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

Abstract

The present invention provides a photosensitive resin composition containing a photocurable compound and a photoinitiator, wherein the photocurable compound contains an epoxy (meth)acrylic polymer and a photocurable compound having an adamantane ring. The photocurable compound having an adamantane ring can be a (meth)acrylic compound having an adamantane ring. The photocurable compound can further contain a (meth)acrylic compound having an isocyanurate ring. The photocurable compound can further contain a (meth)acrylic compound having a hydroxyl group.

Description

Technical Field

[0001] This invention relates to a photosensitive resin composition, a molded article and a method for manufacturing the same, and an electronic device. Background Technology

[0002] The insulating resin layer (insulating material) constituting the redistribution layer formed on a semiconductor wafer is sometimes formed by a photosensitive resin composition (e.g., Patent Document 1).

[0003] Previous technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2021-196482 Summary of the Invention

[0006] The technical problem to be solved by the invention

[0007] Cured products formed from photosensitive resin compositions require high elongation (Tg) to enable application in a wide range of products. To achieve high Tg, the formulation of multifunctional (meth)acrylic resins is being investigated. While increasing the crosslinking density through multifunctional (meth)acrylic resins can improve Tg, cured products formed from photosensitive resin compositions lack sufficient elongation, making them brittle and difficult to use as protective materials, dam materials, etc.

[0008] Therefore, the object of the present invention is to provide a photosensitive resin composition capable of forming a cured product having a high Tg (e.g., above 120°C) and excellent elongation.

[0009] means for solving technical problems

[0010] One aspect of the present invention includes, for example, the following [1] to

[14] .

[0011] [1] A photosensitive resin composition comprising a photocurable compound and a photoinitiator, wherein,

[0012] The photocurable compound comprises epoxy (meth)acrylate polymers and photocurable compounds having an adamantane ring.

[0013] [2] According to the photosensitive resin composition of [1], wherein the photocurable compound having an adamantane ring is a (meth)acrylic acid compound having an adamantane ring.

[0014] [3] The photosensitive resin composition according to [1] or [2], wherein the photocurable compound further comprises a (meth)acrylic compound having an isocyanurate ring.

[0015] [4] The photosensitive resin composition according to any one of [1] to [3], wherein the photocurable compound further comprises a (meth)acrylic acid compound having hydroxyl groups.

[0016] [5] The photosensitive resin composition according to any one of [1] to [4], wherein the photocurable compound further comprises a (meth)acrylic compound having a cycloalkane ring.

[0017] [6] The photosensitive resin composition according to any one of [1] to [5] further contains inorganic filler.

[0018] [7] The photosensitive resin composition according to [6], wherein the inorganic filler comprises a filler that has been surface-treated with silane.

[0019] [8] The photosensitive resin composition according to any one of [1] to [7] further comprises an adhesion promoter.

[0020] [9] The photosensitive resin composition according to any one of [1] to [8] further contains an ion trapping agent.

[0021]

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

[0022]

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

[10] is used to form a molded article.

[0023]

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

[10] .

[0024]

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

[10] .

[0025]

[14] A method for manufacturing a molded article, comprising:

[0026] The process of coating the photosensitive resin composition of any one of [1] to

[10] onto a substrate using a coating apparatus; and

[0027] A process of curing the photosensitive resin composition on the substrate by irradiating it with light.

[0028] Invention Effects

[0029] According to the present invention, a photosensitive resin composition capable of forming a cured product having a high Tg (e.g., above 120°C) and excellent elongation can be provided. Attached Figure Description

[0030] Figure 1 This is a schematic top view illustrating one embodiment of an electronic device. Detailed Implementation

[0031] The embodiments of the present invention will now be described in detail.

[0032] <Definition>

[0033] In this specification, the numerical range indicated by "~" represents the range encompassed by the values ​​before and after "~" 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 representations of (meth)acrylic acid resins, etc.

[0034] In this specification, when multiple substances equivalent to each component are present in the composition, unless otherwise specified, the amount of each component in the composition represents the total amount of the multiple substances present in the composition. In this specification, "solid component" refers to the non-volatile component in the photosensitive resin composition after removing volatile substances (water, solvent, etc.). That is, "solid component" refers to components other than the solvent that remain after drying the photosensitive resin composition, and also includes components that are liquid, syrupy, or paraffinic at room temperature (25°C).

[0035] <Photosensitive Resin Composition>

[0036] The photosensitive resin composition of this embodiment includes a photocurable compound and a photoinitiator. The photocurable compound in the photosensitive resin composition includes an epoxy (meth)acrylate polymer and a photocurable compound having an adamantane ring. The photosensitive resin composition containing the epoxy (meth)acrylate polymer and the photocurable compound having an adamantane ring can form a cured product with high Tg (e.g., above 120°C) and excellent elongation.

[0037] (Photocurable compounds)

[0038] The photosensitive resin composition of this embodiment contains a photocurable compound as a curing component, and also contains an epoxy (meth)acrylic acid polymer and a photocurable compound having an adamantane ring as photocurable compounds. There are no particular limitations on the photocurable compound, as long as it is a compound that cures by light irradiation; for example, it can be a free radical polymerizable compound.

[0039] Epoxy (meth)acrylate polymers are polymers having an epoxy (meth)acrylate structure (a structure in which epoxy groups are (meth)acrylated). Epoxy (meth)acrylate polymers have a structure represented by the following formula (1).

[0040]

[0041] In equation (1), R 1 This indicates a hydrogen atom or a methyl group.

[0042] Epoxy (meth)acrylate polymers can be polymers with multiple epoxy (meth)acrylate structures. The presence of multiple epoxy (meth)acrylate structures in epoxy (meth)acrylate polymers increases the crosslinking density, making it easier to form cured products with higher Tg and superior elongation.

[0043] From the perspective of easily forming cured products with higher Tg and better elongation, the weight average molecular weight of epoxy (meth)acrylic acid polymers can be above 1000, above 1500 or above 2000, or below 5000, below 4000 or below 3000.

[0044] In this specification, the weight-average molecular weight mentioned above represents the weight-average molecular weight of polystyrene measured using GPC (Gel Permeation Chromatography). An example of the measurement conditions for the GPC method is shown below.

[0045] Apparatus: HCl-8320GPC, UV-8320 (product name, manufactured by TOSOH CORPORATION) or HPLC-8020 (product name, manufactured by TOSOH CORPORATION)

[0046] Column: TSKgel superMultiporeHZ-M×2 or 2 pieces of GMHXL + 1 piece of G-2000XL

[0047] Detector: RI or UV detector

[0048] Column temperature: 25~40℃

[0049] Eluent: Choose a solvent that dissolves the high molecular weight components. Examples of suitable solvents include THF (tetrahydrofuran), DMF (N,N-dimethylformamide), DMA (N,N-dimethylacetamide), NMP (N-methylpyrrolidone), and toluene. Alternatively, when choosing a polar solvent, the concentration of phosphoric acid can be adjusted to 0.05–0.1 mol / L (typically 0.06 mol / L), and the concentration of LiBr can be adjusted to 0.5–1.0 mol / L (typically 0.63 mol / L).

[0050] Flow rate: 0.30–1.5 mL / min

[0051] Standard material: polystyrene

[0052] Examples of epoxy (meth)acrylate polymers include phenolic varnish-type epoxy (meth)acrylate resins, bisphenol A type (meth)acrylate resins, bisphenol F type (meth)acrylate resins, and cresol varnish-type (meth)acrylate resins. From the viewpoint of easily forming cured products with higher Tg and superior elongation, phenolic varnish-type epoxy (meth)acrylate polymers are preferred.

[0053] From the viewpoint of easily forming cured products with higher Tg and better elongation, the content of epoxy (meth)acrylic polymer in the photocurable compound can be more than 1%, more than 3%, or more than 5% by mass, or less than 30%, less than 20%, or less than 15% by mass, based on the total mass of the photocurable compound.

[0054] Photocurable compounds containing an adamantane ring are compounds that have an adamantane ring (adamantyl group) and are cured by light irradiation. Photocurable compounds containing an adamantane ring can be (meth)acrylate compounds, urethane compounds, or epoxy compounds. From the viewpoint of easily forming cured products with higher Tg and better elongation, photocurable compounds containing an adamantane ring can be (meth)acrylate compounds.

[0055] From the viewpoint that it is easy to form cured products with higher Tg and better elongation, the molecular weight of (meth)acrylic compounds with adamantane rings can be 100 or more, 150 or more, or 200 or more, or 500 or less, 400 or less, or 300 or less.

[0056] Examples of photocurable compounds containing an adamantane ring include 1-adamantane (meth)acrylate, 1-methyl-(meth)acrylate, and 1-ethyl-(meth)acrylate. From the viewpoint of easily forming cured products with higher Tg and superior elongation, 1-adamantane (meth)acrylate is a suitable photocurable compound.

[0057] From the viewpoint of easily forming cured products with higher Tg and better elongation, the content of photocurable compounds with adamantane rings can be more than 10% by mass, more than 20% by mass, or more than 25% by mass, or less than 60% by mass, less than 50% by mass, or less than 45% by mass, based on the total mass of the photocurable compounds.

[0058] From the viewpoint of easily forming cured products with higher Tg and better elongation, the ratio of the mass reference content of the photocurable compound with adamantane ring to the mass reference content of the epoxy (meth)acrylate polymer (mass reference content of the photocurable compound with adamantane ring / mass reference content of the epoxy (meth)acrylate polymer) can be 1 or more, 1.5 or more, or 2 or more, or 10 or less, 7 or less, or 5 or less.

[0059] The photosensitive resin composition may further include a (meth)acrylic compound having an isocyanurate ring as a photocurable compound. By further including a (meth)acrylic compound having an isocyanurate ring in the photocurable compound, there is a tendency to form cured products with higher Tg and better elongation.

[0060] From the viewpoint of easily forming cured products with higher Tg and better elongation, (meth)acrylic compounds with isocyanurate rings can be polyfunctional (meth)acrylic compounds with multiple (meth)acrylic groups. The number of (meth)acrylic groups in (meth)acrylic compounds with isocyanurate rings can be 2 or more, or 5 or less, 4 or less, or 3 or less.

[0061] From the viewpoint that it is easy to form cured products with higher Tg and better elongation, the molecular weight of (meth)acrylic compounds with isocyanurate rings can be 200 or more, 300 or more, or 350 or more, or 1000 or less, 800 or less, or 600 or less.

[0062] Examples of (meth)acrylic compounds containing an isocyanurate ring include tris-(2-(meth)acryloxyethyl)isocyanurate, tris-(2-(meth)acryloyloxyethyl)isocyanurate, and triallyl isocyanurate. From the viewpoint of easily forming cured products with higher Tg and superior elongation, tris-(2-(meth)acryloxyethyl)isocyanurate is a suitable (meth)acrylic compound with an isocyanurate ring.

[0063] From the viewpoint of easily forming cured products with higher Tg and better elongation, the content of (meth)acrylic compounds with isocyanurate rings can be more than 5% by mass, more than 10% by mass, or more than 13% by mass, or less than 40% by mass, less than 30% by mass, or less than 25% by mass, based on the total mass of the photocurable compound.

[0064] From the viewpoint of easily forming cured products with higher Tg and better elongation, the ratio of the mass reference content of (meth)acrylic compounds with isocyanurate rings to the mass reference content of epoxy (meth)acrylic polymers (mass reference content of (meth)acrylic compounds with isocyanurate rings / mass reference content of epoxy (meth)acrylic polymers) can be 0.5 or more, 1 or more, or 1.5 or more, or 10 or less, 5 or less, or 3 or less.

[0065] The photosensitive resin composition may further include a hydroxyl-containing (meth)acrylic acid compound as a photocurable compound. By further including a hydroxyl-containing (meth)acrylic acid compound in the photocurable compound, there is a tendency to form cured products with higher Tg and superior elongation.

[0066] From the viewpoint of easily forming cured products with higher Tg and better elongation, hydroxyl-containing (meth)acrylic acid compounds can be polyfunctional (meth)acrylic acid compounds with multiple (meth)acrylic acid groups. The number of (meth)acrylic acid groups in hydroxyl-containing (meth)acrylic acid compounds can be 2 or more, or 5 or less, 4 or less, or 3 or less.

[0067] From the viewpoint that it is easy to form cured products with higher Tg and better elongation, the molecular weight of hydroxyl-containing (meth)acrylic compounds can be 100 or more, 150 or more, or 200 or more, or 500 or less, 400 or less, or 300 or less.

[0068] Examples of hydroxyl-containing (meth)acrylate compounds include propyl 2-hydroxy-3-(meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and hydroxypentyl (meth)acrylate. From the viewpoint of easily forming cured products with higher Tg and superior elongation, propyl 2-hydroxy-3-(meth)acrylate is a suitable hydroxyl-containing (meth)acrylate compound.

[0069] From the viewpoint of easily forming cured products with higher Tg and better elongation, the content of hydroxyl-containing (meth)acrylic compounds can be more than 10%, more than 20%, or more than 25% by mass, or less than 50%, less than 40%, or less than 30% by mass, based on the total mass of the photocurable compound.

[0070] From the viewpoint of easily forming cured products with higher Tg and better elongation, the ratio of the mass reference content of hydroxyl-containing (meth)acrylic compounds to the mass reference content of epoxy (meth)acrylic polymers (mass reference content of hydroxyl-containing (meth)acrylic compounds / mass reference content of epoxy (meth)acrylic polymers) can be 1 or more, 2 or more, or 2.5 or more, or it can be 10 or less, 5 or less, or 3 or less.

[0071] The photosensitive resin composition may further include a (meth)acrylic compound having a cycloalkane ring as a photocurable compound. By further including a (meth)acrylic compound having a cycloalkane ring in the photocurable compound, there is a tendency to easily form cured products with higher Tg and superior elongation.

[0072] From the viewpoint of easily forming cured products with higher Tg and better elongation, (meth)acrylic acid compounds with cycloalkane rings can be polyfunctional (meth)acrylic acid compounds with multiple (meth)acrylic acid groups. The number of (meth)acrylic acid groups in (meth)acrylic acid compounds with cycloalkane rings can be 2 or more, or 5 or less, 4 or less, or 3 or less.

[0073] From the viewpoint that it is easy to form cured products with higher Tg and better elongation, the molecular weight of (meth)acrylic compounds with cycloalkane rings can be 100 or more, 200 or more, or 250 or more, or 600 or less, 500 or less, or 400 or less.

[0074] Examples of (meth)acrylic compounds containing cycloalkane rings include tricyclodecanediethanol diacrylate, cyclohexyl acrylate, and 1,4-cyclohexanediethanol monoacrylate. From the viewpoint of easily forming cured products with higher Tg and superior elongation, tricyclodecanediethanol diacrylate is a suitable (meth)acrylic compound containing a cycloalkane ring.

[0075] From the viewpoint of easily forming cured products with higher Tg and better elongation, the content of (meth)acrylic compounds with cycloalkane rings can be more than 10%, more than 15%, or more than 20% by mass, or less than 50%, less than 40%, or less than 30% by mass, based on the total mass of the photocurable compound.

[0076] From the viewpoint of easily forming cured products with higher Tg and better elongation, the ratio of the mass reference content of (meth)acrylic compounds with cycloalkane rings to the mass reference content of epoxy (meth)acrylic polymers (mass reference content of (meth)acrylic compounds with cycloalkane rings / mass reference content of epoxy (meth)acrylic polymers) can be 1 or more, 2 or more, or 2.5 or more, or it can be 10 or less, 5 or less, or 3 or less.

[0077] The photosensitive resin composition may further comprise a polyfunctional (meth)acrylic acid compound as a photocurable compound. By further comprising a polyfunctional (meth)acrylic acid compound as the photocurable compound, there is a tendency to easily form cured products with higher Tg and superior elongation. The polyfunctional (meth)acrylic acid compound may be a (meth)acrylic acid compound having the aforementioned isocyanurate ring, a (meth)acrylic acid compound having a hydroxyl group, a (meth)acrylic acid compound having a cycloalkane ring, or a (meth)acrylic acid compound other than these (meth)acrylic acid compounds (hereinafter also referred to as "other (meth)acrylic acid compounds").

[0078] In other (meth)acrylic acid compounds, the number of (meth)acrylic acid groups can be 2 or more, or 3 or less, or 5 or less, 4 or less, or 3 or less.

[0079] From the viewpoint that it is easy to form cured products with higher Tg and better elongation, the molecular weight of other (meth)acrylic acid compounds can be 100 or more, 200 or more, or 250 or more, or 600 or less, 500 or less, or 400 or less.

[0080] Other (meth)acrylic acid compounds include, for example, trimethylolpropane triacrylate, pentaerythritol hexaacrylate, 1,6-hexanediol diacrylate, and polyethylene glycol diacrylate. From the viewpoint of easily forming cured products with higher Tg and superior elongation, other (meth)acrylic acid compounds may include trimethylolpropane triacrylate and / or pentaerythritol hexaacrylate.

[0081] From the viewpoint of easily forming cured products with higher Tg and better elongation, the content of other (meth)acrylic compounds (total content when multiple other (meth)acrylic compounds are included) can be more than 10% by mass, more than 20% by mass, or more than 25% by mass, or less than 60% by mass, less than 50% by mass, or less than 40% by mass, based on the total mass of the photocurable compound.

[0082] From the viewpoint of easily forming cured products with higher Tg and better elongation, the content of (meth)acrylic compounds in photocurable compounds can be more than 50% by mass, more than 80% by mass, or more than 90% by mass, or substantially 100% by mass, based on the total mass of the photocurable compounds.

[0083] From the viewpoint of easily forming cured products with higher Tg and better elongation, the content of photocurable compound is based on the mass of all components in the photosensitive resin composition except solvent (total mass of solid components), and can be 1% or more by mass, 5% or more by mass, 10% or more by mass, 15% or more by mass, or 18% or more by mass, or less than 40% by mass, less than 30% by mass, less than 25% by mass, or less than 20% by mass.

[0084] (Photoinitiator)

[0085] The photosensitive resin composition of this embodiment contains a photoinitiator (also called a photocuring agent). The photoinitiator is a compound that generates free radicals through photodecomposition, and can be a compound comprising at least one of the groups selected from free radical polymerizing photoinitiators and cationic polymerizing photoinitiators. Examples of photoinitiators include compounds having structures such as oxime ester, diimidazole, acridine, α-aminoalkylphenyl ketone, aminobenzophenone, N-phenylglycine, acylphosphine oxide, benzyl dimethyl ketal, and α-hydroxyalkylphenyl ketone. One photoinitiator can be used alone, or two or more can be used in combination.

[0086] Examples of compounds with oxime ester structures 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-benzoyl oxime, 1,3-diphenyltrione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxytrione-2-(o-benzoyl)oxime, 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(o-benzoyl oxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(o-acetyl oxime), etc.

[0087] 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.

[0088] The content of the photoinitiator is based on the mass of all components in the photosensitive resin composition except the solvent (total mass of solid components), and can be more than 0.001% by mass, more than 0.005% by mass, or more than 0.01% by mass, or less than 1% by mass, less than 0.5% by mass, or less than 0.1% by mass.

[0089] The content of the photoinitiator relative to 100 parts by mass of the total photocurable compound can be more than 0.01 parts by mass, more than 0.05 parts by mass, or more than 0.1 parts by mass, or less than 10 parts by mass, less than 5 parts by mass, or less than 1 part by mass.

[0090] (Thermosetting resin)

[0091] The photosensitive resin composition of this embodiment may further contain a thermosetting resin. By further containing a thermosetting resin, the thermomechanical properties are improved, for example. From the viewpoint of achieving carbon neutralization without using a thermosetting oven, the photosensitive resin composition of this embodiment may not contain a thermosetting resin.

[0092] There are no particular restrictions on thermosetting resins as long as they are resin components that are cured by heat. Examples of thermosetting resins include epoxy resins, oxetine resins, melamine resins, polyester resins, silicone resins, urethane resins, benzoxazine resins, and phenolic resins. A single thermosetting resin can be used, or two or more can be used in combination.

[0093] Examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, phenolic varnish type epoxy resin, cresol phenolic varnish type epoxy resin, phenolic alkyl type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, and dicyclopentadiene type epoxy resin, among other multifunctional epoxy resins.

[0094] The content of thermosetting resin is based on the mass of all components in the photosensitive resin composition excluding the solvent (total mass of solid components), and can be 1% or more by mass, 10% or more by mass, or 20% or more by mass, or less than 30% by mass or less than 25% by mass. When the thermosetting resin includes epoxy resin, the content of epoxy resin is based on the mass of all components in the photosensitive resin composition excluding the solvent, and can be within the above-mentioned range.

[0095] The content of thermosetting resin relative to 100 parts by mass of the total amount of photocurable compound can be more than 100 parts by mass, more than 200 parts by mass, or more than 300 parts by mass, or less than 500 parts by mass or less than 400 parts by mass.

[0096] (Thermosetting agent)

[0097] The photosensitive resin composition of this embodiment may further contain a thermosetting agent. The thermosetting agent is a compound that reacts with a thermosetting resin by heating. Examples of thermosetting agents for epoxy resins include acid anhydride curing agents, amine curing agents, phenol curing agents, and polythiol curing agents. One thermosetting agent may be used alone, or two or more may be used in combination.

[0098] Examples of amine curing agents include imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole trimellitic acid, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-symmetric triazine and 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-symmetric triazine isocyanuric acid adducts, hexamethylenediamine, octamethylenediamine, decamethylenediamine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraspiro[5.5]undecane, bis(4-aminocyclohexyl)methane, m-phenylenediamine, and diaminodiphenyl sulfone.

[0099] Examples of polythiol curing agents include trimethylolpropane tri-3-mercaptopropionate, pentaerythritol tetra-3-mercaptopropionate, and dipentaerythritol hexa-3-mercaptopropionate.

[0100] The content of the thermosetting agent is based on the mass of all components in the photosensitive resin composition except the solvent (total mass of solid components), and can be more than 0.1% by mass, more than 0.3% by mass, or more than 0.5% by mass, or less than 10% by mass, less than 5% by mass, less than 3% by mass, or less than 2% by mass.

[0101] The aforementioned photocurable compounds and thermosetting resins (hereinafter, both are collectively referred to as curable compounds) can be in liquid, solid, or other forms. When the curable compound is solid, it can be dissolved by mixing with a liquid resin or solvent and used in liquid form.

[0102] (Inorganic packing)

[0103] The photosensitive resin composition of this embodiment may further contain inorganic fillers. Examples of inorganic fillers include silica, alumina (Al2O3), aluminum hydroxide, and titanium dioxide. The inorganic filler may contain at least one selected from the group consisting of silica, alumina, aluminum hydroxide, and titanium dioxide, or it may contain silica. One type of inorganic filler may be used alone, or two or more may be used in combination.

[0104] Silica can be crystalline or amorphous. From the perspective of easy control over particle size and shape, it can be amorphous silica.

[0105] From the viewpoint of the flowability of the photosensitive resin composition, the inorganic filler can be a surface-treated inorganic filler. Furthermore, when the inorganic filler contains silica, from the above viewpoint, the silica can be surface-treated silica. As a surface treatment, it can be a silane surface treatment (a surface treatment based on a silane coupling agent), and examples include surface treatments based on epoxy silanes, amino silanes, phenyl silanes, phenylamino silanes, acrylic silanes, vinyl silanes, siloxanes, etc.

[0106] The average particle size of inorganic fillers can be greater than 1.0 μm, greater than 1.3 μm, greater than 1.5 μm, greater than 3.0 μm, greater than 5.0 μm, greater than 8.0 μm, or greater than 10 μm, or less than 50 μm, less than 40 μm, less than 30 μm, less than 20 μm, or less than 15 μm. The average particle size of inorganic fillers can be measured using a particle size analyzer.

[0107] From the viewpoint of improving the flowability of the photosensitive resin composition and further enhancing the filling properties of the inorganic filler, the inorganic filler can comprise multiple inorganic fillers with different average particle sizes. By using multiple inorganic fillers with different average particle sizes in combination, the gaps between inorganic fillers with larger average particle sizes can be filled by inorganic fillers with smaller average particle sizes. The presence of multiple inorganic fillers with different average particle sizes in the 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 observing the peak values ​​of the particle sizes among multiple particle sizes.

[0108] From the viewpoint of achieving excellent flowability of the photosensitive resin composition and further improving the filling properties of the inorganic filler, the inorganic filler may include a first inorganic filler and a second inorganic filler. The average particle size of the first inorganic filler is 10 μm or more, and the average particle size of the second inorganic filler may be less than 10 μm. In selecting the average particle size of various inorganic fillers, for example, the average particle size that best achieves the densest filling of various inorganic fillers can be selected based on Furnas type, Suzuki type, etc.

[0109] The average particle size of the first inorganic filler can be above 11μm, above 12μm, above 13μm, or above 14μm, or below 50μm, below 40μm, below 30μm, below 20μm, or below 15μm.

[0110] The average particle size of the second inorganic filler can be above 1.0 μm, above 1.1 μm, above 1.3 μm, above 1.4 μm, or above 1.5 μm, or below 9.0 μm or below 8.0 μm.

[0111] The fact that the photosensitive resin composition contains a first inorganic filler having the above-mentioned average particle size and a second inorganic filler having the above-mentioned average particle size can be confirmed by measuring the particle size distribution of the inorganic filler contained in the photosensitive resin composition and observing that a peak is generated within the above-mentioned particle size range.

[0112] The first inorganic filler and the second inorganic filler can be the same component or different components. From the viewpoint of excellent flowability of the photosensitive resin composition, both the first inorganic filler and the second inorganic filler can be silica or surface-treated silica.

[0113] When the inorganic filler includes both a first inorganic filler and a second inorganic filler, from the viewpoint of excellent thermomechanical properties, the content of the first inorganic filler can 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 filler contained in the photosensitive resin composition. The content of the first inorganic filler, based on the total mass of the inorganic filler contained in the photosensitive resin composition, can be less than 100% by mass, or less than 95% by mass or less than 90% by mass.

[0114] The content of the second inorganic filler is based on the total mass of the inorganic filler contained in the photosensitive resin composition, and can be less than 50% by mass, less than 40% by mass, less than 30% by mass, or less than 20% by mass, or more than 0% by mass, or more than 5% by mass, or more than 10% by mass.

[0115] The content of inorganic fillers (or the total content when multiple inorganic fillers are used) can 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 solvents (total mass of solid components). The content of inorganic fillers can 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 solvents (total mass of solid components). From these viewpoints, the content of inorganic fillers, based on the total mass of the photosensitive resin composition excluding solvents (total mass of solid components), can be between 50% and 95% by mass.

[0116] From the viewpoint of improving sensitivity during exposure and achieving greater curing depth, the content of inorganic filler relative to 100 parts by mass of the total curable compound (the combined amount of photocurable compound and thermosetting resin) can 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. The content of inorganic filler relative to 100 parts by mass of the total curable compound (the combined amount of photocurable compound and thermosetting resin) can 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. From these viewpoints, the content of inorganic filler relative to 100 parts by mass of the total curable compound (the combined amount of photocurable compound and thermosetting resin) can be 100 to 2000 parts by mass.

[0117] When the inorganic filler comprises a first inorganic filler and a second inorganic filler, the content of the first inorganic filler, based on the total mass of the photosensitive resin composition excluding the solvent (total mass of the solid components), can be 40% or more by mass, 50% or more by mass, or 60% or more by mass. The content of the first inorganic filler, based on the total mass of the photosensitive resin composition excluding the solvent (total mass of the solid components), can be 90% or less by mass, 80% or less by mass, or 70% or less by mass.

[0118] When the inorganic filler comprises a first inorganic filler and a second inorganic filler, the content of the second inorganic filler, based on the total mass of the photosensitive resin composition excluding the solvent (total mass of the solid components), may be 40% by mass or less, 30% by mass or less, or 20% by mass or less. The content of the second inorganic filler, based on the total mass of the photosensitive resin composition excluding the solvent (total mass of the solid components), may exceed 0% by mass, exceed 5% by mass, or exceed 10% by mass.

[0119] When the inorganic filler includes both a first inorganic filler and a second inorganic filler, from the viewpoint of further increasing the curing depth, the ratio of the content of the first inorganic filler to the content of the second inorganic filler (content of the first inorganic filler / content of the second inorganic filler) can be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more. This ratio can be 15 or less, 10 or less, 9 or less, 8 or less, or 7 or less.

[0120] (Other ingredients)

[0121] The photosensitive resin composition of this embodiment may further contain other additives. Examples of other additives include coupling agents, dyes, photochromic agents, heat-resistant color-developing agents, plasticizers, pigments, defoamers, flame retardants, stabilizers, adhesion promoters, ion trapping agents, leveling agents, peel accelerators, antioxidants, fragrances, and imaging agents. The content of other additives, based on the total mass of the photosensitive resin composition excluding solvents (total mass of solid components), may be 0.01% by mass or more, 0.1% by mass or more, or 0.5% by mass or more, or 10% by mass or less, or 1% by mass or less. The content of other additives may be substantially 0% by mass.

[0122] From the viewpoint of excellent flowability, the viscosity of the photosensitive resin composition of this embodiment at 25°C can 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.

[0123] 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 can also be used as a dam material (dam material for the manufacture of electronic devices; dam material composition).

[0124] Dam material is the material that forms a dam (a solidified dam material) to prevent the outflow of the underfill material. This underfill material is used in the manufacture of electronic devices (semiconductor devices) for sealing the connection bumps between semiconductor components and the substrate, flip-chip (FC) mounting, through-silicon via (TSV) connections, and other sealing of multilayer semiconductor components. More specifically, such as... Figure 1 As shown, the electronic device 10 includes a substrate 1, a semiconductor element 2 disposed on the substrate 1, a connecting bump 3 that connects the substrate 1 and the semiconductor element 2, a bottom filler material 4 that fills the space between the substrate 1 and the semiconductor element 2, and a dam material (or a solidified dam material) 5 disposed on the substrate 1, wherein the dam material 5 suppresses the outflow of the bottom filler material 4.

[0125] In recent years, due to the requirement for high-density mounting, it is necessary to reduce the spacing between semiconductor packages. However, if the spacing between semiconductor packages is reduced, the underfill material overflows from the semiconductor packages, making it difficult to reduce the spacing between semiconductor packages. By forming dams, underfill material can be filled into the gaps between semiconductor elements and the substrate, and between semiconductor elements themselves, without causing the underfill material to overflow from the substrate. By using the above-mentioned photosensitive resin composition as the dam material, the outflow of underfill can be suppressed. The dam (or the cured form of the dam material) can, for example, be a dam (or the cured form of the dam material) having a width of 50 to 300 μm and a thickness of 100 to 300 μm.

[0126] The photosensitive resin composition can be suitably used for forming molded articles. The molded article can be formed, for example, by irradiating the photosensitive resin composition with light (wavelength 365–405 nm) and curing it. After curing by light irradiation (primary curing), it can be further cured by heating (e.g., 100–200°C, 1–8 hours). That is, another embodiment of the present invention is a cured product of the above-described photosensitive resin composition, i.e., a molded article. Furthermore, another embodiment of the present invention is a method for manufacturing a molded article comprising the following steps: a step of coating the above-described photosensitive resin composition onto a substrate using a coating apparatus; and a step of curing the photosensitive resin composition on the substrate by light irradiation.

[0127] The aforementioned photosensitive resin composition can be used in the manufacture of electronic devices. For example, when the aforementioned photosensitive resin composition is used as a dam material, by coating the aforementioned photosensitive resin composition onto a substrate and curing the photosensitive resin composition to form a dam on the substrate, the outflow of the underfill material is suppressed, and sealing of semiconductor devices with multilayer structures such as semiconductor element-to-substrate connection bumps, flip-chip (FC) mounting, and through-silicon via (TSV) connections can be performed, thereby enabling the manufacture of electronic devices. That is, another embodiment of the present invention is an electronic device comprising a cured product of the aforementioned photosensitive resin composition. Furthermore, another embodiment of the present invention is a method for manufacturing an electronic device comprising the following steps: a step of coating the aforementioned photosensitive resin composition onto a substrate using a coating apparatus; and a step of curing the photosensitive resin composition on the substrate by irradiation with light.

[0128] The molded article may have a portion with a minimum distance of 400 μm, 600 μm, or 700 μm to its surface (the outer surface capable of being irradiated by light). Even when forming a molded article with a portion (deep part) far from the surface, the photosensitive resin composition of this embodiment can be used to fully cure that portion (deep part).

[0129] Example

[0130] The present invention will now be specifically described through embodiments. However, the present invention is not limited to the embodiments described below.

[0131] <Adjustment of the photosensitive resin composition>

[0132] The following details the components used in the photosensitive resin compositions of the examples and comparative examples.

[0133] (Photocurable compounds)

[0134] • Cresol-phenolic varnish type epoxy acrylate resin (manufactured by Resonac Corporation, product name: SP-4060)

[0135] • Trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: ATMPT)

[0136] • 1-Adamantyl methacrylate (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD., product name: ADMA)

[0137] • Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: DPHA)

[0138] • Tri-(2-Acryloyloxyethyl)isocyanurate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: A9300)

[0139] • 2-Hydroxy-3-methacryloylpropyl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: 701A)

[0140] • Tricyclodecanediethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: A-DCP)

[0141] (Photoinitiator)

[0142] • Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (manufactured by BASF, product name: Irg-819)

[0143] (Inorganic packing)

[0144] • Silica filler surface-treated with silane coupling agent (manufactured by Admatechs Co., Ltd., product name: SC-5500-SQ, average particle size 1.5μm)

[0145] • Silica filler with epoxy silane surface treatment (manufactured by Admatechs Co., Ltd., product name: FEB25G-SED, average particle size 8μm)

[0146] • Silica filler with phenylaminosilane surface treatment (manufactured by Admatechs Co., Ltd., product name: FEB45G-SED, average particle size 14μm)

[0147] (Example 1)

[0148] In a light-shielded container, the photocurable compound and photoinitiator, in the amounts (parts by weight, solids content) shown in Table 1, were stirred for 1 hour at 50°C, and this mixture was prepared as Mixture 1. The amounts of inorganic filler shown in Table 1 were added to a 50 mL container (product name: AIBOY) and mixed for 5 minutes. Then, Mixture 1, restored to room temperature (25°C), was added to the container containing the inorganic filler. The mixture was stirred at 2000 rpm for 10 minutes using a rotary mixer (manufactured by THINKY CORPORATION, product name: AwatoriRentaro), followed by degassing at 2200 rpm for 5 minutes, thereby obtaining the photosensitive resin composition. The obtained photosensitive resin composition contains the amounts of inorganic filler shown in Table 1, with the residue containing the photocurable compound and photoinitiator.

[0149] (Examples 2-7, Comparative Examples 1-2)

[0150] The amounts of each component were changed to those shown in Table 1, and the photosensitive resin composition was otherwise obtained in the same manner as in Example 1.

[0151] [Measurement of Tg]

[0152] A 20×20mm silicone rubber sheet with an 8mm aperture and a thickness of 2mm was placed in an aluminum cup, and a photosensitive resin composition was supplied into the aperture. Then, heating was repeated for 5 minutes with a heating plate heated to 80°C, followed by 10 minutes of vacuuming until no bubbles were generated. After the bubbles disappeared, the photosensitive resin composition was irradiated for 30 seconds using a fiber optic LED spot UV irradiation device (manufactured by USHIOINC., product name: Spot Cure SPL-2, irradiation wavelength: 365nm) (light intensity 800mW / cm²). 2After heating, the cured photosensitive resin composition was ground with a 1000-grit file until the bottom and top surfaces were parallel, and used as a sample for thermal property measurement. The glass transition temperature (Tg) of the obtained thermal measurement sample was measured using a thermomechanical analysis apparatus (manufactured by Hitachi High-Tech Corporation, product name: TMA / SS-6000) under the following measurement conditions. The measurement results are shown in Table 1. Additionally, the cured photosensitive resin composition of Comparative Example 2 was very brittle, making it impossible to measure its glass transition temperature.

[0153] Sample dimensions: φ8mm × height 2mm

[0154] • Measurement mode: Compression mode

[0155] • Load: 1gF

[0156] ·1stRan: Measurement range: room temperature (25℃) to 220℃, heating rate: 20℃ / min

[0157] ·2ndRan: Measurement range 0~220℃, heating rate 5℃ / min

[0158] [Elongation and Modulus of Elasticity]

[0159] A Purex film (manufactured by TOYOBO FILM SOLUTION, Inc., product name A3100, 38μm thick) was prepared as the substrate film. A Teflon sheet (registered trademark) with a rectangular opening (50mm long, 10mm wide) was fixed onto the substrate film, allowing varnish to flow into the opening. A photosensitive resin composition was then applied to the substrate film using a scraper. Next, the photosensitive resin composition was irradiated for 30 seconds using a fiber optic LED spot UV irradiation device (manufactured by USHIO INC., product name: Spot Cure SPL-2, irradiation wavelength: 365nm) (light intensity 800mW / cm²). 2 An evaluation film was obtained. The substrate film and Teflon sheet were removed from the evaluation film to obtain a test piece. The stress-strain curve of the test piece was measured using an automatic stereographic analyzer (manufactured by Shimadzu Corporation, product name: EZ-LX), and the elongation and elastic modulus were determined from the stress-strain curve. The clamping distance was set to 20 mm, the stretching speed was set to 50 mm / min, and a total of 4 measurements were performed. The elongation at break of the test piece was measured. The average thickness and elongation of the evaluation film are shown in Table 1. Note that the evaluation film made from the photosensitive resin composition of Comparative Example 2 was very brittle and could not be used for the measurements.

[0160] [Table 1]

[0161]

[0162] Symbol Explanation

[0163] 1-Substrate, 2-Semiconductor element, 3-Connecting bump, 4-Bottom filler material, 5-Dam material (cured dam material), 10-Electronic device.

Claims

1. A photosensitive resin composition comprising a photocurable compound and a photoinitiator, wherein, The photocurable compounds include epoxy (meth)acrylate polymers and photocurable compounds having adamantane rings.

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

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

4. The photosensitive resin composition according to claim 1, wherein, The photocurable compound further comprises (meth)acrylic acid compounds having hydroxyl groups.

5. The photosensitive resin composition according to claim 1, wherein, The photocurable compound further comprises (meth)acrylic acid compounds having cycloalkane rings.

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 includes filler that has undergone silane surface treatment.

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

9. The photosensitive resin composition according to claim 1, further comprising an ion-scavenging agent.

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

11. The photosensitive resin composition according to any one of claims 1 to 10, used to form a molded article.

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 shaped article, comprising: The process of coating the photosensitive resin composition according to any one of claims 1 to 10 onto a substrate using a coating apparatus; and A process of curing the photosensitive resin composition on the substrate by irradiating it with light.

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