Photosensitive resin composition, layered body, display device, and information terminal

Abstract

One purpose of the present invention is to provide a photosensitive resin composition with which it is possible to form a cured film that combines high light scattering, high light transmission, microfabricability, and flatness. The present invention is a photosensitive resin composition that is characterized by including (A) organic polymer particles, (B) a binder resin, (C) a photosensitizer, and (D) a polymerization inhibitor, wherein the included quantity of the (A) organic polymer particles is 1 part by weight to 40 parts by weight per 100 parts by weight of the included quantity of the (B) binder resin, and the refractive index (nA) at a wavelength of 633 nm of the (A) organic polymer particles and the refractive index (nB) at a wavelength of 633 nm of the components other than the (A) organic polymer particles in a cured film of the photosensitive resin composition satisfy the following general expression (I). (I): 0.10≤nA–nB≤0.70

Description

Photosensitive resin composition, laminate, display device, and information terminal

[0001] The present invention relates to a photosensitive resin composition, a laminate having a substrate and a cured film, a display device, and an information terminal.

[0002] In lighting fixtures such as organic EL (OLED) lighting and LED lighting, display devices such as laser displays, liquid crystal displays, OLED displays, and microLED displays, and various other optical devices, it is known that laminates having a light-scattering layer are formed on the light source to scatter light from the light source. Furthermore, particularly in display device applications, development is underway on configurations in which laminates have a light-scattering layer on the light source to suppress the decrease in light extraction efficiency caused by the reflection of light emitted from the light source at the interfaces of each layer in the display device, or to improve the appearance quality of the display device by suppressing the reflection of external light from electrodes in the display device. In these applications, the light-scattering layer generally requires high reliability against heat and light.

[0003] As a resin composition for forming such a light-scattering layer, a material has been proposed in which a light-scattering agent is added to a highly reliable binder resin (see, for example, Patent Document 1).

[0004] International Publication No. 2021 / 049401

[0005] However, the light-scattering resin composition disclosed in Patent Document 1 had the problem of insufficient light transmittance, which reduced the efficiency of extracting light from a light source and lowered brightness. In addition, resin compositions used for display applications generally require microfabrication and flatness by photolithography.

[0006] Therefore, the object of the present invention is to provide a photosensitive resin composition that can produce a cured film that achieves both high light scattering properties, high light transmittance, and fine processability and flatness.

[0007] To solve the above problems, the present invention has the following configuration. That is, the photosensitive resin composition of the present invention contains (A) organic polymer particles, (B) binder resin, (C) photosensitive agent, and (D) polymerization inhibitor, wherein the content of (A) organic polymer particles is 1 to 40 parts by weight per 100 parts by weight of the content of (B) binder resin, and the refractive index (nA) of the (A) organic polymer particles at a wavelength of 633 nm and the refractive index (nB) of the components other than the (A) organic polymer particles in the cured film of the photosensitive resin composition at a wavelength of 633 nm satisfy the following general formula (I): 0.10 ≤ nA - nB ≤ 0.70 ... (I)

[0008] The photosensitive resin composition of the present invention can produce a cured film that achieves both high light scattering, high light transmission, and excellent microprocessability and flatness.

[0009] This is a cross-sectional view showing one embodiment of a laminate of the present invention having a cured film. This is a cross-sectional view showing one embodiment of a laminate of the present invention having a patterned light scattering layer as a cured film. This is a cross-sectional view showing one embodiment of a laminate of the present invention having a light scattering layer formed as a cured film and a color filter layer. This is a cross-sectional view showing one embodiment of a display device of the present invention having a light-emitting light source selected from a light source having an organic EL element, a light source having a mini LED element, and a light source having a micro LED element, and a light source having a color filter layer formed as a cured film.

[0010] The present invention will be described in more detail below. Preferred embodiments of the photosensitive resin composition, laminate, display device, and information terminal of the present invention will be specifically described below, but the present invention is not limited to the following embodiments and can be modified in various ways depending on the purpose and application.

[0011] The photosensitive resin composition of the present invention comprises (A) organic polymer particles, (B) binder resin, (C) photosensitive agent, and (D) polymerization inhibitor, wherein the content of (A) organic polymer particles is 1 to 40 parts by weight per 100 parts by weight of the content of (B) binder resin, and the refractive index (nA) of the (A) organic polymer particles at a wavelength of 633 nm and the refractive index (nB) of the components other than the (A) organic polymer particles in the cured film of the photosensitive resin composition at a wavelength of 633 nm satisfy the following general formula (I): 0.10 ≤ nA - nB ≤ 0.70 ... (I) Furthermore, the laminate of the present invention is a laminate having a substrate and a cured film of the photosensitive resin composition.

[0012] In the laminate of the present invention, the substrate refers to the base substrate in the laminate of the present invention. Examples of substrates include glass substrates, resin plates, resin films, and drive substrates such as TFTs and PCBs. As the material of the glass substrate, alkali-free glass is preferred. As the material of the resin plate and resin film, polyester, (meth)acrylic polymer, transparent polyimide, polyethersulfone, etc. are preferred. The thickness of the glass plate and resin plate is preferably 1 mm or less, and more preferably 0.8 mm or less. As the material of the resin film, polyethylene terephthalate, TAC (triacetylcellulose), polyimide, cycloolefin polymer, polycarbonate, etc. The thickness of the resin film is preferably 100 μm or less.

[0013] Furthermore, when using a drive substrate such as a TFT or PCB as the base material, it is preferable to have a light-emitting light source selected from a light source having an organic EL element or a light source having an LED element, as described later, on the base material. The light source having an LED element may be a light source having a mini LED element and / or a light source having a micro LED element.

[0014] Figure 1 shows a cross-sectional view of one embodiment of the laminate of the present invention having a substrate and a cured film. The laminate has a cured film 2 on a base substrate 1.

[0015] The photosensitive resin composition of the present invention can be microfabricated by photolithography. Photolithography is a technique for performing microfabrication by exposing a material to light, such as by exposure through a photomask, and then developing it. Examples of photosensitive resin compositions for microfabrication by photolithography include a negative-type photosensitive resin composition, which hardens by light irradiation and forms a pattern by removing unexposed areas in a development process described later, and a positive-type photosensitive resin composition, which hardens mainly by heat and forms a pattern by removing exposed areas in a development process described later. The photosensitive resin composition preferably has the composition described later.

[0016] A method for forming a cured film in the laminate of the present invention may include, for example, a coating step of (i) applying a photosensitive resin composition to a substrate and drying it to obtain a dried film, an exposure step of (ii) irradiating the obtained dried film with light, a developing step of (iii) dissolving and removing the portion of the dried film after exposure that is soluble in the developer, and a heating step of curing the film after development.

[0017] If the photosensitive resin composition is a photocurable resin composition, it is preferable to have at least (i) a coating step and (ii) an exposure step. If the photosensitive resin composition is a negative-type photosensitive resin composition, it is preferable to have at least (i) a coating step, (ii) an exposure step, (iii) a development step, and (iv) a heating step. If the photosensitive resin composition is a positive-type photosensitive resin composition and no pattern is formed, it is preferable to have at least (i) a coating step, (ii) an exposure step, and (iv) a heating step in this order, and if a pattern is formed, it is preferable to have at least (i) a coating step, (ii) an exposure step, (iii) a development step, and (iv) a heating step in this order. The cured film in the laminate of the present invention may be either the patterned film or a solid film without a pattern.

[0018] (i) Examples of coating methods in the coating process include slit coating and spin coating. (i) As for drying methods in the coating process, it is preferable to use a drying device such as an oven or a hot plate. The atmosphere of the drying device is not particularly limited and can be under nitrogen or air. The drying temperature is preferably 70 to 120°C and the drying time is preferably 1 to 60 minutes.

[0019] (ii) Examples of exposure equipment used in the exposure process include proximity exposure machines and reduction projection exposure machines. (ii) Examples of active light rays used in the exposure process include near-infrared light, visible light, and ultraviolet light, with ultraviolet light being preferred. Among ultraviolet light rays, it is more preferable to use wavelengths selected from the i-line with a wavelength of 365 nm, the h-line with a wavelength of 405 nm, and the g-line with a wavelength of 436 nm. Examples of light sources include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, halogen lamps, and germicidal lamps, with high-pressure mercury lamps and ultra-high-pressure mercury lamps being preferred. The exposure conditions can be appropriately selected depending on the thickness of the dry film to be exposed. Generally, 1 to 100 mW / cm² ２ Using an ultra-high pressure mercury lamp with an output of 1 to 10,000 mJ / cm², ２ It is preferable to expose with the exposure amount. (ii) In the exposure step, exposure may be performed via a photomask having a predetermined opening in order to form a pattern such as a partition wall, as described later, or an arbitrary pattern may be drawn directly using laser light or the like without using a photomask.

[0020] (iii) Examples of development methods in the development process include immersion, spray, and brush methods. As for the developer solution used, a solvent capable of dissolving unwanted parts of the film after exposure can be appropriately selected, and an aqueous solution mainly composed of water is preferred. Examples of developer solutions include inorganic alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, and calcium hydroxide; and organic alkaline aqueous solutions such as tetramethylammonium hydroxide and trimethylbenzylammonium hydroxide. Among these, potassium hydroxide aqueous solution or tetramethylammonium hydroxide aqueous solution is preferred from the viewpoint of improving resolution. From the viewpoint of improving developability, the concentration of the alkaline aqueous solution is preferably 0.01% by weight or more, and more preferably 0.03% by weight or more. On the other hand, from the viewpoint of suppressing peeling and corrosion of the pre-heating pattern, the concentration of the alkaline aqueous solution is preferably 5% by weight or less, and more preferably 1% by weight or less. Furthermore, from the viewpoint of improving resolution, the developer solution may contain a surfactant. The development temperature is preferably 20 to 50°C to facilitate process control.

[0021] (iv) Examples of heating devices used in the heating process include ovens and hot plates. The atmosphere of the heating device is not particularly limited and can be under nitrogen or air. The heating temperature is preferably 80 to 250°C, and the heating time is preferably 1 to 60 minutes.

[0022] The photosensitive resin composition of the present invention is characterized by containing (A) organic polymer particles, (B) binder resin, (C) photosensitive agent, and (D) polymerization inhibitor. By containing (A) organic polymer particles, a cured film with both high light scattering and high light transmission can be obtained. By containing (B) binder resin, it becomes possible to form a cured film. Furthermore, by containing (C) photosensitive agent, pattern processing becomes possible by exposure and development. In addition, by containing (D) polymerization inhibitor, reactions due to leaked light during exposure are suppressed, enabling fine pattern processing, and the rate of radical polymerization during photocuring is slowed, significantly improving the flatness of the film. Furthermore, by patterning the cured film in the laminate of the present invention, it is possible to improve interference uniformity without affecting the visibility in the display device. "Visibility" in the present invention consists of two viewpoints: brightness due to transmittance and the small number of bright spots on the film surface.

[0023] The photosensitive resin composition of the present invention comprises (A) organic polymer particles, (B) binder resin, (C) photosensitive agent, and (D) polymerization inhibitor.

[0024] (A) Organic polymer particles In the present invention, (A) organic polymer particles refer to organic resins that maintain their particle shape within a photosensitive resin composition.

[0025] Examples of (A) organic polymer particles in the present invention include melamine resin particles, styrene resin particles, and acrylic resin particles, but are not limited to these. Two or more types may be included. Among these, melamine resin particles are preferred because they can achieve both high light scattering and high light transmission.

[0026] (A) The content of organic polymer particles is characterized by being 1 to 40 parts by weight per 100 parts by weight of the binder resin (B). By using 1 part by weight or more, high light scattering properties can be obtained when the cured film described later is formed. By using 40 parts by weight or less, high light transmittance and low light reflectivity can be obtained when the cured film described later is formed.

[0027] In the present invention, it is preferable that the average particle diameter of the (A) organic polymer particles is 300 nm or more and 2,000 nm or less. By making the average particle diameter of the organic polymer particles 300 nm or more, the forward scattering component increases with increasing particle diameter, resulting in more favorable light scattering properties when the cured film described later is formed. As a result, interference unevenness can be effectively suppressed. On the other hand, by making it 2,000 nm or less, film flatness when the cured film described later is formed can be ensured.

[0028] The average particle diameter of the organic polymer particles is more preferably 500 nm or more, and even more preferably 800 nm or more. On the other hand, the average particle diameter of the organic polymer particles is more preferably 1,500 nm or less, and even more preferably 1,300 nm or less. (A) The average particle diameter of the organic polymer particles is determined by dynamic light scattering (DLS) using a dynamic light scattering particle size distribution analyzer (for example, nanoPartica SZ-100V2 Series nanoparticle analyzer (Horiba, Ltd.)). Details shall be measured by the method described in the examples.

[0029] (A) The refractive index (nA) of the organic polymer particles at a wavelength of 633 nm is preferably 1.60 or higher, and more preferably 1.62 or higher from the viewpoint of improving light scattering properties. It is preferable that the (A) organic polymer particles are particles made from melamine resin. Among organic polymer particles, using melamine resin particles (n=1.66) can improve light scattering and light transmission properties when forming the cured film described later. The refractive index (nA) can be measured by known methods such as the immersion method. For convenience, the refractive index at a wavelength of 633 nm of non-organic polymer particles used for comparison may also be treated as the refractive index (nA).

[0030] (A) It is preferable to use organic polymer particles as a dispersion obtained by mixing them with a dispersant and a solvent described later, and to prepare a photosensitive resin composition. Therefore, the photosensitive resin composition of the present invention may contain a dispersant.

[0031] Examples of the dispersant include polyoxyethylene, polyphosphoric acid, phosphate polyester, polyacrylamide, siloxane resin, acrylic resin, polystyrene resin, polycarbonate resin, vinyl chloride resin, polyester resin, vinyl acetate resin, and polyimide resin.

[0032] (B) Binder resin The (B) binder resin in the present invention refers to a resin, other than the (A) organic polymer particles in the photosensitive resin composition of the present invention, having a content of 5% by weight or more based on the total solid content of the photosensitive resin composition. When two or more types of resins each having a content of 5% by weight or more based on the total solid content of the photosensitive resin composition are contained, the mixture thereof is regarded as (B) the binder resin.

[0033] Examples of the (B) binder resin in the present invention include siloxane resin, acrylic resin, polystyrene resin, polycarbonate resin, vinyl chloride resin, polyester resin, vinyl acetate resin, and polyimide resin, and it is preferable to contain a siloxane resin or an acrylic resin.

[0034] From the viewpoint of film flatness, the content of (B) the binder resin is preferably 20% by weight or more, more preferably 35% by weight or more, based on the total solid content of the photosensitive resin composition. In the present specification, the solid content concentration of each component of the photosensitive resin composition indicates a mass ratio (% by weight) based on the mass of the total solid content obtained by removing the solvent from the photosensitive resin composition.

[0035] It is more preferable to contain a siloxane resin as (B) the binder resin. The siloxane resin is a hydrolysis / dehydration condensation product of an organosilane compound having a siloxane skeleton (Si-O bond) as the main skeleton. By containing a siloxane resin as (B) the binder resin, a cured film excellent in heat resistance, weather resistance, flatness and transparency can be obtained.

[0036] The siloxane resin preferably contains at least one radical polymerizable group. That is, it is preferable that (B) the binder resin is a siloxane resin containing at least one radical polymerizable group.

[0037] The siloxane resin is more preferably a siloxane resin having a trifunctional organosilane unit. That is, it is preferable that (B) the binder resin is a siloxane resin containing a trifunctional organosilane unit. Among these, a siloxane resin having a trifunctional organosilane unit represented by general formula (1) is more preferable.

[0038]

[0039] In the above general formula (1), R １ represents a monovalent organic group having 1 to 20 carbon atoms. Two or more types of repeating units represented by general formula (1) having different R １ may be included in the siloxane resin. R １ preferably contains a group selected from an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms, from the viewpoint of facilitating adjustment of the molecular weight of the siloxane resin during polymerization. However, in the alkyl group and the aryl group, at least a part of hydrogen atoms thereof may be substituted with other substituents.

[0040] A siloxane resin having a repeating unit represented by general formula (1), by including a repeating unit derived from a trifunctional organosilane compound, increases the crosslinking density of the siloxane resin in a cured film, and can improve the hardness and chemical resistance of the film.

[0041] The repeating unit represented by general formula (1) is derived from an organosilane compound represented by the following general formula (2). That is, the siloxane resin containing the repeating unit represented by general formula (1) can be obtained by hydrolyzing and polycondensing an organosilane compound represented by the following general formula (2). Other organosilane compounds may also be used. In general formula (2), the notation of "-(OR ２ ) ３ " means that three "-(OR ２ )" groups are bonded to the Si atom.

[0042]

[0043] In the above general formula (2), R １ is R in the above general formula (1) １It represents the same group as above. In the general formula (2) above, R ２ These may be the same or different, and represent a monovalent organic group having 1 to 20 carbon atoms or hydrogen, with alkyl groups having 1 to 6 carbon atoms being preferred.

[0044] Examples of organosilane compounds represented by general formula (2) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and 3-glycidoxypropyltri Methoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-ethyl-3-{[3-(trimethoxysilyl)propoxy]methyl}oxetane, 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane, phenyltrimethoxysilane, phenyltriethoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxy Silane, tolyltrimethoxysilane, tolyltriethoxysilane, styryltrimethoxysilane, styryltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropyltriethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropyltriethoxysilane, 3-trimethoxysilylpropionic acid, 3-triethoxysilyl Examples include lupropionic acid, 4-trimethoxysilyl butyrate, 4-triethoxysilyl butyrate, 5-trimethoxysilylvaleric acid, 5-triethoxysilylvaleric acid, 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-trimethoxysilylpropyl cyclohexyldicarboxylic acid anhydride, 3-triethoxysilylpropyl cyclohexyldicarboxylic acid anhydride, 3-trimethoxysilylpropyl phthalic acid anhydride, and 3-triethoxysilylpropyl phthalic acid anhydride. Two or more of these may be used.

[0045] Other organosilane compounds may also be included. Examples of other organosilane compounds include bifunctional organosilane compounds such as dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenylsilanediol, styrylmethyldimethoxysilane, and styrylmethyldiethoxysilane, as well as tetrafunctional organosilane compounds such as tetramethoxysilane, tetraethoxysilane, and silicate 51 (tetramethoxysilane oligomer). Two or more of these may be used.

[0046] As described above, the siloxane resin preferably contains at least one radical polymerizable group. That is, it is preferable that the siloxane resin contains at least one radical polymerizable group-containing organosilane compound as the organosilane compound represented by general formula (2). By containing a radical polymerizable group-containing organosilane compound in the siloxane resin, a crosslinking reaction can proceed with radicals generated from the photopolymerization initiator described later upon light irradiation, thereby increasing the degree of curing of the exposed area. Examples of radical polymerizable groups include vinyl groups, methacrylic groups, acrylic groups, allyl groups, and styryl groups. Two or more of these may be included. Among these, from the viewpoint of photoreactivity, it is preferable that the siloxane resin contains methacrylic groups, acrylic groups, and styryl groups, and it is even more preferable that the siloxane resin contains at least a styryl group. By containing a styryl group, excellent pattern processability and film flatness can be ensured when a cured film described later is formed.

[0047] The siloxane resin preferably contains 1 to 60 mol% of repeating units having a styryl group in the total repeating units. By making the repeating units having a styryl group 1 mol% or more in the total repeating units, sufficient photoreactivity can be ensured and the film flatness of the cured film can be secured. By making the repeating units having a styryl group 60 mol% or less in the total repeating units of the cured film, the increase in the refractive index of the (B) binder resin at a wavelength of 633 nm can be suppressed, the interfacial reflectance between the (A) organic polymer particles and components other than the (A) organic polymer particles in the cured film can be increased, and the light scattering properties can be further improved. More preferably, the repeating units having a styryl group are 10 mol% or more in the total repeating units, and even more preferably 15 mol% or more. More preferably, the repeating units having a styryl group are 50 mol% or less in the total repeating units, and even more preferably 45 mol% or less.

[0048] The siloxane resin preferably contains at least one organosilane compound containing a carboxyl group and / or a carboxylic anhydride group, as an organosilane compound represented by general formula (2). Including an organosilane compound containing a carboxyl group and / or a carboxylic anhydride group can improve developability during pattern formation.

[0049] From the viewpoint of coatability, the weight-average molecular weight (Mw) of the siloxane resin is preferably 1,000 or more, and more preferably 2,000 or more. On the other hand, from the viewpoint of developability, the Mw of the siloxane resin is preferably 500,000 or less, and more preferably 300,000 or less. Here, the Mw of the siloxane resin in this invention refers to the polystyrene equivalent value measured by gel permeation chromatography (GPC). The measurement method is as described in the examples below.

[0050] Siloxane resins can be obtained by hydrolyzing the aforementioned organosilane compounds and then subjecting the hydrolyzed products to a dehydration condensation reaction in the presence or absence of a solvent. Catalysts such as acids or bases may be used in the hydrolysis and dehydration condensation reactions.

[0051] (C) Photosensitive agent The (C) photosensitive agent in the present invention includes, but is not limited to, photoradical generators, photoacid generators, photobase generators, and naphthoquinone diazide compounds. Two or more of these may be included. Among these, it is preferable that the (C) photosensitive agent is a photoradical generator or a naphthoquinone diazide compound.

[0052] The photoradical generator can be any agent that decomposes and / or reacts with the active light irradiated in the (ii) exposure step to generate radicals, and is preferably one that decomposes and / or reacts with at least one of the i, h, or g rays to generate radicals. Examples of photoradical generators include α-aminoalkylphenone compounds such as 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; and 2,4,6-trimethylbenzoylphenylphosphine. Acylphosphine oxide compounds such as oxides, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-phosphine oxide; 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)], 1-phenyl Examples include oxime ester compounds such as ru-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, and ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime); α-hydroxyketone compounds such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, and 1-hydroxycyclohexyl-phenylketone; and acetophenone compounds such as 2,2-diethoxyacetophenone, 2,3-diethoxyacetophenone, 4-t-butyldichloroacetophenone, benzalacetophenone, and 4-azidobenzalacetophenone. These may contain two or more types.Among these, it is preferable that the photoradical generator contains at least an oxime ester compound, from the viewpoint of generating radicals that are resistant to oxygen damage, increasing reactivity on the surface of the cured film, and reducing the surface roughness of the cured film. Furthermore, it is preferable that the acylphosphine oxide compound is included, from the viewpoint of absorbing long-wavelength light, exhibiting a photobleaching effect, and maintaining the transparency of the film.

[0053] The content of the photoradical generator is preferably 0.5 to 20% by weight, and more preferably 1 to 10% by weight, of the total solid content of the photosensitive resin composition. By increasing the content of the photoradical generator to 0.5% by weight or more, radical curing can be effectively promoted. On the other hand, by keeping it at 20% by weight or less, the elution of residual (C) photosensitive agent can be suppressed.

[0054] Examples of naphthoquinone diazide compounds include compounds in which a phenolic hydroxyl group is bonded to the sulfonic acid of naphthoquinone diazide via an ester.

[0055] The naphthoquinone diazide compound used is not particularly limited, but a compound having a phenolic hydroxyl group is preferably bonded to the sulfonic acid of naphthoquinone diazide via an ester. Examples of compounds having phenolic hydroxyl groups used here include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (tetrakiss P-DO-BPA), TrisP-HAP, TrisP-PA, BisOFP-Z, BisRS-2P, BisPG-26X, and BisR Examples include S-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T-OCHP, Methylenethris-FR-CR, BisRS-26X, BisRS-OCHP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.), 4,4'-Sulfonyldiphenol (manufactured by Wako Pure Chemical Industries, Ltd.), and BPFL (trade name, manufactured by JFE Chemical Corporation).

[0056] Among these, examples of compounds having preferred phenolic hydroxyl groups include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisPC-OCHP, methylenethris-FR-CR, BisRS-26X, BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F, and the like. Among these, particularly preferred compounds having phenolic hydroxyl groups include, for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR-BIPC-F, 4,4'-sulfonyldiphenol, and BPFL. While compounds having phenolic hydroxyl groups to which 4-naphthoquinone diazidosulfonic acid is introduced via ester bonds are preferred, other compounds can also be used. The molecular weight of the naphthoquinone diazide compound is preferably 300 to 1,500, and more preferably 350 to 1,200. A molecular weight of 300 or higher provides an effect of inhibiting the dissolution of unexposed areas. Furthermore, a molecular weight of 1,500 or lower provides a good pattern without development residue.

[0057] These naphthoquinone diazide compounds may be used individually or in combination of two or more. The content of these naphthoquinone diazide compounds is preferably 1 to 30% by weight of the total solid content of the photosensitive resin composition. A content of 1% by weight or more allows for pattern formation with practical sensitivity. A content of 30% by weight or less yields a photosensitive resin composition with excellent pattern processability.

[0058] Furthermore, when naphthoquinone diazide compounds are added, unreacted photosensitive agents may remain in unexposed areas, potentially causing discoloration of the film after heat curing. To obtain a cured film with minimal discoloration, it is preferable to irradiate the entire film with ultraviolet light and heat it after development.

[0059] (D) Polymerization Inhibitor In the present invention, the (D) polymerization inhibitor is preferably one that has the effect of inhibiting radical polymerization. Examples of polymerization inhibitors include hindered phenol compounds, quinone compounds, amine compounds, and aromatic polyol compounds. Specific examples of hindered phenol compounds include di-t-butylhydroxytoluene, butylhydroxyanisole, 4-methoxyphenol, 1,4-benzoquinone, and t-butylcatechol. Examples of commercially available polymerization inhibitors include "IRGANOX" (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425, 1520, 245, 259, 3114, 565, and 295 (all trade names, manufactured by BASF Japan Ltd.). Two or more of these may be included. By using polymerization inhibitors that have the effect of suppressing radical polymerization, the rate of radical polymerization during photocuring can be controlled, and the flatness of the film can be significantly improved. Furthermore, by suppressing the gelation of the varnish, which occurs as the resin reaction progresses within the varnish, the flatness of the film at the time of formation can be maintained even after time has passed.

[0060] (D) The content of the polymerization inhibitor is preferably 0.1 to 5% by weight, and more preferably 0.2 to 1% by weight, of the total solid content of the photosensitive resin composition. (D) By increasing the content of the polymerization inhibitor to 0.1% by weight or more, pattern processability can be improved. On the other hand, by keeping it at 5% by weight or less, a cured film can be produced without reducing sensitivity.

[0061] The photosensitive resin composition of the present invention is characterized in that the refractive index (nA) of the (A) organic polymer particles at a wavelength of 633 nm (nB) of the components other than the (A) organic polymer particles in the cured film of the photosensitive resin composition at a wavelength of 633 nm (nB) satisfies the following relationship (I): 0.10 ≤ nA - nB ≤ 0.70 ... (I) By making the refractive index difference (nA - nB) 0.10 or more, high light scattering properties can be obtained when the cured film described later is formed. Furthermore, by making the refractive index difference (nA - nB) 0.70 or less, excessive interfacial reflection between the (A) organic polymer particles and the components other than the (A) organic polymer particles in the cured film can be suppressed, and light transmittance can be further improved.

[0062] The refractive index can be measured using a prism coupler on the cured film, as described in the examples below. The method for preparing the cured film is not particularly limited, but it can be prepared as described above, for example.

[0063] Figure 2 shows a cross-sectional view of one embodiment of the laminate of the present invention having a substrate and a patterned light-scattering layer as a cured film. The laminate has a patterned light-scattering layer 3 on a base substrate 1.

[0064] The thickness of the cured film is not particularly limited, but when it is laminated on a light source or the like, as described later, it is preferably 0.5 μm to 10 μm. By setting the thickness of the light scattering layer to this range, better light extraction efficiency can be achieved. In this invention, 2 μm was selected as a representative value for the thickness of the light scattering layer, and attention was paid to the haze value, transmittance, and reflectance per 2 μm of film thickness.

[0065] In the present invention, it is preferable that the cured film of the photosensitive resin composition has a haze value (hazeλ = 550nm) of 20% or more and less than 80% at a wavelength of 550nm with a film thickness of 2 μm. A hazeλ = 550nm of 20% or more makes it possible to exhibit better light scattering properties. On the other hand, a hazeλ = 550nm of less than 80% makes it possible to suppress light scattering during exposure and achieve better pattern processing properties. The hazeλ = 550nm can be satisfied as 20% or more and less than 80% by controlling the difference between (A) the refractive index of organic polymer particles at a wavelength of 633nm (nA) and (A) the refractive index of components other than organic polymer particles in the cured film at a wavelength of 633nm (nB), (A) the average particle diameter of organic polymer particles, and (A) the content of organic polymer particles in (B) the binder resin per 100 parts by weight. Hazeλ = 550nm is more preferably 25% or more, and even more preferably 30% or more. Hazeλ = 550nm is more preferably less than 70%, and even more preferably less than 60%.

[0066] In the present invention, the cured film of the photosensitive resin composition preferably has a haze value (Hazeλ = 450nm) of 25% or more and less than 90% at a wavelength of 450nm with a film thickness of 2 μm, and preferably satisfies the following general formula (II). That is, it is preferable that Hazeλ = 450nm is the same as or higher than Hazeλ = 550nm. Hazeλ = 450nm ≥ Hazeλ = 550nm ... (II) By having Hazeλ = 450nm be the same as or higher than Hazeλ, it becomes possible to scatter light more effectively.

[0067] The haze value can be measured for the cured film using a haze meter (HSP-150Vis (manufactured by Murakami Color Technology Research Institute Co., Ltd.)) as described in the examples below. The method for preparing the cured film is not particularly limited, but it can be prepared as described above, for example.

[0068] In the present invention, it is preferable that the cured film has a transmittance of 85% or more and 100% or less at a wavelength of 550 nm at a film thickness of 2 μm, and a reflectance of 5.0% or more and 10.0% or less at a wavelength of 550 nm at a film thickness of 2 μm. This suppresses a reduction in light extraction efficiency and ensures sufficient brightness.

[0069] The transmittance can be measured on the cured film using a spectrophotometer (Hitachi High-Tech Corporation, U-4100) as described in the examples below, and the reflectance can be measured on the cured film using a spectrocolorimeter (Konica Minolta, Inc., CM-2600d) as described in the examples below. The method for preparing the cured film is not particularly limited, but for example, it can be prepared as described above.

[0070] In addition, means for achieving the above ranges for the haze value, transmittance, and reflectance of the light scattering layer include, for example, forming a cured film using a preferred composition of the photosensitive resin composition described later.

[0071] In the present invention, the surface roughness Ra of the cured film of the photosensitive resin composition is preferably 30 nm or less. This makes it less susceptible to the effects of film thickness unevenness, even in thin films, and allows for uniform scattering of light. Therefore, when applied as a light scattering layer to a display device, it is possible to suppress changes in color and brightness when viewed from different angles.

[0072] In the present invention, the maximum height roughness Rz of the cured film is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. This suppresses strong localized scattering and improves visibility.

[0073] The surface roughness Ra and maximum height roughness Rz can be measured for the cured film using a Surfcom stylus-type film thickness measuring device (manufactured by Tokyo Seimitsu Co., Ltd.), as described in the examples below. The method for preparing the cured film is not particularly limited, but it can be prepared as described above, for example.

[0074] In the present invention, it is preferable that the content of (A) organic polymer particles is 1% to 27% by weight of the total solid content of the photosensitive resin composition. It is more preferable that it is 15% by weight or less. When the content of (A) organic polymer particles is 1% by weight or more of the total solid content of the photosensitive resin composition, the light scattering properties are improved. Furthermore, when the content of organic polymer particles is 27% by weight or less of the total solid content of the photosensitive resin composition, development residue is suppressed and a higher resolution pattern can be formed.

[0075] In the present invention, it is preferable that the (B) binder resin is a transparent resin whose transmittance in the wavelength range of 450 nm to 650 nm is 90% to 100% when a cured film with a thickness of 2 μm is made using the (B) binder resin. A transmittance of 90% or more suppresses the reduction in light extraction efficiency when light passes through the cured film, ensures sufficient brightness, and improves visibility. As described in the examples below, the transmittance of the cured film can be measured using a spectrophotometer (Hitachi High-Tech Corporation, U-4100). The method for making the cured film is not particularly limited, but for example, it can be made by having (i) a coating step and (iv) a heating step in that order, with a heating temperature of 100°C and a heating time of 60 minutes.

[0076] Regarding the binder resin (B) described above, it is preferable that the refractive index at a wavelength of 633 nm is 1.30 to 1.55 when a cured film with a thickness of 2 μm is made using the binder resin (B). By making the refractive index at a wavelength of 633 nm of the cured film of the binder resin (B) 1.30 or higher, excessive interfacial reflection between the binder resin (B) and the organic polymer particles (A) can be suppressed, and light transmittance can be further improved. On the other hand, by making the refractive index at a wavelength of 633 nm of the cured film of the binder resin (B) 1.55 or lower, interfacial reflection between the binder resin (B) and the organic polymer particles (A) can be increased, and light scattering can be further improved. The refractive index at a wavelength of 633 nm of the cured film of the binder resin (B) can be measured using a prism coupler for a cured film with a thickness of 2 μm, as described in the examples below. The method for making the cured film is not particularly limited, but for example, it can be made as described above.

[0077] The photosensitive resin composition of the present invention may contain components other than those described in (A) to (D) above, and may optionally contain photopolymerizable compounds, solvents, surfactants, adhesion modifiers, metal chelates, etc.

[0078] The photosensitive resin composition of the present invention preferably contains a photopolymerizable compound. A photopolymerizable compound is a compound having two or more ethylenically unsaturated double bonds in its molecule. Considering the ease of radical polymerization, the photopolymerizable compound preferably contains a vinyl group, an allyl group, a methacrylic group, an acrylic group, or a styryl group, and more preferably a methacrylic group, an acrylic group, or a styryl group.

[0079] Examples of photopolymerizable compounds include 1,6-hexanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecanediacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, tetrapentaerythritol nonamethacrylate, and tetrapentaerythritol decamethacrylate. Two or more of these may be included.

[0080] The content of the photopolymerizable compound is preferably 1 to 50% by weight of the total solid content of the photosensitive resin composition. A content of 1% by weight or more effectively promotes radical curing. On the other hand, a content of 50% by weight or less suppresses excessive radical reactions and improves resolution.

[0081] The photosensitive resin composition of the present invention preferably further contains a solvent. The solvent has the function of adjusting the viscosity of the photosensitive resin composition to a range suitable for application and improving application uniformity. As the solvent, it is preferable to combine a solvent with a boiling point at atmospheric pressure greater than 150°C and 250°C or less, and a solvent with a boiling point of 150°C or less.

[0082] Examples of solvents include alcohols such as isopropanol and diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and diethylene glycol ethyl methyl ether; methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, and methyl ethyl ketone. Examples include ketones such as clopentanone; amides such as dimethylformamide and dimethylacetamide; acetates such as ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, and butyl lactate; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, and cyclohexane; γ-butyrolactone, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. Two or more of these may be included.

[0083] The solvent content can be arbitrarily set depending on the coating method and other factors. For example, when forming a film by spin coating, the solvent content is generally 50 to 95% by weight in the photosensitive resin composition.

[0084] The photosensitive resin composition of the present invention can improve leveling properties during application by containing surfactants that do not have photopolymerizable groups. Examples of surfactants that improve leveling properties include silicone-based surfactants such as "BYK" (registered trademark)-333, 301, 331, 345, and 307 (all trade names, manufactured by Bic Chemie Japan Co., Ltd.); polyalkylene oxide-based surfactants; and poly(meth)acrylate-based surfactants. Two or more of these may be contained.

[0085] The photosensitive resin composition of the present invention can improve adhesion to a substrate by containing an adhesion modifier. Examples of adhesion modifiers include alicyclic epoxy compounds and silane coupling agents.

[0086] Examples of alicyclic epoxy compounds include 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 1,2-epoxy-4-vinylcyclohexane, butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone, 3,4-epoxycyclohexylmethyl methacrylate, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol E diglycidyl ether, hydrogenated bisphenol A bis(propylene glycol glycidyl ether) ether, hydrogenated bisphenol A bis(ethylene glycol glycidyl ether) ether, 1,4-cyclohexanedicarboxylic acid diglycidyl, and 1,4-cyclohexanedimethanol diglycidyl ether. Two or more of these may be included.

[0087] As silane coupling agents, organosilane compounds, such as those exemplified as raw materials for siloxane resins, can be suitably used.

[0088] The content of the adhesion improver is preferably 0.1 to 20% by weight of the total solid content of the photosensitive resin composition. A content of 0.1% by weight or more can further improve adhesion to the substrate. On the other hand, a content of 20% by weight or less can maintain pattern processing properties. A content of 1% by weight or more of the adhesion improver is more preferable. On the other hand, a content of 10% by weight or less of the adhesion improver is more preferable.

[0089] The cured film in the laminate of the present invention may be a cured film of a photosensitive resin composition containing a metal chelating agent. The metal chelating agent refers to a complex compound having a structure in which one or more polydentate ligands are chelated to a metal atom.

[0090] By including a metal chelating agent, (iv) even when the heating step is performed at a low temperature of 80 to 100°C, a cured film with low surface roughness can be formed. This is because all or part of the metal chelating agent is incorporated into the film, and the metal chelating agent can promote the condensation reaction between unreacted silanol groups remaining in the siloxane resin component.

[0091] The metal chelating agent is preferably a metal chelating agent represented by the following general formula (3).

[0092]

[0093] (M indicates a metal atom, R ３ Each of these is independently a hydrogen atom, an alkyl group, an aryl group, or an alkenyl group, and R ４ and R ５Each of these is independently a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, or an alkoxy group, where j is an integer from 0 to 8 and k is an integer from 1 to 4.) Examples of metal atoms M from the viewpoint of low coloration of the formed cured film include titanium, zirconium, aluminum, zinc, cobalt, molybdenum, lanthanum, barium, strontium, magnesium, or calcium. Among these, from the viewpoint of low coloration of the cured film and low surface free energy, zirconium or aluminum is preferred as the metal atom M, and aluminum is more preferred. That is, it is preferable to use an aluminum chelate compound or a zirconium chelate compound as the metal chelating agent.

[0094] The metal chelating agent represented by general formula (3) has R ３ Alkyl groups, aryl groups and alkenyl groups in, and R ４ and R ５ The alkyl, aryl, alkenyl, and alkoxy groups in this compound may all be substituted with other substituents.

[0095] In general formula (3), R ３ Examples of these groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decanyl, octadecanyl, phenyl, vinyl, allyl, or oleyl groups. Among these, from the viewpoint of the stability of the metal chelating agent, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-octadecyl, or phenyl groups are preferred. ４ and R ５Examples of these include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, phenyl group, vinyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-octadecyl group, or benzyloxy group. Among these, methyl group, t-butyl group, phenyl group, methoxy group, ethoxy group, or n-octadecyl group are preferred from the viewpoint of ease of synthesis and stability of the metal chelating agent.

[0096] Examples of zirconium chelate compounds in which the metal atom M is zirconium include zirconium tetran-propoxide, zirconium tetran-butoxide, zirconium tetraphenoxide, and zirconium tetraacetylacetonate.

[0097] Examples of aluminum chelate compounds in which the metal atom M is aluminum include aluminum trisacetylacetonate and aluminum tris(2,2,6,6-tetramethyl-3,5-heptanedione).

[0098] The content of the metal chelating agent is preferably 0.1 to 5% by weight. A content of 0.1% or more by weight can reduce the surface roughness of the cured film. On the other hand, a content of 5% or less by weight can suppress discoloration of the cured film. More preferably, the content of the metal chelating agent is 0.5 to 3% by weight of the total solid content of the photosensitive resin composition.

[0099] The laminate in the present invention preferably further includes a color filter layer (hereinafter sometimes referred to as "color filter"). The color filter has the function of transmitting visible light in a specific wavelength range and making the transmitted light a desired hue. By including a color filter, the color purity of the display device can be improved.

[0100] Figure 3 shows a cross-sectional view of one embodiment of the laminate of the present invention having a color filter layer. A color filter layer 4 is provided on a base material 1, and a light scattering layer 2 formed as a cured film is provided on the same.

[0101] Examples of color filters include those used in flat panel displays such as liquid crystal displays, which utilize pigment-dispersed materials in which pigments are dispersed in a photoresist. More specifically, examples include a blue color filter section that selectively transmits wavelengths of 400 nm to 550 nm, a green color filter section that selectively transmits wavelengths of 500 nm to 600 nm, a yellow color filter section that selectively transmits wavelengths of 500 nm or more, and a red color filter section that selectively transmits wavelengths of 600 nm or more. A black material may be included as a black matrix separating each color filter section. Alternatively, an overcoat section may be formed by applying a transparent overcoat material after forming each color filter section and the black matrix. When a black matrix and each color filter section are present, for example, as shown in Figure 3, a configuration in which the black matrix 5 and each color filter section 6 are formed on a light scattering layer is preferred.

[0102] Next, the display device of the present invention will be described.

[0103] The display device of the present invention comprises the laminate of the present invention described above, and a light source selected from a light source consisting of a liquid crystal element and a backlight, a light source having an organic EL element, and a light source having an LED element. The light source having an LED element may be a light source having a mini LED element and / or a light source having a micro LED element. In a light source consisting of a liquid crystal element and a backlight, the liquid crystal element refers to an element that controls the orientation of light, including a liquid crystal layer, electrodes, a glass substrate, a polarizing plate, etc. The backlight in a light source consisting of a liquid crystal element and a backlight is not limited in type or size, and examples include cold cathode fluorescent lamps, LEDs, and mini LEDs described later. A light source having an organic EL element refers to a self-emissive light source having at least an organic EL light-emitting layer. A light source having a mini LED refers to a self-emissive light source having a mini LED. A mini LED refers to an LED with a length and width of about 100 μm to 1 mm. A light source having a micro LED refers to a self-emissive light source having a micro LED. A micro LED refers to an LED with a length and width of less than 100 μm. The light-emitting light sources may be separated by a patterned cured film.

[0104] Figure 4 shows a cross-sectional view of one embodiment of the display device of the present invention having a light-emitting light source selected from a light source having an organic EL element, a light source having a mini LED element, and a light source having a micro LED element, and pixels. Between the base substrate 1 and the light scattering layer 2 formed on the upper part of the base substrate 1, there is a light-emitting light source 7 selected from a light source having an organic EL element, a light source having a mini LED element, and a light source having a micro LED element, and further on there is a color filter layer 4.

[0105] The method for manufacturing the display device of the present invention will be described using an example of a display device having a laminate of the present invention and a light source having an organic EL element. A photosensitive polyimide resin is applied to a glass substrate, and an insulating film with openings is formed using photolithography. After sputtering aluminum on top of that, aluminum patterning is performed using photolithography to form a back electrode layer made of aluminum in the openings where there is no insulating film. Subsequently, tris(8-quinolinolato)aluminum (hereinafter abbreviated as Alq3) is deposited on top of that as an electron transport layer by vacuum deposition, and then a white light-emitting layer is formed as a light-emitting layer by doping Alq3 with dicyanomethylenepyran, quinacridone, and 4,4'-bis(2,2-diphenylvinyl)biphenyl. Next, N,N'-diphenyl-N,N'-bis(α-naphthyl)-1,1'-biphenyl-4,4'-diamine is deposited as a hole transport layer by vacuum deposition. Finally, ITO is deposited as a transparent electrode by sputtering to create an organic EL cell having a white light-emitting layer. By bonding the laminate having the aforementioned cured film and the organic EL cell thus obtained opposite each other with a encapsulant, a display device can be fabricated.

[0106] Next, the information terminal of the present invention will be described.

[0107] The information terminal of the present invention is an information terminal having the display device of the present invention as described above, and is an electronic device used as a display, such as a personal computer, smartphone, tablet, smartwatch, smart glasses, smart home appliance, etc.

[0108] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these. The names of the compounds used, where abbreviations are used, are shown below: PGMEA: Propylene glycol monomethyl ether acetate; PGME: Propylene glycol monomethyl ether; BHT: Di-t-butylhydroxytoluene.

[0109] The solid content concentrations of the siloxane resin solutions and acrylic resin solutions in Synthesis Examples 1 to 7 were determined by the following method: 1.00 g of the siloxane resin solution was weighed into an aluminum cup and heated on a hot plate at 250°C for 30 minutes to evaporate the liquid. The weight of the solids remaining in the aluminum cup after heating was weighed, and the solid content concentration was determined from the ratio to the weight before heating.

[0110] The weight-average molecular weight of the siloxane resin solutions and acrylic resin solutions in Synthesis Examples 1-7 was measured as polystyrene-based weight-average molecular weight by the following method: Apparatus: GPC analyzer with RI detector (2695), Waters Corporation Column: PLgel MIXED-C column (Polymer Laboratories, 300 mm) x 2 (connected in series) Measurement temperature: 40°C Flow rate: 1 mL / min Solvent: Tetrahydrofuran (THF) 0.5 wt% solution Standard substance: Polystyrene Detection mode: RI.

[0111] The transmittance of the cured films of siloxane resin and acrylic resin in Synthesis Examples 1 to 7 was measured by the following method. A 10 cm square alkali-free glass substrate (manufactured by AGC Techno Glass Co., Ltd., thickness 0.5 mm; the same applies hereinafter) was used as the substrate. The siloxane resin solution and acrylic resin solution from Synthesis Examples 1 to 7 were applied to it by spin coating, and the film was dried at 90°C for 3 minutes using a hot plate (product name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.; the same applies hereinafter) to produce a dried film. The prepared dried film was heated in air at 100°C for 60 minutes using an oven (product name IHPS-222, manufactured by ESPEC Corporation; the same applies hereinafter) to obtain a solid film (cured film) with a thickness of 2 μm on the glass substrate. The transmittance of the obtained cured film was measured in the wavelength range of 300 nm to 800 nm using a spectrophotometer U-4100 (manufactured by Hitachi High-Tech Corporation), and the value at 550 nm was taken as the representative value.

[0112] The refractive indices of the siloxane resin solutions and cured acrylic resin films in Synthesis Examples 1 to 7 were measured by the following method. A solid film (cured film) with a thickness of 2 μm was obtained on a Si wafer (6 inches) in the same manner as the transmittance measurement method described above, except that a Si wafer was used as the substrate. The refractive index of the obtained cured film was measured by irradiating the cured film surface with light of a wavelength of 633 nm from a direction perpendicular to the cured film surface using a prism coupler (PC-2000 (manufactured by Metricon Corporation)) under atmospheric pressure and 20°C, and the value was rounded to the third decimal place.

[0113] Synthesis Example 1: Siloxane Resin (PSL-1) Solution In a 1000 ml three-necked flask, 82.04 g (0.35 mol) of 3-acryloxypropyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, 47.67 g (0.35 mol) of methyltrimethoxysilane, 26.23 g (0.10 mol) of 3-trimethoxysilylpropyl succinic anhydride, 0.37 g of BHT, and 182.9 g of PGMEA were charged. While stirring at 40°C, an aqueous phosphoric acid solution, prepared by dissolving 0.39 g of phosphoric acid (0.2% by weight relative to the charged monomers) in 55.80 g of water, was added over 60 minutes. After that, the flask was immersed in an oil bath at 70°C and stirred for 60 minutes, and then the oil bath was heated to 110°C over 30 minutes. One hour after the start of heating, the solution temperature (internal temperature) reached 100°C. The mixture was then heated and stirred for two hours (internal temperature 100-110°C) to obtain a siloxane resin solution. During heating and stirring, a mixed gas of 95% nitrogen and 5% oxygen was supplied at a rate of 0.05 liters / min. A total of 127 g of methanol and water, by-products, distilled off during the reaction. PGMEA was added to the obtained siloxane resin solution to achieve a solid content concentration of 40% by weight to obtain a siloxane resin (PSL-1) solution. The obtained siloxane resin (PSL-1) contained radical polymerizable groups and trifunctional organosilane units represented by general formula (1). It had a weight-average molecular weight of 3,500, a transmittance of 99.5%, and a refractive index of 1.49.

[0114] Synthesis Example 2 Siloxane Resin (PSL-2) Solution In a 1000 ml three-necked flask, 40.66 g (0.175 mol) of 3-methacryloxypropylmethyldimethoxysilane, 12.32 g (0.05 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 81.72 g (0.60 mol) of methyltrimethoxysilane, 45.91 g (0.175 mol) of 3-trimethoxysilylpropyl succinic anhydride, 0.57 g of BHT, and 124.80 g of PGMEA were charged. While stirring at 40°C, an aqueous phosphoric acid solution prepared by dissolving 1.81 g of phosphoric acid (1.0 wt%) in 54.00 g of water (relative to the charged monomers) was added over 30 minutes. Then, the flask was immersed in an oil bath at 70°C and stirred for 60 minutes, after which the oil bath was heated to 120°C over 30 minutes. One hour after the start of heating, the solution temperature (internal temperature) reached 100°C. The mixture was then heated and stirred for 1.5 hours (internal temperature 100-110°C) to obtain a siloxane resin solution. During heating and stirring, a mixed gas of 95% nitrogen and 5% oxygen was supplied at a rate of 0.1 liters / min. A total of 123 g of methanol and water, by-products, distilled off during the reaction. PGMEA was added to the obtained siloxane resin solution to achieve a solid content concentration of 40% by weight to obtain a siloxane resin (PSL-2) solution. The obtained siloxane resin (PSL-2) contained radical polymerizable groups and trifunctional organosilane units represented by general formula (1). It had a weight-average molecular weight of 13,500, a transmittance of 99.6%, and a refractive index of 1.46.

[0115] Synthesis Example 3 Siloxane Resin (PSL-3) Solution In a 1000 ml three-necked flask, 40.66 g (0.175 mol) of 3-methacryloxypropylmethyldimethoxysilane, 44.87 g (0.20 mol) of p-styryltrimethoxysilane, 12.32 g (0.05 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 54.48 g (0.4 mol) of methyltrimethoxysilane, 45.91 g (0.175 mol) of 3-trimethoxysilylpropyl succinic anhydride, 0.66 g of BHT, and 142.25 g of PGMEA were charged. An aqueous phosphoric acid solution, prepared by dissolving 1.98 g of phosphoric acid (1.0 wt%) relative to the charged monomers) in 54.00 g of water, was added over 30 minutes while stirring at 40°C. Subsequently, the flask was immersed in a 70°C oil bath and stirred for 60 minutes, after which the oil bath was heated to 120°C over 30 minutes. One hour after the start of heating, the solution temperature (internal temperature) reached 100°C, and it was heated and stirred for 1.5 hours thereafter (internal temperature 100-110°C) to obtain the siloxane resin solution. During heating and stirring, a mixed gas of 95% nitrogen and 5% oxygen was flowed at a rate of 0.05 liters / min. During the reaction, a total of 123 g of methanol and water, which were by-products, distilled off. PGMEA was added to the obtained siloxane resin solution to a solid content concentration of 40% by weight to obtain the siloxane resin (PSL-3) solution. The obtained siloxane resin (PSL-3) contained radical polymerizable groups and trifunctional organosilane units represented by general formula (1), with a weight-average molecular weight of 6,500, a transmittance of 99.6%, and a refractive index of 1.50.

[0116] Synthesis Example 4 Siloxane Resin (PSL-4) Solution In a 1000 ml three-necked flask, 40.66 g (0.175 mol) of 3-methacryloxypropylmethyldimethoxysilane, 89.73 g (0.40 mol) of p-styryltrimethoxysilane, 12.32 g (0.05 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 27.24 g (0.20 mol) of methyltrimethoxysilane, 45.91 g (0.175 mol) of 3-trimethoxysilylpropyl succinic anhydride, 0.75 g of BHT, and 159.70 g of PGMEA were charged. An aqueous phosphoric acid solution, prepared by dissolving 2.16 g of phosphoric acid (1.0 wt%) relative to the charged monomers) in 54.00 g of water, was added over 30 minutes while stirring at 40°C. Subsequently, the flask was immersed in a 70°C oil bath and stirred for 60 minutes, after which the oil bath was heated to 120°C over 30 minutes. One hour after the start of heating, the solution temperature (internal temperature) reached 100°C, and it was heated and stirred for 1.5 hours thereafter (internal temperature 100-110°C) to obtain a siloxane resin solution. During heating and stirring, a mixed gas of 95% nitrogen and 5% oxygen was flowed at a rate of 0.1 liters / min. During the reaction, a total of 123 g of methanol and water, which were by-products, distilled off. PGMEA was added to the obtained siloxane resin solution to a solid content concentration of 40% by weight to obtain a siloxane resin (PSL-4) solution. The obtained siloxane resin (PSL-4) contained radical polymerizable groups and trifunctional organosilane units represented by general formula (1), with a weight-average molecular weight of 6,000, a transmittance of 99.6%, and a refractive index of 1.53.

[0117] Synthesis Example 5 Siloxane Resin (PSL-5) Solution In a 1000 ml three-necked flask, 40.66 g (0.175 mol) of 3-methacryloxypropylmethyldimethoxysilane, 134.60 g (0.60 mol) of p-styryltrimethoxysilane, 12.32 g (0.05 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 45.91 g (0.175 mol) of 3-trimethoxysilylpropyl succinic anhydride, 0.83 g of BHT, and 177.15 g of PGMEA were charged. While stirring at 40°C, an aqueous phosphoric acid solution prepared by dissolving 2.34 g of phosphoric acid (1.0 wt%) relative to the charged monomers in 54.00 g of water was added over 30 minutes. Subsequently, the flask was immersed in a 70°C oil bath and stirred for 60 minutes, after which the oil bath was heated to 120°C over 30 minutes. One hour after the start of heating, the solution temperature (internal temperature) reached 100°C, and it was heated and stirred for 1.5 hours thereafter (internal temperature 100-110°C) to obtain a siloxane resin solution. During heating and stirring, a mixed gas of 95% nitrogen and 5% oxygen was flowed at a rate of 0.1 liters / min. During the reaction, a total of 123 g of methanol and water, which were by-products, distilled off. PGMEA was added to the obtained siloxane resin solution to a solid content concentration of 40% by weight to obtain a siloxane resin (PSL-5) solution. The obtained siloxane resin (PSL-5) contained radical polymerizable groups and trifunctional organosilane units represented by general formula (1), with a weight-average molecular weight of 3,500, a transmittance of 99.6%, and a refractive index of 1.55.

[0118] Synthesis Example 6 Siloxane Resin (PSL-6) Solution In a 1000 ml three-necked flask, 44.47 g (0.30 mol) of vinyltrimethoxysilane, 67.29 g (0.30 mol) of p-styryltrimethoxysilane, 53.12 g (0.39 mol) of methyltrimethoxysilane, 2.62 g (0.01 mol) of 3-trimethoxysilylpropyl succinic anhydride, 0.56 g of BHT, and 148.02 g of PGMEA were charged. While stirring at 40°C, an aqueous phosphoric acid solution prepared by dissolving 0.34 g of phosphoric acid (0.2% by weight relative to the charged monomers) in 54.18 g of water was added over 30 minutes. After that, the flask was immersed in an oil bath at 70°C and stirred for 60 minutes, and then the oil bath was heated to 120°C over 30 minutes. One hour after the start of heating, the solution temperature (internal temperature) reached 100°C. The mixture was then heated and stirred for two hours (internal temperature 100-110°C) to obtain a siloxane resin solution. During heating and stirring, a mixed gas of 95% nitrogen and 5% oxygen was supplied at a rate of 0.2 liters / min. A total of 123 g of methanol and water, by-products, distilled off during the reaction. PGMEA was added to the obtained siloxane resin solution to achieve a solid content concentration of 40% by weight to obtain a siloxane resin (PSL-6) solution. The obtained siloxane resin (PSL-6) contained radical polymerizable groups and trifunctional organosilane units represented by general formula (1). It had a weight-average molecular weight of 7,000, a transmittance of 99.7%, and a refractive index of 1.49.

[0119] Synthesis Example 7 Siloxane Resin (PSL-7) Solution In a 1000 ml three-necked flask, 82.04 g (0.35 mol) of 3-acryloxypropyltrimethoxysilane, 69.41 g (0.35 mol) of phenyltrimethoxysilane, 27.24 g (0.20 mol) of methyltrimethoxysilane, 26.23 g (0.10 mol) of 3-trimethoxysilylpropyl succinic anhydride, 0.37 g of BHT, and 194.25 g of PGMEA were charged. While stirring at 40°C, an aqueous phosphoric acid solution, prepared by dissolving 0.41 g of phosphoric acid (0.2% by weight relative to the charged monomers) in 55.80 g of water, was added over 60 minutes. After that, the flask was immersed in an oil bath at 70°C and stirred for 60 minutes, and then the oil bath was heated to 110°C over 30 minutes. One hour after the start of heating, the solution temperature (internal temperature) reached 100°C. The mixture was then heated and stirred for two hours (internal temperature 100-110°C) to obtain a siloxane resin solution. During heating and stirring, a mixed gas of 95% nitrogen and 5% oxygen was supplied at a rate of 0.05 liters / min. A total of 127 g of methanol and water, by-products, distilled off during the reaction. PGMEA was added to the obtained siloxane resin solution to achieve a solid content concentration of 40% by weight to obtain a siloxane resin (PSL-7) solution. The obtained siloxane resin (PSL-7) contained radical polymerizable groups and trifunctional organosilane units represented by general formula (1). It had a weight-average molecular weight of 3,200, a transmittance of 99.6%, and a refractive index of 1.50.

[0120] Table 1 summarizes the compositions of the siloxane resin solutions for synthesis examples 1 to 7.

[0121]

[0122] Synthesis Example 8 Synthesis of Acrylic Resin (PAL-1) Solution In a 500 mL three-necked flask, 3.00 g of 2,2'-azobis(isobutyronitrile) and 50.0 g of PGMEA were charged. Then, 30.0 g (0.349 mol) of methacrylic acid, 22.48 g (0.216 mol) of styrene, and 35.0 g (0.149 mol) of tricyclo[5.2.1.02,6]decane-8-ylmethacrylate were charged. The mixture was stirred at room temperature for a while, then the flask was purged with nitrogen, and the mixture was heated and stirred at 70°C for 5 hours. Next, 15.00 g (0.106 mol) of glycidyl methacrylate, 1.00 g of triphenylphosphine, 0.200 g of p-methoxyphenol, and 100 g of PGMEA were added to the resulting solution, and the mixture was heated and stirred at 90°C for 4 hours to obtain an acrylic resin solution. PGMEA was added to the obtained acrylic resin solution to achieve a solid content concentration of 40% by weight, and this was prepared as an acrylic resin (PAL-1) solution. The weight-average molecular weight of the acrylic resin (PAL-1) was 16,000, the transmittance was 99.4%, and the refractive index was 1.52.

[0123] Example 1 Photosensitive resin composition (P-1) 0.940 g of melamine resin particles ("Epostor" (registered trademark) S12; manufactured by Nippon Shokubai Co., Ltd. (hereinafter referred to as "Epostor S12")) (average particle size 1,200 nm, refractive index (nA) 1.66) were mixed with 0.175 g of a siloxane resin (PSL-7) solution obtained in Synthesis Example 7 as a dispersant, and 9.000 g of PGMEA as a solvent. The mixture was dispersed using a mill-type disperser filled with zirconia beads to obtain a particle dispersion (MW-1). Next, 5.242 g of the siloxane resin (PSL-1) solution obtained by Synthesis Example 1, 5.392 g of the particle dispersion (MW-1), and 0.100 g of "TR-PBG" (registered trademark) 358, manufactured by Changzhou Strong Electronic New Materials Co., Ltd., China (hereinafter referred to as "PBG-358"), as a photosensitive agent, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide ("Omnirad" 819) 0.10 g of BASF Japan Ltd. (hereinafter referred to as "Omnirad-819"), 0.750 g of pentaerythritol triacrylate ("Light Acrylate" (registered trademark) PE-3A, manufactured by Kyoeisha Chemical Co., Ltd. (hereinafter referred to as "PE-3A")) as a photopolymerizable compound, and 9,9-bis[4-(2-hydroxyethoxy)phenyl]ful orange acrylate ("EA" (registered trademark) 0250 P, 2.499 g of a 50% PGMEA diluted solution of Osaka Gas Chemical Co., Ltd. (hereinafter referred to as "EA-0250P"), 0.150 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane ("KBM"® 303, manufactured by Shin-Etsu Chemical Co., Ltd. (hereinafter referred to as "KBM-303")) as an adhesion improver, and "Irganox"® 1010 as a polymerization inhibitor, BAS 0.015 g of Irganox 1010 (manufactured by F Japan Co., Ltd.) and 0.02 g of a 10% by weight diluted solution of a silicone-based surfactant (BYK® 333, manufactured by Bic Chemie Japan Co., Ltd. (hereinafter referred to as BYK-333)) in PGMEA (corresponding to a concentration of 100 ppm) were dissolved in 4.010 g of PGMEA, 1.475 g of PGME, and 0.248 g of distilled water, and the mixture was stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain a photosensitive resin composition (P-1).

[0124] Example 2 Photosensitive resin composition (P-2) A photosensitive resin composition (P-2) was obtained in the same manner as in Example 1, except that the amount of siloxane resin (PSL-1) solution added was changed to 5.914 g, the amount of particle dispersion (MW-1) added was changed to 2.696 g, the amount of PGMEA added was changed to 6.040 g, the amount of PGME added was changed to 1.476 g, and the amount of distilled water added was changed to 0.241 g.

[0125] Example 3 Photosensitive resin composition (P-3) A photosensitive resin composition (P-3) was obtained in the same manner as in Example 2, except that the amount of siloxane resin (PSL-1) solution added was changed to 6.182 g, the amount of particle dispersion (MW-1) added was changed to 1.618 g, the amount of PGMEA added was changed to 6.852 g, and the amount of distilled water added was changed to 0.238 g.

[0126] Example 4 Photosensitive resin composition (P-4) A photosensitive resin composition (P-4) was obtained in the same manner as in Example 2, except that the amount of PE-3A added was changed to 1.749 g, the amount of EA-0250P added to 0.500 g, the amount of PGMEA added to 7.040 g, and the amount of distilled water added to 0.241 g.

[0127] Example 5 Photosensitive resin composition (P-5) A photosensitive resin composition (P-5) was obtained in the same manner as in Example 4, except that 5.914 g of siloxane resin (PSL-2) solution was added instead of siloxane resin (PSL-1) solution.

[0128] Example 6 Photosensitive resin composition (P-6) A photosensitive resin composition (P-6) was obtained in the same manner as in Example 4, except that 5.914 g of siloxane resin (PSL-3) solution was added instead of siloxane resin (PSL-1) solution.

[0129] Example 7 Photosensitive resin composition (P-7) A photosensitive resin composition (P-7) was obtained in the same manner as in Example 6, except that 3.499 g of a 50% diluted solution of dipentaerythritol hexaacrylate ("KAYARAD" (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd. (hereinafter referred to as "DPHA")) was added instead of PE-3A, and the amount of PGMEA added was changed to 5.290 g.

[0130] Example 8 Photosensitive resin composition (P-8) A photosensitive resin composition (P-8) was obtained in the same manner as in Example 4, except that 5.914 g of siloxane resin (PSL-4) solution was added instead of siloxane resin (PSL-1) solution.

[0131] Example 9 Photosensitive resin composition (P-9) A photosensitive resin composition (P-9) was obtained in the same manner as in Example 4, except that 5.914 g of siloxane resin (PSL-5) solution was added instead of siloxane resin (PSL-1) solution.

[0132] Example 10 Photosensitive resin composition (P-10) 7.475 g of siloxane resin (PSL-6) solution, 6.469 g of particle dispersion (MW-1), 0.200 g of PHAP-280 (manufactured by Toyo Gosei Co., Ltd. (hereinafter referred to as "PHAP-280")) as a photosensitive agent, and 0.200 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane ("KBM" (registered trademark) 303, manufactured by Shin-Etsu Chemical Co., Ltd. (hereinafter referred to as "KBM-303")) as an adhesion improver. 160 g of PGMEA, 0.004 g of BHT (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization inhibitor, and 0.02 g of a 10% by weight diluted solution of a silicone-based surfactant ("BYK"® 333, manufactured by BIC Chemie Japan Co., Ltd. (hereinafter referred to as "BYK-333")) in PGMEA, 5.308 g of solvent, 1.579 g of PGME, and 0.225 g of distilled water were dissolved in these solutions and stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain a photosensitive resin composition (P-10).

[0133] Example 11 Photosensitive resin composition (P-11) A photosensitive resin composition (P-11) was obtained in the same manner as in Example 4, except that 5.914 g of acrylic resin (PAL-1) solution was added instead of siloxane resin (PSL-1) solution.

[0134] Example 12 Photosensitive resin composition (P-12) Instead of melamine resin particles "Epostor S12", melamine resin particles ("Epostor" (registered trademark) S6; manufactured by Nippon Shokubai Co., Ltd. (hereinafter referred to as "Epostor S6")) (average particle size 400 nm, refractive index (nA) 1.66), 0.175 g of siloxane resin (PSL-7) solution obtained in Synthesis Example 7 as a dispersant, and 9.000 g of PGMEA as a solvent were mixed, and a particle dispersion (MW-2) was obtained using a mill-type disperser filled with zirconia beads. A photosensitive resin composition (P-12) was obtained in the same manner as in Example 5, except that the amount of siloxane resin (PSL-2) solution added was changed to 5.242 g, the amount of particle dispersion (MW-2) added instead of particle dispersion (MW-1) was changed to 5.392 g, the amount of PGMEA added was changed to 5.009 g, the amount of PGME added was changed to 1.475 g, and the amount of distilled water added was changed to 0.248 g.

[0135] Example 13 Photosensitive resin composition (P-13) A photosensitive resin composition (P-13) was obtained in the same manner as in Example 5, except that the amount of siloxane resin (PSL-2) solution added was changed to 4.974 g, the amount of particle dispersion (MW-1) added to 6.470 g, the amount of PGMEA added to 4.197 g, the amount of PGME added to 1.475 g, and the amount of distilled water added to 0.250 g.

[0136] Example 14 Photosensitive resin composition (P-14) A photosensitive resin composition (P-14) was obtained in the same manner as in Example 5, except that the amount of siloxane resin (PSL-2) solution added was changed to 7.570 g, the amount of particle dispersion (MW-1) added to 8.088 g, the amount of EA-0250P 50% PGMEA diluted solution added to 0.100 g, the amount of PE-3A added to 0.750 g, the amount of PGMEA added to 1.406 g, the amount of PGME added to 1.478 g, and the amount of distilled water added to 0.224 g.

[0137] Example 15 Photosensitive resin composition (P-15) A photosensitive resin composition (P-15) was obtained in the same manner as in Example 5, except that the amount of siloxane resin (PSL-2) solution added was changed to 6.950 g, the amount of particle dispersion (MW-1) added to 0.539 g, the amount of EA-0250P 50% PGMEA diluted solution added to 0.100 g, the amount of PGMEA added to 8.569 g, the amount of PGME added to 1.477 g, and the amount of distilled water added to 0.230 g.

[0138] Example 16 Photosensitive resin composition (P-16) A photosensitive resin composition (P-16) was obtained in the same manner as in Example 2, except that the amount of siloxane resin (PSL-1) solution added was changed to 6.451 g, the amount of particle dispersion (MW-1) added was changed to 0.539 g, the amount of PGMEA added was changed to 7.665 g, and the amount of distilled water added was changed to 0.235 g.

[0139] Example 17 Photosensitive resin composition (P-17) A photosensitive resin composition (P-17) was obtained in the same manner as in Example 2, except that the amount of siloxane resin (PSL-1) solution added was 5.914 g, 2.696 g of particle dispersion (MW-2) was added instead of particle dispersion (MW-1), and the amount of PGMEA added was changed to 6.040 g.

[0140] The compositions of the photosensitive resin compositions of Examples 1 to 17 are summarized in Table 2.

[0141]

[0142] Comparative Example 1 Photosensitive Resin Composition (P-18) 0.94 g of acrylic resin particles (MX-30BD; manufactured by Soken Chemical Co., Ltd. (hereinafter referred to as "MX-30BD")) (average particle diameter 300 nm, refractive index (nA) 1.49) were mixed with 0.175 g of siloxane resin (PSL-7) solution obtained in Synthesis Example 7 and 9.000 g of PGMEA as a solvent. The mixture was dispersed using a mill-type disperser filled with zirconia beads to obtain particle dispersion (MW-3). Photosensitive resin composition (P-18) was obtained in the same manner as in Example 2, except that the amount of siloxane resin (PSL-1) solution added was 5.914 g and 2.696 g of particle dispersion (MW-3) was added instead of particle dispersion (MW-1).

[0143] Comparative Example 2 Photosensitive resin composition (P-19) 0.94 g of acrylic resin particles (MX-80H3wT; manufactured by Soken Chemical Co., Ltd. (hereinafter referred to as "MX-80H3wT")) (average particle size 800 nm, refractive index (nA) 1.49) as particles, 0.175 g of siloxane resin (PSL-7) solution obtained in Synthesis Example 7, and 9.000 g of PGMEA as a solvent were mixed and dispersed using a mill-type disperser filled with zirconia beads to obtain particle dispersion (MW-4). Photosensitive resin composition (P-19) was obtained in the same manner as in Comparative Example 1, except that 2.696 g of particle dispersion (MW-4) was added instead of particle dispersion (MW-3).

[0144] Comparative Example 3 Photosensitive Resin Composition (P-20) 5.00 g of titanium dioxide white pigment (CR-97; manufactured by Ishihara Sangyo Co., Ltd. (hereinafter referred to as "CR-97")) (average particle size 250 nm, refractive index (nA) 2.71) as particles, 0.67 g of polyester phosphate DISPERBY K-111 as a dispersant, and 4.33 g of PGMEA as a solvent were mixed and dispersed using a mill-type disperser filled with zirconia beads to obtain particle dispersion (MW-5). A photosensitive resin composition (P-20) was obtained in the same manner as in Comparative Example 1, except that 0.350 g of particle dispersion (MW-5) was added instead of particle dispersion (MW-1), the amount of siloxane resin (PSL-1) solution added was changed to 6.089 g, the amount of PGMEA added was changed to 8.212 g, and the amount of distilled water added was changed to 0.239 g.

[0145] Comparative Example 4 Photosensitive resin composition (P-21) A photosensitive resin composition (P-21) was obtained in the same manner as in Comparative Example 3, except that the amount of siloxane resin (PSL-1) solution added was changed to 5.876 g, the amount of particle dispersion (MW-5) added to 0.500 g, the amount of PGMEA added to 8.273 g, and the amount of distilled water added to 0.241 g.

[0146] Comparative Example 5 Photosensitive Resin Composition (P-22) 45 g of zirconia particles (UEP-100 zirconium oxide; manufactured by Daiichi Rare Elements Chemical Industry Co., Ltd. (hereinafter referred to as "UEP-100 zirconium oxide")) (average particle size 340 nm, refractive index (nA) 2.10) were mixed with 1.8 g of polyester phosphate DISPERBY K-111 as a dispersant and 53.2 g of PGMEA as a solvent. The mixture was dispersed using a mill-type disperser filled with zirconia beads to obtain a particle dispersion (MW-6). A photosensitive resin composition (P-22) was obtained in the same manner as in Comparative Example 4, except that the amount of siloxane resin (PSL-1) solution added was changed to 5.935 g, 0.555 g of particle dispersion (MW-6) was added instead of particle dispersion (MW-5), and the amount of PGMEA added was changed to 8.159 g.

[0147] Comparative Example 6 Photosensitive resin composition (P-23) A photosensitive resin composition (P-23) was obtained in the same manner as in Example 4, except that the amount of siloxane resin (PSL-1) solution added was changed to 4.571 g, the amount of particle dispersion (MW-1) added was changed to 8.088 g, the amount of PGMEA added was changed to 2.979 g, the amount of PGME added was changed to 1.475 g, and the amount of distilled water added was changed to 0.254 g.

[0148] Comparative Example 7 Photosensitive resin composition (P-24) A photosensitive resin composition (P-24) was obtained in the same manner as in Example 4, except that the amount of siloxane resin (PSL-1) solution added was 5.951 g, the amount of PGMEA added was 7.018 g, and the addition of Irganox 1010 was omitted.

[0149] Comparative Example 8 Photosensitive resin composition (P-25) A photosensitive resin composition (P-25) was obtained in the same manner as in Example 4, except that the amount of siloxane resin (PSL-1) solution added was 6.585 g, the amount of PGMEA added was 9.070 g, the amount of PGME added was 1.477 g, and the particle dispersion (MW-1) was omitted. The compositions of the photosensitive resin compositions of Comparative Examples 1 to 8 are summarized in Table 3.

[0150]

[0151] Examples 18-26, Examples 28-34, Comparative Examples 9-16: As the substrate, a 10 cm square alkali-free glass substrate (manufactured by AGC Technoglass Co., Ltd., thickness 0.5 mm; the same applies hereinafter), a Si wafer (6 inches), or an organic EL device substrate having a color filter was used. On this, the photosensitive resin compositions shown in Tables 2-3 were applied by spin coating, and a dried film was prepared by drying at 90°C for 3 minutes using a hot plate (product name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.; the same applies hereinafter). The prepared dried film was exposed to light at an exposure dose of 500 mJ / cm using a parallel light mask aligner (product name PLA-501F, manufactured by Canon Inc.; the same applies hereinafter) with a light source of ultra-high pressure mercury lamp (g, h, i lines), through a cut filter that transmits only g and h lines, and further partially through a photomask. ２ Exposure was performed using (h-line equivalent value). The photomask used in this study was a grayscale mask with line and space patterns of widths of 50 μm, 40 μm, 30 μm, 20 μm, 15 μm, 10 μm, 7 μm, 5 μm, and 4 μm. Subsequently, using an automatic developing device (Mikasa Corporation, "AD-2000" (product name); the same applies hereafter), the samples were shower-developed for 80 seconds with a 0.045 wt% potassium hydroxide aqueous solution, and then rinsed with water for 30 seconds. Furthermore, the samples were heated in air at 100°C for 60 minutes using an oven (product name IHPS-222, ESPEC Corporation; the same applies hereafter). A laminate was fabricated by forming a solid film (cured film) with a thickness of 2 μm obtained by exposure without a photomask on a glass substrate, and a line and space pattern (pattern portion of the cured film) with a thickness of 2 μm obtained by exposure through the above photomask.

[0152] Example 27 A 10 cm square alkali-free glass substrate, a Si wafer (6 inches), or an organic EL device substrate having a color filter was used as the substrate. A photosensitive resin composition (P-10) was applied thereon by spin coating, and a dried film was prepared by drying it on a hot plate at a temperature of 90°C for 3 minutes. A portion of the prepared dried film was exposed to light at an exposure dose of 500 mJ / cm using a parallel light mask aligner, with a light source of ultra-high pressure mercury lamp (g, h, i lines), through a cut filter that transmits only g and h lines, and further through a photomask.２ Exposure was performed at (h-line equivalent value). The photomask used was a grayscale mask with line and space patterns of widths of 50 μm, 40 μm, 30 μm, 20 μm, 15 μm, 10 μm, 7 μm, 5 μm, and 4 μm. Subsequently, using an automatic developing device, the images were shower-developed for 45 seconds with 2.38 wt% TMAH (tetramethylammonium hydroxide aqueous solution), then allowed to stand for 45 seconds, and then rinsed with water for 30 seconds. Furthermore, exposure was 500 mJ / cm². ２ The entire film was exposed using (h-line equivalent). Then, it was heated in an oven in air at a temperature of 100°C for 60 minutes. A solid film (cured film) with a thickness of 2 μm obtained without exposure and a line and space pattern (pattern portion of the cured film) with a thickness of 2 μm obtained by exposure through the above photomask were formed on a glass substrate to create a laminate. The composition and evaluation results of the laminates for each example and comparative example are shown in Tables 4 and 5.

[0153]

[0154]

[0155] The evaluation methods for laminates having cured films in each example and comparative example are shown below.

[0156] <Film Thickness> For the cured films with a thickness of 2 μm obtained in each example and comparative example, scratches were made in the solid film portion of the cured film, and the film thickness was calculated by measuring the difference between the top of the cured film and the surface of the glass substrate using a Surfcom stylus-type film thickness measuring device (manufactured by Tokyo Seimitsu Co., Ltd.).

[0157] <Transmittance> For the solid film portion of the 2 μm thick cured film in the laminates obtained in each example and comparative example, the transmittance in the wavelength range of 300 nm to 800 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Tech Corporation), and the value at 550 nm was taken as the representative value. For the measurement, the substrate alone was used as a reference, and the measurement was performed on the cured film formed on the substrate.

[0158] <Haze> For the solid portions of the 2 μm thick cured film in the laminates obtained in each example and comparative example, the haze values ​​in the wavelength range of 380 nm to 950 nm were measured using a haze meter HSP-150Vis (manufactured by Murakami Color Technology Laboratory Co., Ltd.). The haze of the substrate alone was measured using the same method, and the difference was taken as the haze of the cured film. In particular, the haze values ​​at a wavelength of 550 nm (Hazeλ = 550 nm), the haze values ​​at a wavelength of 450 nm (Hazeλ = 450 nm), and Hazeλ = 450 nm / Hazeλ = 550 nm were evaluated.

[0159] <Reflectance> For the solid film portion of the cured film in the laminates obtained in each example and comparative example, the reflectance was measured from the solid film side in SCI mode in the wavelength range of 360 nm to 740 nm using a spectrophotometer CM-2600d (manufactured by Konica Minolta, Inc.), and the value at 550 nm was taken as the representative value.

[0160] <Flatness> For the solid portions of the cured film in the laminates obtained in each example and comparative example, the surface roughness (Ra) and maximum height roughness (Rz) were measured from the surface shape of the cured film using a Surfcom stylus-type film thickness measuring device (manufactured by Tokyo Seimitsu Co., Ltd.) in accordance with JIS B0601 (2013).

[0161] <Refractive Index (nB)> In the examples and comparative examples, a photosensitive resin composition was obtained by preparing the mixture in the same manner as in the examples and comparative examples, except that a particle dispersion was not added. Using the obtained photosensitive resin composition, a laminate was obtained in the same manner as in the examples and comparative examples, except that a Si wafer (6 inches) was used as the substrate. The refractive index of the solid portion of the cured film in the obtained laminate was measured by irradiating the cured film surface with light of a wavelength of 633 nm from a direction perpendicular to the cured film surface using a prism coupler (PC-2000 (manufactured by Metricon Corporation)) under atmospheric pressure and 20°C, and rounded to the third decimal place.

[0162] <Average Particle Size> The average particle size of (A) organic polymer particles was measured by dissolving the (A) organic polymer particles in a solvent and using a nanoPartica SZ-100V2 Series nanoparticle analyzer (Horiba, Ltd.) by dynamic light scattering (DLS) method. For the measurement, the particles were dispersed in PGMEA at 25°C. For the analysis, the median value (D50) of the obtained cumulative volume distribution was used for calculation. The particle size obtained in this manner was defined as the average particle size in this specification.

[0163] <Pattern Processability> For the pattern portion of the cured film in the laminates obtained in each example and comparative example, the areas where a 10 μm wide line and space pattern is formed with a 1:1 width were observed using an optical microscope (manufactured by Olympus Corporation) adjusted to a magnification of 100x, and the pattern processability was evaluated according to the following criteria. A: No development residue is observed in the 10 μm wide line and space pattern. B: Development residue is observed in an area range of less than 10% of the edge portion of the 10 μm wide line and space pattern. C: Development residue is observed in an area range of 10 to less than 30% of the edge portion of the 10 μm wide line and space pattern. D: Residue is observed in the edge portion of the 10 μm wide line and space pattern, and localized development residue is also observed outside the edge portion. E: Development residue is observed throughout the exposed area. E is unsuitable because there is a lot of development residue.

[0164] <Interference Unevenness> Interference unevenness was evaluated in laminates obtained by coating and curing the photosensitive resin compositions obtained in each example and comparative example onto an organic EL device substrate having a color filter. A white LED light source (color temperature 6500K) was irradiated from the cured film side of the laminate, and the laminate was observed visually from the cured film side and evaluated based on the following criteria. The observation angle was in the range of 0 to 15 degrees from the direction perpendicular to the cured film surface. A: No interference unevenness is visible at all B: Almost no interference unevenness is visible B-: Very slight interference unevenness is visible C: Slight interference unevenness is visible D: Relatively visible interference unevenness E: Easily visible interference unevenness is easily visible and poses a practical problem, therefore it is unsuitable.

[0165] <Brightness> Brightness was evaluated in laminates obtained by coating an organic EL device substrate having a color filter with the photosensitive resin composition obtained in each example and comparative example, and curing it. The brightness of the display was observed visually and evaluated based on the following criteria: A: No decrease in brightness was observed B: Almost no decrease in brightness was observed C: A slight decrease in brightness was observed D: A slight decrease in brightness was observed E: A decrease in brightness was observed. E is unsuitable because a decrease in brightness was observed, which poses a practical problem.

[0166] <Bright Spots> The occurrence of bright spots was evaluated in laminates obtained by coating and curing the photosensitive resin compositions obtained in each example and comparative example onto an organic EL device substrate having a color filter. Bright spots were observed visually and evaluated based on the following criteria: A: No bright spots observed at all B: Almost no bright spots observed C: Slightly visible bright spots D: Some bright spots observed E: Noticeably visible bright spots E is unsuitable because the bright spots are noticeably visible and pose a practical problem.

[0167] 1. Substrate 2. Light scattering layer H: Thickness of the light scattering layer L: Width of the light scattering layer θ: Taper angle of the light scattering layer 3. Patterned light scattering layer 4. Color filter layer 5. Black matrix 6. Color filter section for each color 7. Light-emitting light source selected from a light source having an organic EL element, a light source having a mini LED element, and a light source having a micro LED element

Claims

1. A photosensitive resin composition comprising (A) organic polymer particles, (B) a binder resin, (C) a photosensitive agent, and (D) a polymerization inhibitor, wherein the content of (A) organic polymer particles is 1 to 40 parts by weight per 100 parts by weight of the content of (B) binder resin, and the refractive index (nA) of the (A) organic polymer particles at a wavelength of 633 nm and the refractive index (nB) of the components other than the (A) organic polymer particles in the cured film of the photosensitive resin composition satisfy the following general formula (I): 0.10 ≤ nA - nB ≤ 0.70 ... (I) 2. The photosensitive resin composition according to claim 1, wherein the (B) binder resin is a siloxane resin containing at least one radical polymerizable group.

3. The photosensitive resin composition according to claim 2, wherein the (B) binder resin is a siloxane resin containing trifunctional organosilane units.

4. The photosensitive resin composition according to claim 2, characterized in that the transmittance at a wavelength of 550 nm at a film thickness of 2 μm is 85% or more and 100% or less, and the reflectance at a wavelength of 550 nm at a film thickness of 2 μm is 5.0% or more and 10.0% or less.

5. The photosensitive resin composition according to claim 2, wherein the haze value (hazeλ = 550nm) at a wavelength of 550nm at a cured film thickness of 2 μm of the photosensitive resin composition is 20% or more and less than 80%.

6. The photosensitive resin composition according to claim 5, characterized in that the haze value at a wavelength of 450 nm (Hazeλ = 450 nm) at a film thickness of 2 μm of the cured film of the photosensitive resin composition is 25% or more and less than 90%, and satisfies the following general formula (II) at each wavelength: Hazeλ = 450 nm ≥ Hazeλ = 550 nm ... (II) 7. The photosensitive resin composition according to claim 2, characterized in that the average particle size of the (A) organic polymer particles is 300 nm or more and 2,000 nm or less.

8. The photosensitive resin composition according to claim 2, characterized in that the average particle size of the (A) organic polymer particles is 800 nm or more and 1,500 nm or less.

9. The photosensitive resin composition according to claim 2, characterized in that the (A) organic polymer particles are particles made from melamine resin.

10. The photosensitive resin composition according to claim 2, characterized in that the surface roughness Ra of the cured film of the photosensitive resin composition is 30 nm or less.

11. The photosensitive resin composition according to claim 2, characterized in that the content of the organic polymer particles (A) is 1% by weight to 27% by weight of the total solid content of the photosensitive resin composition.

12. The photosensitive resin composition according to claim 2, characterized in that the (B) binder resin is a transparent resin having a transmittance of 90% or more and 100% or less in the wavelength range of 450 nm to 650 nm when a cured film with a thickness of 2 μm is made using the (B) binder resin, and the refractive index at a wavelength of 633 nm when a cured film with a thickness of 2 μm is made using the (B) binder resin is 1.30 to 1.

55.

13. The photosensitive resin composition according to claim 2, characterized in that the siloxane resin contains at least a styryl group.

14. The photosensitive resin composition according to claim 2, characterized in that the (C) photosensitive agent is a photoradical generator or a naphthoquinone diazide compound.

15. A laminate having a substrate and a cured film of the photosensitive resin composition according to any one of claims 1 to 14.

16. A display device comprising a laminate according to claim 15, and a light-emitting light source selected from a light source comprising a liquid crystal element and a backlight, a light source having an organic EL element, and a light source having an LED element.

17. The display device according to claim 16, further comprising a color filter layer.

18. An information terminal having the display device described in claim 17.

Images