Polymer, curable resin composition, cured resin article, adhesive composition, adhesive film, and adhesive sheet

Abstract

Disclosed is a polymer comprising structural units represented by formula (I) or formula (II) and structural units having an oxiranyl group. (In formula (I): R1 represents a hydrogen atom or a methyl group; M represents an alkylene group or an alkylene oxide chain; A represents a group represented by formula (a) or formula (b); and R2 represents an alkyl group, an aryl group, an aralkyl group, or a hydrogen atom.) (In formula (a), * represents a bonding position.) (In formula (b), * represents a bonding position.) (In formula (II): R3 represents a hydrogen atom or a methyl group; and R4 represents an alkyl group, an aryl group, an aralkyl group, or a hydrogen atom.)

Description

Polymer, curable resin composition, cured resin product, adhesive composition, film-like adhesive, and adhesive sheet

[0001] The present disclosure relates to a polymer, a curable resin composition, a cured resin, an adhesive composition, a film-like adhesive, and an adhesive sheet.

[0002] Adhesive films are used in the manufacture of semiconductor devices. As a thermosetting resin composition for forming the adhesive film, a thermosetting resin composition containing an acrylic resin and a curing accelerator is known (see, for example, Patent Document 1).

[0003] JP 2016-190964 A

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

[0005] An object of the present disclosure is to provide a novel polymer, a curable resin composition, a cured resin, an adhesive composition, a film-like adhesive, and an adhesive sheet that are excellent in heat resistance and conformability.

[0006] The present disclosure includes the following items [1] to

[10] : [1] A polymer comprising a structural unit represented by the following formula (I) or formula (II) and a structural unit having an oxiranyl group: [In formula (I), R １ represents a hydrogen atom or a methyl group, M represents an alkylene group or an alkylene oxide chain, A represents a group represented by the following formula (a) or formula (b), and R ２ represents an alkyl group, an aryl group, an aralkyl group, or a hydrogen atom. [In formula (a), * represents a bonding position.] [In formula (b), * represents a bonding position.] [In formula (II), R ３ represents a hydrogen atom or a methyl group, R ４represents an alkyl group, an aryl group, an aralkyl group, or a hydrogen atom.] [2] The polymer according to [1], wherein A is a group represented by formula (a). [3] The polymer according to [1] or [2], wherein the content of the structural unit represented by formula (I) or formula (II) is 5 mass% or more based on the total amount of the polymer. [4] A curable resin composition containing the polymer according to any one of [1] to [3]. [5] A cured resin product containing a component derived from the polymer according to any one of [1] to [3]. [6] A cured resin product containing a cured product of the curable resin composition according to [4]. [7] An adhesive composition containing the curable resin composition according to [4]. [8] A film-like adhesive obtained by forming the adhesive composition according to [7] into a film. [9] An adhesive sheet comprising a substrate and the film-like adhesive according to [8] provided on the substrate.

[10] The adhesive sheet according to [9], wherein the substrate is a dicing tape.

[0007] According to the present disclosure, it is possible to provide novel polymers, curable resin compositions, cured resins, adhesive compositions, film-like adhesives, and adhesive sheets that are excellent in heat resistance and conformability.

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

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

[0010] In this specification, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In numerical ranges described in stages in this specification, the upper or lower limit of a certain numerical range may be replaced with the upper or lower limit of another numerical range. Furthermore, in a numerical range described in this specification, the upper or lower limit of that numerical range may be replaced with a value shown in the examples. Furthermore, individually described upper and lower limits can be arbitrarily combined. In a numerical range described as "A to B," the numerical values ​​A and B at both ends are included as the lower and upper limits, respectively, in the numerical range. In this specification, for example, the term "10 or more" means "10" and "a number greater than 10," and this also applies when the numerical values ​​are different. Furthermore, for example, the term "10 or less" means "10" and "a number less than 10," and this also applies when the numerical values ​​are different.

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

[0012] Unless otherwise specified, the materials exemplified below may be used alone or in combination of two or more. When a composition contains multiple substances corresponding to each component, the amount used or content of each component means the total amount of the multiple substances present in the composition, unless otherwise specified.

[0013] [Polymer] The polymer according to this embodiment includes a structural unit represented by formula (I) or formula (II) (hereinafter also referred to as a "first structural unit") and a structural unit having an oxiranyl group (epoxy group) (hereinafter also referred to as a "second structural unit"). By including the first structural unit and the second structural unit, the polymer has excellent heat resistance and conformability. In particular, by including the first structural unit, the polymer has an amide group in the side chain, which tends to result in excellent heat resistance. Furthermore, since the viscosity can be controlled by utilizing the interaction between hydrogen bonds between the amide groups, the polymer also tends to have excellent conformability.

[0014]

[0015] In formula (I), R １ represents a hydrogen atom or a methyl group, M represents an alkylene group or an alkylene oxide chain, A represents a group represented by formula (a) or formula (b), R ２ represents an alkyl group, an aryl group, an aralkyl group, or a hydrogen atom.

[0016] The number of carbon atoms in the alkylene group represented by M may be, for example, 1 to 6, 1 to 4, or 1 to 3. The alkylene group represented by M may be, for example, a methylene group, an ethylene group, a propylene group, or a butylene group. The alkylene group represented by M may be either linear or branched.

[0017] The number of repeating alkylene oxides in the alkylene oxide chain represented by M may be, for example, 1 to 10, 1 to 8, or 1 to 6. The number of carbon atoms in the alkylene oxide may be, for example, 2 to 10, 2 to 6, or 2 to 4. The alkylene oxide chain represented by M may be, for example, an ethylene oxide chain or a propylene oxide chain.

[0018]

[0019] In formula (a), * represents a bonding position. The carbon atom of the group represented by formula (a) is bonded to M in formula (I), and the nitrogen atom is bonded to R in formula (I). ２ Combine with.

[0020]

[0021] In formula (b), * represents a bonding position. The group represented by formula (b) has a nitrogen atom bonded to M in formula (I) and a carbon atom bonded to R in formula (I). ２ Combine with.

[0022] R ２ The number of carbon atoms in the alkyl group represented by R may be 1 to 20, 2 to 15, or 3 to 12. ２ The alkyl group represented by R may be, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, or a dodecyl group. ２The alkyl group represented by R may be linear, branched, or cyclic. ２ -CH contained in the alkyl group represented by ２ The - group may be substituted with a -C(O)- group.

[0023] R ２ The number of carbon atoms in the aryl group represented by R may be 6 to 20, 6 to 15, or 6 to 10. ２ The aryl group represented by may be, for example, a phenyl group or a naphthyl group.

[0024] R ２ The number of carbon atoms in the aralkyl group represented by R may be 7 to 22, 7 to 15, or 7 to 12. ２ The aralkyl group represented by the formula (I) may be, for example, a benzyl group.

[0025] An example of a monomer that provides the first structural unit represented by formula (I), in which A is a group represented by formula (a), is a monomer represented by the following formula (III) (hereinafter also referred to as "amide monomer a"). The amide monomer a has a (meth)acryloyloxy group and an amide group. Note that, １ , M, and R ２ are R in formula (I), respectively. １ , M, and R ２ It is synonymous with CH. ２ =CR １ -COO-M-CO-NHR ２ (III)

[0026] Examples of amide monomer a include a reaction product of a (meth)acrylate of a hydroxy-containing carboxylic acid with an alkylamine, arylamine, or aralkylamine. Examples of hydroxy-containing carboxylic acids include glycolic acid and 3-hydroxypropionic acid. The alkyl group of the alkylamine may have 1 to 20, 2 to 10, or 3 to 6 carbon atoms. Examples of alkyl group amines include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, and decylamine. The aryl group of the arylamine may have 6 to 20, 6 to 15, or 6 to 10 carbon atoms. Examples of arylamines include phenylamine and naphthylamine. The aralkyl group of the aralkylamine may have 7 to 22, 7 to 15, or 7 to 12 carbon atoms. Examples of aralkylamines include benzylamine.

[0027] An example of a monomer that provides the first structural unit represented by formula (I), in which A is a group represented by formula (b), is a monomer represented by the following formula (V) (hereinafter also referred to as "amide monomer b"). The amide monomer b has a (meth)acryloyloxy group and an amide group. Note that, in formula (V), R １ , M, and R ２ are R in formula (I), respectively. １ , M, and R ２ It is synonymous with CH. ２ =CR １ -COO-M-NH-COR ２ (V)

[0028] The amide monomer b may be one that has been appropriately produced, or a commercially available product may be used. The amide monomer b can be produced, for example, by a method including step 1 of reacting an arylcarboxylic acid chloride or an alkylcarboxylic acid chloride with a hydroxyalkylamine or a polyoxyalkyleneamine, and step 2 of reacting the reaction product obtained in step 1 with (meth)acryloyl chloride to obtain the amide monomer b. Examples of arylcarboxylic acid chlorides include benzoyl chloride. Examples of alkylcarboxylic acid compounds include butyryl chloride. Examples of hydroxyalkylamines include 2-aminoethanol.

[0029] Examples of the amide monomer b include a monomer represented by formula (b1) and a monomer represented by formula (b2).

[0030]

[0031]

[0032] In formula (II), R ３ represents a hydrogen atom or a methyl group, R ４ represents an alkyl group, an aryl group, an aralkyl group, or a hydrogen atom.

[0033] R ４ The alkyl group, aryl group, and aralkyl group represented by R ２ Examples of the alkyl group, aryl group, and aralkyl group are the same as those represented by the following formula:

[0034] Examples of the monomer that provides the first structural unit represented by formula (II) include (meth)acrylamide, N-alkyl(meth)acrylamide, N-aryl(meth)acrylamide, and N-aralkyl(meth)acrylamide.

[0035] Examples of N-alkyl(meth)acrylamides include N-isopropyl(meth)acrylamide, N-n-butyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, 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 N-n-dodecyl(meth)acrylamide.

[0036] Examples of N-aryl(meth)acrylamides include N-phenyl(meth)acrylamide and N-naphthyl(meth)acrylamide.

[0037] Examples of N-aralkyl(meth)acrylamides include N-benzyl(meth)acrylamide.

[0038] The polymer may contain either one of the structural units represented by formula (I) and the structural units represented by formula (II), or may contain both. From the viewpoint of heat resistance, the polymer may contain the structural unit represented by formula (II).

[0039] The content of the first structural unit in the polymer (the sum of the structural unit represented by formula (I) and the structural unit represented by formula (II)) 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 viewpoints 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 viewpoints of handleability and adhesiveness. The content of the first structural unit in the polymer may be 5 to 50% by mass, 6 to 45% by mass, 7 to 40% by mass, 7 to 35% by mass, or 7 to 30% by mass, based on the total amount of the polymer.

[0040] Examples of the monomer that provides the second structural unit include compounds having an ethylenically unsaturated group and an oxiranyl group (epoxy group). Examples of such compounds include glycidyl (meth)acrylate, α-ethyl glycidyl (meth)acrylate, α-propyl glycidyl (meth)acrylate, α-butyl glycidyl (meth)acrylate, 2-methyl glycidyl (meth)acrylate, 2-ethyl glycidyl (meth)acrylate, 2-propyl glycidyl (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-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether.

[0041] 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 the polymer, from the viewpoint of handleability of 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 followability. 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 the polymer.

[0042] The polymer may further contain structural units other than the first structural unit and the second structural unit, as long as the effects of the present invention are not impaired. Examples of monomers that provide the other structural units include (meth)acrylic acid, styrene, alkyl (meth)acrylate, (meth)acrylonitrile, and benzyl (meth)acrylate.

[0043] The number of carbon atoms in the alkyl group in the alkyl(meth)acrylate may be 1 to 20, 1 to 10, or 2 to 6. Specific examples of the alkyl(meth)acrylate 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.

[0044] 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 the polymer.

[0045] 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, and may be 50% by mass or less, 45% by mass or less, 40% by mass or less, or 35% by mass or less, based on the total amount of the polymer.

[0046] 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, and may be 60% by mass or less, 55% by mass or less, or 50% by mass or less, based on the total amount of the polymer.

[0047] 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. In particular, 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 by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene. The Mw can be measured, for example, by the method described in the examples.

[0048] The polymer can be obtained, for example, by polymerizing monomers by radical polymerization using a solution polymerization method, more specifically, by polymerizing, in a solvent, monomers including a monomer that provides the first structural unit and a monomer that provides the second structural unit.

[0049] The solvent can be appropriately selected from organic solvents commonly used in the field of radical polymerization. Examples of the solvent include known organic solvents such as 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 the solvent used can be appropriately determined depending on the type of monomer, reaction conditions, solids concentration, and the like.

[0050] When polymerizing the monomers, a thermal radical generator may be added as necessary. Examples of the thermal radical generator include azo compounds such as 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and dimethyl-2,2'-azobis(2-methylpropionate). The amount of the thermal radical generator added can be appropriately set depending on the type of monomer, reaction conditions, etc., and is not particularly limited, but may be 0.01% by mass or more or 0.05% by mass or more, and 10% by mass or less, 5% by mass or less, or 1% by mass or less, relative to the total amount of the monomers.

[0051] The polymerization temperature may be 60 to 100° C. or 70 to 100° C. The polymerization time may be 1 to 15 hours, or 5 to 10 hours.

[0052] [Curable Resin Composition] The curable resin composition according to this embodiment contains the polymer. The content of the polymer 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, and may be 90% by mass or less, 80% by mass or less, or 70% by mass or less, based on the total amount of the curable resin composition.

[0053] The curable resin composition is thermosetting and can reach a semi-cured (B-stage) state and then a fully cured (C-stage) state after a curing treatment. The curable resin composition may further contain various other components depending on the application. Examples of other components include epoxy resins (excluding the above-mentioned polymers), curing agents, curing accelerators, elastomers (excluding the above-mentioned polymers), inorganic fillers, and coupling agents. The curable resin composition may be an adhesive composition.

[0054] Epoxy resins are components that have the property of forming three-dimensional bonds between molecules and curing when heated or the like, and exhibit adhesive properties after curing. Any epoxy resin can be used without particular limitations as long as it has an epoxy group in its molecule. The epoxy resin may have two or more epoxy groups in its molecule.

[0055] Examples of epoxy resins include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol A novolac epoxy resins, bisphenol F novolac epoxy resins, stilbene epoxy resins, triazine skeleton-containing epoxy resins, fluorene skeleton-containing epoxy resins, triphenolmethane epoxy resins, biphenyl epoxy resins, xylylene epoxy resins, biphenyl aralkyl epoxy resins, naphthalene epoxy resins, dicyclopentadiene epoxy resins, polyfunctional phenols, and diglycidyl ether compounds of polycyclic aromatics such as anthracene. The epoxy resin may be an alkyl-substituted, halide, or hydrogenated product of these. Among these, the epoxy resin may be a cresol novolac epoxy resin or a bisphenol epoxy resin.

[0056] The epoxy equivalent of the epoxy resin is not particularly limited, but may be 90 to 600 g / eq, 100 to 500 g / eq, or 120 to 450 g / eq from the viewpoints of reactivity and fluidity.

[0057] The content of the epoxy resin may be 2 to 25% by mass based on the total amount of the curable resin composition. The content of the epoxy resin may be 4% by mass or more, 6% by mass or more, or 8% by mass or more, and may be 22% by mass or less, 20% by mass or less, or 18% by mass or less, based on the total amount of the curable resin composition.

[0058] The curing agent is not particularly limited as long as it is a component that can act as a curing agent for epoxy resins, and examples of the curing agent include phenol resins and active ester resins.

[0059] Any phenolic resin having a phenolic hydroxyl group in the molecule can be used without particular limitation. Examples of the phenolic resin include novolak-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 a compound having an aldehyde group such as formaldehyde under an acidic catalyst, and phenol aralkyl resins, naphthol aralkyl resins, biphenyl aralkyl-type phenolic resins, and phenyl aralkyl-type phenolic resins synthesized from phenols such as phenol and / or naphthols with dimethoxy-para-xylene or bis(methoxymethyl)biphenyl.

[0060] An active ester resin is a component that has an active ester bond to an epoxy group within the molecule and acts as an epoxy resin curing agent. The ester bond of the active ester resin can react with the epoxy group of the epoxy resin to form a three-dimensional bond between molecules. Examples of active ester resins include ester compounds composed of an aliphatic or aromatic carboxylic acid compound and an aliphatic hydroxy compound, an aromatic hydroxy compound (phenol compound), an aromatic thiol compound (thiophenol compound), an N-hydroxyamine compound, or a heterocyclic hydroxy compound.

[0061] The content of the curing agent may be 2 to 20% by mass based on the total amount of the curable resin composition. The content of the curing agent may be 3% by mass or more, 4% by mass or more, or 5% by mass or more, and may be 18% by mass or less, 15% by mass or less, or 12% by mass or less, based on the total amount of the curable resin composition.

[0062] Examples of the curing accelerator include imidazole compounds, organic phosphorus 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 the imidazole compound 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 mass% based on the total amount of the curable resin composition.

[0063] The elastomer may be a thermoplastic resin, or a resin that is thermoplastic at least in an uncured state and forms a crosslinked structure after heating. Examples of the elastomer include (meth)acrylic copolymers having reactive groups (epoxy groups, etc.) other than the above polymers. Examples of the (meth)acrylic copolymer include acrylic glass and acrylic rubber. The (meth)acrylic copolymer may be an acrylic rubber. The acrylic rubber may be formed by copolymerizing an alkyl (meth)acrylate as a main component with a monomer selected from (meth)acrylonitrile and glycidyl (meth)acrylate.

[0064] The content of the elastomer may be 0 to 60% by mass based on the total amount of the curable resin composition. The content of the curing agent may be 5% by mass or more, 10% by mass or more, or 15% by mass or more, and 55% by mass or less, 50% by mass or less, or 45% by mass or less, based on the total amount of the curable resin composition.

[0065] The total content of the polymer and the elastomer 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, and may be 90% by mass or less, 80% by mass or less, or 70% by mass or less, based on the total amount of the curable resin composition.

[0066] 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. The inorganic filler may be surface-treated with a surface treatment agent from the viewpoints of compatibility of the surface with solvents and other components, and adhesive strength. Examples of surface treatment agents include silane coupling agents. Examples of functional groups of silane coupling agents include vinyl groups, (meth)acryloyl groups, epoxy groups, mercapto groups, amino groups, diamino groups, alkoxy groups, and ethoxy groups.

[0067] The content of the inorganic filler may be 1 to 50% by mass based on the total amount of the curable resin composition. The content of the inorganic filler may be 3% by mass or more or 5% by mass or more, and 30% by mass or less or 20% by mass or less, based on the total amount of the curable resin composition.

[0068] Examples of the coupling agent include a silane-based coupling agent, a titanate-based coupling agent, and an aluminum-based coupling agent. 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 mass% based on the total amount of the curable resin composition.

[0069] 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, γ-aminopropylmethyldimethoxysilane, 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- 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 of the silane include anilinopropylmethyldimethoxysilane, γ-(N-ethyl)anilinopropylmethyldimethoxysilane, N-(trimethoxysilylpropyl)ethylenediamine, N-(dimethoxymethylsilylisopropyl)ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-ureidopropyltriethoxysilane.

[0070] The curable resin composition may be used as a varnish of the curable resin composition diluted with a solvent. Examples of the solvent 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; carbonates 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 viewpoints of solubility and boiling point.

[0071] The varnish of the curable resin composition can be prepared by mixing and kneading the above-mentioned polymer, other components, and a solvent. The order of mixing and kneading the components is not particularly limited and can be set appropriately. Mixing and kneading can be performed by appropriately combining a dispersing machine such as a conventional mixer, a mortar and pestle, a three-roll mill, a ball mill, or a bead mill.

[0072] [Cured Resin Product] In one embodiment, the cured resin product according to this embodiment may contain a component derived from the above-described polymer. In one embodiment, the cured resin product according to this embodiment may be a cured product of the above-described curable resin composition. The cured resin product can be formed, for example, by applying a solution of the polymer or a varnish of the curable resin composition to a support film and drying it by heating.

[0073] Examples of the support film include films of polytetrafluoroethylene, polyethylene, polypropylene, polymethylpentene, polyethylene terephthalate, polyimide, and the like.

[0074] As the coating method, a known method can be used, for example, knife coating, roll coating, spray coating, gravure coating, bar coating, and curtain coating. The conditions for heat drying are not particularly limited as long as the solvent used is sufficiently volatilized, and may be, for example, 50 to 200°C for 1 to 90 minutes.

[0075] [Adhesive composition, film-like adhesive, and adhesive sheet] The curable resin composition according to this embodiment contains the above-described polymer, and therefore has excellent heat resistance and conformability. Therefore, the curable resin composition can be suitably used as an adhesive composition used in producing an adhesive film for a semiconductor device. The adhesive composition according to this embodiment contains the above-described curable resin composition. A film-like adhesive can be formed by molding the adhesive composition according to this embodiment into a film.

[0076] FIG. 1 is a schematic cross-sectional view showing a film-like adhesive according to one embodiment. The film-like adhesive 10 is obtained by forming the above-described 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 a varnish of the adhesive composition is used, 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.

[0077] Examples of the support film include films of polytetrafluoroethylene, polyethylene, polypropylene, polymethylpentene, polyethylene terephthalate, polyimide, etc. The thickness of the support film may be, for example, 10 to 200 μm or 20 to 170 μm.

[0078] The method for applying the varnish of the adhesive composition to the support film can be a known method, such as knife coating, roll coating, spray coating, gravure coating, bar coating, curtain coating, etc. The conditions for heat drying are not particularly limited as long as the solvent used is sufficiently volatilized, and may be, for example, 50 to 200°C for 0.1 to 90 minutes.

[0079] The thickness of the film-like adhesive can be adjusted appropriately depending on the application. The thickness of the film-like adhesive may be 5 to 200 μm, 10 to 110 μm, or 15 to 80 μm from the viewpoint of sufficiently filling in irregularities in the semiconductor element (semiconductor chip), wires, wiring circuits of the substrate, etc.

[0080] [Adhesive Sheet] Fig. 2 is a schematic cross-sectional view showing an adhesive sheet according to one embodiment. The adhesive sheet 100 comprises a substrate 20 and the above-described film adhesive 10 provided on the substrate.

[0081] The substrate 20 is not particularly limited, but may be a substrate film. Examples of the substrate film include those exemplified above as the support film. The substrate 20 may be a dicing tape. Such an adhesive sheet can be used as a dicing / die bonding integrated adhesive sheet. That is, the dicing / die bonding integrated adhesive sheet comprises a dicing tape and the above-described film-like adhesive 10 provided on the dicing tape. Such a dicing / die bonding integrated adhesive sheet can be laminated to a semiconductor wafer only once, thereby improving work efficiency.

[0082] Examples of dicing tapes include plastic films such as polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, and polyimide film. Furthermore, the dicing tape may be subjected to surface treatment such as primer application, UV treatment, corona discharge treatment, polishing treatment, and etching treatment, as needed. The dicing tape may be adhesive. Such a dicing tape may be a plastic film provided with adhesive properties, or may be a plastic film having an adhesive layer on one side thereof.

[0083] The adhesive sheet 100 can be formed by applying the adhesive composition or its varnish to a substrate film in the same manner as the method for forming the film-like adhesive described above. The method for applying the adhesive composition or its varnish to the substrate 20 may be the same as the method for applying the adhesive composition or its varnish to a support film described above.

[0084] The adhesive sheet 100 may be formed using a pre-prepared 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, or the like. The adhesive sheet 100 may be formed using a roll laminator in a heated state, as this allows for continuous production and is efficient.

[0085] 3 is a schematic cross-sectional view showing an adhesive sheet according to another embodiment. The adhesive sheet 110 further includes a protective film 30 laminated on the surface of the film-like adhesive 10 opposite the substrate 20. Examples of the protective film 30 include those exemplified above for the support film. The thickness of the protective film 30 may be, for example, 10 to 200 μm or 20 to 170 μm.

[0086] [Semiconductor Device] Figure 4 is a schematic cross-sectional view showing a semiconductor device according to one embodiment. The semiconductor device 200 includes a substrate 90, 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 adhesive 10. The semiconductor element mounting support member 14 and the first semiconductor element Wa are bonded via an adhesive 41. The circuit pattern 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 portion of the first wire 88, are embedded (sealed) with the film adhesive 10. 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 portion of the first wire 88 is embedded. In addition, in the semiconductor device 200, the support member 14 for mounting the semiconductor element and the second semiconductor element Waa are further electrically connected via a second wire 98, and the second semiconductor element Waa is sealed with a sealing material 42.

[0087] 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 adhesive 10 may be a controller chip for driving the semiconductor device 200.

[0088] The support member 14 for mounting semiconductor elements comprises a substrate 90 having two circuit patterns 84, 94 formed on its surface. The substrate 90 may be an organic substrate. The first semiconductor element Wa is bonded onto the circuit pattern 94 via an adhesive 41. The second semiconductor element Waa is bonded to the support member 14 for mounting semiconductor elements via a film adhesive 10 so as to cover the circuit pattern 94, the first semiconductor element Wa, and a portion of the circuit pattern 84 to which the first semiconductor element Wa is not bonded. The film adhesive 10 is embedded in uneven steps caused by the circuit patterns 84, 94 on the support member 14 for mounting semiconductor elements. The second semiconductor element Waa, the circuit pattern 84, and the second wire 98 are sealed with a resin sealing material 42.

[0089] [Method for manufacturing semiconductor device] A semiconductor device can be manufactured by a method including, for example, a wire bonding step of placing a first semiconductor element on a support member having a substrate and 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 applying 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 with the film-like adhesive applied thereto via the film-like adhesive, thereby embedding the first wire and the first semiconductor element, or at least a portion of the first wire, in the film-like adhesive.

[0090] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples.

[0091] (1) Evaluation of Polymer and Curable Resin Composition - 1 [Monomer Synthesis] (Synthesis Example 1) To a tetrahydrofuran (THF, 120 g) solution of 2-carboxyethyl acrylate (5.8 g, 0.040 mol) cooled in an ice bath, butylamine (3.2 g, 0.044 mol) was added with stirring, and then 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM, 12.2 g, 0.044 mol) was slowly added. After the entire amount of DMT-MM was added, the mixture was stirred for 30 minutes. The mixture was then stirred at room temperature (25°C, hereinafter the same) for an additional 6 hours to allow the reaction. Next, the THF was distilled off under reduced pressure, and the mixture was extracted several times with ethyl acetate and water. The ethyl acetate phase was recovered, and water was removed with saturated brine and anhydrous sodium sulfate, followed by distillation under reduced pressure to remove the ethyl acetate. The resulting crude product was purified by silica gel column chromatography to obtain amide monomer A10, the structure of which is shown below.

[0092]

[0093] Synthesis Example 2 To a solution of butylamine (4.8 g, 0.065 mol) in dehydrated toluene (80 g) cooled in an ice bath, 2-isocyanatoethyl methacrylate (10.1 g, 0.065 mol) was slowly added dropwise with stirring. 30 minutes after the end of the addition, the mixture was slowly returned to room temperature and stirred at room temperature for 6 hours to allow the reaction. The toluene was then distilled off under reduced pressure, and the mixture was dried under reduced pressure at 40°C for 2 hours. The obtained crude product was dissolved in the minimum amount of acetone that would dissolve it, and this was slowly added dropwise to hexane with stirring. The precipitate was subjected to solid-liquid separation, and then dried under reduced pressure at 40°C for 4 hours to obtain Monomer a2 having a urea group. The structure of Monomer a2 is shown below.

[0094]

[0095] [Synthesis of Polymer] (Example 1) 15.1 g of a mixed solution of toluene and 1-methoxy-2-propanol (toluene / 1-methoxy-2-propanol = 3:2 (mass ratio)) was added to a monomer mixture of 11.1 g of acrylonitrile, 5.4 g of ethyl acrylate, 14.6 g of n-butyl acrylate, 1.1 g of glycidyl methacrylate, and 5.4 g of amide monomer A10 to prepare solution (a). Separately, 0.038 g of 2,2'-azobis(isobutyronitrile) was added to 10.0 g of a mixed solution of toluene and 1-methoxy-2-propanol (toluene / 1-methoxy-2-propanol = 3:2 (mass ratio)) to prepare solution (b). Both solutions were deoxygenated by passing nitrogen through them, and then solution (a) was heated to 75°C. Solution (b) was slowly added dropwise to solution (a) while stirring and mixed. Two hours after the dropwise addition was completed, the temperature was raised from 75°C to 85°C, and two hours after that, the temperature was raised from 85°C to 95°C and maintained for four hours. The solution was then cooled to room temperature to obtain a solution of polymer B10. The Mw of polymer B10 was 36,800.

[0096] <Measurement of weight average molecular weight (Mw)> Mw was measured by gel permeation chromatography (GPC) and calculated by conversion using a calibration curve of standard polystyrene. The GPC conditions are as follows: Measuring device: Shodex (registered trademark) GPC-101 (manufactured by Resonac Co., Ltd.) Detector: Differential refractometer Shodex RI-71S (manufactured by Resonac Co., Ltd.) Column: Shodex LF-804 + LF-804 (manufactured by Resonac Co., Ltd.) Column temperature: 40°C Eluent: tetrahydrofuran (THF) Flow rate: 1 mL / min

[0097] Examples 2 to 8 Solutions of polymers B11 to B17 were obtained in the same manner as in Example 1, except that amide monomers A11 to A17 were used instead of amide monomer A10.

[0098] Details of the amide monomers A11 to A17 are as follows: A11: N-n-butylacrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.) A12: N-benzyl acrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.) A13: N-tert-butylacrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.) A14: N-isopropylacrylamide (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.) A15: N-phenylacrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.) A16: N-tert-butylmethacrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.) A17: methacrylamide (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.) The structures of the amide monomers A11 to A17 are as follows:

[0099]

[0100] Example 9: 11.1 g of acrylonitrile, 5.4 g of ethyl acrylate, 14.6 g of n-butyl acrylate, 1.1 g of glycidyl methacrylate, and 5.4 g of amide monomer A13 were mixed with 36.8 g of a mixed solution of toluene and 1-methoxy-2-propanol (toluene / 1-methoxy-2-propanol = 1:4 (mass ratio)) to prepare solution (a1). Separately, 0.15 g of 2,2'-azobis(isobutyronitrile) was added to 9.2 g of a mixed solution of toluene and 1-methoxy-2-propanol (toluene / 1-methoxy-2-propanol = 1:4 (mass ratio)) to prepare solution (b1). Both solutions were deoxygenated by bubbling nitrogen through them, and then solution (a1) was heated to 75°C. Solution (b1) was slowly added dropwise to solution (a1) while stirring, and mixed. Two hours after the dropwise addition was completed, the temperature was raised from 75°C to 85°C, and two hours after that, the temperature was raised from 85°C to 95°C, and then maintained at that temperature for four hours. Thereafter, the mixture was cooled to room temperature to obtain a solution of polymer B13-1.

[0101] Example 10: 11.1 g of a mixed solution of toluene and 1-methoxy-2-propanol (toluene / 1-methoxy-2-propanol = 3:2 (mass ratio)) was added to 11.1 g of acrylonitrile, 5.4 g of ethyl acrylate, 14.6 g of n-butyl acrylate, 1.1 g of glycidyl methacrylate, and 5.4 g of amide monomer A13 to prepare solution (a2). Separately, 0.038 g of 2,2'-azobis(isobutyronitrile) was added to 7.4 g of a mixed solution of toluene and 1-methoxy-2-propanol (toluene / 1-methoxy-2-propanol = 3:2 (mass ratio)) to prepare solution (b2). Both solutions were deoxygenated by bubbling nitrogen through them, and then solution (a2) was heated to 75°C. Solution (b2) was slowly added dropwise to solution (a2) while stirring, and the mixture was mixed. Two hours after the dropwise addition was completed, the temperature was raised from 75°C to 85°C, and two hours after that, the temperature was raised from 85°C to 95°C and maintained at that temperature for four hours. Thereafter, the mixture was cooled to room temperature to obtain a solution of polymer B13-2.

[0102] Example 11 The same procedure as in Example 1 was carried out except that the amount of acrylonitrile was changed to 5.7 g, the amount of ethyl acrylate was changed to 10.8 g, and the amide monomer A10 was changed to the amide monomer A13, to obtain a solution of polymer B13-3.

[0103] Example 12 The same procedure as in Example 1 was carried out, except that the amount of acrylonitrile was changed to 5.7 g and 10.8 g of amide monomer A13 was used instead of 5.4 g of amide monomer A10, to obtain a solution of polymer B13-4.

[0104] Example 13 The same procedure as in Example 1 was carried out, except that the amount of acrylonitrile was changed to 11.3 g, the amount of ethyl acrylate was changed to 8.1 g, and 2.7 g of amide monomer A13 was used instead of 5.4 g of amide monomer A10, to obtain a solution of polymer B13-5.

[0105] Example 14 The same procedure as in Example 1 was carried out, except that a monomer mixture of 14.6 g of glycidyl methacrylate, 5.4 g of amide monomer A13, and 17.7 g of benzyl methacrylate was used instead of the monomer mixture in Example 1, to obtain a solution of polymer B13-6.

[0106] Comparative Example 1 A commercially available acrylic polymer b1 (product name: HTR-860P-3, manufactured by Nagase ChemteX Corporation, weight average molecular weight: 860,000, polymer not containing a first structural unit) was prepared.

[0107] Comparative Example 2 The same procedure as in Example 1 was carried out except that the amide monomer A10 was replaced with the monomer a2, to obtain a solution of polymer b2.

[0108] [Evaluation] 1. Handling and Followability 1-1. Handling and Followability of Polymer The polymer solutions (solid content: 1 g) prepared in the Examples and Comparative Examples and a curing accelerator (product name: 2PZ-CN, manufactured by Shikoku Chemicals Corporation, 1-cyanoethyl-2-phenylimidazole) (solid content: 0.01 g) were added to a plastic container, and then an organic solvent (cyclohexanone) was added so that the NV value ([mass of coating component after drying] / [mass of coating component before drying] × 100) was 30 mass %, and the mixture was thoroughly stirred and degassed using a planetary stirrer to prepare Coating Liquid 1. Coating Liquid 1 was applied to a polyethylene terephthalate (PET) film using a precision coating device, and then the resulting film was heated in a dryer at 100°C for 10 minutes to prepare a 15 μm-thick resin film 1.

[0109] Twelve layers of Resin Film 1 were stacked and laminated for 20 seconds at 80°C and 0.4 MPa to prepare an evaluation sample (thickness: approximately 180 μm). An 8 mm diameter sample stage was installed in a viscoelasticity measuring device (product name: ARES G2, manufactured by TA Instruments). The evaluation sample was set on the sample stage, and the complex viscosity was measured while the temperature was increased from 30°C to 160°C at a heating rate of 5°C / min.

[0110] The handling and tracking properties of each sample were evaluated based on the complex viscosity at 30°C and 150°C. Specifically, the handling properties were evaluated when the complex viscosity at 30°C was 3.0 x 10 ４When the viscosity was more than 3.0 x 10 Pa s, it was rated as "A" for excellent handleability. ４ When the complex viscosity was 5.5 × 10 Pa s or less, the evaluation was "B". ３ When the viscosity was less than 5.5 x 10 Pa s, the followability was evaluated as "A" and when the viscosity was less than 5.5 x 10 ３ When the viscosity was Pa·s or more, the evaluation was given as “B.” The evaluation results are shown in Table 2.

[0111] Here, the complex viscosity at 30°C can indicate the viscosity at around room temperature, so if the complex viscosity at 30°C is high, tack and exudation can be suppressed, and it can be said that the handling properties are excellent.The complex viscosity at 150°C can indicate the viscosity of the resin when embedding and molding using a resin layer in a circuit board or the like, so if the complex viscosity at 150°C is low, the resin can follow the recesses of the circuit board, etc., and it can be said that the followability is excellent.

[0112] 1-2. Handling and Followability of Curable Resin Composition Silica filler (product name: R-972, manufactured by Nippon Aerosil Co., Ltd.), coupling agent 1 (A-189, γ-mercaptopropyltrimethoxysilane, manufactured by Momentive Performance Materials Japan), and coupling agent 2 (A-1160, γ-ureidopropyltrimethoxysilane, manufactured by Momentive Performance Materials Japan) were weighed into a plastic container and mixed thoroughly. Next, the polymer solution prepared in the Examples and Comparative Examples, epoxy resin (product name: N-500P-10, manufactured by DIC Corporation, cresol novolac epoxy resin, epoxy equivalent: 204 g / eq), and curing agent (product name: MEH-7800M, manufactured by UBE Corporation, aralkyl phenolic resin) were added to obtain solution c. Separately, cyclohexanone was measured out so that the solids concentration of the coating liquid was 30% by mass, and a portion of this was added to solution c, followed by stirring using a rotary and revolutionary mixer until the solids were dissolved. The remaining cyclohexanone was mixed with a curing accelerator (product name: 2PZ-CN, manufactured by Shikoku Chemicals Corporation, 1-cyanoethyl-2-phenylimidazole) 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 and revolutionary mixer to obtain coating liquid 2. The blending amounts (solids content) of each component of coating liquid 2 are as shown in Table 1.

[0113]

[0114] Coating liquid 2 was applied onto a PET film using a precision coating device, and then the coating was heated in a dryer at 100° C. for 10 minutes to prepare a resin film 2 having a thickness of 20 μm.

[0115] The complex viscosity was measured in the same manner as in item 1-1 above, except that Resin Film 2 was used instead of Resin Film 1.

[0116] The handling and tracking properties of each sample were evaluated based on the complex viscosity at 30°C and 150°C. Specifically, the handling properties were evaluated when the complex viscosity at 30°C was 8.0 x 10 ４ When the viscosity was over 8.0 x 10 Pa s, it was rated as "A" for excellent handling. ４When the complex viscosity at 150°C was 1.0 x 10 Pa s or less, the evaluation was made as "B". ４ When the viscosity was less than 1.0 x 10 Pa s, the followability was evaluated as "A" and when the viscosity was less than 1.0 x 10 ４ When the viscosity was Pa·s or more, the evaluation was given as “B.” The evaluation results are shown in Table 2.

[0117] 2. Heat Resistance The polymer solutions prepared in the Examples and Comparative Examples were applied to a PET film and dried at 140°C for 2 hours to produce a resin film 3. Resin film 3 was heated from room temperature to 400°C at a rate of 10°C / min using a thermogravimetric analyzer (TGA) (apparatus name: DTG-60H, manufactured by Shimadzu Corporation) in an air flow of 100 mL / min, and 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 the reference, the mass loss rate at 280°C (hereinafter also referred to as "mass loss rate") was calculated using the following formula (1). Heat resistance was evaluated by assigning an "S" rating to a mass loss rate of less than 1.0%, an "A" rating to a mass loss rate of 1.0% or more but less than 5.0%, and a "B" rating to a mass loss rate of 5.0% or more. The evaluation results are shown in Table 2. Mass reduction rate (%) = (W1-W2) / W1×100 (1)

[0118]

[0119] (2) Evaluation of polymers and curable resin compositions - 2 [Synthesis of polymers] (Examples 15 to 24) As monomers, acrylonitrile (AN), ethyl acrylate (EA), n-butyl acrylate (BA), glycidyl methacrylate (GMA), and amide monomers were prepared. As amide monomers, A18 to A20 were prepared. Details of amide monomers A18 to A20 are as follows.

[0120] A18: N-(1,1,3,3-tetramethylbutyl)acrylamide (N-tert-octylacrylamide) (manufactured by Tokyo Chemical Industry Co., Ltd.) A19: N-(1,1-dimethyl-3-oxobutyl)acrylamide (diacetoneacrylamide) (manufactured by Tokyo Chemical Industry Co., Ltd.) A20: N-n-dodecylacrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.) The structures of amide monomers A18 to A20 are as follows:

[0121]

[0122] 2,2'-azobis(isobutyronitrile) (AIBN) was prepared as a thermal radical generator, and toluene (TOL) and 1-methoxy-2-propanol (PGM) were prepared as solvents.

[0123] First, the materials (monomers) of Group A and the materials (solvents) of Group B shown in Table 3 were weighed out in a round flask in the proportions (units: g) shown in Table 3 to prepare solution (a). The amount of solvent used in Group B was 70% by mass of the total amount of solvents used in Groups B, C, and D. Next, the materials of Group C shown in Table 3 were weighed out in a separate container in the proportions (units: g) shown in Table 3 and stirred until AIBN was dissolved to prepare solution (b). The amount of solvent used in Group C was 25% by mass of the total amount of solvents used in Groups B, C, and D. After deoxygenating solution (a) and solution (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 completed, the temperature was raised from 75°C to 85°C, and three hours later, the temperature was raised from 85°C to 95°C. Next, the materials of Group D shown in Table 3 were weighed out in a separate container in the proportions (units: g) shown in Table 3 and stirred until AIBN was dissolved to prepare solution (c). The amount of solvent of Group D used was 5% by mass of the total amount of solvents of Groups B, C, and D used. Solution (c) was deoxygenated by passing nitrogen through it, and then the mixture was heated to 95°C and slowly added dropwise to the mixture while stirring. The mixture was further stirred at 95°C for 2 hours and 45 minutes, after which 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 Group A used to the total amount of solvents of Groups B, C, D, and E used was 48 to 50% by mass. After a further 15 minutes, the mixture was cooled to room temperature to obtain solutions of each polymer.

[0124]

[0125] (Measurement of weight average molecular weight (Mw)) The Mw of each polymer was measured in the same manner as in (1) above. The results are shown in Table 5.

[0126] [Evaluation] 1. Handling and Tracking Ability 1-1. Handling and Tracking Ability of Polymer Using the polymer solutions prepared in the Examples and Comparative Examples, the same operation as in (1) above was carried out to prepare a coating solution 1, and a resin film 1 was produced. An evaluation sample was prepared in the same manner as in (1) above, and the complex viscosity of the obtained evaluation sample was measured at 30°C and 150°C by the same operation as in (1) above, and the handling and tracking ability were evaluated according to the same criteria as in (1) above. The results are shown in Table 5.

[0127] 1-2. Handling and followability of curable resin composition Using the polymer solutions prepared in the examples and comparative examples, the same operation as in (1) above was carried out to prepare Coating Solution 2. The blending amounts (solid content) of each component of Coating Solution 2 are as shown in Table 4.

[0128]

[0129] Using the prepared coating solution 2, the same operation as in (1) above was carried out to produce a resin film 2. An evaluation sample was prepared in the same manner as in (1) above, and the complex viscosity of the obtained evaluation sample was measured at 30°C and 150°C by the same operation as in (1) above, and the handleability and followability were evaluated according to the same criteria as in (1) above. The results are shown in Table 5.

[0130] 2. Heat Resistance Using the polymer solutions prepared in the Examples and Comparative Examples, a resin film 3 was formed in the same manner as in (1) above. The resin film 3 was subjected to the same procedure as in (1) above to calculate the mass reduction rate, and the heat resistance was evaluated using the same criteria as in (1) above. The results are shown in Table 5.

[0131]

[0132] As shown in Tables 2 and 5, the polymers of the examples were excellent in both heat resistance and conformability, whereas the polymers of the comparative examples were insufficient in either heat resistance or conformability. These results confirmed that the polymers of the present disclosure are excellent in heat resistance and conformability.

[0133] 10...film-like adhesive, 14...support member for mounting semiconductor element, 20...substrate, 30...protective film, 41...adhesive, 42...sealant, 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 polymer comprising a structural unit represented by the following formula (I) or formula (II) and a structural unit having an oxiranyl group: [In formula (I), R １ represents a hydrogen atom or a methyl group, M represents an alkylene group or an alkylene oxide chain, A represents a group represented by the following formula (a) or formula (b), R ２ represents an alkyl group, an aryl group, an aralkyl group, or a hydrogen atom. [In formula (a), * represents a bonding position.] [In formula (b), * represents a bonding position.] [In formula (II), R ３ represents a hydrogen atom or a methyl group, R ４ represents an alkyl group, an aryl group, an aralkyl group, or a hydrogen atom.

2. The polymer according to claim 1, wherein A is a group represented by formula (a).

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

4. A curable resin composition comprising the polymer according to any one of claims 1 to 3.

5. A cured resin comprising a component derived from the polymer according to any one of claims 1 to 3.

6. A cured resin product comprising the cured product of the curable resin composition according to claim 4.

7. An adhesive composition comprising the curable resin composition according to claim 4.

8. A film-like adhesive obtained by forming the adhesive composition according to claim 7 into a film.

9. An adhesive sheet comprising a substrate and the film-like adhesive according to claim 8 provided on the substrate.

10. The adhesive sheet according to claim 9, wherein the substrate is a dicing tape.