WO2023054226A1 - Composition de résine photosensible, microlentille - Google Patents

Composition de résine photosensible, microlentille Download PDF

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Publication number
WO2023054226A1
WO2023054226A1 PCT/JP2022/035589 JP2022035589W WO2023054226A1 WO 2023054226 A1 WO2023054226 A1 WO 2023054226A1 JP 2022035589 W JP2022035589 W JP 2022035589W WO 2023054226 A1 WO2023054226 A1 WO 2023054226A1
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Prior art keywords
resin composition
photosensitive resin
compound
compound particles
group
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PCT/JP2022/035589
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English (en)
Japanese (ja)
Inventor
雄介 福▲崎▼
小林秀行
諏訪充史
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東レ株式会社
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Priority to CN202280058015.6A priority Critical patent/CN117859098A/zh
Priority to KR1020247004503A priority patent/KR20240072125A/ko
Priority to JP2022575336A priority patent/JPWO2023054226A1/ja
Publication of WO2023054226A1 publication Critical patent/WO2023054226A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G02B3/0006—Arrays
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/22—Exposing sequentially with the same light pattern different positions of the same surface
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06V—IMAGE OR VIDEO RECOGNITION OR UNDERSTANDING
    • G06V40/00—Recognition of biometric, human-related or animal-related patterns in image or video data
    • G06V40/10—Human or animal bodies, e.g. vehicle occupants or pedestrians; Body parts, e.g. hands
    • G06V40/12—Fingerprints or palmprints
    • G06V40/13—Sensors therefor
    • G06V40/1318—Sensors therefor using electro-optical elements or layers, e.g. electroluminescent sensing

Definitions

  • the present invention relates to a photosensitive resin composition, a microlens obtained by curing it, and a light-emitting device, solid-state imaging device, and fingerprint authentication device having the same.
  • Biometric authentication is essential for unlocking and other personal authentication for various mobile display terminals such as smartphones and tablet PCs (personal computers).
  • fingerprint authentication is installed in many terminals because of its low cost, small size, and high convenience.
  • Authentication methods for under-display type fingerprint authentication devices include optical methods and ultrasonic methods. Among them, optical methods are particularly applicable not only to organic light-emitting diode (OLED) displays, but also to liquid crystal displays and the like. It has become mainstream due to its versatility that can also be introduced.
  • OLED organic light-emitting diode
  • Patent Document 1 a thin optical under-display fingerprint authentication device that has high authentication accuracy and can be installed in a very narrow area between the battery and the screen has been proposed (for example, Patent Document 1 and Patent Document 2), these devices incorporate a microlens (lens with a diameter ranging from 1 ⁇ m to 500 ⁇ m) as a member for improving the authentication system.
  • a microlens lacs with a diameter ranging from 1 ⁇ m to 500 ⁇ m
  • Patent Document 1 and Patent Document 2 provide a fingerprint authentication device with excellent authentication accuracy, in order to achieve further improvement in authentication accuracy, the microlenses must have a high refractive index. is necessary.
  • the diameter of the microlens applied to the fingerprint authentication device is about 10 ⁇ m to 40 ⁇ m, which is considerably larger than the microlens with a diameter of about several ⁇ m applied to the CMOS image sensor. Since there is a restriction in the heat resistance of the resin layer that forms the collimator, etc., it is necessary to bake at a temperature of 230° C. or less, so a material with excellent fluidity during baking is required.
  • a siloxane resin composition containing metal compound particles (see, for example, Patent Document 3) is disclosed as a photosensitive material having a high refractive index and transparency. It was difficult to form a microlens with a large .
  • a siloxane resin composition containing metal compound particles As a photosensitive material having a high refractive index and capable of forming a lens, a siloxane resin composition containing metal compound particles (see, for example, Patent Document 4) is disclosed. , the fluidity was low, and the formation of microlenses was difficult.
  • the present invention was invented in view of such problems of the prior art, and forms a large microlens with a diameter of 10 ⁇ m or more, which has a high refractive index and transparency, has high fluidity even at a firing temperature of 230° C. or less. It is an object of the present invention to provide a photosensitive resin composition capable of
  • a photosensitive resin composition containing the following (A) to (E).
  • a microlens array having a plurality of microlenses arranged two-dimensionally, wherein the microlenses have a refractive index of 1.60 or more and 1.80 or less at a wavelength of 633 nm, and a diameter of the microlenses of 10 ⁇ m or more and 50 ⁇ m. and the distance between the microlenses is 0.01 ⁇ m or more and 5.0 ⁇ m or less.
  • A a siloxane resin containing an organosilane 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 , Composite metal compound particles of at least one metal compound and silicon compound selected from the group consisting of titanium compounds, zirconium compounds, tin compounds and aluminum compounds
  • C photosensitive agent
  • D condensed polycyclic aromatic group Organosilane compound [16]
  • a fingerprint authentication device comprising the microlens array of [14] or [15].
  • the photosensitive resin composition of the present invention has a high refractive index and transparency, has high fluidity even at a baking temperature of 230° C. or less, and can form large microlenses with a diameter of 10 ⁇ m or more. be.
  • FIG. 4 is a cross-sectional view showing an example of the shape of a microlens
  • FIG. 4 is a cross-sectional view showing an example of a shape that is not a microlens
  • the photosensitive resin composition of the present invention is a photosensitive resin composition containing the following (A) to (E).
  • A a siloxane resin containing an organosilane 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 from the group consisting of titanium compounds, zirconium compounds, tin compounds and aluminum compounds
  • Composite metal compound particles of at least one selected metal compound and silicon compound (C) a photosensitizer;
  • D an organosilane compound having a condensed polycyclic aromatic group;
  • E an organic solvent;
  • a siloxane resin containing an organosilane unit having a diphenyl group may hereinafter be simply abbreviated as (A) a siloxane resin.
  • a siloxane resin by including (A) the siloxane resin, it is possible to form a microlens having high transparency and excellent heat resistance and weather resistance. This is because (A) the siloxane resin has a siloxane skeleton in its main chain. Furthermore, compared with a siloxane resin composed only of trifunctional T units in which three-dimensional cross-linking proceeds, (A) a siloxane resin containing an organosilane unit having a diphenyl group has a bifunctional diphenyl group.
  • the diphenyl group Since it is a D unit, three-dimensional cross-linking can be appropriately suppressed, and the fluidity of the photosensitive resin composition during baking can be improved. It is possible to control gender.
  • the diphenyl group since the diphenyl group has an increased polarizability due to the ⁇ electrons of the diphenyl group as compared with a dimethyl group, which is also a difunctional D unit, the refractive index of the cured product can be improved.
  • the photosensitive resin composition of the present invention contains (A) a siloxane resin containing an organosilane unit having a diphenyl group.
  • a siloxane resin refers to a polymer having a repeating unit having a siloxane skeleton.
  • the (A) siloxane resin in the present invention contains an organosilane unit having a diphenyl group, and is a resin obtained by hydrolyzing and then condensing an organosilane compound having a diphenyl group and another organosilane compound. is preferred.
  • organosilane compounds having a diphenyl group include diphenylsilanediol and dimethoxydiphenylsilane.
  • the content of the diphenyl group-containing organosilane unit in the siloxane resin (A) is preferably 5 mol % or more, more preferably 8 mol % or more, and even more preferably 10 mol % or more. From the viewpoint of suppressing residue during development and improving resolution, it is preferably 40 mol % or less, more preferably 35 mol % or less, and even more preferably 30 mol % or less.
  • organosilane compounds include methyltrimethoxysilane, methyltriethoxysilane, methyltri(methoxyethoxy)silane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, and ethyltrimethoxysilane.
  • ethyltriethoxysilane hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3- aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-(N,N-diglycidyl)aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino propyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 2-cyanoethyltriethoxysilane,
  • 3-trimethoxysilylpropylsuccinic anhydride 3-triethoxysilylpropylsuccinic anhydride, and 3-triphenoxysilylpropylsuccinic anhydride are used from the viewpoint of suppressing residue during development and improving resolution.
  • Organosilane compounds having a carboxyl group and/or a dicarboxylic acid anhydride structure such as cyclohexyldicarboxylic anhydride, 3-trimethoxysilylpropylcyclohexyldicarboxylic anhydride, and 3-trimethoxysilylpropylphthalic anhydride are preferred.
  • the siloxane resin contains an organosilane unit having a carboxyl group and/or a dicarboxylic anhydride structure.
  • the siloxane resin can suppress residue during development and improve adhesion to the substrate and the resin layer.
  • the siloxane resin can be obtained by hydrolyzing an organosilane compound and then condensing it.
  • it can be obtained by hydrolyzing an organosilane compound and then subjecting the obtained silanol compound to a condensation reaction in the presence or absence of an organic solvent.
  • Various conditions for the hydrolysis reaction can be appropriately set in consideration of the reaction scale, the size and shape of the reaction vessel, and so on. For example, it is preferable to add an acid catalyst and water to an organosilane compound in a solvent over 1 to 180 minutes, and then react the mixture at room temperature to 110° C. for 1 to 180 minutes. By carrying out the hydrolysis reaction under such conditions, a rapid reaction can be suppressed.
  • the reaction temperature is more preferably 30-105°C.
  • the hydrolysis reaction is preferably carried out in the presence of an acid catalyst.
  • an acid catalyst an acidic aqueous solution containing formic acid, acetic acid, phosphoric acid and nitric acid is preferred.
  • the amount of the acid catalyst to be added is preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of all the organosilane compounds used in the hydrolysis reaction. By setting the amount of the acid catalyst within the above range, the hydrolysis reaction can proceed more efficiently.
  • the reaction solution After obtaining the silanol compound by the hydrolysis reaction of the organosilane compound, it is preferable to heat the reaction solution as it is at 50°C or higher and below the boiling point of the solvent for 1 to 100 hours to carry out the condensation reaction. Moreover, in order to increase the degree of polymerization of the siloxane resin, reheating or addition of a base catalyst may be performed.
  • Examples of the organic solvent used for the hydrolysis reaction of the organosilane compound and the condensation reaction of the silanol compound include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, and 4-methyl-2-pen.
  • alcohols such as tanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, 1-t-butoxy-2-propanol, diacetone alcohol; glycols such as ethylene glycol and propylene glycol; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethyl ether, etc.
  • ketones such as methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, 2-heptanone; amides such as dimethylformamide and dimethylacetamide; ethyl acetate, propyl acetate Acetates such as , butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, butyl lactate; toluene , xylene, hexane, cyclohexane and other aromatic or aliphatic hydrocarbons, ⁇ -butyrolactone, N-methyl-2-
  • the cured product obtained by curing the photosensitive resin composition of the present invention can have high transmittance and excellent crack resistance, diacetone alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate , propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ⁇ -butyrolactone and the like are preferably used.
  • the cured product obtained by curing the photosensitive resin composition of the present invention has high transmittance and excellent crack resistance, so that the cured film and microlens using the same have these properties.
  • cured film refers to a cured product in the form of a film that is cured in the form of a film over the entire surface without forming microlenses.
  • a solvent When a solvent is generated by the hydrolysis reaction, it is possible to hydrolyze without a solvent. After completion of the reaction, it is also preferable to adjust the concentration to be appropriate for the resin composition by further adding a solvent. Further, depending on the purpose, after hydrolysis, an appropriate amount of the alcohol produced may be distilled off under heating and/or under reduced pressure, and then a suitable solvent may be added.
  • the amount of solvent used in the hydrolysis reaction is preferably 80 parts by weight or more and 500 parts by weight or less with respect to 100 parts by weight of the total organosilane compound. By setting the amount of the solvent within the above range, the hydrolysis reaction can proceed more efficiently.
  • the water used for the hydrolysis reaction is preferably ion-exchanged water.
  • the amount of water is preferably 1.0 to 4.0 mol per 1 mol of silane atoms.
  • the photosensitive resin composition of the present invention includes (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 titanium compound and a zirconium compound. , at least one selected from the group consisting of tin compounds and aluminum compounds, composite metal compound particles of a metal compound and a silicon compound (hereinafter sometimes abbreviated as (B) metal compound particles or composite metal compound particles) Contains a siloxane resin containing
  • Composite metal compound particles of a metal compound and a silicon compound include silicon oxide-metal compound composite particles obtained by synthesizing metal particles in the presence of a silicon oxide compound, and silane surface-coated metal compound particles obtained by reacting metal particles with a silane coupling agent. etc.
  • titanium compound particles, zirconium compound particles, or composite particles of a titanium compound or a zirconium compound and a silicon compound are preferred.
  • metal compound particles examples include "Nanouse” (registered trademark) OT-RB300M7-20, which is a composite particle of tin oxide, titanium oxide, and silicon oxide, and composite particles of tin oxide, titanium oxide, zirconium oxide, and silicon oxide.
  • the number average particle diameter of the metal compound particles or composite metal compound particles is preferably 1 nm or more from the viewpoint of suppressing crack generation during thick film formation. From the viewpoint of further improving the transparency to visible light of a cured product, particularly a cured film or microlens using the cured product, it is preferably 70 nm or less, more preferably 50 nm or less.
  • the number average particle size of the metal compound particles is measured by a gas adsorption method, a dynamic light scattering method, an X-ray small angle scattering method, a method of directly measuring the particle size with a transmission electron microscope or a scanning electron microscope, or the like. be able to. In the present invention, it refers to the value measured by the dynamic light scattering method.
  • the equipment used is not particularly limited, but examples include a dynamic light scattering altimeter DLS-8000 (manufactured by Otsuka Electronics Co., Ltd.).
  • the metal compound particles or the composite metal compound particles are preferably 20 parts by weight or more and 60 parts by weight or less with respect to 100 parts by weight of the total amount of the siloxane resin. It is more preferable that the amount is not less than 55 parts by weight and not more than 55 parts by weight. This makes it possible to further improve the transmittance and refractive index of the cured film and microlenses while maintaining high sensitivity, resolution and fluidity of the photosensitive resin composition.
  • the refractive index of the cured product obtained by curing the photosensitive resin composition of the present invention at a wavelength of 633 nm is preferably 1.60 or more and 1.80 or less. This is because, when the cured product has such a high refractive index, a high refractive index microlens can be formed.
  • the siloxane resin may be synthesized by hydrolyzing and partially condensing organosilane in the presence of (B) metal compound particles or composite metal compound particles.
  • the particles are surface-treated with the siloxane resin, and a photosensitive resin composition having excellent dispersion stability can be obtained. It is considered that this is because the matrix siloxane resin and the metal compound particles are bonded. This bonded state can be known by observing the interface between the metal compound particles and the siloxane resin with a scanning electron microscope or a transmission electron microscope. When both are bonded, the interface between the two is unclear.
  • the photosensitive resin composition of the present invention contains (C) a photosensitive agent.
  • C) A naphthoquinonediazide compound is preferable as the photosensitive agent.
  • the naphthoquinonediazide compound in addition to exhibiting positive photosensitivity in which the exposed areas are removed by the developer, the dissolution suppression effect is also achieved in the unexposed areas due to the interaction of the silanol groups of the siloxane resin, resulting in improved resolution. It can be improved further.
  • the naphthoquinonediazide compound a compound in which naphthoquinonediazide sulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group is preferable.
  • a naphthoquinonediazide compound can be synthesized by a known esterification reaction between a compound having a phenolic hydroxyl group and naphthoquinonediazide sulfonyl chloride.
  • naphthoquinonediazidesulfonic acid chloride as a raw material, 4-naphthoquinonediazidesulfonic acid chloride or 5-naphthoquinonediazidesulfonic acid chloride can be used.
  • a 4-naphthoquinonediazide sulfonic acid ester compound has absorption in the i-line (wavelength: 365 nm) region, and is therefore suitable for i-line exposure.
  • 5-naphthoquinonediazide sulfonic acid ester compounds have absorption in a wide range of wavelengths, so they are suitable for exposure over a wide range of wavelengths. It is preferable to select a 4-naphthoquinonediazide sulfonic acid ester compound or a 5-naphthoquinonediazide sulfonic acid ester compound depending on the wavelength of exposure.
  • a 4-naphthoquinonediazide sulfonic acid ester compound and a 5-naphthoquinonediazide sulfonic acid ester compound can also be used in combination.
  • the content of the (C) photosensitive agent in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 1% by weight or more, more preferably 3% by weight or more, relative to the total 100% by weight of the (A) siloxane resin. .
  • (A) from the viewpoint of suppressing deterioration of compatibility with siloxane resins and coloring due to decomposition during heat curing, and further improving the transparency of photosensitive resin compositions and cured products, especially cured films and microlenses. , is preferably 30% by weight or less, more preferably 20% by weight or less.
  • the photosensitive resin composition of the present invention contains (D) an organosilane compound having a condensed polycyclic aromatic group.
  • (D) By containing an organosilane compound having a condensed polycyclic aromatic group, bulky substituents are introduced at the ends of the siloxane resin by heating, and cross-linking between the ends is suppressed. The fluidity can be further improved, and the high hydrophobicity of the condensed polycyclic aromatic group enables the formation of microlenses with excellent high-temperature and high-humidity resistance.
  • organosilane compound having a condensed polycyclic aromatic group include the following compounds. 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane, 1-anthracenyltrimethoxysilane, 9-anthracenyltrimethoxysilane, 9-phenanth renyltrimethoxysilane, 9-fluorenyltrimethoxysilane, 2-fluorenyltrimethoxysilane, 1-pyrenyltrimethoxysilane, 2-indenyltrimethoxysilane, 5-acenaphthenyltrimethoxysilane and the like. . You may contain 2 or more types of these.
  • the content of (D) an organosilane compound having a condensed polycyclic aromatic group in the photosensitive resin composition of the present invention is not particularly limited, but from the viewpoint of improving fluidity, the total amount of (A) siloxane resin is 100% by weight. 0.5% by weight or more is preferable, and 1% by weight or more is more preferable. From the viewpoint of suppressing residue during development and improving resolution, it is preferably 15% by weight or less, more preferably 10% by weight or less.
  • the photosensitive resin composition of the present invention contains (E) an organic solvent.
  • the organic solvent is not particularly limited, a compound having an alcoholic hydroxyl group is preferred.
  • the use of an organic solvent having an alcoholic hydroxyl group improves the solubility of (A) the siloxane resin, (B) the metal compound particles, and (C) the photosensitive agent, and improves the transparency of the coating film obtained from the photosensitive resin composition. can be improved.
  • the organic solvent having an alcoholic hydroxyl group is not particularly limited, compounds having a boiling point of 110 to 250°C under atmospheric pressure are preferred. If the boiling point is 110° C. or higher, drying at the time of coating film formation proceeds appropriately, and a coating film with good surface appearance can be easily obtained. On the other hand, if the boiling point is 250° C. or less, the removal of the organic solvent is easy.
  • organic solvents having an alcoholic hydroxyl group include acetol (boiling point: 147°C), 3-hydroxy-3-methyl-2-butanone (boiling point: 140°C), and 4-hydroxy-3-methyl-2-butanone.
  • organic solvents may be contained together with the organic solvent or instead of the organic solvent.
  • 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.
  • esters such as butyl acetate and ethyl acetoacetate, ketones such as methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone and acetylacetone, diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether ethers, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, propylene carbonate, N-methylpyrrolidone, cyclopentanone, cyclohexanone, cycloheptanone and the like.
  • ketones such as methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone and acetylacetone
  • diethyl ether diisopropyl ether
  • the content of the (E) organic solvent in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 10 to 2,000 parts per 100 parts by weight of the total of (A) the siloxane resin and (B) the metal compound particles. 000 parts by weight.
  • the photosensitive resin composition of the present invention may contain an organosilane compound other than (D) the organosilane compound having a condensed polycyclic aromatic group as an adhesion improver.
  • an organosilane compound other than (D) the organosilane compound having a condensed polycyclic aromatic group as an adhesion improver.
  • Organosilane compounds include, for example, 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-biphenyl)dimethoxysilane, bis(4-biphenyl)diethoxysilane, triphenylmethoxysilane , triphenylethoxysilane, triphenylsilanol, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyld
  • the photosensitive resin composition of the present invention may contain a dissolution accelerator.
  • a dissolution accelerator By containing the dissolution accelerator, it is possible to suppress the residue during development and improve the resolution.
  • a compound having a phenolic hydroxyl group is preferable from the viewpoint of compatibility with (A) the siloxane resin and (C) the photosensitive agent.
  • Specific examples of compounds having a phenolic hydroxyl group include the following compounds (all available from Honshu Chemical Industry Co., Ltd.).
  • the photosensitive resin composition of the present invention may contain a surfactant.
  • a surfactant By containing a surfactant, it is possible to improve flowability during application.
  • surfactants include fluorine-based surfactants; silicone-based surfactants; silicone-modified acrylic surfactants; fluorine-containing thermally decomposable surfactants; polyether-modified siloxane-based surfactants; Surfactants; poly(meth)acrylate surfactants; anionic surfactants such as ammonium lauryl sulfate and triethanolamine polyoxyethylene alkyl ether sulfate; cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride; amphoteric surfactants such as lauryl dimethylamine oxide and lauryl carboxymethyl hydroxyethylimidazolium betaine; and nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and sorbitan monoste
  • fluorine-based surfactants silicone-based surfactants, and fluorine-containing thermally decomposable interfaces are used from the viewpoint of suppressing poor coating properties such as repellency and reducing surface tension to suppress unevenness during drying of the coating film.
  • An active agent a polyether-modified siloxane-based surfactant, is preferred.
  • fluorosurfactants include, for example, "Megafac” (registered trademark) F142D, F172, F173, F183, F445, F470, F475, F477 (manufactured by DIC Corporation). ), NBX-15, FTX-218 (manufactured by Neos Co., Ltd.) and the like.
  • silicone-based surfactants examples include “BYK” (registered trademark)-333, BYK-301, BYK-331, BYK-345, and BYK-307 (manufactured by BYK-Chemie Japan Co., Ltd.). be done.
  • fluorine-containing thermally decomposable surfactants include, for example, "Megafac” (registered trademark) DS-21 (manufactured by DIC Corporation).
  • silicone-modified acrylic surfactants include “BYK” (registered trademark)-3550 (manufactured by BYK-Chemie Japan Co., Ltd.).
  • polyether-modified siloxane-based surfactants include, for example, “BYK” (registered trademark)-345, BYK-346, BYK-347, BYK-348, BYK-349 (manufactured by BYK-Chemie Japan Co., Ltd.). (manufactured by Nissin Kagaku Kogyo Co., Ltd.), and "Silface” (registered trademark) SAG002, SAG005, SAG0503A and SAG008 (manufactured by Nissin Chemical Industry Co., Ltd.).
  • the photosensitive resin composition of the present invention may contain a dispersant.
  • dispersants include polyacrylic acid-based dispersants, polycarboxylic acid-based dispersants, phosphoric acid-based dispersants, and silicone-based dispersants.
  • the photosensitive resin composition of the present invention may contain (A) a resin other than the siloxane resin, such as an acrylic resin or an epoxy resin.
  • the photosensitive resin composition of the present invention may optionally contain components other than those listed above such as a cross-linking agent, a cross-linking accelerator, a sensitizer, a thermal radical generator, a dissolution inhibitor, a stabilizer, and an antifoaming agent. Additives such as agents can also be contained.
  • the method for producing the photosensitive resin composition of the present invention includes (A) a siloxane resin, (B) metal compound particles, (C) a photosensitive agent, (D) an organosilane compound having a condensed polycyclic aromatic group, ( E) A common method is to stir and mix an organic solvent and, if necessary, other components.
  • the formation of the dry film is carried out through the process of applying the photosensitive resin composition onto the substrate.
  • a coating film is obtained by coating a photosensitive resin composition on a glass substrate, a silicon wafer substrate, or a resin layer formed on a glass substrate and a silicon wafer.
  • Examples of the method of applying the photosensitive resin composition used at this time include spin coating using a spinner, spray coating, inkjet coating, dispenser coating, die coating, and roll coating.
  • the film thickness of the coating film can be appropriately selected depending on the coating method and the like.
  • the film thickness after drying is generally 1 to 150 ⁇ m.
  • the obtained coating film is dried to obtain a dry film.
  • the drying method include heat drying, air drying, reduced pressure drying, and infrared irradiation.
  • heat drying devices include ovens and hot plates.
  • the drying temperature is preferably 50 to 160° C., and the drying time is preferably 1 minute to several hours.
  • Formation of the cured film is preferably carried out through the following exposure step. That is, the dried film obtained above is exposed (hereinafter referred to as bleaching exposure) to about 100 to 20,000 J/m 2 (converted to a wavelength of 365 nm) using an ultraviolet-visible exposure machine such as PLA. is preferred.
  • the bleaching exposure photolyzes the unreacted naphthoquinonediazide compound remaining in the dry film, thereby further improving the transparency of the resulting cured film.
  • a cured film can be obtained by heating (curing) the bleached dry film in a temperature range of 100 to 450°C for about 30 seconds to 2 hours with a heating device such as a hot plate or an oven.
  • a microlens manufacturing method includes steps of exposing and developing a dry film obtained through the step of applying the photosensitive resin composition onto a substrate, and forming microlenses having a diameter of 10 ⁇ m or more and 50 ⁇ m or less. It is done through the process.
  • the dry film obtained above is irradiated (exposed) with actinic rays through a mask having a desired pattern to obtain an exposed film.
  • Such an exposure operation is called patterning exposure.
  • Actinic rays for patterning exposure include, for example, ultraviolet rays, visible rays, electron beams, and X-rays.
  • a stepper, mirror projection mask aligner (MPA), parallel light mask aligner (PLA) or other UV-visible exposure machine is used, and the exposure is 10 to 10,000 J through a desired mask. It is preferable to carry out patterning exposure under the condition of about /m 2 (converted to a wavelength of 365 nm exposure amount).
  • the obtained exposed film is developed using an alkaline developer or the like to remove the exposed portions, and a plurality of photosensitive resin compositions arranged two-dimensionally based on the pattern, which are the base of the microlenses, are formed. Get a column.
  • the arrangement pattern of the two-dimensionally arranged columns of the photosensitive resin composition is not particularly limited, and the arrangement interval and the size and shape of the bottoms of the columns may be set according to the object to be detected. . These can be arbitrarily set by the pattern of the mask.
  • alkaline compounds used in the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; ethylamine, n-propylamine, and the like.
  • secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH), choline quaternary ammonium salts such as; alcohol amines such as triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol and diethylaminoethanol; Examples include organic alkalis such as cyclic amines such as 1,5-diazabicyclo[4,3,0]-5-nonane and morpholine.
  • the concentration of the alkaline compound in the alkaline developer is generally 0.01-50% by weight, preferably 0.02-3% by weight.
  • a surfactant such as a nonionic surfactant may be added in an amount of 0.1 to 5% by weight.
  • a water-soluble organic solvent such as ethanol, ⁇ -butyrolactone, dimethylformamide, N-methyl-2-pyrrolidone, etc. may be added to the developer.
  • Examples of developing methods include immersion, spray, and paddle methods.
  • the obtained pattern may be rinsed with pure water or the like.
  • the obtained pattern is preferably exposed (bleaching exposure) to the entire surface at about 100 to 20,000 J/m 2 (converted to a wavelength of 365 nm) using an ultraviolet-visible exposure machine such as PLA.
  • bleaching exposure the unreacted naphthoquinonediazide compound remaining in the developed film is photolyzed, and the transparency of the resulting microlens can be further improved.
  • Step of forming a microlens with a diameter of 10 ⁇ m or more and 50 ⁇ m or less The pattern exposed by bleaching is heated (cured) in a temperature range of 100 to 450° C. for about 30 seconds to 2 hours with a heating device such as a hot plate or an oven to melt the columnar bodies of the photosensitive resin composition, Due to the surface tension of the molten photosensitive resin composition, it is possible to form microlenses having a diameter of 10 ⁇ m or more and 50 ⁇ m or less by flowing. In addition, even when the distance between adjacent microlenses is very small, independent arrayed microlenses can be formed without the adjacent columnar bodies being combined due to moderate flow in the molten state.
  • the side cross-sectional shape (curvature radius of the lens) of the microlens can be arbitrarily adjusted by appropriately setting the ratio between the bottom area and the volume of the columnar body of the photosensitive resin composition. These can be arbitrarily set according to the pattern of the mask (the bottom area of the columnar body) and the thickness of the dry film.
  • the photosensitive resin composition of the present invention is suitably used for light-emitting devices such as organic EL light-emitting devices and display devices. More specifically, a cured film, a microlens, and the like formed in the organic EL device for the purpose of improving light extraction efficiency can be mentioned.
  • a cured film or a microlens made of a cured product obtained by curing the photosensitive resin composition of the present invention is suitably used for a solid-state imaging device. More specifically, a cured film or a microlens can be used for a light-collecting microlens formed in a solid-state imaging device or the like, a white (transparent) color filter, an optical waveguide, an antireflection film installed as an optical filter, or the like. is mentioned. Among these, it has a high refractive index and transparency, and it is possible to form a lens shape even in a large microlens with a diameter of 10 ⁇ m or more.
  • a cured film or a microlens made of the cured product is particularly suitably used as a light-condensing microlens formed on a solid-state imaging device in a fingerprint authentication device.
  • a fingerprint authentication device applied to a smartphone equipped with an OLED display
  • uniform fingerprints are placed under the OLED display elements arranged in pentiles or stripes so as to be positioned in the gaps between the sub-pixels of the OLED display elements. It is preferable to arrange a plurality of shaped microlenses two-dimensionally.
  • a group of microlenses arranged two-dimensionally is called a microlens array.
  • the microlenses forming the microlens array preferably have a refractive index of 1.60 or more and 1.80 or less at a wavelength of 633 nm. More preferably, the diameter of the microlens is 10 ⁇ m or more and 50 ⁇ m or less, and the space distance between the microlenses is 0.01 ⁇ m or more and 5.0 ⁇ m or less.
  • the microlenses are preferably made of a cured product obtained by curing a photosensitive resin composition containing (A) to (D) below.
  • A a siloxane resin containing an organosilane 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 , Composite metal compound particles of at least one metal compound and silicon compound selected from the group consisting of titanium compounds, zirconium compounds, tin compounds and aluminum compounds
  • C photosensitive agent
  • D condensed polycyclic aromatic group
  • the microlens array of the present invention is suitable for use in a fingerprint authentication device as described above.
  • the molten photosensitive resin composition of the present invention flows moderately, making it possible to form microlenses with a very small distance between adjacent microlenses. Therefore, etching is unnecessary, the work can be simplified, and deterioration of the wiring portion due to the etching chemical or plasma can be avoided.
  • the photosensitive resin composition obtained in each example and comparative example was spin-coated on the resin layer-coated substrate and dried at 110° C. for 3 minutes. to prepare a dry film.
  • the obtained dry film was patterned and exposed through a reticle having a circle (diameter of 10 ⁇ m, 20 ⁇ m, 30 ⁇ m, 40 ⁇ m)/space (2 ⁇ m).
  • a reticle having a circle (diameter of 10 ⁇ m, 20 ⁇ m, 30 ⁇ m, 40 ⁇ m)/space (2 ⁇ m).
  • Mark-7 manufactured by Tokyo Electron Co., Ltd.
  • shower development was performed with a 2.38% by weight TMAH aqueous solution for 120 seconds, and then rinsed with water for 30 seconds to prepare a film after development.
  • PLA PLA-501F manufactured by Canon Inc.
  • 500 mJ 500 mJ (converted to a wavelength of 365 nm exposure).
  • A All patterns of 10 ⁇ m, 20 ⁇ m, 30 ⁇ m, and 40 ⁇ m have microlens cross-sectional shapes.
  • B Patterns of 10 ⁇ m and 20 ⁇ m have microlens cross-sectional shapes, but patterns of 30 ⁇ m and 40 ⁇ m have microlens shapes.
  • C 10 ⁇ m, 20 ⁇ m, 30 ⁇ m, and 40 ⁇ m all of the patterns do not have a microlens shape in cross section.
  • the photosensitive resin composition obtained in each example and comparative example was spin-coated on an 8-inch silicon wafer substrate and dried at 110° C. for 3 minutes to prepare a dry film.
  • PLA was used to expose the entire surface of the film to an ultra-high pressure mercury lamp at 500 mJ (converted to a wavelength of 365 nm exposure).
  • the refractive index at 22° C. and 550 nm was measured using a spectroscopic ellipsometer FE5000 manufactured by Otsuka Electronics Co., Ltd.
  • the photosensitive resin composition obtained in each example and comparative example was spin-coated using Mark-7 and at 110 ° C. Drying was performed for 3 minutes to prepare a dry film.
  • the film was subjected to shower development with a 2.38% by weight TMAH aqueous solution using Mark-7 for 120 seconds and then rinsed with water for 30 seconds to prepare a post-development film.
  • PLA was used to expose the entire surface of the film to an ultra-high pressure mercury lamp at 500 mJ (converted to a wavelength of 365 nm exposure).
  • the photosensitive resin composition obtained in each example and comparative example was spin-coated using Mark-7 and at 110 ° C. Drying was performed for 3 minutes to prepare a dry film.
  • PLA was used to expose the entire surface of the film to an ultra-high pressure mercury lamp at 500 mJ (converted to a wavelength of 365 nm exposure). Then, it was cured at 200° C. for 30 minutes using an oven to prepare a cured film having a thickness of 5.0 ⁇ m.
  • the resulting cured film was put into a high-temperature and high-humidity tester (trade name “Q-Sun”, manufactured by Q-Lab) under conditions of 85° C./85% for 240 hours. Adhesion was evaluated for the formed cured film. That is, on the surface of the cured film on the resin layer-formed substrate, 11 vertical and horizontal parallel straight lines were drawn at intervals of 1 mm with a cutter knife so as to reach the substrate of the silicon wafer, and a grid of 1 mm ⁇ 1 mm was formed. 100 were produced.
  • a cured film and microlenses were produced by the method described above and evaluated by the method described above.
  • Example 2 A photosensitive resin composition A-2 was prepared in the same manner as in Example 1, except that the siloxane resin solution (PS-2) was used instead of the siloxane resin solution (PS-1). Evaluation was performed in the same manner as in Example 1 using the resulting photosensitive resin composition A-2.
  • Example 3 A photosensitive resin composition A-3 was prepared in the same manner as in Example 1, except that the siloxane resin solution (PS-3) was used instead of the siloxane resin solution (PS-1). Evaluation was performed in the same manner as in Example 1 using the resulting photosensitive resin composition A-3.
  • Example 4 A photosensitive resin composition A-4 was prepared in the same manner as in Example 1, except that the siloxane resin solution (PS-4) was used instead of the siloxane resin solution (PS-1). Evaluation was performed in the same manner as in Example 1 using the resulting photosensitive resin composition A-4.
  • Example 5 A photosensitive resin composition A-5 was prepared in the same manner as in Example 1, except that the siloxane resin solution (PS-5) was used instead of the siloxane resin solution (PS-1). Evaluation was performed in the same manner as in Example 1 using the resulting photosensitive resin composition A-5.
  • Example 6 Photosensitivity was obtained in the same manner as in Example 3 except that the amount of the siloxane resin solution (PS-3) added was changed to 53.12 g and the amount of the metal compound particle dispersion (T-1) added was changed to 30.14 g. A resin composition A-6 was prepared. Evaluation was performed in the same manner as in Example 1 using the resulting photosensitive resin composition A-6.
  • Example 7 Photosensitivity was obtained in the same manner as in Example 3 except that the amount of the siloxane resin solution (PS-3) added was changed to 59.78 g and the amount of the metal compound particle dispersion (T-1) added was changed to 23.48 g. A resin composition A-7 was prepared. Evaluation was performed in the same manner as in Example 1 using the resulting photosensitive resin composition A-7.
  • Example 8 Photosensitivity was obtained in the same manner as in Example 3 except that the amount of the siloxane resin solution (PS-3) added was changed to 39.80 g and the amount of the metal compound particle dispersion (T-1) added was changed to 43.46 g. A resin composition A-8 was prepared. Evaluation was performed in the same manner as in Example 1 using the resulting photosensitive resin composition A-8.
  • Example 9 Photosensitivity was obtained in the same manner as in Example 3 except that the amount of the siloxane resin solution (PS-3) added was changed to 33.14 g and the amount of the metal compound particle dispersion (T-1) added was changed to 50.12 g. A resin composition A-9 was prepared. Evaluation was performed in the same manner as in Example 1 using the resulting photosensitive resin composition A-9.
  • Example 10 First, under a yellow light, the following raw materials were mixed and stirred. ⁇ A mixed solution of 2.76 g of DAA and 5.34 g of EAA using 2.05 g of naphthoquinone diazide compound (QD-1), 1.37 g of naphthoquinone diazide compound (QD-2), and 1.71 g of phenol compound TrisP-PA as an organic solvent. the solution used and dissolved therein, - As an organosilane compound having a condensed polycyclic aromatic group, trade name "Z-6874" manufactured by Dow Toray Industries, Inc.
  • the obtained photosensitive resin composition A-10 was evaluated in the same manner as in Example 1.
  • Example 11 First, under a yellow light, the following raw materials were mixed and stirred. ⁇ A mixed solution of 6.04 g of DAA and 5.34 g of EAA using 1.92 g of naphthoquinone diazide compound (QD-1), 1.28 g of naphthoquinone diazide compound (QD-2), and 1.60 g of phenol compound TrisP-PA as an organic solvent. the solution used and dissolved therein, - As an organosilane compound having a condensed polycyclic aromatic group, trade name "Z-6874" manufactured by Dow Toray Industries, Inc.
  • the obtained photosensitive resin composition A-11 was evaluated in the same manner as in Example 1.
  • a photosensitive resin composition A-12 was prepared in the same manner as in Example 1, except that the siloxane resin solution (PS-6) was used instead of the siloxane resin solution (PS-1). Evaluation was performed in the same manner as in Example 1 using the resulting photosensitive resin composition A-12.
  • the obtained photosensitive resin composition A-11 was evaluated in the same manner as in Example 1.
  • a photosensitive resin composition A-14 was prepared in the same manner as in Example 1, except that the siloxane resin solution (PS-7) was used instead of the siloxane resin solution (PS-1). Evaluation was performed in the same manner as in Example 1 using the resulting photosensitive resin composition A-14.
  • a photosensitive resin composition A-15 was prepared in the same manner as in Example 1, except that the siloxane resin solution (PS-8) was used instead of the siloxane resin solution (PS-1). Evaluation was performed in the same manner as in Example 1 using the resulting photosensitive resin composition A-15.
  • the obtained photosensitive resin composition A-16 was evaluated in the same manner as in Example 1.
  • the obtained photosensitive resin composition A-17 was evaluated in the same manner as in Example 1.
  • Example 10 Same as Example 1 except that vinyltris(2-methoxyethoxy)silane (trade name “KBC-103” manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of “Z-6874” manufactured by Dow Toray Industries, Inc. (trade name).
  • a photosensitive resin composition A-21 was prepared in the same manner. Evaluation was performed in the same manner as in Example 1 using the resulting photosensitive resin composition A-21.
  • Example 11 Same as Example 1 except that 3-methacryloxypropyltrimethoxysilane (trade name “KBM-503” manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of “Z-6874” manufactured by Dow Toray Industries, Inc. (trade name).
  • a photosensitive resin composition A-22 was prepared in the same manner. Evaluation was performed in the same manner as in Example 1 using the resulting photosensitive resin composition A-22.
  • Example 12 Same as Example 1 except that 3-methacryloxyoctyltrimethoxysilane (trade name “KBM-5803” manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of “Z-6874” manufactured by Dow Toray Industries, Inc. (trade name).
  • a photosensitive resin composition A-23 was prepared in the same manner. Evaluation was performed in the same manner as in Example 1 using the resulting photosensitive resin composition A-23.
  • Tables 1 and 2 show the composition of the resin composition in each example and comparative example, and Table 3 shows the evaluation results.
  • the photosensitive resin composition produced in the examples it has a high refractive index and transparency, and has high fluidity even at a baking temperature of 230° C. or less. can be formed.
  • the photosensitive resin composition of the present invention has a high refractive index and transparency, high fluidity even at a baking temperature of 230° C. or less, and forms a lens shape even in large microlenses with a diameter of 10 ⁇ m or more. Therefore, it can be suitably used as a microlens used in a CMOS image sensor or a fingerprint authentication device.

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Abstract

La présente invention vise à fournir une composition de résine photosensible ayant un indice de réfraction élevé et une transparence élevée, ayant une fluidité élevée même à une température de cuisson de 230 °C ou moins, et étant apte à former une grande microlentille ayant un diamètre de 10 µm ou plus. Une composition de résine photosensible est caractérisée en ce qu'elle comprend : (A) une résine de siloxane contenant une unité organosilane ayant un groupe diphényle ; (B) des particules de composé métallique composite d'un composé métallique et d'un composé de silicium d'au moins un type sélectionné dans le groupe constitué par des particules de composé de titane, des particules de composé de zirconium, des particules de composé d'étain et des particules de composé d'aluminium ou au moins un type sélectionné dans le groupe constitué par les composés de titane, les composés de zirconium, les composés d'étain et les composés d'aluminium ; (C) un photosensibilisateur ; (D) un composé organosilane ayant un groupe aromatique polycyclique condensé ; et (E) un solvant organique.
PCT/JP2022/035589 2021-09-29 2022-09-26 Composition de résine photosensible, microlentille WO2023054226A1 (fr)

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JP2015127803A (ja) * 2013-11-29 2015-07-09 東レ株式会社 感光性樹脂組成物、それを硬化させてなる硬化膜ならびにそれを具備する発光素子および固体撮像素子
WO2018216570A1 (fr) * 2017-05-24 2018-11-29 東レ株式会社 Composition de résine photosensible négative et film durci

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CN110473887A (zh) 2018-08-21 2019-11-19 神盾股份有限公司 光学传感器、光学传感系统及其制造方法
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JP2015127803A (ja) * 2013-11-29 2015-07-09 東レ株式会社 感光性樹脂組成物、それを硬化させてなる硬化膜ならびにそれを具備する発光素子および固体撮像素子
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