Photosensitive resin composition, molded body and method for producing same, and electronic device

Abstract

This photosensitive resin composition contains a photocurable compound and a photoinitiator. The photocurable compound includes: an epoxy (meth)acrylic polymer; and a photocurable compound having an adamantane ring. The photocurable compound having an adamantane ring may be a (meth)acrylic compound having an adamantane ring. The photocurable compound may further include a (meth)acrylic compound having an isocyanurate ring. The photocurable compound may further include a (meth)acrylic compound having a hydroxy group.

Description

Photosensitive resin composition, molded article and method for producing the same, and electronic device

[0001] The present invention relates to a photosensitive resin composition, a molded article and a method for producing the same, and an electronic device.

[0002] An insulating resin layer (insulating material) constituting a rewiring layer formed on a semiconductor chip may be formed from a photosensitive resin composition (for example, see Patent Document 1).

[0003] Japanese Patent Application Laid-Open No. 2021-196482

[0004] Since cured products formed from photosensitive resin compositions can be applied to various products, they are required to have a high Tg. In order to achieve a high Tg, the incorporation of polyfunctional (meth)acrylic resins has been considered. Although the polyfunctional (meth)acrylic resins improve the crosslink density and can increase the Tg, the cured products formed from the photosensitive resin compositions are brittle because they do not have sufficient elongation, making it difficult to use the cured products as protective materials, dam materials, etc.

[0005] Therefore, an object of the present invention is to provide a photosensitive resin composition capable of forming a cured product having a high Tg (for example, 120° C. or higher) and excellent elongation.

[0006] One aspect of the present invention includes, for example, the following [1] to

[14] . [1] A photosensitive resin composition containing a photocurable compound and a photoinitiator, wherein the photocurable compound includes an epoxy (meth)acrylic polymer and a photocurable compound having an adamantane ring. [2] The photosensitive resin composition according to [1], wherein the photocurable compound having an adamantane ring is a (meth)acrylic compound having an adamantane ring. [3] The photosensitive resin composition according to [1] or [2], wherein the photocurable compound further includes a (meth)acrylic compound having an isocyanurate ring. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the photocurable compound further includes a (meth)acrylic compound having a hydroxy group. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the photocurable compound further includes a (meth)acrylic compound having a cycloalkane ring. [6] The photosensitive resin composition according to any one of [1] to [5], further comprising an inorganic filler. [7] The photosensitive resin composition according to [6], wherein the inorganic filler comprises a filler surface-treated with silane. [8] The photosensitive resin composition according to any one of [1] to [7], further comprising an adhesion imparting agent. [9] The photosensitive resin composition according to any one of [1] to [8], further comprising an ion scavenger.

[10] The photosensitive resin composition according to any one of [1] to [9], which is a dam material.

[11] The photosensitive resin composition according to any one of [1] to

[10] , which is used for forming a molded body.

[12] A molded body, which is a cured product of the photosensitive resin composition according to any one of [1] to

[10] .

[13] An electronic device, comprising a cured product of the photosensitive resin composition according to any one of [1] to

[10] .

[14] A method for producing a molded product, comprising: a step of applying the photosensitive resin composition according to any one of [1] to

[10] to a substrate using a coating device; and a step of irradiating the photosensitive resin composition on the substrate with light to cure it.

[0007] According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a cured product having a high Tg (for example, 120° C. or higher) and excellent elongation.

[0008] FIG. 1 is a schematic plan view showing an electronic device according to an embodiment.

[0009] Hereinafter, embodiments of the present invention will be described in detail.

[0010] <Definitions> In this specification, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. "(Meth)acrylic acid" means at least one of "acrylic acid" and its corresponding "methacrylic acid." The same applies to other similar expressions such as (meth)acrylic resin.

[0011] In this specification, when a composition contains a plurality of substances corresponding to each component, the amount of each component refers to the total amount of the plurality of substances present in the composition, unless otherwise specified. In this specification, the term "solid content" refers to the non-volatile content of the photosensitive resin composition excluding volatile substances (water, solvent, etc.). In other words, the term "solid content" refers to components other than the solvent that remain without volatilizing during drying of the photosensitive resin composition, as described below, and includes those that are liquid, syrup-like, or waxy at room temperature (25°C).

[0012] <Photosensitive Resin Composition> The photosensitive resin composition according to this embodiment contains a photocurable compound and a photoinitiator, and the photocurable compound includes an epoxy (meth)acrylic polymer and a photocurable compound having an adamantane ring. The photosensitive resin composition including the epoxy (meth)acrylic polymer and the photocurable compound having an adamantane ring can form a cured product having a high Tg (for example, 120°C or higher) and excellent elongation.

[0013] (Photocurable Compound) The photosensitive resin composition according to the present embodiment contains a photocurable compound as a curing component, and the photocurable compound includes an epoxy (meth)acrylic polymer and a photocurable compound having an adamantane ring. The photocurable compound is not particularly limited as long as it is a compound that is cured by light irradiation, and may be, for example, a radical polymerizable compound.

[0014] The epoxy (meth)acrylic polymer is a polymer having an epoxy (meth)acrylate structure (a structure in which an epoxy group is (meth)acrylated). The epoxy (meth)acrylic polymer has a structure represented by the following formula (1): [In formula (1), R １ represents a hydrogen atom or a methyl group.

[0015] The epoxy (meth)acrylic polymer may have a plurality of epoxy (meth)acrylate structures, which improves the crosslinking density and makes it easier to form a cured product having a higher Tg and a better elongation.

[0016] The weight average molecular weight of the epoxy (meth)acrylic polymer may be 1,000 or more, 1,500 or more, or 2,000 or more, and may be 5,000 or less, 4,000 or less, or 3,000 or less, from the viewpoint of easily forming a cured product having a higher Tg and a better elongation.

[0017] In this specification, the weight average molecular weight refers to a weight average molecular weight measured using GPC (gel permeation chromatography) and converted into polystyrene. An example of measurement conditions for the GPC method is shown below. Apparatus: HCl-8320GPC, UV-8320 (product name, manufactured by Tosoh Corporation), or HPLC-8020 (product name, manufactured by Tosoh Corporation) Column: TSKgel superMultiporeHZ-M x 2, or 2 pieces of GMHXL + 1 piece of G-2000XL Detector: RI or UV detector Column temperature: 25 to 40°C Eluent: Select a solvent that dissolves the polymer component. Examples of solvents include THF (tetrahydrofuran), DMF (N,N-dimethylformamide), DMA (N,N-dimethylacetamide), NMP (N-methylpyrrolidone), and toluene. When a polar solvent is selected, the concentration of phosphoric acid may be adjusted to 0.05 to 0.1 mol / L (usually 0.06 mol / L), and the concentration of LiBr may be adjusted to 0.5 to 1.0 mol / L (usually 0.63 mol / L). Flow rate: 0.30 to 1.5 mL / min. Standard material: polystyrene.

[0018] Examples of epoxy(meth)acrylic polymers include phenol novolac epoxy(meth)acrylic resins, bisphenol A (meth)acrylic resins, bisphenol F (meth)acrylic resins, and cresol novolac (meth)acrylic resins. From the viewpoint of facilitating the formation of a cured product having a higher Tg and a higher elongation, the epoxy(meth)acrylic polymer may be a phenol novolac epoxy(meth)acrylic resin.

[0019] From the viewpoint of easily forming a cured product having a higher Tg and a better elongation, the content of the epoxy (meth)acrylic polymer in the photocurable compound may be 1 mass % or more, 3 mass % or more, or 5 mass % or more, and may be 30 mass % or less, 20 mass % or less, or 15 mass % or less, based on the total mass of the photocurable compound.

[0020] The photocurable compound having an adamantane ring is a compound that has an adamantane ring (adamantyl group) and is cured by light irradiation. The photocurable compound having an adamantane ring may be a (meth)acrylic compound having an adamantane ring, a urethane compound having an adamantane ring, or an epoxy compound having an adamantane ring. From the viewpoint of easily forming a cured product having a higher Tg and a better elongation, the photocurable compound having an adamantane ring may be a (meth)acrylic compound having an adamantane ring.

[0021] The molecular weight of the (meth)acrylic compound having an adamantane ring may be 100 or more, 150 or more, or 200 or more, and may be 500 or less, 400 or less, or 300 or less, from the viewpoint of easily forming a cured product having a higher Tg and a better elongation.

[0022] Examples of photocurable compounds having an adamantane ring include 1-adamantyl(meth)acrylate, 1-methyl-1-adamantyl(meth)acrylate, and 1-ethyl-1-adamantyl(meth)acrylate. From the viewpoint of facilitating the formation of a cured product having a higher Tg and a higher elongation, the photocurable compound having an adamantane ring may be 1-adamantyl(meth)acrylate.

[0023] From the viewpoint of easily forming a cured product having a higher Tg and a better elongation, the content of the photocurable compound having an adamantane ring may be 10% by mass or more, 20% by mass or more, or 25% by mass or more, or may be 60% by mass or less, 50% by mass or less, or 45% by mass or less, based on the total mass of the photocurable compound.

[0024] The ratio of the mass-based content of the photocurable compound having an adamantane ring to the mass-based content of the epoxy (meth)acrylic polymer (mass-based content of the photocurable compound having an adamantane ring / mass-based content of the epoxy (meth)acrylic polymer) may be 1 or more, 1.5 or more, or 2 or more, or may be 10 or less, 7 or less, or 5 or less, from the viewpoint of easily forming a cured product having a higher Tg and a better elongation.

[0025] The photosensitive resin composition may further contain a (meth)acrylic compound having an isocyanurate ring as a photocurable compound. When the photocurable compound further contains a (meth)acrylic compound having an isocyanurate ring, a cured product having a higher Tg and a better elongation tends to be formed.

[0026] The (meth)acrylic compound having an isocyanurate ring may be a polyfunctional (meth)acrylic compound having a plurality of (meth)acrylic groups, from the viewpoint of facilitating the formation of a cured product having a higher Tg and a better elongation. The number of (meth)acrylic groups in the (meth)acrylic compound having an isocyanurate ring may be 2 or more, or may be 5 or less, 4 or less, or 3 or less.

[0027] The molecular weight of the (meth)acrylic compound having an isocyanurate ring may be 200 or more, 300 or more, or 350 or more, and may be 1000 or less, 800 or less, or 600 or less, from the viewpoint of easily forming a cured product having a higher Tg and a better elongation.

[0028] Examples of the (meth)acrylic compound having an isocyanurate ring include tris-(2-(meth)acryloxyethyl)isocyanurate, tris-(2-(meth)acryloyloxyethyl)isocyanurate, and triallyl isocyanurate. From the viewpoint of facilitating the formation of a cured product having a higher Tg and a higher elongation, the (meth)acrylic compound having an isocyanurate ring may be tris-(2-(meth)acryloxyethyl)isocyanurate.

[0029] From the viewpoint of facilitating the formation of a cured product having a higher Tg and a better elongation, the content of the (meth)acrylic compound having an isocyanurate ring may be 5% by mass or more, 10% by mass or more, or 13% by mass or more, and may be 40% by mass or less, 30% by mass or less, or 25% by mass or less, based on the total mass of the photocurable compound.

[0030] The ratio of the mass-based content of the (meth)acrylic compound having an isocyanurate ring to the mass-based content of the epoxy (meth)acrylic polymer (mass-based content of the (meth)acrylic compound having an isocyanurate ring / mass-based content of the epoxy (meth)acrylic polymer) may be 0.5 or more, 1 or more, or 1.5 or more, or may be 10 or less, 5 or less, or 3 or less, from the viewpoint of facilitating the formation of a cured product having a higher Tg and a superior elongation.

[0031] The photosensitive resin composition may further contain a (meth)acrylic compound having a hydroxy group as a photocurable compound. When the photocurable compound further contains a (meth)acrylic compound having a hydroxy group, a cured product having a higher Tg and a better elongation tends to be formed.

[0032] The (meth)acrylic compound having a hydroxy group may be a polyfunctional (meth)acrylic compound having a plurality of (meth)acrylic groups, from the viewpoint of facilitating the formation of a cured product having a higher Tg and a better elongation. The number of (meth)acrylic groups in the (meth)acrylic compound having a hydroxy group may be 2 or more, or may be 5 or less, 4 or less, or 3 or less.

[0033] The molecular weight of the (meth)acrylic compound having a hydroxy group may be 100 or more, 150 or more, or 200 or more, and may be 500 or less, 400 or less, or 300 or less, from the viewpoint of easily forming a cured product having a higher Tg and a better elongation.

[0034] Examples of (meth)acrylic compounds having a hydroxy group include 2-hydroxy-3-(meth)acrylpropyl acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and hydroxypentyl (meth)acrylate. From the viewpoint of facilitating the formation of a cured product having a higher Tg and a superior elongation, the (meth)acrylic compound having a hydroxy group may be 2-hydroxy-3-(meth)acrylpropyl acrylate.

[0035] From the viewpoint of easily forming a cured product having a higher Tg and a better elongation, the content of the (meth)acrylic compound having a hydroxy group may be 10% by mass or more, 20% by mass or more, or 25% by mass or more, and may be 50% by mass or less, 40% by mass or less, or 30% by mass or less, based on the total mass of the photocurable compound.

[0036] The ratio of the mass-based content of the (meth)acrylic compound having a hydroxy group to the mass-based content of the epoxy (meth)acrylic polymer (mass-based content of the (meth)acrylic compound having a hydroxy group / mass-based content of the epoxy (meth)acrylic polymer) may be 1 or more, 2 or more, or 2.5 or more, or may be 10 or less, 5 or less, or 3 or less, from the viewpoint of facilitating the formation of a cured product having a higher Tg and a superior elongation.

[0037] The photosensitive resin composition may further contain a (meth)acrylic compound having a cycloalkane ring as a photocurable compound. When the photocurable compound further contains a (meth)acrylic compound having a cycloalkane ring, a cured product having a higher Tg and a better elongation tends to be formed.

[0038] The (meth)acrylic compound having a cycloalkane ring may be a polyfunctional (meth)acrylic compound having a plurality of (meth)acrylic groups, from the viewpoint of facilitating the formation of a cured product having a higher Tg and a better elongation. The number of (meth)acrylic groups in the (meth)acrylic compound having a cycloalkane ring may be 2 or more, or may be 5 or less, 4 or less, or 3 or less.

[0039] The molecular weight of the (meth)acrylic compound having a cycloalkane ring may be 100 or more, 200 or more, or 250 or more, and may be 600 or less, 500 or less, or 400 or less, from the viewpoint of easily forming a cured product having a higher Tg and a better elongation.

[0040] Examples of (meth)acrylic compounds having a cycloalkane ring include tricyclodecane dimethanol diacrylate, cyclohexyl acrylate, and 1,4-cyclohexane dimethanol monoacrylate. From the viewpoint of facilitating the formation of a cured product having a higher Tg and a higher elongation, the (meth)acrylic compound having a cycloalkane ring may be tricyclodecane dimethanol diacrylate.

[0041] From the viewpoint of easily forming a cured product having a higher Tg and a better elongation, the content of the (meth)acrylic compound having a cycloalkane ring may be 10% by mass or more, 15% by mass or more, or 20% by mass or more, or may be 50% by mass or less, 40% by mass or less, or 30% by mass or less, based on the total mass of the photocurable compound.

[0042] The ratio of the mass-based content of the (meth)acrylic compound having a cycloalkane ring to the mass-based content of the epoxy (meth)acrylic polymer (mass-based content of the (meth)acrylic compound having a cycloalkane ring / mass-based content of the epoxy (meth)acrylic polymer) may be 1 or more, 2 or more, or 2.5 or more, or may be 10 or less, 5 or less, or 3 or less, from the viewpoint of easily forming a cured product having a higher Tg and a better elongation.

[0043] The photosensitive resin composition may further contain a polyfunctional (meth)acrylic compound as a photocurable compound. When the photocurable compound further contains a polyfunctional (meth)acrylic compound, it tends to be easier to form a cured product having a higher Tg and better elongation. The polyfunctional (meth)acrylic compound may be the above-mentioned (meth)acrylic compound having an isocyanurate ring, (meth)acrylic compound having a hydroxy group, or (meth)acrylic compound having a cycloalkane ring, or may be a (meth)acrylic compound other than these (meth)acrylic compounds (hereinafter also referred to as "other (meth)acrylic compounds").

[0044] The number of (meth)acrylic groups in the other (meth)acrylic compounds may be 2 or more, or 3 or more, or may be 5 or less, 4 or less, or 3 or less.

[0045] The molecular weight of the other (meth)acrylic compound may be 100 or more, 200 or more, or 250 or more, and may be 600 or less, 500 or less, or 400 or less, from the viewpoint of easily forming a cured product having a higher Tg and a better elongation.

[0046] Examples of other (meth)acrylic compounds include trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, 1,6-hexanediol diacrylate, and polyethylene glycol diacrylate. From the viewpoint of facilitating the formation of a cured product having a higher Tg and a higher elongation, the other (meth)acrylic compound may be trimethylolpropane triacrylate and / or dipentaerythritol hexaacrylate.

[0047] The content of the other (meth)acrylic compounds (the total content when a plurality of other (meth)acrylic compounds are included) may be 10% by mass or more, 20% by mass or more, or 25% by mass or more, or may be 60% by mass or less, 50% by mass or less, or 40% by mass or less, based on the total mass of the photocurable compound, from the viewpoint of easily forming a cured product having a higher Tg and a better elongation.

[0048] The content of the (meth)acrylic compound in the photocurable compound may be 50% by mass or more, 80% by mass or more, or 90% by mass or more, or may be substantially 100% by mass, based on the total mass of the photocurable compound, from the viewpoint of easily forming a cured product having a higher Tg and a better elongation.

[0049] From the viewpoint of easily forming a cured product having a higher Tg and a better elongation, the content of the photocurable compound may be 1 mass % or more, 5 mass % or more, 10 mass % or more, 15 mass % or more, or 18 mass % or more, based on the mass of all components excluding the solvent in the photosensitive resin composition (total mass of the solid content), and may be 40 mass % or less, 30 mass % or less, 25 mass % or less, or 20 mass % or less.

[0050] (Photoinitiator) The photosensitive resin composition according to this embodiment contains a photoinitiator (also referred to as a photocuring agent). The photoinitiator is a compound that decomposes when exposed to light to generate free radicals or the like, and may include at least one selected from the group consisting of radical polymerization photoinitiators and cationic polymerization photoinitiators. Examples of the photoinitiator include compounds having an oxime ester structure, a bisimidazole structure, an acridine structure, an α-aminoalkylphenone structure, an aminobenzophenone structure, an N-phenylglycine structure, an acylphosphine oxide structure, a benzyl dimethyl ketal structure, an α-hydroxyalkylphenone structure, or the like. One type of photoinitiator may be used alone, or two or more types may be used in combination.

[0051] Examples of compounds having an oxime ester structure include 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-o-benzoyloxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(o-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime), and the like.

[0052] Examples of compounds having an acylphosphine oxide structure include bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

[0053] The content of the photoinitiator may be 0.001% by mass or more, 0.005% by mass or more, or 0.01% by mass or more, and may be 1% by mass or less, 0.5% by mass or less, or 0.1% by mass or less, based on the mass of all components excluding the solvent in the photosensitive resin composition (total mass of the solid content).

[0054] The content of the photoinitiator may be 0.01 parts by mass or more, 0.05 parts by mass or more, or 0.1 parts by mass or more, relative to 100 parts by mass of the total amount of the photocurable compound, and may be 10 parts by mass or less, 5 parts by mass or less, or 1 part by mass or less.

[0055] (Thermosetting Resin) The photosensitive resin composition according to this embodiment may further contain a thermosetting resin. When the photosensitive resin composition further contains a thermosetting resin, for example, the thermomechanical properties are improved. The photosensitive resin composition according to this embodiment does not need to contain a thermosetting resin, from the viewpoint of realizing carbon neutrality by not using a thermal curing oven.

[0056] The thermosetting resin is not particularly limited as long as it is a resin component that is cured by heat. Examples of the thermosetting resin include epoxy resin, oxetane resin, melamine resin, polyester resin, silicone resin, urethane resin, benzoxazine resin, and phenol resin. The thermosetting resin may be used alone or in combination of two or more.

[0057] Examples of epoxy resins include polyfunctional epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, naphthalene type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, phenol aralkyl type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, and dicyclopentadiene type epoxy resins.

[0058] The content of the thermosetting resin may be 1% by mass or more, 10% by mass or more, or 20% by mass or more, and may be 30% by mass or less, or 25% by mass or less, based on the mass of all components excluding the solvent in the photosensitive resin composition (total mass of solids). When the thermosetting resin includes an epoxy resin, the content of the epoxy resin may be in the above range based on the mass of all components excluding the solvent in the photosensitive resin composition.

[0059] The content of the thermosetting resin may be 100 parts by mass or more, 200 parts by mass or more, or 300 parts by mass or more, and may be 500 parts by mass or less, or 400 parts by mass or less, relative to 100 parts by mass of the total amount of the photocurable compound.

[0060] (Thermosetting Agent) The photosensitive resin composition according to this embodiment may further contain a thermosetting agent. The thermosetting agent is a compound that reacts with a thermosetting resin when heated. Examples of thermosetting agents for epoxy resins include acid anhydride curing agents, amine curing agents, phenolic curing agents, and polythiol curing agents. The thermosetting agents may be used alone or in combination of two or more.

[0061] Examples of the amine curing agent include imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine and 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, and amine compounds such as hexamethylenediamine, octamethylenediamine, decamethylenediamine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraspiro[5.5]undecane, bis(4-aminocyclohexyl)methane, metaphenylenediamine, and diaminodiphenyl sulfone.

[0062] Examples of polythiol curing agents include trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol hexa-3-mercaptopropionate.

[0063] The content of the heat curing agent may be 0.1 mass % or more, 0.3 mass % or more, or 0.5 mass % or more, and may be 10 mass % or less, 5 mass % or less, 3 mass % or less, or 2 mass % or less, based on the mass of all components excluding the solvent in the photosensitive resin composition (total mass of solids).

[0064] The above-mentioned photocurable compound and thermosetting resin (hereinafter, both are also collectively referred to as curable compounds) may be liquid, solid, etc. When the curable compound is solid, it can be used in liquid form by dissolving the solid curable compound by mixing it with a liquid resin or solvent.

[0065] (Inorganic Filler) The photosensitive resin composition according to this embodiment may further contain an inorganic filler. Examples of the inorganic filler include silica, alumina (Al ２ O ３ ), aluminum hydroxide, titanium oxide, etc. The inorganic filler may contain at least one selected from the group consisting of silica, alumina, aluminum hydroxide, and titanium oxide, and may contain silica. The inorganic filler may be used alone or in combination of two or more.

[0066] The silica may be crystalline silica or amorphous silica, and may be amorphous silica from the viewpoint of easy control of particle size and particle shape.

[0067] The inorganic filler may be a surface-treated inorganic filler from the viewpoint of the fluidity of the photosensitive resin composition. Furthermore, when the inorganic filler contains silica, the silica may be surface-treated from the viewpoint of the above. The surface treatment may be a silane surface treatment (surface treatment with a silane coupling agent), and examples thereof include surface treatments with epoxysilanes, aminosilanes, phenylsilanes, phenylaminosilanes, acrylicsilanes, vinylsilanes, siloxanes, etc.

[0068] The average particle size of the inorganic filler may be 1.0 μm or more, 1.3 μm or more, 1.5 μm or more, 3.0 μm or more, 5.0 μm or more, 8.0 μm or more, or 10 μm or more, and may be 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, or 15 μm or less. The average particle size of the inorganic filler can be measured using a particle size distribution analyzer.

[0069] The inorganic filler may contain multiple inorganic fillers with different average particle sizes, from the viewpoint of improving the fluidity of the photosensitive resin composition and further improving the filling ability of the inorganic filler. By using multiple inorganic fillers with different average particle sizes in combination, the inorganic filler with a smaller average particle size can fill the gaps between the inorganic fillers with a larger average particle size. The inclusion of multiple inorganic fillers with different average particle sizes in a photosensitive resin composition can be confirmed, for example, by measuring the particle size distribution of the inorganic fillers contained in the photosensitive resin composition and finding that particle size peaks occur at multiple particle sizes.

[0070] The inorganic filler may include a first inorganic filler and a second inorganic filler from the viewpoint of providing excellent fluidity to the photosensitive resin composition and further improving the filling property of the inorganic filler. The average particle diameter of the first inorganic filler may be 10 μm or more, and the average particle diameter of the second inorganic filler may be less than 10 μm. In selecting the average particle diameters of the multiple inorganic fillers, an average particle diameter can be selected based on, for example, the Furnas equation or the Suzuki equation so that the multiple inorganic fillers are closest packed.

[0071] The average particle size of the first inorganic filler may be 11 μm or more, 12 μm or more, 13 μm or more, or 14 μm or more, and may be 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, or 15 μm or less.

[0072] The average particle size of the second inorganic filler may be 1.0 μm or more, 1.1 μm or more, 1.3 μm or more, 1.4 μm or more, or 1.5 μm or more, and may be 9.0 μm or less, or 8.0 μm or less.

[0073] Whether the photosensitive resin composition contains the first inorganic filler having the above average particle size and the second inorganic filler having the above average particle size can be confirmed by measuring the particle size distribution of the inorganic fillers contained in the photosensitive resin composition and finding that a peak occurs within the above particle size range.

[0074] The first inorganic filler and the second inorganic filler may be the same component or different components. From the viewpoint of excellent fluidity of the photosensitive resin composition, the first inorganic filler and the second inorganic filler may both be silica or may both be surface-treated silica.

[0075] When the inorganic filler includes a first inorganic filler and a second inorganic filler, the content of the first inorganic filler may be 50% by mass or more, 60% by mass or more, 70% by mass or more, or 80% by mass or more, based on the total mass of the inorganic fillers contained in the photosensitive resin composition, from the viewpoint of excellent thermomechanical properties. The content of the first inorganic filler may be less than 100% by mass, 95% by mass or less, or 90% by mass or less, based on the total mass of the inorganic fillers contained in the photosensitive resin composition.

[0076] The content of the second inorganic filler may be 50% by mass or less, 40% by mass or less, 30% by mass or less, or 20% by mass or less, based on the total mass of the inorganic filler contained in the photosensitive resin composition, or may be more than 0% by mass, 5% by mass or more, or 10% by mass or more.

[0077] The content of the inorganic filler (when multiple inorganic fillers are used in combination, the total content thereof) may be 50% by mass or more, 60% by mass or more, 70% by mass or more, or 80% by mass or more based on the total mass of the photosensitive resin composition excluding the solvent (total mass of the solid content). The content of the inorganic filler may be 95% by mass or less, 90% by mass or less, or 85% by mass or less based on the total mass of the photosensitive resin composition excluding the solvent (total mass of the solid content). From these viewpoints, the content of the inorganic filler may be 50 to 95% by mass based on the total mass of the photosensitive resin composition excluding the solvent (total mass of the solid content).

[0078] The content of the inorganic filler may be 100 parts by mass or more, 300 parts by mass or more, 500 parts by mass or more, 700 parts by mass or more, 900 parts by mass or more, or 1000 parts by mass or more, relative to 100 parts by mass of the total amount of the curable compound (total amount of the photocurable compound and the thermosetting resin), from the viewpoint of increasing the sensitivity during exposure and increasing the cure depth. The content of the inorganic filler may be 2000 parts by mass or less, 1500 parts by mass or less, 1200 parts by mass or less, or 1000 parts by mass or less, relative to 100 parts by mass of the total amount of the curable compound (total amount of the photocurable compound and the thermosetting resin). From these viewpoints, the content of the inorganic filler may be 100 to 2000 parts by mass, relative to 100 parts by mass of the total amount of the curable compound (total amount of the photocurable compound and the thermosetting resin).

[0079] When the inorganic filler includes a first inorganic filler and a second inorganic filler, the content of the first inorganic filler may be 40% by mass or more, 50% by mass or more, or 60% by mass or more based on the total mass of the photosensitive resin composition excluding the solvent (total mass of the solid content). The content of the first inorganic filler may be 90% by mass or less, 80% by mass or less, or 70% by mass or less based on the total mass of the photosensitive resin composition excluding the solvent (total mass of the solid content).

[0080] When the inorganic filler includes a first inorganic filler and a second inorganic filler, the content of the second inorganic filler may be 40% by mass or less, 30% by mass or less, or 20% by mass or less, based on the total mass of the photosensitive resin composition excluding the solvent (total mass of the solid content). The content of the second inorganic filler may be more than 0% by mass, 5% by mass or more, or 10% by mass or more, based on the total mass of the photosensitive resin composition excluding the solvent (total mass of the solid content).

[0081] When the inorganic filler includes a first inorganic filler and a second inorganic filler, from the viewpoint of increasing the cure depth, the ratio of the content of the first inorganic filler to the content of the second inorganic filler (content of first inorganic filler / content of second inorganic filler) may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more. The ratio may be 15 or less, 10 or less, 9 or less, 8 or less, or 7 or less.

[0082] (Other Components) The photosensitive resin composition according to this embodiment may further contain other additives. Examples of other additives include coupling agents, dyes, photocoloring agents, thermal color-developing inhibitors, plasticizers, pigments, defoamers, flame retardants, stabilizers, adhesion promoters, ion scavengers, leveling agents, release promoters, antioxidants, fragrances, and imaging agents. The content of the other additives may be 0.01% by mass or more, 0.1% by mass or more, or 0.5% by mass or more, based on the total mass of the photosensitive resin composition excluding the solvent (total mass of the solids). The content of the other additives may be substantially 0% by mass.

[0083] From the viewpoint of excellent fluidity, the viscosity of the photosensitive resin composition according to this embodiment at 25°C may be 1000 Pa s or less, 500 Pa s or less, 300 Pa s or less, 150 Pa s or less, 100 Pa s or less, 50 Pa s or less, or 30 Pa s or less. The viscosity of the photosensitive resin composition can be measured by the method described in the examples.

[0084] The above-described photosensitive resin composition can be used in the manufacture of electronic devices. For example, the above-described photosensitive resin composition can be used as a dam material. That is, the above-described photosensitive resin composition may be a dam material (a dam material for manufacturing electronic devices; a dam material composition).

[0085] The dam material is a material that forms a dam (a cured product of the dam material) that suppresses the outflow of underfill material used in the manufacture of electronic devices (semiconductor devices) to seal connection bumps between a semiconductor element and a substrate in a semiconductor device, to seal semiconductor elements having a multilayer structure such as flip-chip (FC) mounting, through-silicon via (TSV) connection, etc. More specifically, as shown in Figure 1, an electronic device 10 includes a substrate 1, a semiconductor element 2 disposed on the substrate 1, connection bumps 3 that join the substrate 1 and the semiconductor element 2, an underfill material 4 that fills the gap between the substrate 1 and the semiconductor element 2, and a dam material (or a cured product of the dam material) 5 disposed on the substrate 1, and the dam material 5 suppresses the outflow of the underfill material 4.

[0086] In recent years, there has been a demand for higher-density packaging, making it necessary to narrow the spacing between semiconductor packages. However, narrowing the spacing between semiconductor packages has been difficult because the underfill material overflows from the semiconductor package. By forming a dam, the underfill material can be filled into gaps such as between a semiconductor element and a substrate, or between semiconductor elements, without overflowing from the substrate. By using the above-described photosensitive resin composition as a dam material, it is possible to suppress the overflow of the underfill. The dam (or the cured product of the dam material) may have, for example, a width of 50 to 300 μm and a thickness of 100 to 300 μm.

[0087] The photosensitive resin composition can be suitably used for forming a molded body. The molded body can be formed, for example, by irradiating the photosensitive resin composition with light (wavelength 365 to 405 nm) to cure it. After curing by light irradiation (primary curing), the composition may be further heated (for example, at 100 to 200°C for 1 to 8 hours) to perform secondary curing. That is, another embodiment of the present invention is a molded body that is a cured product of the above-described photosensitive resin composition. Another embodiment of the present invention is a method for producing a molded body, comprising the steps of applying the above-described photosensitive resin composition to a substrate using a coating device and curing the photosensitive resin composition on the substrate by irradiating it with light.

[0088] The above-described photosensitive resin composition can be used in the manufacture of electronic devices. For example, when the above-described photosensitive resin composition is a dam material, the above-described photosensitive resin composition is applied to a substrate, and the photosensitive resin composition is cured to form a dam on the substrate. This prevents the underfill material from flowing out, and enables sealing of connection bumps between a semiconductor element and the substrate, flip-chip (FC) mounting, encapsulation of semiconductor elements having a multilayer structure such as through-silicon via (TSV) connections, etc., to manufacture electronic devices. That is, another embodiment of the present invention is an electronic device including a cured product of the above-described photosensitive resin composition. Another embodiment of the present invention is a method for manufacturing an electronic device, comprising the steps of applying the above-described photosensitive resin composition to a substrate using an application device and irradiating the photosensitive resin composition on the substrate with light to cure it.

[0089] The molded article may have a portion whose shortest distance to its surface (the outer surface that can be irradiated with light) is 400 μm or more, 600 μm or more, or 700 μm or more. Even when forming a molded article having such a portion (deep portion) far from the surface, the portion (deep portion) can be sufficiently cured by using the photosensitive resin composition of this embodiment.

[0090] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

[0091] <Preparation of Photosensitive Resin Composition> Details of each component used in the photosensitive resin compositions of the Examples and Comparative Examples are shown below. (Photocurable Compounds) Cresol novolac epoxy acrylate resin (manufactured by Resonac Corporation, trade name: SP-4060) Trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: ATMPT) 1-Adamantyl methacrylate (manufactured by Osaka Organic Chemical Industry Ltd., trade name: ADMA) Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: DPHA) Tris-(2-acryloxyethyl) isocyanurate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A9300) 2-Hydroxy-3-methacrylpropyl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: 701A) Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-DCP) (Photoinitiators) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (manufactured by BASF, trade name: Irg-819) (inorganic filler) Silica filler surface-treated with a silane coupling agent (manufactured by Admatechs Co., Ltd., trade name: SC-5500-SQ, average particle size 1.5 μm) Silica filler surface-treated with epoxy silane (manufactured by Admatechs Co., Ltd., trade name: FEB25G-SED, average particle size 8 μm) Silica filler surface-treated with phenylaminosilane (manufactured by Admatechs Co., Ltd., trade name: FEB45G-SED, average particle size 14 μm)

[0092] Example 1 The photocurable compound and photoinitiator in the amounts (parts by mass, solid content) shown in Table 1 were stirred in a light-shielding container at 50°C for 1 hour to obtain Mixed Solution 1. The inorganic filler in the amount shown in Table 1 was placed in a 50 mL container (product name: Eye-Boy) and mixed for 5 minutes. Mixed Solution 1, which had been returned to room temperature (25°C), was then added to the container containing the inorganic filler and stirred at 2000 rpm for 10 minutes using a planetary centrifugal mixer (manufactured by Thinky Corporation, product name: Awatori Rentaro), followed by vibration degassing at 2200 rpm for 5 minutes to obtain a photosensitive resin composition. The resulting photosensitive resin composition contained the inorganic filler in the amount shown in Table 1, with the remainder consisting of the photocurable compound and photoinitiator.

[0093] Examples 2 to 7, Comparative Examples 1 and 2 Photosensitive resin compositions were obtained in the same manner as in Example 1, except that the amounts of each component were changed to those shown in Table 1.

[0094] [Measurement of Tg] A 20 x 20 mm, 2 mm thick silicone rubber sheet with a φ8 mm hole was placed on an aluminum cup, and the photosensitive resin composition was supplied to the hole in the silicone rubber sheet. Thereafter, heating for 5 minutes on a hot plate heated to 80°C and evacuation for 10 minutes were repeated until no more bubbles were generated. After no more bubbles were generated, the photosensitive resin composition was irradiated with light (light intensity 800 mW / cm) for 30 seconds using a fiber light source type LED spot UV irradiation device (manufactured by Ushio Inc., product name: Spot Cure SPL-2, irradiation wavelength: 365 nm). ２ ) was applied. After heating, the cured product of the photosensitive resin composition was polished with a #1000 file so that the bottom and top surfaces were parallel to each other, and a sample for measuring thermal properties was prepared. The glass transition temperature (Tg) of the obtained sample for thermal measurement was measured under the following measurement conditions using a thermomechanical analyzer (manufactured by Hitachi High-Tech Science Corporation, product name: TMA / SS-6000). The measurement results are shown in Table 1. Note that the cured product of the photosensitive resin composition of Comparative Example 2 was very brittle, and the glass transition temperature could not be measured. Sample size: φ8 mm x height 2 mm Measurement mode: compression mode Load: 1 gF 1st Ran: Measurement range: room temperature (25°C) to 220°C, heating rate: 20°C / min 2nd Ran: Measurement range: 0 to 220°C, heating rate: 5°C / min

[0095] [Elongation and Elastic Modulus] A Purex film (manufactured by Toyobo Film Solutions Co., Ltd., trade name A3100, thickness 38 μm) was prepared as a substrate film. A Teflon (registered trademark) sheet (with a rectangular opening of 50 mm in length and 10 mm in width) was fixed on the substrate film, varnish was poured into the opening, and a photosensitive resin composition was applied to the substrate film using a squeegee. Next, the photosensitive resin composition was irradiated with light (light intensity 800 mW / cm) for 30 seconds using a fiber light source type LED spot UV irradiation device (manufactured by Ushio Inc., trade name: Spot Cure SPL-2, irradiation wavelength: 365 nm). ２) to obtain a film for evaluation. A test specimen was obtained by removing the base film and Teflon sheet from the film for evaluation. The stress-strain curve of the test specimen was measured using an autograph (Shimadzu Corporation, product name: EZ-LX), and the elongation and modulus of elasticity were determined from the stress-strain curve. The chuck distance during measurement was set to 20 mm, the tensile speed was set to 50 mm / min, and measurements were performed a total of four times. The elongation at which the test specimen broke was measured as the elongation. The thickness and average elongation of the evaluation film are shown in Table 1. The evaluation film prepared using the photosensitive resin composition of Comparative Example 2 was very brittle, and each measurement could not be performed.

[0096]

[0097] REFERENCE SIGNS LIST 1...substrate, 2...semiconductor element, 3...connection bump, 4...underfill material, 5...dam material (cured product of dam material), 10...electronic device

Claims

1. A photosensitive resin composition comprising a photocurable compound and a photoinitiator, the photocurable compound comprising an epoxy (meth)acrylic polymer and a photocurable compound having an adamantane ring.

2. The photosensitive resin composition according to claim 1, wherein the photocurable compound having an adamantane ring is a (meth)acrylic compound having an adamantane ring.

3. The photosensitive resin composition according to claim 1, wherein the photocurable compound further comprises a (meth)acrylic compound having an isocyanurate ring.

4. The photosensitive resin composition according to claim 1, wherein the photocurable compound further comprises a (meth)acrylic compound having a hydroxy group.

5. The photosensitive resin composition according to claim 1, wherein the photocurable compound further comprises a (meth)acrylic compound having a cycloalkane ring.

6. The photosensitive resin composition according to claim 1, further comprising an inorganic filler.

7. The photosensitive resin composition according to claim 6, wherein the inorganic filler comprises a filler that has been surface-treated with silane.

8. The photosensitive resin composition according to claim 1, further comprising an adhesion imparting agent.

9. The photosensitive resin composition according to claim 1, further comprising an ion scavenger.

10. The photosensitive resin composition according to claim 1, which is a dam material.

11. The photosensitive resin composition according to any one of claims 1 to 10, which is used for forming a molded product.

12. A molded article which is a cured product of the photosensitive resin composition according to any one of claims 1 to 10.

13. An electronic device comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 10.

14. A method for manufacturing a molded product, comprising the steps of: applying the photosensitive resin composition according to any one of claims 1 to 10 onto a substrate using a coating device; and irradiating the photosensitive resin composition on the substrate with light to cure it.