CN117859098A

CN117859098A - Photosensitive resin composition and microlens

Info

Publication number: CN117859098A
Application number: CN202280058015.6A
Authority: CN
Inventors: 福崎雄介; 小林秀行; 诹访充史
Original assignee: Toray Industries Inc
Current assignee: Toray Industries Inc
Priority date: 2021-09-29
Filing date: 2022-09-26
Publication date: 2024-04-09
Also published as: TW202323395A; WO2023054226A1

Abstract

A photosensitive resin composition which has a high refractive index and transparency, has high fluidity at a firing temperature of 230 ℃ or lower, and can form a large microlens having a diameter of 10 [ mu ] m or more. A photosensitive resin composition characterized by comprising: (A) A siloxane resin containing organosilane units having diphenyl groups; (B) A metal compound particle or a composite metal compound particle, wherein the metal compound particle is at least 1 metal compound particle selected from the group consisting of a titanium compound particle, a zirconium compound particle, a tin compound particle, and an aluminum compound particle, and the composite metal compound particle is a composite metal compound particle of at least 1 metal compound selected from the group consisting of a titanium compound, a zirconium compound, a tin compound, and an aluminum compound, and a silicon compound; (C) a sensitizer; (D) An organosilane compound having a condensed polycyclic aromatic group; (E) an organic solvent.

Description

Photosensitive resin composition and microlens

Technical Field

The present invention relates to a photosensitive resin composition, a microlens obtained by curing the photosensitive resin composition, and a light emitting element, a solid-state imaging element (solid state image sensor), and a fingerprint authentication device each provided with the microlens.

Background

In various portable display terminals such as smartphones and tablet PCs (personal computers), biometric authentication is indispensable for unlocking and authenticating other subjects. Particularly, fingerprint authentication is mounted on a large number of terminals because it is inexpensive, compact, and highly convenient.

Conventionally, a capacitive fingerprint authentication device is generally mounted in a frame (bezel) portion of a display (in the periphery of the display). However, in the smart phone, the full screen display of the display tends to be displayed, and the frame on which the conventional fingerprint authentication device is mounted tends to be lost. Therefore, the fingerprint authentication device needs to be arranged in the lower part of the display (this configuration is referred to as "under screen").

As an authentication method of the under-screen fingerprint authentication device, an optical type and an ultrasonic type are exemplified, but among them, particularly, an optical type is mainly used because it can be introduced not only into an organic light emitting diode (hereinafter abbreviated as OLED) display but also into versatility such as a liquid crystal display.

As such an under-screen fingerprint authentication device, a thin optical under-screen fingerprint authentication device has been proposed which has high authentication accuracy and can be installed in a very narrow area between a battery and a screen (for example, see patent documents 1 and 2), and a microlens (a lens having a diameter in the range of 1 μm to 500 μm) is incorporated as a means for improving the authentication accuracy in these devices.

As a method of forming microlenses used in the optical under-screen fingerprint authentication device described in patent document 1 or patent document 2, there are a method of processing an inorganic film formed by a CVD method or the like by dry etching and a method of processing a photosensitive material by coating, but in the former method, it is difficult to form a plurality of microlenses into a uniform shape on a substrate having a large substrate size, and the latter method is attracting attention.

Although a fingerprint authentication device having excellent authentication accuracy can be obtained by the techniques described in patent documents 1 and 2, it is necessary to provide a microlens with a high refractive index in order to further improve authentication accuracy.

Further, since the diameter of a microlens applied to a fingerprint authentication device is about 10 μm to 40 μm, which is larger than that of a microlens of a diameter of about several μm applied to a CMOS image sensor or the like, and since there is a limitation in view of heat resistance of a resin layer formed under a lens such as a collimator, it is necessary to burn at a temperature of 230 ℃ or less, and therefore a material excellent in fluidity at the time of burning is required.

As a photosensitive material having a high refractive index and transparency, a silicone resin composition containing metal compound particles is disclosed (for example, see patent document 3), but formation of large microlenses having a diameter of 10 μm or more, such as those used in fingerprint sensors, is difficult.

As a photosensitive material having a high refractive index and capable of forming a lens, a silicone resin composition containing metal compound particles is disclosed (for example, see patent document 4), but the fluidity is low at a firing temperature of 230 ℃ or less, and the formation of microlenses is difficult.

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 2020-35327

Patent document 2: WO2020/038408

Patent document 3: WO2011/040248 number

Patent document 4: japanese patent laid-open No. 2015-127803

Disclosure of Invention

Problems to be solved by the invention

The present invention has been made in view of the problems of the prior art, and provides a photosensitive resin composition which has a high refractive index and transparency and also has high fluidity at a firing temperature of 230 ℃ or lower and can form a large microlens having a diameter of 10 μm or more.

Means for solving the problems

The object of the present invention is achieved by the following constitution. That is to say,

[1] a photosensitive resin composition comprising the following (A) to (E).

(A) A silicone resin comprising an organosilane unit having a diphenyl group,

(B) A metal compound particle or a composite metal compound particle, wherein the metal compound particle is at least 1 selected from the group consisting of a titanium compound particle, a zirconium compound particle, a tin compound particle, and an aluminum compound particle, the composite metal compound particle is a composite metal compound particle of at least 1 selected from the group consisting of a titanium compound, a zirconium compound, a tin compound, and an aluminum compound, and a silicon compound,

(C) The photosensitive agent is used for preparing the photosensitive agent,

(D) An organosilane compound having a condensed polycyclic aromatic group,

(E) An organic solvent.

[2] The photosensitive resin composition according to [1], wherein the silicone resin (A) contains 5mol% or more and 40mol% or less of an organosilane unit having a diphenyl group.

[3] The photosensitive resin composition according to the above [1] or [2], wherein the (A) siloxane resin contains an organosilane unit having a carboxyl group and/or a dicarboxylic anhydride structure.

[4] The photosensitive resin composition according to any one of [1] to [3], wherein the number average particle diameter of the metal compound particles or composite metal compound particles (B) is 1nm to 70nm.

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the total amount of the metal compound particles or composite metal compound particles (B) is 20 parts by weight or more and 60 parts by weight or less based on 100 parts by weight of the silicone resin.

[6] The photosensitive resin composition according to any one of [1] to [5], wherein the sensitizer (C) is a naphthoquinone diazonium compound.

[7] A cured product obtained by curing the photosensitive resin composition according to any one of the above items [1] to [6 ].

[8] The cured product according to [7], wherein the refractive index at a wavelength of 633nm is 1.60 or more and 1.80 or less.

[9] A cured film made of the cured product of the above [7] or [8 ].

[10] A microlens made of the cured product of the above [7] or [8 ].

[11] A method for manufacturing a microlens, comprising the steps of: a step of coating the photosensitive resin composition of any one of [1] to [6] on a substrate; a step of performing exposure; a step of developing; and forming microlenses having a diameter of 10 μm or more and 50 μm or less.

[12] A solid-state imaging device comprising the cured film according to [9] or the microlens according to [10 ].

[13] A fingerprint authentication device comprising the cured film according to [9] or the microlens according to [10 ].

[14] A microlens array having a plurality of microlenses arranged two-dimensionally, wherein the refractive index of the microlenses at a wavelength of 633nm is 1.60 to 1.80 inclusive, the diameter of the microlenses is 10 to 50 [ mu ] m inclusive, and the distance between the microlenses is 0.01 to 5.0 [ mu ] m inclusive.

[15] The microlens array according to item [14], wherein the microlenses are made of a cured product obtained by curing a photosensitive resin composition containing the following (A) to (D).

(A) A silicone resin comprising an organosilane unit having a diphenyl group,

(C) The photosensitive agent is used for preparing the photosensitive agent,

(D) An organosilane compound having a condensed polycyclic aromatic group.

[16] A fingerprint authentication device comprising a microlens array according to [14] or [15] above.

ADVANTAGEOUS EFFECTS OF INVENTION

The photosensitive resin composition of the present invention has a high refractive index and transparency, and also has high fluidity at a firing temperature of 230 ℃ or lower, and can form a large microlens having a diameter of 10 μm or more.

Drawings

Fig. 1 is a sectional view showing an example of the shape of a microlens.

Fig. 2 is a cross-sectional view showing an example of a shape other than a microlens.

Detailed Description

The present invention will be described in further detail below.

The photosensitive resin composition of the present invention is a photosensitive resin composition comprising the following (a) to (E).

(A) A silicone resin comprising an organosilane unit having a diphenyl group,

(B) A metal compound particle or a composite metal compound particle, wherein the metal compound particle is at least 1 metal compound particle selected from the group consisting of a titanium compound particle, a zirconium compound particle, a tin compound particle and an aluminum compound particle, the composite metal compound particle is a composite metal compound particle of at least 1 metal compound selected from the group consisting of a titanium compound, a zirconium compound, a tin compound and an aluminum compound and a silicon compound,

(C) The photosensitive agent is used for preparing the photosensitive agent,

(D) An organosilane compound having a condensed polycyclic aromatic group,

(E) An organic solvent.

In the following, the (a) silicone resin containing an organosilane unit having a diphenyl group may be abbreviated as (a) silicone resin. In the present invention, the silicone resin (a) is contained, whereby a microlens having high transparency and excellent heat resistance and weather resistance can be formed. This is because (a) the silicone resin has a silicone skeleton in the main chain. Further, compared with a siloxane resin composed of only 3-functional T units resulting from 3-dimensional crosslinking, since (a) a siloxane resin containing organosilane units having a diphenyl group is a 2-functional D unit, 3-dimensional crosslinking can be suitably suppressed, fluidity of the photosensitive resin composition at the time of firing can be improved, and fluidity can be controlled by adjusting the content of organosilane units having a diphenyl group. Further, since diphenyl has higher polarization by pi electrons of diphenyl compared with dimethyl or the like which is a 2-functional D unit, the refractive index of the cured product can be improved.

Further, by containing (B) metal compound particles or composite metal compound particles, the metal compound particles are at least 1 metal compound particle selected from the group consisting of titanium compound particles, zirconium compound particles, tin compound particles and aluminum compound particles, and the composite metal compound particles are composite metal compound particles of at least 1 metal compound selected from the group consisting of titanium compounds, zirconium compounds, tin compounds and aluminum compounds and silicon compounds, a cured product having a high refractive index can be obtained, whereby microlenses having a high refractive index can be formed.

By containing the photosensitive agent (C), positive type photosensitivity is exhibited in which the light irradiation portion is removed by the developer, and positive type pattern processing can be performed.

Further, since the organosilane compound having a condensed polycyclic aromatic group is contained in (D), a bulky substituent is introduced into the terminal end of the silicone resin by heating, and crosslinking between the terminal ends is suppressed, the fluidity of the photosensitive resin composition at the time of firing can be further improved, and a microlens excellent in high-temperature and high-humidity resistance can be formed by the high hydrophobicity of the condensed polycyclic aromatic group.

Further, by containing the organic solvent (E), wet coating such as spin coating and slit coating can be performed, and the resin composition can be easily adjusted to a viscosity suitable for coating, thereby improving uniformity of the coating film.

The photosensitive resin composition of the present invention contains (A) a silicone resin containing an organosilane unit having a diphenyl group. The silicone resin is a polymer containing a repeating unit having a silicone skeleton. The silicone resin (a) in the present invention contains an organosilane unit having a diphenyl group, but is preferably a resin obtained by hydrolyzing and condensing an organosilane compound having a diphenyl group with another organosilane compound.

Specific examples of the organosilane compound having a diphenyl group include diphenylsilanediol and dimethoxydiphenylsilane. From the viewpoint of improving flowability, the content of the organosilane unit having a diphenyl group in the (a) silicone resin is preferably 5mol% or more, more preferably 8mol% or more, and still more preferably 10mol% or more. Further, from the viewpoint of suppressing residues at the time of development and improving resolution, it is preferably 40mol% or less, more preferably 35mol% or less, and further preferably 30mol% or less.

Specific examples of the other organosilane compounds include methyltrimethoxysilane, methyltriethoxysilane, methyltrisiloxane (methoxyethoxy) silane, methyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 2-cyanoethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 1-glycidoxylethyl trimethoxysilane, 1-glycidoxylethyl triethoxysilane, 2-glycidoxyethyl triethoxysilane, 2-glycidoxypropyl silane, 2-glycidoxypropyl triethoxysilane, 2-glycidoxypropyl-2-glycidoxypropyl silane, and 2-glycidoxypropyl-triethoxysilane 3-epoxypropoxypropyl trimethoxysilane, 3-epoxypropoxypropyl triethoxysilane, 3-epoxypropoxypropyl tripropoxysilane, 3-epoxypropoxypropyl triisopropoxysilane, 3-epoxypropoxypropyl tributoxysilane, 3-epoxypropoxypropyl tris (methoxyethoxy) silane, 1-epoxypropoxybutyl trimethoxysilane, 1-epoxypropoxybutyl triethoxysilane, 2-epoxypropoxybutyl trimethoxysilane, 2-epoxypropoxybutyl triethoxysilane, 3-epoxypropoxybutyl trimethoxysilane, 3-epoxypropoxybutyl triethoxysilane, 4-epoxypropoxybutyl trimethoxysilane, 4-epoxypropoxybutyl triethoxysilane, (3, 4-epoxycyclohexyl) methyltrimethoxysilane, (3, 4-epoxycyclohexyl) methyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltripropoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltributoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) methyltrimethoxysilane, 3- (3, 4-epoxycyclohexyl) epoxypropyl silane, 3- (3, 4-epoxycyclohexyl) phenyloxy silane 4- (3, 4-epoxycyclohexyl) butyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, epoxypropoxymethyldimethoxysilane, epoxypropoxymethyldiethoxysilane, 1-epoxypropoxyethylmethyldimethoxysilane, 1-epoxypropoxyethylmethyldiethoxysilane, 2-epoxypropoxyethylmethyldimethoxysilane, 2-epoxypropoxyethylmethyldiethoxysilane, 1-epoxypropoxypropylmethyldimethoxysilane, epoxypropoxyethylmethyldimethoxysilane 1-glycidoxypropyl methyl diethoxy silane, 2-glycidoxypropyl methyl dimethoxy silane, 2-glycidoxypropyl methyl diethoxy silane, 3-glycidoxypropyl methyl dimethoxy silane, 3-glycidoxypropyl methyl diethoxy silane, 3-glycidoxypropyl methyl dipropoxy silane, 2-glycidoxypropyl methyl dibutoxy silane, 3-glycidoxypropyl methyl bis (methoxyethoxy) silane, 3-glycidoxypropyl ethyl dimethoxy silane, 3-glycidoxypropyl ethyl diethoxy silane, 3-chloropropylmethyl dimethoxy silane, 3-chloropropylmethyl diethoxy silane, cyclohexyl methyl dimethoxy silane, octadecylmethyldimethoxy silane, tetramethoxy silane, tetraethoxy silane, trifluoromethyl trimethoxy silane, trifluoromethyl triethoxy silane, trifluoropropyl trimethoxy silane, trifluoropropyl triethoxy silane, perfluoropropyl trimethoxy silane, perfluoropropyl triethoxy silane, perfluoropentyl trimethoxy silane, perfluoropentyl triethoxy silane, tridecafluorooctyl trimethoxy silane, tridecafluorooctyl triethoxy silane, tridecafluorooctyl tripropoxy silane, tridecafluorooctyl triisopropoxy silane, heptadecafluorodecyl trimethoxy silane, heptadecafluorodecyl triethoxy silane, bis (trifluoromethyl) dimethoxy silane, bis (trifluoropropyl) diethoxy silane, trifluoropropyl methyl dimethoxy silane trifluoropropyl methyl diethoxy silane, trifluoropropyl ethyl dimethoxy silane, trifluoropropyl ethyl diethoxy silane, heptadecafluoro decyl methyl dimethoxy silane, 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-triphenoxysilylpropyl succinic anhydride, 3-trimethoxysilylpropyl cyclohexyl dimethoxy anhydride, 3-trimethoxysilylpropyl phthalic anhydride, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (methoxyethoxy) silane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethylbis (methoxyethoxy) silane, allyltrimethoxysilane, allyltriethoxysilane, vinyltriethoxysilane, allyl tris (methoxyethoxy) silane, phenyl methyl dimethoxy silane, allyl methyl diethoxy silane, allyl methyl bis (methoxyethoxy) silane, styryl trimethoxy silane, styryl triethoxy silane, styryl tris (methoxyethoxy) silane, styryl methyl dimethoxy silane, styryl methyl diethoxy silane, styryl methyl bis (methoxyethoxy) silane, 3-acryloxypropyl trimethoxy silane, 3-acryloxypropyl triethoxy silane, 3-acryloxypropyl tris (methoxyethoxy) silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxy silane, 3-methacryloxypropyl tris (methoxyethoxy) silane, 3-methacryloxypropyl methyl dimethoxy silane, 3-methacryloxypropyl methyl diethoxy silane, 3-acryloxypropyl methyl dimethoxy silane, 3-acryloxypropyl (methoxyethoxy) silane, 1-naphtyl trimethoxy silane, 1-naphtyl triethoxy silane, 1-naphtyl-trimethoxy silane, 1-naphtyl-9-trimethoxy silane, 9-trimethoxy-naphtyl silane, 2-fluorenyl trimethoxysilane, 2-fluorenonyl trimethoxysilane, 1-pyrenyl trimethoxysilane, 2-indenyl trimethoxysilane, 5-acenaphthylenyl trimethoxysilane, and the like. More than 2 of them may be used. Among them, from the viewpoint of suppressing residues at the time of development and improving resolution, an organosilane compound having a carboxyl group and/or a dicarboxylic anhydride structure such as 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-triphenoxysilylpropyl succinic anhydride, 3-trimethoxysilylpropyl cyclohexyl dicarboxylic anhydride, or 3-trimethoxysilylpropyl phthalic anhydride is preferable. By using such a compound, the (a) siloxane resin contains an organosilane unit having a carboxyl group and/or a dicarboxylic anhydride structure. The silicone resin (a) has such a structure, whereby the residue at the time of development can be suppressed, and the adhesion to the substrate and the resin layer can be improved.

(A) The silicone resin can be obtained by subjecting an organosilane compound to hydrolysis and condensation. For example, the compound can be obtained by hydrolyzing an organosilane compound and then subjecting the obtained silanol compound to a condensation reaction in the presence of an organic solvent or in the absence of a solvent.

The various conditions for the hydrolysis reaction can be appropriately set in consideration of the scale of the reaction, the size and shape of the reaction vessel, and the like. For example, it is preferable that the acid catalyst and water are added to the organosilane compound in a solvent for 1 to 180 minutes and then reacted at room temperature to 110℃for 1 to 180 minutes. By performing the hydrolysis reaction under such conditions, the rapid reaction can be suppressed. The reaction temperature is more preferably 30 to 105 ℃.

The hydrolysis reaction is preferably carried out in the presence of an acid catalyst. The acid catalyst is preferably an acidic aqueous solution containing formic acid, acetic acid, phosphoric acid, and nitric acid. The amount of the acid catalyst to be added is preferably 0.05 to 5 parts by weight based on 100 parts by weight of the total organosilane compound used in the hydrolysis reaction. By setting the amount of the acid catalyst to the above range, the hydrolysis reaction can be performed more efficiently.

Preferably, after the silanol compound is obtained by hydrolysis reaction of the organosilane compound, the reaction solution is directly heated at 50 ℃ or higher and at a temperature of not higher than the boiling point of the solvent for 1 to 100 hours to carry out the condensation reaction. In addition, reheating or addition of a base catalyst may be performed in order to increase the polymerization degree of the silicone resin.

Examples of the organic solvent used in the hydrolysis reaction of the organosilane compound and the condensation reaction of the silanol compound include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, 1-t-butoxy-2-propanol, diacetone alcohol, and the like; glycols such as ethylene glycol and propylene glycol; ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and diethyl ether; ketones such as methyl ethyl ketone, acetyl acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, and 2-heptanone; amides such as dimethylformamide and dimethylacetamide; acetic acid esters 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, gamma-butyrolactone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and the like. More than 2 of them may be used. In order to obtain a cured product having high transmittance and excellent crack resistance, which is obtained by curing the photosensitive resin composition of the present invention, diacetone alcohol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, γ -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, and a cured film and a microlens using the cured product are preferable because of these characteristics. The cured film herein refers to a film-form cured product cured in the form of a whole film without forming microlenses.

In the case where the solvent is produced by the hydrolysis reaction, the hydrolysis can be performed under the condition of no solvent. It is also preferable to adjust the concentration to an appropriate concentration as the resin composition by further adding a solvent after the completion of the reaction. After the hydrolysis according to the purpose, the produced alcohol and the like may be appropriately distilled off and removed under heating and/or reduced pressure, and then a suitable solvent may be added.

The amount of the solvent used in the hydrolysis reaction is preferably 80 parts by weight or more and 500 parts by weight or less relative to 100 parts by weight of the total organosilane compound. By setting the amount of the solvent to the above range, the hydrolysis reaction can be performed more efficiently.

The water used in the hydrolysis reaction is preferably ion-exchanged water. The amount of water is preferably 1.0 to 4.0 moles relative to 1 mole of the silane atom.

The photosensitive resin composition of the present invention contains a silicone resin containing (B) metal compound particles or composite metal compound particles, wherein the metal compound particles are at least 1 metal compound particles selected from the group consisting of titanium compound particles, zirconium compound particles, tin compound particles and aluminum compound particles, and the composite metal compound particles are composite metal compound particles of at least 1 metal compound selected from the group consisting of titanium compounds, zirconium compounds, tin compounds and aluminum compounds and a silicon compound (hereinafter, may be abbreviated as (B) metal compound particles or composite metal compound particles).

Examples of the composite metal compound particles of the metal compound and the silicon compound include silica-metal compound composite particles in which metal particles are synthesized in the presence of a silicon oxide compound, silane surface-coated metal compound particles obtained by reacting metal particles with a silane coupling agent, and the like. Among them, titanium compound particles, zirconium compound particles, or composite particles of a titanium compound or a zirconium compound and a silicon compound are preferable. In addition, 2 or more of them may be contained. By containing the metal compound particles, a high refractive index can be imparted to the cured product. The cured product having a high refractive index can provide a cured film or microlens using the same with a high refractive index.

Examples of the metal compound particles include, for example, the "nude" (registered trademark) OT-RB300M7-20 as composite particles of tin oxide, titanium oxide, and silicon oxide, the "nude" (r/v) OT-RA-305M7-20 (all manufactured by japanese chemical Co., ltd.) as composite particles of tin oxide, titanium oxide, and silicon oxide, the "nude" (registered trademark) TR-502 as composite particles of tin oxide and titanium oxide, the "nude" (r/v) TR-504, the "nude" (r/v) TR-503, the "nude" (r/v) TR-513 ", the" nude "(r/v) TR-504, the" nude "(r/v) TR-513", the "nude" r/v ", the" nude "TR-503, the" nude "TR-513", the "r-503, and the" nude (r "r the" on-the-road "TR-520, the" on-the-road "TR-527, the" on-the-road "TR-528, the" on-the-road "TR-529, the" on-the-road "TR-543, the" on-the-road "TR-544, the" on-the-road "TR-550 of titania particles, the" on-the-road "TR-505 (both of which are manufactured by catalytic chemical industry, inc.), the" on-the-road "OZ-S30M (manufactured by daily chemical industry, inc.), the" DLZ-003W (manufactured by chemical industry, inc.), the "SZR-M (manufactured by chemical industry, inc.) of zirconia particles, and the like. They may be contained in 2 or more kinds thereof.

The number average particle diameter of the metal compound particles or the composite metal compound particles (B) is preferably 1nm or more from the viewpoint of suppressing occurrence of cracks at the time of forming a thick film. In addition, from the viewpoint of further improving the transparency of the cured product, particularly the cured film and microlens using the same, to visible light, it is preferably 70nm or less, more preferably 50nm or less. The number average particle diameter of the metal compound particles can be measured by a method of directly measuring the particle diameter by a gas adsorption method, a dynamic light scattering method, an X-ray small angle scattering method, a transmission electron microscope, a scanning electron microscope, or the like. In the present invention, the value measured by the dynamic light scattering method is referred to. The equipment used is not particularly limited, and examples thereof include dynamic light scattering altimeter DLS-8000 (manufactured by Otsuka electronics Co., ltd.).

In the photosensitive composition of the present invention, the total amount of the metal compound particles or the composite metal compound particles (B) is preferably 20 parts by weight or more and 60 parts by weight or less, more preferably 25 parts by weight or more and 55 parts by weight or less, relative to 100 parts by weight of the silicone resin. This can further improve the transmittance and refractive index of the cured film and the microlens 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 633nm is preferably 1.60 or more and 1.80 or less. The reason is that the cured product has such a high refractive index, and thus a microlens having a high refractive index can be formed.

In the photosensitive composition of the present invention, the siloxane resin (a) can be synthesized by hydrolyzing and partially condensing an organosilane in the presence of the metal compound particles (B) or the composite metal compound particles. Thus, the particles are surface-treated with the silicone resin, and a photosensitive resin composition having excellent dispersion stability can be obtained. This is considered to be because the silicone resin of the matrix is bonded to the metal compound particles. The bonded state can be obtained by observing the boundary portion between the metal compound particles and the silicone resin with a scanning electron microscope and a transmission electron microscope. The interface between the two is not clear in the case where the two are combined.

The photosensitive resin composition of the present invention contains (C) a photosensitive agent. As the sensitizer (C), a naphthoquinone diazonium compound is preferable. By containing the naphthoquinone diazo compound, in addition to the positive photosensitivity in which the exposed portion is removed by the developer, the dissolution inhibiting effect is exerted by the interaction of silanol groups of the silicone resin in the unexposed portion, and therefore the resolution can be further improved. The naphthoquinone diazonium compound is preferably a compound in which naphthoquinone diazonium sulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group.

Specific examples of the compound having a phenolic hydroxyl group include the following compounds (all available from chemical industries, ltd.) below.

The naphthoquinone diazonium compound can be synthesized by a known esterification reaction between a compound having a phenolic hydroxyl group and naphthoquinone diazonium sulfonyl chloride. As the naphthoquinone diazonium sulfonyl chloride to be used as a raw material, 4-naphthoquinone diazonium sulfonyl chloride or 5-naphthoquinone diazonium sulfonyl chloride can be used. The 4-naphthoquinone diazonium sulfonate compound is suitable for i-ray exposure because it has absorption in the i-ray (wavelength 365 nm) region. Further, the 5-naphthoquinone diazonium sulfonate compound is suitable for exposure at a wide range of wavelengths because of its absorption in a wide range of wavelengths. The 4-naphthoquinone diazonium sulfonate compound and the 5-naphthoquinone diazonium sulfonate compound are preferably selected according to the wavelength at which the exposure is performed. It is also possible to use a combination of a 4-naphthoquinone diazonium sulfonate compound and a 5-naphthoquinone diazonium sulfonate compound.

The content of the photosensitive agent (C) 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, based on 100% by weight of the total of the silicone resins (a). Further, from the viewpoint of suppressing the deterioration of compatibility with (a) the silicone resin and the coloration due to decomposition at the time of heat curing, and further improving the transparency of the photosensitive resin composition, cured product, particularly cured film, microlens, it 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. By containing (D) an organosilane compound having a condensed polycyclic aromatic group, a bulky substituent is introduced into the terminal end of the silicone resin by heating, and crosslinking between the terminal ends is suppressed, whereby the fluidity of the film at the time of firing can be further improved, and a microlens excellent in high-temperature and high-humidity resistance can be formed by the high hydrophobicity of the condensed polycyclic aromatic group.

Specific examples of the organosilane compound having a condensed polycyclic aromatic group (D) include the following compounds. Examples thereof include 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane, 1-anthracenyltrimethoxysilane, 9-phenanthrenyltrimethoxysilane, 9-fluorenyltrimethoxysilane, 2-fluorenyltrimethoxysilane, 1-pyrenyltrimethoxysilane, 2-indenyl trimethoxysilane, and 5-acenaphthyltrimethoxysilane. They may be contained in 2 or more kinds thereof.

The content of the organosilane compound having a condensed polycyclic aromatic group in (D) the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.5 wt% or more, more preferably 1 wt% or more, based on 100 wt% of the total of (a) the siloxane resin, from the viewpoint of improving the flowability. Further, from the viewpoint of suppressing residues at the time of 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, but is preferably a compound having an alcoholic hydroxyl group. When an organic solvent having an alcoholic hydroxyl group is used, the solubility of (a) the silicone resin, (B) the metal compound particles, and (C) the photosensitive agent can be improved, and the transparency of a coating film obtained from the photosensitive resin composition can be further improved.

The organic solvent having an alcoholic hydroxyl group is not particularly limited, and a compound having a boiling point of 110 to 250℃at atmospheric pressure is preferable. If the boiling point is 110 ℃ or higher, the drying at the time of forming the coating film proceeds moderately, and a coating film having a good surface appearance can be easily obtained. On the other hand, if the boiling point is 250℃or lower, the removal of the organic solvent is easy.

As specific examples of the organic solvent having an alcoholic hydroxyl group, hydroxyacetone (boiling point: 147 ℃ C.), 3-hydroxy-3-methyl-2-butanone (boiling point: 140 ℃ C.), 4-hydroxy-3-methyl-2-butanone (boiling point: 73 ℃ C.), 5-hydroxy-2-pentanone (boiling point: 144 ℃ C.), 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) (boiling point: 166 ℃ C.), ethyl lactate (boiling point: 151 ℃ C.), butyl lactate (boiling point: 186 ℃ C.), propylene glycol monomethyl ether (boiling point: 118 ℃ C.), propylene glycol monoethyl ether (boiling point: 132 ℃ C.), propylene glycol mono-n-propyl ether (boiling point: about 150 ℃ C.), propylene glycol mono-n-butyl ether (boiling point: 170 ℃ C.), diethylene glycol monomethyl ether (boiling point: 194 ℃ C.), diethylene glycol monoethyl ether (boiling point: 202 ℃ C.), dipropylene glycol monomethyl ether (boiling point: about 190 ℃ C.), 3-methoxy-1-butanol (boiling point: 161 ℃ C.), 3-methyl-3-methoxy-1-butanol (boiling point: 174 ℃ C.), and the like may be mentioned. They may be contained in 2 or more kinds thereof.

In addition, other organic solvents may be contained together with the above-mentioned organic solvents or in place of the above-mentioned organic solvents. Examples of the other organic solvents include ethyl acetate, N-propyl acetate, isopropyl acetate, N-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, esters such as 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1-butyl acetate, ethyl acetoacetate, ketones such as methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, acetylacetone, ethers such as diethyl ether, diisopropyl ether, di-N-butyl ether, diphenyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclopentanone, cyclohexanone, and cycloheptanone.

The content of the organic solvent (E) 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 100 parts by weight of the total of the silicone resin (a) and the metal compound particles (B).

The photosensitive resin composition of the present invention may contain an organosilane compound other than the organosilane compound having a condensed polycyclic aromatic group (D) as an adhesion improver. By containing the organosilane compound, adhesion to the substrate can be improved. Examples of the organosilane compound include diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropyloxysilane, diphenyldi-N-butoxysilane, diphenylsilanediol, bis (4-methylphenyl) dimethoxysilane, bis (4-methylphenyl) diethoxysilane, bis (4-methylphenyl) diisopropyloxysilane, bis (4-methylphenyl) silanediol, 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, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-dimethylaminopropyl-dimethoxypropyl-3-dimethoxypropyl-amino-propylsilane, 3-trimethoxypropyl-aminopropylpropylsilane, 3-trimethoxypropyl-amino-3-methoxypropyl-acrylamido-silane, and 3-trimethoxypropyl-amino-propyl-3-acrylamido-silane, 3-aminopropyl triethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylene) propylamine, 3-mercaptopropyl trimethoxysilane, 3-ureidopropyl triethoxysilane, 3-isocyanatopropyl triethoxysilane, p-styryl trimethoxysilane, and the like. They may be contained in 2 or more kinds thereof.

The photosensitive resin composition of the present invention may contain a dissolution accelerator. By containing the dissolution accelerator, residues at the time of development can be suppressed, and resolution can be improved. The dissolution accelerator is preferably a compound having a phenolic hydroxyl group from the viewpoint of compatibility with the (a) silicone resin and the (C) photosensitizer. Specific examples of the compound having a phenolic hydroxyl group include the following compounds (all available from chemical industries, ltd.) below.

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The photosensitive resin composition of the present invention may contain a surfactant. By containing the surfactant, fluidity at the time of coating can be improved. Examples of the surfactant include, for example,a fluorine-based surfactant; an organosilicon surfactant; a silicone modified acrylic surfactant; a fluorine-containing thermally decomposable surfactant; polyether modified silicone surfactant; a polyalkylene oxide surfactant; a poly (meth) acrylate-based surfactant; anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether triethanolamine sulfate; cationic surfactants such as stearyl amine acetate and lauryl trimethyl ammonium chloride; lauryl dimethyl amine oxide and lauryl carboxyl methyl hydroxyethyl imidazole Amphoteric surfactants such as betaine; nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and sorbitan monostearate. They may be contained in 2 or more kinds thereof.

Among them, from the viewpoints of suppressing coating defects such as dishing and reducing surface tension to suppress unevenness in the drying of the coating film, preferred are fluorine-based surfactants, silicone-based surfactants, fluorine-containing thermally decomposable surfactants, polyether-modified silicone-based surfactants.

Examples of the commercial products of the fluorine-based surfactant include, for example, the part of the back of the large, F142D, the part of the large, F172, the part of the large, F173, F183, F445, F470, F475, F477 (above, DIC), NBX-15, FTX-218 (available from the strain), and the like.

Examples of the commercial products of the silicone surfactants include "BYK" (registered trademark) -333, BYK-301, BYK-331, BYK-345, and BYK-307 (manufactured by doctor-back corporation).

Examples of the commercially available fluorine-containing thermally decomposable surfactant include "the use of the plant" and "the use of the plant" such as DS-21 (DIC (registered trademark). Examples of the commercial products of the silicone-modified acrylic surfactants include "BYK" (registered trademark) -3550 (by the company of the year), and the like.

Examples of the commercial products of the polyether-modified silicone surfactants include "BYK" (registered trademark) -345, BYK-346, BYK-347, BYK-348, BYK-349 (above), by the company "doctor blade", the company "doctor blade" SAG002, the company "registered trademark" SAG005, "doctor blade" SAG0503A, "doctor blade" SAG008 (above), the company "daily chemical industry (product), and the like.

The photosensitive resin composition of the present invention may contain a dispersing agent. Examples of the dispersant include polyacrylic dispersants, polycarboxylic acid dispersants, phosphoric acid dispersants, and silicone dispersants.

The photosensitive resin composition of the present invention may contain a resin other than the (a) siloxane resin, and for example, may contain an acrylic resin, an epoxy resin, or the like.

Further, the photosensitive resin composition of the present invention may contain additives such as a crosslinking agent, a crosslinking accelerator, a sensitizer, a thermal radical initiator, a dissolution inhibitor, a stabilizer, and an antifoaming agent as required, as components other than those previously mentioned.

Next, a method for producing the photosensitive resin composition of the present invention will be described. The method for producing the photosensitive resin composition of the present invention is generally a method of stirring and mixing (a) a silicone resin, (B) metal compound particles, (C) a sensitizer, (D) an organosilane compound having a condensed polycyclic aromatic group, (E) an organic solvent, and other components as needed.

Next, a method for producing a cured film and a microlens (including a microlens array) from the photosensitive resin composition of the present invention will be described by way of example.

[ formation of dried film ]

The step of forming a dry film is a step common to the cured film and the microlenses.

The formation of the dry film is performed through a step of coating the photosensitive resin composition on the substrate.

First, a photosensitive resin composition is applied to a glass substrate, a silicon wafer substrate, or a resin layer formed on a glass substrate and a silicon wafer to obtain a coating film.

Examples of the method for applying the photosensitive resin composition used in this case include spin coating using a spin coater, spray coating, inkjet coating, dispenser coating, die coating, and roll coating. The film thickness of the coating film can be appropriately selected according to the coating method and the like. The film thickness after drying is generally set to 1 to 150. Mu.m.

Next, the obtained coating film was dried to obtain a dried film. Examples of the drying method include heat drying, air drying, reduced pressure drying, and infrared irradiation. Examples of the heat dryer include an oven and an electric hot plate. The drying temperature is preferably 50 to 160℃and the drying time is preferably 1 minute to several hours.

[ formation of cured film ]

The formation of the cured film is preferably performed through the subsequent exposure step shown below. That is, the dried film obtained as described above is preferably subjected to 100 to 20,000J/m over the entire surface by using an ultraviolet-visible exposure machine such as PLA ² Left and right (wavelength 365nm exposure conversion) exposure (hereinafter referred to as bleaching exposure). By performing the bleaching exposure, the unreacted naphthoquinone diazo compound remaining in the dried film can be photodegradation, and the transparency of the obtained cured film can be further improved.

The bleached dried film can be heated (cured) by a heating device such as an electric plate or an oven at a temperature range of 100 to 450 ℃ for about 30 seconds to 2 hours to obtain a cured film.

[ formation of microlens ]

The method for manufacturing the microlens is carried out through the following steps: a step of exposing a dried film obtained by a step of applying the photosensitive resin composition to a substrate, a step of developing, and a step of forming microlenses having a diameter of 10 μm to 50 μm.

(step of exposing)

The dried film obtained above is irradiated via a mask having a desired patternChemical rays (exposure) to obtain an exposed film. Such an exposure operation is referred to as a patterning exposure. Examples of the chemical radiation to be irradiated in the patterning exposure include ultraviolet rays, visible light, electron rays, and X-rays. The photosensitive resin composition of the present invention is preferably exposed to ultraviolet light in a range of 10 to 10,000J/m through a desired mask by using an ultraviolet-visible light exposure machine such as a stepper, a mirror image projection Mask (MPA) or a parallel Photomask (PLA) ² The patterning exposure was performed under the left and right (wavelength 365nm exposure conversion) conditions.

(step of developing)

The resulting exposed film is developed with an alkaline developer or the like to remove the exposed portion, thereby obtaining a plurality of columnar bodies of the photosensitive resin composition which are essential for the microlenses and are arranged two-dimensionally according to the pattern. The arrangement pattern of the columnar bodies of the photosensitive resin composition arranged two-dimensionally is not particularly limited, and the arrangement interval corresponding to the object to be detected, the size of the bottom surface of the columnar bodies, and the shape of the bottom surface may be set. They can be arbitrarily set by the pattern of the above mask. Examples of the alkaline compound used in the alkaline developer include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, and ammonia water; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; quaternary ammonium salts such as tetraalkylammonium hydroxides, e.g., tetramethylammonium hydroxide (TMAH), and choline; alcohol amines such as triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol and diethylaminoethanol; cyclic amines such as pyrrole, piperidine, 1, 8-diazabicyclo [5,4,0] -7-undecene, and 1, 5-diazabicyclo [4,3,0] -5-nonane, and morpholine.

The concentration of the alkaline compound in the alkaline developer is generally 0.01 to 50% by weight, preferably 0.02 to 3% by weight. Further, since the pattern shape after development is more excellent, 0.1 to 5% by weight of a surfactant such as a nonionic surfactant may be added. Further, when the developer is an aqueous alkali solution, a water-soluble organic solvent such as ethanol, γ -butyrolactone, dimethylformamide, or N-methyl-2-pyrrolidone may be added to the developer.

Examples of the development method include a dipping method, a spraying method, and a paddle method. The resulting pattern may be rinsed and washed with pure water or the like.

Then, the entire surface of the obtained pattern is preferably subjected to 100 to 20,000J/m by using an ultraviolet-visible exposure machine such as PLA ² Left and right (wavelength 365nm exposure conversion) exposure (bleaching exposure). By performing the bleaching exposure, the unreacted naphthoquinone diazonium compound remaining in the developing film can be photodegradation, and the transparency of the obtained microlens can be further improved.

(step of Forming microlenses having a diameter of 10 μm or more and 50 μm or less)

The bleached and exposed pattern is heated (cured) by a heating device such as a hot plate or an oven at a temperature range of 100 to 450 ℃ for about 30 seconds to 2 hours, whereby the columnar bodies of the photosensitive resin composition are melted, and the molten photosensitive resin composition is allowed to flow by its surface tension, whereby the microlens shape having a diameter of 10 μm to 50 μm can be formed. In addition, when the distance between adjacent microlenses is extremely small by proper flow in the molten state, the adjacent columnar bodies may not be bonded to form independently arranged microlenses. The side cross-sectional shape (radius of curvature of the lens) of the microlens can be arbitrarily adjusted by appropriately setting the ratio of the bottom area to the volume of the columnar body of the photosensitive resin composition. They can be arbitrarily set by 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 suitable for use in light-emitting elements such as organic EL light-emitting elements and display elements. More specifically, a cured film, a microlens, or the like formed in the organic EL element for the purpose of improving light extraction efficiency is exemplified.

The cured film or microlens made of a cured product obtained by curing the photosensitive resin composition of the present invention is suitable for use in a solid-state imaging device. More specifically, a cured film or a microlens is 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 provided as a filter, or the like. Among them, since a lens shape can be formed in a large microlens having a size of 10 μm or more in diameter, which has a high refractive index and transparency, a cured film or microlens made of a cured product obtained by curing the photosensitive resin composition of the present invention is particularly suitable as a microlens for light collection formed on a solid-state imaging element in a fingerprint authentication device. In the case of being applied to a fingerprint authentication device of a smart phone having an OLED display, it is preferable that a plurality of microlenses of uniform shape are two-dimensionally arranged under display elements of the OLED arranged in a stripe pattern so as to be positioned in gaps between sub-pixels of the display elements of the OLED.

The microlens group which is two-dimensionally arranged is referred to as a microlens array. The refractive index of the microlenses constituting the microlens array is preferably 1.60 or more and 1.80 or less at a wavelength of 633 nm. The diameter of the microlenses is 10 μm or more and 50 μm or less, and more preferably the gap distance between the microlenses is 0.01 μm or more and 5.0 μm or less.

In the microlens array of the present invention, the microlenses are preferably made of a cured product obtained by curing a photosensitive resin composition containing the following (a) to (D).

(A) A silicone resin comprising an organosilane unit having a diphenyl group,

(C) The photosensitive agent is used for preparing the photosensitive agent,

(D) An organosilane compound having a condensed polycyclic aromatic group,

the microlens array of the present invention is suitable for use in a fingerprint authentication device as described above.

Since the photosensitive resin composition of the present invention is properly flowed by the curing treatment after the patterning, and the distance between adjacent microlenses can be made very small, etching is not required, the operation can be simplified, and deterioration of the wiring portion due to etching chemical liquid and plasma can be avoided.

Examples

The present invention will be described in further detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. The following shows the compounds used in abbreviations among the compounds used in the synthesis examples and examples.

DAA: diacetone alcohol

EAA: acetoacetic acid ethyl ester

In the evaluation method, the case where no description of the number of n is made is the evaluation of n=1, and the case where no specific temperature is set under each condition such as evaluation and synthesis is performed at room temperature.

< evaluation method >)

Shape of microlens "

A substrate (hereinafter referred to as a "resin layer-forming substrate") having a transparent resin layer of 5 μm thickness, which was formed by forming a film from a crosslinked product containing a silicone resin and silica particles on an 8-inch silicon wafer substrate by the method shown in example 8 of japanese patent application laid-open No. 2019-214492, was prepared.

The photosensitive resin compositions obtained in examples and comparative examples were spin-coated on a resin layer film-forming substrate using Mark-7 (manufactured by the product of the company of genitals, ltd.) and dried at 110 ℃ for 3 minutes to prepare a dried film.

The dried film obtained through a photomask having a circle (diameter 10 μm, 20 μm, 30 μm, 40 μm)/gap (2 μm) was subjected to pattern formation exposure using an i-ray stepper (NSR-2009 i9C, manufactured by the company コ), and then developed by spraying with a 2.38 wt% TMAH aqueous solution for 120 seconds using Mark-7 (manufactured by the company toyo-je, ltd.) and then rinsing with water for 30 seconds to produce a developed film.

Then, as the bleaching exposure, PLA (PLA-501F manufactured by keisk corporation) was used, and the entire surface of the film was exposed to 500mJ (converted into an exposure amount of 365nm wavelength) by an ultra-high pressure mercury lamp.

Then, the mixture was cured at 200℃for 30 minutes using an oven to prepare a microlens having a film thickness of 5.0. Mu.m. The respective microlenses were observed for cross section by FE-SEM (S-4800, hitachi Co., ltd.), and the cross-sectional shapes of the bottom surfaces were confirmed to be 10 μm, 20 μm, 30 μm and 40 μm, respectively, to evaluate the state of pattern formation. Regarding the cross-sectional shape, the shape shown in fig. 1 was determined to have a microlens shape, the shape shown in fig. 2 was determined to have no microlens shape, and a and B were qualified from the viewpoint of industrial utilization.

A: the cross-sectional shape of the micro-lens pattern was 10 μm, 20 μm, 30 μm, 40 μm

B: the cross-sectional shape had a microlens shape in the 10 μm and 20 μm patterns, but the cross-sectional shape did not have a microlens shape in the 30 μm and 40 μm patterns

C: the cross-sectional shape does not have a microlens shape in all of the patterns of 10 μm, 20 μm, 30 μm, 40 μm.

"refractive index"

The photosensitive resin compositions obtained in each of examples and comparative examples were spin-coated with Mark-7 and dried at 110℃for 3 minutes on an 8-inch silicon wafer substrate to prepare a dried film.

Then, as the bleaching exposure, PLA was used, and the entire film was exposed to 500mJ (converted into exposure amount at 365nm wavelength) by an ultra-high pressure mercury lamp.

Then, the cured film was cured at 200℃for 30 minutes using an oven to obtain a film thickness of 1.0. Mu.m. For each cured film, a refractive index of 550nm at 22℃was measured using a spectroscopic ellipsometer FE5000 manufactured by Otsuka electronics (Inc.).

Resolution "

On a resin layer film-forming substrate produced by the same method as the above-described evaluation of the lens shape, the photosensitive resin compositions obtained in each example and comparative example were spin-coated with Mark-7 and dried at 110 ℃ for 3 minutes to produce a dried film.

After pattern formation exposure was performed using an i-ray stepper, a developed film was produced by spray development with a 2.38 wt% aqueous TMAH solution using Mark-7 for 120 seconds, followed by rinsing with water for 30 seconds.

Then, the mixture was cured at 200℃for 30 minutes using an oven to prepare a microlens having a film thickness of 5.0. Mu.m. The minimum pattern size after curing at the optimal exposure amount was defined as the resolution for each microlens, and a and B were defined as acceptable from the viewpoint of industrial utilization.

A: resolution of less than 5 mu m

B: resolution of 5 μm or more and less than 10 μm

C: resolution of more than 10 mu m

High temperature and high humidity resistance "

Then, as the bleaching exposure, PLA was used, and the entire film was exposed to 500mJ (converted into exposure amount at 365nm wavelength) by an ultra-high pressure mercury lamp. Then, the cured film was cured at 200℃for 30 minutes using an oven to obtain a film thickness of 5.0. Mu.m.

The obtained cured film was subjected to a test input in a high temperature and high humidity tester (trade name "Q-Sun", manufactured by Q-Lab) at 85 ℃/85% for 240 hours, and then adhesion was evaluated on the cured film formed on the resin layer-formed substrate. That is, 100 square grids of 1mm×1mm were produced by drawing 11 orthogonal straight lines in parallel in the longitudinal and transverse directions at 1mm intervals on the cured film surface on the resin layer film-forming substrate so as to reach the base of the silicon wafer with a dicing blade. A cellophane adhesive tape (width=18 mm, adhesive force=3.7N/10 mm) was stuck on the surface of the cut cured film, and the tape was rubbed with an eraser (JIS 6050 acceptable product) to adhere the tape to the tape, and the number of remaining squares at the time of instantaneous peeling off the tape while maintaining a right angle to the board was visually counted. The peeling area by the square was determined as follows, and 4B and 5B were determined to be acceptable.

5B: stripping area = 0%

4B: peel area = more than 0% and less than 5%

3B: peel area = 5% or more and less than 15%

2B: peel area = 15% or more and less than 35%

1B: peel area = 35% or more and less than 65%

0B: peel area = 65% or more and less than 100%.

Synthesis example 1

Into a 500mL three-necked flask, 171.85g of DAA, 43.58g (0.40 mol) of methyltrimethoxysilane, 76.15g (0.48 mol) of phenyltrimethoxysilane, 14.69g (0.07 mol) of 3-trimethoxysilylpropyl succinic acid, and 8.65g (0.05 mol) of diphenylsilanediol were charged, and an aqueous solution of phosphoric acid in which 0.72g (0.5 wt% relative to the charged monomer) of phosphoric acid was dissolved in 42.05g of water was added over 10 minutes using a dropping funnel while being immersed in an oil bath at 40℃and stirred. After stirring at 40℃for 1 hour, the oil bath temperature was set to 70℃and stirred for 1 hour, and the oil bath was further heated to 115℃over 30 minutes. After 1 hour from the start of the temperature rise, the internal temperature of the solution reached 100℃and was stirred for 2 hours (internal temperature: 100 to 110 ℃) from the start. The total of methanol and water distilled off as by-products in the reaction was 96g. To the obtained DAA solution of polysiloxane, DAA was added so that the solid content concentration became 40 mass%, to obtain a silicone resin solution (PS-1).

Synthesis example 2

Into a 500mL three-necked flask, 175.08g of DAA, 43.58g (0.40 mol) of methyltrimethoxysilane, 68.22g (0.43 mol) of phenyltrimethoxysilane, 14.69g (0.07 mol) of 3-trimethoxysilylpropyl succinic acid, and 17.30g (0.10 mol) of diphenylsilanediol were charged, and an aqueous phosphoric acid solution in which 0.71g (0.5 wt% relative to the charged monomer) of phosphoric acid was dissolved in 39.89g of water was added via a dropping funnel over 10 minutes while being immersed in an oil bath at 40℃and stirred. After stirring at 40℃for 1 hour, the oil bath temperature was set to 70℃and stirred for 1 hour, and the oil bath was further heated to 115℃over 30 minutes. After 1 hour from the start of the temperature rise, the internal temperature of the solution reached 100℃and was heated and stirred for 2 hours (internal temperature: 100 to 110 ℃). The total of methanol and water distilled off as by-products in the reaction was 91g. To the obtained DAA solution of polysiloxane, DAA was added so that the solid content concentration became 40 mass%, to obtain a silicone resin solution (PS-2).

[ Synthesis example 3 ]

Into a 500mL three-necked flask, 181.56g of DAA, 43.58g (0.40 mol) of methyltrimethoxysilane, 52.35g (0.33 mol) of phenyltrimethoxysilane, 14.69g (0.07 mol) of 3-trimethoxysilylpropyl succinic acid and 34.61g (0.20 mol) of diphenylsilanediol were charged, and an aqueous phosphoric acid solution in which 0.73g (0.5 wt% relative to the charged monomer) of phosphoric acid was dissolved in 35.57g of water was added to the flask over 10 minutes using a dropping funnel while the flask was immersed in an oil bath at 40℃and stirred. After stirring at 40℃for 1 hour, the oil bath temperature was set to 70℃and stirred for 1 hour, and the oil bath was further heated to 115℃over 30 minutes. After 1 hour from the start of the temperature rise, the internal temperature of the solution reached 100℃and was heated and stirred for 2 hours (internal temperature: 100 to 110 ℃). The total of methanol and water as by-products in the reaction was distilled off by 81g. To the obtained DAA solution of polysiloxane, DAA was added so that the solid content concentration became 40 mass%, to obtain a silicone resin solution (PS-3).

[ Synthesis example 4 ]

Into a 500mL three-necked flask, 188.03g of DAA, 43.58g (0.40 mol) of methyltrimethoxysilane, 36.49g (0.23 mol) of phenyltrimethoxysilane, 14.69g (0.07 mol) of 3-trimethoxysilylpropyl succinic acid, and 51.91g (0.30 mol) of diphenylsilanediol were charged, and an aqueous phosphoric acid solution in which 0.73g (0.5 wt% relative to the charged monomer) of phosphoric acid was dissolved in 31.25g of water was added via a dropping funnel over 10 minutes while being immersed in an oil bath at 40℃and stirred. After stirring at 40℃for 1 hour, the oil bath temperature was set to 70℃and stirred for 1 hour, and the oil bath was further heated to 115℃over 30 minutes. After 1 hour from the start of the temperature rise, the internal temperature of the solution reached 100℃and was heated and stirred for 2 hours (internal temperature: 100 to 110 ℃). The total of methanol and water distilled off as by-products in the reaction was 71g. To the obtained DAA solution of polysiloxane, DAA was added so that the solid content concentration became 40 mass%, to obtain a silicone resin solution (PS-4).

Synthesis example 5

Into a 500mL three-necked flask, 194.51g of DAA, 43.58g (0.40 mol) of methyltrimethoxysilane, 20.62g (0.13 mol) of phenyltrimethoxysilane, 14.69g (0.07 mol) of 3-trimethoxysilylpropyl succinic acid, and 69.22g (0.40 mol) of diphenylsilanediol were charged, and an aqueous solution of phosphoric acid in which 0.74g (0.5 wt% relative to the charged monomer) of phosphoric acid was dissolved in 26.93g of water was added over 10 minutes using a dropping funnel while stirring the mixture by immersing the mixture in an oil bath at 40 ℃. After stirring at 40℃for 1 hour, the temperature of the oil bath was set to 70℃and stirred for 1 hour, and the temperature of the oil bath was further raised to 115℃over 30 minutes. After 1 hour from the start of the temperature rise, the internal temperature of the solution reached 100℃and was heated and stirred for 2 hours (internal temperature: 100 to 110 ℃). The total of methanol and water distilled off as by-products in the reaction was 61g. To the obtained DAA solution of polysiloxane, DAA was added so that the solid content concentration became 40 mass%, to obtain a silicone resin solution (PS-5).

[ Synthesis example 6 ]

Into a 500mL three-necked flask, 168.61g of DAA, 43.58g (0.40 mol) of methyltrimethoxysilane, 84.08g (0.53 mol) of phenyltrimethoxysilane, and 14.69g (0.07 mol) of 3-trimethoxysilylpropyl succinic acid were charged, and while stirring by immersing in an oil bath at 40℃an aqueous solution of phosphoric acid 0.71g (0.5% by weight relative to the amount of the charged monomer) in water 44.21g was added via a dropping funnel over 10 minutes. After stirring at 40℃for 1 hour, the temperature of the oil bath was set to 70℃and stirred for 1 hour, and the temperature of the oil bath was further raised to 115℃over 30 minutes. After 1 hour from the start of the temperature rise, the internal temperature of the solution reached 100℃and was heated and stirred for 2 hours (internal temperature: 100 to 110 ℃). The total of methanol and water distilled off as by-products in the reaction was 101g. To the obtained DAA solution of polysiloxane, DAA was added so that the solid content concentration became 40 mass%, to obtain a silicone resin solution (PS-6).

Synthesis example 7

Into a 500mL three-necked flask, 158.57g of DAA, 43.58g (0.40 mol) of methyltrimethoxysilane, 52.35g (0.33 mol) of phenyltrimethoxysilane, 14.69g (0.07 mol) of 3-trimethoxysilylpropyl succinic acid, and 19.24g (0.20 mol) of dimethyldimethoxysilane were charged, and an aqueous phosphoric acid solution in which 0.65g (0.5 wt% relative to the charged monomer) of phosphoric acid was dissolved in 35.57g of water was added to the flask over 10 minutes with stirring by immersing the flask in an oil bath at 40 ℃. After stirring at 40℃for 1 hour, the temperature of the oil bath was set to 70℃and stirred for 1 hour, and the temperature of the oil bath was further raised to 115℃over 30 minutes. After 1 hour from the start of the temperature rise, the internal temperature of the solution reached 100℃and was heated and stirred for 2 hours (internal temperature: 100 to 110 ℃). The total of methanol and water as by-products in the reaction was distilled off by 81g. To the obtained DAA solution of polysiloxane, DAA was added so that the solid content concentration became 40 mass%, to obtain a silicone resin solution (PS-7).

Synthesis example 8

Into a 500mL three-necked flask, 189.22g of DAA, 43.58g (0.40 mol) of methyltrimethoxysilane, 52.35g (0.33 mol) of phenyltrimethoxysilane, 14.69g (0.07 mol) of 3-trimethoxysilylpropyl succinic acid, 39.74g (0.20 mol) of naphthyltrimethoxysilane were charged, and an aqueous phosphoric acid solution in which 0.75g (0.5 wt% relative to the charged monomer) of phosphoric acid was dissolved in 35.57g of water was added to the flask over 10 minutes with stirring by immersing the flask in an oil bath at 40 ℃. After stirring at 40℃for 1 hour, the temperature of the oil bath was set to 70℃and stirred for 1 hour, and the temperature of the oil bath was further raised to 115℃over 30 minutes. After 1 hour from the start of the temperature rise, the internal temperature of the solution reached 100℃and was heated and stirred for 2 hours (internal temperature: 100 to 110 ℃). The total of methanol and water as by-products in the reaction was distilled off by 81g. To the obtained DAA solution of polysiloxane, DAA was added so that the solid content concentration became 40 mass%, to obtain a silicone resin solution (PS-8).

[ Synthesis example 9 ]

500g of "na" (registered trademark) OT-RB300M7-20 (30 wt% methanol dispersion) as composite particles of tin oxide, titanium oxide and silicon oxide was subjected to solvent substitution while DAA was added thereto at a pressure of 150mbar using a rotary evaporator. Further, the metal compound particle dispersion (T-1) was obtained by concentrating the mixture at a pressure of 20mbar using a rotary evaporator so that the solid content concentration became 40% by weight.

[ Synthesis example 10 ]

Under a dry nitrogen flow, ph-cc-AP-MF (trade name, manufactured by Benzhu chemical industry Co., ltd.) 15.32g (0.05 mol) and 5-naphthoquinone diazosulfonyl chloride 37.62g (0.14 mol) were dissolved in 1, 4-di450g of alkane. Dripping 1, 4-di +.1-into the system at 35 deg.C>Alkane 50g triethylamine 15.58g (0.154 mol) mixed. After the dropwise addition, the mixture was stirred at 30℃for 2 hours. The triethylamine salt was filtered and the filtrate was put into water. Then, the precipitated precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a naphthoquinone diazonium compound (QD-1) having the following structure.

Synthesis example 11

TrisP-HAP (trade name, manufactured by Benzhou chemical industry Co., ltd.) 15.32g (0.05 mol) and 5-naphthoquinone diazosulfonyl chloride 22.84g (0.085 mol) were dissolved in 1, 4-di-n under a dry nitrogen flow Alkane 450g, left at room temperature. 1, 4-di ++is added dropwise to the system at a temperature not higher than 35 DEG C>Alkane 50g triethylamine 9.46g (0.0935 mol) mixed. After the dropwise addition, the mixture was stirred at 30℃for 2 hours. The triethylamine salt was filtered and the filtrate was put into water. Then, the precipitated precipitate was collected by filtration. The precipitate was dried with a vacuum dryer to obtain a naphthoquinone diazonium compound (QD-2) having the following structure.

[ example 1 ]

First, the following raw materials were mixed under a yellow lamp and stirred.

2.00g of the naphthoquinone diazonium compound (QD-1) obtained in Synthesis example 10, 1.33g of the naphthoquinone diazonium compound (QD-2) obtained in Synthesis example 11, and 1.67g of the phenol compound TrisP-PA1.67g were dissolved in an organic solvent using a mixed solvent of 4.04g of DAA and 5.34g of EAA as the organic solvent,

1.67g of 1-naphthyltrimethoxysilane (trade name "Z-6874" manufactured by DOWANYONG Co., ltd.) as an organosilane compound having a condensed polycyclic aromatic group,

0.10g of a5 wt% EAA solution of a fluorine-containing thermally decomposable surfactant (product name: DS-21 DIC Co., ltd.) as a surfactant and 0.60g of an EAA5 wt% solution of a silicone modified acrylic surfactant (trade name "BYK" (registered trademark) -3550 "brand of Ind., ltd.),

46.46g of the silicone resin solution (PS-1) obtained in Synthesis example 1,

36.80g of the metal compound particle dispersion (T-1) obtained in Synthesis example 9,

next, the mixture was filtered through a 1.0 μm filter to prepare a photosensitive resin composition A-1 having a solid content of 40% by weight.

The obtained photosensitive resin composition a-1 was evaluated by the method described above to produce a cured film and a microlens.

[ example 2 ]

A photosensitive resin composition A-2 was prepared in the same manner as in example 1, except that the silicone resin solution (PS-2) was used instead of the silicone resin solution (PS-1). The photosensitive resin composition A-2 thus obtained was used and evaluated in the same manner as in example 1.

[ example 3 ]

A photosensitive resin composition A-3 was prepared in the same manner as in example 1 except that the silicone resin solution (PS-3) was used instead of the silicone resin solution (PS-1). The photosensitive resin composition A-3 was used and evaluated in the same manner as in example 1.

[ example 4 ]

A photosensitive resin composition A-4 was prepared in the same manner as in example 1, except that the silicone resin solution (PS-4) was used instead of the silicone resin solution (PS-1). The photosensitive resin composition A-4 thus obtained was used and evaluated in the same manner as in example 1.

[ example 5 ]

A photosensitive resin composition A-5 was prepared in the same manner as in example 1, except that the silicone resin solution (PS-5) was used instead of the silicone resin solution (PS-1). The photosensitive resin composition A-5 was used and evaluated in the same manner as in example 1.

[ example 6 ]

A photosensitive resin composition A-6 was prepared in the same manner as in example 3 except that the amount of the siloxane resin solution (PS-3) added was changed to 53.12g and the amount of the metal-compound particle dispersion (T-1) added was changed to 30.14 g. The photosensitive resin composition A-6 thus obtained was used and evaluated in the same manner as in example 1.

Example 7

A photosensitive resin composition A-7 was prepared in the same manner as in example 3 except that the amount of the siloxane resin solution (PS-3) added was changed to 59.78g and the amount of the metal-compound particle dispersion (T-1) added was changed to 23.48 g. The photosensitive resin composition A-7 thus obtained was used and evaluated in the same manner as in example 1.

Example 8

A photosensitive resin composition A-8 was prepared in the same manner as in example 3 except that the amount of the siloxane resin solution (PS-3) added was changed to 39.80g and the amount of the metal-compound particle dispersion (T-1) added was changed to 43.46 g. The photosensitive resin composition A-8 was used and evaluated in the same manner as in example 1.

[ example 9 ]

A photosensitive resin composition A-9 was prepared in the same manner as in example 3 except that the amount of the siloxane resin solution (PS-3) added was changed to 33.14g and the amount of the metal-compound particle dispersion (T-1) added was changed to 50.12 g. The photosensitive resin composition A-9 thus obtained was used and evaluated in the same manner as in example 1.

[ example 10 ]

First, the following raw materials were mixed under a yellow lamp and stirred.

A solution obtained by dissolving 2.05g of naphthoquinone diazonium compound (QD-1), 1.37g of naphthoquinone diazonium compound (QD-2) and 1.71g of phenol compound TrisP-PA-1.71 g in an organic solvent using a mixed solution of 2.76g of DAA and 5.34g of EAA,

0.68g of a product of Wako-Ten corporation under the trade name "Z-6874" as an organosilane compound having a condensed polycyclic aromatic group,

0.10g of a5 wt% EAA solution made by DIC under the trade name "DS-21" and 0.60g of a5 wt% EAA solution made by BYK (registered trademark) -3550 "brand as surfactants,

47.65g of silicone resin solution (PS-3),

37.74g of the metal compound particle dispersion (T-1),

Next, the mixture was filtered through a 1.0 μm filter to prepare a photosensitive resin composition A-10 having a solid content concentration of 40% by weight.

The photosensitive resin composition A-10 thus obtained was evaluated in the same manner as in example 1.

[ example 11 ]

First, the following raw materials were mixed under a yellow lamp and stirred.

1.92g of naphthoquinone diazo compound (QD-1), 1.28g of naphthoquinone diazo compound (QD-2) and 1.60g of phenol compound TrisP-PA1.60g were dissolved in an organic solvent using a mixed solution of 6.04g of DAA and 5.34g of EAA,

3.20g of a product of Wako-Kabushiki Kaisha having a condensed polycyclic aromatic group under the trade name "Z-6874",

44.60g of the silicone resin solution (PS-3),

35.33g of the metal compound particle dispersion (T-1).

Next, the mixture was filtered through a 1.0 μm filter to prepare a photosensitive resin composition A-11 having a solid content concentration of 40% by weight.

The photosensitive resin composition A-11 thus obtained was evaluated in the same manner as in example 1.

Comparative example 1

A photosensitive resin composition A-12 was prepared in the same manner as in example 1 except that the silicone resin solution (PS-6) was used instead of the silicone resin solution (PS-1). The photosensitive resin composition A-12 thus obtained was used and evaluated in the same manner as in example 1.

Comparative example 2

First, the following raw materials were mixed under a yellow lamp and stirred.

as organosilane compounds having fused polycyclic aromatic groups trade name "Z-6874" 1.60g of manufactured by Dai-yue (strain)

1.60g of dimethoxydiphenylsilane (trade name "KBM-202SS", manufactured by Xinyue chemical Co., ltd.),

44.60g of the silicone resin solution (PS-3),

35.33g of the metal compound particle dispersion (T-1).

[ comparative example 3 ]

A photosensitive resin composition A-14 was prepared in the same manner as in example 1, except that the silicone resin solution (PS-7) was used instead of the silicone resin solution (PS-1). The photosensitive resin composition A-14 thus obtained was used and evaluated in the same manner as in example 1.

[ comparative example 4 ]

A photosensitive resin composition A-15 was prepared in the same manner as in example 1 except that the silicone resin solution (PS-8) was used instead of the silicone resin solution (PS-1). The photosensitive resin composition A-15 was used and evaluated in the same manner as in example 1.

[ comparative example 5 ]

First, the following raw materials were mixed under a yellow lamp and stirred.

A solution obtained by dissolving 2.00g of naphthoquinone diazonium compound (QD-1), 1.33g of naphthoquinone diazonium compound (QD-2) and 1.67g of phenol compound TrisP-PA using a mixed solution of 4.04g of DAA and 5.34g of EAA as an organic solvent,

1.67g of a product of Wako-DOWN (R) under the trade name "Z-6874" as an organosilane compound having a condensed polycyclic aromatic group,

83.26g of the silicone resin solution (PS-3).

Next, the mixture was filtered through a 1.0 μm filter to prepare a photosensitive resin composition A-16 having a solid content concentration of 40% by weight.

The photosensitive resin composition A-16 thus obtained was evaluated in the same manner as in example 1.

[ comparative example 6 ]

First, the following raw materials were mixed under a yellow lamp and stirred.

A solution obtained by dissolving 2.09g of naphthoquinone diazonium compound (QD-1), 1.39g of naphthoquinone diazonium compound (QD-2) and 1.74g of phenol compound TrisP-PA1.74g in an organic solvent using a mixed solution of DAA1.87g and EAA5.34g as an organic solvent,

3.20g of a product of Wako-Kabushiki Kaisha having a condensed polycyclic aromatic group under the trade name "Z-6874

48.48g of the silicone resin solution (PS-3),

38.40g of the metal compound particle dispersion (T-1).

Next, the mixture was filtered through a 1.0 μm filter to prepare a photosensitive resin composition A-17 having a solid content concentration of 40% by weight.

The photosensitive resin composition A-17 thus obtained was evaluated in the same manner as in example 1.

Comparative example 7

Photosensitive resin compositions a-18 were prepared in the same manner as in example 1 except that phenyltrimethoxysilane (trade name "KBM-103" manufactured by the industrial chemical industry, ltd.) was used instead of "Z-6874" manufactured by dow and by chinese. The photosensitive resin composition A-18 thus obtained was used and evaluated in the same manner as in example 1.

Comparative example 8

Photosensitive resin compositions a-19 were prepared in the same manner as in example 1 except that the trade name "KBM-202SS" manufactured by the shiny-chemical industry (ltd.) was used instead of the trade name "Z-6874" manufactured by dow and chinese. Using the obtained photosensitive resin composition A-19, evaluation was made in the same manner as in example 1.

Comparative example 9

Photosensitive resin compositions a-20 were prepared in the same manner as in example 1 except that tetrapropoxysilane (trade name "N-POS" manufactured by the hitachi chemical industry, ltd.) was used instead of the trade name "Z-6874" manufactured by dow and by dow. Using the obtained photosensitive resin composition A-20, evaluation was made in the same manner as in example 1.

[ comparative example 10 ]

Photosensitive resin composition a-21 was prepared in the same manner as in example 1 except that vinyltris (2-methoxyethoxy) silane (trade name "KBC-103" manufactured by sieveyue chemical industry (ltd.)) was used instead of "Z-6874" manufactured by sieveyue (ltd.). The photosensitive resin composition A-21 was used and evaluated in the same manner as in example 1.

Comparative example 11

Photosensitive resin compositions a-22 were prepared in the same manner as in example 1 except that 3-methacryloxypropyl trimethoxysilane (trade name "KBM-503", manufactured by the company "kum-chemical industry, ltd.) was used instead of the trade name" Z-6874", manufactured by dow and by je. The photosensitive resin composition A-22 thus obtained was used and evaluated in the same manner as in example 1.

[ comparative example 12 ]

Photosensitive resin compositions a-23 were prepared in the same manner as in example 1 except that 3-methacryloxyoctyltrimethoxysilane (trade name "KBM-5803", manufactured by the shiner chemical industry, ltd.) was used instead of the trade name "Z-6874", manufactured by dow and by endo. The photosensitive resin composition A-23 was used and evaluated in the same manner as in example 1.

[ comparative example 13 ]

Photosensitive resin compositions a-24 were prepared in the same manner as in example 1 except that (3-methacryloxypropyl) methyldimethoxysilane (trade name "KBM-502", manufactured by the company "zhi yue chemical industry (ltd)) was used instead of" Z-6874", manufactured by dow and turn (ltd). The photosensitive resin composition A-24 was used and evaluated in the same manner as in example 1.

The compositions of the resin compositions in each example and comparative example are shown in tables 1 and 2, and the evaluation results are shown in table 3.

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TABLE 3 Table 3

The photosensitive resin composition produced in the examples was found to have a high refractive index and transparency, and also to have high fluidity at a firing temperature of 230 ℃ or lower, and to be formed into a lens shape even in a large microlens having a size of 10 μm or more in diameter.

Industrial applicability

The photosensitive resin composition of the present invention has a high refractive index and transparency, and also has high fluidity at a firing temperature of 230 ℃ or lower, and can be formed into a lens shape even in a large microlens having a size of 10 μm or more in diameter, and therefore can be suitably used as a microlens for use in a CMOS image sensor and a fingerprint authentication device.

Claims

1. A photosensitive resin composition comprising the following (A) to (E),

(A) A silicone resin comprising an organosilane unit having a diphenyl group,

(B) A metal compound particle or a composite metal compound particle, the metal compound particle being at least 1 selected from the group consisting of a titanium compound particle, a zirconium compound particle, a tin compound particle, and an aluminum compound particle, the composite metal compound particle being a composite metal compound particle of at least 1 selected from the group consisting of a titanium compound, a zirconium compound, a tin compound, and an aluminum compound, and a silicon compound,

(C) The photosensitive agent is used for preparing the photosensitive agent,

(D) An organosilane compound having a condensed polycyclic aromatic group,

(E) An organic solvent.

2. The photosensitive resin composition according to claim 1, wherein the (a) siloxane resin contains 5mol% or more and 40mol% or less of organosilane units having diphenyl groups.

3. The photosensitive resin composition according to claim 1 or 2, wherein the (a) siloxane resin contains an organosilane unit having a carboxyl group and/or a dicarboxylic anhydride structure.

4. The photosensitive resin composition according to claim 1, wherein the number average particle diameter of the metal compound particles (B) or the composite metal compound particles is 1nm to 70nm.

5. The photosensitive resin composition according to claim 1, wherein the total amount of the metal compound particles (B) or the composite metal compound particles (B) is 20 parts by weight or more and 60 parts by weight or less based on 100 parts by weight of the silicone resin.

6. The photosensitive resin composition according to claim 1, wherein the (C) sensitizer is a naphthoquinone diazonium compound.

7. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 6.

8. The cured product according to claim 7, having a refractive index of 1.60 or more and 1.80 or less at a wavelength of 633 nm.

9. A cured film made from the cured product of claim 7.

10. A microlens made from the cured product of claim 7.

11. A method for manufacturing a microlens, comprising the steps of: a step of applying the photosensitive resin composition according to any one of claims 1 to 6 to a substrate; a step of performing exposure; a step of developing; and forming microlenses having a diameter of 10 μm or more and 50 μm or less.

12. A solid-state imaging device comprising the cured film according to claim 9.

13. A fingerprint authentication device comprising the cured film according to claim 9.

14. A microlens array having a plurality of microlenses arranged two-dimensionally, wherein the refractive index of the microlenses at a wavelength of 633nm is 1.60 to 1.80 inclusive, the diameter of the microlenses is 10 to 50 [ mu ] m inclusive, and the distance between the microlenses is 0.01 to 5.0 [ mu ] m inclusive.

15. The microlens array according to claim 14, wherein the microlenses are formed of a cured product obtained by curing a photosensitive resin composition comprising the following (A) to (D),

(A) A silicone resin comprising an organosilane unit having a diphenyl group,

(C) The photosensitive agent is used for preparing the photosensitive agent,

(D) An organosilane compound having a condensed polycyclic aromatic group.

16. A fingerprint authentication device having the microlens array of claim 14.