Curable resin compositions, cured resin products, adhesive compositions, film-like adhesives, adhesive sheets, and polymers

Abstract

To provide a curable resin composition with excellent adhesion and conformability. [Solution] The curable resin composition according to this disclosure contains a polymer comprising a structural unit represented by the following formula (I) and a structural unit having an oxiranyl group. TIFF2026065982000013.tif33149 [In formula (I), R 1 R represents a hydrogen atom or a methyl group. 2 This represents an alkyl group having a chain-like structure in which four or more carbon atoms are continuously linked by single bonds from an adjacent nitrogen atom, and having a total of five or more carbon atoms.

Description

[Technical Field]

[0001] This disclosure relates to curable resin compositions, cured resin products, adhesive compositions, film-like adhesives, adhesive sheets, and polymers. [Background technology]

[0002] Adhesive films are used in the manufacture of semiconductor devices. Thermosetting resin compositions containing an acrylic resin and a curing accelerator are known for forming adhesive films (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2016-190964 [Overview of the project] [Problems that the invention aims to solve]

[0004] Thermosetting resin compositions used in adhesive films are required to have excellent adhesion and conformability. Conventional thermosetting resin compositions have room for improvement in terms of adhesion and conformability.

[0005] The primary objective of this disclosure is to provide a curable resin composition that exhibits excellent adhesion and conformability. [Means for solving the problem]

[0006] This disclosure includes the following [1] to [9]. [1] A curable resin composition containing a polymer comprising a structural unit represented by the following formula (I) and a structural unit having an oxiranyl group. [ka] [In formula (I), R 1represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having a chain structure in which 4 or more carbon atoms are continuously connected by single bonds from an adjacent nitrogen atom and having 5 or more carbon atoms in total.] [2] The curable resin composition according to [1], wherein the content of the structural unit represented by the formula (I) is 5% by mass or more based on the total amount of the polymer. [3] A resin cured product comprising a cured product of the curable resin composition according to [1] or [2]. [4] An adhesive composition comprising the curable resin composition according to [1] or [2]. [5] A film-like adhesive formed by forming the adhesive composition according to [4] into a film shape. [6] An adhesive sheet comprising a base material and the film-like adhesive according to [5] provided on the base material. [7] The adhesive sheet according to [6], wherein the base material is a dicing tape. [8] A polymer comprising a structural unit represented by the following formula (I) and a structural unit having an oxiranyl group.

Chemical formula

Advantages of the Invention

[0007] According to the present disclosure, it is possible to provide a curable resin composition, a resin cured product, an adhesive composition, a film-like adhesive, an adhesive sheet, and a polymer excellent in adhesiveness and followability.

Brief Description of the Drawings

[0008] <000009FIG. 1 is a schematic cross-sectional view showing a film-like adhesive according to an embodiment. [Figure 2] FIG. 2 is a schematic cross-sectional view showing an adhesive sheet according to an embodiment. [Figure 3] FIG. 3 is a schematic cross-sectional view showing an adhesive sheet according to another embodiment. [Figure 4] FIG. 4 is a schematic cross-sectional view showing a semiconductor device according to an embodiment.

MODE FOR CARRYING OUT THE INVENTION

[0009] Hereinafter, embodiments of the present disclosure will be described. However, the present disclosure is not limited to the following embodiments.

[0010] In this specification, a numerical range indicated by "~" indicates a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in this specification, the upper limit value or the lower limit value of a certain stepwise numerical range may be replaced with the upper limit value or the lower limit value of another stepwise numerical range. Also, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. Further, the individually described upper limit value and lower limit value can be arbitrarily combined. In the notation of the numerical range "A~B", the numerical values A and B at both ends are included in the numerical range as the lower limit value and the upper limit value, respectively. In this specification, for example, the description "10 or more" means "10" and "a numerical value exceeding 10", and the same applies when the numerical values are different. Also, for example, the description "10 or less" means "10" and "a numerical value less than 10", and the same applies when the numerical values are different.

[0011] In this specification, (meth)acrylate means acrylate or the corresponding methacrylate. The same applies to other similar expressions such as (meth)acryloyl.

[0012] The materials exemplified below may be used individually or in combination of two or more, unless otherwise specified. The amount or content of each component refers to the total amount of any multiple substances present in the composition, unless otherwise specified, if multiple substances corresponding to that component exist in the composition.

[0013] [polymer] The polymer according to this embodiment includes a structural unit represented by formula (I) (hereinafter also referred to as the "first structural unit") and a structural unit having an oxyranyl group (epoxy group) (hereinafter also referred to as the "second structural unit"). The polymer exhibits excellent adhesion and conformability due to the inclusion of the first and second structural units. In particular, because the polymer includes the first structural unit, it has a predetermined amide group in its side chain, which tends to result in excellent adhesion, and because viscosity can be controlled by utilizing the interaction of hydrogen bonds between the amide groups, it also tends to exhibit excellent conformability.

[0014] [ka]

[0015] In formula (I), R 1 R represents a hydrogen atom or a methyl group. 2 This represents an alkyl group having a chain-like structure in which four or more carbon atoms are continuously linked by single bonds from an adjacent nitrogen atom, and having a total number of carbon atoms of five or more.

[0016] Here, we will explain alkyl groups that have a chain-like structure in which four or more carbon atoms are continuously linked by single bonds from an adjacent nitrogen atom, and that have a total of five or more carbon atoms, using specific examples.

[0017] [ka]

[0018] The group represented by formula (2A) is a 1,1,3,3 - tetramethylbutyl (tert - octyl) group. * represents the bonding position to the adjacent nitrogen atom, and the group represented by formula (2A) has a chain structure (main chain) in which 4 carbon atoms are successively connected by single bonds from *. Since the group represented by formula (2A) has a predetermined chain structure and the total number of carbon atoms is 8, R 2 is included in the alkyl group represented by.

[0019] The group represented by formula (2B) is a 1,1 - dimethyl - 3 - oxobutyl group. * represents the bonding position to the adjacent nitrogen atom, and the group represented by formula (2B) has a chain structure (main chain) in which 4 carbon atoms are successively connected by single bonds from *. Since the group represented by formula (2B) has a predetermined chain structure and the total number of carbon atoms is 6, R 2 is included in the alkyl group represented by.

[0020] The group represented by formula (2C) is an n - dodecyl group. * represents the bonding position to the adjacent nitrogen atom, and the group represented by formula (2C) has a chain structure (main chain) in which 12 carbon atoms are successively connected by single bonds from *. Since the group represented by formula (2C) has a predetermined chain structure and the total number of carbon atoms is 12, R 2 is included in the alkyl group represented by.

[0021] The group represented by formula (2a) is a tert - butyl group. * represents the bonding position to the adjacent nitrogen atom, and the group represented by formula (2a) has a chain structure (main chain) in which 2 carbon atoms are successively connected by single bonds from *. Since the group represented by formula (2a) does not have a predetermined chain structure, R 2 is not included in the alkyl group represented by.

[0022] The group represented by formula (2b) is an n - butyl group. * represents the bonding position to the adjacent nitrogen atom, and the group represented by formula (2b) has a chain structure (main chain) in which 4 carbon atoms are successively connected by single bonds from *. Although the group represented by formula (2b) has a predetermined chain structure, since the total number of carbon atoms is 4, R2 It is not included in the alkyl group represented by .

[0023] R 2 The number of consecutive carbon atoms constituting the chain structure of the alkyl group represented by may be, for example, 20 or less, 15 or less, or 12 or less.

[0024] The chain structure is not particularly limited as long as four or more carbon atoms are continuously linked by single bonds from an adjacent nitrogen atom. The chain structure may be, for example, a chain structure in which four or more groups are linked together, at least one of which is selected from the group consisting of divalent groups represented by the following formulas (Ia), (Ib), (Ic), and (Id) (except for chain structures in which the divalent group represented by formula (Id) is bonded to an adjacent nitrogen atom). The chain structure may consist of one of the divalent groups represented by formulas (Ia), (Ib), (Ic), and (Id) alone, or it may consist of a combination of two or more.

[0025] [ka]

[0026] In equation (Ia), * indicates the joining position. In equation (Ib), R b1 R represents an alkyl group having 1 to 4 carbon atoms, and * represents the bond position. In formula (Ic), R c1 and R c2 Each of these independently represents an alkyl group with 1 to 4 carbon atoms, and * represents the bond position.

[0027] R b1 , R c1 , and R c2 The alkyl group represented may be, for example, a methyl group, an ethyl group, a propyl group, or a butyl group.

[0028] R 2 The total number of carbon atoms in the alkyl group represented by may be, for example, 6 or more, and may be 20 or less, 15 or less, or 12 or less.

[0029] R 2 Specific examples of alkyl groups represented by include n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, 1,1,3,3-tetramethylbutyl (tert-octyl) group, 2-ethylhexyl group, and 1,1-dimethyl-3-oxobutyl group.

[0030] Examples of monomers that give rise to the first structural unit represented by formula (II) include N-(1,1,3,3-tetramethylbutyl)(meth)acrylamide (N-tert-octyl(meth)acrylamide), N-(1,1-dimethyl-3-oxobutyl)(meth)acrylamide (diacetone(meth)acrylamide), and Nn-dodecyl(meth)acrylamide.

[0031] The content of the first structural unit in the polymer may be 5% by mass or more, 6% by mass or more, or 7% by mass or more, based on the total amount of the polymer, from the viewpoint of heat resistance and conformability, and may be 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, or 30% by mass or less, from the viewpoint of handling and adhesion. The content of the first structural unit in the polymer may be 5-50% by mass, 6-45% by mass, 7-40% by mass, 7-35% by mass, or 7-30% by mass, based on the total amount of the polymer.

[0032] Examples of monomers that provide a second structural unit include compounds having an ethylenically unsaturated group and an oxyranyl group (epoxy group). Examples of such compounds include glycidyl (meth)acrylate, α-ethylglycidyl (meth)acrylate, α-propylglycidyl (meth)acrylate, α-butylglycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-propylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxyheptyl (meth)acrylate, α-ethyl-6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, and p-vinylbenzylglycidyl ether.

[0033] The content of the second structural unit in the polymer may be 0.5% by mass or more, 1.0% by mass or more, 1.5% by mass or more, or 2.0% by mass or more, based on the total amount of polymer, from the viewpoint of handling the polymer, and may be 50% by mass or less, 30% by mass or less, 20% by mass or less, or 10% by mass or less, from the viewpoint of conformability. The content of the second structural unit in the polymer may be 0.5 to 50% by mass, 1.0 to 30% by mass, 1.5 to 20% by mass, or 2.0 to 10% by mass, based on the total amount of polymer.

[0034] The polymer may further contain other structural units other than the first and second structural units, to the extent that they do not impair the effects of the invention of this disclosure. Examples of monomers that give other structural units include (meth)acrylic acid, styrene, alkyl (meth)acrylate, (meth)acrylonitrile, and benzyl (meth)acrylate.

[0035] The number of carbon atoms in the alkyl group of an alkyl(meth)acrylate may be 1 to 20, 1 to 10, or 2 to 6. Specific examples of alkyl(meth)acrylates include methyl(meth)acrylate, ethyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, tert-butyl(meth)acrylate, n-hexyl(meth)acrylate, n-octyl(meth)acrylate, isooctyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isodecyl(meth)acrylate, and dodecyl(meth)acrylate.

[0036] The content of structural units derived from alkyl (meth)acrylate may be 30% by mass or more, 40% by mass or more, or 50% by mass or more, and may be 80% by mass or less, 75% by mass or less, or 70% by mass or less, based on the total amount of polymer.

[0037] The content of structural units derived from (meth)acrylonitrile may be 10% by mass or more, 15% by mass or more, 20% by mass or more, or 25% by mass or more, based on the total amount of polymer, and may be 50% by mass or less, 45% by mass or less, 40% by mass or less, or 35% by mass or less.

[0038] The content of structural units derived from benzyl (meth)acrylate may be 10% by mass or more, 20% by mass or more, 30% by mass or more, or 40% by mass or more, based on the total amount of polymer, and may be 60% by mass or less, 55% by mass or less, or 50% by mass or less.

[0039] The weight-average molecular weight (Mw) of the polymer may be 10,000 or more or 30,000 or more from the viewpoint of heat resistance and film-forming ability, and may be 1,000,000 or less, 500,000 or less, 250,000 or less, or 150,000 or less from the viewpoint of conformability. The weight-average molecular weight of the polymer may be 10,000 to 1,000,000, 10,000 to 500,000, 30,000 to 250,000, or 30,000 to 150,000. Particularly from the viewpoint of heat resistance, the Mw of the polymer may be 50,000 or more, 60,000 or more, 70,000 or more, or 80,000 or more. The Mw of the polymer can be measured using a calibration curve of standard polystyrene by gel permeation chromatography (GPC). Mw can be measured, for example, by the method described below.

[0040] Polymers can be obtained, for example, by polymerizing monomers by radical polymerization using solution polymerization. More specifically, they can be obtained by polymerizing monomers containing a monomer that gives a first structural unit and a monomer that gives a second structural unit in a solvent.

[0041] The solvent can be any organic solvent commonly used in the field of radical polymerization. Examples of solvents include aromatic hydrocarbons such as toluene, xylene, and benzene; aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; ketones such as methyl ethyl ketone and methyl isobutyl ketone; alcohols or glycols such as 1-methoxy-2-propanol, 2-butoxyethanol, ethylene glycol, propylene glycol, and dipropylene glycol; glycol ethers such as methyl cellosolve, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether; and glycol esters such as ethylene glycol diacetate and propylene glycol monomethyl ether acetate. The amount of solvent used can be appropriately set depending on the type of monomer, reaction conditions, solid content concentration, etc.

[0042] When polymerizing monomers, a thermal radical generator may be added as needed. Examples of thermal radical generators include azo compounds such as 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexanecarbonile), 2,2'-azobis(2,4-dimethylvaleronitrile), and dimethyl-2,2'-azobis(2-methylpropionate). The amount of thermal radical generator added can be appropriately set according to the type of monomer, reaction conditions, etc., and is not particularly limited, but may be 0.01% by mass or more, 0.05% by mass or more, 10% by mass or less, 5% by mass or less, or 1% by mass or less, relative to the total amount of monomers.

[0043] The polymerization temperature may be 60-100°C or 70-100°C. The polymerization time may be 1-15 hours or 5-10 hours.

[0044] [Curable resin composition] The curable resin composition according to this embodiment contains the above polymer. The curable resin composition containing the above polymer has excellent adhesion and conformability. The polymer content in the curable resin composition may be 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more, based on the total amount of the curable resin composition, and may be 90% by mass or less, 80% by mass or less, or 70% by mass or less.

[0045] The curable resin composition is thermosetting and can reach a fully cured (C-stage) state after curing treatment, following a semi-cured (B-stage) state. The curable resin composition may further contain various other components depending on the application. Examples of other components include epoxy resins (excluding the polymers mentioned above), curing agents, curing accelerators, elastomers (excluding the polymers mentioned above), inorganic fillers, and coupling agents. The curable resin composition may also be an adhesive composition.

[0046] Epoxy resins are components that harden by forming three-dimensional bonds between molecules upon heating or other means, and exhibit adhesive properties after hardening. Any epoxy resin that contains epoxy groups within its molecule can be used without particular limitations. An epoxy resin may contain two or more epoxy groups within its molecule.

[0047] Examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, stilbene type epoxy resin, triazine skeleton-containing epoxy resin, fluorene skeleton-containing epoxy resin, triphenolmethane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, polyfunctional phenols, and diglycidyl ether compounds of polycyclic aromatics such as anthracene. The epoxy resin may also be an alkyl-substituted, halide, or hydrogenated version of these. Among these, the epoxy resin may be a cresol novolac type epoxy resin or a bisphenol type epoxy resin.

[0048] The epoxy equivalent of the epoxy resin is not particularly limited, but may be 90-600 g / eq, 100-500 g / eq, or 120-450 g / eq from the viewpoint of reactivity and fluidity.

[0049] The epoxy resin content may be 2 to 25% by mass, based on the total amount of the curable resin composition. The epoxy resin content may be 4% or more by mass, 6% or more by mass, or 8% or more by mass, and may be 22% or less by mass, 20% or less by mass, or 18% or less by mass, based on the total amount of the curable resin composition.

[0050] The curing agent is not particularly limited as long as it is a component that can act as a curing agent for epoxy resin. Examples of curing agents include phenolic resins and activated ester resins.

[0051] Phenolic resins can be used without particular limitations as long as they have a phenolic hydroxyl group in their molecule. Examples of phenolic resins include novolac-type phenolic resins obtained by condensing or co-condensing phenols such as phenol, cresol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol, and / or naphthols such as α-naphthol, β-naphthol, and dihydroxynaphthalene with compounds having an aldehyde group such as formaldehyde under an acidic catalyst; phenolic aralkyl resins synthesized from phenols such as allylated bisphenol A, allylated bisphenol F, allylated naphthalenediol, phenol novolac, and / or naphthols with dimethoxyp-xylene or bis(methoxymethyl)biphenyl; naphthol aralkyl resins; biphenyl aralkyl-type phenolic resins; and phenyl aralkyl-type phenolic resins.

[0052] Active ester resins are components that have ester bonds active to epoxy groups within their molecules and act as epoxy resin curing agents. The ester bonds in active ester resins can react with the epoxy groups of epoxy resins to form three-dimensional bonds between molecules. Examples of active ester resins include ester compounds composed of aliphatic or aromatic carboxylic acid compounds and aliphatic hydroxy compounds, aromatic hydroxy compounds (phenol compounds), aromatic thiol compounds (thiophenol compounds), N-hydroxyamine compounds, or heterocyclic hydroxy compounds.

[0053] The curing agent content may be 2 to 20% by mass, based on the total amount of the curable resin composition. The curing agent content may be 3% or more by mass, 4% or more by mass, or 5% or more by mass, and may be 18% or less by mass, 15% or less by mass, or 12% or less by mass, based on the total amount of the curable resin composition.

[0054] Examples of curing accelerators include imidazole compounds, organophosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts. Among these, from the viewpoint of reactivity, the curing accelerator may be an imidazole compound. Examples of imidazole compounds include 2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-methylimidazole. The content of the curing accelerator may be 0.01 to 1.0% by mass based on the total amount of the curable resin composition.

[0055] As the elastomer, a thermoplastic resin, or a resin that is thermoplastic at least in its uncured state and forms a crosslinked structure after heating, can be used. Examples of elastomers include (meth)acrylic copolymers having reactive groups (such as epoxy groups), other than the polymers mentioned above. Examples of (meth)acrylic copolymers include acrylic glass and acrylic rubber. The (meth)acrylic copolymer may be acrylic rubber. The acrylic rubber may be mainly composed of alkyl (meth)acrylate and formed by copolymerization of monomers selected from (meth)acrylonitrile and glycidyl (meth)acrylate.

[0056] The elastomer content may be 0 to 60% by mass, based on the total amount of the curable resin composition. The curing agent content may be 5% or more by mass, 10% or more by mass, or 15% or more by mass, and may be 55% or less by mass, 50% or less by mass, or 45% or less by mass, based on the total amount of the curable resin composition.

[0057] The total content of polymers and elastomers in the curable resin composition may be 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more, based on the total amount of the curable resin composition, and may be 90% by mass or less, 80% by mass or less, or 70% by mass or less.

[0058] Examples of inorganic fillers include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whiskers, boron nitride, crystalline silica, and amorphous silica. Inorganic fillers may be surface-treated with a surface treatment agent from the viewpoint of compatibility between their surface and solvents and other components, as well as adhesive strength. Examples of surface treatment agents include silane-based coupling agents. Examples of functional groups in silane-based coupling agents include vinyl groups, (meth)acryloyl groups, epoxy groups, mercapto groups, amino groups, diamino groups, alkoxy groups, and ethoxy groups.

[0059] The inorganic filler content may be 1 to 50% by mass, based on the total amount of the curable resin composition. The inorganic filler content may be 3% or more by mass, 5% or more by mass, 30% or less by mass, or 20% or less by mass, based on the total amount of the curable resin composition.

[0060] Examples of coupling agents include silane-based coupling agents, titanate-based coupling agents, and aluminum-based coupling agents. Among these, the coupling agent may be a silane-based coupling agent. The content of the coupling agent may be 0.1 to 5.0% by mass, based on the total amount of the curable resin composition.

[0061] Examples of silane coupling agents include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and γ-aminopropylmethyldi Methoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ-(N,N-dimethyl)aminopropyltrimethoxysilane, γ-(N,N-diethyl)aminopropyltrimethoxysilane, γ-(N,N-dibutyl)aminopropyltrimethoxysilane, γ-(N-methyl)anilinopropyltrimethoxysilane, γ-(N-ethyl)anilinopropyltrimethoxysilane, γ-(N,N- Dimethyl)aminopropyltriethoxysilane, γ-(N,N-diethyl)aminopropyltriethoxysilane, γ-(N,N-dibutyl)aminopropyltriethoxysilane, γ-(N-methyl)anilinopropyltriethoxysilane, γ-(N-ethyl)anilinopropyltriethoxysilane, γ-(N,N-dimethyl)aminopropylmethyldimethoxysilane, γ-(N,N-diethyl)aminopropylmethyldimethoxysilane, γ-(N,N-dibutyl)aminopropylmethyldimethoxysilane, γ-(N-methyl) Examples include anilinopropylmethyldimethoxysilane, γ-(N-ethyl)anilinopropylmethyldimethoxysilane, N-(trimethoxysilylpropyl)ethylenediamine, N-(dimethoxymethylsilylisopropyl)ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-ureidopropyltriethoxysilane.

[0062] The curable resin composition may also be used as a varnish for a curable resin composition diluted with a solvent. Examples of solvents include aromatic hydrocarbons such as toluene, xylene, mesitylene, cumene, and p-cymene; aliphatic hydrocarbons such as hexane and heptane; cyclic alkanes such as methylcyclohexane; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and γ-butyrolactone; carbonate esters such as ethylene carbonate and propylene carbonate; and amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. Among these, the solvent may be toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone, from the viewpoint of solubility and boiling point.

[0063] Varnishes made from curable resin compositions can be prepared by mixing and kneading the above-mentioned polymer, other components, and solvent. The order of mixing and kneading of each component is not particularly limited and can be set as appropriate. Mixing and kneading can be carried out using a combination of conventional dispersants such as stirrers, swivels, three-roll mills, ball mills, and bead mills.

[0064] [Cured resin] In one embodiment, the cured resin product according to this embodiment may contain components derived from the polymer described above. In one embodiment, the cured resin product according to this embodiment may be a cured product of the curable resin composition described above. The cured resin product can be formed, for example, by applying a polymer solution or a varnish of the curable resin composition to a support film and heating and drying it.

[0065] Examples of supporting films include polytetrafluoroethylene, polyethylene, polypropylene, polymethylpentene, polyethylene terephthalate, and polyimide.

[0066] Known methods can be used for coating, including, for example, knife coating, roll coating, spray coating, gravure coating, bar coating, and curtain coating. The heating and drying conditions are not particularly limited as long as the solvent used is sufficiently evaporated, but for example, they may be 50 to 200°C for 1 to 90 minutes.

[0067] [Adhesive compositions, film-like adhesives, and adhesive sheets] The curable resin composition according to this embodiment contains the above-mentioned polymer and therefore exhibits excellent heat resistance and conformability. For this reason, the curable resin composition can be suitably used as an adhesive composition for the production of adhesive films for semiconductor devices. The adhesive composition according to this embodiment includes the above-mentioned curable resin composition. By molding the adhesive composition according to this embodiment into a film, a film-like adhesive can be formed.

[0068] Figure 1 is a schematic cross-sectional view showing a film-like adhesive according to one embodiment. The film-like adhesive 10 is formed by forming the above-mentioned adhesive composition into a film. The film-like adhesive 10 may be in a semi-cured (B-stage) state. Such a film-like adhesive 10 can be formed by applying the adhesive composition to a support film. When using a varnish of the adhesive composition, the film-like adhesive 10 can be formed by applying the varnish of the adhesive composition to a support film and removing the solvent by heating and drying.

[0069] Examples of support films include polytetrafluoroethylene, polyethylene, polypropylene, polymethylpentene, polyethylene terephthalate, and polyimide. The thickness of the support film may be, for example, 10 to 200 μm or 20 to 170 μm.

[0070] Known methods can be used to apply the varnish of the adhesive composition to the support film, such as the knife coating method, roll coating method, spray coating method, gravure coating method, bar coating method, and curtain coating method. The heating and drying conditions are not particularly limited as long as the conditions allow the solvent used to evaporate sufficiently, but for example, they may be 50 to 200°C for 0.1 to 90 minutes.

[0071] The thickness of the film adhesive can be adjusted as appropriate depending on the application. The thickness of the film adhesive may be 5-200 μm, 10-110 μm, or 15-80 μm, from the viewpoint of sufficiently embedding irregularities such as semiconductor elements (semiconductor chips), wires, and wiring circuits on substrates.

[0072] [Adhesive Sheet] Figure 2 is a schematic cross-sectional view showing an adhesive sheet according to one embodiment. The adhesive sheet 100 comprises a base material 20 and the above-mentioned film-like adhesive 10 provided on the base material.

[0073] The base material 20 is not particularly limited, but may be a base material film. Examples of base material films include those exemplified in the support film described above. The base material 20 may be a dicing tape. Such an adhesive sheet can be used as a dicing-die bonding integrated adhesive sheet. That is, a dicing-die bonding integrated adhesive sheet comprises a dicing tape and the above-mentioned film-like adhesive 10 provided on the dicing tape. Such a dicing-die bonding integrated adhesive sheet allows for a single lamination process to the semiconductor wafer, thus improving work efficiency.

[0074] Examples of dicing tapes include plastic films such as polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, and polyimide film. The dicing tape may also undergo surface treatments such as primer application, UV treatment, corona discharge treatment, polishing, and etching, as needed. The dicing tape may be adhesive. Such a dicing tape may be a plastic film with adhesive properties, or a plastic film with an adhesive layer on one side.

[0075] The adhesive sheet 100 can be formed by applying the adhesive composition or its varnish to a base film, similar to the method for forming the film-like adhesive described above. The method for applying the adhesive composition or its varnish to the base 20 may be the same as the method for applying the adhesive composition or its varnish to the support film described above.

[0076] The adhesive sheet 100 may be formed using a pre-made film-like adhesive. In this case, the adhesive sheet 100 can be formed by laminating the film-like adhesive 10 onto the substrate 20 under predetermined conditions using a roll laminator, vacuum laminator, etc. The adhesive sheet 100 may be formed using a roll laminator under heated conditions because it can be manufactured continuously and efficiently.

[0077] Figure 3 is a schematic cross-sectional view showing an adhesive sheet according to another embodiment. The adhesive sheet 110 further comprises a protective film 30 laminated on the side of the film-like adhesive 10 opposite to the substrate 20. The protective film 30 is exemplified in the support film described above. The thickness of the protective film 30 may be, for example, 10 to 200 μm or 20 to 170 μm.

[0078] [Semiconductor device] Figure 4 is a schematic cross-sectional view showing a semiconductor device according to one embodiment. The semiconductor device 200 comprises a substrate 90 and a semiconductor element mounting support member 14 having circuit patterns 84, 94 provided on the substrate 90, a first semiconductor element Wa provided on the semiconductor element mounting support member 14, and a second semiconductor element Waa bonded to the first semiconductor element Wa via a film-like adhesive 10. The semiconductor element mounting support member 14 and the first semiconductor element Wa are bonded via an adhesive 41. The circuit patterns 84 and the first semiconductor element Wa are electrically connected via a first wire 88. The first wire 88 and the first semiconductor element Wa, or at least a part of the first wire 88, are embedded (sealed) by the film-like adhesive 10. Here, the semiconductor device may be a semiconductor element (semiconductor chip) embedded type semiconductor device in which the first wire 88 and the first semiconductor element Wa are embedded, or a wire embedded type semiconductor device in which at least a part of the first wire 88 is embedded. Furthermore, in the semiconductor device 200, the semiconductor element mounting support member 14 and the second semiconductor element Waa are electrically connected via a second wire 98, and the second semiconductor element Waa is sealed by a sealing material 42.

[0079] The thickness of the first semiconductor element Wa may be 10 to 170 μm, and the thickness of the second semiconductor element Waa may be 20 to 400 μm. The first semiconductor element Wa embedded inside the film-like adhesive 10 may be a controller chip for driving the semiconductor device 200.

[0080] The semiconductor element mounting support member 14 consists of a substrate 90 on which two circuit patterns 84 and 94 are formed on its surface. The substrate 90 may be an organic substrate. The first semiconductor element Wa is bonded to the circuit pattern 94 via adhesive 41. The second semiconductor element Waa is bonded to the semiconductor element mounting support member 14 via film adhesive 10 such that it covers the circuit pattern 94 to which the first semiconductor element Wa is not bonded, the first semiconductor element Wa, and a portion of the circuit pattern 84. The film adhesive 10 is embedded in the unevenness caused by the circuit patterns 84 and 94 on the semiconductor element mounting support member 14. The second semiconductor element Waa, the circuit pattern 84, and the second wire 98 are then sealed with a resin sealant 42.

[0081] [Manufacturing method for semiconductor devices] A semiconductor device can be manufactured, for example, by a method comprising: a wire bonding step of arranging a first semiconductor element on a substrate and a support member having a circuit pattern provided on the substrate, and electrically connecting the circuit pattern and the first semiconductor element via a first wire; a laminating step of attaching the above-mentioned film-like adhesive to one side of a second semiconductor element; and a die bonding step of pressing the second semiconductor element, to which the film-like adhesive has been attached, via the film-like adhesive, thereby embedding the first wire and the first semiconductor element, or at least a portion of the first wire, into the film-like adhesive. [Examples]

[0082] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples.

[0083] [Synthesis of polymers] (Examples 1-1 to 1-10) As monomers, acrylonitrile (AN), ethyl acrylate (EA), n-butyl acrylate (BA), glycidyl methacrylate (GMA), and amide monomers were prepared. As amide monomers, A1 to A3 were prepared. Details of amide monomers A1 to A3 are as follows.

[0084] A1: N-(1,1,3,3-tetramethylbutyl)acrylamide (N-tert-octylacrylamide) (manufactured by Tokyo Chemical Industry Co., Ltd.) A2: N-(1,1-dimethyl-3-oxobutyl)acrylamide (diacetone acrylamide) (manufactured by Tokyo Chemical Industry Co., Ltd.) A3: Nn-dodecylacrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.) The structures of amide monomers A1 to A3 are as follows:

[0085] [ka]

[0086] 2,2'-azobis(isobutyronitrile) (AIBN) was prepared as a thermal radical generator. Toluene (TOL) and 1-methoxy-2-propanol (PGM) were prepared as solvents.

[0087] First, solution (a) was prepared by measuring out the materials (monomers) of group A and the materials (solvents) of group B shown in Table 1 in the proportions (unit: g) shown in Table 1 into a round-bottom flask. The amount of solvent from group B used was 70% by mass of the total amount of solvents from groups B, C, and D used. Next, solution (b) was prepared by measuring out the materials from group C shown in Table 1 in the proportions (unit: g) shown in Table 1 into a separate container and stirring until AIBN dissolved. The amount of solvent from group C used was 25% by mass of the total amount of solvents from groups B, C, and D used. After deoxygenating solutions (a) and (b) by passing nitrogen through them, solution (a) was heated to 75°C, and solution (b) was slowly added dropwise to solution (a) while stirring and mixed. Two hours after the dropwise addition was complete, the temperature was raised from 75°C to 85°C, and then three hours later, the temperature was raised from 85°C to 95°C. Next, the materials of group D shown in Table 1 were measured out into a separate container in the proportions (unit: g) shown in Table 1, and the mixture was stirred until AIBN dissolved to prepare solution (c). The amount of solvent used for group D was 5% by mass of the total amount of solvents used for groups B, C, and D. Solution (c) was deoxygenated by passing nitrogen through it, and then slowly added dropwise to a mixture heated to 95°C while stirring. After stirring the mixture at 95°C for 2 hours and 45 minutes, group E, which had been deoxygenated by passing nitrogen through it, was added all at once and mixed so that the ratio of the amount of solvent used for group A to the total amount of solvents used for groups B, C, D, and E was 48-50% by mass. After another 15 minutes, the mixture was cooled to room temperature to obtain the solutions of each polymer.

[0088] [Table 1]

[0089] (Reference example 1-1) Solution (a) was prepared by adding 45.6 g of a mixed solution of toluene and 1-methoxy-2-propanol (toluene / 1-methoxy-2-propanol = 3:2 (mass ratio)) to a monomer mixture of 33.4 g of acrylonitrile, 16.2 g of ethyl acrylate, 43.8 g of n-butyl acrylate, 3.4 g of glycidyl methacrylate, and 16.2 g of N-tert-butylacrylamide. Separately, solution (b) was prepared by adding 0.113 g of 2,2'-azobis(isobutyronitrile) to 15.2 g of a mixed solution of toluene and 1-methoxy-2-propanol (toluene / 1-methoxy-2-propanol = 3:2 (mass ratio)). Both solutions were deoxygenated by passing nitrogen through them. After that, solution (a) was heated to 75°C, and solution (b) was slowly added dropwise to solution (a) while stirring and mixed. Two hours after the dropwise addition was complete, the temperature was raised from 75°C to 85°C, and then two hours later, it was raised from 85°C to 95°C, where it was held for four hours. After that, it was cooled to room temperature to obtain a solution of polymer b1-1.

[0090] (Comparative Example 1-1) Solution (a) was prepared by adding 39.0 g of a mixed solution of toluene and 1-methoxy-2-propanol (toluene / 1-methoxy-2-propanol = 3:2 (mass ratio)) to a monomer mixture of 33.4 g of acrylonitrile, 32.4 g of ethyl acrylate, 43.8 g of n-butyl acrylate, and 3.4 g of glycidyl methacrylate. Separately, solution (b) was prepared by adding 0.113 g of 2,2'-azobis(isobutyronitrile) to 13.9 g of a mixed solution of toluene and 1-methoxy-2-propanol (toluene / 1-methoxy-2-propanol = 3:2 (mass ratio)). Both solutions were deoxygenated by passing nitrogen through them. After that, solution (a) was heated to 75°C, and solution (b) was slowly added dropwise to solution (a) while stirring and mixed. Two hours after the dropwise addition was complete, the temperature was raised from 75°C to 85°C, and then two hours later, it was raised from 85°C to 95°C, where it was held for four hours. After that, it was cooled to room temperature to obtain a solution of polymer b2-1.

[0091] <Measurement of weight-average molecular weight (Mw)> The Mw of each polymer was measured by gel permeation chromatography (GPC) and derived by conversion using a calibration curve for standard polystyrene. The measurement results are shown in Table 2. The GPC conditions are as follows. Measuring device: SHODEX® GPC-101 (manufactured by Resonac Corporation) Detector: Differential refractometer SHODEX RI-71S (manufactured by RAZONAC Corporation) Column: Showdex LF-804 + LF-804 (manufactured by Resonac Co., Ltd.) Column temperature: 40℃ Eluent: Tetrahydrofuran (THF) Flow rate: 1mL / min

[0092] [Polymer Evaluation] 1. Handling and responsiveness A polymer solution (solid content: 1 g) prepared in the Examples, Reference Examples, and Comparative Examples, along with a curing accelerator (product name: 2PZ-CN, manufactured by Shikoku Chemicals, Inc., 1-cyanoethyl-2-phenylimidazole) (solid content: 0.01 g), was added to a poly container. Then, an organic solvent (cyclohexanone) was added so that the NV value ([mass of paint after drying] / [mass of paint before drying] × 100) was 30% by mass. The mixture was then thoroughly stirred and degassed using a rotary-rotating stirrer to prepare a coating solution. After applying the coating solution onto a polyethylene terephthalate (PET) film using a precision coating apparatus, a resin film 1 with a thickness of 15 μm was prepared by heat treatment in a dryer at 100°C for 10 minutes.

[0093] Twelve layers of resin film 1 were stacked and laminated at 80°C and 0.4 MPa for 20 seconds to prepare an evaluation sample (thickness: approximately 180 μm). An 8 mm diameter sample stage was set up in a viscoelasticity analyzer (product name: ARES G2, manufactured by TA Instruments), and after setting the evaluation sample on the sample stage, the complex viscosity was measured while the temperature was increased from 30°C to 160°C at a heating rate of 5°C / min.

[0094] The handling and conformability of each sample were evaluated based on its complex viscosity at 30°C and 150°C. Specifically, regarding handling, the complex viscosity at 30°C was 3.0 × 10⁻⁶. 4 If the value exceeds Pa·s, it is considered to have excellent handling properties and is rated "A". 3.0×10 4 A rating of "B" was given if the value was below Pa·s. For conformability, the complex viscosity at 150°C was 2.0 × 10⁻⁶. 4 If the value is less than Pa·s, it is considered to have excellent follow-through and is rated "A". 2.0 × 10 4 Cases meeting the above criteria were rated as "B". The evaluation results are shown in Table 2.

[0095] Here, the complex viscosity at 30°C can represent the viscosity at or near room temperature. Therefore, a high complex viscosity at 30°C can suppress tack and seepage, resulting in excellent handling properties. The complex viscosity at 150°C can represent the viscosity of the resin when embedding and molding a resin layer on a circuit board or the like. Therefore, a low complex viscosity at 150°C allows the resin to conform to recesses and other features of the circuit board, resulting in excellent conformability.

[0096] 2.Heat resistance Polymer solutions prepared in the Examples, Reference Examples, and Comparative Examples were applied to PET films and dried at 140°C for 2 hours to produce resin film 2. Resin film 2 was heated from room temperature to 400°C at a rate of 10°C / min in a 100 mL / min airflow using a thermogravimetric analyzer (TGA) (device name: DTG-60H, manufactured by Shimadzu Corporation). The mass at 100°C (hereinafter also referred to as "W1") and the mass at 280°C (hereinafter also referred to as "W2") were measured. Using the mass at 100°C as a reference, the mass reduction rate at 280°C (hereinafter also referred to as "mass reduction rate") was calculated using the following formula (1). Heat resistance was evaluated as "A" if the mass reduction rate was less than 5.0%, and "B" if the mass reduction rate was 5.0% or more. The evaluation results are shown in Table 2. Mass reduction rate (%)=(W1-W2) / W1×100 (1)

[0097] [Table 2]

[0098] [Preparation of curable resin composition] (Examples 2-1 to 2-16 and Comparative Examples 2-1 and 2-2) Silica filler (product name: R-972, manufactured by Nippon Aerosil Co., Ltd.), coupling agent 1 (A-189, γ-mercaptopropyltrimethoxysilane, manufactured by Momentive Performance Material Japan), and coupling agent 2 (A-1160, γ-ureidopropyltrimethoxysilane, manufactured by Momentive Performance Material Japan) were measured into a poly container and thoroughly mixed. The polymer solutions prepared in the examples, reference examples, and comparative examples, epoxy resin (product name: N-500P-10, manufactured by DIC Corporation, cresol novolac type epoxy resin, epoxy equivalent: 204 g / eq), and curing agent (product name: MEH-7800M, manufactured by UBE Corporation, aralkyl type phenol resin) were added to obtain solution c. Meanwhile, cyclohexanone was measured so that the solid content concentration of the coating solution was 30% by mass, and a portion of it was added to solution c. The mixture was then stirred using a rotary stirrer until the solid content dissolved. In Examples 2-11 to 2-16, a solution of polymer b2-1 from Comparative Example 1-1 was used as the elastomer. The remaining cyclohexanone and a curing accelerator (product name: 2PZ-CN, manufactured by Shikoku Chemicals, Ltd., 1-cyanoethyl-2-phenylimidazole) were mixed to obtain solution d in which the curing accelerator was dissolved. Solution d was added to solution c, and the mixture was thoroughly stirred and degassed using a rotary-rotating stirrer to obtain a coating liquid containing the curable resin compositions of Examples 2-1 to 2-16 and Comparative Examples 2-1 and 2-2. The amounts (solid content) of each component in the coating liquid are shown in Table 3.

[0099] [Table 3]

[0100] [Evaluation of curable resin compositions] 1. Handling and responsiveness A resin film 3 with a thickness of 20 μm was produced by applying the coating solution prepared above onto a PET film using a precision coating apparatus, and then heating it in a dryer at 100°C for 10 minutes.

[0101] Aside from using resin film 3 instead of resin film 1, the procedure was the same as in "1. Handling and conformability" of [Polymer Evaluation], and the complex viscosity was measured.

[0102] The handling and conformability of each sample were evaluated based on its complex viscosity at 30°C and 150°C. Specifically, regarding handling, the complex viscosity at 30°C was 8.0 × 10⁻⁶. 4 If the value exceeds Pa·s, it is considered to have excellent handling properties and is rated "A". 8.0×10 4 If the value was Pa·s or less, it was evaluated as "B". For conformability, the complex viscosity at 150°C was 2.0 × 10⁻⁶. 4 If the value is less than Pa·s, it is considered to have excellent follow-through and is rated "A". 2.0 × 10 4 A score of Pa·s or higher was evaluated as "B". The evaluation results are shown in Table 4.

[0103] 2.Adhesiveness A resin film 3 with a thickness of 20 μm was prepared by performing the same procedure as in "1. Handling and conformability" of [Evaluation of curable resin composition]. A silicon wafer with a thickness of 700 μm was cut to a size of 2 cm x 5 cm, and two pieces of resin film 3, cut to 5 mm x 5 cm, were placed on each edge of the cut silicon wafer. Next, two pieces of copper foil with a thickness of 18 μm were placed so that the roughened surface was on the resin film 3, and a vacuum laminator (product name: V130, manufactured by Nikko Materials Co., Ltd.) was used to bond the silicon wafer and copper foil via the resin film by setting the upper and lower heating plates to 70°C each, vacuuming for 20 seconds, and then pressurizing at 0.4 MPa for 20 seconds. Next, the copper foil and resin film were cut to a width of 10 mm, and a 90° peel test was performed by pulling the copper foil. The 90° peel test was performed at room temperature using a benchtop peel tester (product name: EZ test (model number EZ-LX), manufactured by Shimadzu Corporation) under conditions of a peel angle of 90° and peel speed of 50 mm / min. The 90° peel test was performed with N=8, and the average value was taken as the 90° peel strength (N / cm). A peel strength greater than 1.5 N / cm was evaluated as "S" for excellent adhesion, a peel strength between 0.8 N / cm and 1.5 N / cm was evaluated as "A", and a peel strength of 0.8 N / cm or less was evaluated as "B". The evaluation results are shown in Table 4.

[0104] [Table 4]

[0105] As shown in Table 4, the polymers in the examples exhibited excellent adhesion and conformability, whereas the polymers in the comparative examples were insufficient in either adhesion or conformability. These results confirm that the curable resin composition of this disclosure exhibits excellent adhesion and conformability. [Explanation of Symbols]

[0106] 10...Film-type adhesive, 14...Support member for mounting semiconductor elements, 20...Substrate, 30...Protective film, 41...Adhesive, 42...Sealing material, 84, 94...Circuit pattern, 88...First wire, 90...Substrate, 98...Second wire, 100, 110...Adhesive sheet, 200...Semiconductor device, Wa...First semiconductor element, Waa...Second semiconductor element.

Claims

1. A curable resin composition containing a polymer comprising a structural unit represented by the following formula (I) and a structural unit having an oxiranyl group. 【Chemistry 1】 [In formula (I), R １ R represents a hydrogen atom or a methyl group. ２ This represents an alkyl group having a chain-like structure in which four or more carbon atoms are continuously linked by single bonds from an adjacent nitrogen atom, and having a total of five or more carbon atoms.

2. The curable resin composition according to claim 1, wherein the content of the structural unit represented by formula (I) is 5% by mass or more based on the total amount of the polymer.

3. A resin cured product comprising a cured product of the curable resin composition according to claim 1 or 2.

4. An adhesive composition comprising the curable resin composition according to claim 1 or 2.

5. A film-like adhesive comprising the adhesive composition described in claim 4 formed into a film.

6. An adhesive sheet comprising a base material and a film-like adhesive according to claim 5 provided on the base material.

7. The adhesive sheet according to claim 6, wherein the base material is a dicing tape.

8. A polymer comprising a structural unit represented by the following formula (I) and a structural unit having an oxiranyl group. 【Chemistry 2】 [In formula (I), R １ R represents a hydrogen atom or a methyl group. ２ This represents an alkyl group having a chain-like structure in which four or more carbon atoms are continuously linked by single bonds from an adjacent nitrogen atom, and having a total of five or more carbon atoms.

9. The polymer according to claim 8, wherein the content of the structural unit represented by formula (I) is 5% by mass or more based on the total amount of the polymer.

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