TW201823350A - Resin composition, thermosetting film using same, resin cured product, laminate, printed wiring board and semiconductor device - Google Patents

Abstract

Provided are: a thermosetting film which has excellent bonding strength to a metal foil contained in wiring lines of a printed wiring board and a substrate material such as a polyimide, while exhibiting dielectric characteristics in a high frequency region, specifically, a low dielectric constant (ε) and a low dielectric loss tangent (tan [delta]) in a frequency region of 1-100 GHz; and a resin composition which is used for the production of this thermosetting film. A resin composition which contains (A) an epoxy resin, (B) a resin that has a dielectric loss tangent (tan [delta]) of less than 0.005 in a frequency region of 1-100 GHz and (C) an imidazole compound wherein a side chain having an alkyl group with 5 or more carbon atoms is present at the 1-position of a heterocyclic ring.

Description

Resin composition, thermosetting film using the same, resin cured product, laminate, printed wiring board, and semiconductor device

[0001] The present invention relates to a resin composition, and a thermosetting film, a resin cured product, a laminate, a printed wiring board, and a semiconductor device using the composition.

[0002] In recent years, miniaturization, weight reduction, and high performance of electrical equipment and electronic equipment have been continuously developed. Along with this, printed wiring boards used in these devices, especially multilayer printed wiring boards, are required to have further higher multilayering, higher density, thinner, lighter weight, higher reliability, and formability. In addition, with the recent request for speeding up the transmission of printed wiring boards, the high frequency of transmission signals has been significantly progressed. Therefore, for materials used in printed wiring boards, it is required to reduce the electrical signal loss in the high-frequency region, specifically, the region above 1GHz. [0003] As an indirect coating used in a multilayer printed wiring board, or an adhesive film used as a surface protective film (ie, a cover film) of a printed wiring board, it is required to exhibit excellent dielectric characteristics in a high frequency region ( Low dielectric constant (ε) and low dielectric tangent (tanδ)). Specifically, the dielectric constant in the region of the frequency of 1 to 10 GHz is 3.5 or less, and the dielectric tangent (tan δ) of the region of the frequency of 1 to 10 GHz is 0.010 or less. In the present disclosure, "~" in the numerical range means that the numerical values recorded before and after it are included in this area. That is, the numerical range “X to Y” means X is greater than Y and less than Y. An adhesive film which satisfies the above-mentioned conditions of the dielectric constant and the dielectric tangent is proposed in Patent Document 1, for example. [0004] However, the polyimide contained in the substrate of a printed wiring board is required to further improve the bonding strength. Therefore, the adhesive strength of the adhesive film described in Patent Document 1 may be insufficient. [Prior Art Document] [Patent Document] [0005] [Patent Document 1] Japanese Patent Laid-Open No. 2011-068713

[Problems to be Solved by the Invention] [0006] In order to solve the above-mentioned problems of the prior art, an object of the present invention is to provide the following resin composition, and a thermosetting film, resin cured product, laminate, printing using the composition Wiring boards and semiconductor devices. After this thermosetting film is cured, it has excellent adhesion strength to substrate materials such as metal foil and polyimide contained in the wiring of the printed wiring board. In addition, the thermosetting thin film has a low dielectric constant (ε) and a low dielectric tangent (tan δ) in the dielectric characteristics in a high frequency region, specifically, in a frequency range of 1 to 100 GHz. The said resin composition can be used for manufacture of this thermosetting thin mold. [Means to Solve the Problem] [0007] In order to achieve the above object, the first aspect (the first aspect) of the present disclosure is to provide a resin composition, which is characterized by including (A) epoxy resin, (B) in A resin having a dielectric tangent (tan δ) of less than 0.005 in a frequency range of 1 to 100 GHz, and (C) an imidazole compound having a side chain of an alkyl group having 5 or more carbon atoms at the 1-position of the heterocyclic ring . [0008] The aforementioned (C) imidazole compound contained in the resin composition according to the first aspect is preferably a compound represented by the following formula (I). (In the formula (I), R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m is 0 or 1, and R ⁴ is an alkylene having 1 to 3 carbon atoms. Or -CH ₂ CH ₂ COO-, R ⁵ is an alkyl group having 5 to 10 carbon atoms). [0009] The aforementioned (B) resin contained in the resin composition of the first aspect is preferably made of a modified polyphenylene ether (modified PPE) resin, a styrene-based thermoplastic elastomer, and a polyimide resin. At least one resin selected from the group. [0010] A second aspect of the present disclosure provides a thermosetting thin mold made of the resin composition. [0011] A third aspect of the present disclosure is to provide a cured resin, which is the cured resin composition or the thermosetting film. [0012] A fourth aspect of the present disclosure provides a laminate including the resin hardened body. [0013] A fifth aspect of the present disclosure is to provide a printed wiring board including the resin hardened body. [0014] A sixth aspect of the present disclosure is to provide a semiconductor device including the resin hardened body. [Inventive Effect] [0015] The thermosetting film formed of the resin composition of the first aspect described above has excellent adhesion to substrate materials such as metal foil and polyimide contained in the wiring of a printed wiring board after curing. Intensity, and the dielectric characteristics in the high frequency region, specifically in the frequency range of 1 to 100 GHz, shows a low dielectric constant (ε) and a low dielectric tangent (tan δ).

[0016] An embodiment of the present disclosure will be described in detail below. The resin composition of this embodiment contains (A) an epoxy resin, (B) a resin having a dielectric tangent (tanδ) of less than 0.005 in a region of a frequency of 1 to 100 GHz, and (C) a 1-position heterocyclic There are imidazole compounds having a side chain of an alkyl group having 5 or more carbon atoms. Each component of the resin composition of this embodiment is described below. [0017] (A) Examples of the epoxy resin having the epoxy resin as the component (A) include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, and alicyclic ring. Family epoxy resin, siloxane type epoxy resin, biphenyl type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, hydantoin type resin, epoxy resin containing naphthalene skeleton And epoxy resin containing anthracene skeleton. As the resin composition of this embodiment, the compounds exemplified herein may be used alone, or two or more kinds of compounds may be used in combination. [0018] In addition, from the viewpoint of improving the dielectric characteristics, the epoxy resin of the component (A) preferably includes any of a biphenyl epoxy resin, an epoxy resin containing a naphthalene skeleton, and an epoxy resin containing an anthracene skeleton. One. Examples of commercially available biphenyl epoxy resins include NC-3000H manufactured by Nippon Kayaku Co., Ltd., and commercially available epoxy resins containing a naphthalene skeleton include HP4032D manufactured by DIC Corporation, and An example of a commercially available epoxy resin containing an anthracene skeleton is JERYX8800 manufactured by Mitsubishi Chemical Corporation. [0019] From the viewpoint of dielectric properties and improvement in peel strength to copper foil, the epoxy resin of the component (A) is preferably a naphthalene-type epoxy resin. [0020] For a total of 100 parts by mass of the component (A) and the component (B), the content of the epoxy resin of the component (A) is preferably 2 to 30 parts by mass, more preferably 2 to 20 parts by mass, and even more preferably It is 2 to 10 parts by mass. When the (A) component is too small, the adhesiveness of the thermosetting film formed from the resin composition of the present embodiment is deteriorated. When there are too many (A) components, since the amount of (B) components is relatively reduced, the dielectric characteristics of the high-frequency region of the thermosetting film are deteriorated. [0021] The resin of component (B) has a dielectric tangent (tan δ) of less than 0.005 in a region of a frequency of 1 to 100 GHz. It contributes to the excellent dielectric properties of the thermosetting film formed from the resin composition of the present disclosure in a high frequency region, that is, a low dielectric constant (ε) and a low dielectric tangent (tan δ) at a frequency above 1 GHz . [0022] The resin of component (B) is preferably at least one selected from the group consisting of a modified polyphenylene ether (modified PPE) resin, a styrene-based thermoplastic elastomer, and a polyimide resin. Resin. Only one of these resins may be used, or two or more resins may be used in combination. [0023] When a modified PPE resin is used as the component (B), it is preferred to use a compound represented by the following general formula (1). In formula (1),-(OXO)-is represented by the following general formula (2) or (3). [0024] In the formula (2), R ₁ , R ₂ , R ₃ , R _7, and R ₈ are alkyl groups or phenyl groups having 6 or less carbon atoms, and may be the same as or different from each other. R ₄ , R ₅ , and R ₆ are a hydrogen atom, an alkyl group or a phenyl group having 6 or less carbon atoms, and may be the same as or different from each other. In formula (3), R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are a hydrogen atom, an alkyl group or a phenyl group having 6 or less carbon atoms, and may be They may be the same as each other or different from each other. -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms. [0026] In the formula (1),-(YO)-is represented by the general formula (4). In the formula (1), one structure or two or more structures represented by the formula (4) are randomly arranged. In the formula (4), R ₁₇ and R ₁₈ are an alkyl group or a phenyl group having 6 or less carbon atoms, and may be the same as or different from each other. R ₁₉ and R ₂₀ are a hydrogen atom, an alkyl group or a phenyl group having 6 or less carbon atoms, and may be the same as or different from each other. [0027] In Formula (1), a and b are shown as integers from 0 to 100. Among them, at least one of a and b is not 0. [0028] Examples of -A- in the formula (3) include methylene, ethylene, 1-methylethylene, 1,1-propylene, and 1,4-phenylenebis ( 1-methylethylene), 1,3-phenylenebis (1-methylethylene), cyclohexylene, phenylmethylene, naphthylmethylene, and 1-phenylethylene Equal bivalent organic group. However, this divalent organic group is not limited to these groups. [0029] Among the compounds represented by formula (1), R ₁ , R ₂ , R ₃ , R ₇ , R ₈ , R ₁₇ and R ₁₈ are preferably alkyl groups having 3 or less carbon atoms, and R _{4 , R 5, R 6, R} 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 19 , and R ₂₀ is a hydrogen atom or an alkyl group of 3 or less carbon atoms. The better one is represented by the general formula (2) or the general formula (3)-(OXO)-is the general formula (5), the general formula (6) or the general formula (7); the better is the general formula (4) where-(YO)-is represented by formula (8) or formula (9). [0030] [0031] [0032] The method for producing the compound represented by the formula (1) is not particularly limited. For example, it can be produced by vinyl-benzyl etherification of a terminal phenolic hydroxyl group of a bifunctional phenyl ether oligomer obtained by oxidative coupling of a bifunctional phenol compound and a monofunctional phenol compound. [0033] The number average molecular weight of the compound represented by the formula (1), in terms of polystyrene conversion by the GPC method, is preferably in the range of 500 to 3,000, and more preferably in the range of 1000 to 2500. When the number average molecular weight is 500 or more, the resin composition of this embodiment is less sticky when it is formed into a coating film. In addition, if the number average molecular weight is 3,000 or less, a decrease in the solubility in a solvent can be suppressed. [0034] The styrene-based thermoplastic elastomer as the component (B) refers to a thermoplastic elastomer containing styrene, a homologue thereof, or the like. Examples of the (B) styrene-based thermoplastic elastomer include polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene (SEEPS) and polystyrene-poly (ethylene / butylene). Olefin) block-polystyrene (SEBS), styrene-butadiene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and polybutadiene (PB ). The elastomers exemplified here may be used singly or in combination of two or more kinds. From the viewpoint of improving the dielectric properties of substrate materials such as metal foil and polyimide contained in the wiring of a printed wiring board, SEEPS is preferred. [0035] When a polyfluorene imine resin is used as the component (B), a solvent-soluble polyfluorene imine resin is preferably used. In the present embodiment, the term "solvent-soluble" means that at least one solvent selected from the group consisting of solvents shown below is dissolved at 23 ° C by 20% by weight or more. This solvent is toluene, xylene of hydrocarbon solvents, acetone of ketone solvents, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, and 1,4-dioxane of ether solvents. , Tetrahydrofuran, Diethylene glycol dimethyl ether, Methyl cellosolve of glycol ether solvents, Ethyl cellosolve, Propylene glycol monomethyl ether, Propylene glycol monoethyl ether, Propylene glycol monobutyl ether, Diethylene glycol methylethyl Ethers are ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, benzyl alcohol, N-methylpyrrolidone, N, N-dimethylformamide, and N, N-diethyl ether. Methylacetamide. [0036] The solvent-soluble polyfluorene imine of this embodiment can be obtained by reacting a diamine with a tetracarboxylic acid component at a temperature of 130 ° C. or higher and subjecting it to imidization. The solvent-soluble polyimide is preferably a polyimide resin having excellent flexibility, toughness, and heat resistance. Polyfluorene imine resin can be obtained by reacting a tetracarboxylic acid component with a dimer diamine. In the reaction to produce this solvent-soluble polyfluorene imine, a part of the dimer diamine may be substituted by polysiloxane diamine. [0037] Examples of the tetracarboxylic acid component used herein include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4 , 4'-biphenylphosphonium tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4, 4'-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilane Carboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-Dicarboxyphenoxy) diphenylarsine dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'- Perfluoroisopropyl diphthalic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene -Bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether Dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride and 4,4 '-(4,4'-isopropylidenediphenoxy) diphthalic acid Dianhydride, etc. [0038] Examples of the dimer diamine include VERSAMINE 551 (trade name, manufactured by BASF Japan Co., Ltd .; 3,4-bis (1-aminoheptyl) -6-hexyl-5- ( 1-octenyl) cyclohexene), VERSAMINE 552 (trade name, manufactured by Cognix Japan Co., Ltd .; hydride of VERSAMINE 511), PRIAMINE 1075 and PRIAMINE 1074 (both trade names, manufactured by Croda Japan Co., Ltd.), etc. . [0039] The solvent-soluble polyfluorene imine resin has a molecular structure of a polyfluorene imine formed by a reaction between a tetracarboxylic acid component and a dimer diamine. An acid anhydride group or an amine group is present at the molecular structure end. The dimer acid as a raw material of the dimer diamine is obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms (a mixture of oleic acid, linoleic acid, and linolenic acid). By the dimerization reaction, a mixture corresponding to the reaction probability can be obtained, which contains a reaction product of an alicyclic ring or an aromatic ring having a linear, alicyclic or double bond. A dimer diamine was obtained by directly aminating this reaction mixture. Therefore, the solvent-soluble polyfluorene imide resin obtained by polymerizing a tetracarboxylic acid and a dimer diamine is produced by the irregular bonding of molecules of the dimer acid contained in the above reaction mixture, which is complicated. Molecular structure. This complex molecular structure cannot be specifically identified. However, examples of speculable molecular structures include molecular structures represented by the following chemical structure formulas. The solvent-soluble polyimide resin used in this embodiment is considered to be a mixture of polyimide resins having such a molecular structure (these structural formulas are merely examples. Of the solvent-soluble polyimide resins used in this embodiment, The molecular structure is not limited to these examples). In the above chemical formula, n is an integer. R ¹⁰ , R ²⁰ , R ³⁰ and R ⁴⁰ are organic groups. For example, R ¹⁰ and R ²⁰ _are- (CH ₂ ) _n1- (CH = CH) _n2- (CH ₂ ) _n3 -CH ₃ , which may be the same as or different from each other. R ³⁰ and R ⁴⁰ _are- (CH ₂ ) _n1- (CH = CH) _n2- (CH ₂ ) _n3 , which may be the same as or different from each other. n1 and n3 are integers from 0 to 18. n2 is an integer of 0, 1, or 2. The total number of carbon atoms in the dimer diamine component was 36. [0040] For a total of 100 parts by mass of the components (A) and (B), the resin content of the component (B) is preferably 70 to 98 parts by mass, more preferably 80 to 98 parts by mass, and even more preferably 90 to 98 parts by mass. 98 parts by mass. If the resin of the component (B) is too small, it is difficult for the thermosetting film formed of the resin composition of the present embodiment to obtain the desired dielectric characteristics in a high-frequency region. When there is too much (B) component resin, the quantity of (A) component will decrease relatively. Therefore, the adhesiveness and hardenability of the thermosetting film formed from the resin composition of this embodiment are deteriorated. [0041] The action of the imidazole compound of the component (C) varies depending on the resin used as the component (B). The resin used as the component (B) is a polyimide resin. In the case of a resin that causes a hardening reaction with the epoxy resin of the component (A), the imidazole compound of the (C) component functions as a curing catalyst. . On the other hand, when the resin used as the (B) component is a modified PPE resin or a styrene-based thermoplastic elastomer, and the resin which does not react with the epoxy resin of the (A) component, the imidazole compound of the (C) component is used. The hardening catalyst of the epoxy resin itself as the component (A) functions. [0042] The imidazole compound has been used as a curing agent or a curing catalyst for epoxy resins. In the resin composition of this embodiment, as the component (C), an imidazole compound having a side chain having an alkyl group having 5 or more carbon atoms and having a specific structure is used at the 1-position of the heterocyclic ring. As a result, the thermosetting film formed of the resin composition has excellent bonding strength to substrate materials such as metal foil and polyimide contained in the wiring of the printed wiring board, and has dielectric properties in the high frequency region. Specifically, it shows a low dielectric constant (ε) and a low dielectric tangent (tan δ) in a region of a frequency of 1 to 100 GHz. The reason is detailed below. [0043] When the imidazole compound functions as a curing agent or a curing catalyst for an epoxy resin, a non-shared electron pair of a nitrogen atom at the 3-position of its heterocyclic ring contributes to its curing reaction. On the other hand, a long-chain hydrocarbon chain such as an alkyl group having 5 or more carbon atoms at the 1-position of the heterocyclic ring helps to improve the dielectric characteristics in the high frequency region, meaning that the frequency is lower in the region of 1 to 100 GHz. Dielectric constant (ε) and low dielectric tangent (tanδ). An imidazole compound having a side chain of an alkyl group having 5 or more carbon atoms exists at the 1-position of the heterocyclic ring. It can be used at a frequency of 1 to 100 GHz without impairing the reactivity when used as a hardener for epoxy resins as a hardening catalyst. Low dielectric constant (ε) and low dielectric tangent (tan δ) of the region. In this regard, it is clear from the results of the examples described later. The imidazole compound used in Comparative Example 3 described later has a long-chain hydrocarbon chain as a heterocyclic side chain. However, the side chain is present at the 2-position of the heterocyclic ring. Therefore, due to steric hindrance, its reactivity is impaired when it acts as a hardener or hardening catalyst for epoxy resins. In addition, when the imidazole compound used in the examples is thermally decomposed, 2-ethyl-4-methylimidazole and 2-ethylhexyl are generated. However, even if these are used, it will be understood from Comparative Examples 3 and 5 described later that the reactivity is insufficient when acting as a curing agent or a curing catalyst for epoxy resins. [0044] The imidazole compound of the component (C) is not particularly limited as long as a side chain having an alkyl group having 5 or more carbon atoms is present at the 1-position of the heterocyclic ring. For example, an imidazole compound represented by the following formula (1) can be used. In Formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. m is 0 or 1. R ⁴ is an alkylene group having 1 to 3 carbon atoms or -CH ₂ CH ₂ COO-. R ⁵ is an alkyl group having 5 to 10 carbon atoms. [0045] Preferable examples of the imidazole compound as the component (C) include the following formulae (I1) to (I4). Only one of the examples of these imidazole compounds may be used, or two or more kinds of imidazole compounds may be used in combination. Among these, from the viewpoint of low dielectric constant (ε) and low dielectric tangent (tan δ) in the 100 GHz region, the following formulae (I3) and (I4) are preferred. From the viewpoint of controlling reactivity, the following formula (I4) is more preferable. [0046] For a total of 100 parts by mass of the epoxy resin of the component (A) and the resin of the component (B), the content of the imidazole compound of the component (C) is preferably 0.1 to 5.0 parts by mass, and more preferably 0.5 to 3.0 parts by mass Serving. If the content of the component (C) is too small, the hardenability of the thermosetting film formed from the resin composition of the present embodiment is deteriorated, and the adhesiveness, toughness, and heat resistance of the thermosetting film may decrease. On the other hand, if the content of the (C) component is too large, the thermosetting film formed from the resin composition of the present embodiment may deteriorate the storage life. In addition, as a result of impairing the physical properties of the cured product of the thermosetting film, the adhesiveness, toughness, and heat resistance of the cured product may be reduced. [0047] The resin composition of this embodiment can be obtained by dissolving or dispersing a raw material containing the components (A) to (C) and other components added as necessary in an organic solvent. There are no particular restrictions on other ingredients. Examples of other components include inorganic fillers such as silica fillers, flame retardants, coupling agents, leveling agents, dispersants, and defoamers. The means for dispersing or dissolving these raw materials is not particularly limited. As a mixer equipped with a heating device, a dissolver, an upright mixer, a crusher, a three-roll rolling mill, a ball mill, or a bead mill can be used. In addition, these devices can be used in appropriate combination. [0048] The resin composition of this embodiment has suitable characteristics shown below. First, the resin composition of the present embodiment has a resin hardened body having sufficient adhesion strength. Specifically, the peel strength (180-degree peel) of the resin cured product to the polyimide film measured in accordance with JISC6481 is preferably 6.5 N / cm or more, more preferably 7.0 N / cm or more, and even more preferably 7.5 N / cm or more. In addition, the peel strength (180-degree peel) of the cured surface of the resin hardened material to the glossy side of the copper foil measured according to JISC6481 is preferably 6.5 N / cm or more, more preferably 7.0 N / cm or more, and even more preferably 7.5 N / cm or more . [0049] The cured product of the resin composition of this embodiment preferably has excellent dielectric properties in a high frequency region. Specifically, the dielectric constant (ε) of the cured product in the region of the frequency of 1 to 100 GHz is preferably 3.5 or less, and more preferably 3.0 or less. In addition, the dielectric tangent (tan δ) in the region of the frequency of 1 to 100 GHz is preferably 0.010 or less, and more preferably 0.0095 or less. [0050] The thermosetting film of this embodiment is formed from the resin composition. Specifically, a thermosetting film is obtained by drying a resin composition applied to at least one side of a desired support. As the support system, a support having a desired form is appropriately selected in accordance with a method for producing a thermosetting film. The specific support is not particularly limited. Examples of a usable support include metal foils such as copper or aluminum, carrier films of polyester fibers, and resins such as polyethylene. When the thermosetting film of this embodiment is provided in the form of a film peeled from a support, it is preferred that the support system be demoulded with a mold release agent such as polysiloxane. [0051] The method for applying the resin composition to the support is not particularly limited. From the viewpoint of thin film formation and film thickness control, a preferred method is a micro gravure printing method, a slit die method, or a doctor blade method. By the slit die method, a film having a thickness of, for example, 5 to 500 μm can be obtained. [0052] The drying conditions are appropriately set in accordance with the type, amount, coating thickness, and the like of the organic solvent used in the resin composition. For example, drying can be performed at 50 to 120 ° C for about 1 to 30 minutes. In addition, the film can be peeled from the support at a desired time. [0053] The film obtained through the above procedure can be heat-cured at a temperature of, for example, 130 ° C to 250 ° C, preferably 150 ° C to 200 ° C, for 30 to 180 minutes. When the thin film obtained through the above procedure is used as an adhesive film or a layer indirectly for electrical or electronic use, it is preferred that the resin composition is cured under the above-mentioned hardening conditions. [0054] The thickness of the film obtained through the above procedure is preferably 5 μm or more and 200 μm or less. If the thickness of the film is less than 5 μm, the required film characteristics such as insulation properties may not be obtained. The thickness of the film is more preferably 15 μm to 150 μm, and still more preferably 20 μm to 100 μm. [0055] The thermosetting film of this embodiment having the above-mentioned characteristics of the resin cured product is suitable for an adhesive film, an indirect film, and a cover film for electrical or electronic applications. [0056] In the semiconductor device according to this embodiment, the layers of the constituent elements indirectly use the resin composition of the present disclosure. Specifically, for example, the layer of the electronic component and the substrate is indirectly bonded using the resin composition of the present disclosure. Alternatively, in a semiconductor device containing an electronic component, a thermosetting film formed of the resin composition of this embodiment is used. [Examples] [0057] Hereinafter, this embodiment will be described in detail through examples. However, this embodiment is not limited to these examples. [Examples 1 to 11, Comparative Examples 1 to 4] A specific amount of each resin (A-1, A-2, A-3, and B) was measured in a container according to the blending shown in the following table. -1, B-2, B-3, B-4 and B-5) and a specific amount of toluene. Next, the mixture of resin and toluene was heated and dissolved using a heating stirrer, and then cooled to room temperature. Next, a specific amount of an imidazole compound or the like (C-1, C'-1, C'-2, C'-3, and C'-4) is added to the mixture. Then, the obtained mixture of (A) component, (B) component, and (C) component or (C ') component is stirred and mixed with a rotation or revolution type mixer (MAZERUSTAR (brand name), Kurabo Industries Co., Ltd.) 3 minutes while preparing the resin composition. However, in Example 11, a molten spherical silica filler (MP-15EF, manufactured by Longsen Co., Ltd., with an average particle diameter of 1.5 μm) was further added to the resin composition as an inorganic filler, and then a bead mill was used. Silica dioxide filler is dispersed in the resin composition. By adjusting the viscosity of the resin composition thus obtained with toluene, a coating liquid containing the resin composition is prepared. The components used in preparing the resin composition are as follows. (A) Component: Epoxy resin (A-1): Epoxy resin containing naphthalene skeleton, HP4032D (trade name), manufactured by DIC Corporation, epoxy equivalent 136 to 148 (A-2); Epoxy resin, JERYX8800 (trade name), manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 180 (A-3); and epoxy resin containing biphenyl skeleton, NC-3000H (trade name), Nippon Kayaku Co., Ltd. Company-made, epoxy equivalent 288. [0060] Component: Resin (B-1) having a tan δ of less than 0.005 in the region of the frequency of 1 to 100 GHz: a solvent-soluble polyimide resin synthesized by the following procedure will be commercially available aromatic four Carboxylic dianhydride (BTDT-UP (trade name), manufactured by Evonik Japan Co., Ltd.) 210.0 g, cyclohexanone 1008.0 g, and methylcyclohexane 201.6 g are fed into a mixer, a water separator, a thermometer, and a nitrogen introduction tube Reaction container. The solution in the reaction vessel was heated to 60 ° C. Next, 341.7 g of a commercially available dimer diamine (PRIAMINE (trade name) 1075, Croda Japan Co., Ltd.) was dropped into the reaction solution. Then, the amidine imidization reaction was performed at 140 ° C for 10 hours. Then, the solvent was distilled off under reduced pressure and toluene was substituted to obtain a solution (nonvolatile content 30.1%) of a solvent-soluble polyfluorene imine resin (A-2). The number average molecular weight (Mn) measured by GPC was 15,000. The dielectric tangent (tan δ) measured by the procedure described later was 0.0029. (B-2): 190.0 g of a commercially available aromatic tetracarboxylic dianhydride (BTDT-UP (trade name), manufactured by Evonik Japan Co., Ltd.) of a solvent-soluble polyimide resin synthesized by the following procedure, 912.0 g of cyclohexanone and 182.4 g of methylcyclohexane were fed into the same reaction vessel as (B-1). The solution in the reaction vessel was heated to 60 ° C. Next, a commercially available dimer diamine (PRIAMINE 1075 (trade name), Croda Japan Co., Ltd.) 288.1 g, and a commercially available polysiloxane (KF-8010 (trade name)), Shin-Etsu Chemical Industry Co., Ltd. 24.7 g of the product was dropped into the reaction solution. Then, the amidine imidization reaction was performed at 140 ° C for 10 hours. In this way, a solution of polyfluorene imide resin (non-volatile content of 30.8%) was obtained. The number average molecular weight (Mn) determined by GPC was 14,000. The dielectric tangent (tan δ) measured by the procedure described later was 0.0036. (B-3): 65.0 g of a commercially available aromatic tetracarboxylic dianhydride (BisDA1000 (trade name), manufactured by SABIC Japan Co., Ltd.), a solvent-soluble polyimide resin synthesized by the following procedure, cyclohexanone 266.5 g of ketone and 44.4 g of methylcyclohexane were fed into the same reaction vessel as (B-1). The solution in the reaction vessel was heated to 60 ° C. Next, 43.7 g of a commercially available dimer diamine (PRIAMINE (trade name) 1075, Croda Japan Co., Ltd.) and 5.4 g of 1,3-bisaminomethylcyclohexane were dropped into the reaction solution. Then, the amidine imidization reaction was performed at 140 ° C for 10 hours. In this way, a solution (non-volatile content of 29.5%) of a solvent-soluble polyfluorene imine resin (B-1) was obtained. The number average molecular weight (Mn) measured by GPC was 15,000. The dielectric tangent (tan δ) measured by the procedure described later was 0.0019. (B-4): Modified PPE resin represented by the above general formula (1), OPE-2St (Mn = 2200), dielectric material manufactured by Mitsubishi Gas Chemical Co., Ltd. and measured by the same procedure as (B-1) The tangent (tan δ) is 0.0040. (B-5): Thermoplastic elastomer (SEEPS), SEPTON4044 (trade name), dielectric tangent (tan δ) measured by the same procedure as (B-1) manufactured by KURARAY Co., Ltd. is 0.0008. (C) Component: Imidazole compound (C-1): An imidazole compound having a structure represented by the following formula, EH-2021 (trade name), manufactured by ADEKA Co., Ltd. (C'-1): 1-benzyl-2-phenylimidazole, 1B2PZ (trade name), manufactured by Shikoku Chemical Industry Co., Ltd. (C'-2): 2-ethyl-4-methylimidazole, 2E4MZ (trade name), manufactured by Shikoku Chemical Industries, Ltd. (C'-3): 1-cyanoethyl-2-undecylimidazole, C11ZCN (trade name), manufactured by Shikoku Chemical Industries, Ltd. ( C'-4): 2-ethylhexyl acrylate, manufactured by NACALAI TESQUE Co., Ltd. [0062] The following evaluation was performed using the coating solution prepared in accordance with the procedure described above. 1. PI peel strength Use a coater to apply a coating solution on the surface of a 50 μm-thick PET film on which the release agent is applied, so that the dry coating film has a film thickness of 25 ± 5 μm. The substrate coated with the coating solution was dried at 80 ° C for 15 minutes. The substrate was peeled from the unhardened film thus prepared. Thereafter, the laminated film obtained by sandwiching the uncured film between two pieces of polyimide film (UPILEX (registered trademark) 12.5CA, manufactured by Ube Industries, Ltd.) was hardened under pressure using a vacuum laminator ( 200 ° C × 60 minutes 1MPa). The obtained laminated film containing a cured film was cut into a width of 10 mm to obtain a test piece. Using a universal testing machine, the peeling strength of the cured film was measured by tearing off the two cured polyimide films of the test piece from each other in opposite directions. An average value of the values obtained in the five measurements was calculated and used as a measured value of the peel strength. 2. Dielectric constant (ε) and dielectric tangent (tan δ) After the uncured film obtained in 1. was cured on the surface of the substrate at 200 ° C for 60 minutes, the substrate was peeled from the cured film. The ε and tan δ cut into a hardened film of 130 × 70 mm were measured at 2GHz of the dielectric resonance frequency by the SPDR method. The results are shown in the following table. [0063] Examples 1 to 11 all showed a PI peel strength of 7.0 N / cm or more, a dielectric constant (ε) of 3.0 or less, and a dielectric tangent (tan δ) of 0.010 or less. In addition, in Examples 2 and 3, the blend ratio of the imidazole compound of the component (C) is different from Example 1. Examples 4 and 5 are different from Example 1 in the type of epoxy resin of the component (A). Examples 6 to 9 are different from Example 1 in the resin type of the component (B). Examples 10 to 11 and Example 1 differ in the blending ratio of the component (B) to the component (A). Among them, in Example 11, a silicon dioxide filler was further used. In Comparative Example 1, an imidazole compound having a benzyl group at the 1-position of a heterocyclic ring was used instead of the imidazole compound of the component (C). In Comparative Example 2, an alkyl group having 5 or more carbon atoms did not exist at the 1-position of the heterocyclic ring of the imidazole compound. In Comparative Example 3, instead of the imidazole compound of the component (C), an imidazole compound having a side chain having an alkyl group having 5 or more carbon atoms at the 2-position of the heterocyclic ring was used. In Comparative Example 4, a compound equivalent to the thermal decomposition product of the imidazole compound (C-1) used in the examples was blended. Comparative Examples 1 to 4 each showed a PI peel strength of less than 7.0 N / cm and a dielectric tangent (tan δ) exceeding 0.010. The resin composition according to the embodiment of the present disclosure may be the following resin compositions of the first to third aspects. The above-mentioned first resin composition contains (A) an epoxy resin, (B) a resin having a dielectric tangent (tan δ) of less than 0.005 at a frequency of 1 to 100 GHz, and (C) having a C5 or higher alkyl side chain imidazole compounds. The second resin composition is the first resin composition in which the (C) imidazole compound is the following formula (1). (In formula (1), R ¹ , R ^2, and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m is 0 or 1, and R ⁴ represents an alkylene group having 1 to 3 carbon atoms. Group or group: -CH ₂ CH ₂ COO-, R ⁵ represents an alkyl group having 5 to 10 carbon atoms). The third resin composition is at least one resin selected from the group consisting of a modified polyphenylene ether (modified PPE) resin, a styrene-based thermoplastic elastomer, and a polyimide resin. The first or second resin composition described above. The thermosetting film according to the embodiment of the present disclosure can be formed from any of the resin compositions described in the first to third embodiments. The resin cured product according to the embodiment of the present disclosure may be any one of the resin compositions of the first to third embodiments or the resin cured product after the thermosetting film is cured. The laminated board according to the embodiment of the present disclosure may be a laminated board containing the above-mentioned resin cured product. The printed wiring board according to the embodiment of the present disclosure may be a printed wiring board containing the resin cured product. The semiconductor device according to the embodiment of the present disclosure may be a semiconductor device containing the resin hardened body.

Claims (8)

A resin composition comprising (A) an epoxy resin, (B) a resin having a dielectric tangent (tan δ) of less than 0.005 in a frequency range of 1 to 100 GHz, and (C) in a heterocyclic At the 1-position, an imidazole compound having a side chain of an alkyl group having 5 or more carbon atoms is present. If the resin composition of claim 1 contains the aforementioned (C) imidazole compound represented by the following formula (I), (In the formula (I), R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m is 0 or 1, and R ⁴ is an alkylene having 1 to 3 carbon atoms. Or -CH ₂ CH ₂ COO-, R ⁵ is an alkyl group having 5 to 10 carbon atoms). For example, the resin composition of claim 1 or 2, wherein the (B) resin is selected from the group consisting of a modified polyphenylene ether (modified PPE) resin, a styrene-based thermoplastic elastomer, and a polyimide resin. At least 1 species. A thermosetting thin mold characterized by being formed of the resin composition according to any one of claims 1 to 3. A hardened resin, which is characterized by a hardened resin composition according to any one of claims 1 to 3 or a thermosetting film according to claim 4. A laminated board comprising a hardened resin as claimed in claim 5. A printed wiring board characterized in that it comprises a cured resin as claimed in claim 5. A semiconductor device characterized in that it comprises a cured resin as claimed in claim 5.