Resin composition

Abstract

Provided is a resin composition capable of forming an insulating layer having low dielectric loss tangent at high temperatures and high frequencies and excellent dirt removal properties. A resin composition comprising (A) an epoxy resin, (B-1) an active ester resin containing a butadiene skeleton, and (B-2) an active ester resin not containing a butadiene skeleton.

Description

Technical Field

[0001] The present invention relates to a resin composition and a cured product thereof, a resin sheet, a circuit board, and a semiconductor device. Background Art

[0002] Circuit substrates such as printed circuit boards are widely used in various electronic devices. As the manufacture method of circuit substrate, it is known that the method of manufacturing by alternately laminating insulating layers and conductor layers on an inner substrate is carried out in a lamination mode. The insulating layer is formed by, for example, a cured product of a resin combination (patent documentation 1 and 2). If a specific example is given, then by forming a resin combination layer comprising a resin combination, and the resin combination layer is cured, thereby forming an insulating layer comprising the cured product of a resin combination.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2022-100697

[0006] Patent Document 2: Japanese Patent Application Laid-Open No. 2023-037522 Summary of the Invention

[0007] Problems to be solved by the invention

[0008] High-speed communications, such as those in fifth-generation mobile communication systems (5G), require minimizing transmission loss during operation in high-frequency environments. Furthermore, circuit substrates can sometimes reach high temperatures due to heat dissipation from semiconductor chips. Therefore, the present inventors have attempted to develop an insulating layer capable of reducing the dielectric loss tangent under high-temperature and high-frequency conditions.

[0009] However, it is clear that the smear removal property of the cured product of the resin composition with low dielectric loss tangent is poor. Specifically as described below. Generally speaking, when an insulating layer is formed by a cured product, holes such as through holes and vias are sometimes formed in the insulating layer. When a hole is formed in this way, a resin residue called "smear" is sometimes formed in the hole. Thus, a decontamination (desmear) process for removing the smear is usually carried out after forming the hole. However, when an insulating layer is formed by a cured product with low dielectric loss tangent, it is sometimes impossible to fully remove the smear by carrying out a decontamination process.

[0010] The present invention has been made in view of the aforementioned problems, and its object is to provide a resin composition capable of forming an insulating layer having a low dielectric loss tangent and excellent dirt removability under high temperature and high frequency conditions; a resin sheet comprising the resin composition; a cured product of the resin composition; a circuit substrate comprising the cured product of the resin composition; and a semiconductor device comprising the aforementioned circuit substrate.

[0011] Means used to solve problems

[0012] The present inventors conducted intensive research to solve the aforementioned problems and have discovered that a resin composition comprising (A) an epoxy resin, (B-1) an active ester resin containing a butadiene skeleton, and (B-2) an active ester resin not containing a butadiene skeleton can solve the aforementioned problems, thereby completing the present invention.

[0013] That is, the present invention includes the following inventions.

[0014] <1> A resin composition comprising: (A) an epoxy resin, (B-1) an active ester resin containing a butadiene skeleton, and (B-2) an active ester resin not containing a butadiene skeleton.

[0015] <2> according to <1> The resin composition, wherein the epoxy resin (A) comprises at least one selected from epoxy resins containing a naphthalene skeleton and epoxy resins containing a biphenyl skeleton.

[0016] <3> according to <1> or <2> In the resin composition, the active ester resin (B-1) containing a butadiene skeleton comprises a structure represented by the following formula (B1).

[0017] [Chemistry 1]

[0018]

[0019] (In formula (B1), R b Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms; * represents a bonding site.

[0020] <4> according to <1> ~ <3> The resin composition described in any one of the preceding claims further comprises (C) an inorganic filler.

[0021] <5> according to <4> The resin composition, wherein the amount of the (C) inorganic filler is 50% by mass or more relative to 100% by mass of the non-volatile components of the resin composition.

[0022] <6> according to <1> ~ <5> The resin composition described in any one of the preceding claims, comprising (D) a radically polymerizable resin.

[0023] <7> according to <6> In the resin composition, (D) the radical polymerizable resin comprises a maleimide resin.

[0024] <8> A resin sheet comprising a support and a resin composition layer provided on the support,

[0025] The resin composition layer comprises <1> ~ <7> The resin composition described above.

[0026] <9> solidified material, which is <1> ~ <7> A cured product of any one of the resin compositions.

[0027] <10> A circuit substrate comprising <1> ~ <7> A cured product of any one of the resin compositions.

[0028] <11> Semiconductor device comprising <10> The circuit substrate.

[0029] Effects of the Invention

[0030] According to the present invention, there can be provided a resin composition capable of forming an insulating layer having a low dielectric loss tangent and excellent dirt removability under high temperature and high frequency conditions; a resin sheet comprising the resin composition; a cured product of the resin composition; a circuit substrate comprising the cured product of the resin composition; and a semiconductor device comprising the aforementioned circuit substrate. DETAILED DESCRIPTION

[0031] Hereinafter, the present invention will be described with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be implemented with modifications within the scope of the claims and their equivalents.

[0032] In this specification, the term "optionally having a substituent" with respect to a compound or group refers to the following two cases: a case where hydrogen atoms of the compound or group are not substituted by a substituent; and a case where some or all of the hydrogen atoms of the compound or group are substituted by a substituent.

[0033] <Overview of Resin Composition>

[0034] The resin composition described in one embodiment of the present invention comprises: (A) epoxy resin, (B-1) active ester resin containing a butadiene skeleton, and (B-2) active ester resin without a butadiene skeleton. In the following description, "(B-1) active ester resin containing a butadiene skeleton" is sometimes referred to as "first active ester resin". In addition, "(B-2) active ester resin without a butadiene skeleton" is sometimes referred to as "(B-2) second active ester resin". According to the resin composition, an insulating layer having a low dielectric loss tangent under high temperature and high frequency and excellent dirt removability can be formed. In addition, according to the resin composition, the linear thermal expansion coefficient of the insulating layer can usually be reduced. Furthermore, according to the resin composition, the crack resistance of the insulating layer can usually be improved.

[0035] The present inventors have speculated the following mechanism for achieving the above-mentioned excellent effects, but the technical scope of the present invention is not limited to the following mechanism.

[0036] In the resin combination described in present embodiment, the epoxy group(s) of (A) epoxy resin reacts with the active ester group(s) of (B-1) the first active ester resin and (B-2) the second active ester resin and forms a key, and this resin combination is solidified as a result.And, as the layer of the cured product of the resin combination obtained like this, insulating layer can be formed.By the reaction of epoxy group(s) and active ester group(s), polar groups such as hydroxyl are not usually generated, and therefore, the polarity of the gained cured product is little.Thus, this cured product can have low dielectric loss tangent, and therefore, insulating layer also can have low dielectric loss tangent.

[0037] The resin composition includes the (B-1) first active ester resin having a butadiene skeleton, so the cured product can include a butadiene skeleton. In addition, the carbon-carbon double bond contained in the butadiene skeleton sometimes causes the (B-1) first active ester resins to undergo free radical polymerization with each other. Furthermore, when the resin composition includes the (D) free radical polymerizable resin, free radical polymerization sometimes occurs between the (B-1) first active ester resin and the (D) free radical polymerizable resin. When these free radical polymerizations occur, the cured product may include carbon-carbon bonds generated by the free radical polymerization. These butadiene skeletons and the carbon-carbon bonds generated by free radical polymerization are generally easily oxidized by oxidants. Therefore, even if the polarity of the cured product is low, the aforementioned butadiene skeleton and the carbon-carbon bonds generated by free radical polymerization can be smoothly oxidized, and therefore, dirt can be smoothly removed by oxidation, and therefore, high dirt removability can be achieved.

[0038] The resin composition includes a second active ester resin (B-2) in combination with the first active ester resin (B-1). Since the first active ester resin (B-1) contains a butadiene skeleton, it tends to have a large active ester group equivalent, and thus, there is a tendency to reduce the density of crosslinking points in the cured product. Here, the active ester group equivalent represents the mass of the resin per 1 equivalent of the active ester group. Furthermore, the butadiene skeleton contained in the first active ester resin (B-1) is soft, and the bonds formed by free radical polymerization of the carbon-carbon double bonds of the butadiene skeleton are usually also soft. Therefore, if only the epoxy resin (A) and the first active ester resin (B-1) are combined, there is a tendency for the thermal expansion of the cured product to increase. However, in this embodiment, the second active ester resin (B-2) is further combined. Since the second active ester resin (B-2) does not contain a butadiene skeleton, it usually has a smaller active ester equivalent than the first active ester resin (B-1), and thus acts to increase the density of crosslinking points in the cured product. Furthermore, the second active ester resin (B-2) does not contain a butadiene skeleton and therefore generally has higher molecular rigidity than the first active ester resin (B-1). Therefore, by further including the second active ester resin (B-2) in combination with the epoxy resin (A) and the first active ester resin (B-1), the resin composition according to this embodiment can produce a cured product with a low degree of thermal expansion, thereby providing an insulating layer with a low linear thermal expansion coefficient.

[0039] Furthermore, in the cured product of the resin composition, as described above, the bonds formed by free radical polymerization of the butadiene skeleton contained in the first active ester resin (B-1) and the carbon-carbon double bonds of the butadiene skeleton are soft. Consequently, these soft skeletons and bonds absorb stress in the cured product, resulting in high toughness. Consequently, the insulating layer comprising this cured product can suppress cracking caused by stress, thereby achieving high crack resistance.

[0040] <(A) Epoxy Resin>

[0041] The resin composition according to this embodiment includes an epoxy resin (A) as the component (A). The epoxy resin (A) may be a curable resin having an epoxy group. The epoxy resin (A) may be used alone or in combination of two or more.

[0042] Examples of the epoxy resin (A) include bixylene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, bisphenol AF-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol novolac-type epoxy resins, phenol novolac-type epoxy resins, tert-butyl-catechol-type epoxy resins, naphthalene-type epoxy resins, naphthol-type epoxy resins, anthracene-type epoxy resins, glycidylamine-type epoxy resins, glycidylester-type epoxy resins. Epoxy resins, cresol novolac epoxy resins, phenol aralkyl epoxy resins, biphenyl epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, epoxy resins containing a spiro ring, cyclohexane epoxy resins, cyclohexanedimethanol epoxy resins, naphthyl ether epoxy resins, trimethylol epoxy resins, tetraphenylethane epoxy resins, isocyanurate epoxy resins, phenol phthalimide epoxy resins, etc. Generally, these epoxy resins do not contain non-aromatic carbon-carbon unsaturated bonds that can undergo free radical polymerization.

[0043] From the viewpoint of obtaining a cured product having excellent heat resistance, the (A) epoxy resin preferably includes an epoxy resin containing an aromatic structure. An aromatic structure refers to a chemical structure generally defined as an aromatic structure, and also includes polycyclic aromatics and aromatic heterocycles. Examples of epoxy resins containing an aromatic structure include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, dimethylphenol type epoxy resin, glycidylamine type epoxy resin with an aromatic structure, epoxy resin with an aromatic structure. Water glycerol ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin with an aromatic structure, epoxy resin containing a butadiene structure with an aromatic structure, alicyclic epoxy resin with an aromatic structure, heterocyclic epoxy resin, epoxy resin with an aromatic structure and containing a spiro ring, cyclohexanedimethanol type epoxy resin with an aromatic structure, naphthyl ether type epoxy resin, trimethylol type epoxy resin with an aromatic structure, tetraphenylethane type epoxy resin with an aromatic structure, etc.

[0044] Among these, preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin and biphenyl type epoxy resin, more preferably naphthalene type epoxy resin and biphenyl type epoxy resin.Naphthalene type epoxy resin represents an epoxy resin containing a naphthalene skeleton.In addition, biphenyl type epoxy resin represents an epoxy resin containing a biphenyl skeleton.In the case where (A) epoxy resin comprises more than one epoxy resin selected from naphthalene type epoxy resin and biphenyl type epoxy resin, dielectric loss tangent, dirt removal, linear thermal expansion coefficient and crack resistance under high temperature and high frequency can be made particularly good.

[0045] The epoxy resin (A) preferably comprises an epoxy resin having two or more epoxy groups per molecule. The proportion of the epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the non-volatile component of the epoxy resin (A) is preferably 50% by mass or greater, more preferably 60% by mass or greater, and even more preferably 70% by mass or greater.

[0046] The epoxy resin (A) includes epoxy resins that are liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resin") and epoxy resins that are solid at 20°C (hereinafter sometimes referred to as "solid epoxy resin"). The epoxy resin (A) may contain only the liquid epoxy resin, only the solid epoxy resin, or a combination of the liquid epoxy resin and the solid epoxy resin.

[0047] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule. Preferred liquid epoxy resins include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol AF epoxy resins, naphthalene epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, phenol novolac epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane epoxy resins, cyclohexanedimethanol epoxy resins, and epoxy resins having a butadiene structure.

[0048] Specific examples of liquid epoxy resins include "HP-4032", "HP-4032-D", and "HP-4032-SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "825", and "EPIKOTE" manufactured by Mitsubishi Chemical Corporation; "828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD" and "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycidol type epoxy resin) manufactured by ADEKA Corporation; "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA Corporation; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA Corporation; "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; Nagase "EX-721" (glycidyl ester type epoxy resin) manufactured by ChemteX Corporation; "CELLOXIDE2021P" (alicyclic epoxy resin with an ester skeleton) manufactured by Daicel Corporation; "PB-3600" manufactured by Daicel Corporation, "JP-100" and "JP-200" (epoxy resins with a butadiene structure) manufactured by Nippon Soda Co., Ltd.; "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical & Material, etc.

[0049] The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, and more preferably an aromatic solid epoxy resin having three or more epoxy groups in one molecule. Preferred solid epoxy resins include bixylene-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, naphthol novolac-type epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthol-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, phenol aralkyl-type epoxy resins, tetraphenylethane-type epoxy resins, and phenol phthalimide-type epoxy resins.

[0050] Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resins) manufactured by DIC Corporation; "N-690" (cresol novolac-type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac-type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene-type epoxy resins) manufactured by DIC Corporation; and "EXA-73 11", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; Nippon Steel Chemical & Material Co., Ltd. "ESN475V", "ESN4100V" (naphthalene type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", "YL7890" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX880 0" (anthracene type epoxy resin); "YX7700" (phenol 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; "WHR991S" (phenol benzopyrrolidone type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., etc.

[0051] When the epoxy resin (A) contains a liquid epoxy resin and a solid epoxy resin in combination, the mass ratio thereof (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.

[0052] The epoxy equivalent of the epoxy resin (A) is preferably in the range of 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 3,000 g / eq., even more preferably 80 g / eq. to 2,000 g / eq., and particularly preferably 110 g / eq. to 1,000 g / eq. The epoxy equivalent represents the mass of the resin per equivalent of epoxy groups. This epoxy equivalent can be measured in accordance with JIS K7236.

[0053] The weight average molecular weight (Mw) of the epoxy resin (A) 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 measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0054] The scope of the amount of (A) epoxy resin is preferably more than 1 mass %, more preferably more than 2 mass %, more preferably more than 5 mass %, preferably less than 60 mass %, more preferably less than 40 mass %, more preferably less than 20 mass %, more preferably less than 10 mass %. Unless otherwise specified, the non-volatile component in the resin combination represents the composition except (I) solvent in the resin combination. In the case where the amount of (A) epoxy resin is in the aforementioned range, dielectric loss tangent, dirt removal, linear thermal expansion coefficient and crack resistance under high temperature and high frequency can be made particularly good.

[0055] The range of the amount of (A) epoxy resin is preferably more than 5 mass %, more preferably more than 10 mass %, more preferably more than 20 mass %, preferably less than 60 mass %, more preferably less than 50 mass %, more preferably less than 40 mass %.As long as there is no special instructions, the resin component in the resin composition represents the composition except (C) inorganic filler among the non-volatile components in the resin composition.When the amount of (A) epoxy resin is in the aforementioned range, it is possible to make the dielectric loss tangent, dirt removability, linear thermal expansion coefficient and crack resistance under high temperature and high frequency particularly good.

[0056] <(B-1) First Active Ester Resin>

[0057] The resin composition according to this embodiment includes a first active ester resin (B-1) as component (B-1). The first active ester resin (B-1) is an active ester resin containing a butadiene skeleton. Therefore, the first active ester resin (B-1) can be a curable resin comprising a combination of an active ester group and a butadiene skeleton. The first active ester resin (B-1) can be used alone or in combination of two or more.

[0058] An active ester group refers to a group formed by an ester bond directly bonded to an aromatic ring. The active ester group includes not only the ester bond contained in the structure of aromatic carbon-C(=O)-O-aromatic carbon, but also the ester bond contained in the structure of aliphatic carbon-C(=O)-O-aromatic carbon as long as it can react with an epoxy group to form a bond. In addition, the term "aromatic ring" refers to a ring that follows the Huckel rule that the number of electrons contained in the π electron system on the ring is 4p+2 (p is a natural number), including a monocyclic aromatic ring and a fused polycyclic aromatic ring obtained by condensing two or more monocyclic aromatic rings. In addition, the aromatic ring can be an aromatic carbon ring having only carbon atoms as ring atoms or an aromatic heterocycle having heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms as ring atoms on the basis of carbon atoms. As the aromatic ring, preferably a benzene ring, a naphthalene ring and an anthracene ring, and particularly preferably a benzene ring and a naphthalene ring. The term "aromatic carbon" refers to the carbon atoms that constitute the aromatic ring.

[0059] The number of active ester groups contained in one molecule of the first active ester resin (B-1) is usually 1 or more, preferably 2 or more.

[0060] The butadiene skeleton represents the carbon skeleton contained in the butenediyl group. Here, the butenediyl group includes 2-butene-1,4-diyl and 3-butene-1,2-diyl (i.e., vinyl ethylene). The aforementioned 2-butene-1,4-diyl may be a cis-isomer or a trans-isomer. In the (B-1) first active ester resin, the structure containing the butadiene skeleton is sometimes appropriately referred to as a "butadiene structure". The butadiene structure includes the aforementioned 2-butene-1,4-diyl and 3-butene-1,2-diyl, and groups in which the hydrogen atoms contained in these groups are substituted by substituents. As substituents, halogen atoms; saturated aliphatic hydrocarbon groups such as alkyl and cycloalkyl groups; aromatic hydrocarbon groups such as aryl groups; hydrocarbonoxy groups such as alkoxy groups, cycloalkoxy groups, and aryloxy groups; and the like.

[0061] Preferred examples of the butadiene structure include structures represented by the following formulae (B1) and (B2).

[0062] [Chemistry 2]

[0063]

[0064] *-CR b 2-CR b =CR b -CR b 2-* (B2)

[0065] In formula (B1) and formula (B2), R b Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms; preferably represents a hydrogen atom or a halogen atom; more preferably represents a hydrogen atom. In addition, * represents a bonding site.

[0066] Among the above, the butadiene structure is preferably a structure represented by formula (B1). Therefore, the first active ester resin (B-1) preferably includes the butadiene structure represented by formula (B1) as a structure having a butadiene skeleton, and may include only the butadiene structure represented by formula (B1).

[0067] The number of butadiene structures contained in one molecule of the first active ester resin (B-1) is usually 1 or more, preferably 2 or more. Among them, the first active ester resin (B-1) more preferably contains a polybutadiene structure in which two or more butadiene structures are bonded to each other.

[0068] The first active ester resin (B-1) generally has a larger active ester group equivalent weight than the second active ester resin (B-2). The active ester group equivalent weight of the first active ester resin (B-1) is preferably 200 g / eq. or greater, more preferably 300 g / eq. or greater, and even more preferably 400 g / eq. or greater, and preferably 3,000 g / eq. or less, more preferably 2,000 g / eq. or less, and even more preferably 1,500 g / eq. or less. As described above, the active ester group equivalent weight represents the mass of the resin per 1 equivalent of active ester groups.

[0069] The weight average molecular weight (Mw) of the first active ester resin (B-1) is preferably 500 or more, more preferably 1000 or more, and is preferably 10000 or less, more preferably 5000 or less, and even more preferably 3000 or less.

[0070] Examples of the first active ester resin (B-1) include resins represented by the following formula (b-1). In formula (b-1), each R independently represents an aryl group optionally having a substituent, preferably a phenyl group optionally having a substituent or a naphthyl group optionally having a substituent. The substituent is preferably a hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group, and even more preferably an alkyl group having 1 to 6 carbon atoms. In formula (b-1), a and m each represent a repeating number, specifically a number greater than 0.

[0071] [Chemistry 3]

[0072]

[0073] When the number of epoxy groups of (A) epoxy resin is set to 1, the number of active ester groups of (B-1) first active ester resin is preferably 0.01 or more, more preferably 0.02 or more, further preferably 0.05 or more, preferably 1 or less, more preferably 0.5 or less, further preferably 0.1 or less. The "number of epoxy groups of (A) epoxy resin" in the resin composition represents: the value obtained by adding up the mass of the non-volatile components of the (A) epoxy resin present in the resin composition and the value obtained by dividing the mass of the non-volatile components of the (B-1) first active ester resin present in the resin composition and the value obtained by dividing the mass of the non-volatile components of the (B-1) first active ester resin present in the resin composition and the value obtained by dividing the mass of the active ester equivalent of the first active ester resin. When the number of active ester groups of (B-1) first active ester resin is within the aforementioned range, the dielectric loss tangent, dirt removal, linear thermal expansion coefficient and crack resistance under high temperature and high frequency can be made particularly good.

[0074] The amount of the first active ester resin (B-1) is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, relative to 100% by mass of the non-volatile components in the resin composition, and is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less. When the amount of the first active ester resin (B-1) is within the aforementioned range, the dielectric loss tangent, contaminant removability, linear thermal expansion coefficient, and crack resistance at high temperatures and high frequencies can be particularly improved.

[0075] The amount of the first active ester resin (B-1) is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to 100% by mass of the resin component in the resin composition, and is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less. When the amount of the first active ester resin (B-1) is within the aforementioned range, the dielectric loss tangent, contaminant removability, linear thermal expansion coefficient, and crack resistance at high temperatures and high frequencies can be particularly improved.

[0076] <(B-2) Second Active Ester Resin>

[0077] The resin composition described in this embodiment includes a second active ester resin (B-2) as component (B-2). The second active ester resin (B-2) is an active ester resin that does not contain a butadiene backbone. Therefore, the second active ester resin (B-2) can be a curable resin that has an active ester group but does not have a butadiene backbone. The second active ester resin (B-2) can be used alone or in combination of two or more.

[0078] The second active ester resin (B-2) is preferably a compound having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds.

[0079] The second active ester resin (B-2) is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the perspective of improving heat resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include 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, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadiene-type diphenol compounds, and phenol novolacs. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

[0080] Specifically, the second active ester resin (B-2) is preferably a dicyclopentadiene-type active ester resin, a naphthalene-type active ester resin containing a naphthalene structure, an active ester resin containing an acetylated product of a phenol novolac, or an active ester resin containing a benzoylated product of a phenol novolac. Among them, a naphthalene-type active ester resin is more preferred. The dicyclopentadiene-type active ester resin is preferably an active ester resin containing a dicyclopentadiene-type diphenol structure.

[0081] Examples of commercially available products of the second active ester resin (B-2) include "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "EXB-8000H", and "NE-V-1100-70T" (manufactured by DIC Corporation) as active ester resins containing a dicyclopentadiene-type diphenol structure; and "EXB-8100L-65T", "EXB-8150-60T", and "EXB-8150-60T" as active ester resins containing a naphthalene structure. Examples of the active ester resins include "EXB-150-62T", "EXB-9416-70BK", "HPC-8150-62T", and "HPC-8151-62T" (manufactured by DIC Corporation); examples of the phosphorus-containing active ester resins include "EXB9401" (manufactured by DIC Corporation); examples of the active ester resins containing acetylated products of phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation); examples of the active ester resins containing benzoylated products of phenol novolac include "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); and examples of the active ester resins containing styryl and naphthalene structures include "PC1300-02-65MA" (manufactured by Airwater Corporation).

[0082] The second active ester resin (B-2) generally has a smaller active ester group equivalent weight than the first active ester resin (B-1). The active ester group equivalent weight of the second active ester resin (B-2) is preferably 50 g / eq. or greater, more preferably 100 g / eq. or greater, and preferably 3,000 g / eq. or less, more preferably 1,000 g / eq. or less, even more preferably 500 g / eq. or less, and particularly preferably 300 g / eq. or less.

[0083] The weight average molecular weight (Mw) of the second active ester resin (B-2) may be in the same range as the weight average molecular weight (Mw) of the epoxy resin (A).

[0084] When the number of epoxy groups of the epoxy resin (A) is set to 1, the number of active ester groups of the second active ester resin (B-2) is preferably 0.1 or more, more preferably 0.2 or more, even more preferably 0.5 or more, preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less. The "number of active ester groups of the second active ester resin (B-2)" in the resin composition refers to the total value obtained by dividing the mass of the non-volatile components of the second active ester resin (B-2) present in the resin composition by the active ester group equivalent thereof. When the number of active ester groups of the second active ester resin (B-2) is within the above range, the dielectric loss tangent, dirt removability, linear thermal expansion coefficient, and crack resistance under high temperature and high frequency conditions can be made particularly good.

[0085] The amount of the second active ester resin (B-2) is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more, relative to 100% by mass of the non-volatile components in the resin composition, and is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less. When the amount of the second active ester resin (B-2) is within the aforementioned range, the dielectric loss tangent, contaminant removability, linear thermal expansion coefficient, and crack resistance at high temperatures and high frequencies can be particularly improved.

[0086] The amount of the second active ester resin (B-2) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, relative to 100% by mass of the resin component in the resin composition, and is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less. When the amount of the second active ester resin (B-2) is within the aforementioned range, the dielectric loss tangent, contaminant removability, linear thermal expansion coefficient, and crack resistance at high temperatures and high frequencies can be particularly improved.

[0087] Typically, a larger amount of the second active ester resin (B-2) is used than the first active ester resin (B-1). The ratio of the first active ester resin (B-1) to the second active ester resin (B-2) (the second active ester resin (B-2) / the first active ester resin (B-1)) is preferably 1.0 or greater, more preferably 1.5 or greater, even more preferably 2.0 or greater, and even more preferably 2.5 or greater, and preferably 30 or less, more preferably 15.0 or less, even more preferably 10.0 or less, even more preferably 7.0 or less, and even more preferably 5.0 or less. When the ratio (the second active ester resin (B-2) / the first active ester resin (B-1)) is within the aforementioned range, particularly good dielectric loss tangent, contaminant removability, linear thermal expansion coefficient, and crack resistance at high temperatures and high frequencies can be achieved.

[0088] <Total amount of active ester resin>

[0089] The amount of the active ester resin as a whole comprising the first active ester resin (B-1) and the second active ester resin (B-2) can be represented by the total amount of the first active ester resin (B-1) and the second active ester resin (B-2). The range of the amount of the active ester resin as a whole is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, preferably 60% by mass or less, more preferably 40% by mass or less, further preferably 20% by mass or less relative to 100% by mass of the non-volatile component in the resin composition. When the amount of the active ester resin as a whole is within the aforementioned range, the dielectric loss tangent, dirt removal property, linear thermal expansion coefficient, and crack resistance under high temperature and high frequency can be made particularly good.

[0090] The total amount of the active ester resin is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, even more preferably 40% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, relative to 100% by mass of the resin component in the resin composition. When the total amount of the active ester resin (B) is within the aforementioned range, the dielectric loss tangent, contaminant removability, linear thermal expansion coefficient, and crack resistance at high temperatures and high frequencies can be particularly improved.

[0091] When the number of epoxy groups in the epoxy resin (A) is set to 1, the number of active ester groups in the active ester resin is preferably 0.1 or greater, more preferably 0.5 or greater, and even more preferably 0.8 or greater, and is preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less. The "number of active ester groups in the active ester resin" in the resin composition refers to the total value obtained by dividing the mass of the non-volatile components of the active ester resin present in the resin composition by the active ester group equivalent. When the number of active ester groups in the active ester resin falls within the aforementioned range, the dielectric loss tangent, dirt removability, linear thermal expansion coefficient, and crack resistance at high temperatures and high frequencies can be particularly improved.

[0092] The total amount of the epoxy resin (A), the first active ester resin (B-1), and the second active ester resin (B-2) 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 resin component in the resin composition, and is preferably 98% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less. When the total amount of the epoxy resin (A), the first active ester resin (B-1), and the second active ester resin (B-2) is within the aforementioned range, the dielectric loss tangent, contaminant removability, linear thermal expansion coefficient, and crack resistance at high temperatures and high frequencies can be particularly improved.

[0093] <(C) Inorganic Filler>

[0094] The resin composition described in this embodiment may include an inorganic filler (C) as an optional component. The inorganic filler (C) as component (C) is a particle of an inorganic material. Thus, the inorganic filler (C) is included in the resin composition in a particle state, and is usually included in the cured product while maintaining the particle state.

[0095] As the inorganic material forming (C) inorganic filling material, inorganic compounds are generally used. As the material of (C) inorganic filling material, for example, silica, aluminum oxide, 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, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate etc. can be listed. Among these, it is suitable to be silica and aluminum oxide, particularly suitable to be silica. Thus, (C) inorganic filling material preferably includes silica, and can only include silica. As silica, for example, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica etc. can be listed. Furthermore, as silica, spherical silica is preferred. (C) The inorganic filler may be used alone or in combination of two or more.

[0096] Examples of commercially available inorganic fillers (C) include "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C," "YA050C," "YA050C-MJE," "YA010C," "SC2500SQ," "SO-C4," "SO-C2," and "SO-C1" manufactured by ADMATEC HS; "UFP-30," "DAW-03," and "FB-105FD" manufactured by DENKA; "Silfair NSS-3N," "Silfair NSS-4N," and "Silfair NSS-5N" manufactured by Tokuyama Corporation; and "Silsfills" and "MGH-005" manufactured by Pacific Cement Co., Ltd.

[0097] The average particle size of the inorganic filler (C) is preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.1 μm or more, and preferably 10 μm or less, more preferably 5 μm or less, further preferably 3 μm or less, further preferably 1 μm or less.

[0098] (C) The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be made according to the volume basis by a laser diffraction scattering particle size distribution measuring device, and its median particle size is used as the average particle size for measurement. The determination sample can be obtained by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing it for 10 minutes using ultrasound. For the determination sample, a laser diffraction particle size distribution measuring device can be used, and the wavelength of the light source is set to blue and red, and the particle size distribution of the volume basis of the inorganic filler is measured using a flow cell method, and the average particle size is calculated in the form of median particle size according to the obtained particle size distribution. As a laser diffraction particle size distribution measuring device, for example, "LA-960" manufactured by Horiba Manufacturing Co., Ltd. can be listed.

[0099] (C) The specific surface area of the inorganic filler is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, particularly 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, particularly preferably 40m 2 (C) The specific surface area of the inorganic filler can be measured by the BET method using a specific surface area measuring apparatus (Macsorb HM-1210 manufactured by MOUNTECH) by allowing nitrogen to adsorb onto the sample surface and calculating the specific surface area using the BET multipoint method.

[0100] From the viewpoint of improving moisture resistance and dispersibility, the (C) inorganic filler is preferably treated with a surface treatment agent. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. One surface treatment agent may be used alone, or two or more may be used in any combination.

[0101] Commercially available products of the surface treatment agent include, for example, “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “SZ-31” (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-4803” (long-chain epoxy-type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM-7103” (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.

[0102] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with a surface treatment agent is preferably within a specific range. Specifically, 100% by mass of the inorganic filler is preferably surface treated with 0.2% to 5% by mass of a surface treatment agent, more preferably 0.2% to 3% by mass of a surface treatment agent, and even more preferably 0.3% to 2% by mass of a surface treatment agent.

[0103] The degree of surface treatment by the surface treatment agent can be evaluated based on the amount of carbon per unit surface area of the inorganic filler. From the perspective of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 More than 0.1 mg / m 2 More preferably, 0.2 mg / m 2 On the other hand, from the viewpoint of preventing the melt viscosity of the resin composition layer from increasing, it is preferably 1.0 mg / m 2 Below, more preferably 0.8 mg / m 2 Below, more preferably 0.5 mg / m 2 the following.

[0104] (C) The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is cleaned with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK is added as a solvent to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid component, a carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd., etc. can be used.

[0105] The amount of the inorganic filler (C) 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 components in the resin composition, and is 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 the inorganic filler (C) is within the aforementioned range, the dielectric loss tangent, contaminant removability, linear thermal expansion coefficient, and crack resistance at high temperatures and high frequencies can be particularly improved.

[0106] The total amount of the epoxy resin (A), the first active ester resin (B-1), the second active ester resin (B-2), and the inorganic filler (C) 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 components of the resin composition, and is preferably 100% by mass or less, more preferably 99% by mass or less, and even more preferably 97% by mass or less. When the total amount of the epoxy resin (A), the first active ester resin (B-1), the second active ester resin (B-2), and the inorganic filler (C) is within the aforementioned range, the dielectric loss tangent, contaminant removability, linear thermal expansion coefficient, and crack resistance at high temperatures and high frequencies can be particularly improved.

[0107] <(D) Radically polymerizable resin>

[0108] The resin composition according to this embodiment may include a (D) radically polymerizable resin as an optional component. The (D) radically polymerizable resin as component (D) does not include the substances included in the above-mentioned components (A) to (C). The (D) radically polymerizable resins may be used alone or in combination of two or more.

[0109] As the (D) radical polymerizable resin, a resin containing a non-aromatic carbon-carbon unsaturated bond can be used. Therefore, the (D) radical polymerizable resin can generally have a polymerizable unsaturated group containing a non-aromatic carbon-carbon unsaturated bond. Examples of the polymerizable unsaturated group include unsaturated hydrocarbon groups such as vinyl, allyl, 1-propenyl, 3-cyclohexenyl, 3-cyclopentenyl, 2-vinylphenyl, 3-vinylphenyl, and 4-vinylphenyl; and α,β-unsaturated carbonyl groups such as acryloyl, methacryloyl, and maleimide (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl). Regarding the (D) radical polymerizable resin having these polymerizable unsaturated groups, the (D) radical polymerizable resins can generally react with each other or with the carbon-carbon unsaturated bonds that may be contained in the butadiene skeleton of the (B-1) first active ester resin by free radical polymerization. (D) The radical polymerizable resin preferably has two or more polymerizable unsaturated groups.

[0110] Preferred examples of the radically polymerizable resin (D) include maleimide resins. Therefore, the radically polymerizable resin (D) preferably includes a maleimide resin, and may include only a maleimide resin. A maleimide resin is a resin containing one or more, preferably two or more, maleimide groups per molecule.

[0111] As maleimide resin, for example, an aromatic maleimide resin with a maleimide group directly bonded to an aromatic ring, an aliphatic maleimide resin with a maleimide group directly bonded to an aliphatic group can be listed. Maleimide resin can only include aromatic maleimide resin, can only include aliphatic maleimide resin, can also combine to include aromatic maleimide resin and aliphatic maleimide resin. Wherein, from the viewpoint of obtaining the insulating layer with a little linear thermal expansion coefficient, preferably include aromatic maleimide resin. In addition, from the viewpoint of obtaining the insulating layer with a low dielectric loss tangent, preferably include aliphatic maleimide resin.

[0112] In addition, the maleimide resin preferably contains a specific molecular skeleton. Preferred molecular skeletons include, for example, biphenyl skeletons and alicyclic skeletons. Maleimide resins containing these molecular skeletons can achieve particularly good properties such as dielectric loss tangent, dirt removal, crack resistance, and linear thermal expansion coefficient. Among alicyclic skeletons, maleimide resins containing indane skeletons have excellent compatibility and can therefore particularly improve the aforementioned properties.

[0113] Preferred examples of maleimide resins include those containing a partial structure represented by the following formula (D1). Typically, maleimide resins containing a partial structure represented by formula (D1) are aliphatic maleimide resins. Furthermore, the number of maleimide groups in a maleimide resin containing a partial structure represented by formula (D1) is preferably 2 or more, more preferably 2, per molecule.

[0114] [Chemistry 4]

[0115]

[0116] (In formula (D1), ring B d represents an aliphatic hydrocarbon ring optionally having a substituent; i d and j d Each independently represents an integer greater than 0 or 1, and i d With j d The total number of is 6 or more; * indicates a bonding site.)

[0117] In formula (D1), ring B drepresents an aliphatic hydrocarbon ring optionally having a substituent. The aliphatic hydrocarbon ring may be a saturated aliphatic hydrocarbon ring or an unsaturated aliphatic hydrocarbon ring. Furthermore, the aliphatic hydrocarbon ring may be a monocyclic aliphatic hydrocarbon ring having one ring or a polycyclic aliphatic hydrocarbon ring having multiple rings. The number of carbon atoms in the aliphatic hydrocarbon ring is preferably 4 or more, more preferably 5 or more, and preferably 14 or less, more preferably 10 or less, and even more preferably 6 or less.

[0118] Among the aforementioned, ring B d The aliphatic hydrocarbon ring is preferably a monocyclic aliphatic hydrocarbon ring, more preferably a monocyclic saturated aliphatic hydrocarbon ring. Examples of the monocyclic saturated aliphatic hydrocarbon ring include monocyclic alkane rings such as cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, and cyclooctane ring, preferably a cyclohexane ring.

[0119] As ring B d The substituents that the aliphatic hydrocarbon ring may have include, for example, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an aralkyl-oxy group, etc. Among them, an alkyl group and an alkenyl group are preferred, and an alkyl group is more preferred.

[0120] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0121] The alkyl group may be a linear, branched, or cyclic monovalent aliphatic saturated hydrocarbon group. The number of carbon atoms in the alkyl group is preferably 1 to 14, more preferably 1 to 6, and even more preferably 1 to 3. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, neopentyl, tert-pentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, tert-octyl, cyclopentyl, cyclohexyl, and cyclohexylmethyl.

[0122] The alkenyl group may be a linear, branched, or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. The number of carbon atoms in the alkenyl group is preferably 2 to 14, more preferably 2 to 6, and even more preferably 2 or 3. Examples of the alkenyl group include ethenyl, propenyl (allyl, 1-propenyl, isopropenyl), butenyl (1-butenyl, crotyl, methacryl, isocrotyl, etc.), pentenyl (1-pentenyl, etc.), hexenyl (1-hexenyl, etc.), heptenyl (1-heptenyl, etc.), octenyl (1-octenyl, etc.), cyclopentenyl (2-cyclopentenyl, etc.), and cyclohexenyl (3-cyclohexenyl).

[0123] The aryl group may be a monovalent aromatic hydrocarbon group obtained by removing one hydrogen atom from an aromatic carbocyclic ring. The number of carbon atoms in the aryl group is preferably 6 to 14, more preferably 6 to 10. Examples of the aryl group include phenyl, 1-naphthyl, and 2-naphthyl.

[0124] The aralkyl group may be an alkyl group substituted with one or two or more (preferably one) aryl groups. The aralkyl group preferably has 7 to 15 carbon atoms, more preferably 7 to 11 carbon atoms. Examples of the aralkyl group include benzyl, phenethyl, hydrocinnamyl, α-methylbenzyl, α-cumyl, 1-naphthylmethyl, and 2-naphthylmethyl.

[0125] In formula (D1), i d and j d Each independently represents an integer greater than 0 or 1. d and j d The total of is usually 6 or more, preferably 8 or more, more preferably 10 or more. d and j d It is preferably an integer of 0 to 20, more preferably an integer of 1 to 20, and still more preferably an integer of 5 to 10. d and j d They can be the same or different. d and j d 8 is particularly preferred.

[0126] Examples of the maleimide resin containing the partial structure represented by formula (D1) include maleimide resins represented by the following formula (D2).

[0127] [Chemistry 5]

[0128]

[0129] (In formula (D2), R d10 Each independently represents a substituent; Ring C d Each independently represents an aromatic ring optionally having a substituent; D d1 and D d2 Each independently represents a single bond, -C(R x )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO- or -OCO-; R x Each independently represents a hydrogen atom or an alkyl group; c d Each independently represents 0 or 1; d d Each independently represents an integer greater than 0 or 1; e d Each independently represents 0, 1 or 2; n d represents an integer greater than 0 or 1; other symbols are as described above. d Unit, d d Unit and n d Units, each unit can be the same or different.)

[0130] In formula (D2), Rd10 Each independently represents a substituent. d10 Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, and an aralkyl-oxy group.

[0131] In formula (D2), ring C d Each independently represents an aromatic ring optionally having a substituent. The aromatic ring is preferably an aromatic carbocyclic ring. The aromatic ring is preferably a 5- to 14-membered aromatic ring, more preferably a 6- to 14-membered aromatic ring, and even more preferably a 6- to 10-membered aromatic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. A benzene ring or a naphthalene ring is more preferred, and a benzene ring is even more preferred.

[0132] As ring C d The substituent that the aromatic ring of may have includes, for example, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an aralkyl-oxy group, etc. Among them, an alkyl group is preferred.

[0133] In formula (D2), D d1 and D d2 Each independently represents a single bond, -C(R x )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO- or -OCO-, preferably a single bond, -C(R x )2- or -O-, more preferably -O-. R x Each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.

[0134] In formula (D2), c d Each independently represents 0 or 1, preferably 1.

[0135] In formula (D2), d d Each independently represents an integer of 0 or 1 or greater, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2, and even more preferably 0.

[0136] In formula (D2), e d Each independently represents 0, 1 or 2, preferably 0.

[0137] In formula (D2), n d It represents an integer of 0 or 1 or greater, and is preferably 0.

[0138] Examples of the partial structure represented by the following formula (D3) included in formula (D2) include partial structures represented by formulae (d-1) to (d-3) described later.

[0139] [Chemistry 6]

[0140]

[0141] [Chemistry 7]

[0142]

[0143] (Where * indicates the bonding site.)

[0144] Commercially available products of maleimide resins containing a partial structure represented by formula (D1) include, for example, "BMI-689", "BMI-1500", "BMI-1700", and "BMI-3000J" manufactured by Designer Molecules Inc.; "SLK-1500" (a compound of the following formula (d-4)) and "SLK-6895" (a compound of formula (d-5)) manufactured by Shin-Etsu Chemical Co., Ltd.

[0145] [Chemistry 8]

[0146]

[0147] Other preferred examples of the maleimide resin include a maleimide resin represented by formula (D4).

[0148] [Chemistry 9]

[0149]

[0150] (In formula (D4), R d20 Each independently represents a hydrogen atom or an alkyl group; Ring E d 、Ring F d and Ring G d Each independently represents an aromatic ring optionally having a substituent; Z d1 Each independently represents a single bond, -C(R z )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH- or -NHCO-; R z Each independently represents a hydrogen atom or an alkyl group; f d Indicates an integer greater than 1; g d Each independently represents 0 or 1; h d Each independently represents 0, 1, 2 or 3. d Unit and h d Units, each unit can be the same or different.)

[0151] In formula (D4), R d20 Each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

[0152] In formula (D4), ring E d 、Ring F d and Ring G d Each independently represents an aromatic ring which may have a substituent. d 、Ring F d and Ring G d Examples of the substituents in include halogen atoms, alkyl groups, alkenyl groups, aryl groups, aralkyl groups, alkyl-oxy groups, alkenyl-oxy groups, aryl-oxy groups, and aralkyl-oxy groups. d 、Ring F d and Ring G d It is preferably a benzene ring optionally having a substituent, more preferably a benzene ring optionally substituted with a group selected from an alkyl group and an aryl group, and further preferably an unsubstituted benzene ring.

[0153] In formula (D4), Z d1 Each independently represents a single bond, -C(R z )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH- or -NHCO-, preferably a single bond. z Each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.

[0154] In formula (D4), f d It represents an integer of 1 or greater, and is preferably an integer of 1-10.

[0155] In formula (D4), g d Each independently represents 0 or 1, preferably 1.

[0156] In formula (D4), h d Each independently represents 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1, and further preferably 1.

[0157] Examples of commercially available products of the maleimide resin represented by formula (D4) include "MIR-3000-70MT" and "MIR-5000-60T" manufactured by Nippon Kayaku Co., Ltd.

[0158] Still another preferred example of the maleimide resin is a maleimide resin represented by formula (D5).

[0159] [Chemistry 10]

[0160]

[0161] (In formula (D5), R d30 Each independently represents an alkyl group; Ring H d and Ring I dEach independently represents an aromatic ring optionally having a substituent; m d represents an integer greater than 1. d Units, each unit can be the same or different.)

[0162] In formula (D5), R d30 Each independently represents an alkyl group, preferably a methyl group.

[0163] In formula (D5), ring H d Each independently represents an aromatic ring which may have a substituent. d Examples of the substituents in include halogen atoms, alkyl groups, alkenyl groups, aryl groups, aralkyl groups, alkyl-oxy groups, alkenyl-oxy groups, aryl-oxy groups, and aralkyl-oxy groups. d It is preferably a benzene ring optionally having a substituent, more preferably a benzene ring optionally substituted with an alkyl group, and still more preferably a benzene ring substituted with an alkyl group.

[0164] In formula (D5), ring I d Each independently represents an aromatic ring which may have a substituent. d Examples of the substituents in include halogen atoms, alkyl groups, alkenyl groups, aryl groups, aralkyl groups, alkyl-oxy groups, alkenyl-oxy groups, aryl-oxy groups, and aralkyl-oxy groups. d It is preferably a benzene ring optionally having a substituent, more preferably a benzene ring optionally substituted with an alkyl group, and still more preferably an unsubstituted benzene ring.

[0165] In formula (D5), m d It represents an integer of 1 or greater, and is preferably an integer of 1-20.

[0166] The maleimide resin represented by formula (D5) can be produced using, for example, the method described in Japan Invention Association Publication No. 2020-500211 or a method based on this method.

[0167] The maleimide group equivalent weight of the maleimide resin is preferably 30 g / eq. or more, more preferably 75 g / eq. or more, even more preferably 150 g / eq. or more, even more preferably 200 g / eq. or more, even more preferably 250 g / eq. or more, even more preferably 300 g / eq. or more, and is preferably 2,500 g / eq. or less, more preferably 2,000 g / eq. or less, even more preferably 1,500 g / eq. or less, even more preferably 1,000 g / eq. or less, and even more preferably 500 g / eq. or less. The maleimide group equivalent weight represents the mass of the resin per 1 equivalent of maleimide groups.

[0168] The weight average molecular weight of the maleimide resin is preferably 100 or more, more preferably 150 or more, further preferably 200 or more, further preferably 400 or more, further preferably 500 or more, further preferably 600 or more, and is preferably 10,000 or less, more preferably 7,000 or less, further preferably 5,000 or less, further preferably 3,000 or less.

[0169] The amount of the maleimide resin is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 0.9% by mass or more, relative to 100% by mass of the non-volatile components in the resin composition, and is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. When the amount of the maleimide resin is within the aforementioned range, the dielectric loss tangent, contaminant removability, linear thermal expansion coefficient, and crack resistance at high temperatures and high frequencies can be particularly improved.

[0170] The amount of the maleimide resin is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, relative to 100% by mass of the resin component in the resin composition, and is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less. When the amount of the maleimide resin is within the aforementioned range, the dielectric loss tangent, contaminant removability, linear thermal expansion coefficient, and crack resistance at high temperatures and high frequencies can be particularly improved.

[0171] The range of the molar ratio of the maleimide resin to the (B-1) first active ester resin (maleimide resin / (B-1) first active ester resin) is preferably 0.01 or more, more preferably 0.1 or more, and even more preferably 0.2 or more, and is preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less, on a mass basis. When the molar ratio (maleimide resin / (B-1) first active ester resin) is within the aforementioned range, the dielectric loss tangent, contaminant removability, linear thermal expansion coefficient, and crack resistance at high temperatures and high frequencies can be particularly improved.

[0172] Examples of the (D) polymerizable unsaturated resin include (meth)acrylic polymerizable unsaturated resins, styrene polymerizable unsaturated resins, and allyl polymerizable unsaturated resins.

[0173] As the (meth)acrylic polymerizable unsaturated resin, a resin having one or more, preferably two or more, acryloyl groups and / or methacryloyl groups in one molecule can be used. Examples of the (meth)acrylic polymerizable unsaturated resin include low molecular weight (molecular weight less than 1000) aliphatic (meth)acrylate compounds such as cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; and dioxanediol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate, and the like. Low molecular weight (molecular weight less than 1000) ether-containing (meth)acrylate compounds such as di(meth)acrylate, 3,6,9-trioxaundecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, ethoxylated bisphenol A di(meth)acrylate, and propoxylated bisphenol A di(meth)acrylate; low molecular weight (molecular weight less than 1000) isocyanurate-containing (meth)acrylate compounds such as tris(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, and ethoxylated isocyanuric acid tri(meth)acrylate; high molecular weight (molecular weight of 1000 or more) acrylate compounds such as (meth)acrylic-modified polyphenylene ether resin, etc. Examples of commercially available (meth)acrylic polymerizable unsaturated resins include "A-DOG" (dioxanediol diacrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "DCP-A" (tricyclodecane dimethanol diacrylate), "DCP" (tricyclodecane dimethanol dimethacrylate), and "BPE-1300N" (ethoxylated bisphenol A dimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd., "KAYARAD R-684" (tricyclodecane dimethanol diacrylate), and "KAYARAD R-604" (dioxanediol diacrylate) manufactured by Nippon Kayaku Co., Ltd., and "SA9000" and "SA9000-111" (methacrylic modified polyphenylene ether) manufactured by SABIC.

[0174] As the styrene-based polymerizable unsaturated resin, a resin having one or more, preferably two or more, vinyl groups directly bonded to aromatic carbon atoms in one molecule can be used. As styrene-based polymerizable unsaturated resins, for example, divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, bis(4-vinylphenyl)ether and other low molecular weight (molecular weight less than 1000) styrene-based compounds; vinylbenzyl modified polyphenylene ether resin, styrene-divinylbenzene copolymer and other high molecular weight (molecular weight of 1000 or more) styrene-based compounds and the like can be listed. Among these styrene-based polymerizable unsaturated resins, a resin containing a monovinyl aromatic compound unit and a divinyl aromatic compound unit in combination is preferred. The monovinyl aromatic compound unit refers to a structural unit having a structure formed by polymerizing a monovinyl compound such as styrene having an aromatic ring directly bonded to one vinyl group. In addition, the divinyl aromatic compound unit refers to a structural unit having a structure formed by polymerizing a divinyl aromatic compound such as divinylbenzene having an aromatic ring directly bonded to two vinyl groups. As the preferred styrene-based polymerizable unsaturated resin, the resins described in International Publication No. 2017 / 115813 can be cited. As commercially available products of styrene-based polymerizable unsaturated resins, for example, "ODV-XET (X03)", "ODV-XET (X04)", "ODV-XET (X05)" (styrene-divinylbenzene copolymer) made by Nippon Steel Chemical & Material Co., Ltd., "OPE-2St1200", "OPE-2St2200" (vinyl benzyl modified polyphenylene ether resin) made by Mitsubishi Gas Chemical Co., Ltd. can be cited.

[0175] As the allyl polymerizable unsaturated resin, a resin having one or more, preferably two or more, allyl groups in one molecule can be used. Examples of the allyl polymerizable unsaturated resin include aromatic carboxylic acid allyl ester compounds such as diallyl biphenylate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, and diallyl 2,3-naphthalenedicarboxylate; and aromatic carboxylic acid allyl ester compounds such as 1,3,5-triallyl isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate. Compounds; aromatic allyl compounds containing epoxy groups such as 2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane; aromatic allyl compounds containing benzoxazine such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane; aromatic allyl compounds containing ethers such as 1,3,5-triallyletherbenzene; allylsilane compounds such as diallyldiphenylsilane, etc. Among them, resins having an allyl group at the end are preferred. Commercially available products of allyl-based polymerizable unsaturated resins include, for example, “TAIC” (1,3,5-triallyl isocyanurate) manufactured by Nippon Chemical Co., Ltd., “DAD” (diallyl biphenylate) manufactured by Nichido TechnoFine Chemical Co., Ltd., “TRIAM-705” (triallyl trimellitate) manufactured by Fujifilm Wako Pure Chemical Co., Ltd., and Nichido Techno Fine Chemical Co., Ltd. Trade names include "DAND" (diallyl 2,3-naphthalenecarboxylate) manufactured by Shikoku Chemical Co., Ltd., "ALP-d" (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane) manufactured by Shikoku Chemical Co., Ltd., "RE-810NM" (2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane) manufactured by Nippon Kayaku Co., Ltd., "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Chemical Co., Ltd., and "NE-V-1100-70T" manufactured by DIC Corporation.

[0176] (D) The polymerizable unsaturated resin may include a resin including a polyphenylene ether skeleton in its molecular skeleton.

[0177] The polymerizable unsaturated group equivalent weight of the polymerizable unsaturated resin (D) is preferably 20 g / eq. to 3,000 g / eq., more preferably 50 g / eq. to 2,500 g / eq., further preferably 70 g / eq. to 2,000 g / eq., and particularly preferably 90 g / eq. to 1,500 g / eq. The polymerizable unsaturated group equivalent weight represents the mass of the resin per 1 equivalent of the polymerizable unsaturated group.

[0178] The weight average molecular weight (Mw) of the polymerizable unsaturated resin (D) is preferably 40,000 or less, more preferably 10,000 or less, further preferably 5,000 or less, and particularly preferably 3,000 or less. The lower limit is not particularly limited, and may be, for example, 150 or more.

[0179] The amount of the polymerizable unsaturated resin (D) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, relative to 100% by mass of the non-volatile components in the resin composition, and is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. When the amount of the polymerizable unsaturated resin (D) is within the aforementioned range, the dielectric loss tangent, contaminant removability, linear thermal expansion coefficient, and crack resistance at high temperatures and high frequencies can be particularly improved.

[0180] The amount of the polymerizable unsaturated resin (D) is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, relative to 100% by mass of the resin component in the resin composition, and is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less. When the amount of the polymerizable unsaturated resin (D) is within the aforementioned range, the dielectric loss tangent, contaminant removability, linear thermal expansion coefficient, and crack resistance at high temperatures and high frequencies can be particularly improved.

[0181] The range of the molar ratio of the (D) polymerizable unsaturated resin to the (B-1) first active ester resin ((D) polymerizable unsaturated resin / (B-1) first active ester resin) is preferably 0.01 or more, more preferably 0.1 or more, and even more preferably 0.2 or more, and is preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less, on a mass basis. When the molar ratio ((D) polymerizable unsaturated resin / (B-1) first active ester resin) is within the aforementioned range, the dielectric loss tangent, contaminant removability, linear thermal expansion coefficient, and crack resistance at high temperatures and high frequencies can be particularly improved.

[0182] <(E) Optional Curing Agent>

[0183] In the resin composition described in this embodiment, as an optional component, an optional curing agent (E) other than the first active ester resin (B-1) and the second active ester resin (B-2) may be included. The optional curing agent (E) as the (E) component refers to a resin that can react with the epoxy resin to cure the resin composition. The optional curing agent (E) does not include substances belonging to the above-mentioned (A) to (D) components. For example, in the presence of a suitable catalyst, a maleimide resin can react with the epoxy resin (A), but the maleimide resin is not classified into the optional curing agent (E). One of the optional curing agents (E) can be used alone, or two or more can be used in combination.

[0184] Preferred examples of the (E) optional curing agent include phenol resins, benzoxazine resins, cyanate resins, carbodiimide resins, acid anhydride resins, and amine resins.

[0185] As the phenolic resin, a resin having one or more, preferably two or more, hydroxyl groups bonded to aromatic rings such as a benzene ring or a naphthalene ring (phenolic hydroxyl groups) in one molecule can be used. From the viewpoints of heat resistance and water resistance, a phenolic resin having a novolac structure is preferred. In addition, from the viewpoint of adhesion, a nitrogen-containing phenolic resin is preferred, and a phenolic resin containing a triazine skeleton is more preferred. Among them, from the viewpoint of highly satisfying heat resistance, water resistance and adhesion, a phenol novolac resin containing a triazine skeleton is preferred.

[0186] Specific examples of phenolic resins include "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" manufactured by Meiwa Chemicals; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd.; and "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", and "SN-495V" manufactured by Nippon Steel Chemical & Material Co., Ltd. ", "SN-375", "SN-395"; "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", "TD-2090-60M" manufactured by DIC Corporation; "GDP-6115L", "GDP-6115H", "ELPC75" and so on manufactured by Qunrong Chemical Co., Ltd.

[0187] As the benzoxazine resin, a resin having one or more, preferably two or more, benzoxazine rings per 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 High Molecular Co., Ltd.; and "Pd," "Fa," and "ALP-d" manufactured by Shikoku Chemical Industry Co., Ltd.

[0188] As the cyanate resin, a resin having one or more, preferably two or more, cyanate groups per molecule can be used. Examples of the cyanate resin include difunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyano)phenylpropane, 1,1-bis(4-cyanophenylmethane), bis(4-cyano-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanophenyl-1-(methylethylene))benzene, bis(4-cyanophenyl)sulfide, and bis(4-cyanophenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers obtained by partially triazinizing these cyanate resins. Specific examples of cyanate resins include "PT30" and "PT60" (phenol novolac-type multifunctional cyanate resins) manufactured by Arxada, "BA230" and "BA230S75" (prepolymers in which a portion or all of bisphenol A dicyanate is triazinated to form a trimer), etc.

[0189] As the carbodiimide resin, a resin having one or more, preferably two or more, carbodiimide structures in one molecule can be used. Specific examples of the carbodiimide resin include aliphatic biscarbodiimides such as tetramethylene-bis(tert-butylcarbodiimide) and cyclohexanebis(methylene-tert-butylcarbodiimide); aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide); and aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide). Aromatic polycarbodiimides such as poly(naphthylenecarbodiimide), poly(toluenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide] are also included. Examples of commercially available carbodiimide resins include "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.

[0190] As the acid anhydride resin, a resin having one or more, preferably two or more, acid anhydride groups in one molecule can be used. Specific examples of the acid anhydride resin 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-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, Polymer-type acid anhydrides such as benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride), and styrene-maleic acid resin obtained by copolymerizing styrene and maleic acid. Commercially available products of the acid anhydride resin include, for example, "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by Shin Nippon Chemical Co., Ltd.; "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Corporation; "HN-2200" manufactured by Resonac; and "EF-30", "EF-40", "EF-60", and "EF-80" manufactured by Cray Valley Corporation.

[0191] As the amine resin, a resin having one or more, preferably two or more, amino groups in one molecule can be used. Examples of the amine resin include aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, and the like, among which aromatic amines are preferred. The amine resin is preferably a primary amine or a secondary amine, more preferably a primary amine. Specific examples of the amine resin include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, metaphenylenediamine, metaphenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxybenzene) phenyl) sulfone, bis(4-(4-aminophenoxy)phenyl) sulfone, and the like. Commercially available products of amine resins include, for example, "SEIKACURE-S" manufactured by SEIKA Corporation; "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", and "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd.; "EPICURE W" manufactured by Mitsubishi Chemical Corporation; and "DTDA" manufactured by Sumitomo Seika Chemicals.

[0192] The active group equivalent weight of the optional curing agent (E) 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 weight represents the mass of the resin per 1 equivalent of the active group. The active group of the optional curing agent (E) refers to a group that can react with the epoxy group of the epoxy resin (A), and examples thereof include phenolic hydroxyl groups. For example, the active group equivalent weight of a phenolic resin represents the phenolic hydroxyl group equivalent weight, which represents the mass of the resin per 1 equivalent of the phenolic hydroxyl group.

[0193] The weight average molecular weight (Mw) of the (E) optional curing agent may be in the same range as the weight average molecular weight (Mw) of the (A) epoxy resin.

[0194] The amount of the optional curing agent (E) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, and is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, relative to 100% by mass of the non-volatile components in the resin composition.

[0195] The amount of the optional curing agent (E) is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 5% by mass or more, and is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, relative to 100% by mass of the resin component in the resin composition.

[0196] Regarding the total number of active ester groups of (B-1) the first active ester resin, the total number of active ester groups of (B-2) the second active ester resin and the total number of active groups of (E) the optional curing agent, when the number of epoxy groups of (A) the epoxy resin is set to 1, it is preferably 0.1 or more, more preferably 0.5 or more, further preferably 1.0 or more, preferably 10 or less, more preferably 5.0 or less, further preferably 3.0 or less, further preferably 2.0 or less. The "number of active groups of (E) the optional curing agent" in the resin composition refers to the value obtained by adding up all the values obtained by dividing the mass of the non-volatile components of the optional curing agent (E) present in the resin composition by the active group equivalent thereof. When the total number of active ester groups of (B-1) the first active ester resin, the total number of active ester groups of (B-2) the second active ester resin and the total number of active groups of (E) the optional curing agent is within the aforementioned range, the dielectric loss tangent, dirt removability, linear thermal expansion coefficient and crack resistance under high temperature and high frequency can be made particularly good.

[0197] <(F) Organic Filler>

[0198] The resin composition described in this embodiment may include an (F) organic filler as an optional component. The (F) organic filler as the (F) component does not include substances belonging to the above-mentioned (A) to (E) components. The (F) organic filler is generally incompatible with resin components other than the (F) organic filler and is included in the resin composition in a granular state. The granular state is maintained and included in the cured product. In addition, the (F) organic filler can be used alone or in combination of two or more.

[0199] As (F) organic filler, particles of organic material can be used. As the organic material contained in the (F) organic filler, a rubber component is preferably used. As the rubber component, silicone elastomers such as polydimethylsiloxane can be listed; olefin 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, ethylene-propylene-butylene terpolymer; thermoplastic elastomers such as acrylic thermoplastic elastomers such as poly(meth)propyl acrylate, poly(meth)butyl acrylate, poly(meth)cyclohexyl acrylate, poly(meth)octyl acrylate, etc. can be mixed with the rubber component. Furthermore, silicone rubbers such as polyorganosiloxane rubber can be mixed with the rubber component. The glass transition temperature of the rubber component contained in the rubber particles is, for example, 0°C or lower, preferably -10°C or lower, more preferably -20°C or lower, and further preferably -30°C or lower.

[0200] (F) The organic filler may be a core-shell rubber particle composed of a core particle containing the aforementioned rubber component and a shell portion, wherein the core particle is obtained by graft copolymerization of a monomer component copolymerizable with the rubber component contained in the core particle. The term "core-shell" herein does not necessarily refer only to a type in which the core particle and the shell portion are clearly distinguishable, but also includes a type in which the boundary between the core particle and the shell portion is unclear, and the core particle may not be completely covered by the shell portion.

[0201] Specific examples of the (F) organic filler include "CHT" manufactured by Samsung SDI; "B602" manufactured by Techno UMG; "PARALOID EXL-2602", "PARALOID XL-2603", "PARALOID EXL-2655", "PARALOID EXL-2311", "PARALOID EXL-2313", "PARALOID EXL-2315", "PARALOID KM-330", "PARALOID KM-336P", and "PARALOID KCZ-201" manufactured by Dow; and "METABLEN C-223A", "METABLEN E-901", "METABLEN S-2001", and "METABLEN W-450A" manufactured by Mitsubishi Rayon. SRK-200"; "Kane Ace (カネエース) M-511", "Kane Ace M-600", "Kane Ace M-400", "Kane Ace M-580", "Kane" manufactured by KANEKA AceMR-01"; "スタフィロイドAC3355", "スタフィロイドAC3816", "スタ" manufactured by Aica Industrial Co., Ltd. "スィロイドAC3816N", "スタフィロイドAC3832", "スタフィロイドAC4030", "スタフィロイドAC3364", etc.

[0202] The amount of the organic filler (F) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more, and is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less, relative to 100% by mass of the non-volatile components in the resin composition.

[0203] The amount of the organic filler (F) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, and is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to 100% by mass of the resin component in the resin composition.

[0204] <(G) Curing Accelerator>

[0205] The resin composition described in this embodiment may include a (G) curing accelerator as an optional component. The (G) curing accelerator as the (G) component does not include substances included in the above-mentioned components (A) to (F). The (G) curing accelerator can act as a catalyst in the reaction of the (A) epoxy resin, thereby accelerating the curing of the resin composition.

[0206] Examples of the curing accelerator (G) 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. The curing accelerator (G) may be used alone or in combination of two or more.

[0207] Phosphorus curing accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitic acid salt, 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, para-methyl Aromatic phosphonium salts such as phenyltriphenylphosphonium tetra-p-tolyl borate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolyl borate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(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, di-tert-butylphosphine Aliphatic phosphines such as butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl-2-butenyl) phosphine, and tricyclohexyl phosphine; dibutylphenyl phosphine, di-tert-butylphenyl phosphine, methyldiphenyl phosphine, ethyldiphenyl phosphine, butyldiphenyl phosphine, diphenylcyclohexyl phosphine, 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 such as tris(dimethylphenyl)phosphine, 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 are also included.

[0208] Examples of the urea-based curing accelerator 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, Aromatic dimethylureas such as 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].

[0209] Examples of the guanidine-based curing accelerator 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, and 1-(o-tolyl)biguanidine.

[0210] Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1') imidazole compounds such as 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins. Commercially available imidazole curing accelerators include, for example, "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", "2MA-OK-PW", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", and "C11Z-A" manufactured by Shikoku Chemical Industry Co., Ltd.; and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0211] Examples of metallic 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) acetylacetonate and cobalt (III) acetylacetonate; organocopper complexes such as copper (II) acetylacetonate; organozinc complexes such as zinc (II) acetylacetonate; organoiron complexes such as iron (III) acetylacetonate; organonickel complexes such as nickel (II) acetylacetonate; and organomanganese complexes such as manganese (II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0212] 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 may be used, and examples thereof include "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0213] The amount of the curing accelerator (G) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more, relative to 100% by mass of the non-volatile components in the resin composition, and is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less.

[0214] The amount of the curing accelerator (G) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 1% by mass or more, relative to 100% by mass of the resin component in the resin composition, and is preferably 10% by mass or less, more preferably 6% by mass or less, and even more preferably 3% by mass or less.

[0215] <(H) Optional Additives>

[0216] The resin composition described in this embodiment may further include (H) optional additives as optional components. The (H) optional additives as the (H) component do not include substances belonging to the above-mentioned (A) to (G) components. As the (H) optional additives, organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as BENTON and montmorillonite; defoamers such as silicone-based defoamers, acrylic-based defoamers, fluorine-based defoamers, and vinyl resin-based defoamers; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion enhancers such as urea silane; adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; hindered phenol-based antioxidants Antioxidants such as oxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate compounds, phosphazene compounds, phosphinic 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-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid stabilizers, and carboxylic anhydride stabilizers. (H) Optional additives may be used alone or in combination of two or more.

[0217] The resin composition may include a photopolymerization initiator such as a photoacid generator and a light radical generator. The resin composition described in the present embodiment preferably has thermosetting properties, and thus, the resin composition preferably does not contain a photopolymerization initiator. Specifically, when the resin component in the resin composition is set to 100% by mass, the amount of the photopolymerization initiator is preferably less than 0.1% by mass, less than 0.05% by mass, less than 0.04% by mass, less than 0.02% by mass, less than 0.01% by mass, less than 0.01% by mass, less than 0.005% by mass, less than 0.001% by mass or less than 0.001% by mass. The amount of the photopolymerization initiator can be 0% by mass.

[0218] <(I) Solvent>

[0219] The resin composition described in this embodiment may further contain (I) a solvent as an optional volatile component in combination with the non-volatile components such as the above-mentioned (A) to (H) components. As the (I) solvent, an organic solvent is generally used. Examples of the organic solvent 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; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methoxy Ether ester solvents such as methyl propionate; 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; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene, etc. (I) The solvent may be used alone or in combination of two or more.

[0220] The amount of the solvent (I) 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, relative to 100% by mass of all components in the resin composition, or may be 0% by mass.

[0221] <Method for producing resin composition>

[0222] The resin combination described in the present embodiment can be manufactured by, for example, mixing the components that can be included in the resin combination. The above-mentioned components can be mixed in part or all at the same time, or can be mixed in sequence. In the process of mixing each component, the temperature can be appropriately set, thereby, heating and / or cooling can be performed temporarily or all the time. In addition, in the process of mixing each component, stirring or vibration can be performed.

[0223] <Characteristics of Cured Resin Composition>

[0224] By curing the resin composition described in this embodiment, a cured product of the resin composition can be obtained. Furthermore, an insulating layer can be formed from the cured product. Generally, heat is applied during the curing of the resin composition. Therefore, among the components contained in the resin composition, volatile components such as (I) solvent may volatilize due to the heat during curing. Therefore, the cured product obtained by curing the resin composition may contain non-volatile components such as (A) to (H) components or their reaction products.

[0225] The cured product of the resin composition described in this embodiment can have excellent dielectric properties, specifically, can have a low dielectric loss tangent Df. In one example, the dielectric loss tangent Df of the cured product is preferably 0.0030 or less, more preferably 0.0027 or less, and further preferably 0.0025 or less. The lower limit of the dielectric loss tangent Df is not particularly limited, and for example, can be 0.0010 or more.

[0226] The dielectric loss tangent Df of the cured product can be measured using the split cylinder method at a measurement frequency of 10 GHz and a measurement temperature of 90°C. If the sample is an uncured resin composition, the resin composition can be cured at 190°C for 90 minutes to obtain a cured product, and the dielectric loss tangent Df of the cured product can be measured. The specific measurement method can be the method described in "Test 1. Dielectric Loss Tangent Measurement Test" in the Examples described below.

[0227] The cured product of the resin composition described in this embodiment generally exhibits excellent stain removability. For example, when an insulating layer is formed from the cured product and its stain removability is evaluated using the method described in "Test 3. Stain Removability Evaluation Test" in the Examples described below, the maximum stain length can be reduced to less than 5 μm.

[0228] The cured product of the resin composition according to this embodiment generally exhibits excellent crack resistance. For example, when an insulating layer is formed from the cured product and its crack resistance is evaluated using the method described in "Test 4. Evaluation of Crack Resistance after Decontamination Treatment" in the Examples described below, the number of cracks can be reduced to 10 or less.

[0229] The cured product of the resin composition according to this embodiment can have a low linear thermal expansion coefficient. In one example, the average linear thermal expansion coefficient of the cured product is preferably 25 ppm / °C or less, more preferably 20 ppm / °C or less, and even more preferably 16 ppm / °C or less. The lower limit of the average linear thermal expansion coefficient of the cured product is not particularly limited, but can be, for example, 5 ppm / °C or greater.

[0230] The average linear thermal expansion coefficient of the cured product can be measured using a thermomechanical analyzer under the following conditions: a temperature range of 25°C to 250°C and a heating rate of 5°C / minute. If the sample is a pre-cured resin composition, the resin composition can be cured at 190°C for 90 minutes to obtain a cured product, and the average linear thermal expansion coefficient of the cured product can be measured. The specific measurement method can be the method described in "Test 2. Measurement of Coefficient of Linear Thermal Expansion (CTE)" in the Examples described below.

[0231] <Application of resin composition>

[0232] The resin combination described in the present embodiment can be used for the formation purposes of insulating layer, and is particularly preferably used for the insulating layer formation purposes of circuit substrate. In addition, resin combination can be used for the manufacturing purposes of resin sheet. Usually, this resin sheet is used to carry out the formation of insulating layer. In addition, resin combination can be used for other purposes, can be used for purposes such as solder resist, bottom filling material, chip bonding material, hole filling resin, sealing resin, component embedding resin.

[0233] <Resin Sheet>

[0234] The resin sheet according to one embodiment of the present invention comprises a support and a resin composition layer formed on the support. The resin composition layer comprises the above-mentioned resin composition, and preferably comprises only the above-mentioned resin composition.

[0235] From the perspective of thinning, the thickness of the resin composition layer of 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 may be, for example, 1 μm or more, 3 μm or more, or 5 μm or more.

[0236] Examples of the support include a film of a plastic material, a metal foil, and release paper, and a film of a plastic material and a metal foil are preferred.

[0237] When a film of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate (hereinafter sometimes referred to as "PEN"); acrylics such as polycarbonate (hereinafter sometimes referred to 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.

[0238] When a metal foil is used as a support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. The copper foil may be made of copper alone or an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0239] The surface of the support that contacts the resin composition layer may be subjected to surface treatment such as matte treatment, corona treatment, or antistatic treatment.

[0240] As the support, a support with a release layer having a release layer on the surface bonded to the resin composition layer can be used. As a release agent used in the release layer of the support with a release layer, for example, one or more release agents selected from alkyd release agents, polyolefin release agents, urethane release agents, and silicone release agents can be listed. Commercially available products can be used for the support with a release layer, for example, "PET501010", "SK-1", "AL-5", and "AL-7" manufactured by LINTEC, which are PET films having a release layer with a silicone release agent or an alkyd resin release agent as the main component; "LUMIRROR T60" manufactured by Toray Industries, "Purex" manufactured by Teijin, and "Unipeel" manufactured by UNITIKA.

[0241] The thickness of the support is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, and even more preferably 10 μm or more, and is preferably 75 μm or less, more preferably 60 μm or less, and even more preferably 50 μm or less. When a support with a release layer is used, the overall thickness of the support with the release layer is preferably within the above range.

[0242] The resin sheet may have optional components as needed. For example, the resin sheet may have a protective film that protects the resin composition layer. The protective film is usually provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface on the opposite side of the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. In the case of having a protective film, it is possible to suppress the adhesion and damage of dirt to the surface of the resin composition layer.

[0243] The resin sheet can be manufactured by, for example, a method including forming a resin composition layer on a support. If a specific example is given, then by directly applying a liquid (varnish-like) resin composition on a support, or, mixing a solvent with the resin composition to prepare a liquid (varnish-like) resin composition, and applying it on a support, and then, drying it as needed to form a hot resin composition layer, thus manufacturing a resin sheet. As a solvent, a solvent identical to the (I) solvent described as a component of the resin composition can be used.

[0244] The resin composition can be applied using a coating device such as a die coater. In addition, drying can be performed by a drying method such as heating or blowing hot air. The drying conditions are not particularly limited, and the resin composition layer is dried so that the solvent content is generally 10% by mass or less, preferably 5% by mass or less. It 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 a solvent, the resin composition layer can be formed by drying it at 50° C. to 150° C. for 3 minutes to 10 minutes.

[0245] The produced resin sheet can be stored in a roll. When the resin sheet has a protective film, the resin sheet can usually be used by peeling off the protective film.

[0246] <Circuit Board>

[0247] The circuit substrate described in one embodiment of the present invention includes a cured product of the resin composition. Typically, the circuit substrate includes an insulating layer, and the insulating layer includes a cured product of the resin composition. The insulating layer may only include a cured product of the resin composition. The thickness of the insulating layer is not particularly limited, for example, it may be within the same range as the thickness of the resin composition layer provided by the resin sheet. In addition, the insulating layer may typically have the same properties as the cured product of the resin composition.

[0248] The circuit substrate preferably includes an inner substrate, on which the aforementioned insulating layer is disposed. Alternatively, the circuit substrate may include a conductive layer. For example, the conductive layer may be disposed on the insulating layer. The following describes an example of a preferred method for manufacturing the circuit substrate.

[0249] The manufacturing method of the circuit substrate described in the preferred embodiment includes:

[0250] Step (I) of forming a resin composition layer on an inner substrate; and

[0251] Step (II) of curing the resin composition layer.

[0252] "Inner layer substrate" refers to a component that serves as the base material of a circuit substrate, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. In addition, the inner layer substrate may have a conductor layer on one or both sides thereof. In addition, the conductor layer possessed by the inner layer substrate may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate is sometimes referred to as an "inner layer circuit substrate." In addition, intermediate products in which an insulating layer and / or a conductor layer should be further formed when manufacturing a circuit substrate are also included in the term "inner layer substrate." In addition, an inner layer substrate with built-in components may be used.

[0253] The resin composition layer is formed on the inner substrate by, for example, a forming method including applying a resin composition on the inner substrate and drying as needed, preferably using a resin sheet. The method of using a resin sheet to form a resin composition layer generally includes laminating a resin sheet with an inner substrate. The lamination of the resin sheet and the inner substrate is carried out in a manner such that the resin composition layer of the resin sheet is bonded to the inner substrate. The lamination can be carried out by, for example, heating and pressing the resin sheet from the support side to the inner substrate. As a component for heat-pressing the resin sheet to the inner substrate (hereinafter also referred to as "heat-pressing component"), for example, a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller, etc.) can be cited. It should be noted that it is preferred that the heat-pressing component is not directly pressed on the resin sheet, but is pressurized via an elastic material such as heat-resistant rubber in a manner such that the resin sheet fully follows the surface unevenness of the inner substrate.

[0254] Lamination of the inner layer 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 in the range of 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 in the range of 0.29 MPa to 1.47 MPa, and the heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions of 26.7 hPa or less.

[0255] Lamination can be performed using a commercially available vacuum laminator, such as a vacuum press laminator manufactured by Meiki Manufacturing Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., and a batch vacuum press laminator.

[0256] The method for manufacturing a circuit substrate may include: after lamination, smoothing the resin sheet by applying pressure to a heat-pressing member under normal pressure (atmospheric pressure), for example, from the support side. The pressurizing conditions for the smoothing treatment may be the same as the heat-pressing conditions for the lamination. The smoothing treatment may be performed using a commercially available laminator. Lamination and smoothing treatment may be performed continuously using the commercially available vacuum laminator.

[0257] The method for producing a circuit board according to this embodiment includes a step (II) of curing the resin composition layer after step (I). By curing the resin composition layer in step (II), an insulating layer composed of a cured product of the resin composition can be formed.

[0258] The resin composition layer is typically cured by thermal curing. Thermal curing conditions for 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. Furthermore, 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.

[0259] The method for manufacturing a circuit substrate may include preheating the resin composition layer at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, the resin composition layer may be preheated at a temperature of 50°C to 150°C, preferably 60°C to 140°C, and more preferably 70°C to 130°C, for a period of 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and further preferably 15 minutes to 100 minutes, before the resin composition layer is thermally cured. Preheating is usually performed after step (I). In addition, when smoothing treatment is performed after lamination of the inner substrate and the resin sheet, preheating can usually be performed after the smoothing treatment.

[0260] When a resin sheet is used, the method for manufacturing a circuit substrate may include the step of peeling off the support of the resin sheet after lamination of the inner substrate and the resin sheet. The peeling off of the support may be performed between step (I) and step (II), or after step (II). In addition, when the method for manufacturing a circuit substrate includes a step (III) of forming a hole in the insulating layer, a step (IV) of roughening the insulating layer, and a step (V) of forming a conductor layer as described later, the peeling off of the support may be performed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V).

[0261] The method for manufacturing a circuit substrate may include: after step (II), step (III) of forming holes such as through holes and vias in the insulating layer. The method for forming the holes can be selected according to factors such as the composition of the resin composition used to form the insulating layer. For example, the holes can be formed by processing methods such as drilling, laser processing, and plasma processing, wherein laser processing is preferred. For example, the holes can be formed by irradiating the insulating layer with a laser after peeling off the support, or by irradiating the insulating layer with a laser through the support. The size and shape of the holes can be appropriately determined according to the design of the circuit substrate.

[0262] The method for manufacturing a circuit substrate may include a step (IV) of roughening the insulating layer. The roughening treatment can roughen the surface of the insulating layer. In addition, the roughening treatment can remove dirt (resin residue) from the insulating layer. Therefore, the roughening treatment is sometimes referred to as a "decontamination treatment." For example, if a hole is formed in step (III), dirt may form in the hole. Therefore, it is preferable to perform the roughening treatment of step (IV) after step (III) to remove the aforementioned dirt.

[0263] The steps and conditions for the roughening treatment are not particularly limited, and known steps and conditions commonly used in forming an insulating layer of a circuit substrate may be employed. For example, the roughening treatment may be performed by sequentially subjecting the insulating layer to swelling treatment with a swelling solution, oxidation treatment with an oxidizing agent, and neutralization treatment with a neutralizing solution.

[0264] Examples of the swelling liquid used in the roughening treatment include alkaline solutions and surfactant solutions, preferably alkaline solutions. More preferably, the alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling liquids include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan. The swelling treatment using the swelling liquid can be performed by, for example, immersing the insulating layer in the swelling liquid at a temperature of 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, the insulating layer is preferably immersed in a swelling liquid at 40° C. to 80° C. for 5 to 15 minutes.

[0265] As the oxidizing agent used in the roughening treatment, an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide can be cited. The oxidation treatment based on an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. As commercially available oxidizing agents, alkaline permanganate solutions such as "Concentrate Compact CP (Concentrate Retrieval·Conpack CP)" and "Dosing solution Securiganth P (Dosing Solution Securiganth P)" manufactured by Atotech Japan can be cited.

[0266] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution. Commercially available products include, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan. Neutralization treatment with the neutralizing solution can be performed by immersing the surface treated with an oxidizing agent in the neutralizing solution at a temperature of 30°C to 80°C for 5 to 30 minutes. From the perspective of workability, immersing the surface treated with an oxidizing agent in the neutralizing solution at a temperature of 40°C to 70°C for 5 to 20 minutes is preferred.

[0267] The method for producing a circuit substrate may include step (V) of forming a conductive layer on the insulating layer. When the method for producing a circuit substrate includes step (III) or (IV), step (V) of forming the conductive layer is usually preferably performed after steps (III) and (IV).

[0268] 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 the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloys, copper-nickel alloys and copper-titanium alloys). Among them, from the viewpoints of versatility, cost, ease of patterning, etc. in forming the conductor layer, 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, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy is more preferred, and a single metal layer of copper is even more preferred.

[0269] The conductor layer may have a single-layer structure or a multilayer structure including two or more single metal layers or alloy layers formed of different types of metals or alloys. In the case of a multilayer structure of the 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 a nickel-chromium alloy.

[0270] The thickness of the conductor layer depends on the design of the circuit board, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm.

[0271] The conductor layer can be formed by plating. For example, the surface of the insulating layer can be plated using conventionally known techniques such as a semi-additive process or a fully additive process to form a conductor layer having a desired wiring pattern. From the perspective of manufacturing simplicity, the semi-additive process is preferred. The following illustrates an example of forming a conductor layer using a semi-additive process.

[0272] 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 an electrolytic plating layer is formed on the exposed electroless plating layer by electrolytic plating, the mask pattern is removed. Subsequently, the unnecessary electroless plating layer is removed by etching, forming a conductor layer with the desired wiring pattern.

[0273] As another example, the conductor layer can be formed using metal foil. When a metal foil is used to form the conductor layer, process (V) is suitable for implementation between process (I) and process (II). For example, after process (I), the support is removed and a metal foil is laminated on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil can be implemented by a vacuum lamination method. The lamination conditions can be set to the same conditions as those described for process (I). Then, process (II) is implemented to form an insulating layer. Thereafter, the metal foil on the insulating layer can be utilized and a conductor layer with a desired wiring pattern can be formed by known techniques such as a subtractive method and a modified semi-additive method. The metal foil can be manufactured by known methods such as an electrolytic method and a calendering method. Commercially available products of metal foil include, for example, HLP foil and JXUT-III foil manufactured by JX Metals; 3EC-III foil and TP-III foil manufactured by Mitsui Mining and Smelting Co., Ltd.

[0274] When a conductive layer is formed on an insulating layer, the method for manufacturing a circuit board may include performing an annealing treatment after forming the conductive layer. Annealing can improve the adhesion between the insulating layer and the conductive layer. Annealing can be performed, for example, by heating at 150°C to 210°C for 20 to 180 minutes.

[0275] In the method for manufacturing a circuit substrate, each of the above steps may be performed only once or repeatedly two or more times. For example, steps (I) to (V) may be repeated to form a circuit substrate having a multilayer structure, such as a multilayer printed wiring board having multiple insulating layers and conductive layers.

[0276] The method for manufacturing a circuit substrate may further include an optional step in combination with the above-mentioned steps. For example, the method for manufacturing a circuit substrate may include a step of setting a semiconductor chip in a manner bonded to a conductor layer. To give a specific example, in the case of manufacturing a circuit substrate for a semiconductor chip package having a semiconductor chip, the method for manufacturing a circuit substrate may include a step of setting a semiconductor chip. The semiconductor chip may adopt appropriate conditions that enable the terminal electrodes of the semiconductor chip to be conductively connected to the conductor layer formed on the insulating layer. For example, the conditions used in flip-chip mounting may be adopted. In addition, the semiconductor chip may be bonded with the aid of an insulating adhesive or by reflow soldering. Furthermore, the semiconductor chip may be filled with a mold bottom filling material as needed. In addition, the method for manufacturing a circuit substrate may include, for example, a step of forming a sealing layer, a step of forming a solder resist layer, a step of cutting the manufactured circuit substrate into individual pieces, and the like.

[0277] Examples of the circuit substrate include printed circuit boards and semiconductor chip packages. Examples of the semiconductor chip package include FC-CSP, MIS-BGA packages, ETS-BGA packages, fan-out WLP (Wafer Level Package), fan-in WLP, fan-out PLP (Panel Level Package), and fan-in PLP. In these semiconductor chip packages, the redistribution layer serving as the insulating layer is preferably formed from a cured product obtained by curing the resin composition. The circuit substrate is not limited to the circuit substrates exemplified herein.

[0278] <Semiconductor Device>

[0279] The aforementioned circuit substrate can be used to manufacture a semiconductor device. A semiconductor device includes the aforementioned circuit substrate. Examples of semiconductor devices include various semiconductor devices used in electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical devices, and televisions) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft).

[0280] Example

[0281] Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

[0282] In the following description, "parts" and "%" indicating amounts mean "parts by mass" and "mass %" respectively unless otherwise specified. Furthermore, temperature and pressure conditions unless otherwise specified are room temperature (23° C.) and atmospheric pressure (1 atm).

[0283] In the following description, unless otherwise specified, "Mw" means weight average molecular weight, and "Mn" means number average molecular weight.

[0284] <Synthesis Example 1: Synthesis of Active Ester Resin A-1>

[0285] In a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer, 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 placed and stirred at room temperature while purging with nitrogen. The temperature was then raised to 150°C, and the resulting water was distilled out of the system while stirring for 4 hours. After the reaction was completed, 900 g of methyl isobutyl ketone and 5.4 g of a 20% aqueous sodium hydroxide solution were added for neutralization. The aqueous layer was then removed by separation, and the mixture was washed three times with 280 g of water. The methyl isobutyl ketone was removed under reduced pressure to yield 460 g of a benzyl-modified naphthalene compound (A'). The resulting benzyl-modified naphthalene compound (A') was a black solid with a hydroxyl equivalent weight of 180 g / eq.

[0286] In a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer, 203.0 g of isophthaloyl chloride (number of moles of acyl chloride groups: 2.0 mol) and 1400 g of toluene were added, and the atmosphere in the system was purged with nitrogen under reduced pressure to allow dissolution. Subsequently, 72.4 g (0.67 mol) of o-cresol and 240 g of a benzyl-modified naphthalene compound (A') (number of moles of phenolic hydroxyl groups: 1.33 mol) were added, and the atmosphere in the system was purged with nitrogen under reduced pressure to allow dissolution. Subsequently, 0.70 g of tetrabutylammonium bromide was dissolved, and while purging with nitrogen, the atmosphere in the system was controlled to below 60°C, 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was continued under these conditions for 1.0 hour to allow the reaction to proceed.

[0287] After the reaction was completed, the mixture was allowed to stand for separation, and the aqueous layer was removed. Furthermore, water was added to the toluene layer containing the reactants, stirred and mixed for 15 minutes, and the mixture was allowed to stand for separation, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7. Subsequently, water was removed by decanting to obtain active ester resin A-1 as a toluene solution containing 65% by mass of non-volatile matter. The active ester equivalent weight of the resulting active ester resin A-1 was 238 g / eq.

[0288] <Synthesis Example 2: Synthesis of Active Ester Resin A-2>

[0289] In a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer, 165 g of a dicyclopentadiene-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, and the atmosphere was purged with nitrogen under reduced pressure. Next, 203 g (1.0 mol) of isophthaloyl dichloride was added, and the atmosphere was purged with nitrogen under reduced pressure. 0.6 g of tetrabutylammonium bromide was added, and while nitrogen purging was continued, the atmosphere was controlled to below 60°C. 412 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the addition was complete, the mixture was stirred for 1.0 hour. After the reaction was complete, the mixture was allowed to stand and separate, and the aqueous layer was removed. Water was further added to the resulting toluene layer, and the mixture was stirred for 15 minutes. The aqueous layer was then removed by standing and separating. This procedure was repeated until the pH of the aqueous layer reached 7. Then, the non-volatile content was adjusted to 70% by mass by heat drying to obtain an active ester resin A-2 represented by the following formula.

[0290] [Chemistry 11]

[0291]

[0292] <Synthesis Example 3: Synthesis of Maleimide Resin B>

[0293] According to Synthesis Example 1 of the Invention Association Public Technical Report No. 2020-500211, a MEK solution of maleimide resin B represented by the following formula (d-6) (non-volatile content: 62% by mass) was prepared. The Mw / Mn ratio of maleimide resin B was 1.81, and t″ in formula (d-6) was 1.47 (mainly 1, 2, or 3).

[0294] [Chemistry 12]

[0295]

[0296] <Synthesis Example 4: Synthesis of Vinyl Resin C>

[0297] According to Example 1 of International Publication No. 2017 / 115813, 3.0 mol (390.6 g) of divinylbenzene, 1.8 mol (229.4 g) of ethylvinylbenzene, 10.2 mol (1066.3 g) of styrene and 15.0 mol (1532.0 g) of n-propyl acetate were placed in a 5.0 L reactor, 600 mmol of diethyl ether complex of boron trifluoride was added at 70°C, and the mixture was reacted for 4 hours. The polymerization solution was stopped with an aqueous sodium bicarbonate solution. Thereafter, the oil layer was washed three times with pure water, degased under reduced pressure at 60°C, and the polymer was recovered. The obtained polymer was weighed, and it was confirmed that 896.7 g of vinyl resin C was obtained as the polymer. The weight average molecular weight Mw of vinyl resin C was 41300.

[0298] <Examples 1 to 15 and Comparative Examples 1 to 4>

[0299] (1) Production of resin composition:

[0300] According to the compounding compositions described in Tables 1, 2, and 3 below, the components were weighed and mixed. 10 parts of MEK and 10 parts of cyclohexanone were further added and uniformly dispersed using a high-speed rotary stirrer to obtain a resin composition (resin varnish). It should be noted that the compounding compositions described in Tables 1, 2, and 3 represent the amount (parts by mass) of the non-volatile component. Details of the components described in Tables 1, 2, and 3 are as follows.

[0301] (A) Epoxy resin:

[0302] ZX1059: Epoxy equivalent weight 170 g / eq., manufactured by Nippon Steel Chemical & Material Co., Ltd., a 1:1 mixture of bisphenol A and bisphenol F epoxy resins.

[0303] HP-4032-SS: Epoxy equivalent weight 144 g / eq., manufactured by DIC Corporation, naphthalene-based epoxy resin.

[0304] NC-3000L: Biphenyl-type epoxy resin with an epoxy equivalent weight of 270 g / eq., manufactured by Nippon Kayaku Co., Ltd.

[0305] (B-1) First active ester resin:

[0306] Active ester resin C: an active ester resin having an active ester group equivalent weight of 990 g / eq. and represented by the following formula (b-2): In formula (b-2), a and m each represent a repeating number, specifically a number greater than 0.

[0307] [Chemistry 13]

[0308]

[0309] (B-2) Second active ester resin:

[0310] HPC-8150-62T: a toluene solution having an active ester group equivalent of 230 g / eq. and a non-volatile content of 61.5% by mass, manufactured by DIC Corporation; an active ester resin having a naphthalene structure.

[0311] HPC-8000L-65MT: A toluene / MEK solution with an active ester equivalent of 223 g / eq. and a nonvolatile content of 65% by mass, manufactured by DIC Corporation. This active ester resin contains a dicyclopentadiene-type diphenol structure.

[0312] Active ester resin A-1: an active ester resin synthesized in Synthesis Example 1 having an active ester group equivalent of 238 g / eq.

[0313] Active ester resin A-2: an active ester resin synthesized in Synthesis Example 2 with an active ester group equivalent of 214 g / eq., a toluene solution containing 70% by mass of a nonvolatile component.

[0314] Active ester resin B: a compound having an active ester group equivalent of 250 g / eq. and represented by the following formula (b-3).

[0315] [Chemistry 14]

[0316]

[0317] (C) Inorganic filling materials:

[0318] SO-C2: Spherical silica surface-treated with an amino-based silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), with an average particle size of 0.5 μm and a specific surface area of 5.8 m 2 / g, manufactured by ADMATECHS.

[0319] (D) Radical polymerizable resin:

[0320] Maleimide resin B: maleimide resin B synthesized in Synthesis Example 3.

[0321] MIR-3000-70MT: a toluene-MEK solution containing 70% by mass of nonvolatile matter, manufactured by Nippon Kayaku Co., Ltd., a maleimide resin having a structure represented by the following formula (d-7) (in formula (d-7), n represents 1 to 100).

[0322] [Chemistry 15]

[0323]

[0324] SLK-6895: manufactured by Shin-Etsu Chemical Co., Ltd., an aliphatic maleimide resin.

[0325] SLK-1500: manufactured by Shin-Etsu Chemical Co., Ltd., an aliphatic maleimide resin.

[0326] OPE-2St-1200: A toluene solution containing 65% by mass of nonvolatile matter, manufactured by Mitsubishi Gas Chemical Co., Ltd., a styrene-based radical polymerizable resin having a polyphenylene ether skeleton.

[0327] Vinyl resin C: Resin C synthesized in Synthesis Example 4.

[0328] (E) Optional Curing Agent:

[0329] LA-3018-50P: a phenolic resin having a phenolic hydroxyl group equivalent of 151 g / eq. and a nonvolatile content of 50% by mass in 1-methoxy-2-propanol solution, manufactured by DIC Corporation.

[0330] (D) Organic filling materials:

[0331] EXL-2655: Made by Dow Chemical, an organic filler containing rubber.

[0332] (H) Curing accelerator

[0333] 1B2PZ: manufactured by Shikoku Chemical Industry Co., Ltd., an imidazole-based curing accelerator.

[0334] (2) Manufacture of resin sheets:

[0335] A polyethylene terephthalate film ("AL5" manufactured by LINTEC, 38 μm thick) with a release layer was prepared as a support. The resulting resin composition was evenly applied onto the release layer of the support so that the thickness of the resin composition layer after drying was 40 μm. The resin composition was then dried at 80°C to 100°C (90°C on average) for 4 minutes to obtain a resin sheet A having a layer structure of resin composition layer / support.

[0336] Furthermore, a resin sheet B was produced by the same production method as that of the resin sheet A, except that the coating thickness of the resin composition was changed so that the thickness of the resin composition layer after drying would be 25 μm.

[0337] <Test 1. Dielectric Loss Tangent Measurement Test>

[0338] 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 product of the resin composition layer. This cured product was cut into pieces 80 mm long and 2 mm wide to obtain a cured product sample for dielectric loss tangent measurement.

[0339] The dielectric loss tangent Df of the cured product sample was measured using a measuring device ("HP8362B" manufactured by Agilent Technologies) by the split cylinder method at a measuring frequency of 10 GHz and a measuring temperature of 90° C. The measurement was performed using two test pieces, and the average was calculated.

[0340] <Test 2. Measurement of Coefficient of Thermal Expansion (CTE)>

[0341] The resin sheet A was cured in an oven at 190 °C for 90 minutes, and then the support was peeled off to obtain a cured film. The cured film was cut into pieces 20 mm long and 6 mm wide to obtain cured sample for measuring the linear thermal expansion coefficient. For this cured sample, using a TMA device (thermomechanical analyzer, manufactured by Rigaku Corporation), the average linear thermal expansion coefficient (CTE) was measured from 25 °C to 250 °C at a heating rate of 5 °C / min. The same test piece was measured twice, and the value of the second measurement was recorded.

[0342] <Test 3. Evaluation test for dirt removal property>

[0343] (1) Preparation of inner layer substrate:

[0344] For both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness: 18 μm, substrate thickness: 0.4 mm, "R1515A" manufactured by Panasonic Corporation) with inner layer circuits formed thereon, 1 μm etching was carried out using a micro-etchant ("CZ8101" manufactured by Meck Corporation) to roughen the copper surface, and an inner layer substrate was obtained.

[0345] (2) Lamination of resin sheet A:

[0346] Using an intermittent vacuum pressure laminator (two-stage laminator "CVP700" manufactured by Nikko Materials Company), the resin sheet A was laminated on both sides of the inner layer substrate in such a manner that the resin composition layer was in contact with the inner layer substrate. The lamination was carried out by reducing the pressure for 30 seconds and adjusting the air pressure to 13 hPa or less, and then pressing it at 120 °C and a pressure of 0.74 MPa for 30 seconds. Then, it was hot-pressed at 100 °C and a pressure of 0.5 MPa for 60 seconds to smooth the resin composition layer.

[0347] (3) Thermal curing of resin composition layer:

[0348] Thereafter, the inner layer substrate laminated with the resin sheet A was put into an oven at 130 °C and heated for 30 minutes, and then transferred to an oven at 170 °C and heated for 30 minutes to thermally cure the resin composition layer and form an insulating layer. Thereafter, the support was peeled off to obtain a cured substrate having a structure of insulating layer / inner layer substrate / insulating layer.

[0349] (4) Formation of through holes:

[0350] The insulating layer of the resulting cured substrate was subjected to drilling using a CO2 laser processing machine ("LK-2K212 / 2C" manufactured by Viamerics) at a frequency of 2000 Hz, a pulse width of 3 μs, an output of 0.95 W, and a shot count of 3 to form through-holes. The resulting through-holes had an opening diameter (diameter, top diameter) of 50 μm on the surface of the insulating layer and a diameter (bottom diameter) of 50 μm on the bottom surface of the insulating layer.

[0351] (5) Roughening treatment:

[0352] The insulating layer of the cured substrate in which the through-holes were formed was subjected to a desmear treatment as a roughening treatment. As the desmear treatment, the following wet desmear treatment was performed.

[0353] (Wet decontamination treatment)

[0354] The cured substrate was immersed in a swelling solution ("Swelling DipSecuriganth P" manufactured by Atotech Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 10 minutes. Next, the cured substrate was immersed in an oxidizing solution ("Concentrate CompactP" manufactured by Atotech Japan, an aqueous solution with a potassium permanganate concentration of approximately 6% and a sodium hydroxide concentration of approximately 4%) at 80°C for 25 minutes. Finally, the cured substrate was immersed in a neutralizing solution ("Reduction solution Securiganth P" manufactured by Atotech Japan, an aqueous solution of sulfuric acid) at 40°C for 5 minutes. Thereafter, the cured substrate was dried at 80°C for 15 minutes. Hereinafter, the cured substrate after this decontamination treatment is sometimes referred to as "evaluation substrate A".

[0355] (6) Evaluation of dirt removal performance:

[0356] The area around the bottom of the through-holes of evaluation substrate A was observed using a scanning electron microscope (SEM). Based on the resulting image, the length of the longest stain (resin residue) extending from the wall surface of the through-hole bottom was measured (maximum stain length) and evaluated according to the following criteria.

[0357] “Good”: The maximum dirt length is less than 5 μm.

[0358] "Not good": The maximum dirt length is 5 μm or more.

[0359] <Test 4. Evaluation Test of Crack Resistance after Decontamination Treatment>

[0360] (1) Preparation of inner substrate:

[0361] As the inner layer substrate, a core material ("E705GR" manufactured by RESONAC, thickness 400 μm) was prepared in which circular copper pads with a diameter of 350 μm (copper thickness 35 μm) were arranged in a lattice pattern at intervals of 400 μm so that the residual copper ratio was 60%.

[0362] (2) Lamination of resin sheet B:

[0363] Using a batch vacuum press laminator (Nikko Materials, two-stage laminator "CVP700"), resin sheet B was laminated onto both surfaces of the inner substrate, with the resin composition layer in contact with the inner substrate. Lamination was performed by reducing the pressure for 30 seconds to adjust it to 13 hPa or less, followed by press-bonding at 100°C and a pressure of 0.74 MPa for 30 seconds. Subsequently, heat pressing was performed at 100°C and a pressure of 0.5 MPa for 60 seconds to smooth the resin composition layer.

[0364] (3) Thermal curing of the resin composition layer:

[0365] The inner layer substrate, laminated with resin sheet B, was then placed in a 130°C oven and heated for 30 minutes. The resin composition layer was then thermally cured in a 175°C oven and heated for 40 minutes to form an insulating layer. The support was then peeled off, yielding a cured substrate having a structure of insulating layer / inner layer substrate / insulating layer.

[0366] (4) Decontamination treatment:

[0367] The obtained cured substrate was immersed in a swelling solution ("Swelling DipSecuriganth P" manufactured by Atotech Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 10 minutes. Next, the cured substrate was immersed in an oxidizing solution ("Concentrate Compact P" manufactured by Atotech Japan, an aqueous solution with a potassium permanganate concentration of approximately 6% and a sodium hydroxide concentration of approximately 4%) at 80°C for 30 minutes. Finally, the cured substrate was immersed in a neutralizing solution ("Reduction solution Securiganth P" manufactured by Atotech Japan, an aqueous solution of sulfuric acid) at 40°C for 5 minutes. Thereafter, the cured substrate was dried at 80°C for 15 minutes. Hereinafter, the cured substrate after this decontamination treatment is sometimes referred to as "evaluation substrate B".

[0368] (5) Evaluation of crack resistance:

[0369] For the evaluation substrate B, 100 copper pads were observed to confirm the presence or absence of cracks in the insulating layer, and the crack resistance was evaluated according to the following criteria.

[0370] “Good”: The number of cracks is 10 or less.

[0371] “Bad”: More than 10 cracks.

[0372] <Results>

[0373] The results of the above examples and comparative examples are shown in Tables 1 to 3 below. In the following tables, "Amount of component (A)", "Amount of component (B-1)", and "Amount of component (B-2)" represent values relative to 100% by mass of the resin component in the resin composition. Furthermore, "Amount of component (C)" represents values relative to 100% by mass of the non-volatile component in the resin composition. Furthermore, the values in the "Stain Removability" column represent the maximum stain length. Furthermore, the values in the "Crack Resistance" column represent the number of cracks.

[0374] [Table 1]

[0375] [Results of Examples 1 to 7]

[0376]

[0377] [Table 2]

[0378] [Results of Examples 8 to 15]

[0379]

[0380] [Table 3]

[0381] [Results of Comparative Examples 1 to 4]

Claims

1. A resin composition comprising: (A) an epoxy resin, (B-1) an active ester resin containing a butadiene skeleton, and (B-2) an active ester resin not containing a butadiene skeleton.

2. The resin composition according to claim 1, wherein (A) The epoxy resin contains one or more types selected from epoxy resins containing a naphthalene skeleton and epoxy resins containing a biphenyl skeleton.

3. The resin composition according to claim 1, wherein (B-1) The active ester resin containing a butadiene skeleton comprises a structure represented by the following formula (B1), [Chemistry 1] In formula (B1), R b Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, and * represents a bonding site. The resin composition according to claim 1 , comprising (C) an inorganic filler.

5. The resin composition according to claim 4, wherein (C) The amount of the inorganic filler is 50% by mass or more relative to 100% by mass of the non-volatile component of the resin composition. The resin composition according to claim 1 , comprising (D) a radical polymerizable resin.

7. The resin composition according to claim 6, wherein (D) The radical polymerizable resin includes a maleimide resin.

8. A resin sheet comprising a support and a resin composition layer provided on the support. The resin composition layer contains the resin composition according to any one of claims 1 to 7. 9 . A cured product, which is a cured product of the resin composition according to claim 1 . 10 . A circuit board comprising a cured product of the resin composition according to claim 1 .

11. A semiconductor device comprising the circuit substrate according to claim 10.

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