Photosensitive resin composition, cured film, and color filter, solid-state imaging element, and fingerprint authentication device using said cured film

Abstract

The present invention addresses the problem of providing a photosensitive resin composition that, when in the form of a cured film, has high transparency and chemical resistance, has low film stress, and has high adhesion to metal layers containing molybdenum, aluminum, or nickel. In order to solve such a problem, the present invention proposes a photosensitive resin composition comprising a metal chelator, a photo-radical polymerization initiator, and a siloxane resin having a radically-polymerizable group, where the content of an organosilane unit (D unit) represented by (R)2SiO2 / 2 (R is an organic group) in the siloxane resin having a radically-polymerizable group is 30-85 mol% with respect to 100 mol% of all of the organosilane units.

Description

Photosensitive resin composition and cured film, and color filter, solid-state imaging device, and fingerprint authentication device using the cured film

[0001] The present invention relates to a photosensitive resin composition, a cured film, and a color filter, a solid-state imaging device, and a fingerprint authentication device each including the photosensitive resin composition.

[0002] In recent years, mobile display devices such as smartphones and tablet PCs (personal computers) have been equipped with biometric authentication functions for unlocking and identity authentication. Among biometric authentication methods, fingerprint authentication in particular is installed in many devices due to its low cost, small size, and high convenience.

[0003] Traditionally, fingerprint authentication has typically been achieved by mounting a capacitive fingerprint authentication device on the bezel of the display (around the edge of the display). However, with the trend toward full-screen displays on smartphones, the bezel is becoming less and less prominent. This has created a need for fingerprint authentication devices to be mounted below the display, in a so-called "under-display" configuration.

[0004] The main authentication methods being considered for under-display fingerprint authentication devices are ultrasonic and optical. Ultrasonic methods are characterized by high authentication accuracy and fast authentication speed, but their adoption rate is still low and manufacturing costs remain high. On the other hand, optical methods are currently the mainstream method due to their versatility, allowing them to be applied to not only organic light-emitting diode displays but also liquid crystal displays, and manufacturing costs are on the decline.

[0005] Generally, optical fingerprint authentication devices have the problem of lower authentication accuracy than ultrasonic types, but a thin optical under-display fingerprint authentication device that can be installed in the very narrow space between the battery and the screen has been proposed as an optical fingerprint authentication device with high authentication accuracy (see, for example, Patent Document 1 and Patent Document 2).

[0006] The optical under-display fingerprint authentication device described in Patent Document 2 is composed of a substrate, a sensor, a light-shielding layer, a transparent medium layer, and a microlens. Methods for forming the transparent medium layer include a method of forming it by screen printing and a method of forming it by photolithography using a photosensitive material, but the latter method has attracted attention because it excels in positional accuracy and dimensional accuracy, which are important for improving authentication accuracy.

[0007] Furthermore, a photosensitive resin composition containing a specific alkali-soluble silicone resin or the like has been proposed as a photosensitive material capable of forming a thick film and having excellent heat resistance, transparency, crack resistance, and resistance to thermal shock tests (see, for example, Patent Document 3). Also, a photosensitive resin composition containing polysiloxane, a photosensitizer, a polymerizable compound having a phosphorus atom, and a silane compound having a ureido group has been proposed as a photosensitive material having excellent adhesion to glass substrates and metal substrates and excellent chemical resistance (see, for example, Patent Document 4).

[0008] JP 2020-35327 A International Publication No. 2020 / 038408 International Publication No. 2013 / 031985 International Publication No. 2019 / 102655

[0009] Microlenses used in fingerprint authentication devices generally have larger diameters than microlenses used in CMOS image sensors, resulting in a longer focal length, i.e., the distance from the center of the microlens to the image sensor. Therefore, the transparent medium layer formed between the microlens and the image sensor must be approximately 10 μm to 200 μm thick. When forming such a thick film, film stress becomes important. Film stress refers to the mechanical stress that occurs when a cured film is formed on a flat substrate, such as the contraction stress accumulated within the film. High film stress can lead to significant warping of the substrate during film formation, resulting in issues such as errors during substrate transport. Therefore, there is a need for materials that have low film stress when cured to suppress substrate warpage.

[0010] Furthermore, since the production lines for manufacturing fingerprint authentication devices often utilize TFT (thin film transistor) production lines, metal layers containing molybdenum, aluminum, or nickel are generally used as light-shielding layers and sensor lead-out wiring in fingerprint authentication devices. Therefore, the material for forming the transparent medium layer must be resistant to chemical solutions used when laminating these metal layers on top of each other, and must also have excellent adhesion to these metal layers.

[0011] That is, the material for forming the transparent medium layer of the optical under-display type fingerprint authentication device must have high transparency and chemical resistance, low film stress, and high adhesion to the metal layer containing molybdenum, aluminum, or nickel. Furthermore, there are cases where it is required to be able to form a pattern of a thick film with a film thickness of 10 μm or more.

[0012] On the other hand, as mentioned above, for example, Patent Documents 3 and 4 propose various materials, but the material described in Patent Document 3 has low adhesion to metal layers containing molybdenum, aluminum, or nickel, and in the case of thick films with a thickness of more than 10 μm used in fingerprint authentication devices, the film stress of the cured film is large, which causes the substrate to warp.

[0013] Furthermore, the material described in Patent Document 4 has a similar problem in that when the thickness of the cured film exceeds 10 μm, the film stress of the cured film is large and warpage occurs in the substrate.

[0014] The present invention has been made in view of the above problems of the conventional art, and an object of the present invention is to provide a photosensitive resin composition which, when formed into a cured film, has high transparency and chemical resistance, low film stress, and high adhesion to a metal layer containing molybdenum, aluminum, or nickel.

[0015] The object of the present invention is achieved by the following configuration.

[0016] A photosensitive resin composition comprising the following components (a) to (c), wherein in component (a), (R) ２ SiO ２／２A photosensitive resin composition containing organosilane units represented by the formula (R is an organic group) (hereinafter, such organosilane units will be referred to as "D units") in an amount of 30 mol % to 85 mol % based on 100 mol % of all organosilane units: component (a): a siloxane resin having a radical polymerizable group; component (b): a metal chelating agent; and component (c): a photoradical polymerization initiator.

[0017] Further, more preferred aspects of the present invention are, for example, as follows: - The photosensitive resin composition described above, in which either or both of an aluminum chelate compound and a zirconium chelate compound are used as component (b). - The photosensitive resin composition described above, in which the content of component (b) is 0.1% by weight or more and 5% by weight or less, based on 100% by weight of the solid content of the photosensitive resin composition. - The photosensitive resin composition described above, in which component (b) is either or both of an aluminum chelate compound and a zirconium chelate compound, the content of component (b) is 0.1% by weight or more and 5% by weight or less, based on 100% by weight of the solid content of the photosensitive resin composition, and further in which R in the D units is a phenyl group, and the content of D units is 30 mol% or more and 65 mol% or less, based on 100 mol% of all organosilane units. The photosensitive resin composition, wherein component (b) is either or both of an aluminum chelate compound and a zirconium chelate compound, the content of component (b) is 0.1% by weight or more and 5% by weight or less based on 100% by weight of the solid content of the photosensitive resin composition, and further wherein R in the D units is a phenyl group and the content of D units is 30% by weight or more and 65% by weight or less based on 100% by weight of all organosilane units, and the component (a) contains either or both of a carboxyl group and a dicarboxylic acid anhydride group. The photosensitive resin composition, further comprising the following component (d): component (d): monofunctional (meth)acrylate

[0018] According to the photosensitive resin composition of the present invention, it is possible to provide a photosensitive resin composition that, when cured, has high transparency and chemical resistance, low film stress, and high adhesion to a metal layer containing molybdenum, aluminum, or nickel.

[0019] The present invention will be described in more detail below. Preferred embodiments of the photosensitive resin composition, cured film, color filter, solid-state imaging device, and fingerprint authentication device of the present invention will be specifically described below, but the present invention is not limited to the following embodiments and can be practiced with various modifications depending on the purpose and application.

[0020] The photosensitive resin composition of the present invention contains the following components (a) to (c): component (a): a siloxane resin having a radical polymerizable group, (b) a metal chelating agent, and (c) a photoradical polymerization initiator.

[0021] In the component (a), (R) ２ SiO ２／２ The content of organosilane units (D units) represented by (R is an organic group) is 30 mol % or more and 85 mol % or less with respect to 100 mol % of all organosilane units.

[0022] The siloxane resin used as component (a) in the photosensitive resin composition of the present invention refers to a polymer having a siloxane skeleton (-Si-O- bond) as a repeating unit. Furthermore, in the present invention, the organosilane unit refers to a silane unit having at least one organic group on a side chain of the siloxane skeleton. Furthermore, R contained in the D unit is an organic group, and this organic group refers to a group having a carbon atom bonded to a silicon atom of the siloxane skeleton, specific examples of which are described below.

[0023] The inclusion of component (a) makes it possible to form a cured film that is highly transparent and has excellent heat resistance and weather resistance, which is due to the fact that component (a) has a siloxane skeleton in its main chain.

[0024] The weight average molecular weight (Mw) of component (a) is preferably 500 or more, more preferably 1,000 or more, from the viewpoint of further improving chemical resistance. On the other hand, the weight average molecular weight of component (a) is preferably 10,000 or less, more preferably 5,000 or less, from the viewpoint of improving solubility in a developer during pattern formation. Here, the weight average molecular weight of component (a) refers to a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

[0025] Component (a) contains 30 mol% or more and 85 mol% or less of D units relative to 100 mol% of all organosilane units. When the content of D units is 30 mol% or more relative to 100 mol% of all organosilane units, three-dimensional crosslinking can be moderately suppressed, and a cured film with low film stress and excellent crack resistance can be formed. The content of D units is more preferably 35 mol% or more, and even more preferably 40 mol% or more, relative to 100 mol% of all organosilane units. Furthermore, when the content of D units is 85 mol% or less relative to 100 mol% of all organosilane units, the crosslinking density of the film can be increased, and it is possible to maintain excellent moist heat resistance and sufficient chemical resistance to acids and alkalis. The content of D units is more preferably 75 mol% or less, and even more preferably 65 mol% or less, relative to 100 mol% of all organosilane units. The D units contained in the component (a) may be of one type or multiple types.

[0026] In addition, in component (a), it is preferable that the two R contained in the D unit each independently contain a functional group selected from the group consisting of a methyl group, a phenyl group, a cyclopentyl group, and a cyclohexyl group. However, the two R are not simultaneously methyl groups. It is also preferable that the two R are each independently a functional group selected from the group consisting of a methyl group, a phenyl group, a cyclopentyl group, and a cyclohexyl group (however, the two R are not simultaneously methyl groups). By using component (a) containing such D units, three-dimensional crosslinking can be appropriately suppressed due to steric hindrance between the functional groups, and a cured film with low film stress and excellent crack resistance can be formed. The proportion of such D units is preferably 65 mol% or more and 92% mol or less, assuming that all D units are 100 mol%. From the viewpoint of forming a cured film with low film stress and excellent crack resistance, it is preferable to have D units in which both R are phenyl groups. From the same viewpoint, it is preferable that the D units in which both R are phenyl groups account for 30 mol % to 65 mol % of all organosilane units (100 mol %). Note that, in addition to the D units described above as a preferred embodiment, component (a) used in the present invention may also contain other organosilane units, such as organosilane units derived from an organosilane compound having a radical polymerizable group, as described below.

[0027] The D units contained in component (a) can be obtained by hydrolysis and condensation of a bifunctional organosilane compound.

[0028] Examples of such bifunctional organosilane compounds include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-t-butyldimethoxysilane, di-t-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, and dicyclopentyldimethoxysilane. Silane, dicyclopentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, diheptyldimethoxysilane, diheptyldiethoxysilane, dioctyldimethoxysilane, dioctyldiethoxysilane, dinonyldimethoxysilane, dinonyldiethoxysilane, didecyldimethoxysilane, didecyldiethoxysilane, ethylmethyldimethoxysilane, ethylmethyldiethoxysilane, n-propylmethyldimethoxysilane, n-propyl pylmethyldiethoxysilane, isopropylmethyldimethoxysilane, isopropylmethyldiethoxysilane, n-butylmethyldimethoxysilane, n-butylmethyldiethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, n-pentylmethyldimethoxysilane, n-pentylmethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, n-hexylmethyldimethoxysilane, n-hexylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, Cyclohexylmethyldiethoxysilane, heptylmethyldimethoxysilane, heptylmethyldiethoxysilane, octylmethyldimethoxysilane, octylmethyldiethoxysilane, nonylmethyldimethoxysilane, nonylmethyldiethoxysilane, decylmethyldimethoxysilane, decylmethyldiethoxysilane, diphenylsilanediol, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, naphthylmethyldimethoxysilane, naphthylmethyldiethoxysilane,Examples of such silanes include biphenylmethyldimethoxysilane, biphenylmethyldiethoxysilane, cyclopentylphenyldimethoxysilane, cyclopentylphenyldiethoxysilane, cyclopentylcyclohexyldimethoxysilane, cyclopentylcyclohexyldiethoxysilane, cyclohexylphenyldimethoxysilane, and cyclohexylphenyldiethoxysilane. Two or more of these may be used.

[0029] Among these, from the viewpoint of being able to form a cured film that has excellent resistance to moist heat and chemicals, low film stress, and excellent crack resistance, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, diphenylsilanediol, diphenyldimethoxysilane, diphenyl Preferred are cyclopentylphenyldimethoxysilane, cyclopentylphenyldiethoxysilane, cyclopentylphenyldiethoxysilane, cyclopentylcyclohexyldimethoxysilane, cyclopentylcyclohexyldiethoxysilane, cyclohexylphenyldimethoxysilane, and cyclohexylphenyldiethoxysilane, and more preferably selected from diphenylsilanediol, diphenyldimethoxysilane, and diphenyldiethoxysilane.

[0030] The component (a) used in the present invention has a radical polymerizable group. The radical polymerizable group refers to a functional group having a double bond that reacts with radicals generated from a radical polymerization initiator. Examples of the radical polymerizable group include a vinyl group, an allyl group, a methacryl group, an acrylic group, and a styryl group. From the viewpoint of high radical reactivity and further improving the chemical resistance of the cured film and the sensitivity during pattern processing, a methacryl group, an acrylic group, and a styryl group are preferred.

[0031] A simple method for introducing a radically polymerizable group into component (a) is to use an organosilane compound having a radically polymerizable group and subject it to hydrolysis and condensation.

[0032] Examples of organosilane compounds having a radical polymerizable group include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. Silane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-methacryloxymethyltrimethoxysilane, 3-methacryloxymethyltriethoxysilane, 3-methacryloxymethylmethyldimethoxysilane, 3-methacryloxymethylmethyldiethoxysilane, 3-acryloxymethylmethyldimethoxysilane, 3-acryloxymethylmethyldiethoxysilane, 3-methacryloxyoctyltrimethoxysilane, 3-methacryloxyoctyltriethoxysilane, 3-methacryloxyoctylmethyldimethoxysilane, 3-methacryloxyoctylmethyldiethoxysilane, 3-acryloxyoctylmethyldimethoxysilane, and 3-acryloxyoctylmethyldiethoxysilane. Two or more of these may be used.

[0033] Among these, from the viewpoint of further improving the chemical resistance of the cured film and the sensitivity during pattern processing, styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-Methacryloxymethyltrimethoxysilane, 3-methacryloxymethyltriethoxysilane, 3-methacryloxymethylmethyldimethoxysilane, 3-methacryloxymethylmethyldiethoxysilane, 3-acryloxymethylmethyldimethoxysilane, 3-acryloxymethylmethyldiethoxysilane, 3-methacryloxyoctyltrimethoxysilane, 3-methacryloxyoctyltriethoxysilane, 3-methacryloxyoctylmethyldimethoxysilane, 3-methacryloxyoctylmethyldiethoxysilane, 3-acryloxyoctylmethyldimethoxysilane, and 3-acryloxyoctylmethyldiethoxysilane are preferred.

[0034] Among these, from the viewpoint of being able to form a cured film that has excellent moist heat resistance and chemical resistance, and that has low film stress and excellent crack resistance, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-methacryloxyoctylmethyldimethoxysilane, 3-methacryloxyoctylmethyldiethoxysilane, 3-acryloxyoctylmethyldimethoxysilane, and 3-acryloxyoctylmethyldiethoxysilane are more preferred, and bifunctional organosilane compounds such as 3-methacryloxypropylmethyldimethoxysilane and 3-acryloxypropylmethyldimethoxysilane are even more preferred. Incidentally, to avoid any doubt, it should be noted that structural units derived from these bifunctional organosilane compounds having a radical polymerizable group correspond to D units.

[0035] Component (a) preferably contains 5 mol% to 50 mol% of organosilane units having radical polymerizable groups, based on 100 mol% of all organosilane units. When component (a) contains 5 mol% or more of organosilane units having radical polymerizable groups relative to 100 mol% of all organosilane units, the crosslinking density of the cured film can be increased, and the moist heat resistance and chemical resistance can be improved. The proportion of organosilane units having radical polymerizable groups is more preferably 7 mol% or more, and even more preferably 10 mol% or more, relative to 100 mol% of all organosilane units. Furthermore, when component (a) contains 50 mol% or less of organosilane units having radical polymerizable groups relative to 100 mol% of all organosilane units, excessive radical reaction can be suppressed, residue during development can be suppressed, and stress on the cured film can be further reduced. The proportion of organosilane units having a radical polymerizable group is more preferably 30 mol % or less, and even more preferably 12 mol % or less, relative to 100 mol % of all organosilane units.

[0036] The component (a) used in the present invention preferably contains either a carboxyl group or a dicarboxylic acid anhydride group, or both. By including a carboxyl group or a dicarboxylic acid anhydride group in its molecular structure, component (a) suppresses residues during development, improves resolution, enables the formation of patterns with excellent resolution even in thick films with a film thickness of 10 μm or more, and improves adhesion to the underlying substrate, metal layer, or resin layer. Examples of the carboxyl group and dicarboxylic acid anhydride group include alkylene carboxyl groups, succinic acid groups, succinic anhydride groups, phthalic acid groups, and phthalic anhydride groups.

[0037] The component (a) having a carboxyl group or a dicarboxylic anhydride group can be obtained by hydrolysis and condensation of an organosilane compound having a carboxyl group or a dicarboxylic anhydride group.

[0038] Examples of organosilane compounds having a carboxyl group or a dicarboxylic acid anhydride group include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-triphenoxysilylpropyl succinic anhydride, 3-trimethoxysilylpropyl cyclohexyl dicarboxylic anhydride, and 3-trimethoxysilylpropyl phthalic anhydride. Two or more of these may be used. Among these, 3-trimethoxysilylpropyl succinic anhydride and 3-triethoxysilylpropyl succinic anhydride are preferred from the viewpoints of suppressing residues during development, improving resolution, and being able to form patterns with excellent resolution even in thick films with a film thickness of 10 μm or more.

[0039] Component (a) preferably contains 1 mol% to 30 mol% of organosilane units having a carboxyl group or a dicarboxylic anhydride group, based on 100 mol% of all organosilane units. Having the proportion of organosilane units having a carboxyl group or a dicarboxylic anhydride group of 1 mol% or more relative to 100 mol% of all organosilane units suppresses residue during development, improves resolution, and enables the formation of patterns with excellent resolution even in thick films with a thickness of 10 μm or more. The proportion of organosilane units having a carboxyl group or a dicarboxylic anhydride group is more preferably 3 mol% or more, and even more preferably 5 mol% or more, relative to 100 mol% of all organosilane units. Furthermore, having the proportion of organosilane units having a carboxyl group or a dicarboxylic anhydride group of 30 mol% or less relative to 100 mol% of all organosilane units suppresses film loss during development and improves patterning properties. The proportion of organosilane units having a carboxyl group or a dicarboxylic anhydride group is more preferably 25 mol % or less, and even more preferably 20 mol % or less, relative to 100 mol % of all organosilane units.

[0040] The component (a) is preferably a hydrolysis condensation product of a bifunctional organosilane compound that provides D units, an organosilane compound having the radical polymerizable group, and an organosilane compound having either or both of a carboxyl group and a dicarboxylic acid anhydride group, and may further be a hydrolysis condensation product of any of these organosilane compounds with other organosilane compounds.

[0041] Other organosilane compounds include, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-(N,N-diglycidyl)aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, Sisilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 2-cyanoethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 1-glycidoxyethyltrimethoxysilane, 1-glycidoxyethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 1-glycidoxypropyltrimethoxysilane, 1-glycidoxypropyl glycidoxypropyltriethoxysilane, 2-glycidoxypropyltrimethoxysilane, 2-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltripropoxysilane, 3-glycidoxypropyltriisopropoxysilane, 3-glycidoxypropyltributoxysilane, 3-glycidoxypropyltri(methoxyethoxy)silane, 1-glycidoxybutyltrimethoxysilane, 1-glycidoxybutyltriethoxysilane, 2-glycidoxypropyltriethoxysilane butyltrimethoxysilane, 2-glycidoxybutyltriethoxysilane, 3-glycidoxybutyltrimethoxysilane, 3-glycidoxybutyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltripropoxysilane, 2-(3,4-epoxycyclohexyl)ethyltributoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltriethoxysilane, 4-(3,4-epoxycyclohexyl)butyltrimethoxysilane, 4-(3,4-epoxycyclohexyl)butyltriethoxysilane, trifluoro Methyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, perfluoropropyltrimethoxysilane, perfluoropropyltriethoxysilane, perfluoropentyltrimethoxysilane, perfluoropentyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctyltripropoxysilane, tridecafluorooctyltriisopropoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, bis(trifluoromethyl)dimethoxysilane, bis(trifluoropropyl)dimethoxysilane, bis(trifluoropropyl)diethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane, heptadecafluorodecylmethyl Examples of such silane include dimethoxysilane, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 2-naphthyltrimethoxysilane, 1-anthracenyltrimethoxysilane, 9-anthracenyltrimethoxysilane, 9-phenanthrenyltrimethoxysilane, 9-fluorenyltrimethoxysilane, 2-fluorenyltrimethoxysilane, 2-fluorenonyltrimethoxysilane, 1-pyrenyltrimethoxysilane, 2-indenyltrimethoxysilane, and 5-acenaphthenyltrimethoxysilane. Two or more of these may be used.

[0042] Component (a) can be obtained by hydrolysis and condensation of an organosilane compound, for example, by hydrolyzing an organosilane compound and then subjecting the resulting silanol compound to a condensation reaction in the presence of an organic solvent or without a solvent.

[0043] The various conditions for the hydrolysis reaction can be appropriately set taking into consideration the reaction scale, size, shape, etc. of the reaction vessel. For example, it is preferable to add an acid catalyst and water to an organosilane compound in a solvent over 1 to 180 minutes, and then react at room temperature to 110°C for 1 to 180 minutes. By carrying out the hydrolysis reaction under such conditions, a rapid reaction can be suppressed. The reaction temperature is more preferably 30 to 105°C.

[0044] In order to promote the hydrolysis reaction and the dehydration condensation reaction, it is preferable to use a catalyst. Examples of the catalyst include acids such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acids and their anhydrides, bases such as monoethanolamine, diethanolamine, triethanolamine, 3,3-dimethylbutylamine, methylpentylamine, n-butylethylamine, dibutylamine, n-butylamine, pentylamine, isopentylamine, cyclopentylamine, hexylamine, cyclohexylamine, dimethylhexylamine, N,N-dimethylbutylamine, N,N-dimethylhexadecylamine, and N,N-dimethyl-n-octylamine, and bases such as pyridine methanesulfonate and pyridine ethanesulfonate. Examples of organic salts that can be used include silane salts, pyridine propanesulfonate, pyridine benzenesulfonate, pyridine p-toluenesulfonate, pyridine xylenesulfonate, pyridine trifluoromethanesulfonate, pyridine trifluoroethanesulfonate, pyridine trifluoropropanesulfonate, pyridine trifluoroacetate, 2,4,6-trimethylpyridine p-toluenesulfonate, aniline p-toluenesulfonate, tetramethylammonium p-toluenesulfonate, tetraethylammonium p-toluenesulfonate, tetramethylammonium hydroxide, and tetraethylammonium hydroxide. The amount of catalyst added is preferably 0.05 to 5 parts by weight per 100 parts by weight of the total organosilane compounds used in the hydrolysis reaction. By using the catalyst in this range, the hydrolysis reaction can proceed more efficiently.

[0045] After obtaining the silanol compound by the hydrolysis reaction of the organosilane compound, the reaction solution is preferably heated as is at 50° C. or higher and below the boiling point of the solvent for 1 to 100 hours to carry out the condensation reaction.

[0046] Examples of organic solvents used in the hydrolysis and condensation reaction of organosilane compounds 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, and diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol monomethyl ether. Examples of suitable solvents include ethers such as dibutyl ether and diethyl ether; ketones such as methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, and 2-heptanone; amides such as dimethylformamide and dimethylacetamide; acetates such as ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, and butyl lactate; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, and cyclohexane; γ-butyrolactone, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. Two or more of these may be used. From the viewpoints of the transmittance of the cured film and the solubility of each component, diacetone alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, γ-butyrolactone, and the like are preferred.

[0047] When the hydrolysis reaction produces a compound listed above as an organic solvent or a compound that acts as a solvent, it is possible to carry out the hydrolysis without a solvent. After the reaction is completed, it is also preferable to add a solvent to adjust the concentration to an appropriate level for the resin composition. Depending on the purpose, after the hydrolysis, an appropriate amount of the produced alcohol may be distilled and removed by heating or under reduced pressure, and then a suitable solvent may be added.

[0048] The amount of solvent used in the hydrolysis reaction is preferably 50 parts by weight or more and 500 parts by weight or less per 100 parts by weight of the organosilane compound used as a raw material. By setting the amount of solvent within this range, the hydrolysis reaction can proceed more efficiently.

[0049] The water used in the hydrolysis reaction is preferably ion-exchanged water, and the amount of water is preferably 1.0 to 4.0 moles per mole of silane atoms contained in the organosilane compound.

[0050] The photosensitive resin composition of the present invention contains a metal chelating agent (component (b)). The metal chelating agent refers to a complex compound having a structure in which one or more multidentate ligands are chelated to a metal atom.

[0051] By including component (b), the photosensitive resin composition of the present invention can form a cured film that maintains high transparency, low film stress, and high crack resistance while improving adhesion to a metal layer containing molybdenum, aluminum, or nickel and chemical resistance. This is because all or a part of component (b) is incorporated into the film, and component (b) can promote a condensation reaction between unreacted silanol groups remaining in component (a).

[0052] The component (b) is preferably a metal chelating agent represented by the following general formula (3).

[0053]

[0054] (M represents a metal atom, R ５ are each independently a hydrogen atom, an alkyl group, an aryl group, or an alkenyl group, and R ６and R ７ are each independently hydrogen, an alkyl group, an aryl group, an alkenyl group, or an alkoxy group, j is an integer of 0 to 8, and k is an integer of 1 to 4.) Examples of the metal atom M include titanium, zirconium, aluminum, zinc, cobalt, molybdenum, lanthanum, barium, strontium, magnesium, and calcium, from the viewpoint of high transparency of the formed cured film. Among these, from the viewpoint of improving adhesion to a metal layer containing molybdenum, aluminum, or nickel while maintaining high transparency, low film stress, and excellent crack resistance, and from the viewpoint of improving chemical resistance, zirconium or aluminum is preferred as the metal atom M, and zirconium is more preferred. That is, as component (b), it is preferable to use an aluminum chelate compound or a zirconium chelate compound, and it is more preferable to use a zirconium chelate compound.

[0055] R of the metal chelating agent represented by general formula (3) ５ The alkyl, aryl and alkenyl groups in R ６ and R ７ The alkyl group, aryl group, alkenyl group and alkoxy group in the formula (I) may each be substituted with another substituent.

[0056] In general formula (3), R ５ Examples of R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decanyl group, an octadecanyl group, a phenyl group, a vinyl group, an allyl group, and an oleyl group. Among these, from the viewpoint of the stability of the metal chelating agent, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-octadecyl group, and a phenyl group are preferred. ６ and R ７Examples of the alkyl group include hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, phenyl, vinyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-octadecyl, and benzyloxy. Among these, from the viewpoint of ease of synthesis and stability of the metal chelating agent, methyl, t-butyl, phenyl, methoxy, ethoxy, and n-octadecyl are preferred.

[0057] Examples of aluminum chelate compounds in which the metal atom M is aluminum include aluminum trisisopropoxide, aluminum tris-n-propoxide, aluminum tris-sec-butoxide, aluminum tris-n-butoxide, aluminum trisphenoxide, aluminum trisacetylacetonate, aluminum tris(2,2,6,6-tetramethyl-3,5-heptanedionate), aluminum trisethylacetoacetate, aluminum trismethylacetoacetate, aluminum trismethylmalonate, aluminum trisethylmalonate, aluminum ethylacetate di(isopropoxide), aluminum acetylacetonate) di(isopropoxide), aluminum methylacetoacetate di(isopropoxide), aluminum octadecylacetoacetate di(isopropylate), and aluminum monoacetylacetonate bis(ethylacetoacetate).

[0058] Examples of zirconium chelate compounds in which the metal atom M is zirconium include zirconium tetra n-propoxide, zirconium tetra n-butoxide, zirconium tetra-sec-butoxide, zirconium tetraphenoxide, zirconium tetraacetylacetonate, zirconium tetra(2,2,6,6-tetramethyl-3,5-heptanedionate), zirconium tetramethylacetoacetate, zirconium tetraethylacetoacetate, zirconium tetramethylmalonate, zirconium tetraethylmalonate, zirconium tetrabenzoylacetonate, zirconium tetradibenzoylmethanate, and zirconium mono n-butoxy. Examples of such acetylacetonate include acetylacetonate bis(ethyl acetoacetate), zirconium mono n-butoxyethyl acetoacetate bis(acetylacetonate), zirconium mono n-butoxytris(acetylacetonate), zirconium mono n-butoxytris(acetylacetonate), zirconium di(n-butoxy)bis(ethyl acetoacetate), zirconium di(n-butoxy)bis(acetylacetonate), zirconium di(n-butoxy)bis(ethyl malonate), zirconium di(n-butoxy)bis(benzoylacetonate), zirconium di(n-butoxy)bis(dibenzoylmethanate), and zirconium tetraacetylacetonate.

[0059] Among these, from the viewpoint of improving adhesion to a metal layer containing molybdenum, aluminum, or nickel and chemical resistance while maintaining high transparency, low film stress, and excellent crack resistance, zirconium tetra-normal propoxide, zirconium tetra-normal butoxide, zirconium tetraphenoxide, zirconium tetraacetylacetonate, zirconium tetraacetylacetonate, aluminum trisacetylacetonate, and aluminum tris(2,2,6,6-tetramethyl-3,5-heptanedionate) are preferred, and zirconium tetraacetylacetonate is more preferred.

[0060] The content of component (b) in the photosensitive resin composition of the present invention is preferably 0.1% by weight or more, and more preferably 0.5% by weight or more, based on 100% by weight of the solid content in the photosensitive resin composition, from the viewpoint of improving adhesion to a metal layer containing molybdenum, aluminum, or nickel and chemical resistance; on the other hand, from the viewpoint of maintaining high film transparency and low film stress, the content is preferably 5% by weight or less, and more preferably 3% by weight or less.

[0061] The photosensitive resin composition of the present invention contains a photoradical polymerization initiator (component (c)). A photoradical polymerization initiator refers to a compound that decomposes and / or reacts to generate radicals when irradiated with ultraviolet light having a wavelength of 300 nm to 430 nm. When the photosensitive resin composition contains component (c), radicals generated from component (c) upon irradiation with ultraviolet light react with the radically polymerizable groups in component (a) described above, or the monofunctional (meth)acrylate compound and polyfunctional (meth)acrylate compound described below, thereby imparting photocurability and negative photosensitivity.

[0062] Examples of component (c) include benzoin compounds, benzil ketal compounds, acetophenone compounds, α-aminoalkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, benzophenone compounds having an amino group, and benzoic acid ester compounds having an amino group. Two or more of these compounds may be used. Among these, from the viewpoints of enhancing the curability of the film and maintaining high transparency, it is preferable to use acetophenone compounds, α-aminoalkylphenone compounds, acylphosphine oxide compounds, and oxime ester compounds, and acetophenone compounds and oxime ester compounds are more preferable.

[0063] Examples of acetophenone compounds include 2,2-dimethoxy-2-phenylacetophenone, α-hydroxyacetophenone, 1-hydroxycyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, and 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropynoyl)benzyl)phenyl)-2-methylpropan-1-one.

[0064] Examples of the α-aminoalkylphenone compound include 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1.

[0065] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-phosphine oxide.

[0066] Examples of oxime ester compounds include 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], 1-phenyl-1,2-butadione-2-(o-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime).

[0067] The amount of component (c) contained in the photosensitive resin composition of the present invention is preferably 0.01% by weight or more, and more preferably 0.1% by weight or more, when the solid content of the photosensitive resin composition is taken as 100% by weight, from the viewpoint of sufficiently promoting radical polymerization and improving the chemical resistance of the cured film; on the other hand, from the viewpoint of improving the transparency of the cured film, it is preferably 10% by weight or less, and more preferably 8% by weight or less.

[0068] The photosensitive resin composition of the present invention preferably further contains a monofunctional (meth)acrylate (component (d)). A monofunctional (meth)acrylate refers to a compound having one methacrylic group or one acrylic group in the molecule. The term "(meth)acrylate" collectively refers to acrylates (acrylic acid esters) and methacrylates (methacrylic acid esters). Hereinafter, a compound containing a methacrylic group may be referred to as a methacrylate, and a compound containing an acrylic group may be referred to as an acrylate. By including component (d), radicals generated from component (c) upon irradiation with ultraviolet light react with the methacrylic group or acrylic group, resulting in photocuring of the film. Furthermore, by including component (d), the stress of the formed film can be reduced, crack resistance can be improved, and resolution can be improved compared to when a polyfunctional (meth)acrylate described below is used. Herein, the "monofunctional" in monofunctional (meth)acrylate refers to the presence of one methacrylic group or acrylic group in the molecule.

[0069] Examples of the component (d) include n-butyl (meth)acrylate, n-hexyl (meth)acrylate, isobutyl (meth)acrylate, isoamyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, isostearyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and the like. (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 2-cyanoethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-butyloxypropyl (meth)acrylate, 2-hydroxy-3-(2-ethylhexyloxy)propyl (meth)acrylate, dimethylaminoethyl (meth)acrylate acrylate, diethylaminoethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, N-(meth)acryloyloxyethyl hexahydrophthalimide, trifluoroethyl (meth)acrylate, ethyl carbitol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, Examples thereof include 2-ethylhexyl EO-modified (meth)acrylate, phenol EO-modified (meth)acrylate, p-nonylphenol EO-modified (meth)acrylate, p-nonylphenol PO-modified (meth)acrylate, o-phenylphenol EO-modified (meth)acrylate, p-cumylphenol EO-modified (meth)acrylate, methoxytriethylene glycol (meth)acrylate, p-phenoxyphenol EO-modified (meth)acrylate, and p-phenoxyphenol PO-modified (meth)acrylate. Two or more of these can be used.

[0070] Among these, from the viewpoint of reducing the stress of the film to be formed and improving the crack resistance, it is preferable to use, as component (d), 2-ethylhexyl EO-modified (meth)acrylate, phenol EO-modified (meth)acrylate, p-nonylphenol EO-modified (meth)acrylate, p-nonylphenol PO-modified (meth)acrylate, o-phenylphenol EO-modified (meth)acrylate, p-cumylphenol EO-modified (meth)acrylate, p-phenoxyphenol EO-modified (meth)acrylate, or p-phenoxyphenol PO-modified (meth)acrylate.

[0071] Furthermore, it is preferable to use a phenol-modified (meth)acrylate as the component (d), and it is particularly preferable to use a monofunctional (meth)acrylate represented by the following general formula (1) or general formula (2). These may be used in combination. In other words, it is preferable to use either or both of a monofunctional (meth)acrylate represented by the following general formula (1) and a monofunctional (meth)acrylate represented by the following general formula (2) as the component (d).

[0072]

[0073] (R １ represents a hydrogen atom or a methyl group, R ２ represents an alkylene group. X is a substituent bonded to the benzene ring and represents an alkyl group or an aryl group. p is an integer of 0 to 5 and represents the number of substituents (X) bonded to the benzene ring. The benzene ring may have two or more types of X. Furthermore, m represents a positive integer preferably ranging from 2 to 8.

[0074]

[0075] (R ３ represents a hydrogen atom or a methyl group, R ４ represents an alkylene group, and n represents a positive integer preferably ranging from 2 to 8.

[0076] In the monofunctional (meth)acrylates represented by the general formula (1) and the general formula (2), from the viewpoint of reducing the film stress of the cured film and improving the crack resistance, it is preferable that m and n are each 2 or more, and more preferably 4 or more.

[0077] The content of the component (d) in the photosensitive resin composition of the present invention is preferably 3% by weight or more, and more preferably 5% by weight or more, when the solid content of the photosensitive resin composition is taken as 100% by weight, from the viewpoint of reducing the film stress of the cured film and improving the crack resistance. On the other hand, from the viewpoint of improving the chemical resistance of the cured film, the content is preferably 40% by weight or less, and more preferably 35% by weight or less.

[0078] The photosensitive resin composition of the present invention may contain a polyfunctional (meth)acrylate in addition to component (d). The polyfunctional (meth)acrylate refers to a compound having two or more groups selected from methacrylic groups and acrylic groups. By including the polyfunctional (meth)acrylate, the photocuring described above can be further promoted, and the crosslinking density of the film can be improved, thereby improving chemical resistance.

[0079] Examples of polyfunctional (meth)acrylates include bifunctional (meth)acrylates such as 2,2-[9H-fluorene-9,9-diylbis(1,4-phenylene)bisoxy]diethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, glycerin di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate. Examples of such acrylates include trifunctional or higher functional (meth)acrylates such as acrylates of tris(2-hydroxyethyl)isocyanuric acid, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, pentaerythritol undeca(meth)acrylate, and pentaerythritol dodeca(meth)acrylate. Two or more of these may be used.

[0080] The photosensitive resin composition of the present invention preferably further contains an adhesion improver. An adhesion improver refers to a compound having one or more reactive functional groups in the molecule that improve adhesion to the substrate. By containing an adhesion improver, it is possible to improve the adhesion between the coating film and the base substrate. Examples of adhesion improvers include silane coupling agents having an alkoxysilyl group and / or a silanol group, alicyclic epoxy compounds having an epoxy group, phosphate ester compounds having a phosphate group, and (meth)acrylamide compounds having an amide group. Among these, silane coupling agents and (meth)acrylamide compounds are preferred from the viewpoint of further improving the adhesion between the coating film and the base substrate.

[0081] Examples of the silane coupling agent include the organosilane compounds listed above as raw materials for component (a). Two or more types of silane coupling agents may be used.

[0082] Among these, from the viewpoint of having a reactive functional group and reacting with other components to improve adhesion and chemical resistance between the coating film and the base substrate, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, vinyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, and p-thrityltrimethoxysilane are preferred.

[0083] Examples of the (meth)acrylamide compound include N-methylacrylamide, N-ethylacrylamide, N-n-propylacrylamide, N-isopropylacrylamide, N-cyclopropylacrylamide, N-hydroxyethylacrylamide, N-methylolacrylamide methyl ether, N-methylolacrylamide ethyl ether, N-methylolacrylamide propyl ether, N-methylolacrylamide butyl ether, N-methoxymethylacrylamide, N-butoxymethylacrylamide, N,N'-methylenebisacrylamide, acryloylmorpholine, diacetone acrylamide, and N Examples of the methylmethacrylamide include N-methyl methacrylamide, N-ethyl methacrylamide, N-n-propyl methacrylamide, N-isopropyl methacrylamide, N-cyclopropyl methacrylamide, N-methoxymethyl methacrylamide, N-butoxymethyl methacrylamide, N,N'-methylenebismethacrylamide, diacetone methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-methyl,N-ethyl acrylamide, N,N-dimethyl methacrylamide, N,N-diethyl methacrylamide, N,N-dimethylaminopropyl acrylamide, and N-methyl,N-ethyl methacrylamide. Two or more of these may be used.

[0084] As the adhesion improver, from the viewpoint of improving adhesion to a metal layer containing molybdenum, aluminum, or nickel, it is preferable to use N-methylolacrylamide methyl ether, N-methylolacrylamide ethyl ether, N-methylolacrylamide propyl ether, N-methylolacrylamide butyl ether, N-butoxymethylacrylamide, N-butoxymethylmethacrylamide, N-methoxymethylacrylamide, or N-methoxymethylmethacrylamide.

[0085] The photosensitive resin composition of the present invention preferably further contains a polymerization inhibitor. The polymerization inhibitor refers to a compound having a functional group that captures radicals. By containing the polymerization inhibitor, the storage stability and resolution of the photosensitive resin composition can be further improved.

[0086] Examples of polymerization inhibitors include phenol, catechol, resorcinol, hydroquinone, 4-t-butylcatechol, 2,6-di(t-butyl)-p-cresol, phenothiazine, and 4-methoxyphenol. Commercially available polymerization inhibitors include "IRGANOX" (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425, 1520, 245, 259, 3114, 565, and 295 (all trade names, manufactured by BASF Japan Ltd.). Two or more polymerization inhibitors may be used.

[0087] The content of the polymerization inhibitor in the photosensitive resin composition of the present invention is preferably 0.01% by weight or more, and more preferably 0.05% by weight or more, when the solid content of the photosensitive resin composition is taken as 100% by weight, from the viewpoint of further improving the storage stability and resolution of the photosensitive resin composition and enabling the formation of a pattern with excellent resolution even in a thick film with a film thickness of 10 μm or more. On the other hand, from the viewpoint of further improving the chemical resistance of the cured film, the content is preferably 3% by weight or less, and more preferably 1% by weight or less.

[0088] The photosensitive resin composition of the present invention may contain an ultraviolet absorber. By containing an ultraviolet absorber, the weather resistance of the cured film can be further improved. As the ultraviolet absorber, from the viewpoints of transparency and non-coloring property, benzotriazole-based compounds, benzophenone-based compounds, and triazine-based compounds are preferred.

[0089] The photosensitive resin composition of the present invention preferably further contains a solvent, which adjusts the viscosity of the resin composition to a range suitable for coating and improves coating uniformity.

[0090] Examples of the solvent include alcohols such as isopropanol and diacetone alcohol; 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, and diethylene glycol ethyl methyl ether; methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexane. Examples of suitable solvents include ketones such as cyclopentanone; amides such as dimethylformamide and dimethylacetamide; acetates such as ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, and butyl lactate; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, and cyclohexane; γ-butyrolactone, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. Two or more of these may be used. Among these, diacetone alcohol, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclopentanone are preferred from the viewpoint of coatability.

[0091] The content of the solvent can be set arbitrarily depending on the application method, etc. For example, when forming a film by spin coating, the content of the solvent in the photosensitive resin composition is generally 30% by weight or more and 90% by weight or less.

[0092] The photosensitive resin composition of the present invention preferably contains a surfactant. By including a surfactant, the coating uniformity of the photosensitive resin composition can be improved. Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, fluorine-containing thermally decomposable surfactants, polyether-modified siloxane-based surfactants, polyalkylene oxide-based surfactants, poly(meth)acrylate-based surfactants, ammonium lauryl sulfate, polyoxyethylene alkyl ether triethanolamine sulfate, stearylamine acetate, lauryl trimethylammonium chloride, lauryl dimethylamine oxide, lauryl carboxymethyl hydroxyethyl imidazolium betaine, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearate. Two or more surfactants may be used. Among these, silicone-based surfactants and poly(meth)acrylate-based surfactants are preferred from the viewpoints of improving coating uniformity and being environmentally friendly.

[0093] Commercially available silicone surfactants include, for example, BYK (registered trademark)-333, BYK-301, BYK-331, BYK-345, and BYK-307 (manufactured by BYK Japan KK). Commercially available poly(meth)acrylate surfactants include, for example, BYK (registered trademark)-352 (manufactured by BYK Japan KK).

[0094] The photosensitive resin composition of the present invention may contain a liquid-repellent surfactant as a surfactant when it is desired to impart liquid repellency to the film surface. The liquid-repellent surfactant refers to a surfactant having one or more reactive functional groups and one or more liquid-repellent groups in the molecule. The reactive functional group is preferably a methacrylic group or an acrylic group. Examples of the liquid-repellent group include a silicone group, a fluoroalkyl group, and a fluoroalkylene group.

[0095] Next, the cured film of the present invention will be described.

[0096] The cured film of the present invention is obtained by curing the photosensitive resin composition of the present invention described above. The cured film of the present invention can be suitably used as a sealing layer for a display or a semiconductor, as well as for a color filter, a solid-state imaging device, or a fingerprint authentication device, which will be described later.

[0097] A method for producing a cured film using the photosensitive resin composition of the present invention will be described below with examples. The method for producing a cured film of the present invention preferably includes a step of curing by light and / or heat without a step of removing all of the component (a) by baking or a stripping solution treatment. Specifically, a preferred method involves applying the photosensitive resin composition of the present invention to a base substrate, drying the composition to obtain a dried film, exposing the dried film to light, developing it as needed, and heating (post-baking) to cure it.

[0098] Examples of the base substrate include glass substrates, metal laminate substrates, silicon wafers, and various films, and can be selected depending on the purpose.

[0099] The coating can be carried out by a coating method such as microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, or slit die coating, and the coating method can be selected depending on the purpose.

[0100] Drying is preferably performed using a vacuum hot plate to remove the solvent, followed by drying using a heating device. The vacuum hot plate is preferably dried at 20 to 80°C under a pressure of 10 to 1000 Pa for 30 to 600 seconds. Examples of the heating device that can be used include a hot air oven, a nitrogen oven, and a hot plate. The drying temperature using the heating device is preferably 80 to 120°C, and the drying time is preferably 1 to 60 minutes.

[0101] Exposure is a process in which a necessary portion of the dry film is photocured by irradiating light from an exposure device, thereby making any portion of the dry film soluble in a developer. In the exposure process, exposure may be performed through a photomask having predetermined openings, or any desired pattern may be directly drawn using laser light or the like without using a photomask. Alternatively, the entire surface may be exposed without using a photomask.

[0102] Examples of exposure devices include a mask aligner (LA series, manufactured by Nanotec Corporation) and a mirror projection mask aligner (MPA series, manufactured by Canon Inc.). Examples of actinic rays irradiated in the exposure step include near-infrared rays, visible light, and ultraviolet rays, with ultraviolet rays being preferred. Among ultraviolet rays, it is preferable to use one or more wavelengths selected from 365 nm (i-line), 405 nm (h-line), and 436 nm (g-line). Examples of light sources include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, halogen lamps, and germicidal lamps, with high-pressure mercury lamps and ultra-high-pressure mercury lamps being preferred. Exposure conditions can be appropriately selected depending on the thickness of the dried film to be exposed. Generally, 1 to 100 mW / cm ２ Using an ultra-high pressure mercury lamp with an output of 10 to 10,000 mJ / cm ２ It is preferable to perform exposure at an exposure amount of 1000 nm (equivalent to an exposure amount at a wavelength of 365 nm).

[0103] Development is carried out when it is desired to dissolve unexposed areas and obtain a negative pattern. Examples of development methods include showering, dipping, and puddling. The development time is preferably 5 seconds to 10 minutes. Examples of the developer include known alkaline developers, and specific examples include aqueous solutions containing one or more of inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates, and borates; amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine; and quaternary ammonium salts such as tetramethylammonium hydroxide and choline. After development, the film is preferably rinsed with water, and can also be subsequently dry baked at a temperature ranging from 50 to 150°C.

[0104] The post-baking is preferably carried out using the above-mentioned heating device, with the heating temperature preferably being 85 to 300° C. and the heating time preferably being 10 minutes to 2 hours.

[0105] The cured film of the present invention preferably has a film thickness of 10 μm or more and 200 μm or less. Furthermore, the film stress of the cured film of the present invention is preferably 0.01 MPa or more and 10 MPa or less. Because such a cured film has low film stress, it does not have cracks after post-baking even when a thick film is formed. From the viewpoint of compatibility with the chemical resistance of the cured film, the film stress is more preferably 1 MPa or more. From the viewpoint of suppressing warpage of the substrate after post-baking, the film stress is more preferably 6 MPa or less. The film stress can be measured by the method described in the Examples section.

[0106] From the viewpoint of improving the optical properties of a solid-state imaging element or a fingerprint authentication device described below, the cured film of the present invention preferably has a transmittance at a wavelength of 400 nm per 10 μm of film thickness of 90% or more and 100% or less, more preferably 92% or more, and even more preferably 94% or more, of the cured film at a wavelength of 400 nm per 10 μm of film thickness.

[0107] Next, the color filter, solid-state imaging device, or fingerprint authentication device of the present invention will be described.

[0108] The color filter, solid-state imaging device or fingerprint authentication device of the present invention has the cured film of the present invention described above.

[0109] Examples of the color filter include a color filter using a pigment-dispersed material in which a pigment is dispersed in a photoresist, which is used in flat panel displays such as liquid crystal displays. The color filter of the present invention may have the cured film of the present invention between a substrate and a color filter layer, or on a color filter layer.

[0110] Examples of solid-state imaging devices include CCD image sensors and CMOS image sensors, with CMOS image sensors being more preferred.

[0111] Examples of fingerprint authentication devices include ultrasonic fingerprint authentication devices, optical fingerprint authentication devices, etc. Optical under-display fingerprint authentication devices are more preferred because they have higher authentication accuracy.

[0112] The solid-state imaging element or fingerprint authentication device of the present invention is composed of, for example, a substrate, a sensor, wiring, a light-shielding layer, a transparent medium layer, and a microlens. The transparent medium layer is preferably the cured film of the present invention. The wiring or the light-shielding layer is preferably a metal layer containing any one selected from the group consisting of molybdenum, aluminum, and nickel.

[0113] Therefore, one preferred embodiment of the present invention is a solid-state imaging element or fingerprint authentication device having the cured film of the present invention, wherein the solid-state imaging element or the fingerprint authentication device includes wiring or a light-shielding layer, and the wiring or the light-shielding layer contains any one selected from the group consisting of molybdenum, aluminum, and nickel.

[0114] The present invention will be described in more detail below with reference to specific examples, but these are merely illustrative and the present invention should not be construed as being limited to the following examples. Among the compounds used below, those for which abbreviations are used are shown below. PGMEA: Propylene glycol monomethyl ether acetate BHT: Di-t-butylhydroxytoluene (2,6-di-t-butyl-p-cresol) D-1: Diphenylsilanediol D-2: Methylphenyldimethoxysilane D-3: Cyclohexylmethyldimethoxysilane D-4: Dicyclopentyldimethoxysilane D-5: 3-methacryloxypropylmethyldimethoxysilane D-6: Dimethyldimethoxysilane D'-1: 3-methacryloxypropyltrimethoxysilane D'-2: Methyltrimethoxysilane D'-3: 3-trimethoxysilylpropylsuccinic anhydride D'-4: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane Furthermore, with regard to the evaluation method, if the number of evaluation samples is not stated, the evaluation is based on one evaluation sample, and if the temperature is not specified in the evaluation and synthesis conditions, the evaluation was performed at room temperature.

[0115] The weight average molecular weights of the siloxane resins in Synthesis Examples 1 to 14 and the acrylic resin in Synthesis Example 15 were determined by gel permeation chromatography (GPC). The details are as follows, and the values ​​were determined as polystyrene equivalent values. Apparatus: Waters GPC measurement apparatus (2695) equipped with an RI detector Column: Two PLgelMIXED-C columns (300 mm, manufactured by Polymer Laboratories) (connected in series) Measurement temperature: 40°C Flow rate: 1 mL / min Solvent: 0.5% by mass solution of tetrahydrofuran (THF) Standard substance: polystyrene Detection mode: RI

[0116] [Synthesis Example 1] Siloxane resin solution (PS-1) A 500 mL three-neck flask was charged with 79.43 g of PGMEA, 34.05 g (0.25 mol) of methyltrimethoxysilane, 34.85 g (0.15 mol) of 3-methacryloxypropylmethyldimethoxysilane, 12.32 g (0.05 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 97.43 g (0.45 mol) of diphenylsilanediol, and 0.174 g of BHT (0.50 wt % relative to the 3-methacryloxypropylmethyldimethoxysilane), and the flask was immersed in a 40°C oil bath and stirred. An aqueous phosphoric acid solution prepared by dissolving 2.05 g of phosphoric acid (1.0 wt % relative to the charged monomers) in 28.80 g of water was added as a catalyst using a dropping funnel over 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C and stirring was continued for 1 hour, and the oil bath temperature was then raised to 120°C. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was then heated and stirred for 2 hours (internal temperature: 100-110°C). A total of 66 g of by-products, methanol and water, were distilled off during the reaction. To the resulting PGMEA solution of siloxane resin, PGMEA was added so that the siloxane resin concentration was 65% by weight. To 100 parts by weight of this solution, 2 parts by weight of a weakly basic ion exchange resin ("Amberlite" (registered trademark) A21, manufactured by Organo Corporation) was added and stirred at room temperature for 12 hours to remove the phosphoric acid catalyst. The ion exchange resin was then removed by filtration, yielding a siloxane resin solution (PS-1). The weight-average molecular weight of the resulting siloxane resin was measured by GPC and found to be 2,500 (polystyrene equivalent).

[0117] [Synthesis Example 2] Siloxane resin solution (PS-2) A siloxane resin solution (PS-2) was obtained in the same manner as in Synthesis Example 1, except that the amounts of PGMEA added at the beginning of the polymerization were changed to 89.06 g, the amounts of methyltrimethoxysilane added to 20.43 g (0.15 mol), and diphenylsilanediol added to 118.97 g (0.55 mol), and a phosphoric acid aqueous solution prepared by dissolving 2.13 g of phosphoric acid (1.0 wt% based on the charged monomers) in 23.40 g of water was used as the catalyst. The weight average molecular weight of the obtained siloxane resin was measured by GPC and found to be 2,300 (polystyrene equivalent).

[0118] [Synthesis Example 3] Siloxane resin solution (PS-3) A siloxane resin solution (PS-3) was obtained in the same manner as in Synthesis Example 1, except that the amounts of PGMEA added at the beginning of the polymerization were changed to 98.69 g, the amounts of methyltrimethoxysilane added to 6.81 g (0.05 mol), and diphenylsilanediol added to 140.60 g (0.65 mol), and a phosphoric acid aqueous solution prepared by dissolving 2.21 g of phosphoric acid (1.0 wt% based on the charged monomers) in 18.00 g of water was used as the catalyst. The weight average molecular weight of the obtained siloxane resin was measured by GPC and found to be 2,000 (polystyrene equivalent).

[0119] [Synthesis Example 4] Siloxane resin solution (PS-4) A siloxane resin solution (PS-4) was obtained in the same manner as in Synthesis Example 1, except that the amounts of PGMEA added at the beginning of the polymerization were changed to 64.98 g, the amounts of methyltrimethoxysilane added to 54.48 g (0.40 mol), and diphenylsilanediol added to 64.89 g (0.30 mol), and that an aqueous phosphoric acid solution prepared by dissolving 1.93 g of phosphoric acid (1.0 wt% based on the charged monomers) in 36.90 g of water was used as the catalyst. The weight average molecular weight of the obtained siloxane resin was measured by GPC and found to be 2,700 (polystyrene equivalent).

[0120] [Synthesis Example 5] Siloxane resin solution (PS-5) A siloxane resin solution (PS-5) was obtained in the same manner as in Synthesis Example 1, except that the amounts of PGMEA added at the beginning of the polymerization were changed to 50.53 g, the amounts of methyltrimethoxysilane added to 74.91 g (0.55 mol), and diphenylsilanediol added to 32.45 g (0.15 mol), and a phosphoric acid aqueous solution prepared by dissolving 1.81 g of phosphoric acid (1.0 wt% based on the charged monomers) in 45.00 g of water was used as the catalyst. The weight average molecular weight of the obtained siloxane resin was measured by GPC and found to be 2,800 (polystyrene equivalent).

[0121] [Synthesis Example 6] Siloxane resin solution (PS-6) A siloxane resin solution (PS-6) was obtained in the same manner as in Synthesis Example 1, except that the amount of PGMEA added at the beginning of the polymerization was changed to 55.14 g, 82.03 g (0.45 mol) of methylphenyldimethoxysilane was added instead of diphenylsilanediol, and an aqueous phosphoric acid solution prepared by dissolving 1.90 g of phosphoric acid (1.0 wt % based on the charged monomers) in 45.00 g of water was used as the catalyst. The weight average molecular weight of the obtained siloxane resin was measured by GPC and was found to be 2,500 (polystyrene equivalent).

[0122] [Synthesis Example 7] Siloxane resin solution (PS-7) A siloxane resin solution (PS-7) was obtained in the same manner as in Synthesis Example 1, except that the amount of PGMEA added at the beginning of the polymerization was changed to 56.57 g, 84.74 g (0.45 mol) of cyclohexylmethyldimethoxysilane was added instead of diphenylsilanediol, and an aqueous phosphoric acid solution prepared by dissolving 1.92 g of phosphoric acid (1.0 wt % based on the charged monomers) in 45.00 g of water was used as the catalyst. The weight average molecular weight of the obtained siloxane resin was measured by GPC and found to be 3,000 (polystyrene equivalent).

[0123] [Synthesis Example 8] Siloxane resin solution (PS-8) A siloxane resin solution (PS-8) was obtained in the same manner as in Synthesis Example 1, except that the amount of PGMEA added at the beginning of the polymerization was changed to 66.10 g, 102.78 g (0.45 mol) of dicyclopentyldimethoxysilane was added instead of diphenylsilanediol, and an aqueous phosphoric acid solution prepared by dissolving 2.10 g of phosphoric acid (1.0 wt % based on the charged monomers) in 45.00 g of water was used as the catalyst. The weight average molecular weight of the obtained siloxane resin was measured by GPC and found to be 2,800 (polystyrene equivalent).

[0124] [Synthesis Example 9] Siloxane resin solution (PS-9) A siloxane resin solution (PS-9) was obtained in the same manner as in Synthesis Example 1, except that the amount of PGMEA added at the beginning of the polymerization was changed to 40.37 g, 54.09 g (0.45 mol) of dimethyldimethoxysilane was added instead of diphenylsilanediol, and an aqueous phosphoric acid solution prepared by dissolving 1.62 g of phosphoric acid (1.0 wt % based on the charged monomers) in 45.00 g of water was used as the catalyst. The weight average molecular weight of the obtained siloxane resin was measured by GPC and was found to be 3,000 (polystyrene equivalent).

[0125] Synthesis Example 10 Siloxane Resin Solution (PS-10) A siloxane resin solution (PS-10) was obtained in the same manner as in Synthesis Example 1, except that 3-trimethoxysilylpropylsuccinic anhydride was not added, the amounts of PGMEA and methyltrimethoxysilane added at the beginning of the polymerization were changed to 34.85 g and 47.67 g (0.35 mol), respectively, and an aqueous phosphoric acid solution prepared by dissolving 1.92 g of phosphoric acid (1.0 wt % based on the charged monomers) in 27.00 g of water was used as the catalyst. The weight-average molecular weight of the resulting siloxane resin was measured by GPC and found to be 2,000 (polystyrene equivalent).

[0126] [Synthesis Example 11] Siloxane resin solution (PS-11) A siloxane resin solution (PS-11) was obtained in the same manner as in Synthesis Example 1, except that methyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane were not added, the amount of PGMEA added at the beginning of the polymerization was changed to 105.41 g, the amount of diphenylsilanediol added was changed to 162.23 g (0.75 mol), and an aqueous phosphoric acid solution prepared by dissolving 2.23 g of phosphoric acid (1.0 wt % based on the charged monomers) in 12.60 g of water was used as the catalyst. The weight average molecular weight of the obtained siloxane resin was measured by GPC and was found to be 1,200 (polystyrene equivalent).

[0127] [Synthesis Example 12] Siloxane resin solution (PS-12) A siloxane resin solution (PS-12) was obtained in the same manner as in Synthesis Example 1, except that the amounts of PGMEA added at the beginning of the polymerization were changed to 45.71 g, the amounts of methyltrimethoxysilane added to 81.72 g (0.60 mol), and diphenylsilanediol added to 21.63 g (0.10 mol), and that an aqueous phosphoric acid solution prepared by dissolving 1.77 g of phosphoric acid (1.0 wt% based on the charged monomers) in 47.70 g of water was used as the catalyst. The weight average molecular weight of the obtained siloxane resin was measured by GPC and found to be 2,700 (polystyrene equivalent).

[0128] Synthesis Example 13 Siloxane Resin Solution (PS-13) A siloxane resin solution (PS-13) was obtained in the same manner as in Synthesis Example 1, except that diphenylsilanediol and 3-methacryloxypropylmethyldimethoxysilane were not added, the amounts of PGMEA and methyltrimethoxysilane added at the beginning of the polymerization were changed to 34.65 g and 95.34 g (0.70 mol), 37.26 g (0.15 mol) of 3-methacryloxypropyltrimethoxysilane were newly added, and an aqueous phosphoric acid solution prepared by dissolving 1.71 g of phosphoric acid (1.0 wt % based on the charged monomers) in 55.80 g of water was used as the catalyst. The weight average molecular weight of the resulting siloxane resin was measured by GPC and found to be 5,000 (polystyrene equivalent).

[0129] Synthesis Example 14 Siloxane Resin Solution (PS-14) A siloxane resin solution (PS-14) was obtained in the same manner as in Synthesis Example 1, except that 3-methacryloxypropylmethyldimethoxysilane was not added, the amounts of PGMEA added at the beginning of the polymerization were changed to 83.55 g, the amounts of methyltrimethoxysilane added to 34.05 g (0.25 mol), and the amount of diphenylsilanediol added to 129.79 g (0.60 mol), and an aqueous phosphoric acid solution prepared by dissolving 2.02 g of phosphoric acid (1.0 wt % based on the charged monomers) in 23.40 g of water was used as the catalyst. The weight average molecular weight of the resulting siloxane resin was measured by GPC and found to be 2,000 (polystyrene equivalent).

[0130] Synthesis Example 15 Siloxane Resin Solution (PS-15) A siloxane resin solution (PS-15) was obtained in the same manner as in Synthesis Example 1, except that the amounts of PGMEA added at the beginning of the polymerization were changed to 80.25 g, the amounts of 3-methacryloxypropylmethyldimethoxysilane added to 27.88 g (0.12 mol), and the amounts of diphenylsilanediol added to 103.83 g (0.48 mol), and a phosphoric acid aqueous solution prepared by dissolving 2.04 g of phosphoric acid (1.0 wt % based on the charged monomers) in 27.72 g of water was used as the catalyst. The weight average molecular weight of the obtained siloxane resin was measured by GPC and found to be 2,300 (polystyrene equivalent).

[0131] Synthesis Example 16 Siloxane Resin Solution (PS-16) A siloxane resin solution (PS-16) was obtained in the same manner as in Synthesis Example 1, except that the amounts of PGMEA added at the beginning of the polymerization were changed to 80.80 g, the amounts of 3-methacryloxypropylmethyldimethoxysilane added to 23.24 g (0.10 mol), and the amounts of diphenylsilanediol added to 108.16 g (0.50 mol), and a phosphoric acid aqueous solution prepared by dissolving 2.04 g of phosphoric acid (1.0 wt% based on the charged monomers) in 27.00 g of water was used as the catalyst. The weight average molecular weight of the obtained siloxane resin was measured by GPC and found to be 2,300 (polystyrene equivalent).

[0132] Synthesis Example 17 Siloxane Resin Solution (PS-17) A siloxane resin solution (PS-17) was obtained in the same manner as in Synthesis Example 1, except that the amounts of PGMEA added at the beginning of the polymerization were changed to 81.63 g, the amounts of 3-methacryloxypropylmethyldimethoxysilane added to 16.26 g (0.070 mol), and the amounts of diphenylsilanediol added to 114.64 g (0.53 mol), and that an aqueous phosphoric acid solution prepared by dissolving 2.04 g of phosphoric acid (1.0 wt % based on the charged monomers) in 25.92 g of water was used as the catalyst. The weight average molecular weight of the obtained siloxane resin was measured by GPC and found to be 2,200 (polystyrene equivalent).

[0133] [Synthesis Example 18] Siloxane resin solution (PS-18) A siloxane resin solution (PS-18) was obtained in the same manner as in Synthesis Example 1, except that the amounts of PGMEA added at the beginning of the polymerization were changed to 82.18 g, the amounts of 3-methacryloxypropylmethyldimethoxysilane added to 11.62 g (0.050 mol), and diphenylsilanediol added to 118.97 g (0.55 mol), and the catalyst used was an aqueous phosphoric acid solution prepared by dissolving 2.03 g of phosphoric acid (1.0 wt% based on the charged monomers) in 25.20 g of water. The weight average molecular weight of the resulting siloxane resin was measured by GPC and found to be 2,200 (polystyrene equivalent).

[0134] [Synthesis Example 19] Siloxane resin solution (PS-19) A siloxane resin solution (PS-19) was obtained in the same manner as in Synthesis Example 1, except that the amounts of PGMEA added at the beginning of the polymerization were changed to 82.45 g, the amounts of 3-methacryloxypropylmethyldimethoxysilane added to 9.29 g (0.040 mol), and the amounts of diphenylsilanediol added to 121.13 g (0.56 mol), and a phosphoric acid aqueous solution prepared by dissolving 2.03 g of phosphoric acid (1.0 wt % based on the charged monomers) in 24.84 g of water was used as the catalyst. The weight average molecular weight of the obtained siloxane resin was measured by GPC and was found to be 2,100 (polystyrene equivalent).

[0135] The compositional information of Synthesis Examples 1 to 19 is summarized in Table 1.

[0136]

[0137] Synthesis Example 20 Acrylic Resin Solution (PA-1) 3 g of 2,2'-azobis(isobutyronitrile) and 50 g of PGMEA were charged into a 500 ml flask. Then, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo[5.2.1.02,6]decan-8-yl methacrylate were charged and stirred at room temperature for a while. The atmosphere in the flask was replaced with nitrogen, and the mixture was heated and stirred at 70°C for 5 hours. Next, 15 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the resulting solution, and the mixture was heated and stirred at 90°C for 4 hours. PGMEA was added to the resulting PGMEA solution of acrylic resin to achieve a solids concentration of 50 wt%, yielding acrylic resin solution (PA-1). The weight-average molecular weight of the resulting acrylic resin was measured by GPC and found to be 10,000. The acid value of the resulting acrylic resin was 118 mgKOH / g.

[0138] Example 1 Photosensitive Resin Composition (A-1) Under yellow light, 5.36 g of the siloxane resin solution (PS-1) obtained in Synthesis Example 1 was used as the component (a), 0.050 g of zirconium tetraacetylacetonate (trade name "Orgatix" (registered trademark) ZC-150, manufactured by Matsumoto Fine Chemical Co., Ltd. (hereinafter referred to as "ZC-150") was used as the component (b), and 1,2-octanedione, 1-[4-(phenylthio)-2-methyl-2-propanol]-4-one was used as the component (c). )-2-(O-benzoyloxime)] (trade name "Irgacure" (registered trademark) OXE01, manufactured by BASF Japan Ltd. (hereinafter referred to as "OXE-01")) 0.10 g, p-nonylphenol EO-modified acrylate (trade name "Aronix" (registered trademark) M-113, manufactured by Toagosei Co., Ltd. (hereinafter referred to as "M-113")) as component (d) 1.00 g, 2-(3,4-ethylenediaminetetraacetic acid)-2-(O-benzoyloxime) as an adhesion improver 0.10 g of (oxycyclohexyl)ethyltrimethoxysilane (trade name KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd. (hereinafter referred to as "KBM-303")), 0.25 g of N-methoxymethylacrylamide, 0.015 g of ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] ("Irganox" (registered trademark) 1010, manufactured by BASF Japan Ltd. (hereinafter referred to as "IRGANOX1010")) as a polymerization inhibitor, and 0.030 g of a 10 wt % diluted solution (equivalent to a concentration of 300 ppm) of a poly(meth)acrylate surfactant ("BYK" (registered trademark) 352, manufactured by BYK Japan KK (hereinafter referred to as "BYK-352")) as a surfactant in PGMEA were dissolved in 3.10 g of PGMEA and stirred. The resulting mixture was filtered through a 1.0 μm filter to prepare a photosensitive resin composition (A-1) with a solids concentration of 50% by weight. Since the concentration of BYK-352 was extremely low, this was omitted from the weight fractions shown in the table. Also, BYK-352 was omitted from the table.

[0139] Examples 2 to 10 Photosensitive Resin Compositions (A-2) to (A-10) (a) Photosensitive resin compositions (A-2) to (A-10) were prepared in the same manner as in Example 1, except that the siloxane resin solutions (PS-2) to (PS-10) obtained in Synthesis Examples 2 to 10, respectively, were used as the siloxane resin.

[0140] Example 11 Photosensitive Resin Composition (A-11) A photosensitive resin composition (A-11) was prepared in the same manner as in Example 1, except that the amount of siloxane resin solution (PS-1) added was 5.40 g, the amount of metal chelating agent ZC-150 added was 0.025 g, and the amount of PGMEA added was 3.08 g.

[0141] Example 12 Photosensitive Resin Composition (A-12) A photosensitive resin composition (A-12) was prepared in the same manner as in Example 1, except that the amount of siloxane resin solution (PS-1) added was 5.431 g, the amount of metal chelating agent ZC-150 added was 0.0050 g, and the amount of PGMEA added was 3.07 g.

[0142] Example 13 Photosensitive Resin Composition (A-13) A photosensitive resin composition (A-13) was prepared in the same manner as in Example 1, except that the amount of siloxane resin solution (PS-1) added was 5.435 g, the amount of metal chelating agent ZC-150 added was 0.0020 g, and the amount of PGMEA added was 3.07 g.

[0143] Example 14 Photosensitive Resin Composition (A-14) A photosensitive resin composition (A-14) was prepared in the same manner as in Example 1, except that the amount of siloxane resin solution (PS-1) added was 5.21 g, the amount of metal chelating agent ZC-150 added was 0.15 g, and the amount of PGMEA added was 3.15 g.

[0144] Example 15 Photosensitive Resin Composition (A-15) A photosensitive resin composition (A-15) was prepared in the same manner as in Example 1, except that the amount of siloxane resin solution (PS-1) added was 5.05 g, the amount of metal chelating agent ZC-150 added was 0.25 g, and the amount of PGMEA added was 3.21 g.

[0145] Example 16 Photosensitive Resin Composition (A-16) A photosensitive resin composition (A-14) was prepared in the same manner as in Example 1, except that the amount of siloxane resin solution (PS-1) added was 4.97 g, the amount of metal chelating agent ZC-150 added was 0.30 g, and the amount of PGMEA added was 3.23 g.

[0146] Example 17 Photosensitive Resin Composition (A-17) A photosensitive resin composition (A-17) was prepared in the same manner as in Example 1, except that 0.050 g of zirconium monoacetylacetonate (trade name "Orgatix" (registered trademark) ZC-540, manufactured by Matsumoto Fine Chemical Co., Ltd. (hereinafter referred to as "ZC-540")) was added instead of ZC-150 as the component (b).

[0147] Example 18 Photosensitive Resin Composition (A-18) A photosensitive resin composition (A-18) was prepared in the same manner as in Example 1, except that 0.050 g of zirconium ethylacetoacetate (trade name "Orgatix" (registered trademark) ZC-580, manufactured by Matsumoto Fine Chemical Co., Ltd. (hereinafter referred to as "ZC-580")) was added instead of ZC-150 as the component (b).

[0148] Example 19 Photosensitive Resin Composition (A-19) A photosensitive resin composition (A-19) was prepared in the same manner as in Example 1, except that 0.050 g of aluminum tris(acetylacetonate) (trade name Aluminum Chelate A(a), manufactured by Kawaken Fine Chemicals Co., Ltd. (hereinafter referred to as "AL-A(a)")) was added instead of ZC-150 as the component (b).

[0149] Example 20 Photosensitive Resin Composition (A-20) A photosensitive resin composition (A-20) was prepared in the same manner as in Example 1, except that 0.050 g of aluminum tris(ethylacetoacetate) (ALCH-TR, manufactured by Kawaken Fine Chemicals Co., Ltd. (hereinafter referred to as "ALCH-TR")) was added as component (b) instead of ZC-150.

[0150] Example 21 Photosensitive Resin Composition (A-21) A photosensitive resin composition (A-21) was prepared in the same manner as in Example 1, except that 0.050 g of aluminum alkyl acetoacetate diisopropylate (trade name: Aluminum Chelate M, manufactured by Kawaken Fine Chemicals Co., Ltd. (hereinafter referred to as "AL-M")) was added as component (b) instead of ZC-150.

[0151] Example 22 Photosensitive Resin Composition (A-22) A photosensitive resin composition (A-22) was prepared in the same manner as in Example 1, except that 0.050 g of bisacetylacetonatozinc (hereinafter, "Zn(acac)2") was added instead of ZC-150 as the component (b).

[0152] Example 23 Photosensitive Resin Composition (A-23) A photosensitive resin composition (A-23) was prepared in the same manner as in Example 1, except that 1.00 g of 3-phenoxybenzyl acrylate ("Light Acrylate" (registered trademark) POB-A, manufactured by Kyoeisha Chemical Co., Ltd. (hereinafter referred to as "POB-A")) was added instead of M-113 as the component (d).

[0153] Example 24 Photosensitive Resin Composition (A-24) A photosensitive resin composition (A-24) was prepared in the same manner as in Example 1, except that 1.00 g of isobornyl acrylate ("Light Acrylate" (registered trademark) IB-XA, manufactured by Kyoeisha Chemical Co., Ltd. (hereinafter referred to as "IB-XA")) was added instead of M-113 as component (d).

[0154] Example 25 Photosensitive Resin Composition (A-25) A photosensitive resin composition (A-25) was prepared in the same manner as in Example 1, except that 1.00 g of an EO adduct diacrylate of bisphenol A ("Light Acrylate" (registered trademark) BP-4EAL, manufactured by Kyoeisha Chemical Co., Ltd. (hereinafter referred to as "BP-4EAL")), which is a bifunctional acrylate, was added instead of M-113, which is the component (d).

[0155] Example 26 Photosensitive Resin Composition (A-26) A photosensitive resin composition (A-26) was prepared in the same manner as in Example 1, except that 0.10 g of the acetophenone compound 2,2-dimethoxy-2-phenylacetophenone (trade name "Omnirad" (registered trademark) 651, manufactured by BASF Japan Ltd. (hereinafter referred to as "Omnirad 651")) was added instead of OXE-01 as the component (c).

[0156] Example 27 Photosensitive Resin Composition (A-27) A photosensitive resin composition (A-27) was prepared in the same manner as in Example 1, except that 0.10 g of an acylphosphine oxide compound, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name "Omnirad" (registered trademark) 819, manufactured by BASF Japan Ltd. (hereinafter referred to as "Omnirad 819")), was added instead of OXE-01 as the component (c).

[0157] Example 28 Photosensitive Resin Composition (A-28) A photosensitive resin composition (A-28) was prepared in the same manner as in Example 1, except that 0.10 g of an α-aminoalkylphenone compound, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (trade name "Omnirad" (registered trademark) 907, manufactured by BASF Japan Ltd. (hereinafter referred to as "Omnirad 907")), was added instead of OXE-01 as the component (c).

[0158] Examples 29 to 33 Photosensitive Resin Compositions (A-29) to (A-33) (a) Photosensitive resin compositions (A-29) to (A-33) were prepared in the same manner as in Example 1, except that the siloxane resin solutions (PS-15) to (PS-19) obtained in Synthesis Examples 15 to 19, respectively, were used as the siloxane resin.

[0159] Comparative Examples 1 to 4 Photosensitive Resin Compositions (A-34) to (A-37) Photosensitive resin compositions (A-34) to (A-37) were prepared in the same manner as in Example 1, except that the siloxane resin solution (PS-1) was replaced with the siloxane resin solutions (PS-11) to (PS-14) obtained in Synthesis Examples 11 to 14, respectively.

[0160] Comparative Example 5 Photosensitive Resin Composition (A-38) A photosensitive resin composition (A-38) was prepared in the same manner as in Example 1, except that 6.97 g of the acrylic resin solution (PA-1) obtained in Synthesis Example 15 was added instead of the siloxane resin solution (PS-1), and the amount of PGMEA added was changed to 1.49 g.

[0161] Comparative Example 6 Photosensitive Resin Composition (A-39) A photosensitive resin composition (A-39) was prepared in the same manner as in Example 1, except that component (b), ZC-150, was not added, the amount of siloxane resin solution (PS-1) added was 5.44 g, and the amount of PGMEA added was 3.07 g.

[0162] Comparative Example 7 Photosensitive Resin Composition (A-40) A photosensitive resin composition (A-40) was prepared in the same manner as in Example 1, except that OXE-01, which is component (c), was not added, and the amount of siloxane resin solution (PS-1) added was 5.51 g and the amount of PGMEA added was 3.04 g.

[0163] The compositions of Examples 1 to 33 and Comparative Examples 1 to 7 are shown in Table 2, i.e., Tables 2-1 to 2-6. Note that BYK-352 is omitted. The amount of resin (wt%) is shown based on the resin solid content.

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170] The evaluation methods for each example are shown below.

[0171] <Evaluation Method> "Crack Resistance" The photosensitive resin composition sample was spin-coated onto a 10 cm square alkali-free glass substrate (glass thickness: 0.5 mm) using a spin coater (MS-A150 manufactured by Mikasa Co., Ltd.), and then pre-baked at 100°C for 2 minutes using a hot plate (HHP-230SQ manufactured by AS ONE Corporation) to produce pre-baked films with film thicknesses of 15 μm, 37 μm, 60 μm, and 115 μm, respectively. The obtained pre-baked films were then exposed to light at an exposure dose of 200 mJ / cm using a mask aligner (LA-610 manufactured by Minei Electric Mfg. Co., Ltd.) with an ultra-high pressure mercury lamp (g, h, i lines) as the light source. ２(i-line equivalent value). Thereafter, using an automatic developing apparatus (AD-1200 manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed using a 2.38 wt % TMAH aqueous solution for 60 seconds, followed by rinsing with water for 30 seconds. Finally, using an oven (DHS-42 manufactured by Espec Corp.), the film was cured in air at 230°C for 30 minutes to produce cured films with thicknesses of 10 μm, 30 μm, 50 μm, and 100 μm, respectively.

[0172] The resulting glass substrates having the cured films were visually observed, and the "crack resistance" of the cured films was evaluated according to the following criteria. If even one crack was observed, it was judged that "cracks were present" at that film thickness. AA is the most excellent. A rating of B or higher can be said to indicate excellent crack resistance. AA: No cracks at film thicknesses of 10 μm, 30 μm, 50 μm, and 100 μm. A: No cracks at film thicknesses of 10 μm, 30 μm, and 50 μm. Cracks present at film thicknesses of 100 μm. B: No cracks at film thicknesses of 10 μm and 30 μm. Cracks present at film thicknesses of 50 μm and 100 μm. C: No cracks at film thickness of 10 μm. Cracks present at film thicknesses of 30 μm, 50 μm, and 100 μm. D: Cracks present at film thicknesses of 10 μm, 30 μm, 50 μm, and 100 μm.

[0173] "Film stress" Using the sample photosensitive resin composition, a cured film with a thickness of 10 μm was produced on a 6-inch (15.24 cm) silicon wafer in the same manner as in the evaluation of "crack resistance." For the resulting cured film on the 6-inch (15.24 cm) silicon wafer, the stress of the cured film was measured at room temperature of 23°C using a thin film stress measuring device (manufactured by Toho Technology Co., Ltd.), and the "film stress" was evaluated according to the following criteria. AAA is the best. B or higher was judged to be acceptable. AAA: Film stress less than 3 MPa. AA: Film stress 3 MPa or more but less than 5 MPa. A: Film stress 5 MPa or more but less than 10 MPa. B: Film stress 10 MPa or more but less than 15 MPa. C: Film stress 15 MPa or more. D: Cracks occurred, making measurement impossible.

[0174] "Transmittance" Using the sample photosensitive resin composition, a 10 μm-thick cured film was formed on a Tempax glass substrate (manufactured by AGC Technoglass Co., Ltd.) in the same manner as in the evaluation of "crack resistance." Using a UV-Visible-Near-Infrared Spectrophotometer U-4100 (manufactured by Hitachi High-Tech Science Corporation), the UV-Visible absorption spectrum of the Tempax glass substrate alone was measured and used as a reference. Next, the light transmittance of the resulting Tempax glass substrate with cured film was measured in the wavelength range of 300 nm to 800 nm from the side on which the cured film was formed, and the "transmittance" was evaluated according to the transmittance value at a wavelength of 400 nm based on the following criteria: A was the best, and B or higher was considered to be acceptable. A: Transmittance of 95% or more and 100% or less. B: Transmittance of 90% or more and less than 95%. C: Transmittance less than 90%.

[0175] "Resolution" The photosensitive resin composition samples were spin-coated onto 10 cm square alkali-free glass substrates (glass thickness: 0.5 mm) using a spin coater (MS-A150 manufactured by Mikasa Co., Ltd.), and then pre-baked for 2 minutes at 100°C using a hot plate (HHP-230SQ manufactured by AS ONE Corporation) to produce pre-baked films with a film thickness of 15 μm. The resulting pre-baked films were then irradiated with light using a mask aligner (LA-610 manufactured by Minaga Electric Mfg. Co., Ltd.) with an ultra-high pressure mercury lamp (g, h, i lines) as a light source through a mask having line and space patterns with widths of 15, 25, 50 μm, and 100 μm, at a mask gap of 100 μm and an exposure dose of 100 mJ / cm. ２ Thereafter, using an automatic developing apparatus (AD-1200 manufactured by Takizawa Sangyo Co., Ltd.), the film was shower-developed with a 2.38 wt % aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, and then rinsed with water for 30 seconds.

[0176] The developed pattern was observed under magnification using a microscope adjusted to 100x magnification, and the narrowest line width among the patterns in which no residue was observed in the unexposed areas was taken as the resolution. However, if there was residue in the unexposed areas near the 100 μm wide pattern or if pattern peeling occurred, it was rated as ">100 μm," and if there was no residue in the 15 μm wide pattern and pattern processing was possible, it was rated as "≦15 μm." Note that a resolution of "25 μm" or less can be said to be excellent in resolution.

[0177] "Adhesion to Metal Layer" A substrate (hereinafter referred to as "metal laminate substrate") was prepared by depositing molybdenum-nickel alloy / aluminum / molybdenum-nickel alloy (film thickness: 20 nm / 300 nm / 20 nm) in this order on an alkali-free glass substrate (glass thickness 0.5 mm). A 10 μm thick cured film was formed on this metal laminate substrate using the sample photosensitive resin composition in the same manner as in the evaluation of "crack resistance". An adhesion test was then conducted on the cured film formed on the metal laminate substrate. For the adhesion test, 11 parallel lines, each perpendicular to each other, were drawn at 1 mm intervals on the surface of the cured film using a cutter knife so that they reached the base of the metal laminate substrate, creating 100 1 mm x 1 mm grids. Cellophane adhesive tape (width = 18 mm, adhesive strength = 3.7 N / 10 mm) was then attached to the cut cured film surface, and the attached cellophane adhesive tape was rubbed with an eraser (JIS S6050 compliant product) to adhere the tape to the surface. Next, one end of the cellophane adhesive tape was held, and the tape was instantaneously peeled off while keeping the peeling tape perpendicular to the plate. The cured film after the tape was peeled was observed, and the number of squares remaining that were not peeled off out of the 100 squares was visually counted. The "adhesion" to the metal layer was evaluated based on the peeled area of ​​the squares according to the following criteria. A rating of 4B or higher was considered acceptable. 5B: Peeled area = 0%. 4B: Peeled area = more than 0% but less than 5%. 3B: Peeled area = 5% or more but less than 15%. 2B: Peeled area = 15% or more but less than 35%. 1B: Peeled area = 35% or more but less than 65%. 0B: Peeled area = 65% or more.

[0178] "Chemical Resistance" Using the sample photosensitive resin composition, a metal laminate substrate having a cured film with a thickness of 10 μm was prepared in the same manner as in the evaluation of "adhesion to a metal layer." This was immersed in a resist stripper solution, N300 (trade name, manufactured by Nagase ChemteX Corporation), at 50°C for 5 minutes, then washed with ultrapure water for 1 minute and air-dried. The metal laminate substrate having the cured film after such treatment was subjected to an adhesion test using cellophane adhesive tape, in the same manner as in the evaluation of "adhesion to a metal layer." "Chemical resistance" was evaluated based on the peeled area of ​​the grid according to the following criteria. A rating of 4B or higher was deemed acceptable: 5B: peeled area = 0%; 4B: peeled area = more than 0% but less than 5%; 3B: peeled area = 5% or more but less than 15%; 2B: peeled area = 15% or more but less than 35%; 1B: peeled area = 35% or more but less than 65%; 0B: peeled area = 65% or more.

[0179] "Moisture and Heat Resistance" Using the photosensitive resin composition sample, a 10 μm thick cured film was formed on a 10 cm square alkali-free glass substrate (glass thickness 0.5 mm) using the same method as in the evaluation of "crack resistance." This was placed in a thermo-hygrostat chamber at a temperature of 85°C and a humidity of 85% for 100 hours. The glass substrate with the cured film removed from the thermo-hygrostat chamber was then subjected to an adhesion test using cellophane adhesive tape, similar to the evaluation of "adhesion to metal layer." "Moisture and heat resistance" was evaluated based on the peeled area of ​​the grid and visual observation of the appearance, according to the following criteria: AA is the most excellent. A rating of B or higher indicates excellent moisture and heat resistance. AA: The peeled area was 0%, and no abnormalities were observed in the appearance. A: The peeled area was greater than 0% and less than 5%, and no abnormalities were observed in the appearance. B: The peeled area was 5% or more and less than 15%, and no abnormalities were observed in the appearance. C: The peeled area is less than 5%, but abnormalities are observed in the appearance and the film is cloudy. D: The peeled area is 5% or more but less than 15%, and abnormalities are observed in the appearance and the film is cloudy. E: The peeled area is 15% or more.

[0180] The evaluation results of each example and comparative example are shown in Table 3, that is, Table 3-1 to Table 3-3.

[0181]

[0182]

[0183]

[0184] The effect film of the photosensitive resin composition of the present invention can be used for color filters, solid-state image pickup devices, fingerprint authentication devices, and the like.

Claims

1. A photosensitive resin composition comprising a siloxane resin having a radical polymerizable group (hereinafter referred to as "component (a)"), a metal chelating agent (hereinafter referred to as "component (b)"), and a photoradical polymerization initiator, wherein in component (a), (R) ２ SiO ２／２ (R is an organic group) (hereinafter, such organosilane units are referred to as "D units") in a content of 30 mol % or more and 85 mol % or less relative to 100 mol % of all organosilane units.

2. The photosensitive resin composition according to claim 1, wherein component (b) is either or both of an aluminum chelate compound and a zirconium chelate compound.

3. The photosensitive resin composition according to claim 1, wherein the content of component (b) is from 0.1% by weight to 5% by weight based on 100% by weight of the solid content of the photosensitive resin composition.

4. The photosensitive resin composition according to claim 1, which uses a component (a) containing D units in which R contained in the D units is each independently an R containing any functional group selected from the group consisting of a methyl group, a phenyl group, a cyclopentyl group, and a cyclohexyl group (however, the R cannot simultaneously be a methyl group).

5. The photosensitive resin composition according to claim 1, wherein R contained in the D units is a phenyl group, and the content of such D units contained in component (a) is 30 mol % or more and 65 mol % or less, relative to 100 mol % of all organosilane units.

6. The photosensitive resin composition according to claim 1, wherein component (a) contains either or both of a carboxyl group and a dicarboxylic acid anhydride group.

7. The photosensitive resin composition according to claim 1, further comprising a monofunctional (meth)acrylate (hereinafter referred to as "component (d)").

8. The photosensitive resin composition according to claim 7, wherein as component (d), either or both of a monofunctional (meth)acrylate represented by the following general formula (1) and a monofunctional (meth)acrylate represented by the following general formula (2) are used: (R １ represents a hydrogen atom or a methyl group, R ２ represents an alkylene group. X is a substituent bonded to the benzene ring and represents an alkyl group or an aryl group. p is an integer of 0 to 5 and represents the number of substituents (X) bonded to the benzene ring. The benzene ring may have two or more types of X. In addition, m represents a positive integer. (R ３ represents a hydrogen atom or a methyl group, R ４ represents an alkylene group, and n represents a positive integer.

9. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 8.

10. The cured film according to claim 9, having a film stress of 0.01 MPa or more and 10 MPa or less.

11. The cured film according to claim 9, having a film thickness of 10 μm or more and 200 μm or less.

12. The cured film according to claim 9, which has a transmittance at a wavelength of 400 nm per 10 μm of film thickness of 90% or more and 100% or less.

13. A color filter having the cured film according to claim 9.

14. A solid-state imaging device having the cured film according to claim 9.

15. A fingerprint authentication device having the cured film according to claim 9.

16. The solid-state imaging device according to claim 14, wherein the solid-state imaging device includes wiring or a light-shielding layer, the wiring or the light-shielding layer containing any one selected from the group consisting of molybdenum, aluminum, and nickel.

17. The fingerprint authentication device according to claim 15, wherein the fingerprint authentication device includes wiring or a light-shielding layer, and the wiring or the light-shielding layer contains any one selected from the group consisting of molybdenum, aluminum, and nickel.

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