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

Abstract

To provide a photosensitive resin composition that, 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.SOLUTION: There is provided a photosensitive resin composition comprising a siloxane resin having a radical polymerizable group, a metal chelating agent and a photo-radical polymerization initiator, wherein in the siloxane resin having the radical polymerizable group, the content of an organosilane unit (D unit) represented by (R)2SiO2 / 2 (R is an organic group) is 30 mol% or more and 85 mol% or less based on 100 mol% of all the organosilane units.SELECTED DRAWING: None

Description

Technical Field

[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 including the same.

Background Art

[0002] In recent years, mobile display terminals such as smartphones and tablet PCs (personal computers) are equipped with a biometric authentication function for unlocking and personal authentication. Among biometric authentications, fingerprint authentication is currently installed in many terminals because it is inexpensive, small, and highly convenient.

[0003] Conventionally, fingerprint authentication has generally been mounted with a capacitive fingerprint authentication device on the bezel portion (periphery of the display) of the display. However, in smartphones, full-screen displays are trending, and the bezel portion is tending to disappear. Therefore, there has been a need to mount the fingerprint authentication device in a so-called "under-display type" configuration installed below the display.

[0004] As authentication methods for under-display type fingerprint authentication devices, mainly ultrasonic and optical methods have been studied. The ultrasonic method has characteristics such as high authentication accuracy and high authentication speed, but its penetration rate is still low, and the manufacturing cost remains high. On the other hand, the optical method has become the current mainstream method due to its versatility that can be introduced not only into organic light-emitting diode displays but also into liquid crystal displays, etc., and the manufacturing cost is showing a downward trend.

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

[0006] An optical under-display type fingerprint authentication device as described in Patent Document 2 is composed of a substrate, a sensor, a light-shielding layer, a transparent medium layer, and a microlens. As methods for forming the transparent medium layer, there are a method of forming by screen printing and a method of forming by photolithography using a photosensitive material. Among them, the latter method, which is excellent in positional accuracy and dimensional accuracy important for improving authentication accuracy, has attracted attention.

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

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0009] The microlens applied to a fingerprint authentication device generally has a larger diameter compared to the microlens applied to a CMOS image sensor or the like, so the focal length, which is the distance from the center point of the microlens to the imaging element, becomes longer. Therefore, the transparent media layer formed between the microlens and the imaging element requires a thickness of about 10 μm to 200 μm. When forming a film with such a large thickness, film stress becomes important. Film stress refers to the mechanical stress generated when a cured film is formed on a flat substrate, for example, the shrinkage stress accumulated inside the film. When the film stress is large, the warping of the substrate becomes large during film formation, and problems such as errors occurring during substrate conveyance will occur. Therefore, a material with low film stress when used as a cured film is required to suppress the warping of the substrate.

[0010] In addition, since the production line for manufacturing a fingerprint authentication device often utilizes the production line of TFT (thin film transistor), a metal layer containing molybdenum, aluminum, or nickel is generally used as the light-shielding layer or the lead-out wiring of the sensor in the fingerprint authentication device. Therefore, the material for forming the transparent media layer also requires resistance to the chemical solutions used when laminating these metal layers on the upper layer and excellent adhesion to these metal layers.

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

[0012] On the other hand, as described above, for example, in Patent Documents 3 and 4, various materials have been proposed. However, the material described in Patent Document 3 has low adhesion to a metal layer containing molybdenum, aluminum, or nickel, and in the case of a thick film with a film thickness exceeding 10 μm used in a fingerprint authentication device, there is a problem that the film stress of the cured film is large and the substrate warps.

[0013] In addition, the material described in Patent Document 4 has the same problem that when the film thickness exceeds 10 μm, the film stress of the cured film becomes large and the substrate warps.

[0014] The present invention was devised in view of such problems of the prior art, and when formed into a cured film, it has high transparency and chemical resistance, low film stress, and high adhesion to a metal layer containing molybdenum, aluminum, or nickel. An object of the present invention is to provide a photosensitive resin composition having such properties.

Means for Solving the Problems

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

[0016] A photosensitive resin composition containing the following components (a) to (c), wherein in component (a), an organosilane unit represented by (R)2SiO 2 / 2 (where R is an organic group) (such an organosilane unit is hereinafter referred to as “D unit”) is contained in an amount of 30 mol% or more and 85 mol% or less based on 100 mol% of all organosilane units. (a) Component: A siloxane resin having a radically polymerizable group (b) Component: A metal chelating agent (c) Component: A photo radical polymerization initiator.

[0017] Moreover, more preferable embodiments in the present invention are as follows, for example. · The above photosensitive resin composition in which any one or both of an aluminum chelate compound and a zirconium chelate compound are used as component (b). · The above photosensitive resin composition 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 component (b) is either or both of an aluminum chelate compound and a zirconium chelate compound, the content of the 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 the D unit, R is a phenyl group, and the content of the D unit is 30 mol% or more and 65 mol% or less based on 100 mol% of all the organosilane units. The photosensitive resin composition as described above. ·The component (b) is either or both of an aluminum chelate compound and a zirconium chelate compound, the content of the 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 the D unit, R is a phenyl group, the content of the D unit is 30 mol% or more and 65 mol% or less based on 100 mol% of all the organosilane units, and the component (a) contains either or both of a carboxyl group and a dicarboxylic anhydride group. The photosensitive resin composition as described above. ·Furthermore, the photosensitive resin composition as described above contains the following component (d). Component (d): Monofunctional (meth)acrylate

Advantages of the Invention

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

Embodiments for Carrying Out the Invention

[0019] Hereinafter, the present invention will be described in more detail. Hereinafter, 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, but the present invention is not limited to the following embodiments and can be variously modified and implemented according to the purpose and application.

[0020] The photosensitive resin composition of the present invention contains the following components (a) to (c). (a) Component: A siloxane resin having a radically polymerizable group. (b) Metal chelating agent. (c) Photo radical polymerization initiator.

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

[0022] The siloxane resin used as the 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. Further, in the present invention, the organosilane unit refers to a silane unit having at least one or more organic groups in the side chain of the siloxane skeleton. Also, R contained in the D unit is an organic group, and such an organic group refers to a group having a carbon atom bonded to the silicon atom of the siloxane skeleton, and specific examples thereof are as described below.

[0023] By containing such a component (a), a cured film having high transparency and excellent heat resistance and weather resistance can be formed. This is due to the fact that the component (a) has a siloxane skeleton in the main chain.

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

[0025] (a) component contains 30 mol% or more and 85 mol% or less of D units with respect to 100 mol% of all organosilane units. By the content ratio of D units being 30 mol% or more with respect 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 ratio of D units is more preferably 35 mol% or more, and even more preferably 40 mol% or more with respect to 100 mol% of all organosilane units. Also, by the content ratio of D units being 85 mol% or less with respect to 100 mol% of all organosilane units, the crosslinking density of the film can be increased, and it is possible to maintain excellent heat and humidity resistance and sufficient chemical resistance against acids and alkalis. The content ratio of D units is more preferably 75 mol% or less, and even more preferably 65 mol% or less with respect to 100 mol% of all organosilane units. Note that the D units contained in the (a) component may be one kind or a plurality of kinds.

[0026] In the component (a), it is preferable that each of the two Rs contained in the D unit independently contains any functional group selected from the group consisting of a methyl group, a phenyl group, a cyclopentyl group, and a cyclohexyl group. However, the two Rs do not simultaneously become a methyl group. Further preferably, each of the two Rs is independently any functional group (however, the two Rs do not simultaneously become a methyl group) selected from the group consisting of a methyl group, a phenyl group, a cyclopentyl group, and a cyclohexyl group. By using the component (a) containing such a D unit, due to the steric hindrance between the functional groups, the three-dimensional crosslinking can be moderately suppressed, and a cured film with low film stress and excellent crack resistance can be formed. The proportion occupied by such a D unit is preferably 65 mol% or more and 92 mol% or less when the total 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 a D unit in which the two Rs are both phenyl groups. Further, from the same viewpoint, it is preferable to contain 30 mol% or more and 65 mol% or less of the D unit in which the two Rs are both phenyl groups with respect to 100 mol% of all the organosilane units. It should be noted that the component (a) used in the present invention may contain other organosilane units such as organosilane units derived from organosilane compounds having a radically polymerizable group described later, in addition to the D unit as the preferable embodiment described above.

[0027] The D unit contained in the component (a) can be obtained by using a bifunctional organosilane compound and subjecting it to hydrolysis and condensation.

[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, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, diheptyldimethoxysilane, diheptyldiethoxysilane, dioctyldimethoxysilane, dioctyldiethoxysilane, dinonyldimethoxysilane, dinonyldiethoxysilane, didecyldimethoxysilane, didecyldiethoxysilane, ethylmethyldimethoxysilane, ethylmethyldiethoxysilane, n-propylmethyldimethoxysilane, n-propylmethyldiethoxysilane, 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,Biphenylmethyldimethoxysilane, biphenylmethyldiethoxysilane, cyclopentylphenyldimethoxysilane, cyclopentylphenyldiethoxysilane, cyclopentylcyclohexyldimethoxysilane, cyclopentylcyclohexyldiethoxysilane, cyclohexylphenyldimethoxysilane, cyclohexylphenyldiethoxysilane can be mentioned. Two or more of these may be used.

[0029] Among these, from the viewpoint of forming a cured film excellent in heat and humidity resistance and chemical resistance, and having low film stress and excellent crack resistance, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, diphenylsilanediol, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, cyclopentylphenyldimethoxysilane, cyclopentylphenyldiethoxysilane, cyclopentylcyclohexyldimethoxysilane, cyclopentylcyclohexyldiethoxysilane, cyclohexylphenyldimethoxysilane, cyclohexylphenyldiethoxysilane are preferable, and it is more preferable to select from diphenylsilanediol, diphenyldimethoxysilane, diphenyldiethoxysilane.

[0030] The component (a) used in the present invention has a radically polymerizable group. The radically polymerizable group refers to a functional group having a double bond that reacts with radicals generated from a radical polymerization initiator. Examples of the radically 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 preferable.

[0031] As a method for introducing a radical polymerizable group into the (a) component, a method of using an organosilane compound having a radical polymerizable group and obtaining it by hydrolysis and condensation is convenient.

[0032] Examples of the organosilane compound 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, 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, 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, 3-acryloxyoctylmethyldiethoxysilane are preferable.

[0034] Among these, from the viewpoint of forming a cured film that is excellent in heat and moisture resistance and chemical resistance, has low film stress, and is excellent in crack resistance, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-methacryloxyoctylmethyldimethoxysilane, 3-methacryloxyoctylmethyldiethoxysilane, 3-acryloxyoctylmethyldimethoxysilane, and 3-acryloxyoctylmethyldiethoxysilane are more preferable, and bifunctional organosilane compounds such as 3-methacryloxypropylmethyldimethoxysilane and 3-acryloxypropylmethyldimethoxysilane are even more preferable. For the sake of clarification, the structural unit derived from these bifunctional organosilane compounds having a radical polymerizable group corresponds to the D unit.

[0035] (Component (a) preferably contains 5 mol% or more and 50 mol% or less of an organosilane unit having a radical polymerizable group when the total organosilane units are 100 mol%. When the proportion of the organosilane unit having a radical polymerizable group in component (a) is 5 mol% or more based on 100 mol% of the total organosilane units, the crosslinking density of the cured film can be increased, and the heat and moisture resistance and chemical resistance are improved. The proportion of the organosilane unit having a radical polymerizable group is more preferably 7 mol% or more, and even more preferably 10 mol% or more based on 100 mol% of the total organosilane units. Also, when component (a) contains 50 mol% or less of the organosilane unit having a radical polymerizable group based on 100 mol% of the total organosilane units, excessive radical reactions can be suppressed, residues during development can be suppressed, and the stress of the cured film can be further reduced. The proportion of the organosilane unit having a radical polymerizable group is more preferably 30 mol% or less, and even more preferably 12 mol% or less based on 100 mol% of the total organosilane units.

[0036] Component (a) used in the present invention preferably contains either or both of a carboxyl group and a dicarboxylic acid anhydride group. When component (a) contains a carboxyl group or a dicarboxylic acid anhydride group in its molecular structure, it can suppress residues during development, improve resolution, and form a pattern with excellent resolution even in a thick film with a film thickness of 10 μm or more. At the same time, it can improve the adhesion to the underlying substrate, metal layer, or resin layer. Examples of the carboxyl group and the dicarboxylic acid anhydride group include an alkylene carboxyl group, a succinic acid group, a succinic anhydride group, a phthalic acid group, a phthalic anhydride group, and the like.

[0037] As a method for obtaining component (a) having the carboxyl group or the dicarboxylic acid anhydride group, there is a method of using an organosilane compound having a carboxyl group or a dicarboxylic acid anhydride group and subjecting it to hydrolysis and condensation.

[0038] Examples of the organosilane compound 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, 3-trimethoxysilylpropyl phthalic anhydride, and the like. Two or more of these may be used. Among these, from the viewpoint of suppressing residues during development, improving resolution, and forming a pattern with excellent resolution even in a thick film with a film thickness of 10 μm or more, 3-trimethoxysilylpropyl succinic anhydride and 3-triethoxysilylpropyl succinic anhydride are preferred.

[0039] Component (a) preferably contains 1 mol% or more and 30 mol% or less of an organosilane unit having a carboxyl group or a dicarboxylic anhydride group when the total organosilane units are 100 mol%. When the proportion of the organosilane unit having a carboxyl group or a dicarboxylic anhydride group is 1 mol% or more based on 100 mol% of the total organosilane units, residues during development can be suppressed, the resolution can be improved, and a pattern with excellent resolution can be formed even in a thick film with a film thickness of 10 μm or more. The proportion of the organosilane unit having a carboxyl group or a dicarboxylic anhydride group is more preferably 3 mol% or more, and even more preferably 5 mol% or more based on 100 mol% of the total organosilane units. Also, when the proportion of the organosilane unit having a carboxyl group or a dicarboxylic anhydride group is 30 mol% or less based on 100 mol% of the total organosilane units, film reduction during development can be suppressed, and the patterning property can be improved. The proportion of the organosilane unit having a carboxyl group or a dicarboxylic anhydride group is more preferably 25 mol% or less, and even more preferably 20 mol% or less based on 100 mol% of the total organosilane units.

[0040] Component (a) is preferably a hydrolytic condensate using a bifunctional organosilane compound that provides a D unit, the organosilane compound having a radical polymerizable group, and the organosilane compound having either or both of the carboxyl group and the dicarboxylic anhydride group. Further, it may be a hydrolytic condensate of these organosilane compounds and other organosilane compounds.

[0041] Examples of other organosilane compounds include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-(N,N-diglycidyl)aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 2-cyanoethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 1-glycidoxyethyltrimethoxysilane, 1-glycidoxyethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 1-glycidoxypropyltrimethoxysilane, 1-glycidoxypropyltriethoxysilane, 2-glycidoxypropyltrimethoxysilane, 2-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltripropoxysilane, 3-glycidoxypropyltriisopropoxysilane, 3-glycidoxypropyltributoxysilane, 3-glycidoxypropyltri(methoxyethoxy)silane, 1-glycidoxybutyltrimethoxysilane, 1-glycidoxybutyltriethoxysilane, 2-glycidoxybutyltrimethoxysilane, 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, trifluoromethyltrimethoxysilane, 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, heptadecafluorodecylmethyldimethoxysilane, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 2-naphthyltrimethoxysilane, 1-anthracenyltrimethoxysilane, 9-anthracenyltrimethoxysilane, 9-phenanthrenyltrimethoxysilane, 9-fluorenyltrimethoxysilane, 2-fluorenyltrimethoxysilane, 2-fluorenonyltrimethoxysilane, 1-pyrenyltrimethoxysilane, 2-indenyltrimethoxysilane, 5-acephenanthrylyltrimethoxysilane, etc. may be mentioned. Two or more of these may be used.,

[0042] (a) The component can be obtained by hydrolytic condensation of an organosilane compound. For example, it can be obtained by hydrolyzing the 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] Various conditions of the hydrolysis reaction can be appropriately set in consideration of the reaction scale, the size and shape of the reaction vessel, etc. For example, in a solvent, an acid catalyst and water are added to the organosilane compound over 1 to 180 minutes, and then it is preferably reacted at room temperature to 110 °C for 1 to 180 minutes. By performing 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, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acids and their anhydrides, and 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, N,N-dimethyl-n-octylamine, and organic salts such as pyridine methanesulfonate, pyridine ethanesulfonate, 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, tetraethylammonium hydroxide. The addition amount of the catalyst is preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the total organosilane compound used during the hydrolysis reaction. By setting the amount of the catalyst within the above range, the hydrolysis reaction can proceed more efficiently.

[0045] After obtaining a silanol compound by the hydrolysis reaction of the organosilane compound, it is preferable to directly heat the reaction solution 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 the organic solvent used in the hydrolysis and condensation reaction of the organosilane compound include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, 1-t-butoxy-2-propanol, 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, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol 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 monot-butyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, γ-butyrolactone, etc. are preferred.

[0047] When the compounds listed as organic solvents above are generated by a hydrolysis reaction or when compounds that act as solvents are generated, it is also possible to perform hydrolysis without a solvent. After the reaction is completed, it is also preferable to adjust to an appropriate concentration as a resin composition by further adding a solvent. Further, depending on the purpose, after hydrolysis, an appropriate amount of the generated alcohol or the like may be distilled off and removed under heating or reduced pressure, and then a suitable solvent may be added.

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

[0049] Also, the water used in the hydrolysis reaction is preferably ion-exchanged water. The amount of water is preferably 1.0 to 4.0 moles with respect to 1 mole of the 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 polydentate ligands are chelated to a metal atom.

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

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

[0053]

Chemical formula

[0054] (M represents a metal atom, and R 5 is independently hydrogen, an alkyl group, an aryl group, or an alkenyl group, and R 6 and R 7 are independently hydrogen, an alkyl group, an aryl group, an alkenyl group, or an alkoxy group, j is an integer from 0 to 8, and k is an integer from 1 to 4.) As the metal atom M, from the viewpoint of the high transparency of the formed cured film, titanium, zirconium, aluminum, zinc, cobalt, molybdenum, lanthanum, barium, strontium, magnesium, calcium, etc. can be mentioned. Among these, from the viewpoints of improving the adhesion to a metal layer containing molybdenum, aluminum, or nickel while maintaining high transparency, low film stress, and excellent crack resistance, and improving chemical resistance, as the metal atom M, zirconium or aluminum is preferable, and zirconium is more preferable. That is, as the 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] The alkyl group, aryl group, and alkenyl group in R 5 in the metal chelating agent represented by the general formula (3), and the alkyl group, aryl group, alkenyl group, and alkoxy group in R 6 and R 7 may all be substituted by other substituents.

[0056] In the general formula (3), R 5Examples 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, or 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, or a phenyl group is preferable. R 6 and R 7 Examples include hydrogen, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a phenyl group, a vinyl group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy 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, or a benzyloxy group. Among these, from the viewpoints of ease of synthesis and stability of the metal chelating agent, a methyl group, a t-butyl group, a phenyl group, a methoxy group, an ethoxy group, or an n-octadecyl group is preferable.

[0057] Examples of the aluminum chelate compound in which the metal atom M is aluminum include aluminum tris isopropoxide, aluminum tris n-propoxide, aluminum tris sec-butoxide, aluminum tris n-butoxide, aluminum tris phenoxide, aluminum tris acetylacetonate, aluminum tris(2,2,6,6-tetramethyl-3,5-heptanedionate), aluminum tris ethylacetoacetate, aluminum tris methylacetoacetate, aluminum tris methylmalonate, aluminum tris ethylmalonate, aluminum ethylacetate di(isopropoxide), aluminum acetylacetonate) di(isopropoxide), aluminum methylacetoacetate di(isopropoxide), aluminum octadecylacetoacetate di(isopropylate), and aluminum monoacetylacetonate bis(ethylacetoacetate).

[0058] Examples of the zirconium chelate compound 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, zirconium mono n-butoxyacetylacetonate bis(ethylacetoacetate), zirconium mono n-butoxyethylacetoacetate bis(acetylacetonate), zirconium mono n-butoxytri(acetylacetonate), zirconium mono n-butoxytri(acetylacetonate), zirconium di(n-butoxy)bis(ethylacetoacetate), zirconium di(n-butoxy)bis(acetylacetonate), zirconium di(n-butoxy)bis(ethylmalonate), zirconium di(n-butoxy)bis(benzoylacetonate), zirconium di(n-butoxy)bis(dibenzoylmethanate), and zirconium tetraacetylacetonate.

[0059] Among these, from the viewpoint of improving the adhesion and chemical resistance to a metal layer containing molybdenum, aluminum, or nickel 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 preferable, and zirconium tetraacetylacetonate is more preferable.

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

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

[0062] Examples of component (c) include benzoin compounds, benzyl 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 viewpoint 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, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one, and the like.

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

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

[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-butanedione-2-(o-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetoxyoxime).

[0067] From the viewpoint of sufficiently promoting radical polymerization and improving the chemical resistance of the cured film, the amount of component (c) contained in the photosensitive resin composition of the present invention is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, when the solid content of the photosensitive resin composition is 100% by weight. On the other hand, from the viewpoint of improving the transparency of the cured film, it is preferably 10% by weight or less, 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)). The monofunctional (meth)acrylate refers to a compound having one methacrylic group or one acrylic group in the molecule. Here, the meaning of "(meth)acrylate" is a general term for acrylate (acrylic acid ester) and methacrylate (methacrylic acid ester). In the following, a compound containing a methacrylic group may be described as methacrylate, and a compound containing an acrylic group may be described as acrylate. By containing component (d), the methacrylic group or acrylic group can react with the radicals generated from component (c) described above by irradiation with ultraviolet light to photocure the film. Further, by containing component (d), the stress of the formed film can be reduced and the crack resistance can be improved compared with the case where a polyfunctional (meth)acrylate described later is used, and the resolution can also be improved. Here, the meaning of "monofunctional" of the monofunctional (meth)acrylate is that it has one methacrylic group or acrylic group in the molecule.

[0069] (d) Examples of components 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, dicyclopentenilyloxyethyl (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, diethylaminoethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinic acid, N-(meth)acryloyloxyethyl hexahydrophthalimide, trifluoroethyl (meth)acrylate, ethyl carbitol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, 2-ethylhexyl EO-modified (meth)acrylate, phenol EO-modified (meth)acrylate, p-nonylphenol EO-modified (meth)acrylate, p-nonylphenol PO-modified (meth)acrylate, о-phenylphenol EO-modified (meth)acrylate, p-cumylphenol EO-modified (meth)acrylate, methoxytriethylene glycol (meth)acrylate, p-phenoxyphenol EO-modified (meth)acrylate, p-phenoxyphenol PO-modified (meth)acrylate, etc. Two or more of these can be used.

[0070] Among these, from the viewpoint of reducing the stress of the formed film and improving the crack resistance, as the 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, p-phenoxyphenol PO-modified (meth)acrylate are preferably used.

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

[0072]

Chemical formula

[0073] (R 1 represents a hydrogen atom or a methyl group, and 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 from 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. Also, m represents a positive integer preferably in the range of 2 or more and 8 or less.)

[0074]

Chemical formula

[0075] (R 3 represents a hydrogen atom or a methyl group, and R 4represents an alkylene group. Also, n represents a positive integer preferably in the range of 2 or more and 8 or less.).

[0076] Regarding the monofunctional (meth)acrylate 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 crack resistance, it is preferable that m and n are each 2 or more, and more preferably 4 or more.

[0077] From the viewpoint of reducing the film stress of the cured film and improving crack resistance, the content of the component (d) in the photosensitive resin composition of the present invention is preferably 3% by weight or more, more preferably 5% by weight or more, when the solid content of the photosensitive resin composition is 100% by weight. On the other hand, from the viewpoint of improving the chemical resistance of the cured film, it is preferably 40% by weight or less, 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 the component (d). The polyfunctional (meth)acrylate refers to a compound having two or more groups selected from a methacryl group and an acrylic group. By containing the polyfunctional (meth)acrylate, the above-mentioned photocuring can proceed further, and the crosslinking density of the film can be improved, thereby improving the chemical resistance.

[0079] Examples of the polyfunctional (meth)acrylate 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, 1,10-decanediol di(meth)acrylate, and polyfunctional (meth)acrylates having three or more functional groups such as acrylic acid esters 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, pentapentaerythritol undeca(meth)acrylate, and pentapentaerythritol 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. The adhesion improver refers to a compound having one or more reactive functional groups in the molecule that improve the adhesion to the substrate. By containing the adhesion improver, the adhesion between the coating film and the underlying substrate can be improved. Examples of the adhesion improver 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, (meth)acrylamide compounds having an amide group, and the like. Among these, from the viewpoint of further improving the adhesion between the coating film and the underlying substrate, silane coupling agents and (meth)acrylamide compounds are preferred.

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

[0082] Among these, from the viewpoint of having reactive functional groups and improving the adhesion and chemical resistance between the coating film and the underlying substrate by reacting with other components, 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-dimethyl-butylidene)propylamine, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, p-styryltrimethoxysilane 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, diacetoneacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-n-propylmethacrylamide, N-isopropylmethacrylamide, N-cyclopropylmethacrylamide, N-methoxymethylmethacrylamide, N-butoxymethylmethacrylamide, N,N'-methylenebis-methacrylamide, diacetonemethacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-methyl,N-ethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylmethacrylamide, N,N-dimethylaminopropylacrylamide, N-methyl,N-ethylmethacrylamide, etc. Two or more of these may be contained.

[0084] From the viewpoint of improving the 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 as the adhesion improver.

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

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

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

[0089] The photosensitive resin composition of the present invention preferably further contains a solvent. The solvent has a function of adjusting the viscosity of the resin composition to a range suitable for coating and improving the 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; ketones such as methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, and 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, dimethyl sulfoxide, and the like. Two or more of these may be contained. Among these, from the viewpoint of coatability, diacetone alcohol, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclopentanone are preferable.

[0091] The content of the solvent can be arbitrarily set according to the coating method and the like. 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 containing a surfactant, the coating uniformity of the photosensitive resin composition can be improved. Examples of the surfactant include fluorosurfactants, silicone surfactants, fluorine-containing thermally decomposable surfactants, polyether-modified siloxane surfactants, polyalkylene oxide surfactants, poly(meth)acrylate surfactants, ammonium lauryl sulfate, triethanolamine polyoxyethylene alkyl ether sulfate, stearylamine acetate, lauryl trimethyl ammonium chloride, lauryl dimethyl amine oxide, lauryl carboxymethyl hydroxyethyl imidazolium betaine, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearate. Two or more surfactants may be used. Among these, from the viewpoints of improving coating uniformity and excellent environmental compatibility, silicone surfactants and poly(meth)acrylate surfactants are preferred.

[0093] Examples of commercially available products of silicone surfactants include, for example, "BYK" (registered trademark)-333, BYK-301, BYK-331, BYK-345, BYK-307 (manufactured by BYK Chemie Japan Co., Ltd.), etc. Examples of commercially available products of poly(meth)acrylate surfactants include, for example, "BYK" (registered trademark)-352 (manufactured by BYK Chemie Japan Co., Ltd.).

[0094] When it is desired to impart liquid repellency to the film surface, the photosensitive resin composition of the present invention may contain a liquid repellent surfactant as the surfactant. The liquid repellent surfactant refers to a surfactant having one or more reactive functional groups in the molecule and one or more liquid repellent groups in the molecule. As the reactive functional group, a methacryl group and an acryl group are preferred. 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 color filter, a solid-state imaging device, a fingerprint authentication device, and the like, as well as a sealing layer for displays and semiconductors, 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 with examples. The method for producing the cured film of the present invention preferably has a step of curing by light and / or heat without going through a step of removing all of the component (a) by baking or treatment with a stripping solution. Specifically, a method in which the photosensitive resin composition of the present invention is applied onto a substrate, dried to obtain a dry film, the obtained dry film is exposed, developed as necessary, and cured by heating (post-baking) is preferred.

[0098] Examples of the substrate include a glass substrate, a metal laminated substrate, a silicon wafer, various films, etc., which can be selected according to the purpose.

[0099] The application can be performed by an application method such as microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit die coating, etc., and the application method can be selected according to the purpose.

[0100] For drying, it is preferable to remove the solvent using a vacuum hot plate and then dry using a heating device. The vacuum hot plate is preferably carried out under the conditions of 20 to 80 °C, a pressure of 10 to 1000 Pa, and for 30 to 600 seconds. As the heating device, for example, a hot air oven, a nitrogen oven, a hot plate, etc. can be used. The drying temperature by the heating device is preferably 80 to 120 °C, and the time is preferably 1 to 60 minutes.

[0101] Exposure is a process of photocuring the necessary parts of the dry film by light irradiation from an exposure apparatus, making any part of the dry film soluble in a developer. In the exposure process, exposure may be performed through a photomask having a predetermined opening, or an arbitrary pattern may be directly drawn using laser light or the like without using a photomask. Also, the entire surface may be exposed without using a photomask.

[0102] Examples of the exposure apparatus include a mask aligner (LA series, manufactured by Nanotec Co., Ltd.), a mirror projection mask aligner (MPA series, manufactured by Canon Inc.), etc. Examples of the actinic rays irradiated in the exposure process include near-infrared rays, visible rays, and ultraviolet rays, and ultraviolet rays are preferable. 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 the light source include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a halogen lamp, a germicidal lamp, etc., and a high-pressure mercury lamp and an ultra-high-pressure mercury lamp are preferable. The exposure conditions can be appropriately selected according to the thickness of the dry film to be exposed. Generally, using an ultra-high-pressure mercury lamp with an output of 1~100 mW / cm 2 and exposing with an exposure amount of 10~10,000 mJ / cm 2 (converted exposure amount at a wavelength of 365 nm) is preferable.

[0103] Development is carried out when it is desired to dissolve the unexposed part and obtain a negative pattern. Examples of the development method include a shower method, a dip method, a paddle method, etc. The development time is preferably 5 seconds to 10 minutes. Examples of the developer include known alkaline developers, and specific examples include inorganic alkalis such as hydroxides, carbonates, phosphates, silicates, and borates of alkali metals, amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine, and aqueous solutions containing one or more of quaternary ammonium salts such as tetramethylammonium hydroxide and choline. After development, it is preferable to rinse with water, and subsequently, a drying bake can also be performed in the range of 50~150 °C.

[0104] Post-baking is preferably carried out using the heating device described above. The heating temperature is preferably 85 to 300 °C, and the heating time is preferably 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. Further, the film stress of the cured film of the present invention is preferably 0.01 MPa or more and 10 MPa or less. Since such a cured film has low film stress, it does not have cracks even after post-baking when forming a thick film. 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 warping of the substrate after post-baking, the film stress is more preferably 6 MPa or less. The method for measuring the film stress is determined by the method described in the Examples section.

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

[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 dispersion type material in which a pigment is dispersed in a photoresist, which is used in a flat panel display such as a liquid crystal display. The color filter of the present invention may have the cured film of the present invention between the substrate and the color filter layer, or may have it on the color filter layer.

[0110] Examples of the solid-state imaging device include a CCD image sensor and a CMOS image sensor. A CMOS image sensor is more preferable.

[0111] Examples of fingerprint authentication devices include, for example, ultrasonic fingerprint authentication devices and optical fingerprint authentication devices. An optical under-display type fingerprint authentication device is more preferable because of higher authentication accuracy.

[0112] The solid-state imaging device 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 described above. The wiring or light-shielding layer is preferably a metal layer containing any one selected from the group consisting of molybdenum, aluminum, and nickel.

[0113] Therefore, one of the preferred embodiments of the present invention is a solid-state imaging device or fingerprint authentication device having the cured film according to the present invention, wherein the solid-state imaging device or the fingerprint authentication device includes a 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.

Example

[0114] Hereinafter, the present invention will be described in more detail with specific examples, but these are merely illustrative and the present invention is not to be construed as being limited to the following examples. Among the compounds used below, those using abbreviations 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-Trimethoxysilylpropyl succinic anhydride D'-4: 2-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane In the evaluation method, for those without the description of the number of evaluation samples, the evaluation is based on 1 evaluation sample, and for those without the temperature specified under each condition such as evaluation and synthesis, it is carried out at room temperature.

[0115] The weight-average molecular weights of the siloxane resin 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 were determined as values in terms of polystyrene. Apparatus: GPC measuring apparatus (2695) equipped with an RI detector manufactured by Waters Column: PLgel MIXED-C column (manufactured by Polymer Laboratories, 300 mm) × 2 (connected in series) Measurement temperature: 40 °C Flow rate: 1 mL / min Solvent: Tetrahydrofuran (THF) 0.5 mass% solution Standard substance: Polystyrene Detection mode: RI.

[0116] 〔Synthesis Example 1〕Siloxane resin solution (PS-1) In a 500 mL three-necked flask, 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-trimethoxysilylpropyl succinic anhydride, 97.43 g (0.45 mol) of diphenylsilanediol, and 0.174 g of BHT (0.50 wt% based on 3-methacryloxypropylmethyldimethoxysilane) were charged. The flask was immersed in an oil bath at 40 °C and stirred. As a catalyst, an aqueous phosphoric acid solution prepared by dissolving 2.05 g of phosphoric acid (1.0 wt% based on the charged monomers) in 28.80 g of water was added dropwise over 10 minutes using a dropping funnel. After stirring at 40 °C for 1 hour, the oil bath temperature was set to 70 °C and stirred for 1 hour, and then the oil bath temperature was raised to 120 °C. One hour after the start of heating, the internal temperature of the solution reached 100 °C, and heating and stirring were continued for 2 hours (the internal temperature was 100 - 110 °C). During the reaction, a total of 66 g of by-products, methanol and water, distilled off. PGMEA was added to the obtained PGMEA solution of the siloxane resin so that the concentration of the siloxane resin was 65 wt%. 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. Then, the ion exchange resin was removed by filtration to obtain a siloxane resin solution (PS-1). When the weight average molecular weight of the obtained siloxane resin was measured by GPC, it was 2,500 (in terms of polystyrene).

[0117] [Synthesis Example 2] Siloxane Resin Solution (PS-2) The addition amount of PGMEA added at the beginning of polymerization was changed to 89.06 g, the addition amount of methyltrimethoxysilane was changed to 20.43 g (0.15 mol), and the addition amount of diphenylsilanediol was changed to 118.97 g (0.55 mol). As a catalyst, a phosphoric acid aqueous solution prepared by dissolving 2.13 g of phosphoric acid (1.0% by weight based on the charged monomers) in 23.40 g of water was used. In the same manner as in Synthesis Example 1, a siloxane resin solution (PS-2) was obtained. When the weight average molecular weight of the obtained siloxane resin was measured by GPC, it was 2,300 (in terms of polystyrene).

[0118] 〔Synthesis Example 3〕Siloxane resin solution (PS-3) The addition amount of PGMEA added at the beginning of polymerization was changed to 98.69 g, the addition amount of methyltrimethoxysilane was changed to 6.81 g (0.05 mol), and the addition amount of diphenylsilanediol was changed to 140.60 g (0.65 mol). As a catalyst, a phosphoric acid aqueous solution prepared by dissolving 2.21 g of phosphoric acid (1.0% by weight based on the charged monomers) in 18.00 g of water was used. In the same manner as in Synthesis Example 1, a siloxane resin solution (PS-3) was obtained. When the weight average molecular weight of the obtained siloxane resin was measured by GPC, it was 2,000 (in terms of polystyrene).

[0119] 〔Synthesis Example 4〕Siloxane resin solution (PS-4) The addition amount of PGMEA added at the beginning of polymerization was changed to 64.98 g, the addition amount of methyltrimethoxysilane was changed to 54.48 g (0.40 mol), and the addition amount of diphenylsilanediol was changed to 64.89 g (0.30 mol). As a catalyst, a phosphoric acid aqueous solution prepared by dissolving 1.93 g of phosphoric acid (1.0% by weight based on the charged monomers) in 36.90 g of water was used. In the same manner as in Synthesis Example 1, a siloxane resin solution (PS-4) was obtained. When the weight average molecular weight of the obtained siloxane resin was measured by GPC, it was 2,700 (in terms of polystyrene).

[0120] 〔Synthesis Example 5〕Siloxane resin solution (PS-5) The addition amount of PGMEA added at the beginning of polymerization was changed to 50.53 g, the addition amount of methyltrimethoxysilane was changed to 74.91 g (0.55 mol), and the addition amount of diphenylsilanediol was changed to 32.45 g (0.15 mol). As a catalyst, a phosphoric acid aqueous solution prepared by dissolving 1.81 g of phosphoric acid (1.0% by weight based on the charged monomers) in 45.00 g of water was used. In the same manner as in Synthesis Example 1, a siloxane resin solution (PS-5) was obtained. When the weight average molecular weight of the obtained siloxane resin was measured by GPC, it was 2,800 (in terms of polystyrene).

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

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

[0123] 〔Synthesis Example 8〕Siloxane resin solution (PS-8) The addition amount of PGMEA added at the beginning of polymerization was changed to 66.10 g, 102.78 g (0.45 mol) of dicyclopentyldimethoxysilane was added instead of diphenyldisilanediol, and a phosphoric acid aqueous 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. A siloxane resin solution (PS-8) was obtained in the same manner as in Synthesis Example 1. When the weight average molecular weight of the obtained siloxane resin was measured by GPC, it was 2,800 (in terms of polystyrene).

[0124] 〔Synthesis Example 9〕Siloxane resin solution (PS-9) The addition amount of PGMEA added at the beginning of polymerization was changed to 40.37 g, 54.09 g (0.45 mol) of dimethyldimethoxysilane was added instead of diphenyldisilanediol, and a phosphoric acid aqueous 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. A siloxane resin solution (PS-9) was obtained in the same manner as in Synthesis Example 1. When the weight average molecular weight of the obtained siloxane resin was measured by GPC, it was 3,000 (in terms of polystyrene).

[0125] 〔Synthesis Example 10〕Siloxane resin solution (PS-10) 3-Trimethoxysilylpropyl succinic anhydride was not added, the addition amount of PGMEA added at the beginning of polymerization was changed to 34.85 g, and the addition amount of methyltrimethoxysilane was changed to 47.67 g (0.35 mol). A phosphoric acid aqueous 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. A siloxane resin solution (PS-10) was obtained in the same manner as in Synthesis Example 1. When the weight average molecular weight of the obtained siloxane resin was measured by GPC, it was 2,000 (in terms of polystyrene).

[0126] 〔Synthesis Example 11〕Siloxane resin solution (PS-11) Without adding methyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, the amount of PGMEA added at the beginning of polymerization was changed to 105.41 g, and the amount of diphenylsilanediol added was changed to 162.23 g (0.75 mol). As a catalyst, a phosphoric acid aqueous 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. In the same manner as in Synthesis Example 1, a siloxane resin solution (PS-11) was obtained. When the weight-average molecular weight of the obtained siloxane resin was measured by GPC, it was 1,200 (polystyrene conversion).

[0127] 〔Synthesis Example 12〕Siloxane Resin Solution (PS-12) The amount of PGMEA added at the beginning of polymerization was changed to 45.71 g, the amount of methyltrimethoxysilane added was changed to 81.72 g (0.60 mol), and the amount of diphenylsilanediol added was changed to 21.63 g (0.10 mol). As a catalyst, a phosphoric acid aqueous 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. In the same manner as in Synthesis Example 1, a siloxane resin solution (PS-12) was obtained. When the weight-average molecular weight of the obtained siloxane resin was measured by GPC, it was 2,700 (polystyrene conversion).

[0128] 〔Synthesis Example 13〕Siloxane Resin Solution (PS-13) Without adding diphenylsilanediol and 3-methacryloxypropylmethyldimethoxysilane, the amount of PGMEA added at the beginning of polymerization was changed to 34.65 g, and the amount of methyltrimethoxysilane added was changed to 95.34 g (0.70 mol). Additionally, 37.26 g (0.15 mol) of 3-methacryloxypropyltrimethoxysilane was newly added. As a catalyst, a phosphoric acid aqueous 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. In the same manner as in Synthesis Example 1, a siloxane resin solution (PS-13) was obtained. When the weight-average molecular weight of the obtained siloxane resin was measured by GPC, it was 5,000 (polystyrene conversion).

[0129] [Synthesis Example 14] Siloxane Resin Solution (PS-14) Without adding 3-methacryloxypropylmethyldimethoxysilane, the amount of PGMEA added at the beginning of polymerization was changed to 83.55 g, the amount of methyltrimethoxysilane added was 34.05 g (0.25 mol), and the amount of diphenylsilanediol added was changed to 129.79 g (0.60 mol). A siloxane resin solution (PS-14) was obtained in the same manner as in Synthesis Example 1, except that 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 obtained siloxane resin was measured by GPC and found to be 2,000 (in terms of polystyrene).

[0130] [Synthesis Example 15] Siloxane Resin Solution (PS-15) The amount of PGMEA added at the beginning of polymerization was changed to 80.25 g, the amount of 3-methacryloxypropylmethyldimethoxysilane added was 27.88 g (0.12 mol), and the amount of diphenylsilanediol added was changed to 103.83 g (0.48 mol). A siloxane resin solution (PS-15) was obtained in the same manner as in Synthesis Example 1, except that an aqueous phosphoric acid 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 (in terms of polystyrene).

[0131] [Synthesis Example 16] Siloxane Resin Solution (PS-16) The amount of PGMEA added at the beginning of polymerization was changed to 80.80 g, the amount of 3-methacryloxypropylmethyldimethoxysilane added was 23.24 g (0.10 mol), and the amount of diphenylsilanediol added was changed to 108.16 g (0.50 mol). A siloxane resin solution (PS-16) was obtained in the same manner as in Synthesis Example 1, except that an aqueous phosphoric acid 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 (in terms of polystyrene).

[0132] [Synthesis Example 17] Siloxane Resin Solution (PS-17) The addition amount of PGMEA added at the beginning of polymerization was changed to 81.63 g, the addition amount of 3-methacryloxypropylmethyldimethoxysilane was changed to 16.26 g (0.070 mol), and the addition amount of diphenylsilanediol was changed to 114.64 g (0.53 mol). A siloxane resin solution (PS-17) was obtained in the same manner as in Synthesis Example 1, except that an aqueous phosphoric acid solution prepared by dissolving 2.04 g of phosphoric acid (1.0% by weight 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 (in terms of polystyrene).

[0133] [Synthesis Example 18] Siloxane Resin Solution (PS-18) The addition amount of PGMEA added at the beginning of polymerization was changed to 82.18 g, the addition amount of 3-methacryloxypropylmethyldimethoxysilane was changed to 11.62 g (0.050 mol), and the addition amount of diphenylsilanediol was changed to 118.97 g (0.55 mol). A siloxane resin solution (PS-18) was obtained in the same manner as in Synthesis Example 1, except that an aqueous phosphoric acid solution prepared by dissolving 2.03 g of phosphoric acid (1.0% by weight based on the charged monomers) in 25.20 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 (in terms of polystyrene).

[0134] [Synthesis Example 19] Siloxane Resin Solution (PS-19) The addition amount of PGMEA added at the beginning of polymerization was changed to 82.45 g, the addition amount of 3-methacryloxypropylmethyldimethoxysilane was changed to 9.29 g (0.040 mol), and the addition amount of diphenylsilanediol was changed to 121.13 g (0.56 mol). A siloxane resin solution (PS-19) was obtained in the same manner as in Synthesis Example 1, except that an aqueous phosphoric acid solution prepared by dissolving 2.03 g of phosphoric acid (1.0% by weight 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 found to be 2,100 (in terms of polystyrene).

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

[0136]

Table 1

[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]decane-8-yl methacrylate were charged, stirred at room temperature for a while, the inside of the flask was purged with nitrogen, and then 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 obtained solution, and heated and stirred at 90 °C for 4 hours. PGMEA was added to the obtained PGMEA solution of the acrylic resin so that the solid content concentration became 50% by weight to obtain an acrylic resin solution (PA-1). When the weight average molecular weight of the obtained acrylic resin was measured by GPC, it was 10,000. Also, the acid value of the obtained acrylic resin was 118 mgKOH / g.

[0138] 〔Example 1〕Photosensitive resin composition (A-1) Under a yellow light, 5.36 g of the siloxane resin solution (PS-1) obtained in Synthesis Example 1 as component (a), 0.050 g of zirconium tetraacetylacetonate (trade name “Organix” (registered trademark) ZC-150, manufactured by Matsumoto Fine Chemical Co., Ltd. (hereinafter referred to as “ZC-150”)) as component (b), 0.10 g of 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)] (trade name “Irgacure” (registered trademark) OXE01, manufactured by BASF Japan Ltd. (hereinafter referred to as “OXE-01”)) as component (c), 1.00 g of 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), 0.10 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (trade name KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd. (hereinafter referred to as “KBM-303”)) and 0.25 g of N-methoxymethylacrylamide as an adhesion improver, 0.015 g of ethylene bis(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 of a poly(meth)acrylate-based surfactant (“BYK” (registered trademark) 352, manufactured by BYK-Chemie Japan Co., Ltd. (hereinafter referred to as “BYK-352”)) in PGMEA (equivalent to a concentration of 300 ppm) were dissolved in 3.10 g of PGMEA and stirred. The resulting mixture was filtered through a 1.0 μm diameter filter to prepare a photosensitive resin composition (A-1) having a solid content concentration of 50 wt%. Since the concentration of BYK-352 is extremely small, it is not shown in the table except in terms of weight fraction. Also, the description of BYK-352 in the table is omitted.

[0139] [Examples 2 to 10] Photosensitive resin compositions (A-2) to (A-10) 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 were used as the siloxane resin (a), respectively.

[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 addition amount of the siloxane resin solution (PS-1) was 5.40 g, the addition amount of the metal chelating agent ZC-150 was 0.025 g, and the addition amount of PGMEA 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 addition amount of the siloxane resin solution (PS-1) was 5.431 g, the addition amount of the metal chelating agent ZC-150 was 0.0050 g, and the addition amount of PGMEA 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 addition amount of the siloxane resin solution (PS-1) was 5.435 g, the addition amount of the metal chelating agent ZC-150 was 0.0020 g, and the addition amount of PGMEA 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 addition amount of the siloxane resin solution (PS-1) was 5.21 g, the addition amount of the metal chelating agent ZC-150 was 0.15 g, and the addition amount of PGMEA 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 addition amount of the siloxane resin solution (PS-1) was 5.05 g, the addition amount of the metal chelating agent ZC-150 was 0.25 g, and the addition amount of PGMEA 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 the siloxane resin solution (PS-1) added was 4.97 g, the amount of the 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 "Organix" (registered trademark) ZC-540, manufactured by Matsumoto Fine Chemical Co., Ltd. (hereinafter referred to as "ZC-540")) was added as the component (b) instead of ZC-150.

[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 "Organix" (registered trademark) ZC-580, manufactured by Matsumoto Fine Chemical Co., Ltd. (hereinafter referred to as "ZC-580")) was added as the component (b) instead of ZC-150.

[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 as the component (b) instead of ZC-150.

[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 the component (b) instead of ZC-150.

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

[0151] 〔Example 22〕Photosensitive resin composition (A-22) (b) component, except that 0.050 g of bis(acetylacetonato)zinc (hereinafter referred to as "Zn(acac)2") was added instead of ZC-150, a photosensitive resin composition (A-22) was prepared in the same manner as in Example 1.

[0152] 〔Example 23〕Photosensitive resin composition (A-23) (d) component, 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, a photosensitive resin composition (A-23) was prepared in the same manner as in Example 1.

[0153] 〔Example 24〕Photosensitive resin composition (A-24) (d) component, 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, a photosensitive resin composition (A-24) was prepared in the same manner as in Example 1.

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

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

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

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

[0158] 〔Examples 29 to 33〕Photosensitive resin compositions (A-29) to (A-33) (a) As the siloxane resin, 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 were used respectively.

[0159] 〔Comparative Examples 1 to 4〕Photosensitive resin compositions (A-34) to (A-37) Except that the siloxane resin solutions (PS-11) to (PS-14) obtained in Synthesis Examples 11 to 14 were used instead of the siloxane resin solution (PS-1), photosensitive resin compositions (A-34) to (A-37) were prepared in the same manner as in Example 1.

[0160] [Comparative Example 5] Photosensitive resin composition (A-38) 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 addition amount of PGMEA was 1.49 g, a photosensitive resin composition (A-38) was prepared in the same manner as in Example 1.

[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 ZC-150 as the component (b) was not added, the addition amount of the siloxane resin solution (PS-1) was 5.44 g, and the addition amount of PGMEA 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 as the component (c) was not added, the addition amount of the siloxane resin solution (PS-1) was 5.51 g, and the addition amount of PGMEA was 3.04 g.

[0163] The compositions of Examples 1 to 33 and Comparative Examples 1 to 7 are summarized in Table 2, that is, Tables 2-1 to 2-6. Note that the description of BYK-352 is omitted. Also, the amount of the resin (% by weight) is shown on the basis of the resin solid content.

[0164]

Table 2-1

[0165]

Table 2-2

[0166]

Table 2-3

[0167]

Table 2-4

[0168]

Table 2-5

[0169]

Table 2-6

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

[0171] <Evaluation Method> "Crack Resistance" The photosensitive resin composition as the sample was spin-coated on a 10 cm square non-alkali 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 prepare pre-baked films with film thicknesses of 15 μm, 37 μm, 60 μm, and 115 μm, respectively. The obtained pre-baked films were exposed using a mask aligner (LA-610 manufactured by Sanyo Electric Co., Ltd.) with an ultra-high pressure mercury lamp (g, h, i lines) as the light source and an exposure amount of 200 mJ / cm 2 (i-line conversion value). Then, using an automatic developing device (AD-1200 manufactured by Takizawa Sangyo Co., Ltd.), it was developed by showering with a 2.38 wt% TMAH aqueous solution for 60 seconds, and then rinsed with water for 30 seconds. Finally, it was cured at 230 °C in air for 30 minutes using an oven (DHS-42 manufactured by ESPEC Corporation) to prepare cured films with film thicknesses of 10 μm, 30 μm, 50 μm, and 100 μm, respectively.

[0172] The glass substrate having the obtained cured film was visually observed, and the "crack resistance" of the cured film was evaluated according to the following criteria. If even one crack was confirmed, it was judged as "with crack" at that film thickness. Note that AA is the best. If it is B or higher, it can be said that the crack resistance is excellent. 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 are present at a film thickness of 100 μm. B: No cracks at film thicknesses of 10 μm and 30 μm. Cracks are present at film thicknesses of 50 μm and 100 μm. C: No cracks at a film thickness of 10 μm. Cracks are present at film thicknesses of 30 μm, 50 μm, and 100 μm. D: Cracks are present at all film thicknesses of 10 μm, 30 μm, 50 μm, and 100 μm.

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

[0174] "Transmittance" Using the photosensitive resin composition as the sample, a cured film with a thickness of 10 μm was formed on a Tempax glass substrate (manufactured by AGC Techno Glass Co., Ltd.) in the same manner as the evaluation of "crack resistance". Using a UV-visible near-infrared spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation), the UV-visible absorption spectrum of only the Tempax glass substrate was measured and used as a reference. Next, for the obtained Tempax glass substrate with the cured film, the light transmittance was measured in the wavelength range of 300 nm to 800 nm from the side of the surface on which the cured film was formed, and the "transmittance" was evaluated according to the following criteria based on the transmittance value at a wavelength of 400 nm. Note that A is the best. It was determined that B or above was qualified. A: Transmittance is 95% or more and 100% or less. B: Transmittance is 90% or more and less than 95%. C: Transmittance is less than 90%.

[0175] "Resolution" The photosensitive resin composition as the sample was spin-coated on a 10 cm square non-alkali 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 prepare pre-baked films with a thickness of 15 μm each. The obtained pre-baked films were exposed using a mask aligner (LA-610 manufactured by Sanyo Electric Co., Ltd.) with an ultra-high pressure mercury lamp (g, h, i lines) as the light source through a mask having line & space patterns with widths of 15, 25, 50 μm, and 100 μm at a mask gap of 100 μm and an exposure amount of 100 mJ / cm 2 (i-line conversion value). Then, using an automatic developing device (AD-1200 manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed for 60 seconds using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH), and then rinsed with water for 30 seconds.

[0176] Regarding the pattern after development, it was magnified and observed using a microscope adjusted to a magnification of 100 times. Among the patterns where no residue was observed in the unexposed area, the narrowest line width was taken as the resolution. However, if there is residue in the unexposed area near the 100-μm-wide pattern or if pattern peeling occurs, it is designated as ">100 μm", and if there is no residue in the 15-μm-wide pattern and pattern processing can be performed, it is evaluated as "≦15 μm". In addition, if the resolution is "25 μm" or less, it can be said that the resolution is excellent.

[0177] "Adhesion to the metal layer" A substrate (hereinafter referred to as "metal laminated substrate") was prepared by depositing molybdenum-nickel alloy / aluminum / molybdenum-nickel alloy (film thickness: 20 nm / 300 nm / 20 nm) in this order on a non-alkali glass substrate (glass thickness 0.5 mm). On this metal laminated substrate, a cured film with a thickness of 10 μm was formed using the photosensitive resin composition as the sample in the same manner as the evaluation of "crack resistance". Then, an adhesion test was performed on the cured film formed on the metal laminated substrate. For the adhesion test, 100 parallel lines, 11 each in the vertical and horizontal directions intersecting at right angles, were drawn at 1-mm intervals on the surface of the cured film so as to reach the substrate of the metal laminated substrate with a cutter knife, creating 100 1-mm×1-mm squares. After that, a cellophane adhesive tape (width = 18 mm, adhesive force = 3.7 N / 10 mm) was attached to the cut surface of the cured film, and rubbed with a rubber eraser (JIS S6050 qualified product) from above the attached cellophane adhesive tape to make it adhere. Next, one end of the cellophane adhesive tape was held, and the tape was peeled off instantaneously while keeping the peeling tape perpendicular to the plate. After peeling the tape, the cured film was observed, and the number of squares that remained without peeling among the 100 squares was counted visually. The "adhesion" to the metal layer was evaluated according to the following criteria based on the peeled area of the squares. In addition, it was judged as qualified if it was 4B or more. 5B: Peeled area = 0% 4B: Peeled area exceeds 0% and is less than 5%. 3B: Peeled area is 5% or more and less than 15%. 2B: Peeled area is 15% or more and less than 35%. 1B: Peeled area is 35% or more and less than 65%. 0B: Peeling area = 65% or more.

[0178] "Chemical resistance" Using the photosensitive resin composition as the sample, a metal laminated substrate having a cured film with a thickness of 10 μm was prepared in the same manner as the evaluation of "adhesion to the metal layer". This was immersed in N300 (trade name, manufactured by Nagase ChemteX Corporation), a resist stripping solution, at 50 °C for 5 minutes, then washed with ultrapure water for 1 minute and air-dried. For the metal laminated substrate having the cured film after such treatment, an adhesion test using cellophane adhesive tape was carried out in the same manner as the evaluation of "adhesion to the metal layer". The "chemical resistance" was evaluated according to the following criteria based on the peeling area of the mesh pattern. Note that 4B or more was judged as passing. 5B: Peeling area = 0% 4B: Peeling area exceeds 0% and is less than 5%. 3B: Peeling area = 5% or more and less than 15%. 2B: Peeling area = 15% or more and less than 35%. 1B: Peeling area = 35% or more and less than 65%. 0B: Peeling area = 65% or more.

[0179] "Moisture and heat resistance" Using the photosensitive resin composition as the sample, a cured film with a thickness of 10 μm was formed on a 10 cm square non-alkali glass substrate (glass thickness 0.5 mm) in the same manner as the evaluation of "crack resistance". This was placed in a thermo-hygrostat at a temperature of 85 °C and a humidity of 85% for 100 hours. Then, for the glass substrate with the cured film taken out from the thermo-hygrostat, an adhesion test using cellophane adhesive tape was carried out in the same manner as the evaluation of "adhesion to the metal layer". In addition to the evaluation of the peeling area of the mesh pattern, the "moisture and heat resistance" was evaluated according to the following criteria based on the observation results of the appearance by visual inspection. Note that AA is the most excellent. Note that if the moisture and heat resistance is B or more, it can be said that the moisture and heat resistance is excellent. AA: Peeling area is 0% and no abnormality is observed in the appearance. A: Peeling area exceeds 0% and is less than 5% and no abnormality is observed in the appearance. B: Peeling area is 5% or more and less than 15% and no abnormality is observed in the appearance. C: The peeling area is less than 5%, but there are abnormalities in the appearance and the film is cloudy. D: The peeling area is 5% or more and less than 15%, and there are abnormalities in the appearance and the film is cloudy. E: The peeling area is 15% or more.

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

[0181]

Table 3-1

[0182]

Table 3-2

[0183]

Table 3-3

Industrial Applicability

[0184] The effect film of the photosensitive resin composition of the present invention can be used in color filters, solid-state imaging devices, fingerprint authentication devices, etc.

Claims

1. A photosensitive resin composition containing a siloxane resin having a radically polymerizable group (hereinafter referred to as "(a) component"), a metal chelating agent (hereinafter referred to as "(b) component"), and a photo radical polymerization initiator. In the (a) component, (R) ２ SiO ２／２ The content of the organosilane unit represented by (R is an organic group) (such an organosilane unit is hereinafter referred to as "D unit") is 30 mol% or more and 85 mol% or less with respect to 100 mol% of all the organosilane units. The photosensitive resin composition.

2. The photosensitive resin composition according to claim 1, wherein as the component (b), any one or both of an aluminum chelate compound and a zirconium chelate compound are used.

3. The photosensitive resin composition according to claim 1, wherein the content of the 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.

4. The photosensitive resin composition according to claim 1, wherein the R contained in the D unit is 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, it does not simultaneously become a methyl group), and the component (a) containing such a D unit is used.

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

6. The photosensitive resin composition according to claim 1, wherein the component (a) contains any one or both of a carboxyl group and a dicarboxylic 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 the component (d), any one 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. 【Chemical 1】 (R １ represents a hydrogen atom or a methyl group, and 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 from 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. Also, m represents a positive integer.) 【Chemical 2】 (R ３ represents a hydrogen atom or a methyl group, and R ４ represents an alkylene group. Also, 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, wherein the film stress is 0.01 MPa or more and 10 MPa or less.

11. The cured film according to claim 9, wherein the film thickness is 10 μm or more and 200 μm or less.

12. The cured film according to claim 9, wherein the transmittance at a wavelength of 400 nm per 10 μm of film thickness is 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 a 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.

17. The fingerprint authentication device according to claim 15, wherein the fingerprint authentication device includes a 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.

Images