Photosensitive resin composition, cured film, and display device

Abstract

The present application aims to provide a photosensitive resin composition capable of obtaining a cured film having high reliability and excellent bending property, excellent processability of a concave-convex pattern, and sufficient light diffusivity. To achieve the above object, the photosensitive resin composition of the present application comprises (A) a siloxane resin containing at least 20 to 60 mol% of repeating units represented by the following general formula (1) in total, (B) particles having a median particle diameter of 0.2 to 0.6 μm, and (C) a naphthoquinonediazide compound.(R 1 represents an aryl group having 6 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms in which all or a part of the hydrogens are substituted.

Description

Technical Field

[0001] This invention relates to photosensitive resin compositions, cured films using the same, methods for manufacturing the same, and display devices. Background Technology

[0002] Typically, light-diffusing resin compositions are widely used as materials for diffusing light from light-emitting sources in lighting fixtures such as organic EL lighting and LED lighting fixtures, laser display devices, various display devices such as liquid crystal displays, and other optical devices. In these applications, high reliability against heat and light is required for light-diffusing resin compositions, leading to the development of materials that incorporate light-diffusing agents into a matrix resin with high reliability (see, for example, Patent Document 1). On the other hand, for novel applications such as organic EL lighting, properties such as thin-filmability and flexibility are also required, and materials that comprehensively satisfy these properties have not yet been proposed. Furthermore, techniques for improving light diffusivity by forming an embossed pattern on a light-diffusing cured film are known, and light-diffusing resin compositions capable of easily and precisely forming embossed patterns on cured films have been proposed (see, for example, Patent Document 2).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2012-208424

[0006] Patent Document 2: Japanese Patent Application Publication No. 2004-325861 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] The light-diffusing resin composition disclosed in Patent Document 1 suffers from insufficient flexibility. Furthermore, Patent Document 2 discloses a light-diffusing composition that forms a fine textured structure via inkjet printing; however, because it contains microparticles, it suffers from the following problem: blockage occurs in the discharge orifice, easily leading to poor discharge and making it difficult to form a highly fine textured structure.

[0009] Therefore, the objective of this invention is to provide a photosensitive resin composition that can produce a cured film with high reliability and excellent flexibility, excellent processability of embossed patterns, and sufficient light diffusion.

[0010] Methods for solving problems

[0011] To address the aforementioned issues, the present invention comprises the following: a photosensitive resin composition comprising (A) a siloxane resin, (B) particles with a median particle size of 0.2 to 0.6 μm, and (C) a naphthoquinone diazide compound, wherein the (A) siloxane resin contains at least 20 to 60 mol% of repeating units represented by the following general formula (1), and the (B) particles with a median particle size of 0.2 to 0.6 μm constitute 5 to 50% by weight of the total solid components in the photosensitive resin composition.

[0012] [Chemical Formula 1]

[0013]

[0014] (R 1 This refers to an aryl group with 6 to 18 carbon atoms, or an aryl group with 6 to 18 carbon atoms in which all or some hydrogen atoms are substituted.

[0015] The effects of the invention

[0016] The photosensitive resin composition of the present invention not only exhibits excellent light diffusivity, heat resistance, and lightfastness, and possesses good flexibility, but also enables the precise formation of raised and recessed patterns using a photosensitive method. Furthermore, the photosensitive resin composition according to the present invention can yield a cured film with high light diffusivity, excellent heat resistance, lightfastness, and good flexibility. Attached Figure Description

[0017] [ Figure 1 This is a cross-sectional view showing one embodiment of the substrate with a cured film of the present invention having a cured film obtained by pattern formation.

[0018] [ Figure 2 This is a cross-sectional view showing one embodiment of the substrate with a cured film of the present invention, having a cured film and a black layer obtained by patterning. Detailed Implementation

[0019] The photosensitive resin composition of the present invention contains (A) a siloxane resin, (B) particles with a median particle size of 0.2 to 0.6 μm, and (C) a naphthoquinone diazide compound. By containing (A) the siloxane resin, the thermal polymerization (condensation) of the siloxane resin is carried out by heating, increasing the crosslinking density; therefore, a cured film with excellent heat and light resistance can be obtained. Furthermore, by containing (B) particles with a median particle size of 0.2 to 0.6 μm, good light diffusion properties are achieved. Moreover, by containing (C) the naphthoquinone diazide compound, positive photosensitivity is exhibited, preventing the exposed portion from being removed by the developing solution.

[0020] (A) Siloxane resin

[0021] (A) The siloxane resin is a hydrolysis-dehydration condensate of an organosilane, and in this invention, it contains a total of 20 to 60 mol% of repeating units represented by the following general formula (1). By containing a total of 20 to 60 mol% of repeating units represented by general formula (1) in the siloxane resin, the siloxane resin can be easily compatible with other components, and therefore, can exhibit excellent resolution.

[0022] [Chemical Formula 2]

[0023]

[0024] (R 1 This refers to an aryl group with 6 to 18 carbon atoms, or an aryl group with 6 to 18 carbon atoms in which all or some hydrogen atoms are substituted.

[0025] Furthermore, it is more preferable to contain a total of 30 to 50 mol% of repeating units represented by general formula (1). The content ratio of organosilane units having repeating units represented by general formula (1) can be determined by utilizing... 29 The Si-NMR determination is obtained. That is, it can be obtained by calculating the ratio of the integral value of Si from the organosilane unit having repeating units represented by general formula (1) to the integral value of Si from the organosilane as a whole.

[0026] Furthermore, the siloxane resin of the present invention preferably contains a total of 5 to 20 mol% of repeating units represented by the following general formula (2). By containing 5 mol% or more of the repeating units represented by the following general formula (2), the siloxane resin rapidly crosslinks upon heating, suppressing flowability and thus suppressing dimensional changes in the processing before and after heating. Furthermore, by containing 20 mol% or less of the repeating units represented by the following general formula (2), excessive silanol groups can be prevented, improving the storage stability of the photosensitive resin composition. The content ratio of the organosilane units represented by the following general formula (2) can be determined by: [The following text is incomplete and requires further context to translate accurately.] 29 Si-NMR measurements were performed to calculate the ratio of the integral value of Si from organosilane units having the following general formula (2) to the integral value of Si from the whole organosilane.

[0027] [Chemical Formula 3]

[0028]

[0029] Furthermore, the siloxane resin of the present invention preferably contains a total of 1 to 20 mol% of repeating units represented by the following general formula (3). By containing more than 1 mol% of repeating units represented by the following general formula (3), the refractive index of (A) the siloxane resin is reduced, and the interfacial reflection with (B) particles with a median particle size of 0.2 to 0.6 μm is improved, thus exhibiting good light diffusion properties. In addition, the cured film also has good flexibility. On the other hand, by making the repeating units represented by the following general formula (3) less than 20 mol%, the compatibility of the siloxane resin with other components in the composition is prevented from decreasing, and good resolution can be achieved. The content ratio of the organosilane units represented by the following general formula (3) can be determined by the following method: 29 Si-NMR measurements are performed to calculate the ratio of the integral value of Si from organosilane units having the following general formula (3) to the integral value of Si from the organosilane as a whole. Furthermore, when the organosilane contains repeating units other than those represented by general formulas (1) to (3), the content is preferably 10 to 50 mol%.

[0030] [Chemical Formula 4]

[0031]

[0032] (R 2 R indicates an alkyl, alkenyl, aryl, or arylalkyl group with 1 to 10 carbon atoms in which all or part of the hydrogen atoms are replaced by fluorine. 3 This indicates a single bond, -O-, -CH2-CO-, -CO-, or -O-CO-.

[0033] As R 2 From the viewpoint of further reducing the refractive index of the siloxane resin, alkyl groups in which all or part of the hydrogen atoms are replaced by fluorine are preferred. In this case, the alkyl group preferably has 1 to 6 carbon atoms. As R 3 From the viewpoint of reducing the refractive index of siloxane resin, groups selected from alkyl groups having 1 to 6 carbon atoms and acyl groups having 2 to 10 carbon atoms are preferred.

[0034] Each repeating unit represented by the above general formulas (1) to (3) is derived from an alkoxysilane compound represented by the following general formulas (4) to (6). That is, a siloxane resin containing a repeating unit represented by the above general formula (1) and / or a repeating unit represented by general formula (2) and a repeating unit represented by general formula (3) can be obtained by hydrolyzing and polycondensing a variety of alkoxysilane compounds containing an alkoxysilane compound represented by general formula (4) and / or an alkoxysilane compound represented by general formula (5) and an alkoxysilane compound represented by general formula (6). In addition, other alkoxysilane compounds can also be used.

[0035] [Chemical Formula 5]

[0036]

[0037] In the above general formulas (4) to (6), R 1 R 2 R 3 Represent R in general formulas (1) to (3) respectively 1 R 2 R 3 Same group. R 4 They can be the same or different, representing a monovalent organic group with 1 to 20 carbon atoms, preferably an alkyl group with 1 to 6 carbon atoms.

[0038] Examples of organosilane compounds represented by general formula (4) include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, naphthyltrimethoxysilane, naphthyltriethoxysilane, naphthyltripropoxysilane, etc. Two or more of these may be used.

[0039] Examples of organosilane compounds represented by general formula (5) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, etc. Two or more of these may be used.

[0040] Examples of organosilane compounds represented by general formula (6) include, for example, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, perfluoropentyltrimethoxysilane, perfluoropentyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctyltripropoxysilane, tridecafluorooctyltriisopropoxysilane, heptadecafluorodecyltrimethoxysilane, and heptadecafluorodecyltriethoxysilane. Two or more of these may be used.

[0041] Examples of organosilane compounds other than those of general formulas (4) to (6) include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-(N,N-glycidyl)aminopropyltrimethoxysilane, 3-glycidyl Glyceryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, glycidyloxymethyltrimethoxysilane, glycidyloxymethyltriethoxysilane, α-glycidyloxyethyltrimethoxysilane, α-glycidyloxyethyltriethoxysilane, β-glycidyloxypropyltrimethoxysilane, β-glycidyloxypropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltri(methoxyethoxy)silane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, σ-glycidoxybutyltrimethoxysilane, σ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexane) (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltripropoxysilane, 2-(3,4-epoxycyclohexyl)ethyltributoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltriethoxysilane, 4-(3,4-epoxycyclohexyl)butyltrimethoxysilane, 4-(3,4-epoxycyclohexyl)butyltrimethoxysilane, 4-(3,4-epoxycyclohexyl)methyltrimethoxysilane, 4-(3,4-epoxycyclohexyl)methyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltripropoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimeth ...4-Epoxycyclohexyl)butyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropylmethyldimethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldimethoxysilane Methyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, β-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldi(methoxyethoxy)silane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, octadecylmethyldimethoxysilane, 3-trimethoxysilylpropylpropylsuccinic anhydride, 3-triethoxysilylpropylpropylsuccinic anhydride, 3-triphenoxysilylpropylpropylsuccinic anhydride, 3-trimethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-trimethoxysilylpropylphthalic anhydride, etc. You can use more than two of these.

[0042] From the viewpoint of coating properties, the weight-average molecular weight (Mw) of the (A) siloxane resin is preferably 1,000 or more, more preferably 2,000 or more. On the other hand, from the viewpoint of developability, the Mw of the (A) siloxane resin is preferably 50,000 or less, more preferably 20,000 or less. Here, the Mw of the (A) siloxane resin in this invention refers to the value converted to polystyrene by gel permeation chromatography (GPC).

[0043] In the photosensitive resin composition of the present invention, the content of (A) siloxane resin can be arbitrarily set according to the desired film thickness and application, and is preferably 10 to 80% by weight in the solid component of the photosensitive resin composition. Furthermore, the content of (A) siloxane resin is more preferably 20% by weight or more in the solid component of the photosensitive resin composition, and even more preferably 30% by weight or more. On the other hand, the content of (A) siloxane resin is more preferably 70% by weight or less in the solid component of the photosensitive resin composition.

[0044] (A) Siloxane resins can be obtained by hydrolyzing the aforementioned organosilane compound and then subjecting the hydrolysate to a dehydration condensation reaction in the presence of a solvent or in the absence of a solvent.

[0045] Various conditions in hydrolysis can be set considering the reaction scale, the size and shape of the reaction vessel, and the physical properties appropriate for the target application. Examples of these conditions include, for instance, acid concentration, reaction temperature, and reaction time.

[0046] Acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acids, their anhydrides, and ion exchange resins can be used in the hydrolysis reaction. Among these, acidic aqueous solutions containing formic acid, acetic acid, and / or phosphoric acid are preferred.

[0047] When an acid catalyst is used in the hydrolysis reaction, from the viewpoint of accelerating the hydrolysis, the amount of acid catalyst added is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, relative to 100 parts by weight of all alkoxysilane compounds used in the hydrolysis reaction. On the other hand, from the viewpoint of moderately adjusting the progress of the hydrolysis reaction, the amount of acid catalyst added is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, relative to 100 parts by weight of all alkoxysilane compounds. Here, the amount of "all alkoxysilane compounds" refers to the total amount including the alkoxysilane compound, its hydrolysate, and its condensate, and the same applies below.

[0048] The hydrolysis reaction can be carried out in a solvent. The solvent can be appropriately selected considering factors such as the stability, wettability, and volatility of the photosensitive resin composition. Examples of solvents include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, and diacetone alcohol; diols 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, propylene glycol monotert-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and diethyl ether; and methyl ethyl ketone and acetylacetone. Ketones such as methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, and 2-heptanone; amides such as dimethylformamide and dimethylacetamide; acetates such as ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, and butyl lactate; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, and cyclohexane; and γ-butyrolactone, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. Two or more of these can be used.

[0049] Among these, considering the transmittance and crack resistance of the cured film, diacetone alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monotert-butyl ether, and γ-butyrolactone are preferred.

[0050] In cases where a solvent is generated due to the hydrolysis reaction, hydrolysis can also be carried out under solvent-free conditions. After the hydrolysis reaction is completed, it is also preferable to adjust the concentration to an appropriate level for the photosensitive resin composition by further adding solvent. Alternatively, after hydrolysis, the total amount or a portion of the alcohols generated can be distilled off by heating and / or reducing the pressure, and then a suitable solvent can be added.

[0051] When a solvent is used in the hydrolysis reaction, from the viewpoint of suppressing gel formation, the amount of solvent added is preferably 50 parts by weight or more, more preferably 80 parts by weight or more, relative to 100 parts by weight of the total alkoxysilane compound. On the other hand, from the viewpoint of making the hydrolysis proceed more rapidly, the amount of solvent added is preferably 500 parts by weight or less, more preferably 200 parts by weight or less, relative to 100 parts by weight of the total alkoxysilane compound.

[0052] Furthermore, ion-exchanged water is preferred for use in the hydrolysis reaction. The amount of water can be set arbitrarily, but is preferably 1.0 to 4.0 moles relative to 1 mole of all alkoxysilane compounds.

[0053] As a method for dehydration condensation reaction, for example, one method is to directly heat a solution of silanol compound obtained from the hydrolysis reaction of an organosilane compound. The heating temperature is preferably 50°C or higher and below the boiling point of the solvent, and the heating time is preferably 1 to 100 hours. Alternatively, to increase the degree of polymerization of the siloxane resin, further heating or the addition of an alkaline catalyst may be performed. Furthermore, depending on the purpose, an appropriate amount of the generated alcohol may be distilled off under heating and / or reduced pressure after hydrolysis, and then a suitable solvent may be added.

[0054] From the viewpoint of the storage stability of the photosensitive resin composition, the siloxane resin solution after hydrolysis and dehydration condensation preferably does not contain the aforementioned catalyst, and the catalyst can be removed as needed. As a catalyst removal method, from the viewpoint of ease of operation and removability, water washing, ion exchange resin-based treatment, etc., are preferred. Water washing refers to the following method: after diluting the siloxane resin solution with a suitable hydrophobic solvent, washing it several times with water, and concentrating the resulting organic layer using an evaporator or the like. Ion exchange resin-based treatment refers to a method of contacting the siloxane resin solution with a suitable ion exchange resin.

[0055] The refractive index of the (A) siloxane resin at a wavelength of 587.5 nm is preferably 1.35 to 1.55. By making the refractive index of the (A) siloxane resin 1.35 or higher, excessive interfacial reflection between the (A) siloxane resin and particles with a median particle size of 0.2 to 0.6 μm in (B) can be suppressed, further improving the resolution. The refractive index of the (A) siloxane resin is more preferably 1.40 or higher. On the other hand, by making the refractive index of the (A) siloxane resin 1.55 or lower, the interfacial reflection between particles with a median particle size of 0.2 to 0.6 μm in (B) and the (A) siloxane resin can be increased, further improving the light diffusivity. Here, the refractive index of (A) siloxane resin is determined as follows: For a cured film of siloxane resin formed on a silicon wafer, a prism coupler (PC-2000 (manufactured by Metricon Co., Ltd.)) is used, and light with a wavelength of 587.5 nm is irradiated from a direction perpendicular to the surface of the cured film at atmospheric pressure and 20°C. The third decimal place is rounded. It should be noted that the cured film of siloxane resin is prepared as follows: a siloxane resin solution obtained by dissolving the siloxane resin in an organic solvent at a solid content concentration of 40% by weight is spin-coated onto a silicon wafer, dried on a 90°C heating plate for 2 minutes, and then cured in air at 170°C for 30 minutes using an oven. When the photosensitive resin composition contains two or more (A) siloxane resins, it is preferable that the refractive index of at least one is within the above-mentioned range.

[0056] (B) Particles with a median particle size of 0.2–0.6 μm

[0057] (B) Particles with a median particle size of 0.2–0.6 μm can scatter incident light over a wide range, exhibiting sufficient light diffusion. With particles having a median particle size less than 0.2 μm, the scattering of light caused by the particles is insufficient, and sufficient light diffusion cannot be ensured. On the other hand, when using particles with a median particle size greater than 0.6 μm, the scattering of light is concentrated in the forward direction, thus failing to ensure sufficient light diffusion.

[0058] As particles with a median particle size of 0.2 to 0.6 μm in (B), examples include compounds selected from titanium dioxide, zirconium oxide, aluminum oxide, talc, mica, white carbon, magnesium oxide, zinc oxide, barium carbonate, and these composite compounds. Two or more of these may be included. Among these, titanium dioxide and / or zirconium oxide, which have high light diffusivity and are readily available for industrial use, are preferred.

[0059] Surface treatment can be performed on particles with a median particle size of 0.2–0.6 μm (B). Preferably, surface treatment using Al, Si, and / or Zr can improve the dispersibility of particles with a median particle size of 0.2–0.6 μm (B) in the photosensitive resin composition, further improving the lightfastness and heat resistance of the cured film. The median particle size refers to the average primary particle size of particles with a median particle size of 0.2–0.6 μm (B) calculated based on the particle size distribution measured by laser diffraction.

[0060] Examples of titanium dioxide used as particles with a median particle size of 0.2–0.6 μm for (B) include: R960; DuPont Corporation (SiO2 / Al2O3 surface treatment, median particle size 0.21 μm), CR-97; Ishihara Sangyo Corporation (Al2O3 / ZrO2 surface treatment, median particle size 0.25 μm), JR-301; Tayca Corporation (Al2O3 surface treatment, median particle size 0.30 μm), JR-405; Tayca Corporation (Al2O3 surface treatment, median particle size... Examples of zirconium oxide include: JR-600A (Al2O3 surface-treated, median particle size 0.25μm); JR-603; Tayca Co. (Al2O3 / ZrO2 surface-treated, median particle size 0.28μm); 3YI-R (Toray Industries, Ltd., Al2O3 surface-treated, median particle size 0.50μm); and AO-502 (Admatechs Co., Ltd., untreated, median particle size 0.25μm). Aluminum oxide may contain two or more of these.

[0061] The refractive index of the particles with a median particle size of 0.2 to 0.6 μm (B) is preferably 1.70 to 2.90. By making the refractive index of the particles with a median particle size of 0.2 to 0.6 μm (B) 1.70 or higher, the interfacial reflection between the particles with a median particle size of 0.2 to 0.6 μm (B) and the siloxane resin (A) can be increased, thereby further improving the reflectivity. The refractive index of the particles with a median particle size of 0.2 to 0.6 μm (B) is more preferably 2.20 or higher, and even more preferably 2.40 or higher. On the other hand, by making the refractive index of the particles with a median particle size of 0.2 to 0.6 μm (B) 2.90 or lower, excessive interfacial reflection between the siloxane resin (A) and the particles with a median particle size of 0.2 to 0.6 μm (B) can be suppressed, thereby further improving the resolution. The refractive index of particles with a median particle size of 0.2 to 0.6 μm (B) referred to herein is the representative refractive index of the material constituting the particles. The refractive index of the material constituting the particles can be determined by forming a solidified film of the material constituting the particles on a silicon wafer using vacuum evaporation, sputtering, or similar methods. Using a prism coupler (PC-2000 (manufactured by Metricon Corporation)), light with a wavelength of 587.5 nm is irradiated from a direction perpendicular to the surface of the solidified film at atmospheric pressure and 20°C. The third decimal place is rounded. The measurement wavelength is a standard 587.5 nm. When the material contains two or more particles with a median particle size of 0.2 to 0.6 μm (B), it is preferable that the refractive index of at least one of them is within the above range.

[0062] The refractive index difference between (A) the siloxane resin and (B) particles with a median particle size of 0.2 to 0.6 μm at a wavelength of 587.5 nm is preferably 0.20 to 1.40. By making the refractive index difference 0.20 or more, the interfacial reflection between (A) the siloxane resin and (B) particles with a median particle size of 0.2 to 0.6 μm is increased, thereby improving light diffusivity. The refractive index difference is more preferably 0.50 or more, and even more preferably 1.00 or more. On the other hand, by making the refractive index difference 1.40 or less, excessive interfacial reflection between (A) the siloxane resin and (B) particles with a median particle size of 0.2 to 0.6 μm can be suppressed, thereby further improving resolution. The refractive index difference is more preferably 1.35 or less.

[0063] From the viewpoint of further improving diffusivity, the content of particles with a median particle size of 0.2 to 0.6 μm in (B) of the photosensitive resin composition of the present invention is preferably 5% by weight or more of the solid component, more preferably 10% by weight or more, even more preferably 20% by weight or more, and even more preferably 40% by weight or more. On the other hand, from the viewpoint of suppressing development residue and forming a higher resolution pattern, the content of particles with a median particle size of 0.2 to 0.6 μm in (B) is preferably 65% ​​by weight or less of the solid component, even more preferably 60% by weight or less. The solid component referred to herein means all components contained in the photosensitive resin composition except for volatile components such as solvents. The amount of solid component can be determined by heating the photosensitive resin composition at 170°C for 30 minutes to evaporate the volatile components and measuring the remaining components obtained.

[0064] The photosensitive resin composition of the present invention, by containing a pigment dispersant along with particles of median particle size (B) of 0.2 to 0.6 μm, can improve the dispersibility of particles of median particle size (B) of 0.2 to 0.6 μm in the photosensitive resin composition. The pigment dispersant can be appropriately selected according to the type and surface state of the particles of median particle size (B) of 0.2 to 0.6 μm used. The pigment dispersant preferably contains acidic groups and / or basic groups. Examples of commercially available pigment dispersants include, for example, "Disperbyk" (registered trademark) 106, 108, 110, 180, 190, 2001, 2155, 140, and 145 (trade names, manufactured by BYK-Chemie Co., Ltd.). Two or more of these can be contained.

[0065] (C) Naphthoquinone diazide compound

[0066] As a (C)naphthoquinone diazide compound, for example, a compound obtained by ester bonding of the sulfonic acid of diazidonaphthoquinone to a compound having a phenolic hydroxyl group can be cited.

[0067] There are no particular limitations on the (C)-naphthoquinone diazide compound used, but compounds obtained by ester bonding of the sulfonic acid of diazidonaphthoquinone to a compound having a phenolic hydroxyl group are preferred. Examples of compounds having a phenolic hydroxyl group used herein include, for example, 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, and Bis26X. -IPZ, BisOTBP-CP, TekP-4HBPA (TrisP-DO-BPA), TrisP-HAP, TrisP-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T-OCHP, Methylene tris-FR-CR, BisRS-26X, BisRS-OCHP (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (trade names, manufactured by Asahi Organic Materials Co., Ltd.), 4,4'-sulfonyl diphenol (manufactured by Wako Pure Chemicals Co., Ltd.), BPFL (trade name, manufactured by JFE Chemical Co., Ltd.).

[0068] Among these, preferred compounds having phenolic hydroxyl groups include, for example, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene tris-FR-CR, BisRS-26X, BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F. 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'-sulfonyl diphenol, and BPFL. Compounds obtained by introducing diazidonaphthoquinone-4-sulfonic acid via ester bonds into these compounds having phenolic hydroxyl groups are preferred examples, but other compounds may also be used. (C) The molecular weight of the naphthoquinone diazide compound is preferably 300 to 1500, more preferably 350 to 1200. By setting the molecular weight to 300 or higher, a dissolution suppression effect on the unexposed areas can be obtained. Furthermore, by setting the molecular weight to 1500 or lower, a good pattern free of developing residues can be obtained.

[0069] These (C)naphthoquinone diazide compounds can be used alone or in combination of two or more.

[0070] The content of these (C)naphthoquinone diazide compounds is preferably 1 to 30 parts by weight relative to the (A) siloxane resin. At 1 part by weight or more, pattern formation can be achieved with practical sensitivity. Furthermore, at 30 parts by weight or less, a resin composition with excellent pattern resolution can be obtained.

[0071] Furthermore, when (C)naphthoquinone diazide compounds are added, unreacted photosensitizer may sometimes remain in the unexposed areas, causing film discoloration after heat curing. To obtain a cured film with minimal discoloration, it is preferable to irradiate the entire surface of the developed film with ultraviolet light and then heat it.

[0072] The photosensitive resin composition of the present invention may also contain crosslinking agents, adhesion modifiers, solvents, surfactants, dissolution inhibitors, stabilizers, defoamers, etc., as needed.

[0073] By including a crosslinking agent in the photosensitive resin composition of the present invention, crosslinking of the siloxane resin is promoted during thermosetting, thereby increasing the degree of crosslinking of the cured film. Therefore, the reduction in pattern resolution caused by melting of the fine pattern during thermosetting can be suppressed. Examples of curing agents include nitrogen-containing organic compounds, silicone resin curing agents, isocyanate compounds and their polymers, hydroxymethylated melamine derivatives, hydroxymethylated urea derivatives, various metal alkoxides, various metal chelates, thermally generated acid materials, and photo-generated acid materials. Two or more of these may be included. Among these, hydroxymethylated melamine derivatives, hydroxymethylated urea derivatives, and photo-generated acid materials are preferred from the viewpoints of curing agent stability and coating film processability. The photo-generated acid agent used in the present invention is a compound that generates acid during bleaching exposure, and is a compound that generates acid by irradiation with exposure wavelengths of 365 nm (i-line), 405 nm (h-line), 436 nm (g-line), or a mixture of these lines. Therefore, although acid may also be generated during pattern exposure using the same light source, the exposure amount for pattern exposure is smaller compared to bleaching exposure, so only a small amount of acid is generated and it is not a problem. Furthermore, strong acids such as perfluoroalkyl sulfonic acid and p-toluenesulfonic acid are preferred as the generated acid. (C)naphthoquinone diazide compounds that generate carboxylic acids do not have the function of the photoacid-generating agent mentioned herein, and are different from the curing agent in this invention.

[0074] By including an adhesion modifier in the photosensitive resin composition of the present invention, the adhesion to the substrate is improved, resulting in a highly reliable cured film. Examples of adhesion modifiers include alicyclic epoxy compounds and silane coupling agents. Among these, silane coupling agents are preferred because they exhibit high heat resistance, thus further suppressing color changes after heating.

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

[0076] From the viewpoint of further improving adhesion to the substrate, the content of the adhesion modifier in the photosensitive resin composition ester of the present invention is preferably 0.1% by weight or more in the solid component, more preferably 1% by weight or more. On the other hand, from the viewpoint of further suppressing color change caused by heating, the content of the adhesion modifier is preferably 20% by weight or less in the solid component, more preferably 10% by weight or less.

[0077] By including a solvent in the photosensitive resin composition of the present invention, the viscosity can be easily adjusted to a suitable level for coating, thereby improving the uniformity of the coated film. Preferably, a combination of a solvent with a boiling point exceeding 150°C and below 250°C at atmospheric pressure and a solvent with a boiling point below 150°C is used. By including a solvent with a boiling point exceeding 150°C and below 250°C, the solvent evaporates moderately during coating, allowing the coating film to dry; therefore, uneven coating can be suppressed, and film thickness uniformity can be improved. Furthermore, by including a solvent with a boiling point below 150°C at atmospheric pressure, solvent residue in the cured film of the present invention (described later) can be suppressed. From the viewpoint of suppressing solvent residue in the cured film and further improving chemical resistance and adhesion over a long period, it is preferable to include a solvent with a boiling point below 150°C at atmospheric pressure, comprising at least 50% by weight of the total solvent.

[0078] Examples of solvents with a boiling point below 150°C at atmospheric pressure include ethanol, isopropanol, 1-propanol, 1-butanol, 2-butanol, isoamyl alcohol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, methoxymethyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, 1-methoxypropyl-2-acetate, acetone alcohol, acetylacetone, methyl isobutyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl lactate, toluene, cyclopentanone, cyclohexane, n-heptane, benzene, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, isoamyl acetate, amyl acetate, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, and 5-hydroxy-2-pentanone. Two or more of these may be used.

[0079] Examples of solvents with boiling points exceeding 150°C but below 250°C at atmospheric pressure include, for example, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-tert-butyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-tert-butyl ether, 2-ethoxyethyl acetate, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether propionate, dipropylene glycol methyl ether, diisobutyl ketone, diacetone alcohol, ethyl lactate, butyl lactate, dimethylformamide, dimethylacetamide, γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, cycloheptanone, diethylene glycol monobutyl ether, and ethylene glycol dibutyl ether. Two or more of these may be used.

[0080] The solvent content can be arbitrarily set depending on the coating method, etc. For example, in the case of film formation using spin coating, it is usually 50% by weight or more and 95% by weight or less in the photosensitive resin composition.

[0081] By including a surfactant in the photosensitive resin composition of the present invention, the flowability during coating can be improved. Examples of surfactants include, for instance, fluorinated surfactants such as "MEGAFAC" (registered trademark) F142D, F172, F173, F183, F445, F470, F475, F477 (trade names, manufactured by Dai Nippon Ink Chemical Co., Ltd.), NBX-15, and FTX-218 (trade names, manufactured by NEO Co., Ltd.); organosilicon surfactants such as "Disperbyk" (registered trademark) 333, 301, 331, 345, and 207 (trade names, manufactured by BYK-Chemie Co., Ltd.); polyalkylene oxide surfactants; and poly(meth)acrylate surfactants. Two or more of these may be included.

[0082] The concentration of the solid component in the photosensitive resin composition of the present invention can be arbitrarily set according to the coating method, etc. For example, in the case of film formation by spin coating as described later, the concentration of the solid component is usually 5% by weight or more and 50% by weight or less.

[0083] Next, a method for manufacturing the photosensitive resin composition of the present invention will be described. The photosensitive resin composition of the present invention can be obtained by mixing the aforementioned components (A) to (C) and other components as needed. More specifically, for example, it is preferable to first disperse a mixture of (A) siloxane resin, (B) particles with a median particle size of 0.2 to 0.6 μm, and an organic solvent using a mill-type disperser filled with zirconia beads to obtain a pigment dispersion. Alternatively, it is preferable to add (A) siloxane resin, (C) naphthoquinone diazide compound, and other additives as needed to any solvent, stir to dissolve them, and obtain a diluted solution. Then, it is preferable to mix the pigment dispersion and the diluted solution, stir, and then filter.

[0084] Furthermore, since the photosensitive resin composition of the present invention contains particles with a median particle size of 0.2 to 0.6 μm (B) that have excellent light diffusivity, it can be suitably used as a light diffusion layer forming material for diffusing light from a light source.

[0085] Next, the cured film of the present invention will be described. The cured film of the present invention is formed from the cured product of the aforementioned photosensitive resin composition of the present invention. The thickness of the cured film is preferably 0.3 to 3.0 μm. By making the thickness of the cured film 0.3 μm or more, good light diffusion properties can be exhibited. On the other hand, by making the film thickness 3.0 μm or less, light diffusion during exposure can be suppressed, and good pattern processing properties can be achieved. In addition, the haze of the cured film with a thickness of 1.0 μm is preferably 20% to 98%. By making the haze 20% or more, good light diffusion properties can be exhibited. On the other hand, by making the haze 98% or less, light diffusion during exposure can be suppressed, and good pattern processing properties can be achieved. In addition, the total light transmittance of the cured film with a thickness of 1.0 μm is preferably 40% to 90%. By making the total light transmittance 40% or more, the loss of light when passing through the cured film can be reduced, and sufficient brightness can be ensured. On the other hand, by making the total light transmittance 90% or less, excessive light transmission can be suppressed, and moderate brightness can be achieved. It should be noted that the cured film having the above-mentioned characteristics can be obtained, for example, by using the aforementioned photosensitive resin composition of the present invention and patterning it using the preferred manufacturing method described later.

[0086] The cured film of the present invention can be obtained, for example, by coating the aforementioned photosensitive resin composition of the present invention into a film, patterning it as needed, and then curing it. Preferably, the photosensitive resin composition of the present invention is coated onto a substrate, pre-baked, then exposed and developed to form a positive pattern, exposed again, and then thermally cured.

[0087] Examples of coating methods for applying a photosensitive resin composition to a substrate include microgravure printing coating, spin coating, dip coating, curtain coating, roller coating, spray coating, and slot coating. Examples of pre-baking devices include heating plates and ovens. The pre-baking temperature is preferably 50–130°C, and the pre-baking time is preferably 30 seconds to 30 minutes. The film thickness after pre-baking is preferably 0.1–15 μm.

[0088] Exposure can be performed with or without a desired mask. Examples of exposure machines include stepper machines, mirror projection mask alignment (MPA) machines, and parallel light mask alignment (PLA) machines. The preferred exposure intensity is 10–4000 J / m². 2 The exposure dose is approximately 365nm (based on the exposure dose at a wavelength of 365nm). Examples of suitable light sources for exposure include i-line, g-line, h-line ultraviolet light, KrF (wavelength 248nm) laser, and ArF (wavelength 193nm) laser.

[0089] Examples of developing methods include spraying, immersion, and puddle methods. The immersion time in the developing solution is preferably 5 seconds to 10 minutes. Examples of developing solutions include, for instance, aqueous solutions containing inorganic bases such as alkali metal hydroxides, carbonates, phosphates, silicates, and borates; amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine; and quaternary ammonium salts such as tetramethylammonium hydroxide and choline. After development, rinsing with water is preferred, but drying and baking in the range of 50 to 130°C may also be performed.

[0090] As a reexposure method, ultraviolet-visible exposure machines such as stepper machines, mirror projection mask aligners (MPA), and parallel light mask aligners (PLA) are preferred, with a speed of 100–20000 J / m. 2 Expose the entire surface from left to right (based on the exposure amount at a wavelength of 365nm).

[0091] Heating devices used in thermosetting include heating plates and ovens. The preferred thermosetting temperature is 80–230°C, and the preferred thermosetting time is approximately 15 minutes to 1 hour.

[0092] Next, the substrate of the present invention having a cured film on a substrate, wherein the cured film is patterned from the aforementioned photosensitive resin material and the haze of the cured film is 20-98% when the film thickness is 1 μm, will be described.

[0093] The substrate with a cured film of the present invention has a cured film obtained by patterning on the substrate. The substrate functions as a support in the substrate with the cured film. The cured film functions to diffuse light from a light source. In the present invention, the haze of the cured film obtained by patterning is preferably 20% to 98% when the film thickness is 1 μm. By making the haze at 20% or more when the film thickness is 1 μm, the light from the light source can be sufficiently diffused, and the brightness can be uniform. On the other hand, by making the haze at 98% or less when the film thickness is 1 μm, light diffusion during exposure can be suppressed, and good pattern processing properties can be achieved.

[0094] Furthermore, in the substrate with the cured film of the present invention, the thickness of the cured film is preferably 0.3 to 3.0 μm. By making the thickness of the cured film 0.3 μm or more, good light diffusion properties can be exhibited. On the other hand, by making the film thickness 3.0 μm or less, light diffusion during exposure can be suppressed, and good pattern processing properties can be achieved.

[0095] Furthermore, examples of substrates for the substrate with a cured film according to the present invention include glass substrates and resin substrates containing polyimide. Glass substrates have excellent transparency, and therefore are suitable for use as substrates with a cured film according to the present invention. In addition, resin substrates containing polyimide have excellent flexibility, and therefore are suitable for use as substrates with a cured film according to the present invention.

[0096] Figure 1 A cross-sectional view is shown illustrating one embodiment of the substrate with a cured film according to the present invention. A cured film 2, obtained by patterning, is present on the substrate 1.

[0097] Furthermore, the substrate with the cured film of the present invention preferably has a black layer between the cured film obtained by pattern formation and adjacent cured films. By having a black layer between adjacent cured films, light-shielding properties can be improved, and light leakage from the light source in the display device can be suppressed.

[0098] Figure 2 A cross-sectional view is shown illustrating one embodiment of the substrate with a cured film of the present invention having a black layer. On the substrate 1, a cured film 2, obtained by patterning, is present, and a black layer 3 is present between adjacent cured films 2.

[0099] The optical density of the black layer with a thickness of 1.0 μm is preferably 0.1 to 4.0. Here, as described below, the thickness of the black layer is preferably 0.5 to 10 μm. Therefore, in this invention, 1.0 μm is selected as the representative value of the thickness of the black layer, focusing on the optical density when the thickness is 1.0 μm. By making the optical density of the black layer with a thickness of 1.0 μm 0.1 or more, the light-blocking property can be further improved, and a vivid image with higher contrast can be obtained. The optical density of the black layer with a thickness of 1.0 μm is more preferably 0.5 or more. On the other hand, by making the optical density of the black layer with a thickness of 1.0 μm 4.0 or less, the pattern processing property can be improved. The optical density of the black layer with a thickness of 1.0 μm is more preferably 3.0 or less. The optical density (OD value) of the black layer can be measured by measuring the intensity of the incident light and the transmitted light using an optical density meter (361T (visual); manufactured by X-rite Co., Ltd.) and calculated by the following formula (7).

[0100] OD value = log10(I0 / I)···Equation (7)

[0101] I0: Incident light intensity

[0102] I: Light transmission intensity

[0103] It should be noted that, as a means of bringing the optical concentration within the above range, for example, making the black layer the preferred composition described later can be cited.

[0104] From the viewpoint of improving light-blocking properties, the thickness of the black layer is preferably 0.5 μm or more, and more preferably 1.0 μm or more. On the other hand, from the viewpoint of improving flatness, the thickness of the black layer is preferably 10 μm or less, and more preferably 5 μm or less.

[0105] The black layer preferably contains resin and black pigment. The resin improves the crack resistance and lightfastness of the black layer. The black pigment absorbs incident light and reduces emitted light.

[0106] Examples of resins include epoxy resins, (meth)acrylic polymers, polyurethanes, polyesters, polyimides, polyolefins, and polysiloxanes. Two or more of these may be contained. Among these, polyimides are preferred due to their excellent heat resistance and solvent resistance.

[0107] Examples of black pigments include, for example, black organic pigments, mixed organic pigments, and inorganic pigments. Examples of black organic pigments include, for example, carbon black, perylene black, aniline black, and benzofuranone pigments. These can be coated with resin. Examples of mixed organic pigments include, for example, pigments obtained by mixing two or more pigments selected from red, blue, green, purple, yellow, magenta, and / or cyan, and simulating blackness. Examples of black inorganic pigments include, for example: graphite; microparticles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver; metal oxides; metal composite oxides; metal sulfides; metal nitrides; metal oxynitrides; and metal carbides.

[0108] As a method for patterning a black layer on a substrate, the following method is preferred, for example: using the photosensitive material described in Japanese Patent Application Publication No. 2015-1654, the pattern is formed by photosensitive paste method in the same manner as the aforementioned cured film.

[0109] Next, the display device of the present invention will be described. The display device of the present invention includes the substrate with the cured film described above and a light source. As the light source, mini LED units or micro LED units are preferred from the perspective of excellent light emission characteristics and reliability. Here, a mini LED unit refers to a structure formed by arranging a large number of LED units with a length of 100 μm to 10 mm in both directions. A micro LED unit refers to a structure formed by arranging a large number of LED units with a length of less than 100 μm in both directions.

[0110] Regarding the manufacturing method of the display device of the present invention, an example of a display device having the substrate with a cured film and micro-LED units of the present invention will be described. After forming driving wiring electrodes on the substrate, micro-LED units are disposed. The aforementioned substrate with a cured film and micro-LED units can be bonded together using a sealant, thereby manufacturing the device.

[0111] Example

[0112] The present invention is illustrated below with examples, but the invention is not limited to these examples. The compounds used in the synthesis examples and embodiments, and the substances referred to by abbreviations, are described below.

[0113] PGMEA: Propylene glycol monomethyl ether acetate

[0114] DAA: Diacetone alcohol.

[0115] The solid component concentrations of the siloxane resin solutions and acrylic resin solutions in Synthetic Examples 1-10 were determined using the following method. 1.5 g of either the siloxane resin solution or acrylic resin solution was weighed into an aluminum cup and heated at 250°C for 30 minutes using a heating plate to evaporate the liquid components. The weight of the solid component remaining in the heated aluminum cup was weighed, and the solid component concentration of the siloxane resin solution or acrylic resin solution was determined based on its proportion relative to its weight before heating.

[0116] The weight-average molecular weights of the siloxane resin and acrylic resin solutions in Synthetic Examples 1-10 were determined using the following method. A GPC analysis apparatus (HLC-8220; manufactured by Tosoh Corporation) was used, with tetrahydrofuran as the mobile phase. GPC analysis was performed based on "JISK7252-3 (established on 2008 / 03 / 20)" to determine the weight-average molecular weight converted to polystyrene.

[0117] The content ratio of each organosilane unit in the siloxane resins of Synthetic Examples 1-9 was determined using the following method. The siloxane resin solution was injected into 10 mm diameter Teflon (registered trademark) NMR sample tubes for testing. 29 Si-NMR measurements are performed to calculate the content ratio of each organosilane unit based on the ratio of the integral value of Si from a specific organosilane unit to the integral value of Si from the organosilane as a whole. The following shows... 29 Measurement conditions for Si-NMR.

[0118] Apparatus: Nuclear Magnetic Resonance Imaging System (JNM-GX270; manufactured by Nippon Electron Ltd.)

[0119] Measurement method: Gated decoupling method

[0120] Nuclear frequency measured: 53.6693MHz 29 Si core)

[0121] Spectral width: 20000Hz

[0122] Pulse width: 12μs (45° pulse)

[0123] Pulse repetition time: 30.0 seconds

[0124] Solvent: Acetone-d6

[0125] Reference material: Tetramethylsilane

[0126] Measurement temperature: 23℃

[0127] Sample rotation speed: 0.0 Hz.

[0128] Synthesis Example 1: Siloxane Resin (A-1) Solution

[0129] In a 500 ml three-necked flask, 99.15 g (0.500 mol) of phenyltrimethoxysilane, 31.25 g (0.150 mol) of tetraethoxysilane, 21.82 g (0.100 mol) of trifluoropropyltrimethoxysilane, 24.64 g (0.100 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 20.43 g (0.150 mol) of methyltrimethoxysilane, and 127.47 g of PGMEA were added. While stirring at room temperature, an aqueous solution of phosphoric acid (0.863 g of phosphoric acid dissolved in 56.70 g of water, representing 0.50 wt% relative to the monomers added) was added over 30 minutes. The three-necked flask was then immersed in an oil bath at 70 °C and stirred for 90 minutes. After 30 minutes, the oil bath temperature was increased to 115 °C. One hour after heating began, the internal temperature (solution temperature) of the three-necked flask reached 100°C. Heating and stirring continued for 2 hours (internal temperature 100–110°C) to obtain a siloxane resin solution. It should be noted that nitrogen gas was flowed at a rate of 0.05 L / min during heating and stirring. During the reaction, a total of 125.05 g of methanol and water, as byproducts, was distilled off. PGMEA was added to the obtained siloxane resin solution at a solid content concentration of 40% by weight to obtain a siloxane resin (A-1) solution. It should be noted that the weight-average molecular weight of the obtained siloxane resin (A-1) was 3,500 (converted to polystyrene). Furthermore, according to… 29 According to the Si-NMR determination results, the molar ratios of repeating units from phenyltrimethoxysilane, tetraethoxysilane, trifluoropropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and methyltrimethoxysilane in the siloxane resin (A-1) were 50 mol%, 15 mol%, 10 mol%, 10 mol%, and 15 mol%, respectively.

[0130] Synthesis Example 2: Siloxane Resin (A-2) Solution

[0131] In a 500 ml three-necked flask, 99.15 g (0.500 mol) of phenyltrimethoxysilane, 31.25 g (0.150 mol) of tetraethoxysilane, 24.64 g (0.100 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 34.05 g (0.250 mol) of methyltrimethoxysilane, and 112.44 g of PGMEA were added. While stirring at room temperature, an aqueous solution of phosphoric acid (0.822 g of phosphoric acid dissolved in 56.70 g of water, representing 0.50 wt% relative to the monomers added) was added over 30 minutes. The three-necked flask was then immersed in an oil bath at 70 °C and stirred for 90 minutes. After 30 minutes, the oil bath temperature was increased to 115 °C. One hour after heating began, the internal temperature (solution temperature) of the three-necked flask reached 100°C. Heating and stirring continued for 2 hours (internal temperature 100–110°C) to obtain a siloxane resin solution. It should be noted that nitrogen gas was flowed at a rate of 0.05 L / min during heating and stirring. During the reaction, a total of 129.15 g of methanol and water, as byproducts, was distilled off. PGMEA was added to the obtained siloxane resin solution at a solid content concentration of 40% by weight to obtain a siloxane resin (A-2) solution. It should be noted that the weight-average molecular weight of the obtained siloxane resin (A-2) was 4,100 (converted to polystyrene). Furthermore, according to… 29 According to the Si-NMR determination results, the molar ratios of repeating units from phenyltrimethoxysilane, tetraethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and methyltrimethoxysilane in the siloxane resin (A-2) were 50 mol%, 15 mol%, 10 mol%, and 25 mol%, respectively.

[0132] Synthesis Example 3: Siloxane Resin (A-3) Solution

[0133] In a 500 ml three-necked flask, 99.15 g (0.500 mol) of phenyltrimethoxysilane, 24.64 g (0.100 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 54.48 g (0.400 mol) of methyltrimethoxysilane, and 103.44 g of PGMEA were added. While stirring at room temperature, an aqueous solution of phosphoric acid (0.768 g of phosphoric acid dissolved in 54.00 g of water, representing 0.50% by weight relative to the monomers added) was added over 30 minutes. The three-necked flask was then immersed in an oil bath at 70 °C and stirred for 90 minutes. After 30 minutes, the oil bath temperature was increased to 115 °C. One hour after the start of heating, the internal temperature (solution temperature) of the three-necked flask reached 100 °C. The mixture was then heated and stirred for 2 hours (internal temperature 100–110 °C) to obtain a siloxane resin solution. It should be noted that nitrogen gas was flowed at a rate of 0.05 L / min during heating and stirring. During the reaction, a total of 123.00 g of methanol and water, as byproducts, was distilled off. PGMEA was added to the obtained siloxane resin solution at a solid content concentration of 40% by weight to obtain a siloxane resin (A-3) solution. It should be noted that the weight-average molecular weight of the obtained siloxane resin (A-3) was 4,100 (converted to polystyrene). Furthermore, according to... 29 According to Si-NMR measurements, the molar ratios of repeating units from phenyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and methyltrimethoxysilane in the siloxane resin (A-3) were 50 mol%, 10 mol%, and 40 mol%, respectively.

[0134] Synthesis Example 4: Siloxane Resin (A-4) Solution

[0135] In a 500 ml three-necked flask, 59.49 g (0.300 mol) of phenyltrimethoxysilane, 31.25 g (0.150 mol) of tetraethoxysilane, 21.82 g (0.100 mol) of trifluoropropyltrimethoxysilane, 24.64 g (0.100 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 47.64 g (0.350 mol) of methyltrimethoxysilane, and 112.29 g of PGMEA were added. While stirring at room temperature, an aqueous solution of phosphoric acid (0.801 g of phosphoric acid dissolved in 56.70 g of water, representing 0.50 wt% relative to the monomers added) was added over 30 minutes. The three-necked flask was then immersed in an oil bath at 70 °C and stirred for 90 minutes. After 30 minutes, the oil bath temperature was increased to 115 °C. One hour after heating began, the internal temperature (solution temperature) of the three-necked flask reached 100°C. Heating and stirring continued for 2 hours (internal temperature 100–110°C) to obtain a siloxane resin solution. It should be noted that nitrogen gas was flowed at a rate of 0.05 L / min during heating and stirring. During the reaction, a total of 125.05 g of methanol and water, as byproducts, was distilled off. PGMEA was added to the obtained siloxane resin solution at a solid content concentration of 40% by weight to obtain a siloxane resin (A-4) solution. It should be noted that the weight-average molecular weight of the obtained siloxane resin (A-4) was 4,600 (converted to polystyrene). Furthermore, according to… 29 According to the Si-NMR determination results, the molar ratios of repeating units from phenyltrimethoxysilane, tetraethoxysilane, trifluoropropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and methyltrimethoxysilane in the siloxane resin (A-4) were 30 mol%, 15 mol%, 10 mol%, 10 mol%, and 35 mol%, respectively.

[0136] Synthesis Example 5: Siloxane Resin (A-5) Solution

[0137] In a 500 ml three-necked flask, 59.49 g (0.300 mol) of phenyltrimethoxysilane, 62.49 g (0.300 mol) of tetraethoxysilane, 21.82 g (0.100 mol) of trifluoropropyltrimethoxysilane, 24.64 g (0.100 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 27.24 g (0.200 mol) of methyltrimethoxysilane, and 121.29 g of PGMEA were added. While stirring at room temperature, an aqueous solution of phosphoric acid (0.855 g of phosphoric acid dissolved in 59.40 g of water, representing 0.50% by weight relative to the monomers added) was added over 30 minutes. The three-necked flask was then immersed in an oil bath at 70 °C and stirred for 90 minutes. After 30 minutes, the oil bath temperature was increased to 115 °C. One hour after heating began, the internal temperature (solution temperature) of the three-necked flask reached 100°C. Heating and stirring continued for 2 hours (internal temperature 100–110°C) to obtain a siloxane resin solution. It should be noted that nitrogen gas was flowed at a rate of 0.05 L / min during heating and stirring. During the reaction, a total of 131.20 g of methanol and water, as byproducts, was distilled off. PGMEA was added to the obtained siloxane resin solution at a solid content concentration of 40% by weight to obtain a siloxane resin (A-5) solution. It should be noted that the weight-average molecular weight of the obtained siloxane resin (A-5) was 3,900 (converted to polystyrene). Furthermore, according to… 29 According to the Si-NMR determination results, the molar ratios of repeating units from phenyltrimethoxysilane, tetraethoxysilane, trifluoropropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and methyltrimethoxysilane in the siloxane resin (A-5) were 30 mol%, 30 mol%, 10 mol%, 10 mol%, and 20 mol%, respectively.

[0138] Synthesis Example 6: Siloxane Resin (A-6) Solution

[0139] In a 500 ml three-necked flask, 59.49 g (0.300 mol) of phenyltrimethoxysilane, 31.25 g (0.150 mol) of tetraethoxysilane, 65.46 g (0.300 mol) of trifluoropropyltrimethoxysilane, 24.64 g (0.100 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 20.43 g (0.150 mol) of methyltrimethoxysilane, and 142.36 g of PGMEA were added. While stirring at room temperature, an aqueous solution of phosphoric acid (0.883 g of phosphoric acid dissolved in 56.70 g of water, representing 0.50 wt% relative to the monomers added) was added over 30 minutes. The three-necked flask was then immersed in an oil bath at 70 °C and stirred for 90 minutes. After 30 minutes, the oil bath temperature was increased to 115 °C. One hour after heating began, the internal temperature (solution temperature) of the three-necked flask reached 100°C. Heating and stirring continued for 2 hours (internal temperature 100–110°C) to obtain a siloxane resin solution. It should be noted that nitrogen gas was flowed at a rate of 0.05 L / min during heating and stirring. During the reaction, 116 g of methanol and water, as byproducts, were distilled off. PGMEA was added to the obtained siloxane resin solution at a solid content concentration of 40% by weight to obtain a siloxane resin (A-6) solution. It should be noted that the weight-average molecular weight of the obtained siloxane resin (A-6) was 3,100 (converted to polystyrene). Furthermore, according to… 29 According to the Si-NMR determination results, the molar ratios of repeating units from phenyltrimethoxysilane, tetraethoxysilane, trifluoropropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and methyltrimethoxysilane in the siloxane resin (A-6) were 30 mol%, 15 mol%, 30 mol%, 10 mol%, and 15 mol%, respectively.

[0140] Synthesis Example 7: Siloxane Resin (A-7) Solution

[0141] In a 500 ml three-necked flask, 128.90 g (0.650 mol) of phenyltrimethoxysilane, 31.25 g (0.150 mol) of tetraethoxysilane, 21.82 g (0.100 mol) of trifluoropropyltrimethoxysilane, 12.32 g (0.050 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 6.81 g (0.050 mol) of methyltrimethoxysilane, and 147.18 g of PGMEA were added. While stirring at room temperature, an aqueous solution of phosphoric acid (0.944 g of phosphoric acid dissolved in 56.70 g of water, representing 0.50 wt% relative to the monomers added) was added over 30 minutes. The three-necked flask was then immersed in an oil bath at 70 °C and stirred for 90 minutes. After 30 minutes, the oil bath temperature was increased to 115 °C. One hour after heating began, the internal temperature (solution temperature) of the three-necked flask reached 100°C. Heating and stirring continued for 2 hours (internal temperature 100–110°C) to obtain a siloxane resin solution. It should be noted that nitrogen gas was flowed at a rate of 0.05 L / min during heating and stirring. During the reaction, a total of 125.05 g of methanol and water, as byproducts, was distilled off. PGMEA was added to the obtained siloxane resin solution at a solid content concentration of 40% by weight to obtain a siloxane resin (A-7) solution. It should be noted that the weight-average molecular weight of the obtained siloxane resin (A-7) was 3,100 (converted to polystyrene). Furthermore, according to… 29 According to the Si-NMR determination results, the molar ratios of repeating units from phenyltrimethoxysilane, tetraethoxysilane, trifluoropropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and methyltrimethoxysilane in the siloxane resin (A-7) were 65 mol%, 15 mol%, 10 mol%, 5 mol%, and 5 mol%, respectively.

[0142] Synthesis Example 8: Siloxane Resin (A-8) Solution

[0143] In a 500 ml three-necked flask, 31.25 g (0.150 mol) of tetraethoxysilane, 24.64 g (0.100 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 102.15 g (0.750 mol) of methyltrimethoxysilane, and 74.49 g of PGMEA were added. While stirring at room temperature, an aqueous solution of phosphoric acid (0.667 g of phosphoric acid dissolved in 56.70 g of water, representing 0.50 wt% relative to the monomers added) was added over 30 minutes. The three-necked flask was then immersed in an oil bath at 70 °C and stirred for 90 minutes. After 30 minutes, the oil bath temperature was increased to 115 °C. One hour after the start of heating, the internal temperature (solution temperature) of the three-necked flask reached 100 °C. The mixture was then heated and stirred for 2 hours (internal temperature 100–110 °C) to obtain a siloxane resin solution. It should be noted that nitrogen gas was flowed at a rate of 0.05 L / min during heating and stirring. During the reaction, a total of 129.15 g of methanol and water, as byproducts, was distilled off. PGMEA was added to the obtained siloxane resin solution at a solid content concentration of 40% by weight to obtain a siloxane resin (A-8) solution. It should be noted that the weight-average molecular weight of the obtained siloxane resin (A-8) was 5,100 (converted to polystyrene). Furthermore, according to... 29 According to Si-NMR measurements, the molar ratios of repeating units from tetraethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and methyltrimethoxysilane in the siloxane resin (A-8) were 15 mol%, 10 mol%, and 75 mol%, respectively.

[0144] Synthesis Example 9: Siloxane Resin (A-9) Solution

[0145] In a 500 ml three-necked flask, 21.82 g (0.100 mol) of trifluoropropyltrimethoxysilane, 24.64 g (0.100 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 108.96 g (0.800 mol) of methyltrimethoxysilane, and 80.52 g of PGMEA were added. While stirring at room temperature, an aqueous solution of phosphoric acid (0.654 g of phosphoric acid dissolved in 54.00 g of water, representing 0.50% by weight relative to the monomers added) was added over 30 minutes. The three-necked flask was then immersed in an oil bath at 70 °C and stirred for 90 minutes. After 30 minutes, the oil bath temperature was increased to 115 °C. One hour after the start of heating, the internal temperature (solution temperature) of the three-necked flask reached 100 °C. The mixture was then heated and stirred for 2 hours (internal temperature 100–110 °C) to obtain a siloxane resin solution. It should be noted that nitrogen gas was flowed at a rate of 0.05 L / min during heating and stirring. During the reaction, a total of 118.90 g of methanol and water, as byproducts, was distilled off. PGMEA was added to the obtained siloxane resin solution at a solid content concentration of 40% by weight to obtain a siloxane resin (A-9) solution. It should be noted that the weight-average molecular weight of the obtained siloxane resin (A-9) was 5,100 (converted to polystyrene). Furthermore, according to... 29 According to Si-NMR measurements, the molar ratios of repeating units from trifluoropropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and methyltrimethoxysilane in the siloxane resin (A-9) were 10 mol%, 10 mol%, and 80 mol%, respectively.

[0146] The raw material compositions of the siloxane resins of Examples 1-9 are shown in Tables 1-2.

[0147] [Table 1]

[0148]

[0149] [Table 2]

[0150]

[0151] Synthesis Example 10: Acrylic Resin (a) Solution

[0152] In a 500ml three-necked flask, add 3g of 2,2'-azobis(isobutyronitrile) and 50g of PGMEA. Then, add 30g of methacrylic acid, 35g of benzyl methacrylate, and tricyclic methacrylic acid [5.2.1.0]. 2,635 g of decane-8-yl ester was stirred at room temperature for a short time to induce nitrogen substitution in the flask. The solution was then heated and stirred at 70°C for 5 hours to obtain an acrylic resin solution. PGMEA was added to the obtained acrylic resin solution at a solid content concentration of 40% by weight to obtain acrylic resin (a) solution. The weight-average molecular weight of acrylic resin (a) was 10,000 (converted to polystyrene).

[0153] (1) Pattern processing properties

[0154] The photosensitive resin compositions obtained from the various examples and comparative examples were spin-coated onto a glass substrate (hereinafter referred to as "ITO substrate") with ITO sputtered on its surface using a spin coater (trade name 1H-360S, manufactured by Mikasa Co., Ltd.) and pre-baked at 100°C for 2 minutes using a heating plate (trade name SCW-636, manufactured by Dai Nippon Screen Manufacturing Co., Ltd.) to produce a film with a thickness of 1.0 μm.

[0155] For the fabricated film, a parallel light mask aligner (trade name PLA-501F, manufactured by Canon Corporation) was used with an ultra-high pressure mercury lamp as the light source. Exposure was performed in contact mode through a grayscale mask with line and gap patterns of various widths (50μm, 40μm, 30μm, 20μm, 15μm, 10μm, 7μm, 5μm, and 4μm). Then, an automatic developing apparatus (Takizawa Sangyo Co., Ltd. "AD-2000" (trade name)) was used for 120 seconds of spray development with a 2.38 wt% tetramethylammonium hydroxide (hereinafter referred to as "TMAH") aqueous solution (trade name "ELM-D," manufactured by Mitsubishi Gas Chemical Co., Ltd.), followed by a 30-second rinse with water. Finally, as a whitening exposure, a parallel light mask aligner (trade name PLA-501F, manufactured by Canon Corporation) was used at 1000 mJ / cm². 2 The film was exposed using the exposure amount calculated using the i-line conversion method, and cured in air at 170°C for 30 minutes using an oven (IHPS-222; manufactured by ESPEC Co., Ltd.) to produce a cured film. The exposure amount that forms a 20μm wide line and gap pattern at a 1:1 ratio after exposure and development was defined as the optimal exposure amount. The minimum pattern size after development at the optimal exposure amount was defined as the post-development resolution, and the minimum pattern size after curing was defined as the post-curing resolution.

[0156] In addition, the developed pattern was observed visually and with a microscope adjusted to 50-100x magnification. The development residue was evaluated according to the following criteria based on the degree of undissolved areas in the unexposed areas.

[0157] 5: No residue was observed under visual inspection, and no residue was observed in the fine patterns below 10μm under a microscope.

[0158] 4: No residue was observed under visual inspection. Under microscopic observation, no residue was observed in patterns larger than 10 μm, but residue was observed in patterns smaller than 10 μm.

[0159] 3: No residue was observed under visual inspection, but residue was observed under a microscope in patterns larger than 10 μm.

[0160] 2: Visual inspection revealed residue at the end of the substrate (thick film portion).

[0161] 1: Visual inspection revealed residue in the unexposed area.

[0162] (2) Total light transmittance and haze

[0163] Using a spin coater (trade name 1H-360S, manufactured by Mikasa Co., Ltd.), the photosensitive resin compositions obtained from each example and comparative example were spin-coated onto a 10cm square alkali-free glass substrate with a cured film thickness of 1.0μm. A pre-baked film was formed by pre-baking at 100°C for 2 minutes using a heating plate (SCW-636). No exposure through a mask was performed on the pre-baked film. Otherwise, development, rinsing, bleaching exposure, and curing were performed in the same manner as the evaluation method for <pattern processability> described in (1) above. The cured film was then measured for total light transmittance and haze using a Nippon Denshoku NDH-2000 according to JIS "K7361 (established on 1997 / 01 / 20)".

[0164] (3) Heat resistance evaluation

[0165] Using a spin coater (1H-360S; manufactured by Mikasa Co., Ltd.), the photosensitive resin compositions obtained from each example and comparative example were coated onto a 10cm square alkali-free glass substrate with a cured film thickness of 1.0μm. The cured film was prepared in the same manner as the aforementioned evaluation method for <total light transmittance and haze>.

[0166] For the alkali-free glass substrate with the obtained cured film, the total light transmittance and haze were measured in the same manner as the aforementioned evaluation method for <total light transmittance and haze>, and were recorded as values ​​before additional curing. Then, using an oven (IHPS-222), additional curing was performed in air at 240°C for 2 hours, and then the total light transmittance and haze were measured again, recorded as values ​​after additional curing. The absolute value obtained by subtracting the value before additional curing from the value after additional curing was evaluated as the variation range; the smaller the variation range, the better the heat resistance. The variation range of total light transmittance is preferably 3.0 or less, more preferably 2.0 or less. The variation range of haze is preferably 1.0 or less, more preferably 0.5 or less.

[0167] (4) Evaluation of lightfastness

[0168] Using a spin coater (1H-360S; manufactured by Mikasa Co., Ltd.), the photosensitive resin compositions obtained from each example and comparative example were coated onto a 10cm square alkali-free glass substrate with a cured film thickness of 1.0μm. The cured film was prepared in the same manner as the aforementioned evaluation method for <total light transmittance and haze>.

[0169] For the alkali-free glass substrate with the cured film obtained, the total light transmittance and haze were measured using the same evaluation method as described above for <total light transmittance and haze>, and were taken as values ​​before ultraviolet light irradiation. Furthermore, a wavelength of 365 nm and an illuminance of 0.6 mW / cm² were used. 2 After irradiating the light with ultraviolet light in air at 40°C for 100 hours, the total light transmittance and haze were measured as values ​​after ultraviolet light irradiation. The absolute value obtained by subtracting the value after ultraviolet light irradiation from the value before ultraviolet light irradiation is evaluated as the range of change. The smaller the range of change, the better the light resistance. The range of change in total light transmittance is preferably 0.8 or less, more preferably 0.5 or less. The range of change in haze is preferably 0.4 or less, more preferably 0.2 or less.

[0170] (5) Bending performance evaluation

[0171] Similar to the aforementioned evaluation method for <total light transmittance and haze>, a cured film with a thickness of 1.0 μm was formed on a polyimide film (“Kapton” (registered trademark) EN-100 (trade name), manufactured by Toray Industries, Inc.) using the photosensitive resin compositions obtained in the various examples and comparative examples. Next, the polyimide film substrate with the cured film was cut into 10 pieces, each 50 mm long and 10 mm wide. Then, with the cured film side facing outwards, the polyimide film substrate was bent 180° along a 25 mm line and held for 30 seconds. The bent polyimide film substrate was then opened, and the curved portion along the 25 mm line on the surface of the cured film was observed using an FPD inspection microscope (MX-61L; manufactured by Olympus Corporation) to evaluate the changes in the appearance of the cured film surface. The bending test was conducted within a radius of curvature of 0.1 to 1.0 mm, and the minimum radius of curvature at which no appearance changes such as peeling of the cured film from the polyimide film substrate or cracking of the cured film surface were recorded.

[0172] (6) Preservation stability

[0173] For the photosensitive resin compositions obtained from each example and comparative example, the viscosity (viscosity before storage) was measured after preparation. Furthermore, the photosensitive resin compositions obtained from each example and comparative example were placed in sealed containers, and their viscosity was similarly measured after storage at 23°C for 7 days. Storage stability was evaluated according to the following criteria based on the viscosity change rate ({|viscosity after storage - viscosity before storage| / viscosity before storage}×100).

[0174] A: Viscosity change rate is less than 5%.

[0175] B: Viscosity change rate is greater than 5% and less than 10%.

[0176] Example 1

[0177] In 50.00 g of titanium dioxide (R-960; manufactured by DuPont Corporation (SiO2 / Al2O3 surface-treated, median particle size 0.21 μm)) with a median particle size of 0.2–0.6 μm as (B), 50.00 g of a siloxane resin solution (A-1) obtained from Synthesis Example 1 was mixed with particles having a median particle size of 0.2–0.6 μm. The mixture was dispersed using a mill-type disperser filled with zirconia beads to obtain a particle dispersion (MW-1).

[0178] Next, 5.00 g of particle dispersion (MW-1), 12.338 g of siloxane resin (A-1) solution, 1.000 g of TP5-280M (manufactured by Toyo Synthetic Co., Ltd.) as a (C)naphthoquinone diazide compound, 0.150 g of CGI-MDT (manufactured by Hereus Co., Ltd.) as a curing agent, 0.200 g of melamine resin compound ("NIKALAC" (registered trademark) MX-270 (trade name), manufactured by Sanwa Kasei Co., Ltd.), and a bonding modifier were added. 0.200 g of 3-glycidoxypropylmethyldimethoxysilane (KBM-303 (trade name), manufactured by Shin-Etsu Chemical Co., Ltd.), 1.500 g of a 1% PGMEA diluted solution of a fluorinated surfactant ("MEGAFAC" (registered trademark) F-477 (trade name), manufactured by DIC Co., Ltd.), and 1.500 g (equivalent to a concentration of 300 ppm) were dissolved in a mixed solvent of 8.000 g of DAA and 21.613 g of PGMEA, and the mixture was stirred. The solution was then filtered through a 5.0 μm filter to obtain a photosensitive resin composition (P-1). The obtained photosensitive resin composition (P-1) was evaluated for pattern processability, total light transmittance, haze, heat resistance, lightfastness, flexibility, and storage stability using the aforementioned method.

[0179] Examples 2-6

[0180] Instead of the siloxane resin (A-1) solution, the siloxane resin (A-2) to (A-6) solutions were used respectively, and the process was otherwise carried out in the same manner as in Example 1 to obtain photosensitive resin compositions (P-2) to (P-6). The obtained photosensitive resin compositions (P-2) to (P-6) were evaluated in the same manner as in Example 1.

[0181] Example 7

[0182] The amount of particle dispersion (MW-1) added was changed to 10.00 g, the amount of siloxane resin (A-1) solution added was changed to 3.588 g, and a mixed solvent of 8.000 g of DAA and 25.363 g of PGMEA was used. Otherwise, the procedure was the same as in Example 1 to obtain the photosensitive resin composition (P-7). The obtained photosensitive resin composition (P-7) was evaluated in the same manner as in Example 1.

[0183] Example 8

[0184] The amount of particle dispersion (MW-1) added was changed to 1.000 g, the amount of siloxane resin (A-1) solution added was changed to 19.338 g, and a mixed solvent of 8.000 g of DAA and 18.613 g of PGMEA was used. Otherwise, the procedure was the same as in Example 1 to obtain the photosensitive resin composition (P-8). The obtained photosensitive resin composition (P-8) was evaluated in the same manner as in Example 1.

[0185] Example 9

[0186] As for particles with a median particle size of 0.2 to 0.6 μm (B), titanium dioxide (CR-97; manufactured by Ishihara Sangyo Co., Ltd. (Al2O3 / ZrO2 surface treated, median particle size 0.25 μm)) was used instead of R-960. Otherwise, the procedure was the same as in Example 1 to obtain the photosensitive resin composition (P-9). The obtained photosensitive resin composition (P-9) was evaluated in the same manner as in Example 1.

[0187] Example 10

[0188] As for particles with a median particle size of 0.2 to 0.6 μm (B), zirconium oxide (3YI-R; manufactured by Toray Industries, Inc. (Al2O3 surface treated, median particle size 0.50 μm)) was used instead of R-960. Otherwise, the procedure was the same as in Example 1 to obtain the photosensitive resin composition (P-10). The obtained photosensitive resin composition (P-10) was evaluated in the same manner as in Example 1.

[0189] Example 11

[0190] As for particles with a median particle size of 0.2 to 0.6 μm (B), alumina (AO-502: manufactured by Admatechs Co., Ltd. (untreated, median particle size 0.25 μm)) was used instead of R-960. Otherwise, the procedure was the same as in Example 1 to obtain the photosensitive resin composition (P-11). The obtained photosensitive resin composition (P-11) was evaluated in the same manner as in Example 1.

[0191] Example 12

[0192] The amount of siloxane resin (A-1) solution added was changed to 13.588 g, the amount of (C) naphthoquinone diazide compound TP5-280M added was changed to 0.500 g, and a mixed solvent of 8.000 g DAA and 20.863 g PGMEA was used. Otherwise, the procedure was the same as in Example 1 to obtain the photosensitive resin composition (P-12). The obtained photosensitive resin composition (P-12) was evaluated in the same manner as in Example 1.

[0193] Example 13

[0194] The amount of siloxane resin (A-1) solution added was changed to 11.088 g, and the amount of (C) naphthoquinone diazide compound TP5-280M added was changed to 1.500 g. A mixed solvent of 8.000 g of DAA and 22.363 g of PGMEA was used. Otherwise, the procedure was the same as in Example 1 to obtain the photosensitive resin composition (P-13). The obtained photosensitive resin composition (P-13) was evaluated in the same manner as in Example 1.

[0195] Comparative Examples 1 to 3

[0196] Instead of the siloxane resin (A-1) solution, the siloxane resin (A-7) to (A-9) solutions were used respectively, and the process was otherwise carried out in the same manner as in Example 1 to obtain photosensitive resin compositions (P-14) to (P-16). The obtained photosensitive resin compositions (P-14) to (P-16) were evaluated in the same manner as in Example 1.

[0197] Comparative Example 4

[0198] Instead of the siloxane resin (A-1) solution, an acrylic resin solution (a) was used, and the process was otherwise carried out in the same manner as in Example 1 to obtain a photosensitive resin composition (P-17). The obtained photosensitive resin composition (P-17) was evaluated in the same manner as in Example 1.

[0199] Comparative Example 5

[0200] Instead of particles with a median particle size of 0.2–0.6 μm as in (B), “OPTOLAKE TR-550” (trade name, manufactured by Catashoku Kasei Corporation, composition: 20 wt% titanium dioxide particles, 80 wt% methanol) was used as the dispersion of titanium dioxide particles. It should be noted that the titanium dioxide particles of “OPTOLAKE TR-550” are surface-treated with SiO2 / Al2O3 and have a median particle size of 0.015 μm. Instead of the particle dispersion (MW-1), 12.50 g of OPTOLAKE TR-550 was added, and the amount of siloxane resin (A-1) solution added was changed to 13.588 g. A mixed solvent of 8.000 g of DAA and 12.363 g of PGMEA was used. Otherwise, the process was the same as in Example 1, yielding a photosensitive resin composition (P-18). The obtained photosensitive resin composition (P-18) was evaluated in the same manner as in Example 1.

[0201] Comparative Example 6

[0202] Instead of using the particle dispersion (MW-1), the amount of siloxane resin (A-1) solution added was changed to 21.088 g, and a mixed solvent of 8.000 g of DAA and 17.863 g of PGMEA was used. Otherwise, the procedure was the same as in Example 1 to obtain the photosensitive resin composition (P-19). The obtained photosensitive resin composition (P-19) was evaluated in the same manner as in Example 1.

[0203] Comparative Example 7

[0204] Instead of using TP5-280M as the (C)naphthoquinone diazide compound, the amount of siloxane resin (A-1) solution added was changed to 14.838 g, and a mixed solvent of 8.000 g of DAA and 20.113 g of PGMEA was used. Otherwise, the procedure was the same as in Example 1 to obtain the photosensitive resin composition (P-20). The obtained photosensitive resin composition (P-20) was evaluated in the same manner as in Example 1.

[0205] The compositions of Examples 1-13 and Comparative Examples 1-7 are shown in Tables 3-4, and the evaluation results are shown in Tables 5-6.

[0206] [Table 3]

[0207]

[0208] [Table 4]

[0209]

[0210] [Table 5]

[0211]

[0212] [Table 6]

[0213]

[0214] Industrial availability

[0215] The cured film obtained by curing the photosensitive resin composition of the present invention can be suitably used as a material for diffusing light from a light source in various lighting appliances such as organic EL lighting and LED lighting appliances, laser display devices, or liquid crystal displays, and other various optical devices.

[0216] Explanation of reference numerals in the attached figures

[0217] 1: Substrate

[0218] 2: Cured film

[0219] 3: Black layer

Claims

1. A photosensitive resin composition comprising (A) a silicone resin containing at least 20 to 60 mole% in total of repeating units represented by the following general formula (1), (B) particles having a median particle diameter of 0.21 to 0.6 μm, and (C) a naphthoquinonediazide compound, the content of the (B) particles having a median particle diameter of 0.21 to 0.6 μm in the total solid content of the photosensitive resin composition being 5 to 50% by weight, [Chemical Formula 1] ###0001### (1) the difference between the refractive index of the (A) silicone resin and the (B) particles having a median particle diameter of 0.21 to 0.6 μm being 0.20 to 1.

40. R 1 represents an aryl group having 6 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms wherein all or a part of the hydrogens are substituted.

2. The photosensitive resin composition according to claim 1, wherein The (B) particles having a median particle diameter of 0.21 to 0.6 μm contain one or more selected from the group consisting of titanium dioxide, zirconium oxide, aluminum oxide, talc, mica, white carbon, magnesium oxide, zinc oxide, barium carbonate, and composite compounds thereof.

3. The photosensitive resin composition according to claim 1 or 2, wherein The (B) particles having a median particle diameter of 0.21 to 0.6 μm contain titanium dioxide and / or zirconium oxide.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein The (A) silicone resin further contains 5 to 20 mole% in total of repeating units represented by the following general formula (2), 5. The photosensitive resin composition according to any one of claims 1 to 4, wherein [Chemical Formula 2] ###0002### (2) The (A) silicone resin further contains 1 to 20 mole% in total of repeating units represented by the following general formula (3), 6. The photosensitive resin composition according to any one of claims 1 to 5, wherein [Chemical Formula 3] ###0003### (3) The cured film of the photosensitive resin composition has a haze of 20 to 98% at a film thickness of 1 μm. R 2 represents an alkyl group, an alkenyl group, an aryl group or an arylalkyl group having 1 to 10 carbon atoms of which all or a part of hydrogen is replaced with fluorine; R 3 represents a single bond, -O-, -CH2-CO-, -CO- or -O-CO-.

7. The photosensitive resin composition according to any one of claims 1 to 6, wherein 8. The photosensitive resin composition according to any one of claims 1 to 7, which is used for forming a light diffusion layer.

9. A cured film formed from the photosensitive resin composition according to any one of claims 1 to 8.

10. A method for producing a cured film, comprising the following steps: (I) a step of applying the photosensitive resin composition according to any one of claims 1 to 8 to a substrate to form a coating film; (II) a step of exposing and developing the coating film; (III) a step of re-exposing the developed coating film; and (IV) a step of heating the re-exposed coating film.

11. A substrate with a cured film, which has a cured film formed by patterning with the photosensitive resin composition according to any one of claims 1 to 8 on a substrate, the cured film having a haze of 20 to 98% at a film thickness of 1 μm. The film thickness of the cured film is 0.3 to 3.0 μm. The substrate is a glass substrate or a resin substrate containing polyimide. The cured film formed by patterning on the substrate has a black layer between the cured film and an adjoining cured film.

15. A display device having: the substrate with a cured film according to any one of claims 11 to 14; and, a mini LED or a micro LED. ​ 12. The substrate with a cured film of claim 11, wherein, ​ 13. The substrate with a cured film according to claim 11 or 12, wherein, ​ 14. The substrate with a cured film according to any one of claims 11 to 13, wherein, ​ ​

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