Photosensitive resin composition, microlenses

Abstract

The objective of this invention is to provide a photosensitive resin composition having a high refractive index and transparency, and high fluidity at a calcination temperature below 230°C, which enables it to form large microlenses with a diameter of 10 μm or more. The photosensitive resin composition of the present invention is characterized by comprising: (A) a siloxane resin containing an organosilicon unit having diphenyl groups; (B) at least one metal compound particle selected from the group consisting of titanium compound particles, zirconium compound particles, tin compound particles and aluminum compound particles, or a composite metal compound particle selected from the group consisting of at least one metal compound and a silicon compound; (C) a photosensitizer; (D) an organosilicon compound having a condensed polycyclic aromatic group; and (E) an organic solvent.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a microlens formed by curing the photosensitive resin, and a light-emitting element, a solid-state imaging element and a fingerprint verification device having the microlens. Prior Technology

[0002] Biometric authentication is essential for unlocking and other identity verification on various mobile display terminals such as smartphones and tablet PCs. Fingerprint authentication, in particular, is widely used in many terminals due to its low cost, small size, and high convenience.

[0003] It is conventional to place capacitive fingerprint verification devices on the bezel of a display (around the screen). However, with the trend towards full-screen displays in smartphones, there is a tendency for the bezels around the fingerprint verification device to disappear. Therefore, it is necessary to place the fingerprint verification device under the display (this configuration is called "under-display").

[0004] As for the verification methods of under-display fingerprint verification devices, optical and ultrasonic methods can be listed. Among them, optical methods, in particular, have the versatility to be applied not only to organic light-emitting diode (OLED) displays but also to liquid crystal displays, and have therefore become the mainstream.

[0005] Regarding this type of under-display fingerprint verification device, a thin optical under-display fingerprint verification device (for example, see Patent Document 1 and Patent Document 2) with high verification accuracy and capable of being placed in a very narrow area between the battery and the screen is proposed. In such devices, microlenses (lenses in the range of diameter 1 μm to 500 μm) are assembled as components to improve verification accuracy.

[0006] As for the methods for forming microlenses used in the optical under-display fingerprint verification device described in Patent Document 1 or Patent Document 2, examples include dry etching of an inorganic film formed by chemical vapor deposition (CVD) and other methods, and coating with a photosensitive material and then processing it. Since the former method is difficult to form multiple microlenses into a uniform shape on a substrate with a large substrate size, the latter method has attracted attention.

[0007] The technology described in Patent Document 1 or Patent Document 2 can be used to obtain a fingerprint verification device with excellent verification accuracy. However, in order to further improve the verification accuracy, the microlens needs to have a high refractive index.

[0008] Furthermore, compared to microlenses with diameters of several μm used in complementary metal oxide semiconductor (CMOS) image sensors, the diameters of microlenses used in fingerprint verification devices are quite large, ranging from 10 μm to 40 μm. Moreover, there are limitations in the heat resistance of the resin layer formed below the lens, such as the collimator. Therefore, it is necessary to calcine at a temperature below 230°C, thus requiring materials with excellent flowability during calcine.

[0009] As a photosensitive material with high refractive index and transparency, a silicone resin composition containing metal compound particles has been disclosed (for example, see Patent Document 3), but it is difficult to form large microlenses with a diameter of 10 μm or more, such as those used in fingerprint sensors.

[0010] As a photosensitive material with a high refractive index and capable of forming lenses, a silicone resin composition containing metal compound particles has been disclosed (for example, see Patent Document 4). However, it has low fluidity at calcination temperatures below 230°C, making it difficult to form microlenses. [Previous Technical Documents] [Patent Literature]

[0011] Patent Document 1: Japanese Patent Application Publication No. 2020-35327 Patent Document 2: WO2020 / 038408 Patent Document 3: WO2011 / 040248 Patent Document 4: Japanese Patent Application Publication No. 2015-127803 Summary of the Invention

[0012] (The problem the invention aims to solve)

[0013] The present invention arises in view of the problems of the prior art, and its purpose is to provide a photosensitive resin composition having a high refractive index and transparency, and having high fluidity at a calcination temperature below 230°C, which can form a large microlens with a diameter of more than 10 μm. (Technical means to solve the problem)

[0014] The objective of this invention is achieved through the following configuration: [1] A photosensitive resin composition comprising the following (A) to (E): (A) A siloxane resin containing organosilicon units having diphenyl groups; (B) Select at least one metal compound particle from the group consisting of titanium compound particles, zirconium compound particles, tin compound particles and aluminum compound particles, or Composite metal compound particles selected from at least one metal compound and silicon compound from the group consisting of titanium compounds, zirconium compounds, tin compounds and aluminum compounds; (C) Photosensitizer; (D) Organosilicon compounds having condensed polycyclic aromatic groups; and (E) Organic solvents. [2] As described in [1] above, the photosensitive resin composition, wherein the aforementioned (A) siloxane resin contains 5 mol% or more and 40 mol% or less of an organosilane unit having a diphenyl group. [3] The photosensitive resin composition as described in [1] or [2] above, wherein the aforementioned (A) siloxane resin contains organosilanes having carboxyl groups and / or dicarboxylic anhydride structures. [4] The photosensitive resin composition described in any of [1] to [3] above, wherein the average particle size of the aforementioned (B) metal compound particles or composite metal compound particles is 1 nm to 70 nm. [5] The photosensitive resin composition described in any of [1] to [4] above, wherein the aforementioned (B) metal compound particles or composite metal compound particles are 20 parts by weight or more and 60 parts by weight or less relative to the total amount of 100 parts by weight of the silicone resin. [6] The photosensitive resin composition described in any of [1] to [5] above, wherein the aforementioned (C) photosensitive agent is a diazidonaphthoquinone compound. [7] A hardener formed by hardening a photosensitive resin composition as described in any of [1] to [6] above. [8] The hardened material described above in [7] has a refractive index of 1.60 or higher and 1.80 or lower at a wavelength of 633 nm. [9] A hardened film comprising the hardened material of [7] or [8] above.

[10] A microlens comprising the hardened material described in [7] or [8].

[11] A method for manufacturing a microlens, comprising: a step of coating a photosensitive resin composition as described in any one of [1] to [6] onto a substrate; an exposure step; a development step; and a step of forming a microlens with a diameter of 10 μm or more and 50 μm or less.

[12] A solid-state imaging element having a hardened film as described above [9] or a microlens as described above

[10] .

[13] A fingerprint verification device having a hardened film as described above [9] or a microlens as described above

[10] .

[14] A microlens array having a plurality of microlenses arranged in two dimensions, wherein the refractive index of the microlenses at a wavelength of 633 nm is 1.60 or more and 1.80 or less, the diameter of the microlenses is 10 μm or more and 50 μm or less, and the distance between the microlenses is 0.01 μm or more and 5.0 μm or less.

[15] The microlens array described above in

[14] includes a hardened material formed by curing a photosensitive resin composition containing the following (A) to (D): (A) A siloxane resin containing organosilicon units having diphenyl groups; (B) Select at least one metal compound particle from the group consisting of titanium compound particles, zirconium compound particles, tin compound particles and aluminum compound particles, or Composite metal compound particles selected from at least one metal compound and silicon compound from the group consisting of titanium compounds, zirconium compounds, tin compounds and aluminum compounds; (C) Photosensitizer; and (D) Organosilicon compounds having condensed polycyclic aromatic groups.

[16] A fingerprint verification device having a microlens array as described in

[14] or

[15] above. (Compared to the effectiveness of previous technologies)

[0015] The photosensitive resin composition of the present invention has high refractive index and transparency, and has high fluidity at a calcination temperature below 230°C, enabling it to form large microlenses with a diameter of 10 μm or more. Simple Explanation of the Diagram

[0016] Figure 1 is a cross-sectional view showing an example of the shape of a microlens. Figure 2 is a cross-sectional view showing an example of a shape that is not a microlens. Implementation

[0017] The present invention will now be described in more detail.

[0018] The photosensitive resin composition of the present invention includes the following (A) to (E). (A) A siloxane resin containing organosilicon units having diphenyl groups; (B) At least one metal compound particle selected from the group consisting of titanium compound particles, zirconium compound particles, tin compound particles and aluminum compound particles, or a composite metal compound particle selected from the group consisting of at least one metal compound and silicon compound; (C) Photosensitizer; (D) Organosilicon compounds having condensed polycyclic aromatic groups; and (E) Organic solvents.

[0019] Hereinafter, the silicone resin containing (A) organosilicon units with diphenyl groups will sometimes be referred to simply as (A) silicone resin. In this invention, by using silicone resin containing (A), microlenses with high transparency and excellent heat and weather resistance can be formed. This is because the silicone resin has a silicone backbone in its main chain. Furthermore, compared to silicone resins containing only 3-functional T units that undergo three-dimensional cross-linking, the diphenyl group in the silicone resin containing organosilicon units with diphenyl groups is a 2-functional D unit. Therefore, three-dimensional cross-linking can be moderately suppressed, thereby improving the flowability of the photosensitive resin composition during calcination. The flowability can be controlled by adjusting the content of organosilicon units with diphenyl groups. Moreover, compared to dimethyl groups, which are also 2-functional D units, the polarizability of the diphenyl group is increased due to the π electrons, thus increasing the refractive index of the cured material.

[0020] Furthermore, by using at least one metal compound particle selected from the group consisting of titanium compound particles, zirconium compound particles, tin compound particles and aluminum compound particles, or a composite metal compound particle selected from the group consisting of titanium compound, zirconium compound, tin compound and aluminum compound and silicon compound, a hardened material with a high refractive index can be obtained, thereby enabling the formation of a microlens with a high refractive index.

[0021] By using a photosensitive agent containing (C), positive photosensitivity is demonstrated by removing the light-irradiated area using a developing solution, enabling positive pattern processing.

[0022] Furthermore, by using an organosilicon compound containing (D) a condensed polycyclic aromatic group, a substituent with steric hindrance is introduced at the end of a siloxane resin by heating, and the cross-linking between the ends is suppressed. Therefore, the flowability of the photosensitive resin composition during calcination can be further improved, and the high hydrophobicity of the condensed polycyclic aromatic group can form a microlens with excellent high temperature and high humidity resistance.

[0023] Furthermore, by using an organic solvent containing (E), wet coating methods such as spin coating or slot coating can be performed, and the resin composition can be easily adjusted to a viscosity suitable for coating, thereby improving the uniformity of the coated film.

[0024] The photosensitive resin composition of this invention contains (A) a silicate resin containing diphenyl organosilicon units. A silicate resin refers to a polymer having repeating units containing a silicate backbone. The silicate resin (A) of this invention contains diphenyl organosilicon units, but preferably is a resin formed by the condensation of a diphenyl organosilicon compound with other organosilicon compounds after hydrolysis.

[0025] Specific examples of organosilicon compounds containing diphenyl groups include diphenylsilane diol and dimethoxydiphenylsilane. Regarding the content of diphenyl organosilicon units in (A) the silicate resin, from the viewpoint of improving fluidity, it is preferably 5 mol% or more, more preferably 8 mol% or more, and even more preferably 10 mol% or more. Furthermore, from the viewpoint of suppressing residues during development and thereby improving resolution, it is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less.

[0026] Other specific examples of organosilane compounds include: methyltrimethoxysilane, methyltriethoxysilane, methyltri(methoxyethoxy)silane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-(N,N-diepoxypropyl)aminopropyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane. Silane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 2-cyanoethyltriethoxysilane, epoxypropoxymethyltrimethoxysilane, epoxypropoxymethyltriethoxysilane, 1-epoxypropoxyethyltrimethoxysilane, 1-epoxypropoxyethyltriethoxysilane, 2-epoxypropoxyethyltrimethoxysilane, 2-epoxypropoxyethyltriethoxysilane, 1-epoxypropoxypropyltrimethoxysilane, 1-epoxypropoxypropyltriethoxysilane, 2-epoxypropoxypropyltrimethoxysilane, 2-epoxypropoxypropyltriethoxysilane, 2-epoxypropoxypropyltriethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropyltriethoxysilane, 3-epoxypropoxypropyltrimethoxysilane 3-Epoxypropoxypropyltripropoxysilane, 3-Epoxypropoxypropyltriisopropoxysilane, 3-Epoxypropoxypropyltributoxysilane, 3-Epoxypropoxypropyltri(methoxyethoxy)silane, 1-Epoxypropoxybutyltrimethoxysilane, 1-Epoxypropoxybutyltriethoxysilane, 2-Epoxypropoxybutyltrimethoxysilane, 2-Epoxypropoxybutyltriethoxysilane, 3-Epoxypropoxybutyltrimethoxysilane, 3-Epoxypropoxybutyltriethoxysilane, 4-Epoxypropoxybutyltrimethoxysilane, 4-Epoxypropoxybutyltriethoxysilane, (3,4-Epoxycyclohexyl)methyltrimethoxysilane, (3,4-Epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-Epoxycyclohexyl) 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)butyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane,3-Aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, epoxypropoxymethyldimethoxysilane, epoxypropoxymethylmethyldiethoxysilane, 1-epoxypropoxyethylmethyldimethoxysilane, 1-epoxypropoxyethylmethyldimethoxysilane, 2-epoxypropoxyethylmethyldimethoxysilane, 2-epoxypropoxyethylmethyldiethoxysilane, 1-epoxypropoxypropylmethyldimethoxysilane, 1-epoxypropoxypropylmethyldiethoxysilane, 2-epoxypropoxypropylmethyldimethoxysilane, 2-epoxypropoxypropylmethyldimethoxysilane, 2-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane Silane, 3-epoxypropoxypropylmethyldipropoxysilane, 2-epoxypropoxypropylmethyldibutoxysilane, 3-epoxypropoxypropylmethyldi(methoxyethoxy)silane, 3-epoxypropoxypropylethyldimethoxysilane, 3-epoxypropoxypropylethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane Alkane, cyclohexylmethyldimethoxysilane, octadecylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, trifluoromethyltrimethoxysilane, trifluoroethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, perfluoropropyltrimethoxysilane, perfluoropropyltriethoxysilane, perfluoropentyltrimethoxysilane, perfluoropentyltriethoxysilane Tridecyl fluorooctyl trimethoxysilane, tridecyl fluorooctyl triethoxysilane, tridecyl fluorooctyl tripropoxysilane, tridecyl fluorooctyl triisopropoxysilane, heptadecafluorodecyl trimethoxysilane, heptadecafluorodecyl triethoxysilane, bis(trifluoromethyl)dimethoxysilane, bis(trifluoropropyl)dimethoxysilane, bis(trifluoropropyl)diethoxysilane, trifluoropropylmethyl Trifluoropropylmethyldiethoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane, heptadecafluorodecylmethyldimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-triphenoxysilylpropylsuccinic anhydride, 3-trimethoxysilylpropylcyclohexyldimethoxysilane Carboxylic anhydride, 3-trimethoxysilylpropylphthalic anhydride, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(methoxyethoxy)silane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldi(methoxyethoxy)silane, allyltrimethoxysilane, allyltriethoxysilane, allyltri(methoxyethoxy)silane, phenylmethyldimethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldi(methoxyethoxy)silane, styryltrimethoxysilane, styryltriethoxysilane, styryltri(methoxyethoxy)silane, styrylmethyldimethoxysilane, styrylmethyldiethoxysilane, styryltrimethoxysilaneStyrene-methyl di(methoxyethoxy)silane, 3-propenyloxypropyltrimethoxysilane, 3-propenyloxypropyltriethoxysilane, 3-propenyloxypropyltris(methoxyethoxy)silane, 3-methpropenyloxypropyltrimethoxysilane, 3-methpropenyloxypropyltriethoxysilane, 3-methpropenyloxypropyltris(methoxyethoxy)silane, 3-methpropenyloxypropylmethyldimethoxysilane, 3-methpropenyloxypropylmethyldiethoxysilane, 3-propenyloxypropylmethyldimethoxysilane 3-Acryloxypropylmethyldiethoxysilane, 3-methacryloxypropyl(methoxyethoxy)silane, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane, 1-anthrayltrimethoxysilane, 9-anthrayltrimethoxysilane, 9-phenanthyltrimethoxysilane, 9-tanyltrimethoxysilane, 2-tanyltrimethoxysilane, 2-fluorenonetrimethoxysilane, 1-pyrenetrimethoxysilane, 2-indenetrimethoxysilane, 5-dihydroacenaphthenetrimethoxysilane, etc. Two or more of these may also be used. Among these, from the viewpoint of suppressing residue during development and thus improving resolution, organosilicon compounds having carboxyl and / or dicarboxylic anhydride structures, such as 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-triphenoxysilylpropyl succinic anhydride, 3-trimethoxysilylpropylcyclohexyl dicarboxylic anhydride, and 3-trimethoxysilylpropyl phthalic anhydride, are preferred. By using this compound, (A) silicate resin becomes one containing organosilicon units having carboxyl and / or dicarboxylic anhydride structures. By giving (A) silicate resin this structure, residue during development can be suppressed, and adhesion to the substrate or resin layer can be improved.

[0027] (A) Silicone resins can be obtained by condensing an organosilicon compound after hydrolysis. For example, they can be obtained by hydrolyzing an organosilicon compound and then condensing the resulting silanol compound in the presence of an organic solvent or in the absence of a solvent.

[0028] Various conditions for the hydrolysis reaction can be appropriately set considering the reaction scale, the size and shape of the reaction vessel, etc. For example, it is preferable to add the acid catalyst and water to the organosilicon compound in a solvent for 1 to 180 minutes, and then react at room temperature to 110°C for 1 to 180 minutes. By carrying out the hydrolysis reaction under these conditions, rapid reactions can be suppressed. The reaction temperature is more preferably 30 to 105°C.

[0029] The hydrolysis reaction is preferably carried out in the presence of an acid catalyst. The preferred acid catalyst is an acidic aqueous solution containing formic acid, acetic acid, phosphoric acid, and nitric acid. The amount of acid catalyst added is preferably 0.05 to 5 parts by weight relative to 100 parts by weight of all organosilicon compounds used in the hydrolysis reaction. By setting the amount of acid catalyst within the above range, the hydrolysis reaction can be carried out more efficiently.

[0030] After obtaining silanol compounds through the hydrolysis of organosilanes, it is preferable to directly heat the reaction solution at a temperature above 50°C and below the boiling point of the solvent for 1 to 100 hours to carry out the condensation reaction. Furthermore, to increase the degree of polymerization of the siloxane resin, further heating or the addition of an alkaline catalyst can also be performed.

[0031] Organic solvents used in the hydrolysis of organosilanes and the condensation of silanols include, for example: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tributanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, 1-tert-butoxy-2-propanol, diacetone alcohol, etc.; diols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethyl ether. Ethers; ketones such as methyl ethyl ketone, acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, and 2-heptanone; acetamides such as dimethylformamide and dimethyl acetamide; acetates such as ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, and butyl lactate; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, and cyclohexane; γ-butyrolactone, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. Two or more of these may also be used. In order to obtain a cured product with high transmittance and excellent crack resistance by curing the photosensitive resin composition of the present invention, it is preferable to use diacetone alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monotertyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, γ-butyrolactone, etc.

[0032] The cured material obtained by curing the photosensitive resin composition of the present invention has high transmittance and excellent crack resistance. Therefore, the cured film and microlens using the cured material have the same characteristics and are therefore preferred. The cured film mentioned herein refers to a film-shaped cured material that is cured in the form of a whole film without forming microlenses.

[0033] In cases where a solvent is generated through hydrolysis, hydrolysis can also be carried out without a solvent. It is also preferable to adjust the concentration of the resin component by adding a further solvent after the reaction is complete. Alternatively, depending on the purpose, alcohols or other substances generated after hydrolysis can be distilled off under heating and / or reduced pressure, followed by the addition of a suitable solvent.

[0034] The amount of solvent used in the hydrolysis reaction is preferably between 80 and 500 parts by weight relative to 100 parts by weight of the total organosilane compound. By setting the amount of solvent within the above range, the hydrolysis reaction can be carried out more efficiently.

[0035] Furthermore, the water used in the hydrolysis reaction is preferably ion-exchanged water. The amount of water is preferably 1.0 to 4.0 mol relative to 1 mol of silane atoms.

[0036] The photosensitive resin composition of the present invention contains a silicone resin comprising at least one of (B) titanium compound particles, zirconium compound particles, tin compound particles and aluminum compound particles, or a composite metal compound particle of a metal compound and a silicon compound (hereinafter sometimes simply referred to as (B) metal compound particles or composite metal compound particles) comprising at least one of titanium compound, zirconium compound, tin compound and aluminum compound particles.

[0037] Examples of composite metal compound particles consisting of metal compounds and silicon compounds include: silicon oxide-metal compound composite particles obtained by synthesizing metal particles in the presence of silicon oxide compounds, and silane-coated metal compound particles obtained by reacting metal particles with a silane coupling agent. Among these, titanium compound particles, zirconium compound particles, or composite particles of titanium compounds or zirconium compounds and silicon compounds are preferred. Furthermore, two or more of these may be included. By including the metal compound particles described above, a high refractive index can be imparted to the hardened material. If the hardened material has a high refractive index, a high refractive index can be imparted to the hardened film or microlens using the hardened material.

[0038] Examples of metal compound particles include: "NanoUse" (registered trademark) OT-RB300M7-20, a composite particle of tin oxide, titanium oxide, and silicon oxide; "NanoUse" OT-RA-305M7-20, a composite particle of tin oxide, titanium oxide, zirconium oxide, and silicon oxide (both manufactured by Nissan Chemical Co., Ltd.); "Optolake" (registered trademark) TR-502 and "Optolake" TR-504, composite particles of tin oxide and titanium oxide; and "Optolake" TR-503, "Optolake" TR-513, and "O" (all manufactured by Nissan Chemical Co., Ltd.), composite particles of titanium oxide and silicon oxide. Optolake TR-520, Optolake TR-527, Optolake TR-528, Optolake TR-529, Optolake TR-543, Optolake TR-544, Optolake TR-550, and titanium dioxide particles Optolake TR-505 (all manufactured by Catashoku Chemical Industries, Ltd.); and zirconium oxide particles NanoUse OZ-S30M (manufactured by Nissan Chemical Industries, Ltd.), DLZ-003W (manufactured by Daien Chemical Industries, Ltd.), and SZR-M (manufactured by Sakai Chemical Industries, Ltd.), etc. These may also contain two or more types.

[0039] Regarding the number average particle size of (B) metal compound particles or composite metal compound particles, from the viewpoint of suppressing crack formation during thick film formation, it is preferably 1 nm or more. Furthermore, from the viewpoint of further improving the visible light transparency of the hardened material, especially the hardened film or microlens using the hardened material, it is preferably 70 nm or less, and more preferably 50 nm or less. Here, the number average particle size of the metal compound particles can be measured by gas adsorption, dynamic light scattering, X-ray small-angle scattering, or by directly measuring the particle size using a transmission electron microscope or scanning electron microscope. In this invention, it refers to the value measured by dynamic light scattering. The machine used is not particularly limited; examples include the DLS-8000 dynamic light scattering altimeter (manufactured by Otsuka Electronics Co., Ltd.).

[0040] In the photosensitive composition of the present invention, (B) the metal compound particles or composite metal compound particles, relative to 100 parts by weight of the total amount of the silicone resin, are preferably 20 parts by weight or more than 60 parts by weight, and more preferably 25 parts by weight or more than 55 parts by weight. This allows for the maintenance of high sensitivity, resolution, and flowability of the photosensitive resin composition while further improving the transmittance and refractive index of the hardened film or microlens.

[0041] The hardened material formed by curing the photosensitive resin composition of the present invention preferably has a refractive index of 1.60 or higher and 1.80 or lower at a wavelength of 633 nm. By giving the hardened material this high refractive index, it is possible to form a microlens with a high refractive index.

[0042] In the photosensitive composition of the present invention, in the presence of (B) metal compound particles or composite metal compound particles, (A) silicone resin can be synthesized by hydrolysis and partial condensation of organosilicones. This yields a photosensitive resin composition with surface-treated silicone resin particles and excellent dispersion stability. This is believed to be because the silicone resin matrix is ​​bonded to the metal compound particles. The state of this bonding can be determined by observing the boundary between the metal compound particles and the silicone resin using a scanning electron microscope or a transmission electron microscope. In the case of bonding, the interface between the two is not obvious.

[0043] The photosensitive resin composition of the present invention contains a (C) photosensitizer. Preferably, the (C) photosensitizer is a diazidonaphthoquinone compound. By containing a diazidonaphthoquinone compound, positive photosensitivity is exhibited, allowing the exposed portion to be removed using the developing solution. Furthermore, in the unexposed portion, a dissolution inhibition effect is also observed through the interaction of the silanol groups of the silicone resin, thereby further improving resolution. Preferably, the diazidonaphthoquinone compound is a compound formed by the formation of an ester bond between diazidonaphthoquinone sulfonic acid and a compound having a phenolic hydroxyl group.

[0044] Specific examples of compounds having phenolic hydroxyl groups include the following compounds (all of which can be manufactured and obtained by Honshu Chemical Industry Co., Ltd.).

[0045] [Chemistry 1]

[0046] [Chemistry 2]

[0047] Diazidonaphthoquinone compounds can be synthesized via a known esterification reaction of a compound with a phenolic hydroxyl group and diazidonaphthoquinone sulfonate. 4-Diazidonaphthoquinone sulfonate or 5-diazidonaphthoquinone sulfonate can be used as the starting material. The 4-diazidonaphthoquinone sulfonate compound exhibits absorption in the i-ray (wavelength 365 nm) region, thus making it suitable for i-ray exposure. Furthermore, the 5-diazidonaphthoquinone sulfonate compound exhibits absorption over a wide wavelength range, thus making it suitable for exposure over a wide wavelength range. Preferably, the 4-diazidonaphthoquinone sulfonate compound and the 5-diazidonaphthoquinone sulfonate compound are selected according to the exposure wavelength. Alternatively, the 4-diazidonaphthoquinone sulfonate compound and the 5-diazidonaphthoquinone sulfonate compound can be used in combination.

[0048] The content of the photosensitizer (C) in the photosensitive resin composition of the present invention is not particularly limited, but it is preferably 1% by weight or more, and more preferably 3% by weight or more, relative to 100% by weight of the total (A) silicone resin. Furthermore, from the viewpoint of suppressing coloration caused by decreased compatibility with (A) silicone resin or decomposition during thermosetting, and further improving the transparency of the photosensitive resin composition or cured product, especially the cured film or microlens, it is preferably 30% by weight or less, and more preferably 20% by weight or less.

[0049] The photosensitive resin composition of this invention contains (D) an organosilane compound having a condensed polycyclic aromatic group. By using the organosilane compound containing (D) a condensed polycyclic aromatic group to introduce a substituent with steric hindrance at the end of the silicone resin through heating, cross-linking between the ends is suppressed, thereby further improving the fluidity of the film during calcination. Furthermore, the high hydrophobicity of the condensed polycyclic aromatic group enables the formation of microlenses with excellent high temperature and high humidity resistance.

[0050] Specific examples of organosilanes having condensed polycyclic aromatic groups (D) include the following compounds: 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane, 1-anthrayltrimethoxysilane, 9-anthrayltrimethoxysilane, 9-phenanthyltrimethoxysilane, 9-tanyltrimethoxysilane, 2-tanyltrimethoxysilane, 1-pyrenetrimethoxysilane, 2-indenetrimethoxysilane, 5-dihydroacenaphthenetrimethoxysilane, etc. These may also contain two or more of these groups.

[0051] The content of organosilicon compound (D) having a condensed polycyclic aromatic group in the photosensitive resin composition of the present invention is not particularly limited. From the viewpoint of improving fluidity, it is preferably 0.5% by weight or more, and more preferably 1% by weight or more, relative to 100% by weight of the total siloxane resin (A). Furthermore, from the viewpoint of suppressing residues during development and thereby improving resolution, it is preferably 15% by weight or less, and more preferably 10% by weight or less.

[0052] The photosensitive resin composition of this invention contains (E) an organic solvent. The organic solvent is not particularly limited, but is preferably a compound having alcoholic hydroxyl groups. Using an organic solvent with alcoholic hydroxyl groups improves the solubility of (A) the silicone resin, (B) the metal compound particles, and (C) the photosensitizer, thereby further improving the transparency of the coating film obtained from the photosensitive resin composition.

[0053] There are no particular limitations on the organic solvents containing alcoholic hydroxyl groups, but compounds with a boiling point of 110 to 250°C at atmospheric pressure are preferred. If the boiling point is above 110°C, the drying process during coating film formation will proceed appropriately, and a coating film with a good surface appearance can be easily obtained. On the other hand, if the boiling point is below 250°C, the organic solvent can be easily removed.

[0054] Specific examples of organic solvents containing alcoholic hydroxyl groups include: acetone alcohol (boiling point: 147℃), 3-hydroxy-3-methyl-2-butanone (boiling point: 140℃), 4-hydroxy-3-methyl-2-butanone (boiling point: 73℃), 5-hydroxy-2-pentanone (boiling point: 144℃), 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) (boiling point: 166℃), ethyl lactate (boiling point: 151℃), butyl lactate (boiling point: 186℃), and propylene glycol. Monomethyl ether (boiling point: 118℃), propylene glycol monoethyl ether (boiling point: 132℃), propylene glycol mono-propyl ether (boiling point: approximately 150℃), propylene glycol mono-n-butyl ether (boiling point: 170℃), diethylene glycol monomethyl ether (boiling point: 194℃), diethylene glycol monoethyl ether (boiling point: 202℃), dipropylene glycol monomethyl ether (boiling point: approximately 190℃), 3-methoxy-1-butanol (boiling point: 161℃), 3-methyl-3-methoxy-1-butanol (boiling point: 174℃), etc. These may also contain two or more of these.

[0055] Furthermore, it may also contain other organic solvents, which can be used together with or in place of the aforementioned organic solvents. Examples of other organic solvents include: ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1-butyl acetate, ethyl acetate, etc.; ketones such as methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, acetone, etc.; ethers such as diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, etc.; γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclopentanone, cyclohexanone, cycloheptanone, etc.

[0056] The content of (E) organic solvent in the photosensitive resin composition of the present invention is not particularly limited, but is preferably in the range of 10 to 2,000 parts by weight relative to the total of (A) silicone resin and (B) metal compound particles of 100 parts by weight.

[0057] The photosensitive resin composition of this invention may also contain organosilane compounds other than (D) organosilane compounds having condensed polycyclic aromatic groups as adhesion modifiers. By containing organosilane compounds, adhesion to the substrate can be improved. Examples of organosilane compounds include: diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropoxysilane, diphenyldi-n-butoxysilane, diphenylsilanediol, bis(4-methylphenyl)dimethoxysilane, bis(4-methylphenyl)diethoxysilane, bis(4-methylphenyl)diisopropoxysilane, bis(4-methylphenyl)silanediol, bis(4-methylphenyl)diisopropoxysilane, bis(4-methylphenyl)silanediol, bis(4-methylphenyl)dimethoxysilane ...methoxysilane, bis(4-methylphenyl)diisopropoxysilane, bis(4-methylphenyl)silanediol, bis(4-methylphenyl)dimethoxysilane, bis(4-methylphenyl)dimethoxysilane, bis(4-methylphenyl)dimethoxysilane, bis(4-methylphenyl)dimethoxysilane, bis(4-methylphenyl)dimethoxysilane, bis(4-methylphenyl)dimethoxysilane, bis(4-methylphenyl)dimethoxysilane, bis(4-methylphenyl)dimethoxysilane, bis(4-methylphenyl)dimethoxysilane, bis(4-methylphenyl)dimethoxy Bis(4-biphenyl)dimethoxysilane, bis(4-biphenyl)diethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, triphenylsilanol, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropyltriethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl) Ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-methacryloxypropyl Trimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, 3-mercaptopropyltrimethoxysilane, 3-ureopropyltriethoxysilane, 3-isocyanopropyltriethoxysilane, p-styryltrimethoxysilane, etc. These may also contain two or more of these compounds.

[0058] The photosensitive resin composition of the present invention may also contain a solubility promoter. By containing a solubility promoter, residues during development can be suppressed, thereby improving resolution. As a solubility promoter, in terms of compatibility with (A) the silicone resin or (C) the photosensitive agent, a compound having phenolic hydroxyl groups is preferred. Specific examples of compounds having phenolic hydroxyl groups include the following compounds (all of which can be manufactured and obtained by Honshu Chemical Industry Co., Ltd.).

[0059] [Chemistry 3]

[0060] [Chemistry 4]

[0061] The photosensitive resin composition of this invention may also contain surfactants. By containing surfactants, the flowability during coating can be improved. Examples of surfactants include: fluorinated surfactants; polysiloxane surfactants; polysiloxane-modified acrylic surfactants; fluorinated thermally decomposable surfactants; polyether-modified siloxane surfactants; polyoxyalkylene surfactants; poly(meth)acrylate surfactants; anionic surfactants such as ammonium lauryl sulfate and triethanolamine polyoxyethylene alkyl ether sulfate; cationic surfactants such as stearamine acetate and lauryl trimethylammonium chloride; amphoteric surfactants such as lauryl dimethylamine oxide and lauryl carboxymethyl hydroxyethyl imidazolium betaine; and nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearate. Two or more surfactants may also be contained.

[0062] Among these, from the viewpoint of suppressing poor coatability such as shrinkage, while reducing surface tension and suppressing uneven drying of the coating film, the preferred options are: fluorinated surfactants, polysiloxane surfactants, fluorinated thermally decomposable surfactants, and polyether-modified siloxane surfactants.

[0063] Commercially available fluorinated surfactants include, for example: Megafac (registered trademark) F142D, F172, F173, F183, F445, F470, F475, F477 (all manufactured by DIC), NBX-15, FTX-218 (manufactured by NEOS), etc.

[0064] Commercially available polysiloxane surfactants include, for example, "BYK" (registered trademark)-333, BYK-301, BYK-331, BYK-345, and BYK-307 (manufactured by BYK-Chemical Japan).

[0065] Commercially available products containing fluorinated thermally decomposable surfactants include, for example, "Megafac" (registered trademark) DS-21 (manufactured by DIC Corporation). Commercially available products containing polysiloxane-modified acrylic surfactants include, for example, "BYK" (registered trademark)-3550 (manufactured by BYK-Chemie Japan Corporation).

[0066] Commercially available polyether-modified siloxane surfactants include, for example: "BYK" (registered trademark)-345, BYK-346, BYK-347, BYK-348, BYK-349 (all manufactured by BYK-Chemical Japan), "SILFACE" (registered trademark) SAG002, SAG005, SAG0503A, SAG008 (all manufactured by Nissin Chemical Industries, Ltd.), etc.

[0067] The photosensitive resin composition of the present invention may also contain a dispersant. Examples of dispersants include: polyacrylic acid dispersants, polycarboxylic acid dispersants, phosphoric acid dispersants, and polysiloxane dispersants.

[0068] The photosensitive resin composition of the present invention may also contain resins other than (A) siloxane resin, such as acrylic resin or epoxy resin.

[0069] Furthermore, the photosensitive resin composition of the present invention may, as needed, contain additives such as crosslinking agents, crosslinking promoters, sensitizers, thermal free radical generators, dissolution inhibitors, stabilizers, and defoamers, which are components other than those listed above.

[0070] Next, the method for manufacturing the photosensitive resin composition of the present invention will be described. The method for manufacturing the photosensitive resin composition of the present invention generally involves stirring and mixing (A) a silicate resin, (B) metal compound particles, (C) a photosensitizer, (D) an organosilicon compound having a condensed polycyclic aromatic group, (E) an organic solvent, and other components used as needed.

[0071] Next, an example will be given regarding a method for manufacturing a hardened film and microlenses (including microlens arrays) from the photosensitive resin composition of the present invention.

[0072] [Formation of the Dry Film] The process leading up to the formation of the dry film involves the same steps as for the hardened film and microlenses.

[0073] The dry film is formed by coating a photosensitive resin composition onto a substrate.

[0074] First, a photosensitive resin composition is coated onto a resin layer formed by film deposition on a glass substrate, a silicon wafer substrate, or both a glass substrate and a silicon wafer to obtain a coating film.

[0075] Examples of coating methods for the photosensitive resin composition used at this time include: spin coating using a rotary device, spray coating, inkjet coating, dispensing coating, die coating, and roller coating. The film thickness can be appropriately selected based on the coating method. Typically, the film thickness after drying is set to 1~150 μm.

[0076] The obtained coating is then dried to obtain a dried film. Examples of drying methods include: heat drying, air drying, reduced pressure drying, and infrared irradiation. Examples of heat drying devices include: ovens and heating plates. The preferred drying temperature is 50~160℃, and the preferred drying time is 1 minute to several hours.

[0077] [Formation of a hardened film] The hardened film is preferably formed via the exposure steps described below. Specifically, it is preferable to use a UV-Vis exposure machine such as a Parallel Light Mask Aligner (PLA) to expose the entire surface of the obtained dried film at approximately 100-20,000 J / m² (converted to exposure at a wavelength of 365 nm) (hereinafter referred to as bleaching exposure). By performing bleaching exposure, unreacted diazidonaphthoquinone compounds remaining in the dried film can be photodecomposed, thereby further improving the transparency of the obtained cured film.

[0078] A hardened film can be obtained by heating the bleached dried film at a temperature range of 100~450℃ for about 30 seconds to 2 hours using heating devices such as heating plates or ovens.

[0079] [Formation of Microlenses] The method for manufacturing microlenses comprises the following steps: exposing a dried film obtained by coating the above-mentioned photosensitive resin composition onto a substrate, developing the film, and forming a microlens with a diameter of 10 μm or more and 50 μm or less.

[0080] (Exposure Steps) The dried film obtained above is then exposed to photochemical rays (exposure) through a mask with the desired pattern to obtain an exposed film. This exposure operation is called patterned exposure. Examples of photochemical rays irradiated during patterned exposure include ultraviolet light, visible light, electron beams, and X-rays. Preferably, a UV-Vis exposure machine such as a stepper, a mirror projection mask alignment machine (MPA), or a parallel light mask alignment machine (PLA) is used, and the photosensitive resin composition of the present invention is patterned exposed under conditions of approximately 10 to 10,000 J / m² (converted to an exposure dose of 365 nm wavelength) through the mask.

[0081] (Developing step) The obtained exposed film is developed using an alkaline developer to remove the exposed portion, thereby obtaining a plurality of columnar structures of a photosensitive resin composition arranged in a two-dimensional pattern, which will serve as the raw material for the microlens. Furthermore, the arrangement pattern of these columnar structures of the two-dimensional photosensitive resin composition is not particularly limited; the arrangement interval, the size of the base of the columnar structure, and the shape of the base can be set according to the object being detected. These can be arbitrarily set according to the aforementioned mask pattern. Alkaline compounds used in alkaline developing solutions include, for example: inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilate, and ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH), and quaternary ammonium salts such as choline; alkanolamines such as triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol, and diethylaminoethanol; pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, and 1,5-diazabicyclo[4,3,0]-5-nonane. Organic bases such as cyclic amines and porphyrins.

[0082] The concentration of alkaline compounds in alkaline developing solutions is typically 0.01–50% by mass, preferably 0.02–3% by mass. Furthermore, to improve the shape of the developed pattern, 0.1–5% by mass of nonionic surfactants or other surfactants may be added. Moreover, when the developing solution is an alkaline aqueous solution, water-soluble organic solvents such as ethanol, γ-butyrolactone, dimethylformamide, and N-methyl-2-pyrrolidone may be added.

[0083] Examples of development methods include immersion, spraying, and liquid coating. The obtained pattern can also be rinsed and cleaned with pure water.

[0084] Subsequently, it is preferable to use a UV-Vis exposure machine such as PLA to expose the entire surface of the obtained pattern at approximately 100~20,000 J / m² (converted to exposure at a wavelength of 365 nm) (bleaching exposure). By performing bleaching exposure, unreacted diazidonaphthoquinone compounds remaining in the developing film can be photodecomposed, thereby further improving the transparency of the obtained microlenses.

[0085] (Steps for forming microlenses with a diameter of 10 μm to 50 μm) The bleached and exposed pattern is heated (hardened) at a temperature range of 100~450°C for approximately 30 seconds to 2 hours using heating devices such as heating plates and ovens. This melts the columnar form of the photosensitive resin composition. Under the influence of surface tension, the molten photosensitive resin composition flows, thereby forming microlenses with a diameter of 10 μm to 50 μm. Furthermore, even when the distance between adjacent microlenses is very small due to the moderate flow in the molten state, microlenses can still be formed where adjacent columnar forms are arranged independently and do not merge. The side cross-sectional shape of the microlens (the radius of curvature of the lens) can be arbitrarily adjusted by appropriately setting the ratio of the base area to the volume of the columnar form of the photosensitive resin composition. These can be arbitrarily adjusted by the aforementioned mask pattern (the base area of ​​the columnar form) and the aforementioned thickness of the dried film.

[0086] The photosensitive resin composition of this invention is applicable to light-emitting elements such as organic electroluminescence (EL) light-emitting elements and display elements. More specifically, it can be exemplified by hardened films or microlenses formed in organic EL elements to improve light extraction efficiency.

[0087] The hardened film or microlens, comprising a hardened material formed by curing the photosensitive resin composition of the present invention, is suitable for solid-state imaging elements. More specifically, examples include light-concentrating microlenses, white (transparent) color filters or optical waveguides, and anti-reflective films provided as optical filters formed in solid-state imaging elements. Among these, considering the ability to form lens shapes in larger microlenses with high refractive index and transparency and a diameter of 10 μm or more, the hardened film or microlens, comprising a hardened material formed by curing the photosensitive resin composition of the present invention, is particularly suitable for light-concentrating microlenses formed on solid-state imaging elements in fingerprint verification devices. In the case of fingerprint verification devices for smartphones equipped with organic light-emitting diode (OLED) displays, it is preferable to arrange a plurality of microlenses with uniform shapes in a two-dimensional configuration below the OLED display element, which is arranged in a pixel or strip arrangement, so that they are located in the gaps between the sub-pixels of the aforementioned OLED display element.

[0088] A group of microlenses arranged in two dimensions is called a microlens array. The refractive index of the microlenses constituting the microlens array at a wavelength of 633 nm is preferably 1.60 or higher and 1.80 or lower. Furthermore, the diameter of the microlenses is 10 μm or higher and 50 μm or lower, and the spacing between the microlenses is preferably 0.01 μm or higher and 5.0 μm or lower.

[0089] Furthermore, in the microlens array of the present invention, the microlens are preferably a hardened material formed by hardening a photosensitive resin composition containing the following (A) to (D). (A) A siloxane resin containing organosilicon units having diphenyl groups; (B) Select at least one metal compound particle from the group consisting of titanium compound particles, zirconium compound particles, tin compound particles, and aluminum compound particles, or... Composite metal compound particles selected from at least one metal compound and silicon compound from the group consisting of titanium compounds, zirconium compounds, tin compounds and aluminum compounds; (C) Photosensitizer; and (D) Organosilicon compounds having condensed polycyclic aromatic groups. The microlens array of the present invention, as described above, is suitable for use in fingerprint verification devices.

[0090] By patterning and then hardening the photosensitive resin composition of the present invention, the molten photosensitive resin composition flows appropriately, which can form microlenses with very small distances between adjacent microlenses. Therefore, it can simplify the operation without etching and avoid the deterioration of the wiring caused by etching solution or plasma. [Example]

[0091] The present invention will now be described in more detail using examples and comparative examples, but the present invention is not limited to the following examples. The abbreviations used in the synthetic examples and the compounds used in the examples are shown below.

[0092] DAA: Diacetone alcohol EAA: Ethyl acetate Furthermore, in the evaluation method, those without a recorded number of n are evaluations with n=1, and those without a specified temperature in the evaluation and synthesis conditions are implemented at room temperature.

[0093] <Evaluation Methods> "The shape of microlenses" A substrate (hereinafter referred to as "resin layer film substrate") is prepared by forming a transparent resin layer with a thickness of 5 μm containing a crosslinked material comprising siloxane resin and silicon dioxide particles on an 8-inch silicon wafer substrate using the method shown in Example 8 of Japanese Patent Application Publication No. 2019-214492.

[0094] Using a Mark-7 (manufactured by Tokyo Electron), the photosensitive resin composition obtained in each embodiment and comparative example was coated onto a resin layer film substrate by spin coating, and dried at 110°C for 3 minutes to produce a dry film.

[0095] The dried film was patterned and exposed using an i-ray stepper (NSR-2009i9C manufactured by Nikon Corporation). After exposure, the film was sprayed with a photomask having circles (diameters of 10 μm, 20 μm, 30 μm, and 40 μm) and gaps (2 μm). The film was then sprayed and developed for 120 seconds using a Mark-7 (manufactured by Tokyo Electron) with 2.38% TMAH aqueous solution, followed by a 30-second water rinse to produce the post-developed film.

[0096] Subsequently, as a bleaching exposure, a PLA (manufactured by CANON Corporation, PLA-501F) was used to expose the entire surface of the film under an ultra-high pressure mercury lamp at 500 mJ (converted to an exposure dose of 365 nm wavelength).

[0097] Subsequently, microlenses with a film thickness of 5.0 μm were fabricated by curing in an oven at 200°C for 30 minutes. For each microlens, the cross-section was observed using a FE-SEM (Hitachi S-4800) to confirm the cross-sectional shapes with bottom diameters of 10 μm, 20 μm, 30 μm, and 40 μm, and to evaluate the pattern formation. For the cross-sectional shape, shapes such as those in Figure 1 were determined to have microlenses, while shapes such as those in Figure 2 were determined to not have microlenses. From an industrial application point of view, A and B were considered acceptable. A: In all patterns at 10 μm, 20 μm, 30 μm, and 40 μm, the cross-sectional shape has a microlens shape. B: In patterns of 10 μm and 20 μm, the cross-sectional shape has a microlens shape, but in patterns of 30 μm and 40 μm, the cross-sectional shape does not have a microlens shape. C: In all patterns at 10 μm, 20 μm, 30 μm, and 40 μm, the cross-sectional shape does not have a microlens shape.

[0098] Refractive index Using a Mark-7, the photosensitive resin composition obtained in each embodiment and comparative example was coated onto an 8-inch silicon wafer substrate by spin coating, and dried at 110°C for 3 minutes to prepare a dry film.

[0099] Subsequently, as a bleaching exposure, PLA was used to expose the entire surface of the film under an ultra-high pressure mercury lamp at 500 mJ (converted to an exposure dose of 365 nm wavelength).

[0100] Subsequently, a 1.0 μm thick cured film was prepared by curing in an oven at 200°C for 30 minutes. For each cured film, the refractive index at 550 nm was measured at 22°C using an elliptic polarimeter FE5000 manufactured by Otsuka Electronics Co., Ltd.

[0101] Resolution Using a Mark-7, the photosensitive resin composition obtained in each embodiment and comparative example was coated onto a resin layer film substrate prepared in the same way as the lens shape evaluation described above by spin coating, and a dry film was prepared by drying at 110°C for 3 minutes.

[0102] Using an i-ray stepper, after patterning exposure, a Mark-7 was used for 120 seconds of spray development with 2.38% TMAH aqueous solution, followed by a 30-second water rinse to produce the post-developed film.

[0103] Subsequently, as a bleaching exposure, PLA was used to expose the entire surface of the film under an ultra-high pressure mercury lamp at 500 mJ (converted to an exposure dose of 365 nm wavelength).

[0104] Subsequently, microlenses with a film thickness of 5.0 μm were fabricated by curing in an oven at 200°C for 30 minutes. For each microlens, the smallest pattern size after curing at the optimal exposure was taken as the resolution. From an industrial application point of view, A and B were considered acceptable. A: Resolution is less than 5 μm B: Resolution of 5 μm or higher but less than 10 μm C: Resolution of 10 μm or higher "High temperature and high humidity resistance" Using a Mark-7, the photosensitive resin composition obtained in each embodiment and comparative example was coated onto a resin layer film substrate prepared in the same way as the lens shape evaluation described above by spin coating, and a dry film was prepared by drying at 110°C for 3 minutes.

[0105] Subsequently, as a bleaching exposure, PLA was used to expose the entire surface of the film under an ultra-high pressure mercury lamp at 500 mJ (converted to an exposure dose of 365 nm wavelength). Afterward, a 5.0 μm thick cured film was prepared by curing in an oven at 200°C for 30 minutes.

[0106] The obtained hardened film was subjected to a 240-hour test in a high-temperature and high-humidity testing machine (trade name "Q-Sun", manufactured by Q-Lab) at 85°C / 85% humidity. The adhesion of the hardened film, formed on a resin-coated substrate, was evaluated. Specifically, 100 squares of 1 mm × 1 mm were created by slicing 11 parallel lines (vertical and horizontal) at 1 mm intervals on the surface of the hardened film on the resin-coated substrate, reaching the silicon wafer substrate. Cellulose adhesive tape (width = 18 mm, adhesion = 3.7 N / 10 mm) was applied to the slicing surface of the hardened film and rubbed with an eraser (JIS S6050 compliant) to ensure adhesion. The number of squares remaining when the tape was held at a right angle to the board and instantly peeled off was visually counted. The peeled area of ​​the squares was judged as follows: 4B and 5B were considered acceptable. 5B: Peeling area = 0% 4B: Stripping area = more than 0% but less than 5% 3B: Stripping area = 5% or more but less than 15% 2B: Stripping area = 15% or more but less than 35% 1B: Stripped area = 35% or more but less than 65% 0B: Peeling area = 65% or more but less than 100%.

[0107] [Synthesis example 1] Add 171.85 g of DAA, 43.58 g (0.40 mol) of methyltrimethoxysilane, 76.15 g (0.48 mol) of phenyltrimethoxysilane, 14.69 g (0.07 mol) of 3-trimethoxysilylpropylsuccinic acid, and 8.65 g (0.05 mol) of diphenylsilanediol to a 500 mL three-necked flask. Immerse the flask in an oil bath at 40 °C and, while stirring, add an aqueous solution of phosphoric acid (0.72 g of phosphoric acid, relative to 0.5 wt% of the added monomer) dissolved in 42.05 g of water over 10 minutes using a dropping funnel. After stirring at 40 °C for 1 hour, set the oil bath temperature to 70 °C and stir for 1 hour, then raise the oil bath temperature to 115 °C over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and heating and stirring were carried out for 2 hours (internal temperature 100~110°C). A total of 96 g of methanol and water, which were byproducts of the reaction, were distilled off. DAA was added to the obtained polysiloxane DAA solution at a solids concentration of 40% by mass to obtain a silicone resin solution (PS-1).

[0108] [Synthesis example 2] Add 175.08 g of DAA, 43.58 g (0.40 mol) of methyltrimethoxysilane, 68.22 g (0.43 mol) of phenyltrimethoxysilane, 14.69 g (0.07 mol) of 3-trimethoxysilylpropylsuccinic acid, and 17.30 g (0.10 mol) of diphenylsilanediol to a 500 mL three-necked flask. Immerse the flask in an oil bath at 40 °C and, while stirring, add an aqueous solution of phosphoric acid (0.71 g of phosphoric acid, relative to 0.5 wt% of the added monomer) dissolved in 39.89 g of water over 10 minutes using a dropping funnel. After stirring at 40 °C for 1 hour, set the oil bath temperature to 70 °C and stir for 1 hour, then raise the oil bath temperature to 115 °C over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and heating and stirring were carried out for 2 hours (internal temperature 100~110°C). A total of 91 g of methanol and water, which were byproducts of the reaction, were distilled off. DAA was added to the obtained polysiloxane DAA solution at a solids concentration of 40% by mass to obtain a silicone resin solution (PS-2).

[0109] [Synthesis example 3] Add 181.56 g of DAA, 43.58 g (0.40 mol) of methyltrimethoxysilane, 52.35 g (0.33 mol) of phenyltrimethoxysilane, 14.69 g (0.07 mol) of 3-trimethoxysilylpropylsuccinic acid, and 34.61 g (0.20 mol) of diphenylsilanediol to a 500 mL three-necked flask. Immerse the flask in an oil bath at 40 °C and, while stirring, add an aqueous solution of phosphoric acid (0.73 g of phosphoric acid, relative to 0.5 wt% of the added monomer) dissolved in 35.57 g of water over 10 minutes using a dropping funnel. After stirring at 40 °C for 1 hour, set the oil bath temperature to 70 °C and stir for 1 hour, then raise the oil bath temperature to 115 °C over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and heating and stirring were carried out for 2 hours (internal temperature 100~110°C). A total of 81 g of methanol and water, which were byproducts of the reaction, were distilled off. DAA was added to the obtained polysiloxane DAA solution at a solids concentration of 40% by mass to obtain a silicone resin solution (PS-3).

[0110] [Synthesis Example 4] Add 188.03 g of DAA, 43.58 g (0.40 mol) of methyltrimethoxysilane, 36.49 g (0.23 mol) of phenyltrimethoxysilane, 14.69 g (0.07 mol) of 3-trimethoxysilylpropylsuccinic acid, and 51.91 g (0.30 mol) of diphenylsilanediol to a 500 mL three-necked flask. Immerse the flask in an oil bath at 40 °C and, while stirring, add an aqueous solution of phosphoric acid (0.73 g of phosphoric acid, relative to 0.5 wt% of the added monomer) dissolved in 31.25 g of water over 10 minutes using a dropping funnel. After stirring at 40 °C for 1 hour, set the oil bath temperature to 70 °C and stir for 1 hour, then raise the oil bath temperature to 115 °C over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and heating and stirring were carried out for 2 hours (internal temperature 100~110°C). A total of 71 g of methanol and water, which were byproducts of the reaction, were distilled off. DAA was added to the obtained polysiloxane DAA solution at a solids concentration of 40% by mass to obtain a silicone resin solution (PS-4).

[0111] [Synthesis Example 5] Add 194.51 g of DAA, 43.58 g (0.40 mol) of methyltrimethoxysilane, 20.62 g (0.13 mol) of phenyltrimethoxysilane, 14.69 g (0.07 mol) of 3-trimethoxysilylpropylsuccinic acid, and 69.22 g (0.40 mol) of diphenylsilanediol to a 500 mL three-necked flask. Immerse the flask in an oil bath at 40 °C and, while stirring, add an aqueous solution of phosphoric acid (0.74 g of phosphoric acid, relative to 0.5 wt% of the added monomer) dissolved in 26.93 g of water over 10 minutes using a dropping funnel. After stirring at 40 °C for 1 hour, set the oil bath temperature to 70 °C and stir for 1 hour, then raise the oil bath temperature to 115 °C over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and heating and stirring were carried out for 2 hours (internal temperature 100~110°C). A total of 61 g of methanol and water, which were byproducts of the reaction, were distilled off. DAA was added to the obtained polysiloxane DAA solution at a solids concentration of 40% by mass to obtain a silicone resin solution (PS-5).

[0112] [Synthesis example 6] Add 168.61 g of DAA, 43.58 g (0.40 mol) of methyltrimethoxysilane, 84.08 g (0.53 mol) of phenyltrimethoxysilane, and 14.69 g (0.07 mol) of 3-trimethoxysilylpropylsuccinic acid to a 500 mL three-necked flask. Immerse the flask in a 40°C oil bath and, while stirring, add an aqueous solution of phosphoric acid (0.71 g of phosphoric acid, relative to 0.5 wt% of the added monomer) in 44.21 g of water over 10 minutes using a dropping funnel. After stirring at 40°C for 1 hour, set the oil bath temperature to 70°C and stir for 1 hour. Then, raise the oil bath temperature to 115°C over 30 minutes. After 1 hour of heating, the internal temperature of the solution reaches 100°C, and continue heating and stirring for 2 hours (internal temperature 100–110°C). 101 g of methanol and water, which were distilled off as byproducts of the reaction, were added. DAA was added to the obtained polysiloxane DAA solution at a solids concentration of 40% by mass to obtain a silicone resin solution (PS-6).

[0113] [Synthesis Example 7] Add 158.57 g of DAA, 43.58 g (0.40 mol) of methyltrimethoxysilane, 52.35 g (0.33 mol) of phenyltrimethoxysilane, 14.69 g (0.07 mol) of 3-trimethoxysilylpropylsuccinic acid, and 19.24 g (0.20 mol) of dimethyldimethoxysilane to a 500 mL three-necked flask. Immerse the flask in an oil bath at 40 °C and, while stirring, add an aqueous solution of phosphoric acid (0.65 g of phosphoric acid, relative to 0.5 wt% of the added monomer) dissolved in 35.57 g of water over 10 minutes using a dropping funnel. After stirring at 40 °C for 1 hour, set the oil bath temperature to 70 °C and stir for 1 hour, then raise the oil bath temperature to 115 °C over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and heating and stirring were carried out for 2 hours (internal temperature 100~110°C). A total of 81 g of methanol and water, which were byproducts of the reaction, were distilled off. DAA was added to the obtained polysiloxane DAA solution at a solids concentration of 40% by mass to obtain a silicone resin solution (PS-7).

[0114] [Synthesis example 8] Add 189.22 g of DAA, 43.58 g (0.40 mol) of methyltrimethoxysilane, 52.35 g (0.33 mol) of phenyltrimethoxysilane, 14.69 g (0.07 mol) of 3-trimethoxysilylpropylsuccinic acid, and 39.74 g (0.20 mol) of naphthyltrimethoxysilane to a 500 mL three-necked flask. Immerse the flask in an oil bath at 40 °C and, while stirring, add an aqueous solution of phosphoric acid (0.75 g of phosphoric acid, relative to 0.5 wt% of the added monomer) dissolved in 35.57 g of water over 10 minutes using a dropping funnel. After stirring at 40 °C for 1 hour, set the oil bath temperature to 70 °C and stir for 1 hour, then raise the oil bath temperature to 115 °C over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and heating and stirring were carried out for 2 hours (internal temperature 100~110°C). A total of 81 g of methanol and water, which were byproducts of the reaction, were distilled off. DAA was added to the obtained polysiloxane DAA solution at a solids concentration of 40% by mass to obtain a silicone resin solution (PS-8).

[0115] [Synthesis Example 9] While adding DAA using a rotary evaporator at a pressure of 150 mbar, 500 g of "NanoUse" (registered trademark) OT-RB300M7-20 (a 30 wt% methanol dispersion) containing composite particles of tin oxide, titanium oxide, and silicon oxide was subjected to solvent displacement. Then, the mixture was concentrated using a rotary evaporator at a pressure of 20 mbar to achieve a solids concentration of 40 wt%, yielding a metal compound particle dispersion (T-1).

[0116] [Synthesis Example 10] Under a dry nitrogen stream, 15.32 g (0.05 mol) of Ph-cc-AP-MF (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 37.62 g (0.14 mol) of 5-diazidonaphthoquinone sulfonyl chloride were dissolved in 1,4-di... In 450 g of alkylene, 1,4-dialkylene oxide was added dropwise in a manner that prevented the temperature from exceeding 35°C within the system. 50 g of alkyl groups were mixed with 15.58 g (0.154 mol) of triethylamine. The mixture was added dropwise and stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was added to water. The precipitate was then filtered off. The precipitate was dried using a vacuum dryer to obtain a diazidonaphthoquinone compound (QD-1) with the following structure.

[0117] [Chemistry 5]

[0118] [Synthesis Example 11] Under a dry nitrogen stream, 15.32 g (0.05 mol) of TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 22.84 g (0.085 mol) of 5-diazidonaphthoquinone sulfonyl chloride were dissolved in 1,4-di... In 450 g of alkylene, the temperature was adjusted to room temperature. The mixture was then added dropwise in a manner that prevented the temperature from exceeding 35°C. 50 g of alkyl groups were mixed with 9.46 g (0.0935 mol) of triethylamine. The mixture was added dropwise and stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was added to water. The precipitate was then filtered off. The precipitate was dried using a vacuum dryer to obtain a diazidonaphthoquinone compound (QD-2) with the following structure.

[0119] [Chemistry 6]

[0120] [Example 1] First, under a yellow light, mix and stir the following ingredients. • A solution was prepared by dissolving 2.00 g of the diazidonaphthoquinone compound (QD-1) obtained in Synthesis Example 10, 1.33 g of the diazidonaphthoquinone compound (QD-2) obtained in Synthesis Example 11, and 1.67 g of the phenolic compound TrisP-PA in a mixed solvent of 4.04 g of DAA and 5.34 g of EAA as an organic solvent. • 1-Naphthyltrimethoxysilane (trade name "Z-6874", manufactured by Dow & Toray Industries, Inc.), an organosilicon compound containing condensed polycyclic aromatic groups, 1.67 g. • 0.10 g of a 5% (w / w) EAA solution of a fluorinated thermally decomposable surfactant (trade name "DS-21", manufactured by DIC Co., Ltd.) and 0.60 g of a 5% (w / w) EAA solution of a silicone-modified acrylic surfactant (trade name "BYK-3550", manufactured by BYK-Chemie Japan Co., Ltd.). • 46.46 g of the silicone resin solution (PS-1) obtained in Synthesis Example 1 • 36.80 g of the metal compound particle dispersion (T-1) obtained in Synthesis Example 9 Subsequently, a photosensitive resin composition A-1 with a solid content of 40% by weight was prepared by filtration using a 1.0 μm filter.

[0121] The obtained photosensitive resin composition A-1 was used to prepare a hardened film and a microlens by the aforementioned method, and was evaluated by the aforementioned method.

[0122] [Example 2] Except that a silicone resin solution (PS-2) was used instead of a silicone resin solution (PS-1), photosensitive resin composition A-2 was prepared in the same manner as in Example 1. The obtained photosensitive resin composition A-2 was evaluated in the same manner as in Example 1.

[0123] [Example 3] Except that a silicone resin solution (PS-3) was used instead of a silicone resin solution (PS-1), photosensitive resin composition A-3 was prepared in the same manner as in Example 1. The obtained photosensitive resin composition A-3 was evaluated in the same manner as in Example 1.

[0124] [Example 4] Except that a silicone resin solution (PS-4) was used instead of a silicone resin solution (PS-1), photosensitive resin composition A-4 was prepared in the same manner as in Example 1. The obtained photosensitive resin composition A-4 was evaluated in the same manner as in Example 1.

[0125] [Example 5] Except that a silicone resin solution (PS-5) was used instead of a silicone resin solution (PS-1), photosensitive resin composition A-5 was prepared in the same manner as in Example 1. The obtained photosensitive resin composition A-5 was evaluated in the same manner as in Example 1.

[0126] [Example 6] Except for changing the amount of siloxane resin solution (PS-3) added to 53.12 g and the amount of (B) metal compound particle dispersion (T-1) added to 30.14 g, photosensitive resin composition A-6 was prepared in the same manner as in Example 3. The obtained photosensitive resin composition A-6 was evaluated in the same manner as in Example 1.

[0127] [Example 7] Except for changing the amount of siloxane resin solution (PS-3) added to 59.78 g and the amount of (B) metal compound particle dispersion (T-1) added to 23.48 g, photosensitive resin composition A-7 was prepared in the same manner as in Example 3. The obtained photosensitive resin composition A-7 was evaluated in the same manner as in Example 1.

[0128] [Example 8] Except for changing the amount of siloxane resin solution (PS-3) added to 39.80 g and the amount of (B) metal compound particle dispersion (T-1) added to 43.46 g, photosensitive resin composition A-8 was prepared in the same manner as in Example 3. The obtained photosensitive resin composition A-8 was evaluated in the same manner as in Example 1.

[0129] [Example 9] Except for changing the amount of siloxane resin solution (PS-3) added to 33.14 g and the amount of (B) metal compound particle dispersion (T-1) added to 50.12 g, photosensitive resin composition A-9 was prepared in the same manner as in Example 3. The obtained photosensitive resin composition A-9 was evaluated in the same manner as in Example 1.

[0130] [Example 10] First, under a yellow light, mix and stir the following ingredients. A solution was prepared by dissolving 2.05 g of diazidonaphthoquinone compound (QD-1), 1.37 g of diazidonaphthoquinone compound (QD-2), and 1.71 g of phenolic compound TrisP-PA in a mixed solution of 2.76 g of DAA and 5.34 g of EAA as an organic solvent. • "Z-6874," a trade name for an organosilicon compound containing a condensed polycyclic aromatic group, manufactured by Dow Toray Industries, Inc. 0.68 g • 0.10 g of EAA 5% solution (by weight) manufactured by DIC (stock) under the trade name "DS-21" and 0.60 g of EAA 5% solution (by weight) manufactured by BYK-Chemie Japan (stock) under the trade name "BYK-3550". • Silicone resin solution (PS-3) 47.65 g • Metal compound particle dispersion (T-1) 37.74 g Subsequently, a photosensitive resin composition A-10 with a solid content of 40% by weight was prepared by filtration using a 1.0 μm filter.

[0131] The obtained photosensitive resin composition A-10 was evaluated in the same manner as in Example 1.

[0132] [Example 11] First, under a yellow light, mix and stir the following ingredients. A solution was prepared by dissolving 1.92 g of diazidonaphthoquinone compound (QD-1), 1.28 g of diazidonaphthoquinone compound (QD-2), and 1.60 g of phenolic compound TrisP-PA in a mixed solution of 6.04 g of DAA and 5.34 g of EAA as an organic solvent. • Z-6874, a trade name for an organosilicon compound containing a condensed polycyclic aromatic group, manufactured by Dow Toray Industries, Inc. 3.20 g • 0.10 g of EAA 5% solution manufactured by DIC (stock code: DS-21) and 0.60 g of EAA 5% solution manufactured by BYK-Chemie Japan (stock code: BYK-3550). • Silicone resin solution (PS-3) 44.60 g • Metal compound particle dispersion (T-1) 35.33 g.

[0133] Subsequently, a photosensitive resin composition A-11 with a solid content of 40% by weight was prepared by filtration using a 1.0 μm filter.

[0134] The obtained photosensitive resin composition A-11 was evaluated in the same manner as in Example 1.

[0135] [Comparative Example 1] Except that a silicone resin solution (PS-6) was used instead of a silicone resin solution (PS-1), photosensitive resin composition A-12 was prepared in the same manner as in Example 1. The obtained photosensitive resin composition A-12 was evaluated in the same manner as in Example 1.

[0136] [Comparative Example 2] First, under a yellow light, mix and stir the following ingredients. A solution was prepared by dissolving 1.92 g of diazidonaphthoquinone compound (QD-1), 1.28 g of diazidonaphthoquinone compound (QD-2), and 1.60 g of phenolic compound TrisP-PA in a mixed solution of 6.04 g of DAA and 5.34 g of EAA as an organic solvent. • Z-6874, an organosilicon compound containing condensed polycyclic aromatic groups, manufactured by Dow Toray Industries, Inc. (1.60 g). • Dimethoxydiphenylsilane (trade name "KBM-202SS", manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 1.60 g • 0.10 g of EAA 5% solution manufactured by DIC (stock code: DS-21) and 0.60 g of EAA 5% solution manufactured by BYK-Chemie Japan (stock code: BYK-3550). • Silicone resin solution (PS-3) 44.60 g • Metal compound particle dispersion (T-1) 35.33 g.

[0137] Subsequently, a photosensitive resin composition A-11 with a solid content of 40% by weight was prepared by filtration using a 1.0 μm filter.

[0138] The obtained photosensitive resin composition A-11 was evaluated in the same manner as in Example 1.

[0139] [Comparative Example 3] Except that a silicone resin solution (PS-7) was used instead of a silicone resin solution (PS-1), photosensitive resin composition A-14 was prepared in the same manner as in Example 1. The obtained photosensitive resin composition A-14 was evaluated in the same manner as in Example 1.

[0140] [Comparative Example 4] Except that a silicone resin solution (PS-8) was used instead of a silicone resin solution (PS-1), photosensitive resin composition A-15 was prepared in the same manner as in Example 1. The obtained photosensitive resin composition A-15 was evaluated in the same manner as in Example 1.

[0141] [Comparative Example 5] First, under a yellow light, mix and stir the following ingredients. A solution was prepared by dissolving 2.00 g of diazidonaphthoquinone compound (QD-1), 1.33 g of diazidonaphthoquinone compound (QD-2), and 1.67 g of phenolic compound TrisP-PA in a mixed solution of 4.04 g of DAA and 5.34 g of EAA as an organic solvent. • As a trade name for organosilicon compound containing condensed polycyclic aromatic groups, "Z-6874" is manufactured by Dow Toray Industries, Inc. 1.67 g • 0.10 g of EAA 5% solution manufactured by DIC (stock code: DS-21) and 0.60 g of EAA 5% solution manufactured by BYK-Chemie Japan (stock code: BYK-3550). • 83.26 g of silicone resin solution (PS-3).

[0142] Subsequently, a photosensitive resin composition A-16 with a solid content of 40% by weight was prepared by filtration using a 1.0 μm filter.

[0143] The obtained photosensitive resin composition A-16 was evaluated in the same manner as in Example 1.

[0144] [Comparative Example 6] First, under a yellow light, mix and stir the following ingredients. A solution was prepared by dissolving 2.09 g of diazidonaphthoquinone compound (QD-1), 1.39 g of diazidonaphthoquinone compound (QD-2), and 1.74 g of phenolic compound TrisP-PA in a mixed solution of 1.87 g of DAA and 5.34 g of EAA as an organic solvent. • Z-6874, a trade name for an organosilicon compound containing a condensed polycyclic aromatic group, manufactured by Dow Toray Industries, Inc. 3.20 g • 0.10 g of EAA 5% solution manufactured by DIC (stock code: DS-21) and 0.60 g of EAA 5% solution manufactured by BYK-Chemie Japan (stock code: BYK-3550). • Silicone resin solution (PS-3) 48.48 g • Metal compound particle dispersion (T-1) 38.40 g.

[0145] Subsequently, a photosensitive resin composition A-17 with a solid content of 40% by weight was prepared by filtration using a 1.0 μm filter.

[0146] The obtained photosensitive resin composition A-17 was evaluated in the same manner as in Example 1.

[0147] [Comparative Example 7] Except that phenyltrimethoxysilane (trade name "KBM-103", manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of trade name "Z-6874", manufactured by Dow Toray Industries, Ltd., photosensitive resin composition A-18 was prepared in the same manner as in Example 1. The obtained photosensitive resin composition A-18 was evaluated in the same manner as in Example 1.

[0148] [Comparative Example 8] Except that the trade name "KBM-202SS" manufactured by Shin-Etsu Chemical Industry Co., Ltd. was used instead of the trade name "Z-6874" manufactured by Dow Toray Industries, Ltd., the photosensitive resin composition A-19 was prepared in the same manner as in Example 1. The obtained photosensitive resin composition A-19 was evaluated in the same manner as in Example 1.

[0149] [Comparative Example 9] Except that tetrapropoxysilane (trade name "N-POS", manufactured by Fuso Chemical Industry Co., Ltd.) was used instead of trade name "Z-6874", manufactured by Dow Toray Industries Co., Ltd., the photosensitive resin composition A-20 was prepared in the same manner as in Example 1. The obtained photosensitive resin composition A-20 was evaluated in the same manner as in Example 1.

[0150] [Comparative Example 10] Except that vinyltris(2-methoxyethoxy)silane (trade name "KBC-103", manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of trade name "Z-6874", manufactured by Dow Toray Industries, Ltd., the photosensitive resin composition A-21 was prepared in the same manner as in Example 1. The obtained photosensitive resin composition A-21 was evaluated in the same manner as in Example 1.

[0151] [Comparative Example 11] Except that 3-methylacryloxypropyltrimethoxysilane (trade name "KBM-503", manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of trade name "Z-6874", manufactured by Dow Toray Industries, Ltd., photosensitive resin composition A-22 was prepared in the same manner as in Example 1. The obtained photosensitive resin composition A-22 was evaluated in the same manner as in Example 1.

[0152] [Comparative Example 12] Except that 3-methylacryloxyoctyltrimethoxysilane (trade name "KBM-5803", manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of "Z-6874", manufactured by Dow Toray Industries, Ltd., the photosensitive resin composition A-23 was prepared in the same manner as in Example 1. The obtained photosensitive resin composition A-23 was evaluated in the same manner as in Example 1.

[0153] [Comparative Example 13] Except that (3-methacryloxypropyl)methyldimethoxysilane (trade name "KBM-502", manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of trade name "Z-6874", manufactured by Dow Toray Industries, Ltd., the photosensitive resin composition A-24 was prepared in the same manner as in Example 1. The obtained photosensitive resin composition A-24 was evaluated in the same manner as in Example 1.

[0154] The composition of the resin components in each embodiment and comparative example is shown in Tables 1 and 2, and the evaluation results are shown in Table 3.

[0155] [Table 1] [Table 1] siloxane resin solution Silicone resin The molar ratio of organosilicon units in silicone resins. Diphenyl methyl Phenyl Succinic acid dimethyl Naphthyl Synthesis example 1 PS-1 5 40 48 7 ‒ ‒ Synthesis example 2 PS-2 10 40 43 7 ‒ ‒ Synthesis example 3 PS-3 20 40 33 7 ‒ ‒ Synthesis example 4 PS-4 30 40 twenty three 7 ‒ ‒ Synthesis example 5 PS-5 40 40 13 7 ‒ ‒ Synthesis example 6 PS-6 0 40 53 7 ‒ ‒ Synthesis Example 7 PS-7 0 40 33 7 20 ‒ Synthesis example 8 PS-8 0 40 33 7 ‒ 20

[0156] [Table 2] [Table 2] Photosensitive Tree lipid components (A) Contains an organic compound with diphenyl groups. Silane units of siloxane resins (weight%) (A) Silicone resins contain diphenylene oxides. The unit ratio of organosilicones based on the group (mol%) Other silicon oxides Alkane resin (weight%) (B) Metallic compounds particle (weight%) (C) Photosensitive agent (weight%) (D) Condensed polycyclic aromatic compounds organosilicon compounds (weight%) (E) Organic solvent Other organosilane compounds (weight%) Other compounds (weight%) Example 1 A-1 PS-1(47) 5 ‒ T-1(37) QD-1(5) QD-2(3) Z-6874(4) DAA / EAA ‒ Phenolic compound TrisP-PA (4) Example 2 A-2 PS-2(47) 10 ‒ T-1(37) QD-1(5) QD-2(3) Z-6874(4) DAA / EAA ‒ Phenolic compound TrisP-PA (4) Example 3 A-3 PS-3(47) 20 ‒ T-1(37) QD-1(5) QD-2(3) Z-6874(4) DAA / EAA ‒ Phenolic compound TrisP-PA (4) Example 4 A-4 PS-4(47) 30 ‒ T-1(37) QD-1(5) QD-2(3) Z-6874(4) DAA / EAA ‒ Phenolic compound TrisP-PA (4) Example 5 A-5 PS-5(47) 40 ‒ T-1(37) QD-1(5) QD-2(3) Z-6874(4) DAA / EAA ‒ Phenolic compound TrisP-PA (4) Example 6 A-6 PS-3(54) 20 ‒ T-1(30) QD-1(5) QD-2(3) Z-6874(4) DAA / EAA ‒ Phenolic compound TrisP-PA (4) Example 7 A-7 PS-3(61) 20 ‒ T-1(23) QD-1(5) QD-2(3) Z-6874(4) DAA / EAA ‒ Phenolic compound TrisP-PA (4) Example 8 A-8 PS-3(40) 20 ‒ T-1(44) QD-1(5) QD-2(3) Z-6874(4) DAA / EAA ‒ Phenolic compound TrisP-PA (4) Example 9 A-9 PS-3(33) 20 ‒ T-1(51) QD-1(5) QD-2(3) Z-6874(4) DAA / EAA ‒ Phenolic compound TrisP-PA (4) Example 10 A-10 PS-3(48) 20 ‒ T-1(38) QD-1(5) QD-2(3) Z-6874(2) DAA / EAA ‒ Phenolic compound TrisP-PA (4) Example 11 A-11 PS-3(45) 20 ‒ T-1(35) QD-1(5) QD-2(3) Z-6874(8) DAA / EAA ‒ Phenolic compound TrisP-PA (4) Comparative Example 1 A-12 ‒ ‒ PS-6(47) T-1(37) QD-1(5) QD-2(3) Z-6874(4) DAA / EAA ‒ Phenolic compound TrisP-PA (4) Comparative Example 2 A-13 ‒ ‒ PS-6(45) T-1(35) QD-1(5) QD-2(3) Z-6874(4) DAA / EAA KBM-202SS(4) Phenolic compound TrisP-PA (4) Comparative Example 3 A-14 ‒ ‒ PS-7(47) T-1(37) QD-1(5) QD-2(3) Z-6874(4) DAA / EAA ‒ Phenolic compound TrisP-PA (4) Comparative Example 4 A-15 ‒ ‒ PS-8(47) T-1(37) QD-1(5) QD-2(3) Z-6874(4) DAA / EAA ‒ Phenolic compound TrisP-PA (4) Comparative Example 5 A-16 PS-3(84) 20 ‒ ‒ QD-1(5) QD-2(3) Z-6874(4) DAA / EAA ‒ Phenolic compound TrisP-PA (4) Comparative Example 6 A-17 PS-3(49) 20 ‒ ‒ QD-1(5) QD-2(3) ‒ DAA / EAA ‒ Phenolic compound TrisP-PA (4) Comparative Example 7 A-18 PS-3(47) 20 ‒ ‒ QD-1(5) QD-2(3) ‒ DAA / EAA KBM-103(4) Phenolic compound TrisP-PA (4) Comparative Example 8 A-19 PS-3(47) 20 ‒ ‒ QD-1(5) QD-2(3) ‒ DAA / EAA KBM-202SS(4) Phenolic compound TrisP-PA (4) Comparative Example 9 A-20 PS-3(47) 20 ‒ T-1(37) QD-1(5) QD-2(3) ‒ DAA / EAA N-POS(4) Phenolic compound TrisP-PA (4) Comparative Example 10 A-21 PS-3(47) 20 ‒ T-1(37) QD-1(5) QD-2(3) ‒ DAA / EAA KBC-1003(4) Phenolic compound TrisP-PA (4) Comparative Example 11 A-22 PS-3(47) 20 ‒ T-1(37) QD-1(5) QD-2(3) ‒ DAA / EAA KBM-503(4) Phenolic compound TrisP-PA (4) Comparative Example 12 A-23 PS-3(47) 20 ‒ T-1(37) QD-1(5) QD-2(3) ‒ DAA / EAA KBM-5803(4) Phenolic compound TrisP-PA (4) Comparative Example 13 A-24 PS-3(47) 20 ‒ T-1(37) QD-1(5) QD-2(3) ‒ DAA / EAA KBM-502(4) Phenolic compound TrisP-PA (4)

[0157] [Table 3] [Table 3] Photosensitive resin composition Shape of microlenses Refractive index Resolution High temperature and high humidity resistance Example 1 A-1 B B A B Example 2 A-2 A B A A Actual example 3 A-3 A A A A Actual example 4 A-4 A A B A Actual example 5 A-5 A A C A Actual example 6 A-6 A B A A Actual example 7 A-7 A C A A Actual example 8 A-8 A A B A Actual example 9 A-9 B A C A Actual example 10 A-10 B A A A Actual example 11 A-11 A A B A Comparative Example 1 A-12 C C A C Comparative Example 2 A-13 C C B C Comparative Example 3 A-14 A D A C Comparative Example 4 A-15 C A A B Comparative Example 5 A-16 A E A A Comparative Example 6 A-17 C A A B Comparative Example 7 A-18 C A A B Comparative Example 8 A-19 C A B B Comparative Example 9 A-20 C B A B Comparative Example 10 A-21 C B A B Comparative Example 11 A-22 C B A B Comparative Example 12 A-23 C B A B Comparative Example 13 A-24 C B A B

[0158] According to the photosensitive resin composition prepared in the examples, it can be found that it has high refractive index and transparency, high fluidity at a calcination temperature below 230°C, and can also form a lens shape in a large microlens with a diameter of 10 μm or more. (Industrial applicability)

[0159] The photosensitive resin composition of the present invention has high refractive index and transparency, and has high fluidity at a calcination temperature below 230°C. It can also form a lens shape in a large microlens with a diameter of 10 μm or more, and is therefore suitable for use as a microlens in CMOS image sensors or fingerprint verification devices.

Claims

1. A photosensitive resin composition comprising the following (A) to (E): (A) a siloxane resin containing an organosilicon unit having a diphenyl group; (B) at least one metal compound particle selected from the group consisting of titanium compound particles, zirconium compound particles, tin compound particles and aluminum compound particles, or a composite metal compound particle selected from the group consisting of at least one metal compound and a silicon compound; (C) a photosensitizer; (D) an organosilicon compound having a condensed polycyclic aromatic group; and (E) an organic solvent.

2. The photosensitive resin composition as claimed in claim 1, wherein, The aforementioned (A) silica alkane resin contains 5 mol% or more and 40 mol% or less of organosilane units with diphenyl groups.

3. The photosensitive resin composition as claimed in claim 1 or 2, wherein, The aforementioned (A) siloxane resin contains organosilicon units having a carboxyl group and / or a dicarboxylic anhydride structure.

4. The photosensitive resin composition as claimed in claim 1, wherein, The average particle size of the aforementioned (B) metal compound particles or composite metal compound particles is 1 nm to 70 nm.

5. The photosensitive resin composition as claimed in claim 1, wherein, The aforementioned photosensitizer (C) is a diazidonaphthoquinone compound.

6. A hardened material formed by hardening any one of the photosensitive resin compositions of claims 1 to 5.

7. The hardened material of claim 6 has a refractive index of 1.60 or higher and 1.80 or lower at a wavelength of 633 nm.

8. A hardened film comprising the hardened material of claim 6.

9. A microlens comprising the hardened material of claim 6.

10. A method for manufacturing a microlens, comprising: The step of coating the photosensitive resin composition of any one of the claims 1 to 5 onto the substrate; Exposure steps; development steps; and steps for forming microlenses with diameters of 10 μm to 50 μm.

11. A solid-state imaging element having the hardened film of claim 8.

12. A fingerprint verification device comprising the hardened film of claim 8.

Images