Resin composition

Abstract

To provide a resin composition capable of forming a cured product having good mechanical properties in spite of a low coefficient of linear thermal expansion and excellent in smear removability and tackiness.SOLUTION: A resin composition comprising (A) an epoxy resin, (B) a maleimide resin and / or a polyimide resin, and (C) an inorganic filler, wherein the component (A) comprises (a- 1) an epoxy resin that is liquid at normal temperature and (a- 2) an epoxy resin having a biphenol skeleton, the ratio x / X of the molar number x of epoxy groups in the component (a- 1) to the molar number X of all epoxy groups in the component (A) is 0.4 to 0.9, and the content of the component (B) is 7 to 30% by mass based on 100% by mass of the resin component.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition. The present invention further relates to a resin sheet, a circuit board, and a semiconductor device obtained by using the resin composition. [Background technology]

[0002] A known manufacturing technique for circuit boards such as printed wiring boards is the build-up method, in which insulating layers and conductor layers are alternately stacked. As electronic devices become smaller and more powerful, semiconductor package substrates are increasingly manufactured using the build-up method, resulting in a demand for finer and denser wiring. Furthermore, the widespread use of smartphones and tablet PCs has led to a growing demand for thinner substrates, resulting in a need for thinner core materials and even thinner package substrates with coreless structures. However, thin package substrates are prone to warping, which can lead to problems during the mounting process. Therefore, build-up layers are required to have properties that reduce warping, such as a high modulus of elasticity and a low coefficient of thermal expansion. Resin compositions containing large amounts of inorganic fillers have been investigated (Patent Document 1). Meanwhile, in recent years, there has been an increasing demand for thinner, lighter, and more densely packed semiconductor components. To meet this demand, attention has been focused on using flexible circuit boards as substrates for semiconductor components. Flexible circuit boards are flexible and deformable, so they can be bent for mounting. Therefore, in order to achieve both bendability and a low thermal expansion coefficient, resin compositions containing epoxy resin, polyimide resin, maleimide resin, and inorganic filler have been investigated (Patent Document 2). Furthermore, insulating layers are generally required to have a low dielectric tangent and excellent smear removal properties, and for this reason, resin compositions containing maleimide resins having maleimide groups and long carbon chains have been investigated (Patent Documents 3 and 4). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-36349 [Patent Document 2] Japanese Patent Publication No. 2020-90570 [Patent Document 3] Japanese Patent Application Publication No. 2019-44128 [Patent Document 4] Japanese Patent Application Publication No. 2020-83898 Summary of the Invention [Problem to be solved by the invention]

[0004] However, when a resin composition contains a large amount of inorganic filler, the cured resin composition becomes brittle, which causes problems such as chipping of the cured resin from the edge when handling the package substrate. Furthermore, depending on the type of maleimide resin contained in the resin composition, the dielectric loss tangent may be reduced, but the tackiness may be increased.

[0005] Therefore, an object of the present invention is to provide a resin composition that can form a cured product that has good mechanical properties and is also excellent in smear removability and tackiness, despite having a low linear thermal expansion coefficient of the cured product. [Means for solving the problem]

[0006] As a result of extensive investigations, the present inventors have found that a resin composition containing a combination of specific epoxy resins and further containing an inorganic filler and a specific maleimide resin and / or polyimide resin has sufficient mechanical properties, specifically bending resistance, despite a low linear thermal expansion coefficient of a cured body of the resin composition, and is capable of solving the problem of resin chipping, and further has excellent smear removability and tackiness, thereby completing the present invention.

[0007] That is, the present invention includes the following inventions. [1] (A) an epoxy resin, (B) a maleimide resin and / or a polyimide resin, and (C) an inorganic filler; (A) component (A-1) Epoxy resin that is liquid at room temperature (A-2) a biphenol-skeleton epoxy resin, the ratio x / X of the total number of epoxy groups in component (A) X to the number of epoxy groups in component (A-1) x is 0.4 to 0.9; A resin composition, wherein the content of component (B) is 7 to 30% by mass, assuming that the resin component in the resin composition is 100% by mass. [2] The resin composition according to [1], wherein the maleimide resin of component (B) is a maleimide resin having a dimer acid skeleton. [3] The resin composition according to [1] or [2], wherein the polyimide resin of component (B) is a polyimide resin containing a structural unit represented by the following formula (b1):

[0008] [ka] [In formula (b1), R1 is a tetravalent group represented by the following formula (b1-1): R2 is a divalent group represented by the following formula (b1-2).

[0009] [ka] (In formula (b1-1), Ar 11 , Ar 12 , Ar 13 and Ar 14 each independently represents an aromatic ring which may have a substituent, L 11 , L 12 and L 13 each independently represents a divalent linking group, nc1 represents an integer greater than or equal to 0.)

[0010] [ka] (In formula (b1-2), Ar 21 , Ar 22 , Ar23 and Ar 24 each independently represents an aromatic ring which may have a substituent, L 21 , L 22 and L 23 each independently represents a divalent linking group, nc2 represents an integer equal to or greater than 1.) [4] In formula (b1-1), Ar 11 , Ar 12 , Ar 13 and Ar 14 are each independently an aromatic carbocyclic ring having 6 to 14 carbon atoms which may have a substituent, In formula (b1-2), Ar 21 , Ar 22 , Ar 23 and Ar 24 are each independently an aromatic carbon ring having 6 to 14 carbon atoms which may have a substituent. [3] The resin composition according to [3]. [5] In formula (b1-1), L 11 and L 13 is -O- and L 12 is an alkylene group which may have a substituent, In formula (b1-2), L 21 and L 23 is -O- and L 22 The resin composition according to [3] or [4], wherein is an alkylene group which may have a substituent. [6] The resin composition according to any one of [1] to [5], wherein the content of component (C) is 60 to 80 mass % when the total nonvolatile components in the resin composition is 100 mass %. [7] The resin composition according to any one of [1] to [6], further comprising (D) another thermosetting resin. [8] The resin composition according to [7], wherein the component (D) comprises at least one selected from the group consisting of a phenolic resin, a carbodiimide resin, a benzoxazine resin, and an active ester resin. [9] The resin composition according to any one of [1] to [8], further comprising (E) a curing accelerator.

[10] The resin composition according to any one of [1] to [9], wherein the coefficient of linear thermal expansion (CTE) of a cured product of the resin composition is 30 ppm / °C or less in the range of 25°C to 150°C.

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

[10] , which is used to form an insulating layer.

[12] A resin sheet comprising a support and a resin composition layer provided on the support, the resin composition layer comprising the resin composition according to any one of [1] to

[11] .

[13] A circuit board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to

[11] .

[14] A semiconductor device comprising the circuit board according to

[13] . [Effects of the Invention]

[0011] According to the present invention, there are provided a resin composition which provides a cured product having a low coefficient of linear thermal expansion and excellent mechanical properties and smear removability, and which is capable of exhibiting good tackiness before curing; a resin sheet having a resin composition layer containing the resin composition; a circuit board having an insulating layer formed from a cured product of the resin composition; and a semiconductor device including the circuit board. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention will be described below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be implemented with any modifications within the scope of the claims of the present invention and their equivalents.

[0013] [Resin composition] The resin composition of the present invention comprises (A) an epoxy resin, (B) a maleimide resin and / or a polyimide resin, and (C) an inorganic filler, (A) component (A-1) Epoxy resin that is liquid at room temperature (A-2) a biphenol-skeleton epoxy resin, the ratio x / X of the total number of epoxy groups in component (A) X to the number of epoxy groups in component (A-1) x is 0.4 to 0.9; The content of component (B) is 7 to 30% by mass, assuming the total mass of the resin component in the resin composition to be 100% by mass. Such a resin composition can form a cured product that has a low coefficient of linear thermal expansion, and is excellent in mechanical properties and smear removability. It can also form a resin composition that exhibits good tackiness in the uncured state.

[0014] The resin composition may further contain optional components such as (A-3) other epoxy resins other than the component (A-1) and the component (A-2), (D) other thermosetting resins, (E) curing accelerators, and (F) other additives, as necessary. Each component contained in the resin composition will be described in detail below.

[0015] <(A) Epoxy resin> The (A) epoxy resin contains (A-1) an epoxy resin that is liquid at room temperature and (A-2) a biphenol-skeleton epoxy resin, and may further contain (A-3) other epoxy resins.

[0016] <(A-1) Epoxy resin that is liquid at room temperature> Component (A-1) is an epoxy resin that is liquid at room temperature. "Liquid" means that it has fluidity at room temperature (20°C) and atmospheric pressure (0.1 MPa). Preferably, the viscosity measured using an E-type viscometer at atmospheric pressure, 25°C, and a cone rotation speed of 2.0 rpm is 1500 Pa s or less. An example of an E-type viscometer is the RE-85U E-type viscometer (cone rotor: 3°×R14) (manufactured by Toki Sangyo Co., Ltd.).

[0017] The epoxy resin (A-1) that is liquid at room temperature is preferably a liquid epoxy resin having two or more epoxy groups per molecule, and more preferably an aromatic liquid epoxy resin having two or more epoxy groups per molecule. In the present invention, aromatic epoxy resin means an epoxy resin having an aromatic ring in its molecule.

[0018] Preferred examples of the epoxy resin (A-1) that is liquid at room temperature include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol AF epoxy resins, naphthalene epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, phenol novolac epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane epoxy resins, cyclohexanedimethanol epoxy resins, glycidyl amine epoxy resins, and epoxy resins having a butadiene structure, with bisphenol A epoxy resins and bisphenol F epoxy resins being more preferred. The epoxy resin (A-1) may be used alone or in combination of two or more.

[0019] Specific examples of epoxy resins for component (A-1) include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "825", and "Epikote 828EL" (bisphenol A-type epoxy resins), "806H", "jER807", and "1750" (bisphenol F-type epoxy resins), "jER152" (phenol novolac-type epoxy resins), "630", and "630LSD" (glycidylamine-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; and "ZX-1059" (bisphenol A-type epoxy resins) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. Examples of epoxy resins include a mixture of epoxy resin and bisphenol F type epoxy resin, Nagase ChemteX's "EX-721" (glycidyl ester type epoxy resin), Daicel's "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) and "PB-3600" (epoxy resin having a butadiene structure), Nippon Steel & Sumikin Chemical's "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin), and Mitsubishi Chemical's "630LSD" (glycidylamine type epoxy resin). These may be used alone or in combination of two or more.

[0020] From the viewpoint of obtaining an insulating layer exhibiting good mechanical properties and a suppressed linear thermal expansion coefficient, the content of component (A-1) in the resin composition is preferably 10% by mass or more, more preferably 14% by mass or more, even more preferably 15% by mass or more or 16% by mass or more, when the resin components in the resin composition are taken as 100%. The upper limit of the content of component (A-1) is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less. In the present invention, the term "resin component" in relation to the resin composition refers to the non-volatile components constituting the resin composition excluding (C) the inorganic filler.

[0021] The content of component (A) in the resin composition, i.e., the total epoxy resins including component (A-1), component (A-2) and component (A-3) described below, is: The ratio (x / X) of [x, the total number of epoxy groups in component (A-1)] / [X, the total number of epoxy groups in component (A)] is 0.4 to 0.9, with the lower limit being preferably 0.42 or more, 0.43 or more, 0.44 or more, or 0.45 or more, and the upper limit being preferably 0.85 or less, 0.80 or less, 0.75, or 0.70 or less. By setting the content of component (A-1) in component (A) within this range, it is possible to realize a resin composition that exhibits well-balanced physical properties in terms of the mechanical properties of the cured product of the resin composition, the coefficient of linear thermal expansion, and tackiness in the uncured state.

[0022] <(A-2) Biphenol-based epoxy resin> The component (A-2) is an epoxy resin having a biphenol skeleton. By including the component (A-2) in the resin composition of the present invention together with the component (A-1), it is possible to obtain a resin composition having excellent mechanical properties and smear removability. Here, the term "biphenol skeleton" refers to a skeleton that at least partially contains a divalent structure obtained by removing two hydroxy groups from a biphenol that may have a substituent. The substituent that the biphenol may have is not particularly limited as long as the effects of the present invention are achieved, and examples thereof include a halogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, and a monovalent heterocyclic group. Examples of halogen atoms used as substituents include fluorine, chlorine, bromine, and iodine atoms. The alkyl group used as a substituent may be either linear or branched. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 10, and even more preferably 1 to 8 carbon atoms. The alkenyl group used as a substituent may be either linear or branched. The alkenyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 10, and even more preferably 2 to 8 carbon atoms. The cycloalkyl group used as a substituent preferably has 3 to 12 carbon atoms, more preferably 3 to 10 carbon atoms. The alkoxy group used as a substituent may be either linear or branched. The alkoxy group preferably has 1 to 12 carbon atoms, more preferably 1 to 10, and even more preferably 1 to 8 carbon atoms. The cycloalkyloxy group used as a substituent preferably has 3 to 12 carbon atoms, more preferably 3 to 10 carbon atoms. The aryl group used as a substituent preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms. The aryloxy group used as a substituent preferably has 6 to 14 carbon atoms, more preferably 6 to 10. The arylalkyl group used as a substituent preferably has 7 to 15 carbon atoms, more preferably 7 to 11. The arylalkoxy group used as a substituent preferably has 7 to 15 carbon atoms, more preferably 7 to 11. The monovalent heterocyclic group used as a substituent refers to a group obtained by removing one hydrogen atom from the heterocycle of a heterocyclic compound. The monovalent heterocyclic group preferably has 3 to 15 carbon atoms, more preferably 3 to 9 carbon atoms. The monovalent heterocyclic group also includes a monovalent aromatic heterocyclic group (heteroaryl group). Among these, from the viewpoint of further enjoying the effects of the present invention, the substituent that the biphenol skeleton may have is preferably one or more selected from a halogen atom, an alkyl group, an alkoxy group, an aryl group, and an aryloxy group, and more preferably one or more selected from an alkyl group and an aryl group. When the biphenol skeleton has a substituent, the number of the substituents per biphenyl structure is preferably 1 or more, more preferably 2 or more, 3 or more, or 4 or more, from the viewpoint of being able to further enjoy the effects of the present invention, and the upper limit is preferably 6 or less. Among these, it is preferable that the component (A-2) contains at least one of a di-substituted biphenol skeleton having two substituents per biphenyl structure, a tri-substituted biphenol skeleton having three substituents per biphenyl structure, and a tetra-substituted biphenol skeleton having four substituents per biphenyl structure.

[0023] The biphenol skeleton in component (A-2) may contain other structures as long as it at least partially contains a divalent structure obtained by removing two hydroxy groups from an optionally substituted biphenol. For example, the biphenol skeleton may contain alkylene groups and / or arylene groups in addition to the divalent structure obtained by removing two hydroxy groups from an optionally substituted biphenol. From the viewpoint of being able to enjoy the effects of the present invention more effectively, it is preferable that the biphenol skeleton in component (A-2) at least partially contains a divalent structure formed by removing two hydroxy groups from 4,4'-biphenol which may have a substituent.

[0024] From the viewpoint of being able to further enjoy the effects of the present invention when combined with the above-mentioned component (A-1), the component (A-2) is preferably a di-substituted biphenol-type epoxy resin, a tri-substituted biphenol-type epoxy resin, a tetra-substituted biphenol-type epoxy resin, or the like. Of these, a di-substituted biphenol-type epoxy resin, a tri-substituted biphenol-type epoxy resin, or a tetra-substituted biphenol-type epoxy resin is preferred, and a dialkyl-substituted biphenol-type epoxy resin, a trialkyl-substituted biphenol-type epoxy resin, or a tetraalkyl-substituted biphenol-type epoxy resin is more preferred.

[0025] Of these, the compound represented by the following general formula (1) can be suitably used as the component (A-2).

[0026] [ka] In the formula, R represents a hydrogen atom or a methyl group, and n represents an integer of 0 to 10.

[0027] In general formula (1), n ​​is 0 to 10, and preferably 0 to 5. When the value of n is within the above range, it is easy to realize a resin composition that exhibits an appropriate melt viscosity, which is preferable.

[0028] Component (A-2) may be a mixture of multiple compounds having different values ​​of n in general formula (1). In addition, in such a mixture, it is not excluded that the mixture contains an epoxy resin in which the value of n in general formula (1) exceeds 10.

[0029] A specific example of the compound represented by the above formula (1) is "YX4000H" (tetramethylbiphenol type epoxy resin, epoxy equivalent weight 194 g / eq.) manufactured by Mitsubishi Chemical Corporation.

[0030] From the viewpoint of obtaining good mechanical properties and smear removability, the content of component (A-2) is preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 7% by mass or more, 8% by mass or more, or 10% by mass or more, when the resin component in the resin composition is taken as 100% by mass. From the viewpoint of obtaining the desired effects of the present invention significantly, the upper limit of the content of component (A-2) is preferably 30% by mass or less, more preferably 25% by mass or less.

[0031] <(A-3) Other epoxy resins> The resin composition of the present invention may contain, as an optional component, an epoxy resin other than components (A-1) and (A-2), as long as the effects of the present invention are not impaired. That is, as component (A-3), an epoxy resin that is solid at room temperature and does not contain a biphenol skeleton can be used. The other epoxy resin (A-3) preferably has two or more epoxy groups per molecule. As the component (A-3), bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, and tetraphenylethane-type epoxy resins are preferred, with naphthalene-type epoxy resins being more preferred. Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin), and "EPPN-502H" (trisphenol type epoxy resin) and "NC7000L" (naphthol novolac type epoxy resin), all manufactured by DIC Corporation. Examples of epoxy resins include "NC3000H," "NC3000," "NC3000L," and "NC3100" (biphenyl-type epoxy resins), Nippon Steel & Sumikin Chemical's "ESN-475V" (naphthalene-type epoxy resin) and "ESN485" (naphthol novolac-type epoxy resin), Mitsubishi Chemical's "YL6121" (biphenyl-type epoxy resin), "YX8800" (anthracene-type epoxy resin), Osaka Gas Chemical's "PG-100" and "CG-500," Mitsubishi Chemical's "YL7760" (bisphenol AF-type epoxy resin) and "YL7800" (fluorene-type epoxy resin), Mitsubishi Chemical's "jER1010" (solid bisphenol A-type epoxy resin), and "jER1031S" (tetraphenylethane-type epoxy resin). These may be used alone or in combination of two or more.

[0032] The upper limit of the content of the (A-3) component in the resin composition is preferably 15% by mass or less, more preferably 12% by mass or less, and even more preferably 10% by mass or less, when the resin components in the resin composition are taken as 100%.

[0033] When an epoxy resin that is liquid at room temperature and an epoxy resin that is solid at room temperature are used in combination as component (A), the ratio by mass between them (liquid epoxy resin:solid epoxy resin) is preferably in the range of 1:1 to 1:20, more preferably 1:1 to 1:15, and even more preferably 1:1 to 1:10. By setting the ratio between the liquid epoxy resin and the solid epoxy resin in this range, the resin composition can be used in the form of a resin sheet, whereby it is possible to obtain a cured product with appropriate adhesiveness and flexibility and sufficient breaking strength.

[0034] From the viewpoint of obtaining an insulating layer exhibiting good mechanical strength, the content of component (A) (total epoxy resin) in the resin composition is preferably 15% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more or 30% by mass or more, based on 100% by mass of the resin components in the resin composition. The upper limit of the content of component (A) is not particularly limited as long as the effects of the present invention are achieved, but is preferably 50% by mass or less, more preferably 48% by mass or less, 46% by mass or less, or 45% by mass or less.

[0035] <(B) Maleimide Resin and / or Polyimide Resin> The resin composition of the present invention can contain a maleimide resin as component (B). The (B) maleimide resin has one or more maleimide groups in one molecule. The (B) maleimide resin may be used alone or in combination of two or more.

[0036] The (B) maleimide resin may be an aromatic maleimide resin having a maleimide group directly bonded to an aromatic ring, or an aliphatic maleimide resin having no maleimide group directly bonded to an aromatic ring. When the (B) maleimide resin includes an aliphatic maleimide resin, the aliphatic maleimide resin preferably includes a maleimide resin having a carbon skeleton derived from a dimer acid. When the (B) maleimide resin includes an aromatic maleimide resin, the aromatic maleimide resin preferably includes a maleimide resin having one or more skeletons selected from a biphenyl skeleton and an indane skeleton. Among these, from the viewpoint of obtaining a resin composition exhibiting good mechanical properties, it is preferable to include a maleimide resin having a carbon skeleton derived from a dimer acid.

[0037] A carbon skeleton derived from a dimer acid refers to a carbon skeleton obtained by removing the two terminal carboxyl groups (-COOH) of a dimer acid, or a carbon skeleton obtained by replacing the two terminal carboxyl groups (-COOH) with methylene groups (-CH2-). Dimer acids are known compounds obtained by dimerizing unsaturated fatty acids (preferably those having 11 to 22 carbon atoms, more preferably those having 14 to 20 carbon atoms, and particularly preferably those having 18 carbon atoms), and their industrial production process is largely standardized in the industry. Dimer acids are particularly readily available, primarily consisting of 36-carbon dimer acids obtained by dimerizing 18-carbon unsaturated fatty acids such as oleic acid and linoleic acid, which are inexpensive and readily available. Furthermore, dimer acids may contain arbitrary amounts of monomer acids, trimer acids, other polymerized fatty acids, etc., depending on the production method, degree of purification, etc. Furthermore, although double bonds remain after the polymerization reaction of unsaturated fatty acids, in this specification, hydrogenated products obtained by further hydrogenation to reduce the degree of unsaturation are also included in the term "dimer acid."

[0038] The maleimide resin having a carbon skeleton derived from a dimer acid preferably includes a maleimide resin represented by the following formula (B1).

[0039] [ka]

[0040] (In formula (B1), n1+1 Xs each independently represent a divalent organic group consisting of five or more skeletal atoms selected from carbon atoms, nitrogen atoms (not forming an imide), oxygen atoms, and sulfur atoms, and non-skeletal atoms selected from hydrogen atoms and halogen atoms, and at least one of the n+1 Xs represents a divalent hydrocarbon group derived from a dimer acid; n1 Ys each independently represent a tetravalent organic group consisting of five or more skeletal atoms selected from carbon atoms, nitrogen atoms (not forming an imide), oxygen atoms, and sulfur atoms, and non-skeletal atoms selected from hydrogen atoms and halogen atoms; n1 represents an integer of 0 or 1 or more.

[0041] In formula (B1), n1+1 Xs each independently represent a divalent organic group consisting of five or more (preferably 5 to 200, more preferably 5 to 100, and even more preferably 5 to 50) skeletal atoms selected from carbon atoms, nitrogen atoms (not forming imides), oxygen atoms, and sulfur atoms, and non-skeletal atoms selected from hydrogen atoms and halogen atoms, and at least one of the n+1 Xs represents a divalent hydrocarbon group derived from a dimer acid.

[0042] The divalent hydrocarbon group derived from a dimer acid means a divalent hydrocarbon group obtained by removing the two terminal carboxy groups (-COOH) of a dimer acid, or a divalent hydrocarbon group obtained by replacing the two terminal carboxy groups (-COOH) with methylene groups (-CH-).

[0043] The n1+1 Xs may have a divalent organic group other than a divalent hydrocarbon group derived from a dimer acid, but when the n1+1 Xs are taken as 100 mol%, it is preferable that 30 mol% or more of them are divalent hydrocarbon groups derived from a dimer acid, more preferably 60 mol% or more are divalent hydrocarbon groups derived from a dimer acid, even more preferably 90 mol% or more are divalent hydrocarbon groups derived from a dimer acid, and even more preferably that (all) the n1+1 Xs are divalent hydrocarbon groups derived from a dimer acid.

[0044] The divalent organic group other than the divalent hydrocarbon group derived from a dimer acid among the n1+1 Xs may be a divalent organic group without an aromatic ring, or may be a divalent organic group with an aromatic ring.

[0045] In formula (B1), n1 Ys each independently represent a tetravalent organic group consisting of five or more (preferably 5 to 200, more preferably 5 to 100, and even more preferably 5 to 50) skeletal atoms selected from carbon atoms, nitrogen atoms (not forming imides), oxygen atoms, and sulfur atoms, and non-skeletal atoms selected from hydrogen atoms and halogen atoms. The tetravalent organic group represented by Y may be a tetravalent organic group without an aromatic ring, or may be a tetravalent organic group with an aromatic ring.

[0046] In one embodiment, the tetravalent organic group represented by Y is preferably a tetravalent group selected from the following formulae (Y1) to (Y5).

[0047] [ka]

[0048] (In formulas (Y1) to (Y5), Ring Y 11 , ring Y 21 , ring Y 22 , ring Y 31 , ring Y 32 , ring Y 33 , ring Y 41 , ring Y 42 , ring Y 43, ring Y 44 , ring Y 51 , ring Y 52 , ring Y 53 , ring Y 54 and ring Y 55 each independently represents an aromatic ring which may have a substituent or a non-aromatic ring which may have a substituent; Y 2a , Y 3a , Y 3b , Y 4a , Y 4b , Y 4c , Y 5a , Y 5b , Y 5c and Y 5d are each independently a single bond, -C(R y )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-; R y each independently represents a hydrogen atom or an alkyl group which may be substituted with a halogen atom, or two R y are bonded together to form a non-aromatic ring which may have a substituent; * indicates binding site; The two bonding sites on the same ring represented by * are bonding sites to two adjacent carbon atoms on the ring.

[0049] In the formulae (Y1) to (Y5), the ring Y 11 , ring Y 21 , ring Y 22 , ring Y 31 , ring Y 32 , ring Y 33 , ring Y 41 , ring Y 42 , ring Y 43 , ring Y 44 , ring Y 51 , ring Y 52 , ring Y 53 , ring Y 54 and ring Y 55each independently represents an aromatic ring which may have a substituent, or a non-aromatic ring which may have a substituent. These cyclic structures are preferably aromatic rings which may have a substituent, more preferably benzene rings which may have a substituent, and even more preferably benzene rings which may be substituted with an alkyl group.

[0050] Ring Y 11 , ring Y 21 , ring Y 22 , ring Y 31 , ring Y 32 , ring Y 33 , ring Y 41 , ring Y 42 , ring Y 43 , ring Y 44 , ring Y 51 , ring Y 52 , ring Y 53 , ring Y 54 and ring Y 55 The substituents that may be possessed by are not particularly limited, but include, for example, halogen atoms, -NO2, -CN, -COH, -OH, -SH, -NH2, -COOH, -R c , -COR c , -OR c , -SR c , -SOR c , -SO2R c , -NHR c , -NR c 2. -COOR c , -OCOR c , -CONH2, -CONHR c , -CONR c 2, -NHCOR c (However, R c is as described above.)

[0051] In formulas (Y1) to (Y5), Y 2a , Y 3a , Y 3b , Y 4a , Y 4b , Y 4c , Y 5a , Y 5b , Y 5c and Y 5dare each independently a single bond, -C(R y )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-, and in one embodiment, preferably represents a single bond, -C(R y )2-, or -O-.

[0052] R y each independently represents a hydrogen atom or an alkyl group which may be substituted with a halogen atom, or two R y are bonded together to form a non-aromatic ring which may have a substituent. c The alkyl group in R y are each independently preferably a hydrogen atom or an alkyl group which may be substituted with a halogen atom; more preferably a hydrogen atom or a methyl group which may be substituted with a halogen atom; even more preferably a hydrogen atom, a methyl group, or a trifluoromethyl group; and particularly preferably a hydrogen atom or a methyl group.

[0053] R y The substituents that may be possessed by are not particularly limited, but include, for example, halogen atoms, -NO2, -CN, -COH, -OH, -SH, -NH2, -COOH, -R c , -COR c , -OR c , -SR c , -SOR c , -SO2R c , -NHR c , -NR c 2. -COOR c , -OCOR c , -CONH2, -CONHR c , -CONR c 2, -NHCOR c (However, R c is as described above.)

[0054] In formula (B1), n1 represents 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 10, and more preferably 0.

[0055] The maleimide resin having a carbon skeleton derived from a dimer acid may be used alone or in combination of two or more.

[0056] Commercially available maleimide resins having a carbon skeleton derived from dimer acid include, for example, "BMI-689," "BMI-1500," "BMI-1700," and "BMI-3000J" manufactured by Designer Molecules Inc., and "SLK-6895-T90" manufactured by Shin-Etsu Chemical Co., Ltd.

[0057] The aromatic maleimide resin may be, for example, a maleimide resin represented by formula (B2).

[0058] [ka]

[0059] (In formula (B2), R 10 each independently represents a hydrogen atom or an alkyl group optionally substituted with a halogen atom; each ring D independently represents an aromatic carbocyclic ring which may have a substituent; n2 represents an integer of 1 or greater; The n2 units may be the same or different for each unit.

[0060] In formula (B2), R 10 are each independently a hydrogen atom or an alkyl group which may be substituted with a halogen atom. c The alkyl group in R 10 are each independently preferably a hydrogen atom or an alkyl group; more preferably a hydrogen atom or a methyl group; and even more preferably a hydrogen atom.

[0061] In formula (B2), each ring D independently represents an aromatic carbocyclic ring which may have a substituent. 11 , ring Y 21 , ring Y 22 , ring Y 31 , ring Y 32 , ring Y 33 , ring Y 41 , ring Y 42 , ring Y 43 , ring Y 44 , ring Y 51 , ring Y 52 , ring Y 53 , ring Y 54 and ring Y 55 The "substituent" in ring D may be the same as the aromatic carbocyclic ring described in the section on the aromatic ring in 11 , ring Y 21 , ring Y 22 , ring Y 31 , ring Y 32 , ring Y 33 , ring Y 41 , ring Y 42 , ring Y 43 , ring Y 44 , ring Y 51 , ring Y 52 , ring Y 53 , ring Y 54 and ring Y 55 The substituents may be the same as those in the "aromatic ring which may have a substituent" in the above. Ring D preferably represents a benzene ring which may have a substituent; more preferably represents a benzene ring which may be substituted with a group selected from an alkyl group and an aryl group; and particularly preferably represents an (unsubstituted) benzene ring.

[0062] In formula (B2), n2 represents an integer of 1 or more, and is preferably an integer of 1 to 10.

[0063] The maleimide resin having a biphenyl skeleton preferably includes a maleimide resin represented by the following formula (B3).

[0064] [ka]

[0065] (In formula (B3), R 20 each independently represents a hydrogen atom or an alkyl group optionally substituted with a halogen atom; Ring E, ring F, and ring G each independently represent an aromatic carbocyclic ring which may have a substituent; n3 represents an integer equal to or greater than 1; The n3 units may be the same or different for each unit.

[0066] In formula (B3), R 20 are each independently a hydrogen atom or an alkyl group which may be substituted with a halogen atom. c The alkyl group in R 20 are each independently preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0067] In formula (B3), ring E, ring F, and ring G each independently represent an aromatic carbocyclic ring which may have a substituent. 11 , ring Y 21 , ring Y 22 , ring Y 31 , ring Y 32 , ring Y 33 , ring Y 41 , ring Y 42 , ring Y 43 , ring Y 44 , ring Y 51 , ring Y 52 , ring Y 53 , ring Y 54 and ring Y 55 It may be the same as the aromatic carbocyclic ring explained in the section on the aromatic ring in 1. Ring E, ring F and ring G are preferably benzene rings which may have a substituent, more preferably benzene rings which may be substituted with a group selected from an alkyl group and an aryl group, and further preferably (unsubstituted) benzene rings.

[0068] The substituents that may be possessed by ring E, ring F, and ring G are not particularly limited, but examples thereof include a halogen atom, -NO2, -CN, -COH, -OH, -SH, -NH2, -COOH, -R c , -COR c , -OR c , -SR c , -SOR c , -SO2R c , -NHR c , -NR c 2. -COOR c , -OCOR c , -CONH2, -CONHR c , -CONR c 2, -NHCOR c (However, R c is as described above).

[0069] In formula (B3), n3 represents an integer of 1 or more, and is preferably an integer of 1 to 10.

[0070] Commercially available maleimide resins having a biphenyl skeleton include, for example, "MIR-3000-70MT" and "MIR-5000-60T" manufactured by Nippon Kayaku Co., Ltd.

[0071] The maleimide resin having a biphenyl skeleton may be used alone or in combination of two or more.

[0072] The maleimide resin having an indane skeleton preferably includes a maleimide resin represented by the following formula (B4).

[0073] [ka]

[0074] (In formula (B4), R 30 each independently represents an alkyl group; Ring H and ring I each independently represent an aromatic carbocyclic ring which may have a substituent; n4 represents an integer of 1 or greater; The n4 units may be the same or different for each unit.

[0075] In formula (B4), R 30 R each independently represents an alkyl group. 30 is preferably a methyl group.

[0076] In formula (B4), rings H each independently represent an aromatic ring which may have a substituent. Ring H is preferably a benzene ring which may have a substituent, more preferably a benzene ring which may have a substituent with an alkyl group, and even more preferably a benzene ring substituted with an alkyl group.

[0077] In formula (B4), each ring I independently represents an aromatic ring which may have a substituent. Ring I is preferably a benzene ring which may have a substituent, more preferably a benzene ring which may have an alkyl group, and further preferably an (unsubstituted) benzene ring.

[0078] Substituents that may be carried by ring H and ring I include, but are not limited to, halogen atoms, -NO2, -CN, -COH, -OH, -SH, -NH2, -COOH, -R c , -COR c , -OR c , -SR c , -SOR c , -SO2R c , -NHR c , -NR c 2. -COOR c , -OCOR c , -CONH2, -CONHR c , -CONR c 2, -NHCOR c (However, R c is as described above.)

[0079] In formula (B4), n4 represents an integer of 1 or more, and is preferably an integer of 1 to 20.

[0080] A maleimide resin having an indane skeleton can be produced, for example, by the method described in the Japan Institute of Invention and Innovation's Technical Journal No. 2020-500211 or a method equivalent thereto (see Synthesis Example 1 in the Examples section below).

[0081] The maleimide resin having an indane skeleton may be used alone or in combination of two or more.

[0082] The maleimide group equivalent of the (B) maleimide resin is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, even more preferably 150 g / eq. or more, 200 g / eq. or more, 250 g / eq. or more, or 300 g / eq. or more, and its upper limit is preferably 2,000 g / eq. or less, more preferably 1,000 g / eq. or less, even more preferably 800 g / eq. or less, 600 g / eq. or less, 500 g / eq. or less, or 450 g / eq. or less. The maleimide group equivalent is the mass of the (B) maleimide resin per 1 molar equivalent of maleimide groups.

[0083] The molecular weight of the (B) maleimide resin is preferably less than 5,000, more preferably less than 3,000, even more preferably less than 2,000, less than 1,500, less than 1,200, or less than 1,000. The lower limit is not particularly limited, but can be, for example, 300 or more, 400 or more, 500 or more, etc.

[0084] The resin composition of the present invention can contain a polyimide resin as component (B). Examples of (B) polyimide resins include those containing a structural unit represented by the following formula (b1) (hereinafter also referred to as "structural unit (b1)") (hereinafter sometimes referred to as "first polyimide resin"). In the first polyimide resin, the number of structural units (b1) is 1 or more and is not particularly limited, but may be 100 or less, 50 or less, or 30 or less. When there are multiple structural units (b1), the structural units (b1) may be linked to each other as repeating units, or they may not be linked to each other. When the multiple structural units (b1) are not linked to each other, it is preferable that another structural unit (for example, a structural unit represented by formula (b2) described below) is present between them.

[0085] The structural unit (b1) is represented by the following formula (b1).

[0086] [ka] [In formula (b1), R1 is a tetravalent group represented by the following formula (b1-1): R2 is a divalent group represented by the following formula (b1-2).

[0087] [ka] (In formula (b1-1), Ar 11 , Ar 12 , Ar 13 and Ar 14 each independently represents an aromatic ring which may have a substituent, L 11 , L 12 and L 13 each independently represents a divalent linking group, nc1 represents an integer greater than or equal to 0.)

[0088] [ka] (In formula (b1-2), Ar 21 , Ar22 , Ar 23 and Ar 24 each independently represents an aromatic ring which may have a substituent, L 21 , L 22 and L 23 each independently represents a divalent linking group, nc2 represents an integer equal to or greater than 1.)

[0089] In formula (b1-1), Ar 11 , Ar 12 , Ar 13 and Ar 14 The aromatic ring represented by (hereinafter also referred to as "aromatic ring C") is preferably an aromatic ring having 6 to 100 carbon atoms, more preferably 6 to 50 carbon atoms, even more preferably 6 to 100 carbon atoms, and even more preferably 6 to 50 carbon atoms. Therefore, in a preferred embodiment, in formula (b1-1), Ar 11 , Ar 12 , Ar 13 and Ar 14are each independently an aromatic carbocyclic ring having 6 to 14 carbon atoms, which may have a substituent. Here, the term "aromatic ring" as used herein means a ring that conforms to the Huckel rule, in which the number of electrons contained in the π electron system on the ring is 4n+2 (n is a natural number), and includes a monocyclic aromatic ring and a fused aromatic ring in which two or more monocyclic aromatic rings are fused together. The aromatic ring may be a carbocyclic ring or a heterocyclic ring. Examples of aromatic rings include monocyclic aromatic rings such as a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring; fused rings in which two or more monocyclic aromatic rings are fused, such as a naphthalene ring, an anthracene ring, a benzofuran ring, an isobenzofuran ring, an indole ring, an isoindole ring, a benzothiophene ring, a benzimidazole ring, an indazole ring, a benzoxazole ring, a benzisoxazole ring, a benzothiazole ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, an acridine ring, a quinazoline ring, a cinnoline ring, and a phthalazine ring; and fused rings in which one or more monocyclic aromatic rings are fused to one or more monocyclic non-aromatic rings, such as an indane ring, a fluorene ring, and a tetralin ring. Of these, aromatic carbon rings having 6 to 14 carbon atoms are preferred, and benzene rings are more preferred.

[0090] In formula (b1-1), Ar 11 , Ar 12 , Ar 13 and Ar 14 When represents an aromatic ring having a substituent, the number of the substituents is not limited. Such substituents (hereinafter also referred to as "substituents S") may be, independently of one another, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a monovalent heterocyclic group, an alkylidene group, an amino group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group, and an oxo group.

[0091] In formula (b1-1), L 11 , L 12 and L13 The divalent linking group represented by is preferably a divalent group consisting of one or more (e.g., 1 to 3000, 1 to 1000, 1 to 100, or 1 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, and silicon atoms. Examples of the divalent linking group include -SO2-, -CO-, -COO-, -O-, -S-, -O-C6H4-O- (wherein -C6H4- represents a phenylene group), -O-C6H4-C(CH3)2-C6H4-O-, and -COO-(CH2) q -OCO- (wherein q represents an integer of 1 to 20), -COO-H2C-HC(-OC(=O)-CH3)-CH2-OCO-, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a heteroarylene group, -C(=O)-, -C(=O)-O-, -NR 0 -(where R 0 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) and —C(═O)—NR 0 -. As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferred, an alkylene group having 1 to 6 carbon atoms is more preferred, and an alkylene group having 1 to 5 carbon atoms or an alkylene group having 1 to 4 carbon atoms is even more preferred. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a dimethylmethylene group, and a dimethylmethylene group is preferred. As the alkenylene group, an alkenylene group having 2 to 10 carbon atoms is preferred, an alkenylene group having 2 to 6 carbon atoms is more preferred, and an alkenylene group having 2 to 5 carbon atoms is even more preferred. As the arylene group or heteroarylene group, an arylene group or heteroarylene group having 6 to 20 carbon atoms is preferred, and an arylene group or heteroarylene group having 6 to 10 carbon atoms is more preferred. The alkyl group, alkylene group, alkenylene group, alkynylene group, arylene group, and heteroarylene group may further have a substituent. Examples of the substituent are the same as the examples of the substituent S. 11 , L 12 and L 13 Preferably, the divalent linking group represented by does not contain an aromatic ring. 11 and a divalent linking group represented by L13 and the divalent linking group represented by 11 and a divalent linking group represented by L 12 In a preferred embodiment, in formula (b1-1), L 11 and L 13 is -O- and L 12 is an alkylene group which may have a substituent, and in a more preferred embodiment, in formula (b1-1), Ar 11 , Ar 12 , Ar 13 and Ar 14 are each independently an aromatic carbocyclic ring having 6 to 14 carbon atoms which may have a substituent, and in formula (b1-1), L 11 and L 13 is -O- and L 12 In a more preferred embodiment, in formula (b1-1), L 11 and L 13 is -O- and L 12 is a dimethylmethylene group.

[0092] In formula (b1-2), Ar 21 , Ar 22 , Ar 23 and Ar 24 Examples of the aromatic ring represented by and the substituent that the aromatic ring may have are the same as the examples of the aromatic ring C and the substituent S, respectively. Therefore, in a preferred embodiment, in formula (b1-2), Ar 21 , Ar 22 , Ar 23 and Ar 24 are each independently an aromatic carbocyclic ring having 6 to 14 carbon atoms which may have a substituent. 21 and L 23 is -O- and L 22 is an alkylene group which may have a substituent, and in a more preferred embodiment, in formula (b1-2), Ar 21 , Ar 22 , Ar 23 and Ar 24are each independently an aromatic carbocyclic ring having 6 to 14 carbon atoms which may have a substituent, and in formula (b1-2), L 21 and L 23 is -O- and L 22 In a more preferred embodiment, in formula (b1-2), L 21 and L 23 is -O- and L 22 is a dimethylmethylene group. 11 , Ar 12 , Ar 13 and Ar 14 are each independently an aromatic carbocyclic ring having 6 to 14 carbon atoms which may have a substituent, and in formula (b1-2), Ar 21 , Ar 22 , Ar 23 and Ar 24 are each independently an aromatic carbocyclic ring having 6 to 14 carbon atoms which may have a substituent. 11 and L 13 is -O- and L 12 is an alkylene group which may have a substituent, and in formula (b1-2), L 21 and L 23 is -O- and L 22 In a more particularly preferred embodiment, in formula (b1-1), Ar 11 , Ar 12 , Ar 13 and Ar 14 are each independently an aromatic carbocyclic ring having 6 to 14 carbon atoms which may have a substituent, and in formula (b1-2), Ar 21 , Ar 22 , Ar 23 and Ar 24 are each independently an aromatic carbocyclic ring having 6 to 14 carbon atoms which may have a substituent, and in formula (b1-1), L 11 and L 13 is -O- and L 12is an alkylene group which may have a substituent, and in formula (b1-2), L 21 and L 23 is -O- and L 22 is an alkylene group which may have a substituent.

[0093] In formula (b1-1), nc1 preferably represents an integer of 1 or greater. The upper limit of the integer represented by nc1 is not particularly limited, but may be 50, 40, 30, or 20, for example.

[0094] In formula (b1-2), nc2 preferably represents an integer of 2 or greater. The upper limit of the integer represented by nc2 is not particularly limited, but may be, for example, 60, 50, 40, or 30. In certain embodiments, the integer represented by nc2 in formula (b1-1) is greater than the integer represented by nc1 and less than nc1+5. In specific embodiments, in formula (b1-1), nc1 is 1 and nc2 is 2.

[0095] The structural unit (b1) can be obtained, for example, by a known method for producing a polyimide resin, typically by imidizing a monomer composition containing a tetracarboxylic dianhydride and a diamine compound through polymerization, or by imidizing a monomer composition containing a tetracarboxylic dianhydride and a diisocyanate compound through polymerization. Note that the first polyimide resin may partially contain a polyamic acid structure that may be generated during the imidization process.

[0096] In the specific embodiment, the structural unit (b1) can be obtained, for example, by reacting 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (a compound represented by the following formula (bI); hereinafter, also referred to as "BPADA") with 4,4'-[1,4-phenylenebis[(1-methylethylidene)-4,1-phenyleneoxy]]bisbenzenamine (a compound represented by the following formula (bII); hereinafter, also referred to as "BPPAN"). That is, in the structural unit (b1), R1 is a skeleton derived from BPADA, and R2 is a skeleton derived from BPPAN.

[0097] [ka]

[0098] [ka]

[0099] The first polyimide resin may further include a structural unit represented by the following formula (b2) (hereinafter also referred to as "structural unit (b2)"). Accordingly, in one embodiment, the first polyimide resin is a resin further including a structural unit represented by the following formula (b2). In the first polyimide resin, the number of structural units (b2) is 0 or more, and is not particularly limited, but may be 100 or less, 50 or less, or 30 or less. The structural unit (b2) may be linked to the group R2 of the structural unit (b1) via the nitrogen atom of the imide group, or may not be linked to the structural unit (b1). When there are multiple structural units (b2), the structural units (b2) may be linked to each other as repeating units, or may not be linked to each other. When the multiple structural units (b2) are not linked to each other, it is preferable that another structural unit (e.g., the structural unit (b1)) is interposed between them.

[0100] The structural unit (b2) is represented by the following formula (b2).

[0101] [ka] (In formula (b2), R3 represents a tetravalent aliphatic group which may have a substituent or a tetravalent aromatic group which may have a substituent; R4 represents a divalent aliphatic group which may have a substituent or a divalent aromatic group which may have a substituent, provided that when R3 is the same as R1, R4 is different from R2, and when R4 is the same as R2, R3 is different from R1.

[0102] In formula (b2), the tetravalent aliphatic group represented by R3 contains at least a carbon atom and is preferably a tetravalent group consisting of one or more (e.g., 1 to 3,000, 1 to 1,000, 1 to 100, or 1 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, and silicon atoms. In formula (b2), the tetravalent aliphatic group represented by R3 is more preferably a tetravalent aliphatic group having 1 to 100 carbon atoms, and even more preferably 1 to 50 carbon atoms. In formula (b2), when R3 represents a tetravalent aliphatic group having a substituent, examples of the substituent are the same as the examples of the substituent S.

[0103] In formula (b2), the tetravalent aromatic group represented by R3 is preferably a tetravalent aromatic group having 6 to 100 carbon atoms, more preferably 6 to 50 carbon atoms, and even more preferably a tetravalent aromatic hydrocarbon group having 6 to 100 carbon atoms, and even more preferably 6 to 50 carbon atoms. The aromatic group contains at least an aromatic ring. Examples of the aromatic ring contained in the aromatic group include Ar in formula (b1-1). 11 , Ar 12 , Ar 13 and Ar 14 In formula (b2), when R3 represents a tetravalent aromatic group having a substituent, examples of the substituent are the same as the examples of the substituent S.

[0104] Examples of the tetravalent aromatic group represented by R3 include a group obtained by removing two acid anhydride groups from a tetracarboxylic acid dianhydride having an aromatic group which may have a substituent. The aromatic group contains at least an aromatic ring. Examples of the aromatic ring contained in the aromatic group are the same as the examples of the aromatic ring C. When the aromatic group has a substituent, examples of the substituent are the same as the examples of the substituent S. Specific examples of tetracarboxylic acid dianhydrides having an aromatic group which may have a substituent include BPADA, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, and 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride.

[0105] In formula (b2), the divalent aliphatic group represented by R4 contains at least a carbon atom and is preferably a divalent group consisting of one or more (e.g., 1 to 3,000, 1 to 1,000, 1 to 100, or 1 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, and silicon atoms. In formula (b2), the divalent aliphatic group represented by R4 is more preferably a divalent aliphatic group having 1 to 100 carbon atoms, and even more preferably 1 to 50 carbon atoms. In formula (b2), when R4 represents a divalent aliphatic group having a substituent, examples of the substituent are the same as the examples of the substituent S, for example, an alkyl group having 1 to 6 carbon atoms. Therefore, in one embodiment, R4 is a divalent aliphatic group which may have a substituent, and one of the substituents is an alkyl group having 1 to 6 carbon atoms. In a specific embodiment, R4 is a divalent aliphatic group which may have a substituent, and is a divalent group obtained by removing two amino groups from isophoronediamine.

[0106] When R4 represents a divalent aliphatic group which may have a substituent, it may be a group obtained by removing two amino groups from a diamine compound having an aliphatic group which may have a substituent selected from 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine. These diamine compounds are characterized in that the aliphatic group is linear.

[0107] When R4 represents a divalent aliphatic group which may have a substituent, it may be a group obtained by removing two amino groups from a diamine compound having an aliphatic group which may have a substituent selected from 1,2-diaminopropane, 1,2-diamino-2-methylpropane, 1,3-diamino-2-methylpropane, 1,3-diamino-2,2-dimethylpropane, 1,3-diaminopentane, and 1,5-diamino-2-methylpentane. These diamine compounds are characterized in that the aliphatic group is branched.

[0108] When R4 represents a divalent aliphatic group which may have a substituent, examples thereof include 5-amino-1,3,3-trimethylcyclohexanemethylamine (isophoronediamine), 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-cyclohexanebis(methylamine), 1,3-cyclohexanebis(methylamine), 4,4'-diaminodicyclohexylmethane, bis(4-amino-3-methylcyclohexyl)methane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0] 2,6 ]decane, 2,5(6)-bis(aminomethyl)bicyclo[2.2.1]heptane, 1,3-diaminoadamantane, 3,3'-diamino-1,1'-biadamantyl, and 1,6-diaminoadamantane, from which two amino groups have been removed. These diamine compounds are characterized in that the aliphatic group contains an alicyclic carbon ring.

[0109] In formula (b2), the divalent aromatic group represented by R4 is preferably a divalent aromatic group having 6 to 100 carbon atoms, more preferably 6 to 50 carbon atoms, and even more preferably a divalent aromatic hydrocarbon group having 6 to 100 carbon atoms, even more preferably 6 to 50 carbon atoms. The aromatic group contains at least an aromatic ring. Examples of the aromatic ring contained in the aromatic group are the same as the examples of the aromatic ring C. In formula (b2), when R4 represents a divalent aromatic group having a substituent, examples of the substituent are the same as the examples of the substituent S.

[0110] When R4 represents a divalent aromatic group which may have a substituent, it may be a group obtained by removing two amino groups from a diamine compound having an aromatic group which may have a substituent selected from 4,4'-diaminodiphenyl ether, 1,4-phenylenediamine, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane.

[0111] However, when R3 is the same as R1, R4 is different from R2, and when R4 is the same as R2, R3 is different from R1. In some embodiments, R3 is the same as R1. That is, the structural unit (b2) is different from the structural unit (b1).

[0112] The structural unit (b2) can be obtained, for example, by a known method for producing a polyimide resin. The structural unit (b2) in the specific embodiment can be obtained, for example, by reacting BPADA with isophoronediamine. That is, in the structural unit (b2), R3 is a skeleton derived from BPADA, and R4 is a skeleton derived from isophoronediamine. When R3 is the same as R1, R3 and R1 are skeletons derived from BPADA. It is acceptable for the first polyimide resin to partially contain a polyamic acid structure that may be generated during the imidization process.

[0113] The terminal structure of the first polyimide resin is not particularly limited as long as it has the structural unit (b1). For example, the terminal structure of the polyimide resin may be an acid anhydride group, a carboxyl group, or an amino group derived from the raw material compound of the polyimide resin (e.g., an acid such as BPADA, or an amine compound such as BPPAN). When the raw material compound further contains maleic anhydride, the terminal structure of the polyimide resin may be a maleimide group.

[0114] Polyimide resin glass transition temperature Tg (c) The glass transition temperature (°C) is preferably 140°C or higher, more preferably 145°C or higher, even more preferably 150°C or higher, even more preferably 160°C or higher, and particularly preferably 170°C or higher. There is no particular upper limit, but it can be 300°C or lower. (c) The temperature (°C) can be measured using a TMA device manufactured by Rigaku Corporation at a temperature rise rate of 5°C / min from 25°C to 250°C.

[0115] From the viewpoint of achieving the effects of the present invention more significantly, the content (percentage) of the structural unit (b1) in the polyimide resin is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 40% by mass or more. The content (percentage) of the structural unit (b1) in the polyimide resin may be, for example, 98% by mass or less, 95% by mass or less, 90% by mass or less, or 85% by mass or less. Here, the content (percentage) of the structural unit (b1) can be calculated from the ratio of the amounts (parts by mass) of each material used to synthesize the polyimide resin. Alternatively, the molecular weight of the polyimide resin and the formula weight of the structural unit (b1) may be determined, and the content (percentage) of the structural unit (b1) may be calculated as the ratio of the formula weight of the structural unit (b1) to the molecular weight. When the polyimide resin is a polymer, the content (percentage) of the structural unit (b1) estimated from the degree of polymerization is preferably within the above range.

[0116] When the polyimide resin further contains the structural unit (b2), the content (percentage) of the structural unit (b2) can be 0% by mass (i.e., no structural unit (b2) is contained), and there is no upper limit as long as the effects of the present invention are not excessively impaired. Therefore, the content (percentage) of the structural unit (b2) in the polyimide resin can be, for example, 1% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, or 30% by mass or more, and 95% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, or 60% by mass or less. Here, the content (percentage) of the structural unit (b2) is calculated in the same manner as the content (percentage) of the structural unit (b1). When the polyimide resin is a polymer, the content (percentage) of the structural unit (b2) estimated from the degree of polymerization is preferably within the above-mentioned range.

[0117] The weight-average molecular weight (Mw) of the polyimide resin is usually 1,000 or more, preferably 1,000 to 10,000, more preferably 1,000 to 5,000, and even more preferably 1,000 to 3,000. The weight-average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0118] Another embodiment of the polyimide resin is a resin containing a first skeleton derived from BPADA and a second skeleton derived from BPPAN (hereinafter, sometimes referred to as a "second polyimide resin"). The first skeleton is not limited to BPADA as long as it is the same as the skeleton derived from BPADA. The second skeleton is not limited to BPPAN as long as it is the same as the skeleton derived from BPPAN. In the second polyimide resin, the number of first skeletons is 1 or more and is not particularly limited, but may be 100 or less, 50 or less, or 30 or less. In the second polyimide resin, the number of second skeletons is 1 or more and is not particularly limited, but may be 100 or less, 50 or less, or 30 or less.

[0119] The first and second skeletons described above can be derived from, for example, a known method for producing a polyimide resin, typically a method for imidizing a monomer composition containing a tetracarboxylic dianhydride and a diamine compound by polymerizing it. The first and second skeletons can also be derived from a method for imidizing a monomer composition containing a tetracarboxylic dianhydride and a diisocyanate compound by polymerizing it. Therefore, the second polyimide resin can contain the structural unit (b1) contained in the first polyimide resin. It is acceptable for the second polyimide resin to partially contain a polyamic acid structure that can be generated during the imidization process.

[0120] The second polyimide resin may further include a third skeleton different from the second skeleton. This third skeleton is derived from one or more diamine compounds selected from the group consisting of diamine compounds having an aliphatic group which may have a substituent and diamine compounds having an aromatic group which may have a substituent. Therefore, in one embodiment, the second polyimide resin further includes a third skeleton different from the second skeleton, and this third skeleton is derived from one or more diamine compounds selected from the group consisting of diamine compounds having an aliphatic group which may have a substituent and diamine compounds having an aromatic group which may have a substituent. In the second specific polyimide resin, the number of third skeletons is 0 or more, and is not particularly limited, but may be 100 or less, 50 or less, or 30 or less.

[0121] When the diamine compound is a diamine compound having an aliphatic group, the aliphatic group contains at least a carbon atom, and is preferably a group consisting of one or more (for example, 1 to 3000, 1 to 1000, 1 to 100, or 1 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, and silicon atoms, more preferably an aliphatic group having 1 to 100 carbon atoms, and even more preferably 1 to 50. When the aliphatic group has a substituent, examples of the substituent are the same as the examples of the substituent S.

[0122] When the diamine compound is a diamine compound having an aromatic group, the aromatic group is preferably a tetravalent aromatic group having 6 to 100 carbon atoms, more preferably 6 to 50 carbon atoms, and even more preferably a tetravalent aromatic hydrocarbon group having 6 to 100 carbon atoms, still more preferably 6 to 50 carbon atoms. The aromatic group contains at least an aromatic ring. Examples of the aromatic ring contained in the aromatic group are the same as the examples of the aromatic ring C. When the aromatic group has a substituent, examples of the substituent are the same as the examples of the substituent S.

[0123] The third skeleton may be derived from a diamine compound having an aliphatic group having an alkyl group of 1 to 6 carbon atoms as a substituent. Alternatively, the third skeleton may be derived from isophoronediamine. Therefore, in one embodiment, the second polyimide resin is a resin further including a skeleton derived from a diamine compound having an aliphatic group having an alkyl group of 1 to 6 carbon atoms as a substituent. A specific example of such a skeleton is a skeleton derived from isophoronediamine. The skeleton derived from isophoronediamine (5-amino-1,3,3-trimethylcyclohexanemethylamine) may be a skeleton derived from 5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane.

[0124] The third skeleton may be derived from one or more diamine compounds having an aromatic group which may have a substituent, such as 4,4'-diaminodiphenyl ether, 1,4-phenylenediamine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, etc. Such a third skeleton is characterized by having an aromatic group.

[0125] The third skeleton may be derived from one or more diamine compounds having an aliphatic group which may have a substituent, such as 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, etc. Such a third skeleton is characterized in that the aliphatic group is linear.

[0126] The third skeleton may be derived from one or more diamine compounds having an aliphatic group which may have a substituent, such as 1,2-diaminopropane, 1,2-diamino-2-methylpropane, 1,3-diamino-2-methylpropane, 1,3-diamino-2,2-dimethylpropane, 1,3-diaminopentane, 1,5-diamino-2-methylpentane, etc. Such a third skeleton is characterized in that the aliphatic group is branched.

[0127] The third skeleton is 5-amino-1,3,3-trimethylcyclohexanemethylamine (isophoronediamine), 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-cyclohexanebis(methylamine), 1,3-cyclohexanebis(methylamine), 4,4'-diaminodicyclohexylmethane, bis(4-amino-3-methylcyclohexyl)methane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0]. 2,6 The third skeleton may be derived from one or more diamine compounds having an aliphatic group which may have a substituent, such as 2,5(6)-decane, 2,5(6)-bis(aminomethyl)bicyclo[2.2.1]heptane, 1,3-diaminoadamantane, 3,3'-diamino-1,1'-biadamantyl, and 1,6-diaminoadamantane. Such a third skeleton is characterized in that the aliphatic group contains an alicyclic carbon ring.

[0128] The third skeleton may be formed in the second polyimide resin by, for example, polymerizing a monomer composition containing a tetracarboxylic dianhydride (which can be the material for the first skeleton) and a diamine compound (which can be the material for the second skeleton) to form the second skeleton. The diamine compound or diisocyanate compound may be added to the monomer composition or may be mixed with the monomer composition during polymerization. Therefore, the second polyimide resin may contain the structural unit (b2) that the first polyimide resin can contain. It is acceptable for the second polyimide resin to contain a portion of a polyamic acid structure that may be formed during the imidization process.

[0129] The second polyimide resin may further include a fourth skeleton different from the first skeleton. The fourth skeleton is derived from one or more acids selected from the group consisting of acids other than BPADA. The number of fourth skeletons in the second polyimide resin is 0 or more, and is not particularly limited, but may be 100 or less, 50 or less, or 30 or less.

[0130] Examples of acids other than BPADA include tetracarboxylic acid dianhydrides having an aromatic group which may have a substituent. The aromatic group is preferably an aromatic group having 6 to 100 carbon atoms, more preferably 6 to 50 carbon atoms, and even more preferably an aromatic hydrocarbon group having 6 to 100 carbon atoms, still more preferably 6 to 50 carbon atoms. The aromatic group contains at least an aromatic ring. Examples of the aromatic ring contained in the aromatic group are the same as the examples of the aromatic ring C. When the aromatic group has a substituent, examples of the substituent are the same as the examples of the substituent S. Specific examples of tetracarboxylic acid dianhydrides having an aromatic group which may have a substituent include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride.

[0131] Glass transition temperature Tg of the second polyimide resin (c’)The glass transition temperature (°C) is preferably 140°C or higher, more preferably 145°C or higher, even more preferably 150°C or higher, even more preferably 160°C or higher, and particularly preferably 170°C or higher. There is no particular upper limit, but it can be 300°C or lower. (c’) The temperature (° C.) can be measured in the same manner as in the first polyimide resin.

[0132] From the viewpoint of enhancing the intended effects of the present invention, the total content (percentage) of the first skeleton and the second skeleton in the second polyimide resin is preferably 4% by mass or more, more preferably 9% by mass or more, even more preferably 19% by mass or more, even more preferably 29% by mass or more, and particularly preferably 39% by mass or more. The total content (percentage) of the first skeleton and the second skeleton may be, for example, 97% by mass or less, 94% by mass or less, 89% by mass or less, or 84% by mass or less. Here, the total content (percentage) of the first skeleton and the second skeleton can be calculated from the proportion of the charged amount (parts by mass) contributing to the reaction of each material used to synthesize the second polyimide resin. Alternatively, the molecular weight of the second polyimide resin and the formula weights of the first skeleton and the second skeleton incorporated in the resin may be determined, and the total content (percentage) of the first skeleton and the second skeleton relative to the molecular weight may be calculated. When the second polyimide resin is a polymer, it is preferable that the total content (percentage) of the first skeleton and the second skeleton estimated from the degree of polymerization is within the above range.

[0133] When the second polyimide resin further contains a third skeleton, the content (percentage) of the third skeleton is allowed to be 0% by mass (i.e., no third skeleton is contained), and there is no upper limit as long as the effects of the present invention are not excessively impaired. Therefore, the content (percentage) of the third skeleton in the second polyimide resin may be, for example, more than 0% by mass, 4% by mass or more, 9% by mass or more, 19% by mass or more, or 29% by mass or more, 94% by mass or less, 89% by mass or less, 79% by mass or less, 69% by mass or less, or 59% by mass or less. Here, the content (percentage) of the third skeleton is calculated in the same manner as the content (percentage) of the first skeleton and the content (percentage) of the second skeleton. When the second polyimide resin is a polymer, the content (percentage) of the third skeleton estimated from the degree of polymerization is preferably within the above-mentioned range. When the second polyimide resin further contains a fourth skeleton, the content (percentage) of the fourth skeleton is the same as the content (percentage) of the third skeleton.

[0134] The second polyimide resin is not particularly limited in its terminal structure, as long as it contains a first skeleton derived from BPADA and a second skeleton derived from BPPAN. For example, the terminal structure of the second polyimide resin may be an acid anhydride group, a carboxyl group, or an amino group derived from the raw material compound of the second polyimide resin (e.g., an acid such as BPADA or an amine compound such as BPPAN). When the raw material compound further contains maleic anhydride, the terminal structure of the second polyimide resin may be a maleimide group.

[0135] The weight-average molecular weight (Mw) of the second polyimide resin is usually 1,000 or more, preferably 1,000 to 10,000, more preferably 1,000 to 5,000, and even more preferably 1,000 to 3,000. The weight-average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0136] Another embodiment of the polyimide resin is a resin obtained by polymerizing and imidizing a monomer composition containing at least BPADA and BPPAN (hereinafter, sometimes referred to as a "third polyimide resin"). The polymerization and imidization are typically carried out in a solvent, although not particularly limited thereto. The blending ratio of BPADA to BPPAN during polymerization is preferably determined based on the total number of functional groups possessed by each component. In one embodiment, the ratio of the total number of amino groups possessed by BPPAN to the total number of acid anhydride groups possessed by BPADA in the monomer composition is within the range of 0.1:1 to 10:1, preferably 0.5:1 to 10:1, more preferably 0.8:1 to 10:1, and even more preferably 0.9:1 to 10:1. The imidization is typically carried out in a solvent by heating in the absence of a catalyst, by heating in the presence of a catalyst, or at room temperature in the presence of a catalyst. From the viewpoint of enhancing the intended effects of the present invention, the imidization is preferably carried out by heating in the absence of a catalyst. The third polyimide resin may be a random copolymer, an alternating copolymer, or a block copolymer. The third polyimide resin is not limited to the polymerization and imidization methods. It is acceptable for the third polyimide resin to contain a portion of a polyamic acid structure that may be generated during the imidization process. The third polyimide resin thus obtained contains the aforementioned structural unit (b1) contained in the first polyimide resin. The third polyimide resin thus obtained also contains the aforementioned first skeleton and second skeleton contained in the second polyimide resin.

[0137] The above-mentioned monomer composition may contain, as other monomers, an acid other than BPADA and / or a diamine compound other than BPPAN, or other monomers may be added during the reaction.

[0138] Examples of acids other than BPADA include tetracarboxylic acid dianhydrides having an aromatic group which may have a substituent. The aromatic group is preferably a tetravalent aromatic group having 6 to 100 carbon atoms, more preferably 6 to 50 carbon atoms, and even more preferably a tetravalent aromatic hydrocarbon group having 6 to 100 carbon atoms, even more preferably 6 to 50 carbon atoms. The aromatic group contains at least an aromatic ring. Examples of the aromatic ring contained in the aromatic group are the same as the examples of the aromatic ring C. When the aromatic group has a substituent, examples of the substituent are the same as the examples of the substituent S. Specific examples of tetracarboxylic acid dianhydrides having an aromatic group which may have a substituent include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride. The molar ratio of the content of the acid other than BPADA to the content of BPADA in the monomer composition is not particularly limited, but may be, for example, 0.5 or less, 0.4 or less, or 0.3 or less.

[0139] In one embodiment, the monomer composition further contains one or more diamine compounds selected from the group consisting of diamine compounds having an optionally substituted aliphatic group and diamine compounds having an optionally substituted aromatic group. The molar ratio of the content of the diamine compounds other than BPPAN to the content of BPPAN in the monomer composition is not particularly limited, but may be, for example, 0.5 or less, 0.4 or less, or 0.3 or less.

[0140] When the diamine compound is a diamine compound having an aliphatic group, the aliphatic group contains at least a carbon atom, and is preferably a group consisting of one or more (for example, 1 to 3000, 1 to 1000, 1 to 100, or 1 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, and silicon atoms, more preferably an aliphatic group having 1 to 100 carbon atoms, and even more preferably 1 to 50. When the aliphatic group has a substituent, examples of the substituent are the same as the examples of the substituent S.

[0141] When the diamine compound is a diamine compound having an aromatic group, the aromatic group is preferably a tetravalent aromatic group having 6 to 100 carbon atoms, more preferably 6 to 50 carbon atoms, and even more preferably a tetravalent aromatic hydrocarbon group having 6 to 100 carbon atoms, even more preferably 6 to 50 carbon atoms. The aromatic group contains at least an aromatic ring. Examples of the aromatic ring contained in the aromatic group are the same as the examples of the aromatic ring C. When the aromatic group has a substituent, examples of the substituent are the same as the examples of the substituent S. When the diamine compound is a diamine compound having an aromatic group which may have a substituent, examples thereof include one or more selected from diamine compounds having an aromatic group, such as 4,4'-diaminodiphenyl ether, 1,4-phenylenediamine, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane.

[0142] When the diamine compound is a diamine compound having an aliphatic group which may have a substituent, a first example thereof may be a skeleton derived from one or more selected from diamine compounds having an aliphatic group which may have a substituent, such as 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, etc. The diamine compound according to this first example is characterized in that the aliphatic group is linear.

[0143] When the diamine compound is a diamine compound having an aliphatic group which may have a substituent, a second example thereof may be a skeleton derived from one or more selected from diamine compounds having an aliphatic group which may have a substituent, such as 1,2-diaminopropane, 1,2-diamino-2-methylpropane, 1,3-diamino-2-methylpropane, 1,3-diamino-2,2-dimethylpropane, 1,3-diaminopentane, 1,5-diamino-2-methylpentane, etc. The diamine compound according to this second example is characterized in that the aliphatic group is branched.

[0144] When the diamine compound is a diamine compound having an aliphatic group which may have a substituent, third examples thereof include 5-amino-1,3,3-trimethylcyclohexanemethylamine (isophoronediamine), 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-cyclohexanebis(methylamine), 1,3-cyclohexanebis(methylamine), 4,4'-diaminodicyclohexylmethane, bis(4-amino-3-methylcyclohexyl)methane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0] 2,6 The skeleton may be derived from one or more diamine compounds having an aliphatic group which may have a substituent, such as 2,5(6)-decane, 2,5(6)-bis(aminomethyl)bicyclo[2.2.1]heptane, 1,3-diaminoadamantane, 3,3'-diamino-1,1'-biadamantyl, and 1,6-diaminoadamantane. The diamine compound according to this third example is characterized in that the aliphatic group contains an alicyclic carbon ring.

[0145] Based on the above, in one embodiment, the monomer composition further contains a diamine compound having an aliphatic group having an alkyl group having 1 to 6 carbon atoms as a substituent. In a specific embodiment, the monomer composition further contains isophoronediamine.

[0146] The terminal structure of the third polyimide resin is not particularly limited as long as it is a resin obtained by polymerizing and imidizing the monomer composition. For example, the terminal structure of the third polyimide resin may be an acid anhydride group, a carboxyl group, or an amino group derived from raw material compounds (e.g., acids such as BPADA, or amine compounds such as BPPAN) contained in the monomer composition of the third polyimide resin. When the raw material compounds further contain maleic anhydride, the terminal structure of the third polyimide resin may be a maleimide group.

[0147] The weight-average molecular weight (Mw) of the third polyimide resin is 1,000 or more, preferably 1,000 to 10,000, more preferably 1,000 to 5,000, and even more preferably 1,000 to 3,000. The weight-average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0148] The content of the (B) maleimide resin and / or polyimide resin is 7% by mass or more, preferably 8% by mass or more, and more preferably 10% by mass or more, based on 100% by mass of the resin component in the resin composition. By setting the lower limit of the (B) component content within this range, it is possible to obtain a cured product with excellent adhesion between the insulating layer and the conductor layer and excellent smear removal properties. The upper limit can be set to 30% by mass or less, preferably 25% by mass or less or 20% by mass or less. By setting the upper limit of the (B) component content within this range, it is possible to sufficiently reduce the dielectric loss tangent value and suppress the linear thermal expansion coefficient while improving mechanical properties, specifically bending resistance.

[0149] <(C) Inorganic filler> The resin composition of the present invention contains an inorganic filler as component (C). By containing the inorganic filler (C) in the resin composition, it is possible to obtain a cured product with excellent dielectric properties.

[0150] Inorganic compounds are used as inorganic fillers. Examples of inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Spherical silica is preferred. Component (C) may be used alone or in combination of two or more.

[0151] Commercially available products of component (C) include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C," "YA050C," "YA050C-MJE," "YA010C," "SC2500SQ," "SO-C4," "SO-C2," and "SO-C1" manufactured by Admatechs Co., Ltd.; "UFP-30," "DAW-03," and "FB-105FD" manufactured by Denka Company, Limited; "Silfil NSS-3N," "Silfil NSS-4N," and "Silfil NSS-5N" manufactured by Tokuyama Corporation; and "Cellspheres" and "MGH-005" manufactured by Taiheiyo Cement Corporation.

[0152] From the viewpoint of significantly achieving the desired effects of the present invention, the average particle size of component (C) is preferably 0.01 μm or more, more preferably 0.05 μm or more, and particularly preferably 0.1 μm or more, and is preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less.

[0153] The average particle size of component (C) can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, a volumetric particle size distribution of the inorganic filler is created using a laser diffraction / scattering particle size distribution analyzer, and the median diameter is used as the average particle size. A measurement sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing them ultrasonically for 10 minutes. The volumetric particle size distribution of the inorganic filler was measured using a laser diffraction particle size distribution analyzer with blue and red light source wavelengths using a flow cell system, and the average particle size was calculated as the median diameter from the particle size distribution obtained. Examples of laser diffraction particle size distribution analyzers include the LA-960 manufactured by Horiba, Ltd.

[0154] From the viewpoint of significantly achieving the desired effects of the present invention, the specific surface area of ​​component (C) is preferably 1 m 2 / g or more, more preferably 2m 2 / g or more, particularly preferably 3m 2 / g or more. There is no particular upper limit, but it is preferably 60m 2 / g or less, 50m 2 / g or less or 40m 2 The specific surface area is measured by using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) to adsorb nitrogen gas onto the surface of the sample and calculate the specific surface area using the BET multipoint method.

[0155] From the viewpoint of improving moisture resistance and dispersibility, component (C) is preferably treated with a surface treatment agent. Examples of surface treatment agents include fluorine-containing silane coupling agents such as 3,3,3-trifluoropropyltrimethoxysilane; aminosilane coupling agents such as 3-aminopropyltriethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; epoxysilane coupling agents such as 3-glycidoxypropyltrimethoxysilane; mercaptosilane coupling agents such as 3-mercaptopropyltrimethoxysilane; silane coupling agents; alkoxysilanes such as phenyltrimethoxysilane; organosilazane compounds such as hexamethyldisilazane; and titanate coupling agents. Furthermore, the surface treatment agents may be used alone or in any combination of two or more.

[0156] Examples of commercially available surface treatment agents include Shin-Etsu Chemical Co., Ltd.'s "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd.'s "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM-4803" (long-chain epoxy-type silane coupling agent), and Shin-Etsu Chemical Co., Ltd.'s "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane).

[0157] The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 to 5 parts by mass of the surface treatment agent, more preferably 0.2 to 3 parts by mass, and even more preferably 0.3 to 2 parts by mass.

[0158] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler is set to 0.02 mg / m 2 More than 0.1 mg / m is preferable. 2 More preferably, 0.2 mg / m or more 2 On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, it is more preferable that the amount of the resin varnish is 1 mg / m 2 Less than 0.8 mg / m is preferred 2 Less than 0.5 mg / m is more preferable. 2 The following is even more preferred:

[0159] The carbon content per unit surface area of ​​component (C) can be measured after the surface-treated inorganic filler is washed with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. The supernatant is removed, the solid content is dried, and then the carbon content per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. The carbon analyzer that can be used is the "EMIA-320V" manufactured by Horiba, Ltd.

[0160] From the viewpoint of suppressing the linear thermal expansion coefficient of the cured product obtained from the resin composition, the content of component (C) is preferably 60% by mass or more, more preferably 65% ​​by mass or more, even more preferably 70% by mass or more, and is preferably 80% by mass or less, more preferably 76% by mass or less, even more preferably 72% by mass or less, assuming that the non-volatile components in the resin composition are 100% by mass.

[0161] <(D) Other thermosetting resins> The resin composition of the present invention may further contain, as component (D), another thermosetting resin, that is, a thermosetting resin other than component (A). Examples of component (D) include phenolic resins, active ester resins, benzoxazine resins, carbodiimide resins, cyanate ester resins, amine resins, acid anhydride resins, terminal double bond resins, etc. The thermosetting resins may be used alone or in combination of two or more types in any ratio. It should be noted that phenolic resins, active ester resins, benzoxazine resins, carbodiimide resins, cyanate ester resins, amine resins, and acid anhydride resins also function as curing agents for epoxy resins, and hereinafter these will be collectively referred to as epoxy resin curing agents. From the viewpoint of improving the mechanical properties of the resin composition, these epoxy resin curing agents preferably include at least one selected from the group consisting of phenolic resins, carbodiimide resins, benzoxazine resins, and active ester resins.

[0162] (phenolic resin) The phenolic resin may be a compound having one or more, preferably two or more, hydroxyl groups in one molecule bonded to an aromatic ring such as a benzene ring or a naphthalene ring. When combined with an epoxy resin, the phenolic resin reacts with the epoxy resin to cure the resin composition, and therefore is sometimes called a "phenolic curing agent." The phenolic resin is preferably a phenolic resin having a novolac structure from the viewpoint of achieving the effects of the present invention. Furthermore, from the viewpoint of adhesion, a nitrogen-containing phenolic resin is preferred, and a triazine skeleton-containing phenolic resin is more preferred. Among these, a triazine skeleton-containing phenolic novolac resin is preferred from the viewpoint of achieving the effects of the present invention. Specific examples of phenolic resins include "MEH-7700," "MEH-7810," and "MEH-7851" manufactured by Meiwa Chemical Industry Co., Ltd.; "NHN," "CBN," and "GPH-65" manufactured by Nippon Kayaku Co., Ltd.; "SN-170," "SN-180," "SN-190," "SN-475," "SN-485," "SN-495," "SN-375," and "SN-395" manufactured by Nippon Steel Chemical & Material Co., Ltd.; and "LA-7052," "LA-7054," "LA-3018," "LA-3018-50P," "LA-1356," "TD2090," "TD-2090-60M," and "KA-1163" manufactured by DIC Corporation.

[0163] (Carbodiimide resin) The carbodiimide resin may be a compound having one or more, preferably two or more, carbodiimide structures in one molecule. When combined with an epoxy resin, the carbodiimide resin reacts with the epoxy resin to cure the resin composition, and is therefore sometimes called a "carbodiimide curing agent." Specific examples of carbodiimide resins include aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexanebis(methylene-t-butylcarbodiimide); aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide); poly(phenylenecarbodiimide), poly(naphthalenecarbodiimide); Examples of polycarbodiimides include aromatic polycarbodiimides such as poly(methylenediphenylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide]. Commercially available carbodiimide resins include, for example, "Carbodilite V-02B," "Carbodilite V-03," "Carbodilite V-04K," "Carbodilite V-07," and "Carbodilite V-09" manufactured by Nisshinbo Chemical Inc.; and "Stavaxol P," "Stavaxol P400," and "Hykasil 510" manufactured by Lanxess AG.

[0164] (benzoxazine resin), When combined with an epoxy resin, a benzoxazine resin can react with the epoxy resin to cure the resin composition, and is therefore sometimes called a "benzoxazine-based curing agent." Specific examples of benzoxazine resins include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Corporation; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; and "Pd" and "Fa" manufactured by Shikoku Chemicals Corporation.

[0165] (active ester resin) As the active ester resin, generally, a compound having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., is preferably used. When combined with an epoxy resin, the active ester resin reacts with the epoxy resin to cure the resin composition, and therefore is sometimes called an "active ester curing agent." The active ester resin is preferably one obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. The carboxylic acid compound may be either an aromatic carboxylic acid compound or an aliphatic carboxylic acid compound, and examples thereof include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and halides thereof. Examples of aromatic hydroxy compounds include (i) polyaddition products of unsaturated aliphatic cyclic compounds containing two double bonds in one molecule with phenols, (ii) various bisphenol compounds, (iii) aromatic polyols in which two or more hydroxy groups are bonded to carbon atoms on the aromatic ring, and (iv) aromatic monools in which one hydroxy group is bonded to a carbon atom on the aromatic ring. Examples of the polyaddition reaction products of unsaturated aliphatic cyclic compounds and phenols include polyaddition reaction products of unsaturated aliphatic cyclic compounds such as dicyclopentadiene, tetrahydroindene, norbornadiene, limonene, and vinylcyclohexene with phenols which may have a substituent (e.g., phenol, cresol, xylenol, ethylphenol, propylphenol, vinylphenol, allylphenol, phenylphenol, benzylphenol, halophenol, etc.), and specific examples include dicyclopentadiene-phenol polyaddition products. Examples of bisphenol compounds include bisphenol A, bisphenol F, bisphenol AF, bisphenol AP, bisphenol B, bisphenol BP, bisphenol C, and bisphenol M. Examples of aromatic polyols in which two or more hydroxy groups are bonded to carbon atoms on an aromatic ring include hydroquinone, resorcinol, catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, and phenol novolak. Examples of aromatic monools having one hydroxy group bonded to a carbon atom on an aromatic ring include phenol, cresol, xylenol, ethylphenol, propylphenol, vinylphenol, allylphenol, phenylphenol, benzylphenol, halophenols, naphthol, methylnaphthol, dimethylnaphthol, ethylnaphthol, propylnaphthol, vinylnaphthol, allylnaphthol, phenylnaphthol, benzylnaphthol, and halonaphthol.

[0166] Specifically, the active ester resin is preferably a dicyclopentadiene-type active ester resin, a naphthalene-type active ester resin containing a naphthalene structure, an active ester resin containing an acetylated product of phenol novolac, an active ester resin containing a benzoylated product of phenol novolac, or an active ester resin containing a styryl group and a naphthalene structure, and among these, at least one selected from dicyclopentadiene-type active ester resins and naphthalene-type active ester resins is more preferred. As the dicyclopentadiene-type active ester resin, an active ester resin containing a dicyclopentadiene-type diphenol structure is preferred.

[0167] Commercially available active ester resins include, for example, activated ester resins containing a dicyclopentadiene-type diphenol structure such as "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000L-65T", "HPC-8000", "HPC-8000-65T", "HPC-8000H", and "HPC-8000H-65TM" (manufactured by DIC Corporation); activated ester resins containing a naphthalene structure such as "HP-B-8151-62T", "EXB-8100L-65T", and "EXB-8150-60T"; Examples of such active ester resins include "EXB-8150-62T," "EXB-9416-70BK," "HPC-8150-60T," "HPC-8150-62T," and "EXB-8" (manufactured by DIC Corporation); "EXB9401" (manufactured by DIC Corporation) as a phosphorus-containing active ester resin; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester resin which is an acetylated product of phenol novolac; "YLH1026," "YLH1030," and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester resins which are benzoylated products of phenol novolac; and "PC1300-02-65MA" (manufactured by Air Water Inc.) as an active ester resin containing a styryl group and a naphthalene structure.

[0168] When the resin composition of the present invention contains an activated ester resin as component (D), the ratio of the epoxy resin to the activated ester resin, expressed as the ratio of [total number of epoxy groups in the epoxy resin] to [total number of reactive groups in the activated ester compound], is preferably in the range of 1:0.01 to 1:5, more preferably 1:0.1 to 1:2, and even more preferably 1:0.8 to 1:1.1. By setting the ratio of the epoxy resin to the activated ester resin in this range, the mechanical properties of the cured product of the resin composition can be improved.

[0169] (cyanate ester resin) The cyanate ester resin may be a compound having one or more, preferably two or more, cyanate groups in one molecule. When combined with an epoxy resin, the cyanate ester resin reacts with the epoxy resin to cure the resin composition, and is therefore sometimes called a "cyanate ester curing agent." Examples of cyanate ester resins include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bis(4-cyanatephenyl)ether; multifunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers in which these cyanate resins are partially converted to triazine. Specific examples of cyanate ester resins include "PT30" and "PT60" manufactured by Lonza (both of which are phenol novolac-type multifunctional cyanate resins), "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate has been triazine-converted to form a trimer).

[0170] (amine resin) The amine resin may be a compound having one or more, preferably two or more, amino groups in one molecule. When combined with an epoxy group, the amine resin reacts with the epoxy resin to cure the resin composition, and is therefore sometimes called an "amine-based curing agent." Examples of amine resins include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines, among which aromatic amines are preferred. The amine resin is preferably a primary amine or secondary amine, and more preferably a primary amine. Specific examples of amine resins include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino-4-hydroxyphenyl)propionate. Examples of suitable bis(4-aminophenoxy)benzene include bis(4-aminophenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, and bis(4-(3-aminophenoxy)phenyl)sulfone. Commercially available amine resins include, for example, "SEIKACURE-S" manufactured by Seika Corporation; "KAYABOND C-200S," "KAYABOND C-100," "KAYAHARD AA," "KAYAHARD AB," and "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd.; "Epicure W" manufactured by Mitsubishi Chemical Corporation; and "DTDA" manufactured by Sumitomo Seika Chemicals Co., Ltd.

[0171] (acid anhydride resin) The acid anhydride resin may be a compound having one or more, preferably two or more, acid anhydride groups in one molecule. When combined with an epoxy group, the acid anhydride resin reacts with the epoxy resin to cure the resin composition, and is therefore sometimes called an "acid anhydride curing agent." Specific examples of acid anhydride resins include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic anhydride. Examples of suitable anhydrides include hydrates, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymeric anhydrides such as styrene-maleic acid resin, which is a copolymer of styrene and maleic acid. Commercially available acid anhydride resins include, for example, "HNA-100," "MH-700," "MTA-15," "DDSA," and "OSA" manufactured by New Japan Chemical Co., Ltd.; "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Corporation; "HN-2200" and "HN-5500" manufactured by Resonac; and "EF-30," "EF-40," "EF-60," and "EF-80" manufactured by Cray Valley Chemical Industries, Ltd.

[0172] (Terminal double bond resin) The terminal double bond resin is an ethylenically unsaturated group having one or more (preferably two or more) carbon-carbon double bonds in one molecule, or a radically polymerizable resin having a radically polymerizable group containing an ethylenically unsaturated bond at the molecular end. Examples of the radical polymerizable group include one or more selected from a styryl group, a vinyl group, a propenyl group (1-propenyl group), an allyl group (2-propenyl group), a vinylphenyl group, an acryloyl group, and a methacryloyl group. Of these, from the viewpoint of being able to enjoy the effects of the present invention more effectively, one or more selected from a styryl group, a vinyl group, and an allyl group are preferred. Of these, from the viewpoint of being able to enjoy the effects of the present invention more easily, the terminal double bond resin is preferably a styryl resin, an allyl resin, or a vinyl resin.

[0173] The type of styryl resin is not particularly limited, and it may be a monomer or oligomer, as long as it has one or more (preferably two or more) styryl groups or vinylphenyl groups in one molecule. Examples of styryl resins include "OPE-2St," "OPE-2St 1200," and "OPE-2St 2200" (all manufactured by Mitsubishi Gas Chemical Company, Inc.). Examples of styryl resins include, in addition to styrene monomers, homopolymers of aromatic divinyl compounds such as divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, and bis(4-vinylphenyl)ether, as well as copolymers of these aromatic divinyl compounds with aromatic monovinyl compounds such as styrene, vinyltoluene, ethylstyrene, and vinylnaphthalene.

[0174] The allyl resin is, for example, a compound having one or more, preferably two or more allyl groups. Examples of the allyl resin include aromatic carboxylic acid allyl ester compounds such as diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylic acid, and diallyl 2,3-naphthalenecarboxylic acid; isocyanuric acid allyl ester compounds such as 1,3,5-triallyl isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate; epoxy-containing aromatic allyl compounds such as 2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane; benzoxazine-containing aromatic allyl compounds such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane; ether-containing aromatic allyl compounds such as 1,3,5-triallyl ether benzene; and allyl silane compounds such as diallyldiphenylsilane. Commercially available allyl radical polymerizable compounds include "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Chemical Industry Co., Ltd., "DAD" (diallyl diphenate) manufactured by Nisshoku Techno Fine Chemical Co., Ltd., "TRIAM-705" (triallyl trimellitate) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., "DAND" (2,3-naphthalene carboxylic acid diallyl) manufactured by Nisshoku Techno Fine Chemical Co., Ltd., "ALP-d" (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane) manufactured by Shikoku Chemical Industry Co., Ltd., "RE-810NM" (2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane) manufactured by Nippon Kayaku Co., Ltd., and "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Chemical Industry Co., Ltd.

[0175] Examples of vinyl resins include trialkenyl isocyanurate compounds such as triallyl isocyanurate, polybutadiene resins whose repeating units are 1,2-butadiene, cis-1,4-butadiene, or trans-1,4-butadiene, and vinylbenzyl compounds such as styrene and divinylbenzene having a vinylbenzyl group in the molecule.

[0176] From the viewpoint that the cured product of the resin composition of the present invention can be a cured product exhibiting good mechanical properties, the content of component (D) in the resin composition is preferably 30% by mass or more, more preferably 35% by mass or more, and even more preferably 40% by mass or more, when the resin components in the resin composition are taken as 100% by mass, and the upper limit of the content is preferably 70% by mass or less, more preferably 65% ​​by mass or less.

[0177] <(E) Curing accelerator> In addition to the above-mentioned components, the resin composition of the present invention may further contain a curing accelerator (catalyst) as component (E). By using the curing accelerator (E), curing of the resin composition can be accelerated.

[0178] Examples of (E) curing accelerators include imidazole-based curing accelerators, phosphorus-based curing accelerators, amine-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and peroxide-based curing accelerators. Among these, imidazole-based curing accelerators are particularly preferred. (E) curing accelerators may be used alone or in combination of two or more.

[0179] Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-furan. phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-( 1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2 imidazole compounds such as 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline; and adducts of imidazole compounds with epoxy resins. Among these, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

[0180] As the imidazole-based curing accelerator, commercially available products may be used, for example, "P200-H50" manufactured by Mitsubishi Chemical Corporation and "1B2PZ" manufactured by Shikoku Chemicals Corporation.

[0181] Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate. Among these, triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

[0182] Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene. Of these, 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene are preferred.

[0183] Examples of guanidine curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide. Among these, dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

[0184] Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organic copper complexes such as copper(II) acetylacetonate, organic zinc complexes such as zinc(II) acetylacetonate, organic iron complexes such as iron(III) acetylacetonate, organic nickel complexes such as nickel(II) acetylacetonate, and organic manganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0185] Examples of peroxide-based curing accelerators include cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, and tert-butyl hydroperoxide.

[0186] As the peroxide-based curing accelerator, commercially available products can be used, for example, "Percumyl D" manufactured by NOF Corporation.

[0187] From the viewpoint of obtaining the desired effects of the present invention, the content of component (E) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and preferably 1.5% by mass or less, more preferably 1.0% by mass or less, when the resin component in the resin composition is taken as 100% by mass.

[0188] <(F) Other additives> The resin composition of the present invention may further contain other additives as optional components in addition to the components described above. Examples of such additives include thermoplastic resins, elastomers, organic fillers, thickeners, antifoaming agents, leveling agents, adhesion promoters, and flame retardants. These may be used alone or in combination of two or more in any ratio.

[0189] The resin composition of the present invention can be produced, for example, by mixing the above-mentioned components in any order. Furthermore, heating and / or cooling may be performed by appropriately adjusting the temperature during the process of mixing the components. Furthermore, stirring may be performed using a stirring device such as a mixer during or after mixing the components to uniformly disperse the components. Furthermore, the resin composition may be subjected to a degassing treatment, if necessary.

[0190] <Physical properties of resin composition> The resin composition of the present invention contains a combination of components (A-1) and (A-2) as component (A), and a combination of components (B) and (C), and therefore can provide a cured product that has excellent folding endurance, a low coefficient of linear thermal expansion, and good smear removability. Furthermore, the resin composition in its uncured state has good tackiness.

[0191] The resin composition of the present invention is characterized by producing a cured product exhibiting excellent folding resistance (flexibility). Therefore, when a flexible substrate is produced using the resin composition of the present invention and used as a substrate for semiconductor components, a substrate with excellent folding resistance can be obtained. For example, as described in <Test Example 1: MIT Test (Folding Resistance)> in the Examples section below, a layered cured product obtained by curing a 40 μm-thick resin composition was subjected to an MIT folding resistance test in accordance with JIS C-5016 under the following conditions: load: 2.5 N, bending angle: 90°, bending radius: 1.0 mm, bending speed: 175 times / min. The number of folding times is preferably 1000 or more, more preferably 1400 or more, even more preferably 1800 or more, and particularly preferably 2000 or more.

[0192] The resin composition of the present invention is characterized by producing a cured product with a reduced linear thermal expansion coefficient. Therefore, when the resin composition of the present invention is used to form an insulating layer for use in a semiconductor component, an insulating layer with a reduced linear thermal expansion coefficient can be obtained. For example, as described in <Test Example 2: Measurement of Linear Thermal Expansion Coefficient (CTE)> in the Examples section below, when a layered cured product obtained by curing a 40 μm-thick resin composition is subjected to thermomechanical analysis using a tensile load method, the average linear thermal expansion coefficient from 25°C to 150°C is preferably 30 ppm / °C or less, more preferably 25 ppm / °C or less. The lower limit is not particularly limited, but may be 1 ppm / °C or more, 2 ppm / °C or more, 3 ppm / °C or more, etc.

[0193] The resin composition of the present invention is characterized by providing a cured product with good smear removability. Therefore, by using the resin composition of the present invention, semiconductor components such as circuit boards can be manufactured with high precision. For example, when an insulating layer is formed from a cured product of the resin composition by the method described in <Test 3. Evaluation of Smear Removability> in the Examples below and the smear removability is evaluated, the maximum smear length can be reduced to less than 5 μm.

[0194] The resin composition of the present invention is characterized by providing a resin composition that exhibits low tackiness when uncured. Therefore, by using the resin composition of the present invention, a resin sheet with excellent workability can be obtained. For example, when the tackiness of a resin sheet having a resin composition layer with a thickness of 40 μm was measured by the method described in <Test 4. Evaluation of Tackiness> in the Examples below, a probe was brought into contact with the resin sheet at 25° C., and the tackiness was 1000 gf / cm 2 The peel force when the probe is pulled away at 0.5 cm / sec after being held under a load of 0.5 cm / sec for 1 second may be less than 0.4 N.

[0195] <Applications of resin composition> The resin composition of the present invention is suitable as a resin composition for insulation applications, and particularly suitable as a resin composition for forming an insulating layer. Therefore, for example, the resin composition of the present invention is suitable as a resin composition for forming an insulating layer of a circuit board (a resin composition for forming an insulating layer of a circuit board). The resin composition of the present invention is suitable as a resin composition for forming an interlayer insulating layer of a circuit board (a resin composition for forming an interlayer insulating layer of a circuit board). The resin composition of the present invention is also suitable as a resin composition for forming an insulating layer (a resin composition for forming an insulating layer for forming a conductor layer) to form a conductor layer (including a rewiring layer) formed on an insulating layer. The resin composition of the present invention can also be used in a wide range of applications where resin compositions can be used, such as sheet-like laminate materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-embedding resins, multi-chip packages, package-on-packages, wafer-level packages, panel-level packages, and system-in-packages. In the present invention, the circuit board includes a printed wiring board and a rewiring board.

[0196] Furthermore, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention is also suitable as a resin composition for forming a rewiring formation layer as an insulating layer for forming a rewiring layer (resin composition for forming a rewiring formation layer), and as a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip). When a semiconductor chip package is manufactured, a rewiring layer may be further formed on the encapsulation layer. (1) a step of laminating a temporary fixing film on a substrate; (2) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (3) forming an encapsulation layer on the semiconductor chip; (4) peeling the substrate and the temporary fixing film from the semiconductor chip; (5) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off; and (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0197] [Resin sheet] The resin sheet of the present invention includes a support and a resin composition layer formed from a resin composition and provided on the support.

[0198] The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less, from the viewpoint of making the circuit board thinner and being able to provide a cured product of the resin composition that has excellent insulating properties even when the cured product is thin. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more.

[0199] Examples of the support include films made of plastic materials, metal foils, and release papers, with films made of plastic materials and metal foils being preferred.

[0200] When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, with inexpensive polyethylene terephthalate being particularly preferred.

[0201] When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. The copper foil may be a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0202] The surface of the support that is to be bonded to the resin composition layer may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

[0203] The support may also be a support with a release layer, which has a release layer on the surface that bonds to the resin composition layer. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available products may also be used as the support with a release layer, including, for example, "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, and "Uni-Peel" manufactured by Unitika Limited, which are PET films having a release layer primarily composed of an alkyd resin-based release agent.

[0204] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably 10 μm to 60 μm. When a support with a release layer is used, it is preferable that the thickness of the entire support with a release layer is in the above range.

[0205] When a metal foil is used as the support, a metal foil with a support substrate may be used, which is a thin metal foil with a peelable support substrate attached thereto. In one embodiment, the metal foil with a support substrate includes a support substrate, a release layer provided on the support substrate, and a metal foil provided on the release layer. When a metal foil with a support substrate is used as the support, the resin composition layer is provided on the metal foil.

[0206] In the metal foil with a supporting substrate, the material of the supporting substrate is not particularly limited, but examples thereof include copper foil, aluminum foil, stainless steel foil, titanium foil, copper alloy foil, etc. When copper foil is used as the supporting substrate, it may be electrolytic copper foil or rolled copper foil. Furthermore, the release layer is not particularly limited as long as it allows the metal foil to be released from the supporting substrate, and examples thereof include an alloy layer of an element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, and P; an organic coating, etc.

[0207] In the metal foil with a supporting substrate, the material of the metal foil is preferably, for example, copper foil or copper alloy foil.

[0208] In the metal foil with a supporting substrate, the thickness of the supporting substrate is not particularly limited, but is preferably in the range of 10 μm to 150 μm, more preferably in the range of 10 μm to 100 μm. The thickness of the metal foil may be, for example, in the range of 0.1 μm to 10 μm.

[0209] In one embodiment, the resin sheet may further include other layers as necessary. Examples of such other layers include a protective film conforming to the support and provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust and the like to the surface of the resin composition layer and scratches can be suppressed.

[0210] The resin sheet can be produced, for example, by preparing a resin varnish by dissolving a resin composition in an organic solvent, applying this resin varnish to a support using a die coater or the like, and then drying it to form a resin composition layer.

[0211] Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; and amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. The organic solvents may be used alone or in combination of two or more.

[0212] Drying may be carried out by known methods such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is carried out so that the content of organic solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although this varies depending on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0213] The resin sheet can be stored in a rolled state. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0214] [Circuit board] The resin composition can be used to form an insulating layer of a circuit board. The present invention also provides such a circuit board, i.e., a circuit board including an insulating layer made of a cured product of the resin composition.

[0215] [Printed wiring board] In one embodiment, the circuit board of the present invention is a printed wiring board. Such a printed wiring board includes an insulating layer formed of a cured product obtained by curing the above-described resin composition.

[0216] The printed wiring board can be produced, for example, by using the above-mentioned resin sheet by a method including the following steps (I) and (II). (I) A step of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) Step of curing the resin composition layer to form an insulating layer

[0217] The "inner layer substrate" used in step (I) is a member that will become the substrate of a printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. The substrate may have a conductor layer on one or both sides, and this conductor layer may be patterned. An inner layer substrate having a conductor layer formed on one or both sides of the substrate is sometimes referred to as an "inner layer circuit board." Furthermore, intermediate products on which an insulating layer and / or a conductor layer is to be further formed during the production of a printed wiring board are also included in the "inner layer substrate." When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0218] The inner layer substrate and the resin sheet can be laminated, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of a member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as a "thermocompression bonding member") include a heated metal plate (such as a SUS plate) or a metal roll (such as a SUS roll). Note that rather than pressing the thermocompression bonding member directly onto the resin sheet, it is preferable to press it via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently conform to the surface irregularities of the inner layer substrate.

[0219] The lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, the thermocompression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47MPa, and the thermocompression time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination may be carried out under reduced pressure conditions, preferably at a pressure of 26.7hPa or less.

[0220] The lamination can be performed using a commercially available vacuum laminator, such as a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., or a batch-type vacuum pressure laminator.

[0221] After lamination, the laminated resin sheets may be smoothed under atmospheric pressure, for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression conditions for the lamination. The smoothing treatment may be performed using a commercially available laminator. Note that the lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

[0222] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0223] In step (II), the resin composition layer is cured to form an insulating layer made of a cured product of the resin composition. The curing conditions for the resin composition layer are not particularly limited, and the conditions employed for forming an insulating layer of a printed wiring board may be used. The resin composition layer may be cured by irradiation with active energy rays such as ultraviolet rays, but is usually thermally cured by heating.

[0224] For example, the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, but in one embodiment, the curing temperature is preferably 120° C. to 240° C., more preferably 150° C. to 220° C., and even more preferably 170° C. to 210° C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0225] Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, more preferably 70°C to 110°C for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0226] The method for producing a printed wiring board may further include the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer. When the support is removed after step (II), the support may be removed between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). Furthermore, the formation of the insulating layer and the conductor layer in steps (I) to (V) may be repeated to form a multilayer wiring board, as necessary.

[0227] Step (III) is a step of drilling holes in the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. Step (III) may be performed using, for example, a drill, a laser, plasma, or the like, depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be determined appropriately depending on the design of the printed wiring board.

[0228] Step (IV) is a step of roughening the insulating layer. Usually, smear removal is also performed in this step (IV). The procedure and conditions of the roughening treatment are not particularly limited. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

[0229] Examples of swelling solutions used in the roughening treatment include alkaline solutions and surfactant solutions, with alkaline solutions being preferred. Examples of alkaline solutions include sodium hydroxide solutions and potassium hydroxide solutions. Examples of commercially available swelling solutions include "Swelling Dip Securigance P" and "Swelling Dip Securigance SBU" manufactured by Atotech Japan. The swelling treatment using a swelling solution is not particularly limited, but can be carried out, for example, by immersing the insulating layer in a swelling solution at 30°C to 90°C for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 to 15 minutes.

[0230] Examples of oxidizing agents used in the roughening treatment include alkaline permanganate solutions prepared by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. Roughening treatment using an oxidizing agent such as alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigance P" manufactured by Atotech Japan.

[0231] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and a commercially available product such as "Reduction Solution Securigant P" manufactured by Atotech Japan can be cited. Treatment with a neutralizing solution can be carried out by immersing the surface that has been roughened with an oxidizing agent in a neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From the standpoint of workability, a preferred method is to immerse the object that has been roughened with an oxidizing agent in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

[0232] Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer. Examples of alloy layers include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). Among these, from the viewpoints of versatility in forming the conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy is preferred, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy is more preferred, and a single metal layer of copper is even more preferred.

[0233] The conductor layer may have a single layer structure, or a multi-layer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of a nickel-chromium alloy.

[0234] The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0235] The conductor layer is preferably formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer using a method such as a semi-additive method or a full-additive method. From the viewpoint of ease of production, the conductor layer is preferably formed by a semi-additive method. An example of forming a conductor layer by a semi-additive method will be described below.

[0236] A plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer, exposing a portion of the plating seed layer corresponding to the desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Thereafter, unnecessary plating seed layer is removed by etching or the like, thereby forming a conductor layer having the desired wiring pattern.

[0237] [Semiconductor Devices] A semiconductor device according to one embodiment of the present invention includes the above-described printed wiring board, and can be manufactured using the above-described printed wiring board.

[0238] Examples of semiconductor devices include various semiconductor devices used in electrical appliances (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircraft). [Example]

[0239] The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. Furthermore, the operations described below were carried out in an environment of normal temperature and pressure, unless otherwise specified.

[0240] <Synthesis Example 1: Synthesis of Maleimide Resin A> An MEK solution (62% by mass of non-volatile components) of maleimide X (Mw / Mn = 1.81, t'' = 1.47 (mainly 1, 2, or 3)) synthesized by the method described in Synthesis Example 1 of the Japan Institute of Invention and Innovation's Technical Journal Disclosure No. 2020-500211 was prepared. This maleimide resin A has a structure represented by the following formula.

[0241] [ka]

[0242] <Synthesis Example 2: Synthesis of Polyimide Resin B> A monomer mixture obtained by mixing 46.5 g of 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA), 50.4 g of 4,4'-[1,4-phenylenebis[(1-methylethylidene)-4,1-phenyleneoxy]]bisbenzenamine (BPPAN), 1.1 g of maleic anhydride, and 40 g of toluene into 400 g of N,N-dimethylacetamide (DMAc) was stirred and reacted at room temperature and atmospheric pressure for 3 hours. This resulted in a polyamic acid solution. The resulting polyamic acid solution was heated and then, while maintaining the temperature at approximately 160°C, condensed water was azeotropically removed with toluene under a nitrogen stream. It was confirmed that the specified amount of water had accumulated in the water content receiver and that no water was leaking out. After confirmation, the reaction solution was further heated and stirred at 200°C for 1 hour. It was then cooled. This yielded a varnish containing 20% ​​by mass of polyimide resin B as a non-volatile component.

[0243] <Synthesis Example 3: Synthesis of Polyimide Resin C> A monomer mixture obtained by mixing 46.5 g of BPADA, 37.8 g of BPPAN, 12.8 g of dimer diamine (PRIAMINE 1075), 1.9 g of 5-norbornene-2,3-dicarboxylic anhydride, and 40 g of toluene into 400 g of DMAc was stirred and reacted at room temperature and atmospheric pressure for 3 hours. This resulted in a polyamic acid solution. Using the resulting polyamic acid solution, a varnish containing 20 mass% of polyimide resin C as a non-volatile component was obtained in the same manner as in Synthesis Example 2.

[0244] [Examples 1 to 22, Comparative Examples 1 to 8] <Production of Resin Composition> Each component was weighed out in the parts by mass shown in Table 1, and then mixed with 10 parts of MEK and 2 parts of cyclohexanone, and the mixture was uniformly dispersed using a high-speed rotating mixer to obtain a varnish-like resin composition. Details of each component listed in Table 1 are as follows. (A) Epoxy resin (A-1) Epoxy resin that is liquid at room temperature 806H: Functional group equivalent weight 170, manufactured by Mitsubishi Chemical Corporation HP-4032SS: Functional group equivalent weight 144, manufactured by DIC 2021P: Functional group equivalent weight 137, manufactured by Daicel Corporation (A-2) Biphenol-based epoxy resin YX4000H: Functional group equivalent weight 194, manufactured by Mitsubishi Chemical Corporation Other epoxy resins ESN-475V: Functional group equivalent weight 332, manufactured by Nippon Steel Chemical & Material Co., Ltd.

[0245] (B) Maleimide resin and polyimide resin MIR-3000-70MT: toluene / MEK mixed solution with 70% non-volatile content, manufactured by Nippon Kayaku Co., Ltd. Maleimide resin A: Synthesized in Synthesis Example 1 ·BMI-689: Manufactured by Designer Molecules Inc. ·BMI-1500: Manufactured by Designer Molecules Inc. Polyimide resin B: Synthesized in Synthesis Example 2 Polyimide resin C: Synthesized in Synthesis Example 3 PIAD200: A mixed solution of cyclohexanone, dimethyl glycol, and methylcyclohexane with a non-volatile content of 30% by mass, manufactured by Arakawa Chemical Industries, Ltd. (C) Inorganic filler SO-C2: Spherical silica surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 0.5 μm, specific surface area 5.8 m2 / g, manufactured by Admatechs Co., Ltd.

[0246] (D) Other thermosetting resins OPE-2St: toluene solution with functional group equivalent of 590 and non-volatile content of 65% by mass, manufactured by Mitsubishi Gas Chemical Co., Ltd. GPH-65: Functional group equivalent weight 201, manufactured by Nippon Kayaku Co., Ltd. LA-3018-50P: 1-methoxy-2-propanol solution with a functional group equivalent weight of 151 and a non-volatile content of 50% by mass, manufactured by DIC Corporation V-03: Toluene solution with functional group equivalent weight of 216 and non-volatile content of 50% by mass, manufactured by Nisshinbo Chemical Inc. JBZ-OP100D: Functional group equivalent weight 218, manufactured by JFE Chemical Corporation HPC-8000-65T: Functional group equivalent weight 223, non-volatile content 65% toluene solution, manufactured by DIC HP-B-8151-62T: Toluene solution with functional group equivalent of 238 and non-volatile content of 62%, manufactured by DIC Corporation (E) Curing accelerator 1B2PZ: Shikoku Chemicals Corporation

[0247] <Test Example 1: MIT test (folding endurance)> (1) Preparation of a resin sheet having a resin composition layer thickness of 40 μm A polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, thickness 38 μm) with a release layer was prepared as a support. The varnish-like resin compositions obtained in the Examples and Comparative Examples were uniformly applied onto the release layer of this support so that the thickness of the resin composition layer after drying would be 40 μm. Thereafter, the resin composition was dried at 80°C to 100°C (average 90°C) for 2 minutes to obtain a resin sheet including a support and a resin composition layer.

[0248] (2) Preparation of hardened product The obtained resin sheet was cured for 90 minutes in an oven at 190° C. The support was peeled off from Resin Sheet A after it was taken out of the oven, thereby obtaining a cured product of the resin composition for evaluation.

[0249] (3) MIT Exam The cured product for evaluation was cut into test pieces measuring 15 mm wide and 110 mm long, and the number of folding cycles until breakage of the cured product for evaluation was measured using an MIT testing device (MIT folding fatigue tester "MIT-DA" manufactured by Toyo Seiki Seisaku-sho, Ltd.) in accordance with JIS C-5016 under the following measurement conditions: load 2.5 N, bending angle 90 degrees, bending radius 1.0 mm, bending speed 175 times / min. Measurements were performed on five samples, and the average of the top three was calculated.

[0250] <Test Example 2: Measurement of coefficient of linear thermal expansion (CTE)> The cured product for evaluation obtained in Test Example 1 was cut into test pieces approximately 5 mm wide and 15 mm long, and thermomechanical analysis was performed using a thermomechanical analyzer (Rigaku Corporation, "Thermo Plus TMA8310") by the tensile load method. Specifically, after mounting the test pieces in the thermomechanical analyzer, the linear thermal expansion coefficient (ppm) was measured twice consecutively under measurement conditions of a 1 g load and a heating rate of 5°C / min (the first measurement was performed to 200°C, and the second measurement was performed to 260°C). The average linear expansion coefficient (ppm / °C) was calculated from the thermal expansion coefficient value from 25°C to 150°C in the second measurement.

[0251] <Test Example 3: Evaluation of smear removal ability> (1) Preparation of inner layer board: A glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.8 mm, Panasonic "R1515A") with an inner layer circuit formed on it was etched on both sides by 0.5 μm using MEC "CZ8201" to roughen the copper surface. It was then heated in an oven at 130°C for 30 minutes. This produced an inner layer substrate. (2) Lamination of resin sheets: The resin sheet obtained in Test Example 1 was laminated onto both sides of an inner layer substrate using a batch-type vacuum pressure laminator (a two-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.) so that the resin composition layer was in contact with the inner layer substrate. Lamination was performed by reducing the pressure to 13 hPa or less for 30 seconds, followed by pressure bonding at 100°C and a pressure of 0.74 MPa for 30 seconds. Next, a heat press was performed at 100°C and a pressure of 0.5 MPa for 60 seconds. (3) Hardening of resin sheet: The resin sheet laminated to the inner layer substrate was heated under the curing conditions of 100°C for 30 minutes and then 180°C for 30 minutes. (4) Via hole formation: Using a CO2 laser processing machine (LK-2K212 / 2C) manufactured by Via Mechanics, the insulating layer was processed under the conditions of a frequency of 2000 Hz, a pulse width of 3 μs, an output of 0.95 W, and a shot count of 3, to form via holes with a top diameter of 50 μm on the insulating layer surface and a diameter of 50 μm on the insulating layer bottom surface. After that, the support was peeled off to obtain a circuit board. (5) Roughening treatment The insulating layer surface of the resulting circuit board was immersed in a swelling solution, Atotech Japan's Swelling Dip Securiganth P, for 10 minutes at 60°C. Next, the insulating layer surface of the circuit board was immersed in a roughening solution, Atotech Japan's Concentrate Compact P (aqueous solution of 60 g / L KMnO4 and 40 g / L NaOH), for 25 minutes at 80°C. Finally, the insulating layer surface of the circuit board was immersed in a neutralizing solution, Atotech Japan's Reduction Solution Securiganth P, for 5 minutes at 40°C. (6) Evaluation of residue at the bottom of via holes The periphery of the bottom of the via hole was observed with a scanning electron microscope (SEM), and the maximum smear length from the wall surface of the bottom of the via hole was measured from the obtained image and evaluated according to the following criteria. ○: Maximum smear length is less than 5 μm ×: Maximum smear length is 5 μm or more

[0252] <Test Example 4: Evaluation of tackiness> The tack strength of the resin composition layer of the resin sheet obtained in Test Example 1 was measured using a probe tack tester (TE-6002) with a thermostatic chamber manufactured by Tester Sangyo Co., Ltd. A 5 mm diameter cylindrical probe made of SUS was brought into contact with the resin sheet placed in a thermostatic chamber at a contact speed of 0.5 cm / sec, and a tack strength of 1000 gf / cm was measured. 2 After holding the probe under the load for 1 second, the peel force when the probe was pulled away at 0.5 cm / second was measured and defined as the probe tack. Measurements were carried out three times for each sample, and the average value of each measurement was calculated and evaluated according to the following criteria. ○: Probe tack is less than 0.4N ×: Probe tack is 0.4N or more

[0253] The results of Test Examples 1 to 4 are shown in Tables 1 and 2.

[0254] [Table 1]

[0255] [Table 2]

Claims

1. (A) an epoxy resin, (B) a maleimide resin and / or a polyimide resin, and (C) an inorganic filler; Component (A) (A-1) an epoxy resin that is liquid at room temperature; (A-2) a biphenol-skeleton epoxy resin, the ratio x / X, where X is the total number of epoxy groups in component (A) and x is the number of epoxy groups in component (A-1), is 0.4 to 0.9; A resin composition, wherein the content of the (B) component is 7 to 30 mass % when the resin component in the resin composition is 100 mass %.

2. 2. The resin composition according to claim 1, wherein the maleimide resin of component (B) is a maleimide resin having a dimer acid skeleton.

3. 2. The resin composition according to claim 1, wherein the polyimide resin of component (B) is a polyimide resin containing a structural unit represented by the following formula (b1): 【Chemistry 1】 [In formula (b1), R １ is a tetravalent group represented by the following formula (b1-1): R ２ is a divalent group represented by the following formula (b1-2): 【Chemistry 2】 (In formula (b1-1), Ar １１ , Ar １２ , Ar １３ and Ar １４ each independently represents an aromatic ring which may have a substituent, L １１ , L １２ and L １３ each independently represents a divalent linking group, nc1 represents an integer of 0 or more. 【Transformation 3】 (In formula (b1-2), Ar ２１ , Ar ２２ , Ar ２３ and Ar ２４ each independently represents an aromatic ring which may have a substituent, L ２１ , L ２２ and L ２３ each independently represents a divalent linking group, and nc2 represents an integer of 1 or more.

4. In formula (b1-1), Ar １１ , Ar １２ , Ar １３ and Ar １４ are each independently an aromatic carbocyclic ring having 6 to 14 carbon atoms which may have a substituent, In formula (b1-2), Ar ２１ , Ar ２２ , Ar ２３ and Ar ２４ and each independently represent an aromatic carbon ring having 6 to 14 carbon atoms which may have a substituent.

5. In formula (b1-1), L １１ and L １３ is -O-, and L １２ is an alkylene group which may have a substituent, In formula (b1-2), L ２１ and L ２３ is -O-, and L ２２ The resin composition according to claim 3 , wherein is an alkylene group which may have a substituent.

6. The resin composition according to claim 1, wherein the content of the component (C) is 60 to 80 mass % when the total amount of nonvolatile components in the resin composition is 100 mass %.

7. The resin composition according to claim 1 , further comprising (D) another thermosetting resin.

8. The resin composition according to claim 7, wherein the component (D) comprises at least one selected from the group consisting of a phenolic resin, a carbodiimide resin, a benzoxazine resin, and an active ester resin.

9. The resin composition according to claim 1, further comprising (E) a curing accelerator.

10. 2. The resin composition according to claim 1, wherein the coefficient of linear thermal expansion (CTE) of the cured resin composition is 30 ppm / °C or less in the range of 25°C to 150°C.

11. The resin composition according to claim 1, which is used to form an insulating layer.

12. A resin sheet comprising a support and a resin composition layer provided on the support, the resin composition comprising the resin composition according to any one of claims 1 to 11.

13. A circuit board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 11.

14. A semiconductor device comprising the circuit board according to claim 13.

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