Resin composition

Abstract

The present invention provides a resin composition which can obtain a cured product having low dielectric loss tangent and can suppress warpage. The present invention is a resin composition comprising (A) an epoxy resin, (B) an active ester resin containing a naphthalene skeleton, (C) a polyimide resin containing a dimer diamine skeleton and having a phenolic hydroxyl group, and (D) an inorganic filler, wherein the amount of (D) the inorganic filler is 70% by mass or more relative to 100% by mass of the non-volatile components of the resin composition.

Description

Technical Field

[0001] This invention relates to resin compositions and their cured products, resin sheets, circuit boards, and semiconductor devices. Background Technology

[0002] Circuit boards, such as printed wiring boards and semiconductor chip packaging substrates, are widely used in various electronic devices. As a method for manufacturing circuit boards, a known method involves alternating layers of insulating and conductive layers on an inner substrate in a build-up manner. The insulating layer is formed, for example, using a cured resin composition (Patent Documents 1-3). Specifically, by forming a resin composition layer containing a resin composition and then curing that resin composition layer, an insulating layer containing a cured resin composition is formed.

[0003] Existing technical documents [Patent Literature] [Patent Document 1] International Publication No. 2019 / 188436 [Patent Document 2] International Publication No. 2023 / 112443 [Patent Document 3] Japanese Patent Application Publication No. 2024-14835. Summary of the Invention

[0004] The technical problem to be solved by the invention In high-speed communications such as fifth-generation mobile communication systems (5G), there is a need to suppress transmission loss when operating in high-frequency environments. Furthermore, circuit boards sometimes exhibit high temperatures due to heat generated by semiconductor chips. Therefore, cured resin compositions used as insulating layer forming materials require low dielectric loss tangents at high temperatures and high frequencies.

[0005] In recent years, in particular, the increasing size of semiconductor chip packaging substrates has led to longer wiring lengths and a tendency for increased transmission losses. Therefore, there is a demand for a further significant reduction in the dielectric loss tangent. On the other hand, large semiconductor chip packaging substrates tend to exhibit increased warpage. Therefore, it is desirable for cured resin compositions to suppress warpage of circuit boards such as semiconductor chip packages. However, conventional resin compositions that form cured products with small dielectric loss tangents tend to exhibit large shrinkage after curing, making it difficult to simultaneously reduce the dielectric loss tangent and suppress warpage.

[0006] The present invention was made in view of the aforementioned problems, and its object is to provide: a resin composition that yields a cured product with a low dielectric loss tangent and suppresses warping; a resin sheet comprising the resin composition; a cured product of the resin composition; a circuit board comprising the cured product of the resin composition; and a semiconductor device comprising the aforementioned circuit board.

[0007] Methods for solving technical problems The inventors conducted in-depth research to solve the aforementioned problems. As a result, the inventors discovered that a resin composition comprising (A) an epoxy resin, (B) an active ester resin containing a naphthalene skeleton, (C) a polyimide resin containing a dimer diamine skeleton and having phenolic hydroxyl groups, and (D) an inorganic filler in a specific range, can solve the aforementioned problems, thus completing the present invention. That is, the present invention comprises the following.

[0008] <1> A resin composition comprising (A) an epoxy resin, (B) an active ester resin containing a naphthalene backbone, (C) a polyimide resin containing a dimeric diamine backbone and having phenolic hydroxyl groups, and (D) an inorganic filler. Of which, relative to 100% by mass of the non-volatile components of the resin composition, (D) the amount of inorganic filler is greater than 70% by mass; <2> according to <1> The resin composition, wherein it comprises (E) rubber particles; <3> according to <1> or <2> The resin composition, wherein it comprises (F) a curing accelerator; <4> according to <1> ~ <3> The resin composition according to any one of the following, wherein (D) the inorganic filler has an average particle size of less than 1 μm; <5> according to <1> ~ <4> The resin composition according to any one of the following, wherein component (C) has a number-average molecular weight greater than 5,000; <6> according to <1> ~ <5> The resin composition according to any one of the following methods, wherein the amount of component (C) is 0.01% by mass or more and 10% by mass or less relative to 100% by mass of the non-volatile components of the resin composition; <7> according to <1> ~ <6> The resin composition according to any one of the following, wherein the amount of component (B) is more than 1% by mass and less than 25% by mass relative to 100% by mass of the non-volatile components of the resin composition; <8> A resin sheet comprising a support and a resin composition layer disposed on the support. The resin composition layer contains <1> ~ <7> The resin composition described in any one of the following; <9> <1> ~ <7> The cured product of the resin composition described in any one of the above statements; <10> A circuit board comprising <1> ~ <7> The cured product of the resin composition described in any one of the above statements; <11> A semiconductor device having <10> The circuit board mentioned above.

[0009] The effects of the invention According to the present invention, the following can be provided: a resin composition that yields a cured product with a low dielectric loss tangent and suppresses warping; a resin sheet comprising the resin composition; a cured product of the resin composition; a circuit board comprising the cured product of the resin composition; and a semiconductor device comprising the aforementioned circuit board. Detailed Implementation

[0010] Hereinafter, embodiments and examples of the present invention will be described. However, the present invention is not limited to the embodiments and examples shown below, and can be implemented with modifications that do not depart from the scope of the claims and their equivalents.

[0011] In the following description, unless otherwise stated, the term "dielectric constant" means "relative dielectric constant".

[0012] In this specification, the term "optionally having substituents" as used with respect to a compound or group refers to two situations: where the hydrogen atoms of the compound or group are not substituted by substituents; and where some or all of the hydrogen atoms of the compound or group are substituted by substituents.

[0013] <Summary of the Resin Composition> One embodiment of the present invention relates to a resin composition comprising: (A) an epoxy resin, (B) an active ester resin containing a naphthalene skeleton, (C) a polyimide resin containing a dimericane skeleton and having phenolic hydroxyl groups, and (D) an inorganic filler material in a specific range. In the following description, "(B) an active ester resin containing a naphthalene skeleton" is sometimes referred to as "(B) a naphthalene-type active ester resin." Furthermore, "(C) a polyimide resin containing a dimericane skeleton and having phenolic hydroxyl groups" is sometimes referred to as "(C) a dimericane-type polyimide resin containing hydroxyl groups."

[0014] According to the resin composition of this embodiment, a cured product exhibiting a low dielectric loss tangent Df at high temperatures and high frequencies can be obtained. Furthermore, the cured product of the resin composition of this embodiment can suppress warping of circuit boards containing the cured product. Moreover, the cured product of the resin composition of this embodiment typically has a low relative permittivity Dk at high temperatures and high frequencies. Furthermore, the cured product of the resin composition of this embodiment typically has a high glass transition temperature Tg. Furthermore, the cured product of the resin composition of this embodiment typically has a small coefficient of linear thermal expansion CTE.

[0015] Regarding the mechanism by which the aforementioned excellent effects are achieved, the inventors speculate as follows. However, the scope of the present invention is not limited to the following mechanism.

[0016] In the resin composition of this embodiment, the epoxy groups of (A) the epoxy resin can react with the active ester groups of (B) the naphthalene-type active ester resin. Furthermore, typically, the epoxy groups of (A) the epoxy resin can react with the phenolic hydroxyl groups of (C) the dimeric diamine-type polyimide resin containing hydroxyl groups. As a result of these reactions, bonds are formed, and consequently, the resin composition cures. Thus, as a layer comprising the cured resin composition obtained in this way, an insulating layer for a circuit board can be formed.

[0017] By utilizing the reaction between epoxy groups and reactive ester groups, polar groups such as hydroxyl groups are generally not generated, thus resulting in a less polar cured product. Furthermore, (B) the naphthalene-type reactive ester resin has a rigid molecular skeleton, which reduces molecular vibrations when an alternating current is applied. Moreover, (D) the inorganic filler material typically contains inorganic materials with lower dielectric properties than organic materials. Therefore, by combining these effects, the dielectric loss tangent Df of the cured product can be reduced, which in turn generally reduces the relative permittivity Dk of the cured product.

[0018] Furthermore, the rigid naphthalene skeleton contained in (B) naphthalene-type reactive ester resin can improve the rigidity of the cured product. Moreover, the reaction between epoxy groups and phenolic hydroxyl groups proceeds more smoothly than the reaction between epoxy groups and other functional groups (e.g., maleimide groups; see Comparative Example 4). Therefore, sufficient bonds can be formed not only by the reaction between (A) epoxy resin and (B) naphthalene-type reactive ester resin, but also by the reaction between (A) epoxy resin and (C) hydroxyl-containing dimeric diamine-type polyimide resin. Therefore, a strong cross-linked structure can be formed based on the dense bonds in the cured product, thereby improving the rigidity of the cured product. Furthermore, (A) epoxy resin, (B) naphthalene-type reactive ester resin, and (C) hydroxyl-containing dimeric diamine-type polyimide resin all have polar groups such as epoxy groups, reactive ester groups, and phenolic hydroxyl groups, thus exhibiting high compatibility in the resin composition. Therefore, the cured product formed by curing this resin composition has a homogeneous composition, and thus the cured product as a whole exhibits high rigidity. Therefore, the high rigidity of the cured material can suppress stress-induced deformation. Furthermore, the dimericamine backbone contained in (C) the hydroxyl-containing dimericamine-type polyimide resin is a soft molecular backbone that can absorb stress. Therefore, the stress generated in the cured material can be reduced by utilizing the dimericamine backbone. In addition, the rigid naphthalene backbone contained in (B) the naphthalene-type reactive ester resin can reduce the coefficient of thermal expansion of the cured material. Furthermore, since a strong cross-linked structure can be formed based on the reaction of (A) epoxy resin, (B) naphthalene-type reactive ester resin and (C) the hydroxyl-containing dimericamine-type polyimide resin, the coefficient of thermal expansion of the cured material can be reduced. In addition, the inorganic materials contained in (D) the inorganic filler generally have a lower coefficient of thermal expansion than organic materials. Therefore, the degree of deformation of the cured material due to heat can be reduced, thus reducing the stress generated by heat in the cured material. Therefore, by combining these effects, the warpage of the circuit board containing the cured material can be reduced.

[0019] Furthermore, it is believed that the rigid naphthalene skeleton contained in (B) naphthalene-type reactive ester resin, the formation of sufficient bonds through the reaction of (A) epoxy resin and (C) dimeric diamine-type polyimide resin containing hydroxyl groups, and the homogeneity of the composition of the cured product also contribute to increasing the glass transition temperature Tg of the cured product.

[0020] <(A) Epoxy Resin> The resin composition according to this embodiment includes epoxy resin (A) as component (A). Epoxy resin (A) may be a curable resin having epoxy groups. Epoxy resin (A) may be used alone or in combination of two or more.

[0021] Examples of epoxy resins (A) include: bisphenol A type epoxy resin, bisphenol C type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol phenolic varnish type epoxy resin, phenol phenolic varnish type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, and glycidyl ester type epoxy resin. Epoxy resins include aliphatic, cresol-phenolic varnish-type, phenolic aralkyl-type, biphenyl-type, linear aliphatic epoxy resins, butadiene-structured epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, spirocyclic epoxy resins, cyclohexane-type, cyclohexanediol-type, naphthyl ether-type, tris(hydroxymethyl)-type, tetraphenylethane-type, isocyanurate-type, and bisphenol-type epoxy resins containing an imide backbone. Biphenyl-type epoxy resins refer to epoxy resins with a biphenyl structure, where the biphenyl structure may optionally have substituents such as alkyl, alkoxy, or aryl groups. Therefore, xylenol-type and biphenyl aralkyl-type epoxy resins can also be included within the category of biphenyl-type epoxy resins.

[0022] From the viewpoint of obtaining a cured product with excellent heat resistance, (A) the epoxy resin preferably comprises an epoxy resin containing an aromatic structure. An aromatic structure is a chemical structure generally defined as aromatic, and also includes polycyclic aromatics and aromatic heterocycles. Examples of epoxy resins containing an aromatic structure include: bisphenol A type epoxy resin, bisphenol C type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol phenolic varnish type epoxy resin, phenol phenolic varnish type epoxy resin, tert-butyl-catechol type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, bixylenol type epoxy resin, glycidylamine type epoxy resin with an aromatic structure, and epoxy resins with aromatic structures. Glycidyl ester type epoxy resin, cresol phenolic varnish type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin with aromatic structure, epoxy resin with aromatic structure and butadiene structure, alicyclic epoxy resin with aromatic structure, heterocyclic epoxy resin, spirocyclic epoxy resin with aromatic structure, cyclohexanediol type epoxy resin with aromatic structure, naphthyl ether type epoxy resin, trihydroxymethyl type epoxy resin with aromatic structure, tetraphenylethane type epoxy resin with aromatic structure, etc.

[0023] Preferably, the epoxy resins are bisphenol C type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, and bisphenol type epoxy resin containing an imide skeleton.

[0024] (A) The epoxy resin preferably includes epoxy resin having two or more epoxy groups in one molecule. The proportion of epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, relative to 100% by mass of the non-volatile component of (A) epoxy resin.

[0025] (A) Epoxy resin includes epoxy resin that is liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resin") and epoxy resin that is solid at 20°C (hereinafter sometimes referred to as "solid epoxy resin"). (A) Epoxy resin may contain only liquid epoxy resin, or only solid epoxy resin, or a combination of liquid epoxy resin and solid epoxy resin.

[0026] As a liquid epoxy resin, it is preferable to be a liquid epoxy resin having two or more epoxy groups in one molecule. Preferably, the liquid epoxy resin includes bisphenol A type epoxy resin, bisphenol C type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenolic varnish type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanediethanol type epoxy resin, and epoxy resin having a butadiene structure; more preferably, it includes bisphenol C type epoxy resin and naphthalene type epoxy resin.

[0027] Specific examples of liquid epoxy resins include: DIC's "HP-4032", "HP-4032-D", and "HP-4032-SS" (naphthalene-type epoxy resin); Mitsubishi Chemical's "828US", "828EL", "jER828", "jER828EL", "825", and "EPIKOTE 828EL" (bisphenol A type epoxy resin); Mitsubishi Chemical's "jER807" and "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical's "jER152" (phenolic varnish type epoxy resin); Mitsubishi Chemical's "630", "630LSD", and "604" (glycidylamine type epoxy resin); and ADEKA's "ED-523T" (GLYCIROL type). Epoxy resin); ADEKA's "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resin); ADEKA's "EP-4088S" (dicyclopentadiene type epoxy resin); ADEKA's "ED-506" (polypropylene glycol type epoxy resin); Nippon Steel Chemical Materials Co., Ltd.'s "ZX1059" (a mixture of bisphenol A type 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 with ester skeleton); Daicel's "PB-3600"; Nippon Soda's "JP-100" and "JP-200" (epoxy resin with butadiene structure); and Nippon Steel Chemical Materials' "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin), etc. In addition, the epoxy resin shown in formula (1) as described in Japanese Patent Application Publication No. 2024-85315 can be used.

[0028] As a solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferred. As a solid epoxy resin, bicresol-type epoxy resin, naphthol-type epoxy resin, naphthol-formaldehyde varnish-type epoxy resin, cresol-formaldehyde varnish-type epoxy resin, dicyclopentadiene-type epoxy resin, triphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthylene ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, phenol aralkyl-type epoxy resin, tetraphenylethane-type epoxy resin, and bisphenol-type epoxy resin containing an imide skeleton are more preferred; biphenyl-type epoxy resin and bisphenol-type epoxy resin containing an imide skeleton are even more preferred.

[0029] Specific examples of solid epoxy resins include: DIC's "HP4032H" (naphthalene-type epoxy resin); DIC's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resins); DIC's "N-690" (cresol phenolic varnish type epoxy resin); DIC's "N-695" (cresol phenolic varnish type epoxy resin); DIC's "HP-7200," "HP-7200HH," "HP-7200H," and "HP-7200L" (dicyclopentadiene type epoxy resin); and DIC's "EXA- 7311, EXA-7311-G3, EXA-7311-G4, EXA-7311-G4S, HP-6000, HP-6000L (naphthyl ether type epoxy resin); EPPN-502H (triphenol type epoxy resin) manufactured by Nippon Chemical Co., Ltd.; NC7000L (naphthol phenolic varnish type epoxy resin) manufactured by Nippon Chemical Co., Ltd.; NC3000H, NC3000, NC3000L, NC3000FH, NC3100 (biphenyl type epoxy resin) manufactured by Nippon Chemical Co., Ltd.; Nippon Steel Chemical Co., Ltd. Materials company's "ESN475V", "ESN4100V", "ESN-4100VEK75" (naphthalene-type epoxy resin); Nippon Steel Chemical Materials Co., Ltd.'s "ESN485" (naphthol-type epoxy resin); Nippon Steel Chemical Materials Co., Ltd.'s "ESN375" (dihydroxynaphthalene-type epoxy resin); Mitsubishi Chemical Corporation's "YX4000H", "YX4000", "YX4000HK", "YL7890" (bi-xylenol-type epoxy resin); Mitsubishi Chemical Corporation's "YL6121" (biphenyl-type epoxy resin); Mitsubishi Chemical Corporation's "YX8800" (anthracene-type epoxy resin). Epoxy resins include: "YX7700" (phenolic aralkyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YX7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and "WHR991S" (bisphenol type epoxy resin containing an imide skeleton) manufactured by Nippon Kayaku Co., Ltd., etc.

[0030] (A) When the epoxy resin composition includes liquid epoxy resin and solid epoxy resin, their mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 20:1 to 1:20, more preferably 10:1 to 1:10, and particularly preferably 7:1 to 1:7.

[0031] (A) The epoxy equivalent of the epoxy resin is preferably in the range of 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 3,000 g / eq., further preferably 80 g / eq. to 2,000 g / eq., and particularly preferably 110 g / eq. to 1,000 g / eq. Epoxy equivalent represents the mass of resin per equivalent of epoxy groups. This epoxy equivalent can be determined according to JIS K7236.

[0032] (A) The weight-average molecular weight (Mw) of the epoxy resin is preferably in the range of 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1,500. The weight-average molecular weight can be determined using gel permeation chromatography (GPC) as a value converted from polystyrene.

[0033] The amount of epoxy resin (A) relative to 100% by mass of the non-volatile components of the resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, further preferably 10.5% by mass or less, and particularly preferably 10.2% by mass or less. Unless otherwise stated, the non-volatile components of the resin composition refer to the components in the resin composition other than the solvent (J). When the amount of epoxy resin (A) is within the aforementioned range, it is possible to achieve a high level of reduction in the dielectric loss tangent Df of the cured resin composition and suppression of warpage of the circuit board containing the cured composition, thereby generally effectively reducing the relative permittivity Dk and linear thermal expansion coefficient of the cured composition, and effectively increasing the glass transition temperature Tg.

[0034] The amount of epoxy resin (A) relative to 100% by mass of the resin component of the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 41% by mass or less, further preferably 40% by mass or less, particularly preferably 38% by mass or less. Unless otherwise stated, the resin component of the resin composition refers to the non-volatile components of the resin composition other than (D) the inorganic filler. When the amount of epoxy resin (A) is within the aforementioned range, a high level of reduction in the dielectric loss tangent Df of the cured resin composition and suppression of warpage of the circuit board containing the cured composition can be achieved, thereby generally effectively reducing the relative permittivity Dk and linear thermal expansion coefficient of the cured composition, and effectively increasing the glass transition temperature Tg.

[0035] <(B) Naphthalene-type active ester resin> The resin composition involved in this embodiment includes a (B) naphthalene-type active ester resin as component (B). The (B) naphthalene-type active ester resin can be used alone or in combination of two or more.

[0036] Reactive ester resins generally contain one or more, preferably two or more, reactive ester groups per molecule. Since the reactive ester groups can react with epoxy groups, the reactive ester resin can react with (A) epoxy resin to form a bond. The term "reactive ester group" refers to a group formed by an ester bond directly bonded to an aromatic ring. Unless otherwise specified, the bond between the ester bond and the aromatic ring is "direct," meaning there are no other groups between the ester bond and the aromatic ring. The term "ester bond" can also broadly include thioester bonds (-C(=O)-S-). From the viewpoint of improving the heat resistance of the cured product, a narrower ester bond (-C(=O)-O-) formed by a carbonyl oxygen group is preferred. Furthermore, this reactive ester group includes not only the ester bonds contained in the structure "aromatic carbon-C(=O)-O-aromatic carbon," but also the ester bonds contained in the structure "aliphatic carbon-C(=O)-O-aromatic carbon," provided they can react with epoxy groups to form a bond. Furthermore, the term "aromatic ring" refers to a ring that follows Hückel's rule, containing 4p+2 electrons (p being a natural number) in its π-electron system. This includes monocyclic aromatic rings and fused polycyclic aromatic rings obtained by fusion of two or more monocyclic aromatic rings. Additionally, the aromatic ring can be an aromatic carbon ring having only carbon atoms as ring-forming atoms, or an aromatic heterocycle having oxygen, nitrogen, sulfur, or other heteroatoms as ring-forming atoms in addition to carbon atoms. Benzene rings, naphthalene rings, and anthracene rings are preferred as aromatic rings, with benzene rings and naphthalene rings being particularly preferred. The term "aromatic carbon" refers to the carbon atoms constituting the aromatic ring.

[0037] (B) Naphthalene-type reactive ester resin is an reactive ester resin containing a naphthalene skeleton. Therefore, (B) naphthalene-type reactive ester resin contains a naphthalene skeleton by combining with the aforementioned reactive ester groups. One molecule of (B) naphthalene-type reactive ester resin may contain one or more naphthalene skeletons. From the viewpoint of significantly obtaining the effects of the present invention, it is preferable that each molecule of (B) naphthalene-type reactive ester resin contains two or more naphthalene skeletons.

[0038] The naphthalene skeleton is preferably bonded to the ester bond. (B) When the naphthalene-type active ester resin contains more than two naphthalene skeletons in one molecule, only a portion of the naphthalene skeleton may be bonded to the ester bond, but it is preferred that all of the naphthalene skeleton is bonded to the ester bond.

[0039] For the naphthalene skeleton bonded to the ester bond, it can be directly bonded to the carbonyl group (-C=O)- contained in the ester bond (-OC(=O)-) or directly bonded to the oxygen group (-O-) contained in the ester bond. Unless otherwise specified, the bond between the naphthalene skeleton and the carbonyl group is "direct," meaning that there are no other groups between the naphthalene skeleton and the carbonyl group. Furthermore, unless otherwise specified, the bond between the naphthalene skeleton and the oxygen group is "direct," meaning that there are no other groups between the naphthalene skeleton and the oxygen group. Preferably, the naphthalene skeleton is directly bonded to the oxygen group contained in the ester bond. Therefore, (B) the naphthalene-type reactive ester resin preferably contains the structure shown in "naphthalene skeleton -OC(=O)-".

[0040] (B) The naphthalene-type reactive ester resin preferably comprises a structural unit having a naphthalene skeleton, and the naphthalene skeleton is bonded to two or more ester bonds. In this case, the aforementioned structural unit may contain one or more naphthalene skeletons. For example, the aforementioned structural unit may contain one "naphthalene skeleton bonded to two or more ester bonds." Furthermore, for example, the aforementioned structural unit may contain two or more "naphthalene skeletons bonded to one or two or more ester bonds." In this case, the main skeleton of the resin formed by reacting (A) epoxy resin and (B) naphthalene-type reactive ester resin contains the aforementioned structural unit having a naphthalene skeleton. Therefore, the role of the naphthalene skeleton can be utilized particularly effectively, and the effects of the present invention can be significantly obtained.

[0041] (B) Naphthalene-type reactive ester resins are preferably obtained through a condensation reaction of carboxylic acid compounds and / or thiocarboxylic acid compounds with hydroxyl compounds and / or thiols. Particularly from the viewpoint of improving heat resistance, reactive ester resins obtained from carboxylic acid compounds and hydroxyl compounds are preferred, and more preferably reactive ester resins obtained from carboxylic acid compounds and naphthol compounds. The aforementioned naphthol compounds refer to compounds containing a naphthalene ring and a hydroxyl group directly bonded to that naphthalene ring. Naphthalene compounds having two or more hydroxyl groups directly bonded to the naphthalene ring are particularly preferred. Unless otherwise stated, the bond between the naphthalene ring and the hydroxyl group is described as "direct," meaning that no other groups exist between the naphthalene ring and the hydroxyl group.

[0042] Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of naphthol compounds include α-naphthol, β-naphthol, 1,5-dihydroxynaphthol, 1,6-dihydroxynaphthol, and 2,6-dihydroxynaphthol.

[0043] (B) Naphthalene-type reactive ester resins may have polymerizable unsaturated groups. Polymerizable unsaturated groups refer to groups containing non-aromatic carbon-carbon unsaturated bonds, such as unsaturated hydrocarbon groups like vinyl, allyl, 1-propenyl, 3-cyclohexenyl, 3-cyclopentenyl, 2-vinylphenyl, 3-vinylphenyl, and 4-vinylphenyl; and α,β-unsaturated carbonyl groups like acryloyl, methacryloyl, and maleimide (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl). Unsaturated hydrocarbon groups are preferred, and allyl is more preferred. Polymerizable unsaturated groups are typically formed by free radical polymerization during the curing of the resin composition. (B) A naphthalene-type reactive ester resin may have only one polymerizable unsaturated group per molecule, or it may contain two or more polymerizable unsaturated groups.

[0044] Commercially available (B) naphthalene-type reactive ester resins include, for example: "EXB-9416-70BK", "EXB-8100L-65T", "HPC-8150-62T", "EXB-8150L-65T", "EXB-8100L-65T", and "EXB-8" (manufactured by DIC).

[0045] (B) The active ester equivalent of the naphthalene-type active ester resin is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, more preferably 3,000 g / eq. or less, more preferably 1,000 g / eq. or less, further preferably 500 g / eq. or less, and particularly preferably 300 g / eq. or less. The active ester equivalent indicates the mass of resin per 1 equivalent of active ester groups.

[0046] (B) The range of weight-average molecular weight (Mw) of naphthalene-type reactive ester resins can be the same as the range of weight-average molecular weight (Mw) of (A) epoxy resins.

[0047] The equivalent ratio (active ester group / epoxy group) of the naphthalene-type reactive ester resin to the epoxy group of the epoxy resin in (B) is preferably 0.1 or more, more preferably 0.5 or more, further preferably 0.8 or more, further preferably 1.0 or more, particularly preferably greater than 1.1, preferably 5 or less, more preferably 3 or less, further preferably 2 or less, and further preferably 1.8 or less. The aforementioned equivalent ratio (active ester group / epoxy group) can be obtained by dividing the number of active ester groups in the naphthalene-type reactive ester resin in (B) of the resin composition by the number of epoxy groups in the epoxy resin in (A). The number of epoxy groups in the epoxy resin in (A) of the resin composition represents the sum of all values ​​obtained by dividing the mass of the non-volatile component of the epoxy resin present in the resin composition by its epoxy equivalent. Furthermore, the "number of active ester groups in (B) naphthalene-type active ester resin" in the resin composition represents the sum of all values ​​obtained by dividing the mass of the non-volatile component of the (B) naphthalene-type active ester resin present in the resin composition by its equivalent active ester group. When the aforementioned equivalent ratio (active ester group / epoxy group) is within the aforementioned range, a high level of reduction in the dielectric loss tangent Df of the cured resin composition and suppression of warpage of the circuit board containing the cured composition can be achieved, thereby generally effectively reducing the relative permittivity Dk and linear thermal expansion coefficient of the cured composition, and effectively increasing the glass transition temperature Tg.

[0048] The amount of (B) naphthalene-type active ester resin relative to 100% by mass of the non-volatile components of the resin composition is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, particularly preferably 11% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, and further preferably 16% by mass or less. When the amount of (B) naphthalene-type active ester resin is within the aforementioned range, a high level of reduction in the dielectric loss tangent Df of the cured resin composition and suppression of warpage of the circuit board containing the cured composition can be achieved. Consequently, the relative permittivity Dk and linear thermal expansion coefficient of the cured composition can generally be effectively reduced, and the glass transition temperature Tg can be effectively increased. It should be noted that the amount of (B) naphthalene-type active ester resin relative to 100% by mass of the non-volatile components of the resin composition can be 12% by mass or more, 13% by mass or more, 13% by mass or less, 14% by mass or more, 14% by mass or less, or 15% by mass or less.

[0049] The amount of (B) naphthalene-type active ester resin relative to 100% by mass of the resin component in the resin composition is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, particularly preferably 44% by mass or more, preferably 70% by mass or less, more preferably 65% ​​by mass or less, and further preferably 60% by mass or less. When the amount of (B) naphthalene-type active ester resin is within the aforementioned range, a high level of reduction in the dielectric loss tangent Df of the cured resin composition and suppression of warpage of the circuit board containing the cured composition can be achieved. Consequently, the relative permittivity Dk and linear thermal expansion coefficient of the cured composition can generally be effectively reduced, and the glass transition temperature Tg can be effectively increased. It should be noted that the amount of (B) naphthalene-type active ester resin relative to 100% by mass of the resin component in the resin composition can be 50% by mass or more, or 50% by mass or less, or 55% by mass or more, or 55% by mass or less.

[0050] Based on mass, (B) naphthalene-type reactive ester resin can be less than, more than, or the same amount as (A) epoxy resin. Preferably, based on mass, (B) naphthalene-type reactive ester resin is more than (A) epoxy resin. In one example, the amount of (B) naphthalene-type reactive ester resin relative to 100% by mass of (A) epoxy resin is preferably 10% by mass or more, more preferably 50% by mass or more, further preferably 80% by mass or more, particularly preferably 110% by mass or more, preferably 500% by mass or less, more preferably 400% by mass or less, and further preferably 300% by mass or less. When the amount of (B) naphthalene-type reactive ester resin is within the aforementioned range, a high level of reduction in the dielectric loss tangent Df of the cured resin composition and suppression of warpage of the circuit board containing the cured composition can be achieved. Furthermore, the relative permittivity Dk and linear thermal expansion coefficient of the cured composition can generally be effectively reduced, and the glass transition temperature Tg can be effectively increased. It should be noted that the amount of (A) epoxy resin 100% by mass and (B) naphthalene-type reactive ester resin can be above 120% by mass, above 130% by mass, below 130% by mass, above 150% by mass, below 150% by mass, above 180% by mass, below 180% by mass, or below 220% by mass.

[0051] As described below, the resin composition involved in this embodiment may contain (G) any curing agent. This (G) any curing agent may contain an active ester resin other than (B) naphthalene-type active ester resin. Hereinafter, "active ester resin other than (B) naphthalene-type active ester resin" will sometimes be referred to as "any active ester resin". The equivalent ratio (active ester group / epoxy group) of the active ester groups of all active ester resins containing (B) naphthalene-type active ester resin and any active ester resin to the epoxy groups of (A) epoxy resin is preferably 0.1 or more, more preferably 0.5 or more, further preferably 0.8 or more, further preferably 1.0 or more, particularly preferably greater than 1.1, preferably 5 or less, more preferably 3 or less, further preferably 2 or less, and further preferably 1.8 or less. The aforementioned equivalent ratio (active ester group / epoxy group) can be obtained by dividing the "number of active ester groups of all active ester resins" in the resin composition by the "number of epoxy groups of (A) epoxy resin". The term "number of active ester groups in all active ester resins" in the resin composition refers to the sum of "number of active ester groups in (B) naphthalene-type active ester resins" and "number of active ester groups in any active ester resins". "Number of active ester groups in any active ester resins" is the sum of all values ​​obtained by dividing the mass of the non-volatile component of any active ester resin present in the resin composition by its active ester group equivalent. When the aforementioned equivalent ratio (active ester group / epoxy group) is within the aforementioned range, a high level of reduction in the dielectric loss tangent Df of the cured resin composition and suppression of warpage of the circuit board containing the cured composition can be achieved. Furthermore, the relative permittivity Dk and linear thermal expansion coefficient of the cured composition can generally be effectively reduced, and the glass transition temperature Tg can be effectively increased.

[0052] The amount of all active ester resins, including (B) naphthalene-type active ester resin and any other active ester resin, relative to 100% by mass of the non-volatile components of the resin composition, is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, particularly preferably 11% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, and particularly preferably 16% by mass or less. When the amount of all active ester resins is within the aforementioned range, a high level of reduction in the dielectric loss tangent Df of the cured resin composition and suppression of warpage of the circuit board containing the cured composition can be achieved. Consequently, the relative permittivity Dk and linear thermal expansion coefficient of the cured composition can generally be effectively reduced, and the glass transition temperature Tg can be effectively increased.

[0053] The amount of all active ester resin, including (B) naphthalene-type active ester resin and any other active ester resin, relative to 100% by mass of the resin component in the resin composition is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, particularly preferably 44% by mass or more, preferably 70% by mass or less, more preferably 65% ​​by mass or less, and further preferably 60% by mass or less. When the amount of all active ester resin is within the aforementioned range, a high level of reduction in the dielectric loss tangent Df of the cured resin composition and suppression of warpage of the circuit board containing the cured composition can be achieved. Consequently, the relative permittivity Dk and linear thermal expansion coefficient of the cured composition can generally be effectively reduced, and the glass transition temperature Tg can be effectively increased.

[0054] The equivalent ratio (active group / epoxy group) of the active groups of all curing agents, including (B) naphthalene-type reactive ester resin and (G) any curing agent, to the epoxy groups of (A) epoxy resin is preferably 0.1 or more, more preferably 0.5 or more, further preferably 0.8 or more, further preferably 1.0 or more, further preferably 1.2 or more, preferably 5 or less, more preferably 3 or less, and further preferably 2 or less. The aforementioned equivalent ratio (active group / epoxy group) can be obtained by dividing the "number of active groups of all curing agents" in the resin composition by the "number of epoxy groups of (A) epoxy resin". The "number of active groups of all curing agents" in the resin composition represents the sum of the "number of active ester groups of (B) naphthalene-type reactive ester resin" and the "number of active groups of (G) any curing agent". The "number of active groups of (G) any curing agent" represents the value obtained by summing all values ​​obtained by dividing the mass of the non-volatile component of (G) any curing agent present in the resin composition by its equivalent active group. The active group equivalent represents the mass of resin per 1 equivalent of active group. When the aforementioned equivalent ratio (active group / epoxy group) is within the aforementioned range, it is possible to achieve a high level of reduction in the dielectric loss tangent Df of the cured resin composition and suppression of warpage of the circuit board containing the cured composition. Consequently, it is generally possible to effectively reduce the relative permittivity Dk and linear thermal expansion coefficient of the cured composition and effectively increase the glass transition temperature Tg.

[0055] The amount of all curing agent, comprising (B) naphthalene-type reactive ester resin and (G) any curing agent, relative to 100% by mass of the non-volatile components of the resin composition, is preferably 2% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, particularly preferably 13% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, and further preferably 18% by mass or less. "Amount of all curing agent" refers to the total amount of (B) naphthalene-type reactive ester resin and (G) any curing agent. When the amount of all curing agent is within the aforementioned range, a high level of reduction in the dielectric loss tangent Df of the cured resin composition and suppression of warpage of the circuit board containing the cured composition can be achieved, thereby generally effectively reducing the relative permittivity Dk and linear thermal expansion coefficient of the cured composition, and effectively increasing the glass transition temperature Tg.

[0056] The amount of all curing agent comprising (B) naphthalene-type reactive ester resin and (G) any curing agent, relative to 100% by mass of the resin component in the resin composition, is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, particularly preferably 50% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 65% ​​by mass or less. When the amount of all curing agent is within the aforementioned range, a high level of reduction in the dielectric loss tangent Df of the cured resin composition and suppression of warpage of the circuit board containing the cured composition can be achieved, thereby generally effectively reducing the relative permittivity Dk and linear thermal expansion coefficient of the cured composition, and effectively increasing the glass transition temperature Tg.

[0057] <(C) Dimeric diamine type polyimide resin containing hydroxyl groups> The resin composition involved in this embodiment includes (C) a hydroxyl-containing dimeric diamine type polyimide resin as component (C). The hydroxyl-containing dimeric diamine type polyimide resin (C) can be used alone or in combination of two or more.

[0058] (C) Dimeric diamine-type polyimide resins containing hydroxyl groups have a dimeric diamine backbone. The dimeric diamine backbone refers to the carbon and nitrogen backbone of a compound obtained by replacing the two terminal carboxyl groups (-COOH) of a dimer acid with a primary aminomethyl group (-CH2NH2) or an amino group (-NH2). This dimeric diamine backbone is typically formed by multiple carbon atoms and two nitrogen atoms. Dimer acids are known compounds obtained by dimerizing unsaturated fatty acids (preferably unsaturated fatty acids with 11 to 22 carbon atoms, more preferably unsaturated fatty acids with 18 carbon atoms), and their industrial manufacturing processes are largely standardized in the industry. For dimer acids, dimer acids with 36 carbon atoms, obtained by dimerizing particularly inexpensive and readily available unsaturated fatty acids with 18 carbon atoms such as oleic acid, linoleic acid, and linolenic acid, are readily available as the main component. Furthermore, while double bonds usually remain after the polymerization reaction of unsaturated fatty acids, in this specification, hydrides that further undergo hydrogenation to reduce the degree of unsaturation are also included in the dimer acid.

[0059] (C) Dimeric diamine-type polyimide resins containing hydroxyl groups sometimes contain residues derived from dimeric diamines or dimeryl diisocyanates. In this case, these residues derived from dimeric diamines or dimeryl diisocyanates may contain a dimeric diamine backbone. Dimeric diamines can be obtained, for example, by converting the carboxyl group of a dimer acid to an amino group. Furthermore, dimeryl diisocyanates can be obtained, for example, by converting the carboxyl group of a dimer acid to an isocyanate group. In this case, the dimer acid preferably has 20 or more carbon atoms, more preferably 24 or more, further preferably 28 or more, further preferably 36 or more, preferably 60 or less, more preferably 56 or less, further preferably 48 or less, and further preferably 44 or less. The dimer acid is preferably a dicarboxylic acid compound having a branched structure obtained by subjecting an unsaturated fatty acid to a Diels-Alder reaction. The aforementioned branched structure is preferably a chain structure and a ring structure, more preferably a ring structure. The aforementioned ring structure is preferably one or more aromatic ring structures and aliphatic ring structures, more preferably aliphatic ring structures. When a dimer acid contains two or more ring structures, the two rings can be independent or continuous. Aliphatic ring structures can have one or more double bonds within the ring, or they can have no double bonds within the ring. Examples of methods for converting the carboxyl group of a dimer acid to an amino group include, for example, amidation of a carboxylic acid, followed by amination using a Hofmann rearrangement, and then distillation and purification. Furthermore, examples of methods for converting the carboxyl group of a dimer acid to a diisocyanate group include, for example, isocyanation of a carboxylic acid using a Curtius rearrangement. The amino group in a dimeramine or the isocyanate group in a dimer diisocyanate can be directly bonded to the ring structure. Unless otherwise stated, the bond of the amino group to the ring structure is described as "direct," meaning that no other groups exist between the amino group and the ring structure. Similarly, unless otherwise stated, the bond of the isocyanate group to the ring structure is described as "direct," meaning that no other groups exist between the isocyanate group and the ring structure. The amino group in the dimeramine or the isocyanate group in the dimer diisocyanate is preferably bonded to the ring structure via an aliphatic chain. The aliphatic chain between the amino or isocyanate group and the ring structure preferably has 2 to 25 carbon atoms. As a preferred example of the aforementioned aliphatic chain, a chain-like hydrocarbon group such as an alkylene group can be cited. As a suitable example, a compound in which the two amino or isocyanate groups are respectively bonded to the ring structure via an alkylene group can be described.

[0060] Preferred examples of dimer acids include compounds of the following formulas (c1-1), (c1-2), (c2-1), (c2-2), (c3-1), (c3-2), (c4-1), (c4-2), (c4-3), and (c4-4). However, these are just examples, and dimer acids are not limited to the structures described below.

[0061] [Chemical Formula 1] .

[0062] The number of carbon atoms in the dimeric diamine and diisocyanate is preferably 20 or more, more preferably 24 or more, further preferably 28 or more, even more preferably 36 or more, preferably 60 or less, more preferably 56 or less, even more preferably 48 or less, and even more preferably 44 or less. Examples of commercially available dimeric diamines include: "Priamine 1071", "Priamine 1073", "Priamine 1074", and "Priamine 1075" manufactured by Croda Japan; and "Versamine 551" manufactured by BASF Japan.

[0063] (C) Dimeric diamine-type polyimide resins containing hydroxyl groups typically contain repeating units comprising imide bonds. In this case, the aforementioned repeating unit may comprise a dimeric diamine backbone. For example, residues derived from dimeric diamine or diisocyanate may sometimes be included in the aforementioned repeating unit, and thus the residue may comprise a dimeric diamine backbone, thereby the aforementioned repeating unit may comprise a dimeric diamine backbone.

[0064] (C) In the dimeric diamine type polyimide resin containing hydroxyl groups, some or all of the repeating units may contain a dimeric diamine backbone. In one example, the amount of repeating units containing a dimeric diamine backbone is preferably 80% by mass or more, more preferably 83% by mass or more, and even more preferably 85% by mass or more, and typically 100% by mass or less, relative to 100% by mass of the total repeating units. Preferably, all repeating units containing imide bonds contain a dimeric diamine backbone.

[0065] Preferably, (C) the dimeric diamine type polyimide resin containing hydroxyl groups comprises repeating units shown in formula (C1). In formula (C1), X 1 Each independently represents a tetravalent organic group, X 2 Each independently represents a divalent organic group. Typically, X... 1It combines with the imide bond to form two imide rings. However, in the repeating units of formula (C1) contained in the dimeric diamine type polyimide resin containing hydroxyl groups, in at least a portion of the repeating units, X 2 Residues derived from dimeric diamine and / or diisocyanate.

[0066] [Chemical Formula 2] .

[0067] The following applies to X in equation (C1) 1 To be detailed. As mentioned earlier, X 1 Each of them independently represents a tetravalent organic group. Among them, X 1 Preferably, a tetravalent tetracarboxylic acid residue is used. The term "tetravalent tetracarboxylic acid residue" can include: a tetravalent group having a structure formed by removing four carboxyl groups from a tetracarboxylic acid, and a tetravalent group having a structure formed by removing two anhydride groups from a tetracarboxylic anhydride. As for obtaining X... 1 The tetracarboxylic acid compounds used in the polymerization of tetravalent tetracarboxylic acid residues include, for example, aromatic tetracarboxylic acids containing aromatic groups, aliphatic tetracarboxylic acids containing aliphatic groups, and anhydrides of these tetracarboxylic acids. Tetracarboxylic acids and their anhydrides may contain aromatic and aliphatic groups. Furthermore, the tetravalent tetracarboxylic acid residues may contain heteroatoms such as nitrogen, oxygen, sulfur, selenium, fluorine, chlorine, and bromine atoms. Preferably, aliphatic tetracarboxylic acids and their anhydrides containing aliphatic groups are used, and more preferably, aliphatic tetracarboxylic acids and their anhydrides containing aliphatic groups but not aromatic groups are used. Therefore, X 1 Preferably, it is a tetravalent tetracarboxylic acid residue containing an aliphatic group, and more preferably, it is a tetravalent tetracarboxylic acid residue containing an aliphatic group but not an aromatic group.

[0068] The aliphatic groups in aliphatic tetracarboxylic acids and their anhydrides can be chain-like or cyclic aliphatic groups. Chain-like aliphatic groups can be straight-chain or branched. Cyclic aliphatic groups can be monocyclic or polycyclic. Aliphatic groups can include both chain-like and cyclic aliphatic groups. Aliphatic groups can be saturated or unsaturated. Aliphatic groups may or may not have substituents such as alkyl, halogen, nitro, or cyano groups.

[0069] Examples of aliphatic tetracarboxylic acids and their anhydrides include: 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-pentanetetracarboxylic acid, 1,2,4,5-pentanetetracarboxylic acid, 1,2,3,4-hexanetetracarboxylic acid, 1,2,5,6-hexanetetracarboxylic acid, etc., tetracarboxylic acids containing chain-like aliphatic groups and their anhydrides; cyclobutane-1,2,3,4-tetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, cyclohexane-1,2,3,4-tetracarboxylic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, 1-carboxymethyl-2,3,5-cyclopentanetricarboxylic acid, 3-carboxymethyl-1,2,4-cyclopentanetricarboxylic acid, rel-dicyclohexyl-3,3',4,4'-tetracarboxylic acid, tricyclo[4.2.2.0] 2,5 [2.2.1] Dec-9-en-3,4,7,8-tetracarboxylic acid, 5-carboxymethyl bicyclo[2.2.1] heptane-2,3,6-tricarboxylic acid, bicyclo[2.2.1] heptane-2,3,5,6-tetracarboxylic acid, bicyclo[2.2.2] oct-7-en-2,3,6,7-tetracarboxylic acid, bicyclo[3.3.0] octane-2,4,6,7-tetracarboxylic acid, 7,8-diphenylbicyclo[2.2.2] oct-7-en-2,3,5,6-tetracarboxylic acid, 4,8-diphenyl-1,5-diazabicyclooctane-2,3,6,7-tetracarboxylic acid, 9-oxatricyclo[4.2.1.0] 2,5 Nonane-3,4,7,8-tetracarboxylic acid, 9,14-dioxopentane [8.2.1] 1,11 .1 4 ,7 .0 2,10 .0 3,8 Tetracarboxylic acids and their anhydrides that include tetracarboxylic acids such as tetradecane-5,6,12,13-tetracarboxylic acid, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid, and 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, tetracarboxylic acids having an alicyclic hydrocarbon structure, and tetracarboxylic acids and their anhydrides containing cyclic aliphatic groups; spirocyclic tetracarboxylic acids and their anhydrides such as 2,8-dioxane[4.5]decane-1,3,7,9-tetraone. These compounds may be used individually or in combination of two or more.

[0070] X 1The tetravalent tetracarboxylic acid residue can be a group having a structure formed by removing four carboxyl groups (-COOH) from the tetracarboxylic acid exemplified in the foregoing examples, or a group having a structure formed by removing two anhydride groups (-C(=O)-OC(=O)-) from the tetracarboxylic anhydride exemplified in the foregoing examples. As described above, the tetravalent tetracarboxylic acid residue preferably contains an aliphatic group. Particularly more preferably, in the tetravalent tetracarboxylic acid residue, at least one carbon atom of the tetravalent tetracarboxylic acid residue forming the imide ring of one of the formulas (C1) is directly bonded to at least one other carbon atom of the tetravalent tetracarboxylic acid residue forming the imide ring of the other formula (C1). Unless otherwise stated, the bonding of two carbon atoms as "direct" means that no other groups exist between the two carbon atoms. Alternatively, more preferably, in the tetravalent tetracarboxylic acid residue, at least one carbon atom of the tetravalent tetracarboxylic acid residue forming the imide ring of one of the four formulations (C1) is directly bonded to or contained within an aliphatic group of the tetravalent tetracarboxylic acid residue; and at least one other carbon atom of the tetravalent tetracarboxylic acid residue forming the imide ring of the other formulation (C1) is directly bonded to or contained within an aliphatic group of the tetravalent tetracarboxylic acid residue. Unless otherwise stated, the bond between the carbon atom and the aliphatic group is "direct," meaning that no other group exists between the carbon atom and the aliphatic group. X is a preferred embodiment satisfying the aforementioned requirements. 1 Examples can be given by the groups in formulas (x1-1) to (x1-26) below. In the following formulas, * indicates the binding site.

[0071] [Chemical Formula 3] .

[0072] [Chemical Formula 4] .

[0073] In one example, relative to (C) the tetravalent organic group X contained in the dimeric diamine type polyimide resin containing hydroxyl groups. 1 Of the total 100 mol%, the proportion of tetravalent tetracarboxylic acid residues containing aliphatic groups is preferably 60 mol% or more, more preferably 75 mol% or more, even more preferably 85 mol% or more, and typically 100 mol% or less. Wherein, the tetravalent organic group X... 1 The preferred monomers are tetravalent tetracarboxylic acid residues containing aliphatic groups. Typically, the ratio of monomers used in synthesis is the same as the composition ratio of the residues corresponding to those monomers in the resin. Therefore, the monomers corresponding to the tetravalent organic group X... 1 The proportion of tetracarboxylic acid compounds containing aliphatic groups in 100 mol% of the monomer can be used to determine the proportion of the aforementioned tetravalent tetracarboxylic acid residues containing aliphatic groups.

[0074] Next, for X in equation (C1) 2 A detailed explanation is provided. In equation (C1), X 2 Each independently represents a divalent organic group. However, in the repeating units of formula (C1) contained in the dimeric diamine type polyimide resin containing hydroxyl groups, in at least a portion of the repeating units, X 2 Residues derived from dimeric diamine and / or diisocyanate.

[0075] The term "residues derived from dimeric diamines" may include groups having a structure formed by removing two amino groups (-NH2) from a dimeric diamine. Furthermore, the term "residues derived from diisocyanates" may include groups having a structure formed by removing two isocyanate groups (-N=C=O) from a diisocyanate. Dimeric diamines, diisocyanates, and their corresponding dimer acids are as described above. Specific examples of residues derived from dimeric diamines and residues derived from diisocyanates include groups represented by formulas (c5-1), (c5-2), (c6-1), (c6-2), (c7-1), (c7-2), (c8-1), (c8-2), (c8-3), or (c8-4). In equations (c5-1), (c5-2), (c6-1), (c6-2), (c7-1), (c7-2), (c8-1), (c8-2), (c8-3), and (c8-4), * indicates the joint portion.

[0076] [Chemical Formula 5] .

[0077] (C) In the hydroxyl-containing dimeric diamine type polyimide resin, the proportion of residues derived from dimeric diamine and / or diisocyanate is preferably greater. In one example, the proportion of divalent organic groups X contained in (C) the hydroxyl-containing dimeric diamine type polyimide resin is greater. 2 Of the total 100% by mass, the proportion derived from residues of dimeric diamine and / or diisocyanate is preferably 80% by mass or more, more preferably 83% by mass or more, and even more preferably 85% by mass or more, typically 100% by mass or less. Preferably, (C) the dimeric diamine-type polyimide resin containing hydroxyl groups contains divalent organic groups X... 2 All of them are derived from residues of dimeric diamine and / or diisocyanate. Typically, the ratio of monomers used in synthesis is the same as the composition ratio of the resin corresponding to the residues of that monomer. Therefore, in (C) dimeric diamine-type polyimide resins containing hydroxyl groups synthesized using dimeric diamine or diisocyanate, the monomers can be derived from residues corresponding to the divalent organic groups X.2 The proportion of residues derived from dimeric diamine and / or diisocyanate in 100% by mass of the monomer is used to determine the aforementioned proportion of residues derived from dimeric diamine and / or diisocyanate.

[0078] X is a divalent organic group other than residues derived from dimeric diamine and / or diisocyanate. 2 Examples include residues derived from any diamine other than dimeric diamine, and residues derived from any diisocyanate other than dimeric diisocyanate, preferably residues derived from diamine. Examples of such diamines include: 1,4-diaminobenzene, 1,3-diaminobenzene, 1,2-diaminobenzene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 2,6-diaminotoluene, 2,4-diaminotoluene, 3,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diamino-1,2-diphenylethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, etc. Aromatic diamines such as benzophenone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, and 3,3'-diaminodiphenyl sulfone; aliphatic diamines such as ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,9-nonanediamine, 1,12-dodecanediamine, and m-phenylenediamine; and alicyclic diamines such as isofluranediamine, norbornenediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-diaminodicyclohexylmethane, and piperazine. Furthermore, by using a diamine containing a phenolic hydroxyl group as any of the aforementioned diamines, phenolic hydroxyl groups can be introduced into the (C) dimeric diamine-type polyimide resin containing hydroxyl groups.

[0079] (C) Dimeric diamine-type polyimide resins containing hydroxyl groups contain phenolic hydroxyl groups. A phenolic hydroxyl group refers to a hydroxyl group directly bonded to an aromatic ring. Unless otherwise stated, the "direct" bond between the phenolic hydroxyl group and the aromatic ring means that no other groups exist between the phenolic hydroxyl group and the aromatic ring. Among the aromatic rings, benzene rings, naphthalene rings, and pyridine rings are preferred, with benzene rings being more preferred.

[0080] (C) The phenolic hydroxyl group in the hydroxyl-containing dimeric diamine polyimide resin can be located at the end of the molecular chain of the (C) hydroxyl-containing dimeric diamine polyimide resin, or at the position of a side chain or side group in the main chain backbone of the (C) hydroxyl-containing dimeric diamine polyimide resin. Furthermore, phenolic hydroxyl groups can also be combined and introduced into the molecular chain end, side chain, and side group. The term "molecular chain end" refers to the end of a repeating structural unit constituting the molecular chain of the (C) hydroxyl-containing dimeric diamine polyimide resin, or a non-repeating structure connected to its end.

[0081] As a method for introducing phenolic hydroxyl groups to the molecular chain end of a dimeric diamine-type polyimide resin containing hydroxyl groups (C), examples include reacting an amine compound having phenolic hydroxyl groups after synthesizing an anhydride-terminated polyimide resin. Alternatively, as another method, examples include reacting an amine compound having phenolic hydroxyl groups after synthesizing a carboxylic acid-terminated polyimide resin. The amine compound may have two or more phenolic hydroxyl groups, but one is preferred. As the amine compound having phenolic hydroxyl groups, a monoamine compound having one amino group is generally used, and an amine compound represented by the following formula (C2) is preferred.

[0082] [Chemical Formula 6] .

[0083] In formula (C2), Ar 1 This indicates a divalent group comprising an aromatic ring directly bonded to the hydroxyl group described in formula (C2). Unless otherwise stated, "direct" bonding of the hydroxyl group to the aromatic ring means that no other group exists between the hydroxyl group and the aromatic ring. As stated in Ar... 1 Examples include: a divalent aromatic group optionally having a substituent; and a divalent group comprising "a divalent aromatic group optionally having a substituent" and "an aliphatic group attached to the aromatic group and an amino group in formula (C2)". Preferably, the divalent aromatic group optionally having a substituent is preferred, more preferably a divalent aromatic group having an amino group attached at the meta or ortho position of the aromatic ring based on a phenolic hydroxyl group. Furthermore, as the divalent aromatic group, arylene is preferred, and phenylene is even more preferred. Examples of substituents include alkyl and fluoroalkyl groups having 1 to 10 carbon atoms, and halogen atoms.

[0084] Specific examples of amine compounds represented by formula (C2) include: 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-amino-o-cresol, 5-amino-o-cresol, 4-amino-2,3-dimethylphenol, 4-amino-2,5-dimethylphenol, 4-amino-2,6-dimethylphenol, 4-amino-1-naphthol, 5-amino-2-naphthol, 6-amino-1-naphthol, 4-amino-2,6-diphenylphenol, 2-amino-5-ethylphenol, 2-(1-aminoethyl)phenol, 3-(2-aminoethyl)phenol, 4-(2-aminoethyl)phenol, 2-(2-aminoethyl)phenol, 2-(2-aminomethyl)phenol, 3-(2-aminomethyl)phenol, 2-(2-aminomethyl)phenol, 3-(2-aminomethyl)phenol, and 4-(2-aminopropyl)phenol.

[0085] As another method for introducing phenolic hydroxyl groups to the molecular chain end of a dimeric diamine-type polyimide resin containing hydroxyl groups (C), examples include reacting an anhydride compound or a carboxylic acid compound with phenolic hydroxyl groups after synthesizing an amino-terminated polyimide resin. These anhydride compounds or carboxylic acid compounds may have two or more phenolic hydroxyl groups, but one is preferred. As an anhydride compound with phenolic hydroxyl groups, an anhydride compound having one anhydride group is generally used, and an anhydride compound represented by formula (C3) is preferred. Furthermore, as a carboxylic acid compound with phenolic hydroxyl groups, a carboxylic acid compound having one carboxyl group is generally used, and a carboxylic acid compound represented by formula (C4) is preferred.

[0086] [Chemical Formula 7] .

[0087] In formula (C3), Ar 2 This indicates a group comprising an aromatic ring directly bonded to a hydroxyl group as described in formula (C3). As the Ar 2 Examples include: an aromatic group optionally having a substituent; and a divalent group comprising "a divalent aromatic group optionally having a substituent" and "an aliphatic group connecting the aromatic group to the ether ring in formula (C3)". Preferably, the aromatic group optionally having a substituent is an aromatic group, more preferably an arylene group optionally having a substituent, further preferably a phenylene group optionally having a substituent, and particularly preferably an unsubstituent phenylene group. 2 The substituents in Ar can interact with Ar 1 The substituents in the formula (C3) are the same. Specific examples of anhydride compounds represented by formula (C3) include 3-hydroxyphthalic anhydride, 4-hydroxyphthalic anhydride, etc.

[0088] In formula (C4), Ar 3This indicates a divalent group comprising an aromatic ring directly bonded to a hydroxyl group as described in formula (C4). As the Ar 3 Examples include: a divalent aromatic group optionally having a substituent; and a divalent group comprising "a divalent aromatic group optionally having a substituent" and "an aliphatic group connecting the aromatic group to the carboxyl group in formula (C4)". Preferably, the divalent aromatic group optionally having a substituent is a divalent aromatic group, more preferably an arylene group optionally having a substituent, further preferably a phenylene group optionally having a substituent, and particularly preferably an unsubstituent phenylene group. 4 The substituents in Ar can interact with Ar 1 The substituents in the formula are the same. Specific examples of carboxylic acid compounds represented by formula (C4) include salicylic acid and hydroxybenzoic acid.

[0089] (C) In the case where the hydroxyl-containing dimeric diamine type polyimide resin has phenolic hydroxyl groups at the ends of its molecular chains, (C) the hydroxyl-containing dimeric diamine type polyimide resin may have phenolic hydroxyl groups at all the ends of its molecular chains. Furthermore, (C) the hydroxyl-containing dimeric diamine type polyimide resin may also have phenolic hydroxyl groups at a portion of its molecular chain ends. In this case, (C) the hydroxyl-containing dimeric diamine type polyimide resin may contain molecular chain ends without functional groups, or it may contain molecular chain ends with any functional group other than phenolic hydroxyl groups (e.g., anhydride groups). The proportion of molecular chain ends with phenolic hydroxyl groups relative to 100 mol% of the functional groups at the ends of the molecular chains of (C) the hydroxyl-containing dimeric diamine type polyimide resin is preferably 50 mol% or more, more preferably 70 mol% or more, and typically 100 mol%.

[0090] As a method for introducing phenolic hydroxyl groups into the side chains and / or side groups of a dimeric diamine-type polyimide resin containing hydroxyl groups (C), examples include using compounds having one or more phenolic hydroxyl groups as part or all of the diamine, diisocyanate, and tetracarboxylic acid and its anhydrides in the polymerization process of the polyimide resin. Furthermore, as another method, examples include introducing compounds having phenolic hydroxyl groups into the side chains of the polyimide resin after its synthesis.

[0091] Preferably, the method uses any diamine having a phenolic hydroxyl group. Examples of diamines having a phenolic hydroxyl group include: bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl) ether, bis(3-amino-4-hydroxy)biphenyl, 2,2'-bis(trifluoromethyl)-5,5'-dihydroxy-4,4'-diaminobiphenyl, bis(3-amino-4-hydroxyphenyl)fluorene, 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and 4,4'-diamino-3,3'-dihydroxybisphenyl.

[0092] (C) The hydroxyl-containing dimeric diamine type polyimide resin preferably has phenolic hydroxyl groups at the ends of its molecular chain, or may have phenolic hydroxyl groups only at the ends of its molecular chain. From the viewpoint of significantly obtaining the effects of the present invention, (C) the hydroxyl-containing dimeric diamine type polyimide resin preferably satisfies the following (i) or (ii): (i) (C) A dimeric diamine-type polyimide resin containing hydroxyl groups has phenolic hydroxyl groups at the end of the molecular chain, and then nitrogen atoms from a monoamine that form an imide ring are bonded at the meta or ortho position of the aromatic ring having the phenolic hydroxyl groups. (ii) (C) Dimeric diamine-type polyimide resins containing hydroxyl groups have phenolic hydroxyl groups at the ends of their molecular chains, and have aliphatic groups directly bonded to the aromatic ring having the phenolic hydroxyl groups, and further, nitrogen atoms from the monoamine forming the imide ring are bonded to the aliphatic groups. Unless otherwise stated, the bonding of the aromatic ring to the aliphatic group is "direct" to mean that there are no other groups between the aromatic ring and the aliphatic group.

[0093] (C) The amount of phenolic hydroxyl groups in the hydroxyl-containing dimeric diamine-type polyimide resin can be expressed by the phenolic hydroxyl value. The phenolic hydroxyl value range of the (C) hydroxyl-containing dimeric diamine-type polyimide resin is preferably 1 mg KOH / g or more, more preferably 3 mg KOH / g or more, further preferably 5 mg KOH / g or more, preferably 30 mg KOH / g or less, more preferably 20 mg KOH / g or less, and further preferably 15 mg KOH / g or less. Furthermore, particularly in (C) hydroxyl-containing dimeric diamine-type polyimide resins having phenolic hydroxyl groups in the side chains, the phenolic hydroxyl value is also preferably 1 mg KOH / g to 5 mg KOH / g. The phenolic hydroxyl value can be adjusted by the amount of monomer having phenolic hydroxyl groups fed, the introduction rate of phenolic hydroxyl groups to the molecular chain terminus, and / or the introduction rate of phenolic hydroxyl groups to the side chains.

[0094] The phenolic hydroxyl value can be determined according to JIS K0070. The phenolic hydroxyl value represents the amount (mg) of potassium hydroxide required to neutralize the acetic acid bound to the phenolic hydroxyl group when acetylated the phenolic hydroxyl group in 1g of resin. When calculating the phenolic hydroxyl value of (C) dimeric diamine polyimide resin containing hydroxyl groups, the acid value can be considered, as shown in the following formula (M1). Specifically, approximately 1g of the sample ((C) dimeric diamine polyimide resin containing hydroxyl groups) is accurately weighed into a stoppered Erlenmeyer flask and dissolved in 100mL of cyclohexanone solvent. Then, 5mL of acetylation agent (25g of acetic anhydride dissolved in pyridine and diluted to a volume of 100mL) is accurately added, and the mixture is stirred for approximately 1 hour. Phenolphthalein solution is added as an indicator and stirred for 30 seconds. Then, the solution is titrated with 0.5N ethanol-prepared potassium hydroxide solution until it turns pale pink. The phenolic hydroxyl value can be calculated using the following formula (M1): Phenolic hydroxyl value (mgKOH / g) = [{(ba)×F×28.05} / S] + D (M1) (In formula (M1), S represents the amount of sample taken (g); a represents the amount of 0.5N ethanol-prepared potassium hydroxide solution consumed (mL); b represents the amount of 0.5N ethanol-prepared potassium hydroxide solution consumed in the blank test (mL); F represents the titer of the 0.5N ethanol-prepared potassium hydroxide solution; and D represents the acid value (mgKOH / g).)

[0095] The value of b in formula (M1) can be calculated by titrating 5 mL of acetylation agent (25 g of acetic anhydride dissolved in pyridine and diluted to a volume of 100 mL) with a potassium hydroxide solution prepared by 0.5 N ethanol.

[0096] The acid value D in formula (M1) can be determined according to JIS K0070. Specifically, approximately 1 g of the sample ((C) dimeric diamine type polyimide resin containing hydroxyl groups) is accurately weighed into a stoppered Erlenmeyer flask and dissolved in 100 mL of cyclohexanone solvent. Phenolphthalein solution is added as an indicator, and titration is performed with potassium hydroxide solution prepared in 0.1N ethanol. The endpoint is considered when the indicator remains pale red for 30 seconds. The acid value can be calculated using the following formula (M2): Acid value (mgKOH / g) = (5.611 × a × F) / S (M2) (In formula (M2), S represents the amount of sample taken (g); a represents the amount of potassium hydroxide solution consumed in 0.1N ethanol (mL); and F represents the titer of the potassium hydroxide solution in 0.1N ethanol.)

[0097] Preferred examples of (C) dimeric diamine-type polyimide resins containing hydroxyl groups include: (C) dimeric diamine-type polyimide resins in which all or part of the functional groups at the end of the molecular chain are phenolic hydroxyl groups and do not have phenolic hydroxyl groups in the side groups and side chains; (C) dimeric diamine-type polyimide resins in which all or part of the functional groups at the end of the molecular chain are phenolic hydroxyl groups and also have phenolic hydroxyl groups in the side groups or side chains; (C) dimeric diamine-type polyimide resins in which no functional groups are at the end of the molecular chain but have phenolic hydroxyl groups in the side groups or side chains; and (C) dimeric diamine-type polyimide resins in which any functional group other than phenolic hydroxyl groups (e.g., anhydride groups) is at the end of the molecular chain and has phenolic hydroxyl groups in the side groups or side chains. More preferably, there is a (C) dimeric diamine type polyimide resin in which all functional groups at the ends of the molecular chains are phenolic hydroxyl groups; and a (C) dimeric diamine type polyimide resin in which some molecular chains have phenolic hydroxyl ends and no arbitrary functional groups at the ends of other molecules.

[0098] Within a range that does not significantly impair the effects of the present invention, (C) the hydroxyl-containing dimeric diamine type polyimide resin may have other functional groups such as anhydride groups, amino groups, and carboxyl groups. The anhydride value of (C) the hydroxyl-containing dimeric diamine type polyimide resin is preferably 15 mg KOH / g or less, more preferably 10 mg KOH / g or less, further preferably 5 mg KOH / g or less, and may be 0 mg KOH / g. Furthermore, the amine value of (C) the hydroxyl-containing dimeric diamine type polyimide resin is preferably 15 mg KOH / g or less, more preferably 10 mg KOH / g or less, further preferably 5 mg KOH / g or less, and may be 0 mg KOH / g.

[0099] The method for determining the anhydride group value is as follows. Accurately weigh approximately 1 g of the sample ((C) dimeric diamine-type polyimide resin containing hydroxyl groups) into a stoppered Erlenmeyer flask and dissolve it in 100 mL of 1,4-dioxane solvent. Add 10 mL of a mixed solution of octylamine, 1,4-dioxane, and water (mass-based mixing ratio: octylamine / 1,4-dioxane / water = 1.49 / 800 / 80), which is more abundant than the amount of anhydride group in the sample, and stir for 15 minutes to allow it to react with the anhydride group. Then, titrate the excess octylamine with a mixed solution of 0.02 M perchloric acid and 1,4-dioxane. Additionally, perform the determination using 10 mL of a mixed solution of octylamine, 1,4-dioxane, and water (mass-based mixing ratio: octylamine / 1,4-dioxane / water = 1.49 / 800 / 80) without the sample as a blank. The acid anhydride value can be calculated using the following formula (M3) (unit: mgKOH / g): Acid anhydride value (mgKOH / g) = 0.02 × (BA) × F × 56.11 / S (m3) (In formula (M3), B represents the titration amount (mL) in the blank determination; A represents the titration amount (mL) in the sample determination; S represents the sample volume (g); and F represents the titer of 0.02 mol / L perchloric acid.)

[0100] The method for determining the amine value is as follows. Accurately weigh approximately 1 g of the sample ((C) dimeric diamine-type polyimide resin containing hydroxyl groups) into a stoppered Erlenmeyer flask and dissolve it in 100 mL of cyclohexanone solvent. Add 2 or 3 drops of a separately prepared indicator and hold for 30 seconds; the indicator is prepared by mixing a solution of 0.20 g of methyl orange dissolved in 50 mL of distilled water with a solution of 0.28 g of xylenecyanine FF dissolved in 50 mL of methanol. Then, titrate with 0.1 N ethanol-based hydrochloric acid solution until the solution turns bluish-gray. The amine value can be calculated using the following formula (M4): Amine value (mgKOH / g) = (5.611 × a × F) / S (M4) (In formula (M4), S represents the amount of sample taken (g); a represents the amount of 0.1N ethanol to prepare hydrochloric acid solution consumed (mL); F represents the titer of 0.1N ethanol to prepare hydrochloric acid solution.)

[0101] Within a scope that does not significantly impair the effects of the present invention, (C) the hydroxyl-containing dimeric diamine type polyimide resin may contain any repeating unit other than the repeating unit shown in formula (C1). From the viewpoint of significantly obtaining the effects of the present invention, the proportion of the repeating unit shown in formula (C1) relative to 100% by mass of all repeating units contained in the hydroxyl-containing dimeric diamine type polyimide resin is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and typically 100% by mass or less. Particularly preferred is that all repeating units contained in the hydroxyl-containing dimeric diamine type polyimide resin are represented by formula (C1).

[0102] (C) The number-average molecular weight Mn of the hydroxyl-containing dimeric diamine type polyimide resin is preferably greater than 5,000, more preferably greater than 5,500, further preferably 6,000 or more, preferably 300,000 or less, more preferably 200,000 or less, and further preferably 10,000 or less. When the number-average molecular weight Mn is within the aforementioned range, it is possible to achieve a high level of reduction in the dielectric loss tangent Df of the cured resin composition and suppression of warpage of the circuit board containing the cured composition. Consequently, it is generally possible to effectively reduce the relative permittivity Dk and linear thermal expansion coefficient of the cured composition and effectively increase the glass transition temperature Tg.

[0103] (C) The weight-average molecular weight Mw of the hydroxyl-containing dimeric diamine type polyimide resin is preferably greater than 5,000, more preferably 15,000 or more, further preferably 20,000 or more, preferably 1,000,000 or less, more preferably 100,000 or less, and further preferably 80,000 or less. When the weight-average molecular weight Mw is within the aforementioned range, it is possible to achieve a high level of reduction in the dielectric loss tangent Df of the cured resin composition and suppression of warpage of the circuit board containing the cured composition. Consequently, it is generally possible to effectively reduce the relative permittivity Dk and linear thermal expansion coefficient of the cured composition and effectively increase the glass transition temperature Tg.

[0104] (C) The number-average molecular weight Mn and weight-average molecular weight Mw of dimeric diamine polyimide resins containing hydroxyl groups can be determined as polystyrene equivalents by gel permeation chromatography (GPC).

[0105] As a method for manufacturing (C) a dimeric diamine-type polyimide resin containing hydroxyl groups, an example method includes the following steps: cyclizing a polyamic acid resin or a polyamic ester resin, which is a polyimide precursor, by heating to convert it into an imide group. The polyamic acid resin can be manufactured, for example, by reacting a tetracarboxylic dianhydride with a diamine. Furthermore, the polyamic ester resin can be manufactured, for example, by a method including the following steps: reacting a tetracarboxylic dianhydride with an alcohol to obtain a diester compound; and reacting the diester compound with a diamine in the presence of a condensing agent. Furthermore, the polyamic ester resin can be manufactured, for example, by a method including the following steps: reacting a tetracarboxylic dianhydride with an alcohol to obtain a diester compound; acylchlorinating the remaining dicarboxylic acid in the diester; and then reacting the diester with a diamine. Furthermore, the (C) dimeric diamine-type polyimide resin containing hydroxyl groups can be manufactured, for example, by a method including the step of reacting a tetracarboxylic dianhydride with a diisocyanate. As a method for manufacturing (C) a dimeric diamine-type polyimide resin containing hydroxyl groups, the method described in International Publication No. 2023 / 112443 may be used.

[0106] Relative to 100% by mass of the non-volatile components in the resin composition, the amount of (C) hydroxyl-containing dimeric diamine-type polyimide resin is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 2% by mass or less, and particularly preferably 1.5% by mass or less. When the amount of (C) hydroxyl-containing dimeric diamine-type polyimide resin is within the aforementioned range, a high level of reduction in the dielectric loss tangent Df of the cured resin composition and suppression of warpage of the circuit board containing the cured composition can be achieved. Consequently, the relative permittivity Dk and linear thermal expansion coefficient of the cured composition can generally be effectively reduced, and the glass transition temperature Tg can be effectively increased. It should be noted that, relative to 100% by mass of the non-volatile components in the resin composition, the amount of (C) dimeric diamine-type polyimide resin containing hydroxyl groups can be 0.45% by mass or more, or 0.45% by mass or less, or 0.8% by mass or more, or 0.8% by mass or less.

[0107] The amount of (C) hydroxyl-containing dimeric diamine-type polyimide resin relative to 100% by mass of the resin component in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less. When the amount of (C) hydroxyl-containing dimeric diamine-type polyimide resin is within the aforementioned range, a high level of reduction in the dielectric loss tangent Df of the cured resin composition and suppression of warpage of the circuit board containing the cured composition can be achieved. Consequently, the relative permittivity Dk and linear thermal expansion coefficient of the cured composition can generally be effectively reduced, and the glass transition temperature Tg can be effectively increased. It should be noted that the amount of (C) hydroxyl-containing dimeric diamine-type polyimide resin relative to 100% by mass of the resin component in the resin composition can be 1.5% by mass or more, or 1.5% by mass or less, or 3.5% by mass or more, or 3.5% by mass or less.

[0108] The amount of (C) hydroxyl-containing dimeric diamine-type polyimide resin relative to 100% by mass of (A) epoxy resin is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less. When the amount of (C) hydroxyl-containing dimeric diamine-type polyimide resin is within the aforementioned range, a high level of reduction in the dielectric loss tangent Df of the cured resin composition and suppression of warpage of the circuit board containing the cured composition can be achieved. Consequently, the relative permittivity Dk and linear thermal expansion coefficient of the cured composition can generally be effectively reduced, and the glass transition temperature Tg can be effectively increased. It should be noted that the amount of (C) hydroxyl-containing dimeric diamine-type polyimide resin relative to 100% by mass of (A) epoxy resin can be 4% by mass or more, or 4% by mass or less, or 10% by mass or more, or 10% by mass or less.

[0109] The amount of (C) hydroxyl-containing dimeric diamine-type polyimide resin relative to 100% by mass of (B) naphthalene-type reactive ester resin is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 1.5% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less. When the amount of (C) hydroxyl-containing dimeric diamine-type polyimide resin is within the aforementioned range, a high level of reduction in the dielectric loss tangent Df of the cured resin composition and suppression of warpage of the circuit board containing the cured composition can be achieved. Consequently, the relative permittivity Dk and linear thermal expansion coefficient of the cured composition can generally be effectively reduced, and the glass transition temperature Tg can be effectively increased. It should be noted that the amount of (C) hydroxyl-containing dimeric diamine-type polyimide resin relative to 100% by mass of (B) naphthalene-type reactive ester resin can be 3% by mass or more, or 3% by mass or less, or 7% by mass or more, or 7% by mass or less.

[0110] <(D) Inorganic filler materials> The resin composition according to this embodiment includes an inorganic filler material (D) as component (D). The inorganic filler material (D) is particulate inorganic material. Therefore, the inorganic filler material (D) is contained in the resin composition in particulate form, and this particulate form is generally maintained in the cured product.

[0111] Inorganic compounds are typically used as inorganic materials for forming the (D) inorganic filler. Examples of materials that can be used as the (D) inorganic filler include, for example, silicon dioxide, 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 zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silicon dioxide and alumina are preferred, and silicon dioxide is particularly preferred. Therefore, the (D) inorganic filler preferably contains silicon dioxide, but may contain only silicon dioxide. Examples of silicon dioxide include, for example, amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, and hollow silicon dioxide. Furthermore, spherical silicon dioxide is preferred as the silica. The aforementioned inorganic materials generally possess insulating properties, therefore, (D) inorganic filler materials typically also possess insulating properties. (D) Inorganic filler materials can be used alone or in combination of two or more types.

[0112] Commercially available products as (D) inorganic filler materials include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Yatoma Co., Ltd.; "UFP-30", "DAW-03", and "FB-105FD" manufactured by DENKA Co., Ltd.; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" manufactured by Tokuyama Co., Ltd.; and "CellSpheres" and "MGH-005" manufactured by Pacific Cement Co., Ltd.

[0113] (D) The average particle size of the inorganic filler material is preferably less than 5 μm. More specifically, the range of the average particle size of the inorganic filler material is preferably less than 5 μm, more preferably less than 3 μm, and even more preferably less than 1 μm. The lower limit is preferably 0.01 μm or more, more preferably 0.05 μm or more, and even more preferably 0.1 μm or more. When the inorganic filler material has an average particle size within the aforementioned range, it is possible to achieve a high level of reduction in the dielectric loss tangent Df of the cured resin composition and suppression of warpage of the circuit board containing the cured composition. Consequently, the relative permittivity Dk and linear thermal expansion coefficient of the cured composition can generally be effectively reduced, and the glass transition temperature Tg can be effectively increased. Furthermore, the smaller the average particle size, the more favorable it is for the formation of fine wiring.

[0114] (D) The average particle size of inorganic fillers can be determined using laser diffraction / scattering based on the Mie scattering theory. Specifically, a laser diffraction-scattering particle size distribution measuring device can be used to prepare the particle size distribution of the inorganic filler according to a volume basis, and the median particle size can be used as the average particle size for measurement. The sample for testing can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing it using ultrasound for 10 minutes. For the sample, a laser diffraction-scattering particle size distribution measuring device can be used, with the light source wavelength set to blue and red, to measure the volume-based particle size distribution of the inorganic filler using a flow cell method. The average particle size is then calculated from the obtained particle size distribution in the form of the median particle size. Examples of laser diffraction-scattering particle size distribution measuring devices include the "LA-960" manufactured by Horiba Manufacturing Co., Ltd.

[0115] (D) The specific surface area of ​​the inorganic filler material is preferably 0.1 m². 2 / g or more, more preferably 0.5m 2 / g or more, further preferably 1m 2 / g or more, preferably 3m 2 / g or more, preferably 100m 2 / g or less, more preferably 70m 2 / g or less, more preferably 50m 2 / g or less, preferably 40m 2 / g or less. (D) The specific surface area of ​​inorganic filler materials can be determined as follows: according to the BET method, nitrogen gas is adsorbed onto the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by MOUNTECH), and the specific surface area is calculated using the BET multi-point method.

[0116] From the perspective of improving moisture resistance and dispersibility, (D) inorganic filler materials are preferably treated with surface treatment agents. Examples of surface treatment agents include fluorinated silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, etc. A single surface treatment agent can be used, or two or more can be used in combination.

[0117] Commercially available surface treatment agents include, for example, "KBM403" (3-epoxypropoxypropyltrimethoxysilane), "KBM803" (3-mercaptopropyltrimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane), "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), "SZ-31" (hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane), "KBM-4803" (long-chain epoxy silane coupling agent), and "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), manufactured by Shin-Etsu Chemical Industry Co., Ltd.

[0118] From the viewpoint of improving the dispersibility of inorganic filler materials, the degree of surface treatment using a surface treatment agent is preferably within a specific range. Specifically, 100% by mass of the inorganic filler material is preferably surface treated with 0.2% to 5% by mass of a surface treatment agent, more preferably with 0.2% to 3% by mass of a surface treatment agent, and even more preferably with 0.3% to 2% by mass of a surface treatment agent.

[0119] The extent of surface treatment using surface treatment agents can be evaluated based on the carbon content per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon content per unit surface area of ​​the inorganic filler is preferably 0.02 mg / m². 2 The above, more preferably 0.1 mg / m 2 The above is further preferred to be 0.2 mg / m³. 2 That's all. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition, 1.0 mg / m³ is preferred. 2 The following is more preferably 0.8 mg / m³ 2 The following is a further preferred value: 0.5 mg / m³ 2 the following.

[0120] (D) The carbon content per unit surface area of ​​the inorganic filler material can be determined after cleaning the surface-treated inorganic filler material with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK is added to the surface-treated inorganic filler material, and the material is ultrasonically cleaned at 25°C for 5 minutes. After removing the supernatant and drying the solid components, the carbon content per unit surface area of ​​the inorganic filler material can be determined using a carbon analyzer. A carbon analyzer such as the "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd. can be used.

[0121] The amount of inorganic filler material (D) relative to 100% by mass of the non-volatile components in the resin composition is typically greater than 70% by mass, preferably 71% by mass or more, particularly preferably 72% by mass or more, preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. When the amount of inorganic filler material (D) is within the aforementioned range, it is possible to achieve a high level of reduction in the dielectric loss tangent Df of the cured resin composition and suppression of warpage of the circuit board containing the cured composition. Consequently, it is generally possible to effectively reduce the relative permittivity Dk and linear thermal expansion coefficient of the cured composition and effectively increase the glass transition temperature Tg.

[0122] The total amount of (A) epoxy resin, (B) naphthalene-type reactive ester resin, (C) hydroxyl-containing dimeric diamine-type polyimide resin and (D) inorganic filler material relative to 100% by mass of the non-volatile components of the resin composition is preferably 80% by mass or more, more preferably 85% by mass or more, further preferably 90% by mass or more, preferably 100% by mass or less, more preferably 99% by mass or less, and further preferably 98% by mass or less.

[0123] <(E) Rubber Granules> The resin composition according to this embodiment may include (E) rubber particles as an optional component. The (E) rubber particles, as component (E), do not include components belonging to (A) to (D) described above. The (E) rubber particles are typically included in the resin composition in a particulate state incompatible with the resin components other than (E) rubber particles, and are contained in the cured product in a form that maintains this particulate state. Furthermore, (E) rubber particles may be used alone or in combination of two or more.

[0124] (E) Rubber granules refer to granules containing rubber components. As the rubber component, a resin with rubber elasticity is usually used. As the resin with rubber elasticity, a resin that shows an elastic modulus of less than 1 GPa after a tensile test at 25°C and 40%RH according to Japanese Industrial Standard (JIS K7161) is preferred.

[0125] Examples of rubber components include: silicone elastomers such as polydimethylsiloxane; olefin-based thermoplastic elastomers such as polybutadiene, polyisoprene, polychloroprene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isobutylene copolymer, acrylonitrile-butadiene copolymer, isoprene-isobutylene copolymer, isobutylene-butadiene copolymer, ethylene-propylene-diene terpolymer, and ethylene-propylene-butene terpolymer; and acrylic thermoplastic elastomers such as poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, poly(cyclohexyl methacrylate), and poly(octyl methacrylate). Furthermore, silicone rubbers such as polysiloxane rubber can be mixed into the rubber component. The glass transition temperature of the rubber component contained in the rubber granules is, for example, below 0°C, preferably below -10°C, more preferably below -20°C, and even more preferably below -30°C.

[0126] (E) The rubber particles can be core-shell type rubber particles. Core-shell type rubber particles refer to rubber particles comprising a shell layer located on the surface of the particle and a core layer located inside the shell layer. Examples include core-shell type rubber particles comprising a shell layer formed of a polymer having a relatively high glass transition temperature and a core layer formed of a polymer having a relatively low glass transition temperature. Preferably, the shell layer is formed of a glassy polymer and the core layer is formed of a rubbery polymer. For such core-shell type rubber particles, the shell layer can suppress the aggregation of rubber particles or improve the dispersibility of rubber particles, and the core layer can provide excellent rubber elasticity. Core-shell type rubber particles can be manufactured, for example, by seed polymerization of one or more monomers corresponding to each layer in multiple stages.

[0127] Core-shell rubber granules can have a two-layer structure consisting only of a shell and a core, but they can also have a structure with three or more layers, including any number of layers. For example, core-shell rubber granules can include any layer between the shell and the core, or any layer inside the core. As a specific example, core-shell rubber granules can have a three-layer structure consisting of a shell formed of a glassy polymer, a core formed of a rubbery polymer, and any layer inside the core formed of a glassy polymer.

[0128] Among the aforementioned core-shell type rubber particles, examples of glassy polymers include acrylic polymers such as polymethyl methacrylate; and styrene polymers such as polystyrene and styrene-divinylbenzene copolymers. Among these, acrylic polymers are preferred, and polymethyl methacrylate is particularly preferred.

[0129] Specific examples of core-shell rubber granules include: STAPHYLOID “AC3832”, “AC3816N”, and “IM401-modified 7-17” manufactured by Aica Industries; “METABLEN KW-4426” manufactured by Mitsubishi Chemical Corporation; and PARALOID “EXL-2655” manufactured by Dow Chemical Japan.

[0130] (E) The average particle size of the rubber particles is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.10 μm or more, preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less. (E) The average particle size of the rubber particles can be measured using a zeta potential particle size distribution measuring device.

[0131] The amount of (E) rubber particles relative to 100% by mass of the non-volatile components in the resin composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 2% by mass or less.

[0132] The amount of (E) rubber particles relative to 100% by mass of the resin component in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0133] <(F) Curing Accelerator> The resin composition according to this embodiment may include (F) a curing accelerator as an optional component. The (F) curing accelerator, as component (F), does not include components belonging to (A) to (E) above. The (F) curing accelerator can act as a catalyst in the reaction of the (A) epoxy resin, thereby promoting the curing of the resin composition.

[0134] Examples of (F) curing accelerators include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. A single (F) curing accelerator can be used alone, or two or more can be used in combination.

[0135] Examples of phosphorus-based curing accelerators include: tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitic tert-butylphosphonium, tetrabutylphosphonium hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate, and other aliphatic phosphonium salts; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, and p-methylphosphonium bromide. Aromatic phosphonium salts including phenyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tri(3-methylphenyl)ethylphosphonium tetraphenylborate, tri(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactants; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, and di-tert-butylphosphine. Butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, tricyclohexylphosphine, and other aliphatic phosphines; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri(4-ethylphenyl)phosphine, tri(4-propylphenyl)phosphine, tri(4-isopropylphenyl)phosphine, tri(4-butylphenyl)phosphine, tri(4-tert-butylphenyl)phosphine, tri(2,4-dimethylphenyl)phosphine, tri(2,5-dimethylphenyl)phosphine, tri(2,6- Aromatic phosphines include dimethylphenylphosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether.

[0136] Examples of urea-based curing accelerators include: 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, and 3-(3,4-dimethylphenyl)-1,1-dimethylurea. Aromatic dimethylureas include 1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea)[toluenebisdimethylurea], etc.

[0137] Examples of guanidine-based 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-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, 1-(o-tolyl)biguanidine, etc.

[0138] Examples of imidazole-based curing accelerators include: 2-methylimidazolium, 2-undecylimidazolium, 2-heptadecylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-cyanoethyl-2-undecylimidazolium, 1-cyanoethyl-2-ethyl-4-methylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolium-(1')] Imidazole compounds such as 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-triazine isocyanuric acid adduct, 2-phenylimidazolyl isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, etc., as well as adducts of imidazole compounds with epoxy resins. Commercially available imidazole-based curing accelerators include, for example, those manufactured by Shikoku Chemical Industry Co., Ltd. such as "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", "2MA-OK-PW", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", and "C11Z-A"; and "P200-H50" manufactured by Mitsubishi Chemical Co., Ltd.

[0139] Examples of organometallic 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 organocobalt complexes such as cobalt(II) and cobalt(III) acetylacetone; organocopper complexes such as copper(II) acetylacetone; organozinc complexes such as zinc(II) acetylacetone; organoiron complexes such as iron(III) acetylacetone; organonickel complexes such as nickel(II) acetylacetone; and organomanganese complexes such as manganese(II) acetylacetone. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0140] Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine; 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene. Commercially available amine-based curing accelerators can be used, such as "MY-25" manufactured by Ajinomoto Fine-Techno.

[0141] The amount of (F) curing accelerator relative to 100% by mass of the non-volatile components in the resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less.

[0142] The amount of (F) curing accelerator relative to 100% by mass of the resin component in the resin composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less.

[0143] <(G) Any curing agent> In the resin composition according to this embodiment, (G) any curing agent may be included as an optional component. The (G) optional curing agent, as component (G), refers to a resin capable of reacting with epoxy resin to form a bond, thereby curing the resin composition. The (G) optional curing agent does not include components belonging to (A) to (F) above. For example, (B) naphthalene-type epoxy resin and (C) hydroxyl-containing dimeric diamine-type polyimide resin may react with (A) epoxy resin to form a bond, but these (B) naphthalene-type epoxy resins and (C) hydroxyl-containing dimeric diamine-type polyimide resins are not classified as (G) optional curing agents. The (G) optional curing agent may be used alone or in combination of two or more.

[0144] Preferred examples of any curing agent in (G) include phenolic resins, any reactive ester resins (i.e., reactive ester resins other than (B) naphthalene-type epoxy resins), benzoxazine resins, cyanate ester resins, carbodiimide resins, acid anhydride resins, amine resins, etc.

[0145] As phenolic resins, resins having one or more, preferably two or more, phenolic hydroxyl groups per molecule can be used. From the viewpoint of heat resistance and water resistance, phenolic resins having a phenolic structure are preferred. Furthermore, from the viewpoint of adhesion, nitrogen-containing phenolic resins are preferred, and phenolic resins containing a triazine skeleton are more preferred. Among these, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, linear phenolic resins containing a triazine skeleton are preferred.

[0146] Specific examples of phenolic resins include: "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" manufactured by Meiwa Chemical Co., Ltd.; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd.; and "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-495V", and "SN-3" manufactured by Nippon Steel Chemical Materials Co., Ltd. 75”, SN-395; DIC Company's “TD-2090”, “TD-2090-60M”, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018”, “LA-3018-50P”, “LA-1356”, “TD2090”, “TD-2090-60M”; Qunrong Chemical Company's “GDP-6115L”, “GDP-6115H”, “ELPC75”, etc.

[0147] The amount of phenolic resin relative to 100% by mass of the resin component in the resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 5% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less.

[0148] As any reactive ester resin, a reactive ester resin without a naphthalene skeleton can be used. Among them, as any reactive ester resin, resins having two or more highly reactive ester groups in one molecule, such as phenolic esters, thiophenolic esters, N-hydroxyamine esters, and esters of heterocyclic hydroxyl compounds, are preferred.

[0149] Any reactive ester resin is preferably a resin obtained by the condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxyl compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, reactive ester resins obtained from carboxylic acid compounds and hydroxyl compounds are preferred, and reactive ester resins obtained from carboxylic acid compounds and phenolic compounds are more preferred. Examples of carboxylic acid compounds include, for example, those exemplified as materials for (B) naphthalene-type reactive ester resins. Examples of phenolic compounds include, for example, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyroglucinol, dicyclopentadiene-type diphenol compounds, linear phenolic resins, etc. Here, "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing 2 molecules of phenol into 1 molecule of dicyclopentadiene.

[0150] Among these, an active ester resin containing a butadiene skeleton is preferred. The butadiene skeleton refers to the carbon skeleton contained in the butene diene. Here, the butene diene includes 2-buten-1,4-diyl and 3-buten-1,2-diyl (i.e., vinylethylidene). The aforementioned 2-buten-1,4-diyl can be either cis or trans. Active ester resins containing a butadiene skeleton generally include groups containing this butadiene skeleton. Examples of such groups containing a butadiene skeleton include, for example, the aforementioned 2-buten-1,4-diyl and 3-buten-1,2-diyl, and groups in which the hydrogen atoms contained in these groups are substituted by substituents. Examples of substituents include: halogen atoms; saturated aliphatic hydrocarbon groups such as alkyl and cycloalkyl groups; aromatic hydrocarbon groups such as aryl groups; alkoxy, cycloalkoxy, aryloxy, etc. The butadiene backbone group is preferably 3-butene-1,2-diyl with substituents, and more preferably 3-butene-1,2-diyl without substituents. The number of butadiene backbones contained in one molecule of any active ester resin is generally one or more, preferably two or more. More preferably, any active ester resin contains a polybutadiene structure formed by the combination of two or more butadiene backbones.

[0151] Commercially available reactive ester resins include, for example, reactive ester resins containing a dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "EXB-8000H", "HPC-8000L-65MT", and "EXB-8000L-65TM" (manufactured by DIC Corporation); phosphorus-containing reactive ester resins include "EXB- 9401 (manufactured by DIC Corporation); as an active ester resin containing an acetylated linear phenolic resin, examples include DC808 (manufactured by Mitsubishi Chemical Corporation); as an active ester resin containing a benzoylated linear phenolic resin, examples include YLH1026 (manufactured by Mitsubishi Chemical Corporation), YLH1030 (manufactured by Mitsubishi Chemical Corporation), YLH1048 (manufactured by Mitsubishi Chemical Corporation), and EXB-8500-65T (manufactured by DIC Corporation), etc.

[0152] The amount of any active ester resin relative to 100% by mass of the resin component in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, preferably 10% by mass or less, more preferably 6% by mass or less, and even more preferably 4% by mass or less.

[0153] As benzoxazine resins, resins having one or more, preferably two or more, benzoxazine rings within one molecule can be used. Specific examples of benzoxazine resins include: "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; and "Pd", "Fa", and "ALP-d" manufactured by Shikoku Chemical Industry Co., Ltd.

[0154] As cyanate ester resins, resins having one or more, preferably two or more, cyanate ester groups within one molecule can be used. Examples of cyanate ester resins include, for instance, bisphenol A dicyanate, polyphenol cyanate, oligomeric (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanoxy)phenylpropane, 1,1-bis(4-cyanoxyphenylmethane), bis(4-cyanoxy-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanoxyphenyl-1-(methylethylene))benzene, bis(4-cyanoxyphenyl) sulfide, and bis(4-cyanoxyphenyl) ether, etc.; polyfunctional cyanate ester resins derived from phenolic varnish resins and cresol varnish resins, etc.; and prepolymers obtained by partially triazinizing these cyanate ester resins, etc. Specific examples of cyanate ester resins include Arxada's "PT30" and "PT60" (phenolic varnish type multifunctional cyanate ester resins), "BA230", and "BA230S75" (prepolymers of bisphenol A dicyanate that have been partially or completely triazinized to form trimers).

[0155] As a carbodiimide resin, resins having one or more, preferably two or more, carbodiimide structures within one molecule can be used. Specific examples of carbodiimide resins include: aliphatic bis(tert-butylcarbodiimide), cyclohexanebis(methylene-tert-butylcarbodiimide), and other aliphatic biscarbodiimides; aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylcarbodiimide, poly(methylene biscyclohexylcarbodiimide), and poly(isophoronecarbodiimide); poly(phenylenecarbodiimide), poly... Aromatic polycarbodiimides such as (naphthylcarbodiimide), poly(toluenecarbodiimide), poly(methyldiisopropylphenylcarbodiimide), poly(triethylphenylcarbodiimide), poly(diethylphenylcarbodiimide), poly(triisopropylphenylcarbodiimide), poly(diisopropylphenylcarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylcarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide] are also included. Commercially available carbodiimide resins include, for example, “Carbodilite V-02B”, “Carbodilite V-03”, “Carbodilite V-04K”, “Carbodilite V-05”, “Carbodilite V-07” and “Carbodilite V-09” manufactured by Nisshinbo Chemical Co., Ltd.; and “STABAXOL P”, “STABAXOL P400” and “Hycasyl 510” manufactured by LANXESS Co., Ltd.

[0156] As an anhydride resin, resins having one or more, preferably two or more, anhydride groups within one molecule can be used. Specific examples of anhydride resins include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and diphenyl ether. Polymer anhydrides such as benzophenone tetracarboxylic anhydride, biphenyl tetracarboxylic anhydride, naphthalene tetracarboxylic anhydride, oxydiphthalic anhydride, 3,3'-4,4'-diphenyl sulfone tetracarboxylic anhydride, 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(trimethicone) ester, and styrene-maleic acid resin obtained by copolymerization of styrene and maleic acid. Commercially available anhydride resins include, for example, “HNA-100”, “MH-700”, “MTA-15”, “DDSA”, and “OSA” manufactured by Shin Nippon Rikka Co., Ltd.; “YH-306” and “YH-307” manufactured by Mitsubishi Chemical Co., Ltd.; “HN-2200” manufactured by RESONAC Co., Ltd.; and “EF-30”, “EF-40”, “EF-60”, and “EF-80” manufactured by Cray Valley Co., Ltd.

[0157] As an amine resin, a resin having one or more, preferably two or more, amino groups within one molecule can be used. Examples of amine resins include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines, with aromatic amines being preferred. The amine resin is preferably a primary or secondary amine, 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-phenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybiphenylamine, and 2,2-bis(3-amino-4-hydroxybenzene). 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, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. Commercially available amine resins include, for example, "SEIKACURE-S" manufactured by SEIKA Corporation; "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARDA-B", and "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd.; "EPICURE W" manufactured by Mitsubishi Chemical Co., Ltd.; and "DTDA" manufactured by Sumitomo Seika Co., Ltd.

[0158] (G) The active group equivalent of any curing agent is preferably 50 g / eq. to 3,000 g / eq., more preferably 100 g / eq. to 1,000 g / eq., further preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The active group equivalent represents the mass of resin per 1 equivalent of active group. Furthermore, the active group of any curing agent in (G) represents a group capable of reacting with the epoxy group of (A) epoxy resin, and examples include phenolic hydroxyl groups and active ester groups. For example, the active group equivalent of a phenolic resin represents the phenolic hydroxyl equivalent, indicating the mass of resin per 1 equivalent of phenolic hydroxyl group. Furthermore, the active group equivalent of any active ester resin represents the active ester equivalent.

[0159] (G) The range of weight-average molecular weight (Mw) of any curing agent may be the same as the range of weight-average molecular weight (Mw) of (A) epoxy resin.

[0160] The amount of any curing agent (G) relative to 100% by mass of the non-volatile components in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0161] The amount of any curing agent (G) relative to 100% by mass of the resin component in the resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 5% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less.

[0162] <(H) Polymer Resin> The resin composition according to this embodiment may include (H) polymer resin as an optional component. The (H) polymer resin as component (H) does not include components belonging to (A) to (G) described above. The (H) polymer resin is generally thermoplastic. Furthermore, the (H) polymer resin is generally included in the resin composition in a state compatible with curable resins such as (A) epoxy resin and (B) naphthalene-type reactive ester resin, and is directly included in the cured product in this compatible state. One (H) polymer resin may be used alone, or two or more may be used in combination.

[0163] (H) Polymer resins typically have a large molecular weight. Specifically, the weight-average molecular weight (Mw) of the (H) polymer resin is preferably greater than 5,000, more preferably 8,000 or more, further preferably 10,000 or more, even more preferably 20,000 or more, preferably 100,000 or less, more preferably 70,000 or less, even more preferably 60,000 or less, and even more preferably 50,000 or less. The weight-average molecular weight (Mw) of the (H) polymer resin can be determined by gel permeation chromatography (GPC) as a value converted from polystyrene.

[0164] Examples of (H) polymer resins include: phenoxy resins, polyimide resins, polyvinyl acetal resins, polystyrene resins, polyolefin resins, polybutadiene resins, polyamide-imide resins, polyethersulfone resins, polysulfone resins, polyetherimide resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins. Among these, phenoxy resins are preferred.

[0165] Examples of phenoxy resins include those having one or more skeletons selected from the following: bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, phenolic skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal group of the phenoxy resin can be any functional group such as a phenolic hydroxyl group or an epoxy group. Specific examples of phenoxy resins include: Mitsubishi Chemical Corporation's "1256" and "4250" (both phenoxy resins containing a bisphenol A skeleton); Mitsubishi Chemical Corporation's "YX8100" (phenoxy resin containing a bisphenol S skeleton); Mitsubishi Chemical Corporation's "YX7800BH40" (phenoxy resin containing a fluorene skeleton); Mitsubishi Chemical Corporation's "YX6954" (phenoxy resin containing a bisphenol acetophenone skeleton); and Nippon Steel Chemical Materials Co., Ltd. The "FX280" and "FX293" manufactured by the company; the "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482", "YL7891BH30", "YL7891T30" and "YL9142T30" manufactured by Mitsubishi Chemical Corporation; etc.

[0166] Specific examples of polyimide resins include "PIAD200" manufactured by Arakawa Chemical Co., Ltd., "SLK-6100" manufactured by Shin-Etsu Chemical Industry Co., Ltd., and "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Shin Nippon Rika Co., Ltd. Specific examples of polyimide resins also include linear polyimide resins obtained by reacting difunctional hydroxyl-terminated polybutadiene, diisocyanate compounds, and tetrabasic anhydrides (the polyimide resin described in Japanese Patent Application Publication No. 2006-37083), and modified polyimide resins containing a polysiloxane backbone (the polyimide resins described in Japanese Patent Application Publication Nos. 2002-12667 and 2000-319386, etc.).

[0167] Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, with polyvinyl butyral resins being preferred. Specific examples of polyvinyl acetal resins include the S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemicals Co., Ltd.

[0168] Examples of polystyrene-based resins include: unmodified polystyrene resins, oxazoline-containing modified polystyrene resins, and styrene block copolymers. Examples of styrene block copolymers include: styrene-isoprene-styrene block copolymers (SIS resin), styrene-ethylene / butene-styrene block copolymers (SEBS resin), styrene-ethylene / propylene-styrene block copolymers (SEPS resin), styrene-butadiene-styrene block copolymers (SBS resin), and styrene-isobutylene-styrene block copolymers (SIBS resin). Specific examples of polystyrene-based resins include: Nippon Shokubai's "PX3-RP-37" and "RP-RX-61" (modified polystyrene resins containing oxazoline groups); Kuraray's "HYBRA 5125" (SIS resin); Asahi Kasei's "S1611" (SEBS resin); Asahi Kasei's "H1041," "Tuftec H1043," "Tuftec P2000," and "Tuftec MP10" (hydrogenated styrene-based polymer resins); Daicel's "EPOFRIEND AT501" and "CT310" (epoxidized styrene-butadiene polymer resins); Kuraray's "SEPTON HG252" (hydroxyl-modified polystyrene resin); Asahi Kasei's "Tuftec N503M" (carboxyl-modified polystyrene resin); and Asahi Kasei's "Tuftec..." N501 (modified polystyrene resin with amino groups); Asahi Kasei Corporation's "Tuftec M1913" (modified polystyrene resin with anhydride groups); Kuraray Corporation's "SEPTON S8104" (unmodified polystyrene resin); Kraton Corporation's "FG1924" (styrene-ethylene / butene-styrene block copolymer); "EF-40" (CRAY VALLEY Corporation), etc.

[0169] Examples of polyolefin resins include: low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, and other ethylene-based copolymers; polyolefin polymers such as polypropylene and ethylene-propylene block copolymers.

[0170] Examples of polybutadiene resins include: resins containing a hydrogenated polybutadiene backbone, polybutadiene resins containing hydroxyl groups, polybutadiene resins containing phenolic hydroxyl groups, polybutadiene resins containing carboxyl groups, polybutadiene resins containing acid anhydride groups, polybutadiene resins containing epoxy groups, polybutadiene resins containing isocyanate groups, polybutadiene resins containing urethane groups, and polyphenylene ether-polybutadiene resins.

[0171] Specific examples of polyamide-imide resins include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Other specific examples of polyamide-imide resins include modified polyamide-imides such as "KS9100" and "KS9300" (polyamide-imide containing a polysiloxane backbone) manufactured by Risenok Co., Ltd.

[0172] Specific examples of polyethersulfone resins include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0173] Specific examples of polysulfone resins include polysulfones such as "P1700" and "P3500" manufactured by Solvay Performance Polymers.

[0174] Polyphenylene ether resin can be, for example, a copolymer of polyphenylene ether and polybutadiene.

[0175] Specific examples of polyetherimide resins include "Ultem" manufactured by GE.

[0176] Examples of polycarbonate resins include: hydroxyl-containing carbonate resins, phenolic hydroxyl-containing carbonate resins, carboxyl-containing carbonate resins, anhydride-containing carbonate resins, isocyanate-containing carbonate resins, and urethane-containing carbonate resins. Specific examples of polycarbonate resins include: "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Corporation, and "C-1090," "C-2090," and "C-3090" (polycarbonate diol) manufactured by Kuraray Co., Ltd.

[0177] Specific examples of polyetheretherketone resins include "SUMIPLOY K" manufactured by Sumitomo Chemical Co., Ltd.

[0178] Examples of polyester resins include: polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polypropylene terephthalate resin, polypropylene naphthalate resin, and polycyclohexanedimethyl terephthalate resin.

[0179] The amount of (H) polymer resin relative to 100% by mass of the non-volatile components of the resin composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.3% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1% by mass or less.

[0180] The amount of (H) polymeric resin relative to 100% by mass of the resin component in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, preferably 20% by mass or less, preferably 10% by mass or less, and more preferably 5% by mass or less.

[0181] <(I) Any additives> The resin composition according to this embodiment may further include (I) any additive as an optional component. The (I) optional additive as component (I) does not include components belonging to (A) to (H) described above. As any additive in (I), examples include: organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium dioxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as organosilicon-based leveling agents and acrylic polymer-based leveling agents; thickeners such as BENTON and montmorillonite; defoamers such as organosilicon-based defoamers, acrylic defoamers, fluorine-based defoamers, and vinyl resin-based defoamers; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion enhancers such as ureasilanes; adhesion enhancers such as triazole-based, tetraazole-based, and triazine-based adhesion enhancers; hindered phenolic antioxidants. Antioxidants such as oxidizing agents; fluorescent whitening agents such as diphenylethylene derivatives; surfactants such as fluorinated surfactants and organosilicon surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphonic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester dispersants, polyoxyalkylene dispersants, acetylene dispersants, organosilicon dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate / ester stabilizers, titanate / ester stabilizers, aluminate / ester stabilizers, zirconate / ester stabilizers, isocyanate / ester stabilizers, carboxylic acid stabilizers, and carboxylic anhydride stabilizers. (I) Any additive may be used alone or in combination of two or more.

[0182] <(J) Solvent> The resin composition according to this embodiment may also include, in combination with non-volatile components such as components (A) to (I) above, a solvent (J) as an optional volatile component. Organic solvents are typically used as the solvent (J). Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; and 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diethylene glycol acetate, γ-butyrolactone, and methoxypropyl ether. Ether ester solvents such as methyl lactate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (J) Solvents can be used alone or in combination of two or more.

[0183] The amount of solvent (J) relative to 100% by mass of all components in the resin composition may be, for example, 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less, or may be 0% by mass.

[0184] <Method for manufacturing resin composition> The resin composition described in this embodiment can be manufactured, for example, by mixing components that may be included in the resin composition. These components may be mixed partially or entirely simultaneously, or sequentially. During the mixing of the components, a suitable temperature can be set, thus allowing for temporary or continuous heating and / or cooling. Furthermore, stirring or agitation can be performed during the mixing of the components.

[0185] <Characteristics of cured resin compositions> By curing the resin composition according to this embodiment, a cured product of the resin composition can be obtained. An insulating layer can then be formed using this cured product. Typically, heat is applied during the curing of the resin composition; therefore, volatile components such as solvents (J) may evaporate due to the heat during curing. Consequently, the cured product obtained by curing the resin composition may contain non-volatile components such as components (A) to (I) or their reaction products.

[0186] According to the resin composition of this embodiment, warping can be suppressed when an insulating layer is formed on an inner substrate using a cured resin composition. For example, when a warping measurement test is performed using the method described in Test Example 3 of the following embodiments, the amount of warping can be reduced. In one example, the range of warping amount is preferably 20 mm or less, more preferably 18 mm or less, and even more preferably 16 mm or less.

[0187] The cured resin composition according to this embodiment can have excellent dielectric properties. Specifically, the cured product can have a low dielectric loss tangent Df. In one example, the dielectric loss tangent Df of the cured product is preferably 0.0039 or less, more preferably 0.0037 or less, and even more preferably 0.0035 or less. The lower limit of the dielectric loss tangent Df is not particularly limited, for example, it can be 0.0010 or more.

[0188] Preferably, the cured material has a low relative permittivity Dk. In one example, the relative permittivity Dk of the cured material is preferably 4.0 or less, more preferably 3.8 or less, and even more preferably 3.5 or less. There is no particular limitation on the lower limit of the relative permittivity Dk, for example, it can be 2.0 or more.

[0189] The dielectric loss tangent Df and relative permittivity Dk of the cured material can be measured using the split cylinder method at a measurement frequency of 10 GHz and a measurement temperature of 90 °C. When the sample is a resin composition before curing, the resin composition can be cured at 190 °C for 90 minutes to obtain a cured material, and the dielectric loss tangent Df and relative permittivity Dk of the cured material can be measured. The specific measurement method can be the method described in Test Example 1 of the following embodiments.

[0190] The cured resin composition involved in this embodiment preferably has high heat resistance. Specifically, the cured product may have a high glass transition temperature (Tg). In one example, the glass transition temperature (Tg) of the cured product is preferably 150°C or higher, more preferably 152°C or higher, and even more preferably 154°C or higher. The upper limit may be, for example, 300°C or lower, 250°C or lower, 200°C or lower, etc.

[0191] The glass transition temperature (Tg) of the cured product can be determined by thermomechanical analysis. This thermomechanical analysis can be performed by heating from 25°C to 220°C at a heating rate of 5°C / min. Two measurements can be performed, and the glass transition temperature (Tg) is obtained from the second result. If the sample is a resin composition before curing, the resin composition can be cured at 190°C for 90 minutes to obtain a cured product, and the glass transition temperature (Tg) of the cured product can be determined. The specific determination method can be the method described in Test Example 2 of the following embodiments.

[0192] The cured resin composition involved in this embodiment preferably has a small coefficient of linear thermal expansion (CTE). In one example, the CTE of the cured product is preferably 20 ppm / °C or less, more preferably 18 ppm / °C or less, and even more preferably 16 ppm / °C or less. The lower limit can be, for example, 5 ppm / °C or more.

[0193] The coefficient of linear thermal expansion (CTE) of the cured product can be determined by thermomechanical analysis. This thermomechanical analysis can be performed by heating from 25°C to 220°C at a heating rate of 5°C / min. Two measurements can be performed, and the CTE is obtained from the second result. If the sample is a resin composition before curing, the resin composition can be cured at 190°C for 90 minutes to obtain a cured product, and the CTE of the cured product can be measured. The specific measurement method can be the method described in Test Example 2 of the following embodiments.

[0194] <Uses of Resin Compositions> The resin composition described in this embodiment can be used for forming insulating layers, and is particularly preferred for forming insulating layers on circuit boards. Additionally, the resin composition can be used for manufacturing resin sheets. Typically, these resin sheets are used to form insulating layers. Furthermore, the resin composition can be used for other applications, such as solder resist, underfill material, chip bonding material, via-filling resin, sealing resin, and component embedding resin.

[0195] <Resin Sheets> One embodiment of the present invention relates to a resin sheet comprising a support and a resin composition layer formed on the support. The resin composition layer comprises the aforementioned resin composition, preferably comprising only the aforementioned resin composition.

[0196] From the viewpoint of thinness, the thickness of the resin composition layer in the resin sheet is preferably 200 μm or less, more preferably 150 μm or less, and even more preferably 100 μm or less. The lower limit of the thickness of the resin composition layer can be, for example, 1 μm or more, 3 μm or more, 5 μm or more, etc.

[0197] Examples of supports include films made of plastic materials, metal foils, and release paper, with films made of plastic materials and metal foils being more preferred.

[0198] When using a plastic film as a support, examples of plastic materials include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"); acrylics such as polycarbonate (hereinafter sometimes abbreviated as "PC") and polymethyl methacrylate (PMMA); cyclic polyolefins, cellulose triacetate (TAC), polyether sulfide (PES), polyether ketone, and polyimide. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0199] When using metal foil as a support, examples of metal foil include copper foil and aluminum foil, with copper foil being preferred. Copper foil can be used as a single metal containing copper, or it can be an alloy containing copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0200] Surface treatments such as matte finish, corona treatment, and antistatic treatment can be applied to the surface of the support that is bonded to the resin composition layer.

[0201] As a support, a support with a release layer can be used on the surface that bonds to the resin composition layer. Examples of release agents used in the release layer of the support with a release layer include, for example, one or more release agents selected from alkyd release agents, polyolefin release agents, urethane release agents, and silicone release agents. Commercially available products can be used as supports with release layers, such as "PET501010," "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation, which have a release layer with a silicone or alkyd resin release agent as the main component; "LUMIRROR T60" manufactured by Toray Industries, Ltd.; "Purex" manufactured by Teijin Corporation; and "Unipeel" manufactured by Unitika Corporation.

[0202] The thickness of the support is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, even more preferably 10 μm or more, preferably 75 μm or less, more preferably 60 μm or less, and even more preferably 50 μm or less. When using a support with a release layer, the overall thickness of the support with the release layer is preferably within the above range.

[0203] The resin sheet can have any components as needed. For example, the resin sheet can have a protective film to protect the resin composition layer. The protective film is usually provided on the side of the resin composition layer that is not in contact with the support (i.e., the side opposite to the support). The thickness of the protective film is not particularly limited, for example, from 1 μm to 40 μm. With the protective film, the adhesion and damage of dirt to the surface of the resin composition layer can be inhibited.

[0204] Resin sheets can be manufactured, for example, by forming a resin composition layer on a support. Specifically, a resin sheet can be manufactured by directly applying a liquid (varnish-like) resin composition to the support, or by preparing a liquid (varnish-like) resin composition by mixing a solvent with the resin composition, applying it to the support, and then drying it as needed to form a thermoplastic resin composition layer. The same solvent as described in (J) as a component of the resin composition can be used as the solvent.

[0205] The resin composition can be coated using a coating apparatus such as a die coater. Drying can be performed by methods such as heating or blowing hot air. Drying conditions are not particularly limited, but drying is generally carried out when the solvent content in the resin composition layer is typically 10% by mass or less, preferably 5% by mass or less. The drying conditions may also vary depending on the boiling point of the solvent; for example, when using a resin composition containing 30% to 60% by mass of solvent, a resin composition layer can be formed by drying it at 50°C to 150°C for 3 to 10 minutes.

[0206] The manufactured resin sheets can be stored in rolls. When the resin sheet has a protective film, it can usually be used by peeling off the protective film.

[0207] <Circuit substrate> One embodiment of the present invention relates to a circuit board comprising a cured product of the aforementioned resin composition. Typically, the circuit board includes an insulating layer comprising a cured product of the resin composition. The insulating layer may comprise only the cured product of the resin composition. The thickness of the insulating layer is not particularly limited; for example, it may be in the same range as the thickness of the resin composition layer on the resin sheet. Furthermore, the insulating layer may generally have the same properties as the cured product of the aforementioned resin composition.

[0208] Preferably, the circuit board includes an inner substrate on which the aforementioned insulating layer is provided. Additionally, the circuit board may include a conductor layer. For example, a conductor layer may be provided on the insulating layer. Hereinafter, examples of preferred methods for manufacturing the circuit board will be described.

[0209] The preferred embodiment involves a method for manufacturing a circuit board, which includes: The process of forming a resin composition layer on the inner substrate (I), and Step (II) for curing the resin composition layer.

[0210] "Inner layer substrate" refers to a component that serves as the substrate for a circuit board, such as glass epoxy resin substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. Furthermore, the inner layer substrate may have conductive layers on one or both sides. The conductive layers of the inner layer substrate can also be patterned. An inner layer substrate with conductive layers (circuit) formed on one or both sides of the substrate is sometimes called an "inner circuit board." Additionally, intermediate components that should be further formed with insulating layers and / or conductive layers during the manufacturing of the circuit board are also included in the term "inner layer substrate." Furthermore, inner layer substrates with built-in components can also be used.

[0211] Forming a resin composition layer on an inner substrate can be performed, for example, by coating the resin composition onto the inner substrate and drying it as needed, preferably using a resin sheet. The method of forming the resin composition layer using a resin sheet typically involves laminating the resin sheet to the inner substrate. The lamination of the resin sheet to the inner substrate is performed in such a way that the resin composition layer of the resin sheet is bonded to the inner substrate. This lamination can be performed, for example, by heat-pressing the resin sheet onto the inner substrate from the support side. Examples of components for heat-pressing the resin sheet onto the inner substrate (hereinafter also referred to as "heat-pressing component") include, for example, heated metal plates (SUS end plates, etc.) or metal rollers (SUS rollers, etc.). It should be noted that, preferably, the heat-pressing component is not pressed directly onto the resin sheet, but rather pressed through an elastic material such as heat-resistant rubber, so that the resin sheet fully follows the surface irregularities of the inner substrate.

[0212] The lamination of the inner substrate and the resin sheet can be performed by vacuum lamination. In vacuum lamination, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C; the heating and pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa; and the heating and pressing time is preferably in the range of 10 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions of 26.7 hPa or less.

[0213] Lamination can be performed using commercially available vacuum laminators. Examples of commercially available vacuum laminators include the vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., the vacuum dressing machine manufactured by Nikko Materials Co., Ltd., and the intermittent vacuum pressure laminator.

[0214] A method for manufacturing a circuit board may include: after lamination, smoothing the resin sheet by pressing a heated bonding member under normal pressure (atmospheric pressure), for example, from the support side. The pressing conditions for the smoothing treatment can be set to the same conditions as the heated bonding conditions for the lamination described above. The smoothing treatment can be performed using a commercially available laminator. Lamination and smoothing treatment can be performed continuously using the aforementioned commercially available vacuum laminator.

[0215] The circuit board manufacturing method described in this example includes a step (II) that cures a resin composition layer after step (I). By curing the resin composition layer in step (II), an insulating layer comprising a cured resin composition can be formed.

[0216] The curing of the resin composition layer is usually carried out by heat curing. The heat curing conditions of the resin composition layer may also vary depending on the type of resin composition. For example, 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. In addition, 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.

[0217] A method for manufacturing a circuit board may include preheating the resin composition layer at a temperature lower than the curing temperature before thermal curing. For example, the resin composition layer may be preheated at a temperature typically between 50°C and 150°C, preferably between 60°C and 140°C, more preferably between 70°C and 130°C, for at least 5 minutes, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes, before thermal curing. Preheating is typically performed after step (I). Furthermore, if a smoothing treatment is performed after laminating the inner layer substrate and the resin sheet, preheating can typically be performed after the smoothing treatment.

[0218] When using resin sheets, the method for manufacturing a circuit board may include a step of peeling off a support from the resin sheet after the inner layer substrate and the resin sheet are laminated. The peeling off of the support may be performed between steps (I) and (II), or after step (II). Furthermore, when the method for manufacturing a circuit board, as described below, includes a step (III) of forming holes in an insulating layer, a step (IV) of roughening the insulating layer, and a step (V) of forming a conductor layer, the peeling off of the support may be performed between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V).

[0219] The manufacturing method of the circuit board may include a step (III) after step (II), in which holes such as through holes or vias are formed in the insulating layer. The method for forming the holes may be selected based on factors such as the composition of the resin composition used to form the insulating layer. For example, holes may be formed by processing methods such as drilling, laser processing, or plasma processing, with laser processing being preferred. For example, holes may be formed by irradiating the insulating layer with a laser after the support is peeled off, or holes may be formed by irradiating the insulating layer with a laser through the support. The size and shape of the holes may be appropriately determined according to the design of the circuit board.

[0220] The method for manufacturing a circuit board may include a step (IV) of roughening an insulating layer. This roughening process roughens the surface of the insulating layer. Furthermore, the roughening process removes contaminants (resin residue) from the insulating layer. Therefore, this roughening process is sometimes referred to as a "decontamination process." For example, if a hole is formed in step (III), contaminants may form within the hole; therefore, it is preferable to perform the roughening process (IV) after step (III) to remove the aforementioned contaminants.

[0221] There are no particular limitations on the steps and conditions of the roughening treatment; known steps and conditions commonly used in forming the insulating layer of a circuit board can be adopted. For example, the roughening treatment can be performed by sequentially performing a swelling treatment based on a swelling solution, an oxidation treatment based on an oxidizing agent, and a neutralization treatment based on a neutralizing solution on the insulating layer.

[0222] Examples of swelling solutions used in the roughening process include alkaline solutions and surfactant solutions, with alkaline solutions being preferred. Sodium hydroxide solution and potassium hydroxide solution are more preferred. Commercially available swelling solutions include, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Ammet Japan Co., Ltd. The swelling treatment based on the swelling solution can be performed, 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 the resin swelling of 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.

[0223] Examples of oxidants used in roughening treatments include alkaline permanganate solutions, such as potassium permanganate or sodium permanganate dissolved in an aqueous solution of sodium hydroxide. Oxidation treatment based on alkaline permanganate solutions or similar oxidants is preferably performed by immersing the insulating layer in an oxidant solution heated to 60°C to 100°C for 10 to 30 minutes. Furthermore, the concentration of permanganate in the alkaline permanganate solution is preferably 5% to 10% by mass. Commercially available oxidants include, for example, alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing solution Securiganth P" manufactured by Ammet Japan Co., Ltd.

[0224] The neutralizing solution used in the roughening process is preferably an acidic aqueous solution, and commercially available examples include "Reduction solution Securiganth P" manufactured by Ammet Japan Co., Ltd. The neutralization process based on the neutralizing solution can be performed by immersing the surface treated with the oxidizing agent in a neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From an operational point of view, it is preferable to immerse the object treated with the oxidizing agent in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

[0225] A method for manufacturing a circuit board may include a step (V) of forming a conductor layer on an insulating layer. In cases where the method for manufacturing a circuit board includes step (III) or (IV), the step (V) of forming the conductor layer is generally preferably performed after steps (III) and (IV).

[0226] The conductor material used in the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer comprises one or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer can 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-mentioned metals (e.g., nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). From the viewpoints of versatility in conductor layer formation, cost, and ease of patterning, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy, is preferred. More preferably, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, is preferred. A single metal layer of copper is even more preferred.

[0227] The conductor layer can have a single-layer structure or a multi-layer structure comprising two or more single-metal layers or alloy layers of different types of metals or alloys. In the case of a multi-layer conductor layer, the layer in contact with the insulating layer is preferably a single-metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0228] The thickness of the conductor layer depends on the design of the circuit board, and is preferably 3μm to 35μm, more preferably 5μm to 30μm.

[0229] The conductor layer can be formed by plating. For example, the surface of the insulating layer can be plated using existing known techniques such as semi-additive and fully additive methods to form a conductor layer with the desired wiring pattern. From the viewpoint of ease of manufacturing, the semi-additive method is preferred. An example of forming a conductor layer using the semi-additive method is shown below.

[0230] First, an electroless plating layer (plating seed layer) is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed electroless plating layer, exposing a portion of the electroless plating layer corresponding to the desired wiring pattern. After forming an electrolytic plating layer on the exposed electroless plating layer by electrolytic plating, the mask pattern is removed. Subsequently, the unwanted electroless plating layer is removed by etching, thus forming a conductor layer with the desired wiring pattern.

[0231] As another example, the conductor layer can be formed using metal foil. When using metal foil to form the conductor layer, step (V) is suitable to be performed between steps (I) and (II). For example, after step (I), the support is removed, and metal foil is laminated onto the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil can be performed by vacuum lamination. The lamination conditions can be set to the same conditions described for step (I). Next, step (II) is performed to form an insulating layer. Thereafter, the conductor layer with the desired wiring pattern can be formed using the metal foil on the insulating layer and known techniques such as subtractive processing or modified semi-additive processing. The metal foil can be manufactured by known methods such as electrolysis or rolling. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Metals Corporation; and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Metals Corporation.

[0232] The manufacturing method of a circuit board may include performing an annealing process. Annealing is typically performed after the resin composition layer has cured, and preferably after the conductor layer has been formed. Annealing can improve the adhesion between the insulating layer and the conductor layer. Annealing can be performed, for example, by heating at 150°C to 210°C for 20 to 180 minutes.

[0233] In the manufacturing method of circuit boards, each of the above-mentioned processes may be performed only once or repeatedly more than twice. For example, processes (I) to (V) may be performed repeatedly to form a circuit board with a multilayer structure, such as a multilayer printed circuit board having multiple insulating layers and conductor layers.

[0234] The method for manufacturing a circuit board may further include any steps in combination with the steps described above. For example, the method for manufacturing a circuit board may include a step of setting a semiconductor chip in a manner that bonds it to a conductor layer. Specifically, in the case of manufacturing a circuit board for a semiconductor chip package containing a semiconductor chip, the method for manufacturing the circuit board may include a step of setting the semiconductor chip. The semiconductor chip may be manufactured under appropriate conditions that allow for conductive connection between the terminal electrodes of the semiconductor chip and the conductor layer formed on the insulating layer. For example, conditions used in flip-chip mounting may be used. Furthermore, the semiconductor chip may be bonded via an insulating adhesive or by reflow soldering. Furthermore, the set semiconductor chip may be filled with a molding underfill material as needed. Additionally, the method for manufacturing a circuit board may include, for example, a step of forming a sealing layer, a step of forming a solder resist layer, and a step of cutting the manufactured circuit board to achieve monolithic assembly.

[0235] Examples of circuit boards include printed circuit boards and semiconductor chip packages. Examples of semiconductor chip packages include FC-CSP, MIS-BGA packages, ETS-BGA packages, fan-out type WLP (Wafer Level Package), fan-in type WLP, fan-out type PLP (Panel Level Package), and fan-in type PLP. In these semiconductor chip packages, the rewiring layer, serving as an insulating layer, is preferably formed from a cured product obtained by curing the aforementioned resin composition. The circuit board is not limited to the circuit board exemplified here.

[0236] Semiconductor Devices The aforementioned circuit board can be used to manufacture semiconductor devices. Semiconductor devices include the aforementioned circuit board. Examples of semiconductor devices include various semiconductor devices used in electrical products (e.g., computers, mobile phones, smartphones, tablets, wearable devices, digital cameras, medical devices, and televisions) and vehicles (e.g., motorcycles, automobiles, trams, ships, and aircraft). Example

[0237] The following examples illustrate specific embodiments of the present invention. However, the present invention is not limited to these examples. In the following description, unless otherwise specified, "parts" and "%" refer to "parts by mass" and "% by mass," respectively. Furthermore, unless otherwise specified, the temperature and pressure conditions are room temperature (23°C) and atmospheric pressure (1 atm).

[0238] <Synthesis Example 1. Synthesis of Liquid Epoxy Resin A-1> 100g of 2,2-bis(4-hydroxy-3-methylphenyl)propane was dissolved in 1050g of epichlorohydrin. 0.25g of benzyltriethylammonium chloride was added, and 90g of a 48% sodium hydroxide aqueous solution was added dropwise over 5 hours at 70°C under reduced pressure. The generated water was removed from the system by azeotropic reaction with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the addition, the reaction was continued for 2 hours. The resulting salt was removed by filtration, and the epichlorohydrin was removed by distillation after washing with water. The obtained epoxy resin was dissolved in 400g of methyl isobutyl ketone, and 10g of a 10% sodium hydroxide aqueous solution was added at 85°C, allowing the reaction to proceed for 2 hours. After the reaction, the mixture was filtered, washed with water, and the methyl isobutyl ketone was removed by distillation, yielding 129g of a single-yellow liquid epoxy resin A-1. The epoxy resin A-1 has the structure shown in the following formula (a-1) (where n is 0 to 5), and its epoxy equivalent is 190 g / eq.

[0239] [Chemical Formula 8] .

[0240] <Synthetic Example 2: Synthesis of Active Ester Resin B-1> 320 g (2.0 mol) of 2,7-dihydroxynaphthalene, 184 g (1.7 mol) of benzyl alcohol, and 5.0 g of p-toluenesulfonic acid monohydrate were added to a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer. The mixture was stirred while being purged with nitrogen at room temperature. Then, the temperature was raised to 150 °C, and the generated water was distilled off while stirring for 4 hours. After the reaction was complete, 900 g of methyl isobutyl ketone and 5.4 g of 20% sodium hydroxide aqueous solution were added for neutralization. The aqueous layer was then removed by separation, followed by three washes with 280 g of water. Methyl isobutyl ketone was removed under reduced pressure to obtain 460 g of benzyl-modified naphthalene compound (B'). The obtained benzyl-modified naphthalene compound (B') was a black solid with a hydroxyl equivalent of 180 g / eq.

[0241] 203.0 g of isophthaloyl chloride (2.0 mol of acyl chloride group) and 1400 g of toluene were added to a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer. The system was then purged with nitrogen under reduced pressure to dissolve the chloride. Next, 113.9 g (0.67 mol) of o-phenylphenol and 240 g of benzyl-modified naphthalene compound (B') (1.33 mol of phenolic hydroxyl group) were added, and the system was purged with nitrogen under reduced pressure to dissolve the naphthalene. Then, 0.70 g of tetrabutylammonium bromide was dissolved, and while purging with nitrogen and maintaining the system temperature below 60°C, 400 g of 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. The mixture was then stirred under these conditions for 1 hour.

[0242] After the reaction was completed, the mixture was allowed to stand and separate to remove the aqueous layer. Then, water was added to the toluene layer containing the reactants and stirred for 15 minutes. The mixture was allowed to stand and separate to remove the aqueous layer. This process was repeated until the pH of the aqueous layer reached 7. Water was then removed by decantation to obtain an active ester resin B-1 in the form of a toluene solution containing 65% by mass of non-volatile components. The structure of the obtained active ester resin B-1 is shown in the following formula (b-1). The active ester equivalent of active ester resin B-1 is 238 g / eq.

[0243] [Chemical Formula 9] .

[0244] <Synthesis Example 3: Synthesis of Active Ester Resin B-4> 165 g of a dicyclopentadiene and phenol addition polymerization resin (hydroxyl equivalent: 165 g / eq., softening point 85 °C), 134 g (1.0 mol) of o-allylphenol, and 1200 g of toluene were added to a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer. The system was then purged with nitrogen under reduced pressure. Next, 203 g (1.0 mol) of isophthaloyl chloride was added, and the system was purged with nitrogen under reduced pressure. 0.6 g of tetrabutylammonium bromide was added, and while purging with nitrogen, the system temperature was maintained below 60 °C. 412 g of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours, and the mixture was stirred for 1 hour after the addition was complete. After the reaction was complete, the aqueous layer was removed by sedimentation. Water was further added to the resulting toluene layer, and the mixture was stirred for 15 minutes. The aqueous layer was then removed by sedimentation. This process was repeated until the pH of the aqueous layer reached 7. Then, the non-volatile components are adjusted to 70% by mass by heating and drying, thereby obtaining the active ester resin B-4 as shown in formula (b-4). The active ester equivalent of active ester resin B-4 is 214 g / eq.

[0245] [Chemical Formula 10] .

[0246] <Synthesis Example 4: Synthesis of Polyimide Resin C-1> 200g of cyclohexanone was added to a 1L detachable flask equipped with an oil bath and a stir bar while nitrogen was introduced. Then, 149.8g of dimeric diamine ("PRIAMINE 1075" manufactured by Croda Japan) and 4.7g of m-aminophenol (a monoamine compound) were added while stirring. Next, 67.3g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (a tetracarboxylic dianhydride) was added, and the mixture was stirred at room temperature for 30 minutes. The mixture was then heated to 100°C and stirred for 3 hours. The oil bath was removed, and the mixture was allowed to return to room temperature to obtain a varnish-like polyimide precursor. The distilled water was then removed from the system using a Dean-Stark water separator, and the polyimide precursor was imidized by heating at 170°C for 10 hours to obtain polyimide resin C-1. The resulting polyimide resin C-1 contains a dimeric diamine backbone and has phenolic hydroxyl groups from m-aminophenol at the ends of its molecular chains. The polyimide resin C-1 has a number-average molecular weight of 8,600, a weight-average molecular weight of 20,000, a phenolic hydroxyl value of 11.5 mg KOH / g, an anhydride value of 0.0 mg KOH / g, and an amine value of 0.0 mg KOH / g.

[0247] <Examples 1-16 and Comparative Examples 1-6> (1) Preparation of resin composition: According to the formulations described in Tables 1 to 4 below, each component was weighed and mixed. 10 parts of methyl ethyl ketone and 10 parts of cyclohexanone were further mixed and uniformly dispersed using a high-speed rotary stirrer to obtain a resin composition in the form of a resin varnish. The formulations described in Tables 1 to 4 represent the amount (parts by mass) of non-volatile components. Furthermore, details of each component described in the tables are shown below.

[0248] (A) Epoxy resin: • WHR-991S: 266 g / eq. epoxy equivalent, manufactured by Nippon Kayaku Co., Ltd., a bisphenol-type epoxy resin containing an imide backbone. • HP-4032-SS: Epoxy equivalent 144 g / eq., manufactured by DIC, naphthalene-type epoxy resin • Liquid epoxy resin A-1: ​​epoxy equivalent 190 g / eq., the epoxy resin synthesized in Synthesis Example 1 •NC-3000L: Epoxy equivalent 270g / eq., manufactured by Nippon Kayaku Co., Ltd., biphenyl type epoxy resin.

[0249] (B) Naphthalene-type active ester resin: • Active ester resin B-1: Active ester group equivalent 238 g / eq., the active ester resin synthesized in Synthesis Example 2 • HP-C-8150-62T: Toluene solution with 229 g / eq. of active ester group equivalent and 61.5% by mass of non-volatile components, manufactured by DIC Corporation, naphthalene-type active ester resin. • Active ester resin B-2: Active ester resin with an active ester equivalent of 250 g / eq., as shown in formula (b-2). A toluene solution containing 60% by mass of non-volatile components.

[0250] [Chemical Formula 11] .

[0251] • Active ester resin B-3: Active ester resin with an active ester equivalent of 248 g / eq., as shown in formula (b-3). A toluene solution containing 70% by mass of non-volatile components.

[0252] [Chemical Formula 12] .

[0253] (G) Any curing agent: • Active ester resin B-4: 214 g / eq. of active ester group equivalent, active ester resin synthesized in Synthesis Example 3, and a toluene solution containing 70% by mass of non-volatile components. • Active ester resin B-5: Active ester resin with an active ester equivalent of 1002 g / eq., as shown in the formula (b-5) below.

[0254] [Chemical Formula 13] .

[0255] • HPC-8000L-65MT: Active ester equivalent 223g / eq., non-volatile component 65% by mass toluene / MEK solution, manufactured by DIC, active ester resin without naphthalene skeleton (active ester resin containing dicyclopentadiene type diphenol structure). • LA-3018-50P: Phenolic hydroxyl equivalent 151g / eq., 50% by mass of non-volatile component in 1-methoxy-2-propanol solution, manufactured by DIC Corporation, phenolic resin.

[0256] (C) Dimeric diamine type polyimide resin containing hydroxyl groups: • Polyimide resin C-1: The polyimide resin synthesized in Synthesis Example 4.

[0257] (C') Any polyimide resin: •SLK-1500: An aliphatic maleimide resin (an aliphatic polyimide resin containing maleimide groups at the ends) manufactured by Shin-Etsu Chemical Co., Ltd. •SLK-6100: Aromatic maleimide resin (polyimide resin without dimeric diamine backbone) manufactured by Shin-Etsu Chemical Industry Co., Ltd.

[0258] (D) Inorganic filler materials: • SO-C2: Spherical silica particles with an average particle size of 0.5 μm and a specific surface area of ​​5.8 m², surface-treated with an amino-based silane coupling agent (Shin-Etsu Chemical Co., Ltd. "KBM573"). 2 / g, Made by Yaduma Company.

[0259] (E) Rubber granules: • EXL-2655: Dow Chemical's core-shell rubber granules with an average particle size of 0.2 μm.

[0260] (F) Curing accelerator: • 1B2PZ: Imidazole-based curing accelerator manufactured by Shikoku Chemical Industry Co., Ltd.

[0261] (H) Polymer components: • YX7553BH30: A 1:1 solution of phenoxy resin, 30% by mass of non-volatile MEK and cyclohexanone, weight average molecular weight 35,000, manufactured by Mitsubishi Chemical Corporation.

[0262] (2) Manufacturing of resin sheets: As a support, a polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, 38 μm thick) with a release layer was prepared. The obtained resin composition was uniformly coated onto the release layer of this support, such that the thickness of the dried resin composition layer was 40 μm. The resin composition was then dried at 80°C to 100°C (average 90°C) for 4 minutes to obtain a resin sheet A having a resin composition layer / support layer structure.

[0263] <Experimental Example 1. Test for Determination of Dielectric Properties> Resin sheet A was heated in an oven at 190°C for 90 minutes to cure the resin composition layer. Then, the support was peeled off to obtain the cured resin composition layer. This cured layer was cut into samples 30 mm long and 40 mm wide to obtain cured samples for dielectric property testing.

[0264] For the solidified sample, the relative permittivity Dk and dielectric loss tangent Df were measured using a measuring apparatus (Agilent Technologies HP8362B) via the split-cylinder method at a measurement frequency of 10 GHz and a measurement temperature of 90 °C. Measurements were performed on two samples, and their average values ​​were calculated.

[0265] <Experimental Example 2. Determination of Glass Transition Temperature and Coefficient of Linear Thermal Expansion> Resin sheet A was heated in an oven at 190°C for 90 minutes to cure the resin composition layer. The support was then peeled off to obtain a cured film of the resin composition layer. This cured film was cut into pieces 20 mm long and 6 mm wide to obtain cured samples for thermomechanical analysis.

[0266] For the cured sample, thermomechanical analysis was performed using a TMA apparatus (Thermomechanical Analysis Apparatus, Rigaku Corporation) at a heating rate of 5°C / min, from 25°C to 220°C. Subsequently, the same cured sample was subjected to thermomechanical analysis again at a heating rate of 5°C / min, from 25°C to 220°C. For this second thermomechanical analysis, the glass transition temperature (Tg) and the coefficient of linear thermal expansion (CTE) were determined.

[0267] <Experimental Example 3. Test for Determination of Warpage> (1) Preparation of the inner layer substrate: The inner substrate is obtained by etching away the copper on both sides of a glass cloth substrate epoxy resin double-sided copper-clad laminate (copper foil thickness 18μm, substrate thickness 0.2mm, manufactured by Lisennoco "E700G").

[0268] (2) Lamination of resin sheet A: Resin sheet A was cut to a size of 110mm × 150mm. Additionally, the inner layer substrate was cut to a size of 120mm × 160mm. Using an intermittent vacuum pressure laminator (Nikko Materials, two-stage laminator "CVP1700"), resin sheet A was laminated onto the center of one side of the inner layer substrate, with the resin composition layer attached to the inner layer substrate. The lamination was performed by depressurizing for 30 seconds to adjust the pressure to below 13 hPa, followed by pressing at 140°C and 0.74 MPa for 10 seconds.

[0269] (3) Thermosetting of the resin composition layer: Then, the inner layer substrate with resin sheet A stacked on it is placed in an oven at 130°C and heated for 30 minutes, followed by heating in an oven at 170°C for 30 minutes to thermally cure the resin composition layer and form an insulating layer. Subsequently, the support is peeled off to obtain a cured substrate Y with an insulating layer / inner layer substrate structure.

[0270] (4) Evaluation of warpage after full cure: The cured substrate Y was placed in an oven at 200°C and heated for 90 minutes to obtain a cured substrate Y'. The cured substrate Y' was placed on a flat table, and the two adjacent sides were fixed to the table. The maximum distance in the height direction from the table to the cured substrate Y' was measured with a ruler, and the measured value was recorded as the warpage.

[0271] <Results> The results of the above-described embodiments and comparative examples are shown in the following tables. The abbreviations in the following tables have the following meanings; Dk: Relative permittivity Df: Dielectric loss tangent Tg: Glass transition temperature CTE: Coefficient of linear thermal expansion.

[0272] [Table 1] .

[0273] [Table 2] .

[0274] [Table 3] .

[0275] [Table 4] .

Claims

1. A resin composition comprising (A) an epoxy resin, (B) an active ester resin containing a naphthalene backbone, (C) a polyimide resin containing a dimeric diamine backbone and having phenolic hydroxyl groups, and (D) an inorganic filler. in, The amount of inorganic filler is greater than 70% by mass relative to 100% by mass of the non-volatile components of the resin composition.

2. The resin composition according to claim 1, wherein, Contains (E) rubber particles.

3. The resin composition according to claim 1, wherein, Contains (F) curing accelerator.

4. The resin composition according to claim 1, wherein, (D) Inorganic filler materials have an average particle size of less than 1 μm.

5. The resin composition according to claim 1, wherein, (C) Component has a number-average molecular weight greater than 5000.

6. The resin composition according to claim 1, wherein, The amount of component (C) is 0.01% by mass or more and 10% by mass or less relative to 100% by mass of the non-volatile components of the resin composition.

7. The resin composition according to claim 1, wherein, The amount of component (B) is 1% to 25% by mass relative to 100% by mass of the non-volatile components of the resin composition.

8. A resin sheet comprising a support and a resin composition layer disposed on the support, The resin composition layer comprises the resin composition according to any one of claims 1 to 7.

9. The cured product of the resin composition according to any one of claims 1 to 7.

10. A circuit board comprising a cured form of the resin composition according to any one of claims 1 to 7.

11. A semiconductor device comprising the circuit board of claim 10.

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