 400 nm or less was placed so that light of 400 nm or less was selectively irradiated. The dry film-coated substrate was exposed with an exposure amount of 70 mJ (converted from the spectral irradiance at a wavelength of 365 nm) using the above-mentioned exposure machine without using a photomask. The same method as in Example 1 was used for the subsequent processing of developing the substrate with the dried film after exposure. At this time, the sum of spectral irradiances at wavelengths of 400 nm to 450 nm was 0.97 mW/cm ² , and the sum of spectral irradiances at wavelengths of 300 nm to 400 nm was 44.9 mW/cm ² . Exposure was performed with radiant light in which the sum of spectral irradiances at wavelengths of 400 nm to 450 nm was 2.2% of the sum of spectral irradiances at wavelengths of 300 nm to 400 nm, and which substantially did not contain light with a wavelength of 400 nm or longer. The same method as in Example 1 was used for the subsequent processing of developing the substrate with the dried film after exposure.

(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 amount of exposure before development was changed to 15 mJ.

(Comparative example 2)
Processing was performed in the same manner as in Example 1 except that P-8 was used as the photosensitive resin composition and no exposure was performed before development.

(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 amount before development was changed to 10 mJ. Tables 2 and 3 show the configuration and evaluation results of each example and comparative example.

1: Pattern part 2: Base substrate 3: Coated film of photosensitive resin composition 4: Dry film of photosensitive resin composition 5: Coated film of photosensitive resin composition after development 6: Cured film of photosensitive resin composition H: Film thickness

Claims

A step of providing a coating film of a photosensitive resin composition on a substrate having an uneven structure on its surface, a step of drying the coating film to form a dry film, a step of exposing the dry film, and a dry film after the exposure. A method for producing a cured film-coated substrate comprising, in order, a step of partially developing a surface in the film thickness direction, and a step of heating the developed coating film to form a cured film, wherein the step of exposing the dry film. For the total spectral irradiance (A) in the wavelength range of 300 nm to 450 nm of the synchrotron radiation in the dry film A method for producing a substrate with a cured film, wherein the attenuation ratio (B)/(A) of spectral irradiance per 1 μm of film thickness satisfies the following relational expression (I).
0.001≦(B)/(A)≦0.2 (I)
The method for producing a cured film-coated substrate according to claim 1, wherein the emitted light in the step of exposing the dry film does not substantially contain light with a wavelength of 400 nm or more.
3. The substrate with a cured film according to claim 1 or 2, wherein the radiation light in the step of exposing the dry film contains at least light having a wavelength of 365 ± 5 nm or 385 ± 10 nm at which the illuminance is maximum. Production method.
The method for producing a cured film-coated substrate according to claim 1 or 2, further comprising a step of post-exposure before heating the developed coating film.
In the step of post-exposing the developed coating film, the total value (C) of the spectral irradiance in the region of the wavelength of 300 nm to 450 nm of the radiation light post-exposed to the developed coating film, and the developed coating film Regarding the total value (D) of the spectral irradiance in the wavelength range of 300 nm to 450 nm of the transmitted radiant light, the attenuation ratio (D)/(C) per 1 μm of the dry film thickness satisfies the following relational expression (II). 5. The method for producing a cured film-coated substrate according to claim 4.
0.05≦(D)/(C)≦0.99 (II)
The method for producing a cured film-coated substrate according to claim 1 or 2, wherein the photosensitive resin composition contains (E) a resin, (F) a pigment, and (G) a naphthoquinonediazide compound.
The method for producing a cured film-coated substrate according to claim 6, wherein the resin (E) is polysiloxane.
The method for producing a cured film-coated substrate according to claim 6 or 7, wherein the (F) pigment is (F-1) a white pigment having a median diameter of 0.1 to 0.6 µm.
The method for producing a cured film-coated substrate according to claim 1 or 2, wherein the substrate having an uneven structure on its surface has an LED as a convex structure on the substrate.
A substrate with a cured film manufactured by the method according to claim 1 or 2.
The cured film has an absorbance of 1.0 to 4.0 per 10 μm of film thickness at a wavelength of 365 nm, an absorbance of 0.5 to 2.0 per 10 μm of film thickness at a wavelength of 405 nm, and an absorbance of 10 μm of film thickness at a wavelength of 436 nm. is 0.5 to 2.0, and the absorbance per 10 μm film thickness at a wavelength of 450 nm is 0.5 to 2.0.
The cured film-coated substrate according to claim 10, wherein the cured film has a reflectance of 20 to 80% per 10 µm film thickness at a wavelength of 550 nm.
The cured film-coated substrate according to claim 10, wherein the cured film has an arithmetic mean surface roughness of 0.005 µm to 0.1 µm.
An image display device comprising the substrate with a cured film according to claim 10.
An LED and a cured film having a light-shielding property are provided on a substrate, and the cured film having a light-shielding property contacts and integrates without gaps on the side surface of the LED, and the absorbance of the cured film per 10 μm of the film thickness at a wavelength of 365 nm is 1. 0 to 4.0, the absorbance per 10 μm film thickness at a wavelength of 405 nm is 0.5 to 2.0, the absorbance per 10 μm film thickness at a wavelength of 436 nm is 0.5 to 2.0, and the absorbance 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.