JP6569211B2 - Photosensitive resin composition, cured film obtained by curing the same, and light emitting device and solid-state imaging device comprising the same - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a cured film obtained by curing the photosensitive resin composition, and a light emitting device and a solid-state imaging device including the cured film.

  An organic EL (Electro Luminescence) element has a structure in which a light emitting layer made of an organic material is sandwiched between a pair of electrodes of a cathode and an anode, and when voltage is applied, holes from the anode and electrons from the cathode to the light emitting layer. It is an element that takes out the energy obtained by being injected and recombining holes and electrons in the organic light emitting layer as light.

  However, since the refractive index of the material used for the organic light emitting layer is relatively high and the difference in refractive index between adjacent layers is large, the generated light is totally reflected at the interface with the substrate and trapped in the light emitting layer. There is a problem that efficiency decreases. According to Patent Document 1, in a normal organic electroluminescent device, about 20% of the light generated in the light emitting layer can be extracted outside the device, and the light reaches the substrate but cannot be extracted from the substrate. Is about 30%, and the light that cannot reach the substrate and is confined in the light emitting layer or electrode is about 50%.

  In order to improve the light emission efficiency of the organic EL element, a layer having a refractive index different from that of the electrode is provided on the substrate surface (for example, refer to Patent Document 2), or a lens shape is formed on the light emitting layer (for example, Patent Document 3). Thus, there is a technique for scattering light and improving light extraction efficiency.

  Examples of a general method for manufacturing a lens include a method of processing an inorganic film formed by a CVD method or the like by dry etching, and a method of applying and processing a resin. The former method is currently attracting attention because it is difficult to obtain a refractive index of 1.65 to 2.00 optimum for a lens or an optical waveguide.

  So far, for example, a high refractive index including a photosensitive siloxane composition containing a polysiloxane, a quinonediazide compound, a solvent and a thermally crosslinkable compound (see, for example, Patent Document 4) and a siloxane compound having an aromatic hydrocarbon group. Materials (for example, see Patent Document 5) have been proposed). However, it has been difficult for these materials to obtain a cured film having a high refractive index required for lens materials and the like.

  Further, a positive photosensitive resin composition containing a polyamic acid, a compound having a phenolic hydroxyl group, a quinonediazide compound and inorganic particles (see, for example, Patent Document 6), a silsesquioxane having a phenol unit and a condensed polycyclic type. A silicone copolymer having a hydrocarbon group (see, for example, Patent Document 7) has been proposed. However, since the polyamic acid or the phenolic hydroxyl group is colored at the time of curing, there is a problem that transparency is lowered.

  Examples of the material having a high refractive index and transparency include coating compositions containing organosilane, siloxane oligomer and metal oxide fine particles and / or sol (see, for example, Patent Document 8), metal oxide particles and alkoxysilane. A siloxane-based resin composition (for example, see Patent Document 9) is disclosed. Since these materials are mainly non-photosensitive, patterns are usually processed by a wet etching method using a chemical solution or a dry etching method using plasma.

  Further, a siloxane-based resin composition having a high refractive index and transparency due to positive photosensitivity (for example, see Patent Document 10) has been proposed. However, low-temperature curing at 200 to 220 ° C. has no solvent resistance of the cured film, and a high curing temperature is essential.

JP2012-204103A JP 2003-109747 A JP-A-8-83688 JP 2006-293337 A JP 2008-24832 A JP 2003-75997 A JP 2006-31717 A JP 2001-81404 A JP 2007-246877 A WO2011 / 040248

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a material capable of forming a high refractive index lens capable of improving light extraction efficiency in light emitting elements such as organic EL elements and display elements. There is.

  Conventional materials that have both high refractive index and high transparency require non-photosensitive pattern formation by the etching method, so the work process is complicated and the wiring part is formed by chemicals or plasma during etching. There was a problem of deterioration. For photosensitive materials, the sensitivity and resolution in exposure cannot be kept high even after long-term storage at room temperature, and there is a problem in productivity. The object of the present invention is to have high sensitivity in exposure even after long-term storage at room temperature without impairing the properties of high refractive index and high transparency, excellent resolution and solvent resistance after pattern formation, and curing. This is to develop a photosensitive resin composition that can be reflowed and formed into a lens shape.

In order to solve the above problems, the present invention has the following configuration. (A) one or more metal compound particles selected from aluminum compound particles, tin compound particles, titanium compound particles and zirconium compound particles, or one or more metal compounds selected from aluminum compounds, tin compounds, titanium compounds and zirconium compounds; Composite particles with a silicon compound, (b) Polysiloxane synthesized by hydrolyzing and partially condensing one or more types of organosilane represented by the following general formula (1), and the presence of component (a) Particle-containing polysiloxane synthesized by hydrolyzing and partially condensing one or more organosilanes represented by the general formula (1 ) below, (c) a photosensitizer, (d) the following general formula (2) And / or a silane compound represented by the following general formula (3) and (e) a solvent. Photosensitive resin composition.

(In the general formula (1), ^{R 1} is hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group or an aryl group having a carbon number of 6 to 16 from 2 to 10 carbon atoms and tables, a carboxyl group and / or dicarboxylic good .R ² may have an acid anhydride structure is a hydrogen, an alkyl group having 1 to 6 carbon atoms, .n representing the acyl group or an aryl group having a carbon number of 6 to 16 of 2 to 6 carbon atoms 0 And represents an integer of 3. When n is 2 or more, the plurality of R ¹ may be the same or different, and when n is 2 or less, the plurality of R ² may be the same or different.

(In the general formula (2), ^{R 3} represents a hydrocarbon group having 6 to 20 carbon atoms having an aromatic group.
R ⁴ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 16 carbon atoms. Any of the alkyl group, alkenyl group, and aryl group in R ⁴ may be substituted. Examples of the alkyl group of R ⁴ and its substituent include methyl group, ethyl group, n-propyl group, isopropyl group, and n-butyl. Group, t-butyl group, n-hexyl group, n-decyl group, 3-glycidoxypropyl group, 3-glycidoxyoctyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-acryloxy It represents a propyl group, 3-methacryloxypropyl group, 3-methacryloxy-octyl group, in the alkenyl group and its substitution product, represents a vinyl group, in the aryl group and substituents thereof, phenyl group, tolyl It represents groups, p- hydroxyphenyl group, a naphthyl group, a phenanthrenyl group, a fluorenyl group, a pyrenyl group, an indenyl group, an acenaphthenyl group
R ⁵ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms.
m represents an integer of 0 to 3, o represents an integer of 0 to 2, and m + o represents an integer of 0 to 3. When m and o are 2 or more, the plurality of R ³ and R ⁴ may be the same or different. When m + o is 2 or less, the plurality of R ⁵ may be the same or different.
In the general formula (3), R ⁶ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 16 carbon atoms.
R ⁷ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms.
p represents an integer of 0 to 3. When p is 2 or more, the plurality of R ⁶ may be the same or different. When p is 2 or less, the plurality of R ⁷ may be the same or different.

  According to the photosensitive composition of the present invention, it has high sensitivity in exposure even after long-term storage at room temperature without impairing properties of high refractive index and high transparency, and resolution and solvent resistance after pattern formation. The photosensitive composition which can obtain the cured film excellent in the property can be provided. Further, according to the present invention, since the lens shape can be formed by reflowing in the curing process, processing by etching becomes unnecessary, the work process can be simplified, and deterioration of the wiring portion due to chemicals or plasma at the time of etching is possible. It can be avoided.

It is a figure which shows the shape of the pattern which comprises the shape of a lens. It is a figure which shows the shape of the pattern which does not comprise the shape of a lens.

The photosensitive composition of the present invention is selected from (a) one or more metal compound particles selected from aluminum compound particles, tin compound particles, titanium compound particles and zirconium compound particles, or aluminum compounds, tin compounds, titanium compounds and zirconium compounds. one or more metal compounds and composite particles of silicon compound, (b) the following general formula organosilanes 1 or more represented by (1) hydrolyzing, polysiloxanes synthesized by partial condensation (A) Particle-containing polysiloxane synthesized by hydrolyzing and partially condensing one or more organosilanes represented by the general formula (1) in the presence of the component , (c) a photosensitizer, (d) A silane compound represented by the following general formula (2) and / or the following general formula (3) and (e) a solvent. And a photosensitive resin composition.

(In the general formula (1), ^{R 1} is hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group or an aryl group having a carbon number of 6 to 16 from 2 to 10 carbon atoms and tables, a carboxyl group and / or dicarboxylic good .R ² may have an acid anhydride structure is a hydrogen, an alkyl group having 1 to 6 carbon atoms, .n representing the acyl group or an aryl group having a carbon number of 6 to 16 of 2 to 6 carbon atoms 0 And represents an integer of 3. When n is 2 or more, the plurality of R ¹ may be the same or different, and when n is 2 or less, the plurality of R ² may be the same or different.

(In the general formula (2), R ³ represents a hydrocarbon group having 6 to 20 carbon atoms having an aromatic group. R ⁴ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or Represents an aryl group having 6 to 16 carbon atoms, any of an alkyl group, an alkenyl group and an aryl group in R ⁴ may be substituted, and examples of the alkyl group of R ⁴ and its substituent include a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, 3-glycidoxypropyl group, 3-glycidoxyoctyl group, 2- (3,4 -Epoxycyclohexyl) ethyl group, 3-acryloxypropyl group, 3-methacryloxypropyl group, and 3-methacryloxyoctyl group. Specific examples of the alkenyl group and its substituent include Specific examples of aryl groups and substituted products thereof include phenyl group, tolyl group, p-hydroxyphenyl group, naphthyl group, phenanthrenyl group, fluorenyl group, pyrenyl group, indenyl group, and acenaphthenyl group. . R ⁵ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an integer of .m is 0 to 3 represents an aryl group an acyl group or a 6 to 16 carbon atoms having 2 to 6 carbon atoms, o is from 0 to 2 M + o is an integer of 0 to 3. When m and o are 2 or more, a plurality of R ³ and R ⁴ may be the same or different, and when m + o is 2 or less, a plurality of R ⁵ may be the same or different, and in the general formula (3), R ⁶ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 16 carbon atoms. .R ⁷ water , Alkyl group having 1 to 6 carbon atoms, .p representing an aryl group an acyl group or a 6 to 16 carbon atoms having 2 to 6 carbon atoms in the case of .p is 2 or more represents an integer of 0 to 3, a plurality of R ⁶ may be the same or different, and when p is 2 or less, a plurality of R ⁷ may be the same or different.

  Examples of the metal compound particles include commercially available inorganic particles such as “Op-trake TR-502”, “Op-trake TR-504” of tin oxide-titanium oxide composite particles, and “of silicon oxide-titanium oxide composite particles”. OPTRAKE TR-503 ”,“ OPTRAKE TR-513 ”,“ OPTRAKE TR-520 ”,“ OPTRAKE TR-527 ”,“ OPTRAKE TR-528 ”,“ OPTRAKE TR-529 ”,“ OPTRAIK “TR-543”, “OPTRAIK TR-544”, “OPTRAIK TR-550”, “OPTRAIK TR-505” of titanium oxide particles (trade name, manufactured by Catalyst Chemical Industry Co., Ltd.), zirconium oxide particles (Manufactured by Kojundo Chemical Laboratory Co., Ltd.), tin oxide-zirconium oxide composite particles (manufactured by Catalyst Kasei Kogyo Co., Ltd.), tin oxide particles ((Co., Ltd.) And high purity chemical research laboratory).

  The number average particle diameter of the metal compound particles is preferably 1 nm or more from the viewpoint of suppressing the occurrence of cracks during the formation of a thick film. Moreover, from a viewpoint of improving the transparency with respect to visible light of a cured film, 200 nm or less is preferable and 70 nm or less is more preferable. Here, 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 using a transmission electron microscope or a scanning electron microscope, or the like. be able to. In the present invention, it refers to a value measured by a dynamic light scattering method. Although the apparatus to be used is not specifically limited, Dynamic light scattering altimeter DLS-8000 (made by Otsuka Electronics Co., Ltd.) etc. can be mentioned.

  In the photosensitive composition of the present invention, the metal compound particles are based on 100 parts by weight of the total amount of the organosilane represented by the general formula (1) and the organosilane having a carboxyl group and / or dicarboxylic anhydride structure. The amount is preferably 10 parts by weight or more and 500 parts by weight or less. Thereby, the transmittance | permeability and refractive index of a cured film can be improved more, maintaining the high sensitivity and resolution of the photosensitive resin composition.

  The photosensitive composition of the present invention contains (b) a polysiloxane synthesized by hydrolyzing and partially condensing one or more types of organosilane represented by the following general formula (1).

In the general formula (1), ^{R 1} is hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group or an aryl group having a carbon number of 6 to 16 from 2 to 10 carbon atoms and tables, a carboxyl group and / or dicarboxylic acid It may have an anhydride structure . R ² represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms. n represents an integer of 0 to 3. When n is 2 or more, the plurality of R ¹ may be the same or different from each other. When n is 2 or less, the plurality of R ² may be the same or different.

  Any of the alkyl group, alkenyl group, aryl group, and acyl group may be substituted. Specific examples of the substituent include a hydroxy group, an alkoxy group, an epoxy group, an oxetanyl group, a fluoro group, an amino group, a mercapto group, Examples thereof include an isocyanate group, an acryloxy group, a methacryloxy group, and a carboxy group. The carbon number of the alkyl group, alkenyl group, aryl group, and acyl group does not include the carbon number contained in the substituent. Specific examples of the alkyl group and substituted products thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, and trifluoromethyl group. 3,3,3-trifluoropropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, [(3-ethyl-3-oxetanyl) methoxy] propyl group, 3- Examples include aminopropyl group, 3-mercaptopropyl group, 3-isocyanatopropyl group, 3-acryloxypropyl group, 3-methacryloxypropyl group, 3-methacryloxyoctyl group, 3-succinic anhydride propyl group, and the like. . Specific examples of the alkenyl group and substituted products thereof include a vinyl group. Specific examples of the aryl group and a substituted product thereof include a phenyl group, a tolyl group, a p-hydroxyphenyl group, a naphthyl group which is a condensed polycyclic aromatic hydrocarbon group, a phenanthrenyl group, a fluorenyl group, a pyrenyl group, an indenyl group, An acenaphthenyl group etc. are mentioned. Specific examples of the acyl group and substituted products thereof include an acetyl group.

  In the photosensitive composition of the present invention, the component (b) is synthesized by hydrolyzing and partially condensing one or more organosilanes represented by the general formula (1) in the presence of the component (a). It is preferable that the particle-containing polysiloxane. By using the particle-containing polysiloxane, a photosensitive resin composition having very excellent dispersion stability can be obtained. This is presumably because the matrix polysiloxane and the metal compound particles are bonded. This bonded state can be known by observing the boundary portion between the metal compound particles and the polysiloxane with a scanning electron microscope or a transmission electron microscope. When both are bonded, the interface between them is unclear.

The photosensitive resin composition of the present invention preferably has a carboxyl group and / or a dicarboxylic anhydride structure in R ¹ in the general formula (1) (b). The carboxyl group and / or dicarboxylic anhydride structure can be hydrolyzed to give a carboxyl group in the polysiloxane via a partial condensation reaction. As a result, alkali solubility (developability) is improved, the residue after development is suppressed, and the sensitivity and resolution in exposure can be kept high even after long-term storage at room temperature.

  In the photosensitive resin composition of the present invention, the content ratio of the organosilane having the carboxyl group and / or dicarboxylic acid anhydride structure is a Si atom molar ratio relative to the number of Si atoms in the entire polysiloxane derived from the organosilane. It is preferable that they are 5 mol% or more and 30 mol% or less. Within this range, it is possible to obtain a film having good solvent resistance and high sensitivity and high resolution even after long-term storage at room temperature.

  The content of the carboxyl group in the polysiloxane is determined, for example, by measuring the 29Si-nuclear magnetic resonance spectrum of the polysiloxane, and from the ratio of the peak area of Si to which the carboxyl group is bonded to the peak area of Si to which the carboxyl group is not bonded. Can be sought. When Si and carboxyl groups are not directly bonded, the carboxyl group content of the entire polysiloxane is calculated from the integration ratio between the peak derived from the carboxyl group and the other peaks excluding silanol groups from the 1H-nuclear magnetic resonance spectrum. Then, the content of the carboxyl group indirectly bonded is calculated together with the result of the 29Si-nuclear magnetic resonance spectrum. In addition, the content of the carboxyl group can also be calculated by measuring the acid value after calculating the ratio of the carboxyl group and the silanol group from the 1H-nuclear magnetic resonance spectrum.

  (A) The organosilane compound having a carboxyl group and / or a dicarboxylic anhydride structure constituting the polysiloxane will be specifically described.

  Examples of the organosilane compound having a carboxyl group include a urea group-containing organosilane compound represented by the following general formula (7) or a urethane group-containing organosilane compound represented by the following general formula (8). Two or more of these may be used.

In the above ^formulas, R ^{20, R 22} and ^{R 26} represents a divalent organic group having 1 to 20 carbon atoms. R ²¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ^{23 to} R ²⁵ may be the same as or different from each other, and are an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, or an alkyl having 2 to 6 carbon atoms. A carbonyloxy group or a substituted product thereof is represented. However, at least one of R ^{23 to} R ²⁵ is an alkoxy group, a phenoxy group, or an acetoxy group.

Preferable examples of R ²⁰ and R ²⁶ in the general formulas (7) and (8) include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, a phenylene group, —CH ₂ —C ₆ H ₄ —. _{CH 2 -, - CH 2 -C} 6 H 4 - and hydrocarbon groups such. Among these, from the viewpoint of heat resistance, a hydrocarbon group having an aromatic ring such as a phenylene group, —CH ₂ —C ₆ H ₄ —CH ₂ —, and —CH ₂ —C ₆ H ₄ — is preferable.

R ²¹ in the general formula (7) is preferably hydrogen or a methyl group from the viewpoint of reactivity.

Specific examples of R ^{22 in} the general formulas (7) and (8) include a methylene group, an ethylene group,
Examples thereof include hydrocarbon groups such as n-propylene group, n-butylene group and n-pentylene group, oxymethylene group, oxyethylene group, oxy n-propylene group, oxy n-butylene group and oxy n-pentylene group. . Among these, methylene group, ethylene group, n-propylene group, n-butylene group, oxymethylene group, oxyethylene group, oxy n-propylene group, and oxy n-butylene group are preferable from the viewpoint of easy synthesis.

Of R ^{23 to} R ²⁵ in the general formulas (7) and (8), specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. From the viewpoint of ease of synthesis, a methyl group or an ethyl group is preferable. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group. From the viewpoint of ease of synthesis, a methoxy group or an ethoxy group is preferable. In addition, examples of the substituent of the substituent include a methoxy group and an ethoxy group. Specific examples include a 1-methoxypropyl group and a methoxyethoxy group.

  The urea group-containing organosilane compound represented by the general formula (7) includes an aminocarboxylic acid compound represented by the following general formula (9) and an isocyanate group-containing organosilane compound represented by the following general formula (11). From the above, it can be obtained by a known urea reaction. The urethane group-containing organosilane compound represented by the general formula (8) has a hydroxycarboxylic acid compound represented by the following general formula (10) and an isocyanate group represented by the following general formula (11). It can be obtained from an organosilane compound by a known urethanization reaction.

In the above ^formulas, R ^{20, R 22} and ^{R 26} represents a divalent organic group having 1 to 20 carbon atoms. R ²¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ^{23 to} R ²⁵ represent an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, an alkylcarbonyloxy group having 2 to 6 carbon atoms, or a substituted product thereof. However, at least one of R ^{23 to} R ²⁵ is an alkoxy group, a phenoxy group, or an acetoxy group. Preferred examples of R ²⁰ to R ²⁶ are as described above for ^R 20 ^{to R 26} in the general formula (7) - (8).

  Other specific examples of the organosilane compound having a carboxyl group include compounds represented by the general formula (12).

In the above formula, R ²⁷ represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, an alkylcarbonyloxy group having 2 to 6 carbon atoms, or a substituted product thereof. However, several R <^27> may be the same or different and at least one is an alkoxy group, a phenoxy group, or an acetoxy group. q represents an integer of 1 to 3. r represents an integer of 2 to 20.

  Specific examples of the organosilane compound having a dicarboxylic acid anhydride structure include organosilane compounds represented by any one of the following general formulas (4) to (6). Two or more of these may be used.

In the general formulas (4) to (6), R ^{8 to} R ¹⁰ , R ^{12 to} R ^14, and R ^{16 to} R ¹⁸ are an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, phenyl Group, a phenoxy group or an alkylcarbonyloxy group having 2 to 6 carbon atoms. R ¹¹ , R ¹⁵ and R ¹⁹ are each a single bond or a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 16 carbon atoms, or an alkylcarbonyloxy having 2 to 6 carbon atoms. Represents a group, a carbonyl group, an ether group, an ester group, an amide group, an aromatic group having 6 to 16 carbon atoms, or a divalent group having any of these. The hydrogen atom of these groups is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 16 carbon atoms, an alkylcarbonyloxy group having 2 to 6 carbon atoms, a hydroxy group, or an amino group. , May be substituted with a carboxyl group or a thiol group. h, j, k, and l represent an integer of 0-3.

Specific examples of R ¹¹ , R ¹⁵ and R ¹⁹ include —C ₂ H ₄ —, —C ₃ H ₆ —, —C ₄ H ₈ —, —O—, —C ₃ H ₆ OCH ₂ CH (OH). Examples thereof include CH ₂ O ₂ C—, —CO—, —CO ₂ —, —CONH—, and organic groups listed below.

Specific examples of the organosilane compound represented by the general formula (4) include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylsilylpropyl succinic anhydride, and 3-triphenoxysilylpropyl succinic acid. An anhydride etc. are mentioned. Specific examples of the organosilane compound represented by the general formula (5) include 3-trimethoxysilylsilylpropylcyclohexyl dicarboxylic acid anhydride. Specific examples of the organosilane compound represented by the general formula (6) include 3-trimethoxysilylsilylpropylphthalic anhydride. The photosensitive resin composition of the present invention has 6 to 16 carbon atoms in R ¹ in the general formula (1) from the viewpoint of further improving the compatibility with a naphthoquinonediazide compound which is one of the photosensitizers (c) described later. It is preferable that the aryl group is contained. Further, the content of Si atoms bonded to R ¹ which is an aryl group in the polysiloxane (b) is preferably 30 mol% or more, more preferably 40 mol, based on the total content of Si atoms derived from organosilane. % Or more. Containing 30 mol% or more suppresses phase separation between (b) polysiloxane and (c) naphthoquinonediazide compound, which is a photosensitizing agent, in coating, drying, thermosetting processes, etc. during the preparation of a cured film, and uniform curing A film can be easily formed.

From the viewpoint of further improving the refractive index, sensitivity, and resolution of the cured film, it is preferable that R ^{1 of the} organosilane represented by the general formula (1) is a condensed polycyclic aromatic group. By containing a condensed polycyclic aromatic hydrocarbon group having a high π electron density, a cured film can have a high refractive index. In addition, since the effect of inhibiting dissolution of the unexposed portion is developed during development due to the interaction with naphthoquinonediazide, the contrast between the exposed portion and the unexposed portion is increased. As a result, the sensitivity can be further improved, and further, a reduction in resolution due to a minute undissolved residue can be suppressed. As the condensed polycyclic aromatic hydrocarbon group, a naphthyl group is preferable.

(B) In the metal compound particle-containing polysiloxane, among the organosilanes represented by the general formula (1), an organosilane in which R ¹ is a condensed polycyclic aromatic group is an Si atom mole derived from the organosilane. The molar ratio of Si atoms to the number is preferably 10 mol% or more. By containing 10 mol% or more, the sensitivity and resolution of the photosensitive resin composition can be further improved, and the refractive index of the cured film can be further improved. On the other hand, 60 mol% or less is preferable and 50 mol% or less is more preferable from the viewpoint of suppressing minute dissolution residue during development and further improving the resolution of the photosensitive resin composition.

The content of Si atom bonded to R ¹ which is a condensed polycyclic aromatic hydrocarbon group is determined by measuring the 29Si-NMR spectrum of polysiloxane, and the peak area of Si bonded to the condensed polycyclic aromatic hydrocarbon group. It can be determined from the ratio of the peak areas of Si to which no condensed polycyclic aromatic hydrocarbon group is bonded.

  N in the general formula (1) represents an integer of 0 to 3. A tetrafunctional silane when n = 0, a trifunctional silane when n = 1, a bifunctional silane when n = 2, and a monofunctional silane when n = 3.

Specific examples of the organosilane represented by the general formula (1) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and methyl. Triisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyl Trimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-meta Liloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ) Ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxy Silane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxy Silane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, [(3-ethyl-3- Oxetanyl) methoxy] propyltrimethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic acid, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane, 1-anthracenyltrimethoxysilane, 9-anthracenyltrimethoxysilane, 9-phenanthrenyltrimethoxysilane, 9- full Trifunctional silanes such as oleenyltrimethoxysilane, 2-fluorenyltrimethoxysilane, 1-pyrenyltrimethoxysilane, 2-indenyltrimethoxysilane, 5-acenaphthenyltrimethoxysilane, dimethyldimethoxysilane, dimethyl Diethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, di (1-naphthyl) ) Bifunctional silanes such as dimethoxysilane, di (1-naphthyl) diethoxysilane, trimethylmethoxysilane, tri-n-butylethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, (3-glycidoxypropyl) ) Dimethyl et 1 functional silanes such Shishiran like. Two or more of these organosilanes may be used. Among these organosilanes, trifunctional silanes are preferably used from the viewpoint of improving the hydrolyzability / condensation reactivity at the time of polysiloxane synthesis and further improving the crack resistance and hardness of the cured film. Further, ¹ -naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane, 1-anthracenyl, wherein R ¹ is a condensed polycyclic aromatic hydrocarbon group Rutrimethoxysilane, 9-anthracenyltrimethoxysilane, 9-phenanthrenyltrimethoxysilane, 9-fluorenyltrimethoxysilane, 2-fluorenyltrimethoxysilane, 2-fluorenonyltrimethoxysilane, 1-pyre Nyltrimethoxysilane, 2-indenyltrimethoxysilane, 5-acenaphthenyltrimethoxysilane and the like are preferable.

  In the present invention, (b) polysiloxane is synthesized by hydrolysis and partial condensation of a monomer such as organosilane represented by the general formula (1). Here, partial condensation refers to not allowing all of the hydrolyzed Si—OH to condense, but partially leaving Si—OH in the resulting polysiloxane. In general condensation conditions described later, Si—OH is generally partially left, and the amount of Si—OH to be left is not limited in the present invention. In addition to the organosilane of the general formula (1), other organosilanes may be used. A general method can be used for hydrolysis and partial condensation. For example, a method of adding a solvent, water and, if necessary, a catalyst to the organosilane mixture and heating and stirring at 50 to 150 ° C. for about 0.5 to 100 hours may be mentioned. During the stirring, if necessary, hydrolysis by-products (alcohols such as methanol) and condensation by-products (water) may be distilled off by distillation.

  Although there is no restriction | limiting in particular as said reaction solvent, Usually, the thing similar to the below-mentioned (e) solvent is used. The addition amount of the solvent is preferably 10 to 1500 parts by weight with respect to 100 parts by weight of the monomer such as organosilane. The amount of water used for the hydrolysis reaction is preferably 0.5 to 5 mol with respect to 1 mol of the hydrolyzable group.

  Although there is no restriction | limiting in particular in the catalyst added as needed, An acid catalyst and a base catalyst are used preferably. Specific examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polyvalent carboxylic acid or anhydride thereof, and ion exchange resin. Specific examples of the base catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, amino Examples include alkoxysilanes having groups and ion exchange resins. The addition amount of the catalyst is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer such as organosilane.

  Further, from the viewpoint of the storage stability of the composition, the polysiloxane solution after hydrolysis and partial condensation preferably does not contain the catalyst, and the catalyst can be removed as necessary. The removal method is not particularly limited, but water washing and / or ion exchange resin treatment is preferable from the viewpoint of easy operation and removability. Water washing is a method of concentrating an organic layer obtained by diluting a polysiloxane solution with an appropriate hydrophobic solvent and then washing several times with water with an evaporator or the like. The treatment with an ion exchange resin is a method of bringing a polysiloxane solution into contact with an appropriate ion exchange resin.

  The photosensitive resin composition of the present invention preferably contains a naphthoquinonediazide compound as (c) a photosensitizer. By containing a naphthoquinonediazide compound, the photosensitivity in which the exposed portion is removed with a developer is exhibited. As the naphthoquinone diazide compound, a compound in which naphthoquinone diazide sulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group is preferable.

  Specific examples of the compound having a phenolic hydroxyl group include the following compounds (all available from Honshu Chemical Industry Co., Ltd.).

  The naphthoquinone diazide compound can be synthesized by a known esterification reaction between a compound having a phenolic hydroxyl group and naphthoquinone diazide sulfonic acid chloride. As the naphthoquinone diazide sulfonic acid chloride as a raw material, 4-naphthoquinone diazide sulfonic acid chloride or 5-naphthoquinone diazide sulfonic acid chloride can be used. Since 4-naphthoquinonediazide sulfonic acid ester compound has absorption in the i-line (wavelength 365 nm) region, it is suitable for i-line exposure. Moreover, since 5-naphthoquinone diazide sulfonic acid ester compound has absorption in a wide range of wavelengths, it is suitable for exposure in a wide range of wavelengths. It is preferable to select a 4-naphthoquinone diazide sulfonic acid ester compound or a 5-naphthoquinone diazide sulfonic acid ester compound depending on the wavelength to be exposed. A 4-naphthoquinone diazide sulfonic acid ester compound and a 5-naphthoquinone diazide sulfonic acid ester compound may be used in combination.

  The content of the photosensitizer (c) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 1 part by weight or more based on a total of 100 parts by weight of (a) metal compound particles and (b) polysiloxane. 3 parts by weight or more is more preferable. Further, from the viewpoint of suppressing the coloration due to the degradation of the compatibility with polysiloxane and the decomposition at the time of thermosetting, and further improving the transparency of the photosensitive resin composition and the cured film, it is preferably 30 parts by weight or less, and 20 parts by weight. The following is more preferable.

  The photosensitive resin composition of the present invention contains (d) a silane compound represented by the following general formula (2) and / or the following general formula (3).

In the general formula (2), R ³ represents a hydrocarbon group having 6 to 20 carbon atoms having an aromatic group. R ⁴ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 16 carbon atoms. R ⁵ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms. m represents an integer of 0 to 3, o represents an integer of 0 to 2, and m + o represents an integer of 0 to 4. When m and o are 2 or more, the plurality of R ³ and R ⁴ may be the same or different. When m + o is 2 or less, the plurality of R ⁵ may be the same or different.

Any of the alkyl group, alkenyl group, and aryl group in R ⁴ may be substituted, and specific examples of the substituent include a hydroxy group, an epoxy group, an acryloxy group, and a methacryloxy group. The carbon number of the alkyl group, alkenyl group, and aryl group does not include the carbon number contained in the substituent. Specific examples of the alkyl group and substituted products thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, and 3-glycid. A xylpropyl group, 3-glycidoxyoctyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-acryloxypropyl group, 3-methacryloxypropyl group, 3-methacryloxyoctyl group and the like can be mentioned. Specific examples of the alkenyl group and substituted products thereof include a vinyl group. Specific examples of the aryl group and a substituted product thereof include a phenyl group, a tolyl group, a p-hydroxyphenyl group, a naphthyl group which is a condensed polycyclic aromatic hydrocarbon group, a phenanthrenyl group, a fluorenyl group, a pyrenyl group, an indenyl group, An acenaphthenyl group etc. are mentioned.

In the general formula (3), R ⁶ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 16 carbon atoms. R ⁷ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms. p represents an integer of 0 to 3. When p is 2 or more, the plurality of R ⁶ may be the same or different. When p is 2 or less, the plurality of R ⁷ may be the same or different.

  In addition, these compounds may be used individually or may be used in combination of 2 or more types.

  In the photosensitive resin composition of the present invention, the content of the silane compound represented by general formula (2) and general formula (3) is 100 parts by weight in total of (a) metal compound particles and (b) polysiloxane. On the other hand, the amount is preferably 1 part by weight or more and 20 parts by weight or less. By being 1 part by weight or more, it contributes to the reflow property at the time of the curing process of the photosensitive resin composition of the present invention, and is effective in forming a lens shape. Further, it is more preferably 3 parts by weight or more, which is effective for improving the reflow property, and enables lens formation by curing at a lower temperature. Moreover, it is preferable that it is 20 weight part or less from a viewpoint of suppressing the fall of a sensitivity and the resolution, and the peeling of the fine pattern at the time of image development.

  In the general formula (2), m represents an integer of 0 to 3, o represents an integer of 0 to 2, and m + o = 0 to 3 is an integer. When m + o = 0, tetrafunctional silane, when m + o = 1, trifunctional silane, when m + o = 2, bifunctional silane, and when m + o = 3, monofunctional silane.

  Specific examples of the silane compound represented by the general formula (2) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraacetoxysilane, and tetraphenoxysilane, methyltrimethoxysilane, and methyltriethoxysilane. , Methyltriisopropoxysilane, methyltrin-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n -Butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxy Silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxyoctyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p- Hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane , Trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino Propyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyltriethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propyltrimethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-tri Methoxysilylpropyl succinic acid, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane, 1-anthracenyltrimethoxysilane, 9-anthracenyltri Methoxysilane, 9-phenanthrenyltrimethoxysilane, 9-fluorenyltrimethoxysilane, 2-fluorenyltrimethoxysilane, 1-pyrenyltrimethoxysilane, 2-indenyltrimethoxysilane, 5-acenaphthene Trifunctional silanes such as rutrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, (3-methacryloxypropyl) methyldimethoxysilane, diphenyldimethoxysilane, (3-glycol Bifunctional silanes such as (sidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, di (1-naphthyl) dimethoxysilane, di (1-naphthyl) diethoxysilane, trimethylmethoxysilane, bird - butyl triethoxysilane, (3-glycidoxypropyl) dimethyl silane include monofunctional silanes such as (3-glycidoxypropyl) dimethylethoxysilane.

  The integer of p = 0-3 of General formula (3) is represented. A tetrafunctional silane when p = 0, a trifunctional silane when p = 1, a bifunctional silane when p = 2, and a monofunctional silane when p = 3.

  Specific examples of the silane compound represented by the general formula (3) include tetrafunctional silanes such as tetra (2-methoxyethoxy) silane and tetra (2-ethoxyethoxy) silane, methyltri (2-methoxyethoxy) silane, and methyltri (2-ethoxyethoxy) silane, ethyltri (2-methoxyethoxy) silane, ethyltri (2-ethoxyethoxy) silane, n-propyltri (2-methoxyethoxy) silane, n-propyltri (2-ethoxyethoxy) silane, Isopropyltri (2-methoxyethoxy) silane, isopropyltri (2-ethoxyethoxy) silane, vinyltri (2-methoxyethoxy) silane, vinyltri (2-ethoxyethoxy) silane, 3-methacryloxytri (2-methoxyethoxy) silane , 3-methacryloxytri ( -Ethoxyethoxy) silane, 3-acryloxytri (2-methoxyethoxy) silane, 3-acryloxytri (2-ethoxyethoxy) silane, phenyltri (2-methoxyethoxy) silane, phenyltri (2-ethoxyethoxy) Trifunctional silanes such as silane, 1-naphthyltri (2-methoxyethoxy) silane, 1-naphthyltri (2-ethoxyethoxy) silane, 2-naphthyltri (2-methoxyethoxy) silane, 2-naphthyltri (2-ethoxyethoxy) silane , Dimethyldi (2-methoxyethoxy) silane, dimethyldi (2-ethoxyethoxy) silane, diethyldi (2-methoxyethoxy) silane, diethyldi (2-ethoxyethoxy) silane, ethylmethyldi (2-methoxyethoxy) silane, methylvinyldi (2- Me Xyloxy) silane, methylvinyldi (2-ethoxyethoxy) silane, methyl (3-methacryloxy) di (2-methoxyethoxy) silane, bifunctional silane such as methyl (3-acryloxy) di (2-methoxyethoxy) silane, trimethyl ( And monofunctional silanes such as 2-methoxyethoxy) silane, trimethyl (2-ethoxyethoxy) silane, triethyl (2-methoxyethoxy) silane, and triethyl (2-ethoxyethoxy) silane.

  Two or more of these silane compounds may be used. Among these silane compounds, from the viewpoint of reducing the crosslinking density during curing of the photosensitive resin composition of the present invention or lowering the Tg, from the viewpoint of promoting reflow in the curing process and forming a lens shape, three-dimensionally. A silane compound having a large substituent is preferably used. That is, tetrafunctional silanes such as tetrapropoxysilane, tetraphenoxysilane, and the like, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltri having aromatic hydrocarbons. Methoxysilane, 1-anthracenyltrimethoxysilane, 9-anthracenyltrimethoxysilane, 9-fluorenyltrimethoxysilane, 2-indenyltrimethoxysilane, and / or tetra (2-methoxyethoxy) silane, ethyltri (2-methoxyethoxy) silane, vinyltri (2-methoxyethoxy) silane, phenyltri (2-methoxyethoxy) silane, 1-naphthyltri (2-methoxyethoxy) silane and the like are preferable.

  The photosensitive resin composition of the present invention contains (e) a solvent. Although there is no restriction | limiting in particular in a solvent, The compound which has alcoholic hydroxyl group is preferable. When a solvent having an alcoholic hydroxyl group is used, the solubility of (a) metal compound particles, (b) polysiloxane, and (c) photosensitive agent is improved, and the transparency of the coating film obtained from the photosensitive resin composition is further improved. Can be improved.

  The solvent having an alcoholic hydroxyl group is not particularly limited, but a compound having a boiling point of 110 to 250 ° C. under atmospheric pressure is preferable. When the boiling point is 110 ° C. or higher, drying during the formation of the coating film proceeds moderately, and a coating film with a good surface appearance can be easily obtained. On the other hand, if the boiling point is 250 ° C. or lower, the solvent can be easily removed.

  Specific examples of the solvent having an alcoholic hydroxyl group include acetol (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- Examples include 3-methoxy-1-butanol (boiling point: 174 ° C.). Two or more of these may be contained.

  Moreover, you may contain another solvent with the said solvent instead of the said solvent. Other 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, ethers such as diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol ethyl methyl ether and diethylene glycol dimethyl ether , Γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclopentanone, cyclohex Non, cycloheptanone, and the like.

  Although there is no restriction | limiting in particular in content of (e) solvent in the photosensitive resin composition of this invention, Preferably it is 100-2,000 with respect to a total of 100 weight part of (a) metal compound particle | grains and (b) polysiloxane. The range is parts by weight.

  The photosensitive resin composition of the present invention may contain various surfactants such as various fluorine-based surfactants and silicone-based surfactants in order to improve the flowability during coating. There is no particular limitation on the type of surfactant, for example, “Megafac (registered trademark)” F142D, F172, F173, F183, F445, F470, F475, F477 (above, Dainippon Ink Chemicals, Inc.) Kogyo Co., Ltd.), NBX-15, FTX-218, DFX-18 (manufactured by Neos Co., Ltd.) and other fluorosurfactants, BYK-333, BYK-301, BYK-331, BYK-345, BYK Silicone surfactants such as -307 (manufactured by Big Chemie Japan Co., Ltd.), polyalkylene oxide surfactants, poly (meth) acrylate surfactants, and the like can be used. Two or more of these may be used.

  Furthermore, the photosensitive resin composition of the present invention is optionally provided with a silane coupling agent crosslinking agent, a crosslinking accelerator, a sensitizer, a thermal radical generator, a dissolution accelerator, a dissolution inhibitor, a stabilizer, an antifoaming agent. An additive such as an agent can also be contained.

  Here, the performance evaluation method as a general photosensitive material in the photosensitive resin composition of the present invention will be described.

  The photosensitive resin composition of the present invention is applied onto a substrate by a known method such as spin coating or slit coating, and heated (prebaked) using a heating device such as a hot plate or oven. Pre-baking is preferably performed at a temperature range of 50 to 150 ° C. for 30 seconds to 30 minutes. The film thickness after pre-baking is preferably 1 to 20 μm.

After pre-baking, use a UV-visible exposure machine such as a stepper, mirror projection mask aligner (MPA), parallel light mask aligner (PLA), etc., and a pattern of about 10 to 4000 J / m ² (wavelength 365 nm exposure amount conversion) through a desired mask. Exposure.

After exposure, the exposed portion is dissolved and removed by development to obtain a positive pattern. The resolution of the pattern is
Preferably it is 10 micrometers or less. As a developing method, it is preferable to immerse in a developing solution for 5 seconds to 10 minutes by a method such as showering, dipping, or paddle. As the developer, a known alkali developer can be used. For example, an alkali metal hydroxide, carbonate, phosphate, silicate, borate, or other inorganic alkali, 2-diethylaminoethanol, mono Examples include amines such as ethanolamine and diethanolamine, and aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide (TMAH) and choline. Two or more of these may be used. Moreover, it is preferable to rinse with water after development, and if necessary, dehydration drying baking may be performed in a temperature range of 50 to 150 ° C. with a heating device such as a hot plate or oven.

Then, it is preferable to expose (bleaching exposure) about 100-20,000 J / m < ² > (wavelength 365nm exposure amount conversion) on the whole surface using ultraviolet visible exposure machines, such as PLA. By performing bleaching exposure, the unreacted naphthoquinonediazide compound remaining in the developing film can be photodecomposed, and the transparency of the resulting lens can be further improved.

  The film subjected to bleaching exposure is heated (cured) for 30 seconds to 2 hours in a temperature range of 150 to 450 ° C. with a heating device such as a hot plate or oven to obtain a lens.

The photosensitive resin composition of the present invention, from the viewpoint of productivity in the pattern formation, it is preferable that the sensitivity at the time of exposure is 1500 J / m ² or less, more preferably 1000 J / m ² or less. Such high sensitivity can be easily obtained by a photosensitive resin composition containing polysiloxane using, for example, an organosilane having a carboxyl group and / or a dicarboxylic anhydride structure.

  The sensitivity at the time of exposure is determined by the following method. The photosensitive resin composition is spin-coated on a silicon wafer at an arbitrary rotation number using Mark-7 (manufactured by Tokyo Electron Co., Ltd.) and baked at 100 ° C. for 3 minutes to form a pre-baked film having a thickness of 4 μm. Make it. After this pre-baked film was exposed through a reticle having a line and space (hereinafter referred to as L / S) pattern using an i-line stepper (NSR-2009i9C manufactured by Nikon Corporation), Mark-7 was Shower develop with 2.38 wt% TMAH aqueous solution for 60 seconds, then rinse with water for 30 seconds. In the formed pattern, an exposure amount for resolving a 10 μm L / S pattern with a one-to-one width is obtained as sensitivity.

  Moreover, in order that the photosensitive resin composition of this invention may form a fine lens, it is preferable that the resolution after a cure is 10 micrometers or less. Such resolution can be easily obtained by a photosensitive resin composition containing polysiloxane using, for example, an organosilane having a carboxyl group and / or a dicarboxylic anhydride structure.

  The resolution after curing is determined by the following method. Similar to the above-described method for obtaining the sensitivity at the time of exposure, the exposure amount for resolving the 10 μm L / S pattern with a one-to-one width is obtained as the sensitivity. Then, a cured film is produced by curing at 250 ° C. for 30 minutes using an oven, and the minimum pattern dimension in sensitivity is obtained as the post-cure resolution.

  The cured film obtained by curing the photosensitive resin composition of the present invention preferably has a light transmittance of 90% or more per film thickness of 1 μm at a wavelength of 400 nm, more preferably 92% or more. Such a high transmittance can be easily obtained by a photosensitive resin composition using, for example, highly transparent polysiloxane as a resin component.

The transmittance per 1 μm of film thickness at a wavelength of 400 nm of the cured film is determined by the following method. The photosensitive resin composition is spin-coated on a Tempax glass plate at an arbitrary rotation number using a spin coater, and prebaked at 100 ° C. for 3 minutes using a hot plate. Then, as bleaching exposure, using PLA, the entire surface of the film was exposed to an ultrahigh pressure mercury lamp at 5000 J / m ² (wavelength 365 nm exposure amount conversion), and thermally cured at 220 ° C. in the atmosphere for 5 minutes using a hot plate. A cured film having a thickness of 1 μm is prepared. The ultraviolet-visible absorption spectrum of the obtained cured film is measured using MultiSpec-1500 manufactured by Shimadzu Corporation, and the transmittance at a wavelength of 400 nm is determined. As another method, the extinction coefficient and the film thickness of each target cured film can be measured by a spectroscopic ellipsometer FE5000 manufactured by Otsuka Electronics Co., Ltd., and obtained by the following formula.
Transmittance = exp (−4πkt / λ)
However, k represents an extinction coefficient, t represents a film thickness, and λ represents a measurement wavelength.

  The photosensitive resin composition and cured film of the present invention are suitably used for light-emitting elements such as organic EL light-emitting elements and display elements. More specifically, the organic EL element includes a cured film and a lens formed for the purpose of improving the light extraction efficiency.

  The photosensitive resin composition and the cured film of the present invention are suitably used for a solid-state imaging device. More specifically, a condensing microlens formed on a solid-state imaging device or the like, a white (transparent) color filter or an optical waveguide, an antireflection film installed as an optical filter, or the like. Among these, since both high transparency and a high refractive index can be achieved, it is particularly preferably used as a condensing microlens formed on a solid-state image sensor.

  Since the photosensitive resin composition of the present invention can be formed into a lens shape by a curing process through an etching method, etching is unnecessary and the work can be simplified. Degradation can be avoided.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to these Examples. Of the compounds used in the synthesis examples and examples, those using abbreviations are shown below.
PGMEA: propylene glycol monomethyl ether acetate DAA: diacetone alcohol The solid content concentration of the polysiloxane solution was determined by the following method. 1.5 g of the polysiloxane solution was weighed in an aluminum cup and heated at 250 ° C. for 30 minutes using a hot plate to evaporate the liquid. The solid content remaining in the heated aluminum cup was weighed to determine the solid content concentration of the polysiloxane solution.

Synthesis Example 1 Synthesis of metal compound particle-containing polysiloxane solution (PS-1) In a 500 ml three-necked flask, 16.97 g (0.125 mol) of methyltrimethoxysilane, 38.68 g (0.156 mol) of naphthyltrimethoxysilane, 8.17 g (0.031 mol) of 3-trimethoxysilylpropyl succinic acid, “OPTRAIK” TR-550 (trade name, JGC Catalysts & Chemicals Co., Ltd.), a methanol dispersion of 20.5 wt% titanium oxide-silicon oxide composite particles 209.20 g (manufactured by Co., Ltd., number average particle size is 15 nm) (particle content 100 parts by weight with respect to 100 parts by weight when organosilane is completely condensed (42.89 g)), DAA 159.20 g. Charged 29 g, stirred at room temperature, 17.38 g of water with 0.319 g of phosphoric acid (0.1% relative to charged monomer). Phosphoric acid aqueous solution prepared by dissolving 0 wt%) was added over 10 minutes. The number average particle diameter was measured by a dynamic light scattering method using a dynamic light scattering altimeter DLS-8000 (manufactured by Otsuka Electronics Co., Ltd.). Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 60 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (PS-1). During the temperature rise and heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 197.61 g of methanol and water as by-products were distilled out. The solid content concentration of the obtained metal compound particle-containing polysiloxane solution (PS-1) was 34% by weight.

Synthesis Examples 2 to 10 Synthesis of metal compound particle-containing polysiloxane solution (PS-2 to PS-10) Same as Synthesis Example 1 except that the types and amounts of organosilane and metal compound particles were as shown in Table 1. Polysiloxane solutions (PS-2 to PS-10) were obtained. In addition, Table 1 also shows the outflow amount of by-products (methanol and water) that flowed out during the reaction, and the solid content concentration of the obtained polysiloxane solution.

Synthesis Example 11 Synthesis of naphthoquinone diazide compound (QD-1) Under dry nitrogen stream, Ph-cc-AP-MF (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 15.32 g (0.05 mol) and 5-naphthoquinone diazide 37.62 g (0.14 mol) of sulfonyl chloride was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system would not be 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (QD-1) having the following structure.

Synthesis Example 12 Synthesis of naphthoquinonediazide compound (QD-2) TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 15.32 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride under a dry nitrogen stream 22.84 g (0.085 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. To this, 9.46 g (0.0935 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system would not exceed 35 ° C. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (QD-2) having the following structure.

The silane compounds used in the examples and comparative examples are as follows.
KBM-202SS (Diphenyldimethoxysilane manufactured by Shin-Etsu Silicone Co., Ltd.)
N-POS (Tetrapropoxysilane manufactured by Fuso Chemical Industry Co., Ltd.)
KBC-1003 (Vinyltris (2-methoxyethoxy) silane manufactured by Shin-Etsu Silicone Co., Ltd.)
KBM-503 (3-Methacryloxypropyltrimethoxysilane manufactured by Shin-Etsu Silicone Co., Ltd.)
KBM-5803 (3-Methacryloxyoctyltrimethoxysilane manufactured by Shin-Etsu Silicone Co., Ltd.)
KBM-502 (manufactured by Shin-Etsu Silicone Co., Ltd. (3-methacryloxypropyl) methyldimethoxysilane).

  The photosensitive properties and cured film properties of the compositions in the examples and comparative examples were evaluated by the following methods.

(1) Film thickness measurement Using Lambda Ace STM-602 (trade name, manufactured by Dainippon Screen), the film thickness of each pre-baked film, post-development film, and cured film was measured at a refractive index of 1.70.

(2) Calculation of Photosensitivity For each post-development film, the exposure amount (hereinafter referred to as the optimal exposure amount) for forming a 10 μm L / S pattern with a one-to-one width was calculated as the photosensitivity.

(3) Calculation of resolution The minimum pattern size after development at the optimum exposure amount was taken as the post-development resolution, and the minimum pattern size after curing was taken as the post-cure resolution.

(4) Calculation of refractive index The refractive index at 550 nm at 22 ° C was measured for each cured film (on an 8-inch silicon wafer) using a spectroscopic ellipsometer FE5000 manufactured by Otsuka Electronics Co., Ltd.

(5) Measurement of light transmittance Using MultiSpec-1500 (trade name, manufactured by Shimadzu Corporation), only the Tempax glass substrate was first measured, and its ultraviolet-visible absorption spectrum was used as a reference.
Next, each cured film (on a Tempax glass substrate) was measured with a single beam, the light transmittance at a wavelength of 400 nm per 1 μm was determined, and the difference from the reference was taken as the light transmittance of the cured film.

(6) Lens shape evaluation About each cured film (8 inch silicon wafer), the cross section was observed using FE-SEM (Hitachi Co., Ltd. S-4800), and the shape and the size of the pattern were confirmed. As for the shape of the pattern, “○” indicates the shape of the lens as shown in FIG. 1, and “X” indicates that the shape of the lens is not as shown in FIG. The height of the pattern and the diameter of the bottom were measured.

Example 1
<Production of composition>
38.92 g of the polysiloxane solution (PS-1) obtained in Synthesis Example 1; 1.18 g of the quinonediazide compound (QD-1) obtained in Synthesis Example 11; and KBM-202SS (manufactured by Shin-Etsu Silicone Co., Ltd.) 0 .66 g, BYK-333 (silicone surfactant, manufactured by Big Chemie Co., Ltd.) 100 ppm, DAA 5.74 g, PGMEA 3.01 g were mixed and stirred under a yellow light to obtain a uniform solution. The composition 1 was prepared by filtering with a filter.

<Production of cured film (on 8-inch silicon wafer)>
Immediately after preparation of composition 1, spin coating and baking at 100 ° C. for 3 minutes using Mark-7 (manufactured by Tokyo Electron Co., Ltd.) on an 8-inch silicon wafer, a pre-baked film 1 having a film thickness of about 4.0 μm. Was made. After pattern exposure of the prebaked film through a reticle having 10 μm L / S and 8 μm square / space using an i-line stepper (NSR-2009i9C manufactured by Nikon Corporation), Mark-7 (Tokyo Electron Ltd.) The film 1 was developed by shower development with a 2.38 wt% TMAH aqueous solution for 60 seconds and then rinsing with water for 30 seconds. Then, as bleaching exposure, using PLA (PLA-501F manufactured by Canon Inc.), the entire surface of the film was exposed to 5000 J / m ² (wavelength 365 nm exposure amount conversion) with an ultrahigh pressure mercury lamp. Then, the cured film 1 was produced by curing at 250 ° C. for 30 minutes using an oven.

  Using the obtained pre-baked film 1, the above (1) film thickness measurement was performed. Further, using the obtained post-development film 1, (1) film thickness measurement, (2) photosensitivity calculation, and (3) resolution calculation were performed. The obtained cured film 1 was used to perform the above (1) film thickness measurement, (3) resolution calculation, (4) refractive index calculation, and (6) lens shape evaluation. The results are shown in Table 3.

<Preparation of a film after development (on an 8-inch silicon wafer, after long-term storage of the composition)>
A post-development film 1 ′ was prepared in the same manner as the cured film (on an 8-inch silicon wafer) except that the composition 1 was stored for 1 month at room temperature.

  Using the obtained post-development film 1 ', (2) calculation of photosensitivity and (3) calculation of resolution were performed. The results are shown in Table 3.

<Production of cured film (Tempax glass substrate)>
The composition 1 was spin-coated on a Tempax glass substrate using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.), and then heated at 100 ° C. using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg Co., Ltd.). For 3 minutes to prepare a pre-baked film 1 ′ ′ having a thickness of 1.0 μm. This pre-baked film 1 ′ ′ was developed with a 2.38 wt% TMAH aqueous solution for 60 seconds using an automatic developing machine (Mikasa Co., Ltd. AD-2000), then rinsed with water for 30 seconds, and developed film 1 ′ ′ Was made. Then, as bleaching exposure, using PLA (PLA-501F manufactured by Canon Inc.), the entire surface of the film was exposed to 5000 J / m ² (wavelength 365 nm exposure amount conversion) with an ultrahigh pressure mercury lamp. Then, it cured for 30 minutes at 250 degreeC using oven, and produced cured film 1 ''.

  Using the obtained cured film 1 ′ ′, the light transmittance (5) was measured. The results are shown in Table 3.

Examples 2-26, Comparative Examples 1-3
Compositions 2 to 23 were prepared in the same manner as in Example 1 except that the compositions were as shown in Tables 2 to 3. Each evaluation was performed in the same manner as in Example 1 using each of the obtained compositions. The results are shown in Tables 4-5.

Claims (12)

(A) one or more metal compound particles selected from aluminum compound particles, tin compound particles, titanium compound particles and zirconium compound particles, or one or more metal compounds selected from aluminum compounds, tin compounds, titanium compounds and zirconium compounds and silicon compounds (B) polysiloxane synthesized by hydrolyzing and partially condensing one or more types of organosilane represented by the following general formula (1), in the presence of component (a) Particle-containing polysiloxane synthesized by hydrolyzing and partially condensing one or more types of organosilane represented by the general formula (1), (c) photosensitive agent, (d) the following general formula (2) and / or Or a photosensitive resin comprising a silane compound represented by the following general formula (3) and (e) a solvent: Narubutsu.

(In the general formula (1), R ¹ represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 16 carbon atoms, a carboxyl group and / or a dicarboxylic acid. R ² represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms, n is 0 to 3 When n is 2 or more, the plurality of R ¹ may be the same or different, and when n is 2 or less, the plurality of R ² may be the same or different.

(In the general formula (2), ^{R 3} represents a hydrocarbon group having 6 to 20 carbon atoms having an aromatic group.
R ⁴ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 16 carbon atoms. Any of the alkyl group, alkenyl group, and aryl group in R ⁴ may be substituted. Examples of the alkyl group of R ⁴ and its substituent include methyl group, ethyl group, n-propyl group, isopropyl group, and n-butyl. Group, t-butyl group, n-hexyl group, n-decyl group, 3-glycidoxypropyl group, 3-glycidoxyoctyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-acryloxy It represents a propyl group, 3-methacryloxypropyl group, 3-methacryloxy-octyl group, in the alkenyl group and its substitution product, represents a vinyl group, in the aryl group and substituents thereof, phenyl group, tolyl It represents groups, p- hydroxyphenyl group, a naphthyl group, a phenanthrenyl group, a fluorenyl group, a pyrenyl group, an indenyl group, an acenaphthenyl group
R ⁵ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms.
m represents an integer of 0 to 3, o represents an integer of 0 to 2, and m + o represents an integer of 0 to 3. When m and o are 2 or more, the plurality of R ³ and R ⁴ may be the same or different. When m + o is 2 or less, the plurality of R ⁵ may be the same or different.
In the general formula (3), R ⁶ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 16 carbon atoms.
R ⁷ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms.
p represents an integer of 0 to 3. When p is 2 or more, the plurality of R ⁶ may be the same or different. When p is 2 or less, the plurality of R ⁷ may be the same or different. ) The photosensitive resin composition according to claim 1, wherein R ^{1 of the} organosilane represented by the general formula (1) is a condensed polycyclic aromatic group. Among the organosilanes represented by the general formula (1), an organosilane in which R ¹ has a carboxyl group and / or a dicarboxylic anhydride structure is represented by any one of the following general formulas (4) to (6). The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is a dicarboxylic acid anhydride.

(In said general formula (4)-(6), R < ⁸ > -R < ¹⁰ >, R < ¹² > -R < ¹⁴ > and R < ¹⁶ > -R < ¹⁸ > are a C1-C6 alkyl group, a C1-C6 alkoxy group, Represents a phenyl group, a phenoxy group, or an alkylcarbonyloxy group having 2 to 6 carbon atoms, R ¹¹ , R ¹⁵ and R ^{19 each} represent a single bond or a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms; Having a -16 cycloaliphatic hydrocarbon group, an alkylcarbonyloxy group having 2-6 carbon atoms, a carbonyl group, an ether group, an ester group, an amide group, an aromatic group having 6-16 carbon atoms, or any of these Represents a divalent group in which the hydrogen atom is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 16 carbon atoms, or an alkylcarbonyloxy having 2 to 6 carbon atoms. Group, hydroxy Group, an amino group, may be substituted with a carboxyl group or a thiol group .h, j, k and l represents an integer of 0 to 3.) Among the organosilanes represented by the general formula (1), the content ratio of the organosilane having R ¹ having a carboxyl group and / or a dicarboxylic acid anhydride structure is the number of moles of Si atoms in the whole polysiloxane derived from the organosilane. The photosensitive resin composition according to any one of claims 1 to 3, wherein the molar ratio of Si is 5 mol% to 30 mol%. Among the organosilanes represented by the general formula (1), the organosilane in which R ¹ is a condensed polycyclic aromatic group is 10 mol% in terms of the Si atom molar ratio relative to the number of moles of Si atoms derived from the organosilane. It is the above, The photosensitive resin composition in any one of Claims 2-4 characterized by the above-mentioned. The content of the silane compound represented by the general formula (2) and the general formula (3) is 1 part by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the (b) metal compound particle-containing polysiloxane. The photosensitive resin composition in any one of Claims 1-5 characterized by the above-mentioned. One or more metal compound particles selected from the aluminum compound particles, tin compound particles, titanium compound particles and zirconium compound particles, or one or more metal compounds selected from aluminum compounds, tin compounds, titanium compounds and zirconium compounds and a silicon compound The photosensitive resin composition according to claim 1, wherein the composite particles have a number average particle diameter of 1 nm to 200 nm. One or more metal compound particles selected from the aluminum compound particles, tin compound particles, titanium compound particles and zirconium compound particles, or one or more metal compounds selected from aluminum compounds, tin compounds, titanium compounds and zirconium compounds and a silicon compound The photosensitive resin composition according to claim 1, wherein the composite particles are titanium compound particles, zirconium compound particles, or a composite particle of a titanium compound or a zirconium compound and a silicon compound. One or more metal compound particles selected from the aluminum compound particles, tin compound particles, titanium compound particles and zirconium compound particles, or one or more metal compounds selected from aluminum compounds, tin compounds, titanium compounds and zirconium compounds and a silicon compound The photosensitive resin composition according to claim 1, wherein the composite particles are 10 parts by weight or more and 500 parts by weight or less with respect to 100 parts by weight of the total amount of polysiloxane. The cured film formed by hardening the photosensitive resin composition in any one of Claims 1-9. A light emitting device comprising the cured film according to claim 10. A solid-state imaging device comprising the cured film according to claim 10.

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