Resin composition, resin film, prepreg, laminate, printed wiring board, and semiconductor package

Abstract

To provide a resin composition excellent in low thermal expansion, and to provide a resin film, a prepreg, a laminate, a printed wiring board, and a semiconductor package using the resin composition.SOLUTION: The resin composition contains a maleimide compound (A) and a polyphenylene ether derivative (B) having an ethylenically unsaturated bond-containing group. The component (A) contains: a resin (A1) containing a structure derived from a maleimide resin (ai) having one or more N-substituted maleimide groups and a structure derived from an amine compound (aii) having one or more amino groups; and a maleimide resin (A2) having three or more N-substituted maleimide groups.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a resin composition, a resin film, a prepreg, a laminate, a printed wiring board, and a semiconductor package.

Background Art

[0002] In mobile communication devices typified by mobile phones, network infrastructure devices such as their base station apparatuses, servers, and routers, and large computers, the speed and capacity of signals used are increasing year by year. Along with this, printed wiring boards mounted on these electronic devices need to support higher frequencies, and there is a demand for substrate materials having low dielectric constant and low dielectric tangent (hereinafter, these may be collectively referred to as "high-frequency characteristics") in a high-frequency band (for example, 10 GHz or higher) that enables reduction of transmission loss. In recent years, as applications that handle such high-frequency signals, in addition to the above-described electronic devices, implementation plans and practical applications of new systems that handle high-frequency wireless signals are also progressing in the field of ITS (Intelligent Transport Systems; advanced road traffic systems) and the field of short-range communication indoors. Therefore, in the future, it is expected that low transmission loss substrate materials will also be required for printed wiring boards mounted on these devices.

[0003] Under such circumstances, as a problem of providing a resin composition having particularly good compatibility and having high-frequency characteristics, high adhesiveness to a conductor, excellent heat resistance, high glass transition temperature, low thermal expansion, and high flame retardancy, a resin composition containing a specific polyphenylene ether derivative, a specific thermosetting resin, and a styrene-based thermoplastic elastomer (see Patent Document 1) has been proposed.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] By the way, even in a low transmission loss substrate material, by improving the low thermal expansion property, warpage of a printed wiring board and a semiconductor package can be suppressed. As a means for reducing the thermal expansion property, high filling of an inorganic filler such as silica into the substrate material is known. However, when the inorganic filler is highly filled, problems such as deterioration of various properties such as insulation reliability and adhesiveness to copper foil tend to occur. Therefore, other technological developments for reducing the thermal expansion are expected.

[0006] In view of such a situation, an object of the present disclosure is to provide a resin composition having excellent low thermal expansion property, and to provide a resin film, a prepreg, a laminate, a printed wiring board, and a semiconductor package using the resin composition.

Means for Solving the Problems

[0007] As a result of intensive studies, the present inventors have found that the resin composition of the present disclosure can achieve the above object. The present disclosure includes the following embodiments [1] to

[18] . [1] A resin composition containing a maleimide compound (A) and a polyphenylene ether derivative (B) having an ethylenically unsaturated bond-containing group, wherein the component (A) includes a resin (A1) including a structure derived from a maleimide resin (ai) having one or more N-substituted maleimide groups and a structure derived from an amine compound (aii) having one or more amino groups, and a maleimide resin (A2) having three or more N-substituted maleimide groups. [2] The resin composition according to [1] above, wherein in the component (A1), the maleimide resin (ai) having one or more N-substituted maleimide groups is a bismaleimide resin having two N-substituted maleimide groups or a polymaleimide resin having three or more N-substituted maleimide groups. [3] In the component (A1), the resin composition according to [1] or [2] above, wherein the amine compound (aii) having at least one amino group contains a siloxane compound having at least one amino group. [4] The resin composition according to any one of [1] to [3] above, wherein the component (A2) is a maleimide resin having three or more N-substituted maleimide groups bonded to an aromatic ring. [5] The resin composition according to any one of [1] to [4] above, wherein the component (A2) is a maleimide resin represented by the following general formula (A2-1). [Chemical formula] (In the formula, X A1 is a divalent hydrocarbon group having 1 to 20 carbon atoms, and n A1 is an integer of 2 to 5.) [6] The resin composition according to any one of [1] to [5] above, wherein the content ratio [(A1) / (A2)] (mass ratio) of the component (A1) and the component (A2) is 10 / 90 to 90 / 10. [7] The resin composition according to any one of [1] to [6] above, wherein the component (B) is a polyphenylene ether derivative having an ethylenically unsaturated bond-containing group at the terminal. [8] The resin composition according to any one of [1] to [7] above, wherein in the component (B), the ethylenically unsaturated bond-containing group is an unsaturated aliphatic hydrocarbon group or a group containing a hetero atom and the unsaturated hydrocarbon group. [9] The resin composition according to any one of [1] to [8] above, further containing an inorganic filler (C).

[10] The resin composition according to any one of [1] to [9] above, further containing an elastomer (D).

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

[10] above, further containing a curing accelerator (E).

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

[11] above, further containing a flame retardant (F).

[13] The resin composition according to

[12] above, wherein the flame retardant (F) contains a phosphazene compound.

[14] A resin film containing the resin composition according to any one of [1] to

[13] above or a semi-cured product of the resin composition.

[15] A prepreg containing the resin composition according to any one of [1] to

[13] above or a semi-cured product of the resin composition.

[16] A laminate having a cured product of the resin composition according to any one of [1] to

[13] above and a metal foil.

[17] A printed wiring board having a cured product of the resin composition according to any one of [1] to

[13] above.

[18] A semiconductor package having the printed wiring board according to

[17] above and a semiconductor element. [Effect of the Invention]

[0008] According to the present disclosure, it is possible to provide a resin composition excellent in low thermal expansibility, and to provide a resin film, a prepreg, a laminate, a printed wiring board, and a semiconductor package using the resin composition. [Embodiments for Carrying Out the Invention]

[0009] In the numerical ranges described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. Further, the lower limit value and the upper limit value of the numerical range can be arbitrarily combined with the lower limit value or the upper limit value of other numerical ranges, respectively. In the notation of the numerical range "AA to BB", both numerical values AA and BB at both ends are included in the numerical range as the lower limit value and the upper limit value, respectively. In the present disclosure, for example, the description "10 or more" means 10 and numerical values exceeding 10, and the same applies when the numerical values are different. Further, for example, the description "10 or less" means 10 and numerical values less than 10, and the same applies when the numerical values are different. Also, each component and material exemplified in the present disclosure may be used alone or in combination of two or more, unless otherwise specified. In the present disclosure, the content of each component in the resin composition means the total amount of the plurality of substances present in the resin composition corresponding to each component in the resin composition, unless otherwise specified when there are a plurality of substances corresponding to each component in the resin composition.

[0010] In the present disclosure, the "resin component" refers to all components among the solid components constituting the resin composition, excluding inorganic compounds such as inorganic fillers described later. In the present disclosure, the "solid content" means components other than the solvent, and components that are liquid at 25°C are also regarded as solid content. The expression "containing XX" described in the present disclosure may contain XX in a reacted state if XX can react, may simply contain XX as it is, or may include both of these modes. In the present disclosure, low dielectric constant and low dielectric loss tangent at 10 GHz or higher are referred to as high-frequency characteristics. Aspects in which the matters described in the present disclosure are arbitrarily combined are also included in the present disclosure and the present embodiment.

[0011] [Resin composition] The resin composition of the present embodiment is a resin composition containing a maleimide compound (A) and a polyphenylene ether derivative (B) having an ethylenically unsaturated bond-containing group, wherein the component (A) includes a structure derived from a maleimide resin (ai) having one or more N-substituted maleimide groups and a structure derived from an amine compound (aii) having one or more amino groups, [hereinafter, may be referred to as "modified maleimide resin (A1)".] and a maleimide resin (A2) having three or more N-substituted maleimide groups [hereinafter, may be referred to as "polymaleimide resin (A2)"], and is a resin composition. Hereinafter, the components that the resin composition of the present embodiment may contain will be described.

[0012] [Maleimide compound (A)] The maleimide compound (A) includes the modified maleimide resin (A1) and the polymaleimide resin (A2). Hereinafter, the modified maleimide resin (A1) and the polymaleimide resin (A2) will be described in detail in order.

[0013] [Modified maleimide resin (A1)] The modified maleimide resin (A1) is not particularly limited as long as it is a resin containing a structure derived from a maleimide resin (ai) having one or more N-substituted maleimide groups and a structure derived from an amine compound (aii) having one or more amino groups. The modified maleimide resin (A1) may be used alone or in combination of two or more.

[0014] In the following description, the maleimide resin (ai) having one or more N-substituted maleimide groups may be abbreviated as "maleimide resin (ai)". Also, in the following description, the amine compound (aii) having one or more amino groups may be abbreviated as "amine compound (aii)".

[0015] Here, the structure derived from the maleimide resin (ai) is a structure formed by Michael addition reaction of at least one N-substituted maleimide group among the N-substituted maleimide groups possessed by the maleimide resin (ai) with the amino group possessed by the amine compound (aii) (however, it does not contain an amino group) (see below).

Chemical formula

[0016] Also, the structure derived from the amine compound (aii) is a structure formed by Michael addition reaction of at least one amino group possessed by the amine compound (aii) with the N-substituted maleimide group possessed by the maleimide resin (ai) (however, it does not contain a maleimide group) (see below).

Chemical formula

[0017] 〔Maleimide resin (ai)〕 The maleimide resin (ai) is not particularly limited as long as it is a maleimide resin having one or more N-substituted maleimide groups. The maleimide resin (ai) is preferably a bismaleimide resin having two N-substituted maleimide groups or a polymaleimide resin having three or more N-substituted maleimide groups from the viewpoints of low thermal expansion, conductor adhesiveness, and heat resistance, and more preferably a bismaleimide resin having two N-substituted maleimide groups. The bismaleimide resin having two N-substituted maleimide groups is preferably an aromatic bismaleimide resin having two N-substituted maleimide groups bonded to an aromatic ring. Further, the polymaleimide resin having three or more N-substituted maleimide groups is more preferably an aromatic polymaleimide resin having three or more N-substituted maleimide groups bonded to an aromatic ring.

[0018] In the maleimide resin (ai), it is preferable that the nitrogen atoms of the N-substituted maleimide groups are bonded to each other via an organic group containing an aromatic ring, and it is more preferably a maleimide resin represented by the following general formula (a1-1). [Chemical formula] (In the formula, X a11 is a divalent organic group.)

[0019] In the general formula (a1-1), X a11 is a divalent organic group. In the general formula (a1-1), the divalent organic group represented by X a11 includes a divalent group represented by the following general formula (a1-2), a divalent group represented by the following general formula (a1-3), a divalent group represented by the following general formula (a1-4), and the like.

[0020] [Chemical formula] (In the formula, R a11 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. n a11 is an integer of 0 to 4. * represents a bonding site.)

[0021] In the general formula (a1-2), R a11The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by includes alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, etc.; alkenyl groups having 2 to 5 carbon atoms; alkynyl groups having 2 to 5 carbon atoms, and the like. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. As the aliphatic hydrocarbon group having 1 to 5 carbon atoms, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is even more preferable. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, iodine atom, etc. n in the general formula (a1-2) a11 is an integer of 0 to 4, and from the viewpoint of easy availability, it is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. n a11 When it is an integer of 2 or more, a plurality of Rs a11 may be the same or different from each other.

[0022]

Chemical formula

[0023] R in the general formula (a1-3) a12 and R a13Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by include alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, etc.; alkenyl groups having 2 to 5 carbon atoms; alkynyl groups having 2 to 5 carbon atoms, etc. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. As the aliphatic hydrocarbon group having 1 to 5 carbon atoms, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and methyl group and ethyl group are even more preferable. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, iodine atom, etc.

[0024] X in the general formula (a1-3) a12 Examples of the alkylene group having 1 to 5 carbon atoms represented by include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group, etc. As the alkylene group having 1 to 5 carbon atoms, an alkylene group having 1 to 3 carbon atoms is preferable, an alkylene group having 1 or 2 carbon atoms is more preferable, and methylene group is even more preferable.

[0025] X in the general formula (a1-3) a12 Examples of the alkylidene group having 2 to 5 carbon atoms represented by include ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group, etc. Among these, an alkylidene group having 2 to 4 carbon atoms is preferable, an alkylidene group having 2 or 3 carbon atoms is more preferable, and isopropylidene group is even more preferable.

[0026] n in the general formula (a1-3) a12 and n a13 are each independently an integer of 0 to 4. n a12 or n a13 When is an integer of 2 or more, a plurality of R a12 each other or a plurality of R a13 each other may be the same or different from each other.

[0027] X in the general formula (a1-3) a12 The divalent group represented by the general formula (a1-3-1) represented by is as follows.

Chemical formula

[0028] R in the general formula (a1-3-1) a14 and R a15 Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by include alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, etc.; alkenyl groups having 2 to 5 carbon atoms; alkynyl groups having 2 to 5 carbon atoms, etc. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. As the aliphatic hydrocarbon group having 1 to 5 carbon atoms, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is even more preferable. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, iodine atom, etc.

[0029] X in the general formula (a1-3-1) a13 Examples of the alkylene group having 1 to 5 carbon atoms represented by include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group, etc. As the alkylene group having 1 to 5 carbon atoms, an alkylene group having 1 to 3 carbon atoms is preferable, an alkylene group having 1 or 2 carbon atoms is more preferable, and a methylene group is even more preferable.

[0030] X in the general formula (a1-3-1) a13 Examples of the alkylidene group having 2 to 5 carbon atoms represented by X include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, an isopentylidene group, and the like. Among these, an alkylidene group having 2 to 4 carbon atoms is preferable, an alkylidene group having 2 or 3 carbon atoms is more preferable, and an isopropylidene group is even more preferable.

[0031] X in the general formula (a1-3-1) a13 Among the above options, an alkylidene group having 2 to 5 carbon atoms is preferable, an alkylidene group having 2 to 4 carbon atoms is more preferable, and an isopropylidene group is even more preferable.

[0032] n in the general formula (a1-3-1) a14 and n a15 are each independently an integer of 0 to 4. From the viewpoint of easy availability, both are preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. n a14 or n a15 When is an integer of 2 or more, a plurality of R a14 each other or a plurality of R a15 each other may be the same or different.

[0033] X in the general formula (a1-3) a12 Among the above options, an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, and a divalent group represented by the general formula (a1-3-1) are preferable, and a divalent group represented by the general formula (a1-3-1) is more preferable.

[0034]

Chemical formula

[0035] R in the general formula (a1-4) a16 and R a17 The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by includes alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group; alkenyl groups having 2 to 5 carbon atoms; alkynyl groups having 2 to 5 carbon atoms and the like. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. n in the general formula (a1-4) a16 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 1. When n a16 is an integer of 2 or more, a plurality of R a16 each other or a plurality of R a17 each other may be the same or different from each other.

[0036] Among the maleimide resins represented by the above general formula (a1-1), as X a11 a maleimide resin having a divalent group represented by the general formula (a1-3) is preferred, and as X a12 in the general formula (a1-3), a maleimide resin having a divalent group represented by the general formula (a1-3-1) is more preferred.

[0037] Examples of bismaleimide resins include N,N'-ethylenebismaleimide, N,N'-hexamethylenebismaleimide, N,N'-(1,3-phenylene)bismaleimide, N,N'-[1,3-(2-methylphenylene)]bismaleimide, N,N'-[1,3-(4-methylphenylene)]bismaleimide, N,N'-(1,4-phenylene)bismaleimide, bis(4-maleimidophenyl)methane, bis(3-methyl-4-maleimidophenyl)methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)sulfone, bis(4-maleimidophenyl)sulfide, bis(4-maleimidophenyl)ketone, bis(4-maleimidocyclohexyl)methane, 1,4-bis(4-maleimidophenyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 1,3-bis(3-maleimidophenoxy)benzene, bis[4-(3-maleimidophenoxy)phenyl]methane, bis[4-(4-maleimidophenoxy)phenyl]methane, 1,1-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,1-bis[4-(4-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(4-maleimidophenoxy)phenyl]ethane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 4,4-bis(3-maleimidophenoxy)biphenyl, 4,4-bis(4-maleimidophenoxy)biphenyl, bis[4-(3-maleimidophenoxy)phenyl]ketone, bis[4-(4-maleimidophenoxy)phenyl]ketone, bis(4-maleimidophenyl)disulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfide, bis[4-(4-maleimidophenoxy)phenyl]sulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfoxide, bis[4-(4-maleimidophenoxy)phenyl]sulfoxide, bis[4-(3-maleimidophenoxy)phenyl]sulfone, bis[4-(4-maleimidophenoxy)phenyl]sulfone, bis[4-(3-maleimidophenoxy)phenyl]ether, bis[4-(4-maleimidophenoxy)phenyl]ether, 1,4-bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, aromatic bismaleimides having an indane skeleton, and the like can be mentioned. Among these, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, and bis(4-maleimidophenyl)methane are preferable.,

[0038] In addition, the description regarding the above-mentioned "polymaleimide resin having 3 or more N-substituted maleimide groups", which was given as a preferable embodiment of the maleimide resin (ai), is the same as the description of the "polymaleimide resin (A2)" described later, and the preferable embodiments are also the same.

[0039] The structure derived from the maleimide resin (ai) contained in the modified maleimide resin (A1) may be one kind or two or more kinds.

[0040] (Content of the structure derived from the maleimide resin (ai)) The content of the structure derived from the maleimide resin (ai) in the modified maleimide resin (A1) is not particularly limited, but is preferably 20 to 95% by mass, more preferably 40 to 95% by mass, and still more preferably 60 to 90% by mass. When the content of the structure derived from the maleimide resin (ai) in the modified maleimide resin (A1) is within the above range, the heat resistance, high-frequency characteristics, and handleability when formed into a resin film tend to be better.

[0041] [Amine compound (aii)] The amine compound (aii) is not particularly limited as long as it is an amine compound having one or more amino groups. The amine compound (aii) preferably has two or more amino groups, and more preferably a diamine compound having two amino groups.

[0042] In particular, from the viewpoint of low thermal expansion, the amine compound (aii) preferably contains a siloxane compound having one or more amino groups, more preferably contains a siloxane compound having two or more amino groups, still more preferably contains a siloxane compound having two amino groups, and particularly preferably contains a siloxane compound having two primary amino groups. Further, an embodiment in which the amine compound (aii) contains a siloxane compound having one or more amino groups and an amine compound having no siloxane skeleton is also preferable.

[0043] When the amine compound (aii) contains a siloxane compound having one or more amino groups, the content of the siloxane compound having one or more amino groups is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, particularly preferably 50% by mass or more, based on the amine compound (aii). The upper limit may be 100% by mass, or may be 80% by mass or less, or may be 70% by mass or less, or may be 65% by mass or less. When the amine compound (aii) contains a siloxane compound having two or more amino groups, the content of the siloxane compound having two or more amino groups is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, particularly preferably 50% by mass or more, based on the amine compound (aii). The upper limit may be 100% by mass, or may be 80% by mass or less, or may be 70% by mass or less, or may be 65% by mass or less.

[0044] The amino group(s) possessed by the amine compound (aii) is preferably a primary amino group. As the amine compound (aii), a diamine compound represented by the following general formula (a2-1) is preferable, and a mode in which two or more diamine compounds represented by the following general formula (a2-1) are used in combination is also preferable.

[0045]

Chemical formula

[0046] X in the general formula (a2-1) a21 is preferably a divalent group represented by the following general formula (a2-2).

[0047]

Chemical formula

[0048]

Chemical formula

[0049]

Chemical formula

[0050] In the general formula (a2-2), the general formula (a2-2-1) and the general formula (a2-2-2), R a21, R a22 , R a23 , R a24 and R a25 Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R include alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group; alkenyl groups having 2 to 5 carbon atoms; alkynyl groups having 2 to 5 carbon atoms and the like. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. As the aliphatic hydrocarbon group having 1 to 5 carbon atoms, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group and an ethyl group are even more preferable. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

[0051] X in the general formula (a2-2) a22 , X in the general formula (a2-2-1) a23 and X in the general formula (a2-2-2) a24 and X a25 Examples of the alkylene group having 1 to 5 carbon atoms represented by include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group and the like. As the alkylene group having 1 to 5 carbon atoms, an alkylene group having 1 to 3 carbon atoms is preferable, an alkylene group having 1 or 2 carbon atoms is more preferable, and a methylene group is even more preferable.

[0052] X in the general formula (a2-2) a22 , X in the general formula (a2-2-1) a23 , and X in the general formula (a2-2-2) a24 and X a25 Examples of the alkylidene group having 2 to 5 carbon atoms represented by include ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group and the like. As the alkylidene group having 2 to 5 carbon atoms, an alkylidene group having 2 to 4 carbon atoms is preferable, an alkylidene group having 2 or 3 carbon atoms is more preferable, and an isopropylidene group is even more preferable.

[0053] n in the general formula (a2-2) a21 and n a22 are each independently an integer from 0 to 4, and from the viewpoint of availability, both are preferably integers from 0 to 3, more preferably integers from 0 to 2, and still more preferably 0 or 2. n a21 or n a22 when it is an integer of 2 or more, a plurality of Rs a21 among themselves or a plurality of Rs a22 among themselves may be the same or different from each other.

[0054] n in the general formula (a2-2-1) a23 and n a24 are each independently an integer from 0 to 4, and from the viewpoint of availability, both are preferably integers from 0 to 2, more preferably 0 or 1, and still more preferably 0. n a23 or n a24 when it is an integer of 2 or more, a plurality of Rs a23 among themselves or a plurality of Rs a24 among themselves may be the same or different from each other.

[0055] n in the general formula (a2-2-2) a25 is an integer from 0 to 4, and from the viewpoint of availability, it is preferably an integer from 0 to 2, more preferably 0 or 1, and still more preferably 0. n a25 when it is an integer of 2 or more, a plurality of Rs a25 among themselves may be the same or different from each other.

[0056] In addition, X in the general formula (a2-1) a21 may be a divalent group containing a structure represented by the following general formula (a2-3), or may be a divalent group represented by the following general formula (a2-4). In particular, X in the general formula (a2-1) a21 when it is a diamine compound in which X is a divalent group represented by the general formula (a2-2), and X in the general formula (a2-1) a21A mode of using in combination with a diamine compound which is a divalent group represented by the following general formula (a2-3) or the following general formula (a2-4) is also preferable.

[0057]

Chemical formula

[0058]

Chemical formula

[0059] Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R a26 to R a29 in the general formulas (a2-3) and (a2-4) include alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, etc.; alkenyl groups having 2 to 5 carbon atoms; alkynyl groups having 2 to 5 carbon atoms, etc. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. As the aliphatic hydrocarbon group having 1 to 5 carbon atoms, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is even more preferable. R a26 to R a29Examples of the substituent of the phenyl group in the substituted phenyl group represented by include the above-mentioned aliphatic hydrocarbon groups having 1 to 5 carbon atoms.

[0060] X a26 and X a27 Examples of the divalent organic group represented by include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, or a divalent linking group formed by combining these. Examples of the alkylene group include alkylene groups having 1 to 10 carbon atoms such as a methylene group, an ethylene group, and a propylene group. Examples of the alkenylene group include alkenylene groups having 2 to 10 carbon atoms. Examples of the alkynylene group include alkynylene groups having 2 to 10 carbon atoms. Examples of the arylene group include arylene groups having 6 to 20 carbon atoms such as a phenylene group and a naphthylene group. Among these, X a26 and X a27 are preferably an alkylene group or an arylene group, and more preferably an alkylene group.

[0061] n a26 is an integer of 2 to 100, preferably an integer of 2 to 50, more preferably an integer of 3 to 40, and even more preferably an integer of 5 to 30. n a26 When n is an integer of 2 or more, a plurality of R a26 each other or a plurality of R a27 each other may be the same or different.

[0062] Examples of the amine compound (aii) include 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,3-bis[1-[4-(4-aminophenoxy)phenyl]-1-methylethyl]benzene, 1,4-bis[1-[4-(4-aminophenoxy)phenyl]-1-methylethyl]benzene, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline, 3,3'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 9,9-bis(4-aminophenyl)fluorene and other aromatic diamine compounds; X in the general formula (a2-1) a21 is a divalent group containing a structure represented by the general formula (a2-3), and examples of the diamine compound include a siloxane compound having two amino groups, such as a diamine compound in which X in the general formula (a2-1) a21 is a divalent group represented by the general formula (a2-4). In the present disclosure, the "aromatic diamine compound" means a compound having two amino groups directly bonded to an aromatic ring.

[0063] As the siloxane compound having two primary amino groups, a siloxane compound having primary amino groups at both ends is preferred. The primary amino group equivalent of the siloxane compound having two primary amino groups is not particularly limited, but is preferably 300 to 2,000 g / mol, more preferably 400 to 1,500 g / mol, and still more preferably 500 to 1,000 g / mol.

[0064] (Content of the structure derived from the amine compound (aii)) The content of the structure derived from the amine compound (aii) in the modified maleimide resin (A1) is not particularly limited, but is preferably 5 to 80% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 40% by mass. When the content of the structure derived from the amine compound (aii) in the modified maleimide resin (A1) is within the above range, the high-frequency characteristics, heat resistance, flame retardancy, and glass transition temperature tend to be better.

[0065] The equivalent ratio (Taii / Tai) of the total equivalent (Taii) of the groups derived from the amino groups of the amine compound (aii) and the total equivalent (Tai) of the groups derived from the N-substituted maleimide groups of the maleimide resin (ai) in the modified maleimide resin (A1) is not particularly limited, but from the viewpoints of high-frequency characteristics, heat resistance, flame retardancy, and glass transition temperature, it is preferably 0.05 to 10, more preferably 1 to 8, and still more preferably 3 to 7.

[0066] (Method for producing the modified maleimide resin (A1)) The modified maleimide resin (A1) can be produced, for example, by reacting the maleimide resin (ai) and the amine compound (aii) in an organic solvent. By reacting the maleimide resin (ai) and the amine compound (aii), the maleimide resin (ai) and the amine compound (aii) undergo a Michael addition reaction, and as a result, the modified maleimide resin (A1) is obtained. When reacting the maleimide resin (ai) with the amine compound (aii), a reaction catalyst may be used as necessary.

[0067] From the viewpoints of workability such as reaction rate and suppression of gelation of the product during the reaction, the reaction temperature of the Michael addition reaction is preferably 50 to 160 °C, more preferably 60 to 150 °C, and still more preferably 70 to 140 °C. From the viewpoints of productivity and allowing the reaction to proceed sufficiently, the reaction time of the Michael addition reaction is preferably 0.5 to 10 hours, more preferably 1 to 8 hours, and still more preferably 2 to 6 hours. However, these reaction conditions can be appropriately adjusted according to the type of raw materials used, etc., and are not particularly limited.

[0068] The weight average molecular weight (Mw) of the modified maleimide resin (A1) is not particularly limited, but is preferably 400 to 10,000, more preferably 1,000 to 5,000, still more preferably 1,500 to 4,000, and particularly preferably 2,000 to 3,000. In the present disclosure, the weight average molecular weight is a value converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC), and more specifically, is a value obtained by the measurement method described in the examples.

[0069] (Content of the modified maleimide resin (A1)) In the resin composition of the present embodiment, the content of the modified maleimide resin (A1) is not particularly limited, but is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and still more preferably 25 to 50% by mass with respect to the total amount of the resin components in the resin composition of the present embodiment. When the content of the modified maleimide resin (A1) is at least the lower limit value, the heat resistance, moldability, processability, and conductor adhesiveness tend to be better. Also, when the content of the modified maleimide resin (A1) is at most the upper limit value, the high-frequency characteristics tend to be better.

[0070] <Polymaleimide resin (A2)> As described above, the component (A) contains a maleimide resin (polymaleimide resin (A2)) having three or more N-substituted maleimide groups. By containing the polymaleimide resin (A2) in the component (A), a resin composition excellent in low thermal expansibility and capable of reducing the dielectric tangent (Df) can be obtained. The polymaleimide resin (A2) does not contain the modified maleimide resin (A1). From this point, it is preferable that the polymaleimide resin (A2) is not modified with an amine compound. The polymaleimide resin (A2) is not particularly limited as long as it is a maleimide resin having three or more N-substituted maleimide groups, but it is preferably a maleimide resin having three or more N-substituted maleimide groups bonded to an aromatic ring, and more preferably a maleimide resin represented by the following general formula (A2-1).

[0071] [Chemical formula] (In the formula, X A2-1 is a divalent hydrocarbon group having 1 to 20 carbon atoms, and n A2-1 is an integer of 2 to 5.)

[0072] Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by X A2-1 in the general formula (A2-1) include divalent aliphatic hydrocarbon groups such as an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms, and divalent hydrocarbon groups including an aromatic hydrocarbon group represented by the following general formula (A2-2). Examples of the alkylene group having 1 to 5 carbon atoms include a methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group, etc. As the alkylene group having 1 to 5 carbon atoms, an alkylene group having 1 to 3 carbon atoms is preferable, an alkylene group having 1 or 2 carbon atoms is more preferable, and a methylene group is even more preferable. As the alkylidene group having 2 to 5 carbon atoms, an alkylidene group having 2 to 4 carbon atoms is preferable, an alkylidene group having 2 or 3 carbon atoms is more preferable, and an isopropylidene group is even more preferable.

[0073]

Chem.

[0074] X A2-2 and X A2-3 in the general formula (A2-2) represent, as the divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, the same groups as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms, etc. exemplified as X A2-1 in the general formula (A2-1). Among these, a methylene group is preferable. Examples of the divalent aromatic hydrocarbon group represented by Ar A2-2 in the general formula (A2-2) include a phenylene group, a naphthylene group, a biphenylene group, an anthranylene group, etc. Among these, a biphenylene group is preferable. Examples of the biphenylene group include a 4,2'-biphenylene group, a 4,3'-biphenylene group, a 4,4'-biphenylene group, a 3,3'-biphenylene group, etc. Among these, a 4,4'-biphenylene group is preferable.

[0075] Among the above options, as X A2-1 in the general formula (A2-1), a divalent hydrocarbon group containing an aromatic hydrocarbon group represented by the general formula (A2-2) is preferable. In the general formula (A2-2), X A2-2 and X A2-3 are a methylene group and Ar A2-2 is a 4,4'-biphenylene group, and a divalent hydrocarbon group is more preferable.

[0076] n A2-1 in the general formula (A2-1) is an integer of 2 to 5, preferably an integer of 2 to 4, and more preferably 2 or 3.

[0077] (Content of the polymaleimide resin (A2)) The content of the polymaleimide resin (A2) in the resin composition of the present embodiment is not particularly limited. However, from the viewpoints of high-frequency characteristics, heat resistance, low thermal expansion, and moldability, it is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and still more preferably 25 to 50% by mass with respect to the total amount of the resin components in the resin composition of the present embodiment.

[0078] (Content ratio of the modified maleimide resin (A1) and the polymaleimide resin (A2)) The content ratio [(A1) / (A2)] (mass ratio) of the component (A1) and the component (A2) is not particularly limited. However, from the viewpoints of high-frequency characteristics and low thermal expansion, it is preferably 10 / 90 to 90 / 10, more preferably 20 / 80 to 80 / 20, still more preferably 30 / 70 to 70 / 30, and particularly preferably 40 / 60 to 60 / 40.

[0079] [Polyphenylene ether derivative (B) having an ethylenically unsaturated bond-containing group] The resin composition of the present embodiment may contain a polyphenylene ether derivative having an ethylenically unsaturated bond-containing group (hereinafter, sometimes referred to as "modified polyphenylene ether derivative (B)") as the component (B). When the resin composition of the present embodiment contains the component (B), the high-frequency characteristics tend to be improved. The component (B) is preferably a polyphenylene ether derivative having an ethylenically unsaturated bond-containing group at the terminal, and more preferably a polyphenylene ether derivative having an ethylenically unsaturated bond-containing group at both terminals. In the present disclosure, the "ethylenically unsaturated bond-containing group" means a substituent containing a carbon-carbon double bond capable of an addition reaction, and does not include the double bond of the aromatic ring. The modified polyphenylene ether derivative (B) may be used alone or in combination of two or more.

[0080] Examples of the ethylenically unsaturated bond-containing group include unsaturated aliphatic hydrocarbon groups such as vinyl group, allyl group, 1-methylallyl group, isopropenyl group, 2-butenyl group, 3-butenyl group, and styryl group; and groups containing a heteroatom and the unsaturated hydrocarbon group such as maleimide group and the group represented by the following general formula (B-1). Among these, from the viewpoints of high-frequency characteristics and adhesion to a conductor, the ethylenically unsaturated bond-containing group is preferably a group represented by the following general formula (B-1).

[0081] [Chemical formula] (In the formula, R b1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)

[0082] R b1 The alkyl group having 1 to 20 carbon atoms represented by may be any of a linear alkyl group, a branched-chain alkyl group, or a cyclic alkyl group, and is preferably a linear alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, and particularly preferably 1. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, pentadecyl group, hexadecyl group, heptadecyl group, etc. Among these, the methyl group is preferable. From the viewpoint of high-frequency characteristics, the group represented by the general formula (B-1) is preferably a (meth)acryloyl group (that is, a group in which R b1 in the general formula (B-1) is a hydrogen atom or a methyl group), and more preferably a methacryloyl group.

[0083] In the present disclosure, groups such as maleimide group and the group represented by the general formula (B-1), which have an unsaturated aliphatic hydrocarbon group in part but cannot be said to be an unsaturated aliphatic hydrocarbon group when viewed as the whole group, are not included in the "unsaturated aliphatic hydrocarbon group".

[0084] The modified polyphenylene ether derivative (B) preferably has a group represented by the general formula (B-1) at one end or both ends. When the modified polyphenylene ether derivative (B) has an ethylenically unsaturated bond-containing group at one end or both ends, it may further have an ethylenically unsaturated bond-containing group other than one end or both ends, but it preferably has an ethylenically unsaturated bond-containing group only at both ends. The modified polyphenylene ether derivative (B) is preferably a polyphenylene ether having methacryloyl groups at both ends.

[0085] The number of ethylenically unsaturated bond-containing groups in one molecule of the modified polyphenylene ether derivative (B) is not particularly limited, but is preferably 2 to 5, more preferably 2 to 3, and even more preferably 2. When the number of ethylenically unsaturated bond-containing groups is at least the lower limit value, excellent heat resistance tends to be obtained, and when it is at most the upper limit value, excellent fluidity and moldability tend to be obtained.

[0086] The modified polyphenylene ether derivative (B) has a phenylene ether bond and preferably has a structural unit represented by the following general formula (B-2).

[0087]

Chemical formula

[0088] Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b2 in the general formula (B-2) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, and the like. As the aliphatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is even more preferable. n b1 represents an integer from 0 to 4, preferably 1 or 2, more preferably 2. Here, when n b1 is 1 or 2, R b2 is preferably substituted at the ortho position on the benzene ring (however, based on the substitution position of the oxygen atom). Also, when n b1 is an integer of 2 or more, a plurality of R b2 may be the same as or different from each other. The structural unit represented by the general formula (B-2) is preferably a structural unit represented by the following general formula (B-2’).

[0089]

Chemical formula

[0090] From the viewpoint of compatibility of high-frequency characteristics, the modified polyphenylene ether derivative (B) is preferably a compound represented by the following general formula (B-3).

[0091]

Chemical formula

[0092] R in the general formula (B-3) b3 and R b4 The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R in the general formula (B-2) is described below. b2 This is the same as the explanation for the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by the formula (1). n b2 and n b3 represents an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably 2 or 3. b2 or n b3 If is an integer equal to or greater than 2, multiple R b3 R b4 They may be the same or different from each other. n b4 and n b5 represents an integer of 0 to 20, preferably an integer of 1 to 20, more preferably an integer of 2 to 15, and further preferably an integer of 3 to 10. b4 or n b5 If is an integer equal to or greater than 2, multiple n b1 They may be the same or different. n b4 and n b5 The sum of these is an integer of 1 to 30, preferably an integer of 2 to 25, more preferably an integer of 5 to 20, and even more preferably an integer of 7 to 15.

[0093] In the general formula (B-3), X b1 Examples of the alkylene group having 1 to 5 carbon atoms include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and a 1,5-pentamethylene group. X b1 Examples of the alkylidene group having 2 to 5 carbon atoms include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group. X b1 Among the groups represented by the formula (I), an isopropylidene group is preferred from the viewpoint of high frequency characteristics. Y b1 and Y b2 The preferred embodiments of the ethylenically unsaturated bond-containing group represented by Y are as described above. From the viewpoints of high-frequency characteristics and adhesion to a conductor, the compound represented by the general formula (B-3) is preferably a compound represented by the following general formula (B-4).

[0094]

Chemical formula

[0095] [Weight-average molecular weight (Mw) of the modified polyphenylene ether derivative (B)] The weight-average molecular weight (Mw) of the modified polyphenylene ether derivative (B) is not particularly limited, but is preferably 500 to 7,000, more preferably 800 to 5,000, still more preferably 1,000 to 3,000, and particularly preferably 1,200 to 2,500. When the weight-average molecular weight (Mw) of the component (b) is at least the above lower limit value, a cured product having excellent high-frequency characteristics of polyphenylene ether and excellent heat resistance tends to be obtained, and when it is at most the above upper limit value, excellent moldability tends to be obtained.

[0096] As the synthesis method of the modified polyphenylene ether derivative (B), known synthesis methods and modification methods of polyphenylene ether can be applied, and it is not particularly limited.

[0097] [Content of component (B)] In the resin composition of the present embodiment, the content of component (B) is not particularly limited, but is preferably 1 to 40% by mass, more preferably 3 to 30% by mass, still more preferably 5 to 25% by mass, and particularly preferably 8 to 20% by mass with respect to the total amount of the resin components in the resin composition. When the content of component (B) is at least the above lower limit value, better high-frequency characteristics tend to be obtained, and when it is at most the above upper limit value, better heat resistance, moldability, and processability tend to be obtained.

[0098] [Inorganic filler (C)] The resin composition of the present embodiment may contain an inorganic filler as component (C). By the resin composition of the present embodiment containing component (C), there is a tendency to improve low thermal expansion, heat resistance, and flame retardancy. Component (C) is not particularly limited, but examples include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay (such as fired clay), molybdate compounds such as zinc molybdate, talc, aluminum borate, silicon carbide, etc. Component (C) may be used alone or in combination of two or more. Among these, from the viewpoints of low thermal expansion, heat resistance, and flame retardancy, silica, alumina, mica, and talc are preferred, silica and alumina are more preferred, and silica is still more preferred. Examples of silica include crushed silica, fumed silica, fused silica (fused spherical silica), etc.

[0099] (C) The shape and particle size of the component are not particularly limited, but the particle size is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm, still more preferably 0.2 to 1 μm, and particularly preferably 0.3 to 0.8 μm. Here, the particle size refers to the average particle diameter, which is the particle diameter at the point corresponding to 50% by volume when a cumulative frequency distribution curve by particle diameter is obtained with the total volume of the particles being 100%. The particle size of the (C) component can be measured with a particle size distribution measuring device using the laser diffraction scattering method or the like.

[0100] ((Content of component (C)) When the resin composition of the present embodiment contains the (C) component, the content of the (C) component is not particularly limited, but from the viewpoints of low thermal expansion, heat resistance, and flame retardancy, it is preferably 5 to 70 parts by mass, more preferably 15 to 65 parts by mass, still more preferably 25 to 60 parts by mass, and particularly preferably 35 to 60 parts by mass with respect to 100 parts by mass of the solid content in the resin composition.

[0101] Also, when using the (C) component, for the purpose of improving the dispersibility of the (C) component and the adhesion between the (C) component and the organic components in the resin composition, a coupling agent may be used in combination as necessary. The coupling agent is not particularly limited, and for example, a silane coupling agent or a titanate coupling agent can be appropriately selected and used. The coupling agent may be used alone or in combination of two or more. Also, the amount of the coupling agent used is not particularly limited. In addition, when using a coupling agent, after blending the (C) component in the resin composition, a so-called integral blend treatment method of adding the coupling agent may be used, or a method of using an inorganic filler surface-treated with a coupling agent in a dry or wet manner in advance may be used. By adopting these methods (especially the latter method), the characteristics of the (C) component can be more effectively exhibited.

[0102] When using the component (C) in this embodiment, for the purpose of improving the dispersibility of the component (C) in the resin composition, if necessary, the component (C) can be used as a slurry preliminarily dispersed in an organic solvent. Examples of the organic solvent include the same ones as those described later.

[0103] [Elastomer (D)] Although the resin composition of this embodiment is not particularly limited, from the viewpoint of reducing the dielectric loss tangent (Df), it is preferable to contain an elastomer (D) [hereinafter, sometimes also referred to as the component (D)]. In the present disclosure, an elastomer is defined as a polymer compound having a rubber elasticity at 25°C and a Mw of 1,000 or more. As the rubber elasticity, the elastic modulus (Young's modulus) is preferably 1 to 10 MPa. Examples of the component (D) include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, silicone-based elastomers, and the like. The component (D) may be used alone or in combination of two or more.

[0104] From the viewpoint of reducing the dielectric loss tangent (Df), the component (D) is preferably a styrene-based elastomer, and more preferably a styrene-based thermoplastic elastomer. The styrene-based elastomer only needs to have a structural unit derived from a styrene-based compound, but is preferably a copolymer having a structural unit derived from a styrene-based compound and a structural unit derived from a conjugated diene compound.

[0105] Here, examples of the styrene-based compound include styrene, α-methylstyrene, p-methylstyrene, p-tert-butylstyrene, and the like. Among these, from the viewpoints of availability and productivity, styrene, α-methylstyrene, and 4-methylstyrene are preferable, and styrene is more preferable. Examples of the conjugated diene compound include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 1,3-pentadiene (piperylene), 1-phenyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene, etc. Among these, from the viewpoints of availability and productivity, 1,3-butadiene and isoprene are preferred, and 1,3-butadiene is more preferred.

[0106] (D) component may be a hydrogenated styrene-based elastomer in which at least a part of the structural unit derived from the conjugated diene compound is hydrogenated. In the present disclosure, when simply referred to as a styrene-based elastomer, a hydrogenated styrene-based elastomer is also included. The hydrogenation rate of the hydrogenated styrene-based elastomer is not particularly limited, but is preferably 50 to 100 mol%, more preferably 70 to 100 mol%, still more preferably 80 to 100 mol%, particularly preferably 90 to 100 mol%, and may be 95 to 100 mol%.

[0107] From the viewpoints of reducing the dielectric loss tangent (Df), adhesiveness to a conductor, heat resistance, and low thermal expansion, as the styrene-based elastomer, one or more selected from the group consisting of a hydrogenated product of a styrene-butadiene-styrene block copolymer (SEBS or SBBS), a hydrogenated product of a styrene-isoprene-styrene block copolymer (SEPS), and a styrene-maleic anhydride copolymer (SMA) are preferred, one or more selected from the group consisting of a hydrogenated product of a styrene-butadiene-styrene block copolymer (SEBS) and a hydrogenated product of a styrene-isoprene-styrene block copolymer (SEPS) are more preferred, and a hydrogenated product of a styrene-butadiene-styrene block copolymer (SEBS) is still more preferred. In addition, the styrenic elastomer (excluding the above-mentioned SMA here) is preferably in a form modified with an acid anhydride. Examples of the styrenic elastomer modified with an acid anhydride include SEBS modified with an acid anhydride such as maleic anhydride, and SEPS modified with an acid anhydride such as maleic anhydride. The acid value of the acid-modified styrenic elastomer (excluding the above-mentioned SMA here) is not particularly limited, but is preferably 2 to 20 mg CH3ONa / g, more preferably 5 to 15 mg CH3ONa / g, and even more preferably 7 to 13 mg CH3ONa / g. Here, the acid value can be measured by a titration method using a potassium hydroxide solution.

[0108] In component (D), the content of the structural unit derived from styrene [hereinafter, may be referred to as "styrene content" in some cases] is not particularly limited, but from the viewpoints of reduction of dielectric loss tangent (Df), adhesion to a conductor, heat resistance, and low thermal expansion property, it is preferably 5 to 80% by mass, more preferably 10 to 75% by mass, even more preferably 15 to 60% by mass, particularly preferably 18 to 45% by mass, most preferably 18 to 40% by mass, and may also be 5 to 30% by mass, 10 to 30% by mass, 25 to 60% by mass, 25 to 45% by mass, or 25 to 40% by mass. The weight average molecular weight (Mw) of component (D) is not particularly limited, but is preferably 12,000 to 1,000,000, more preferably 30,000 to 500,000, and may also be 50,000 to 200,000, 100,000 to 200,000, 120,000 to 180,000, 50,000 to 100,000, or 65,000 to 90,000.

[0109] (Content of elastomer (D)) When the resin composition of the present embodiment contains the component (D), the content of the component (D) is not particularly limited, but is preferably 1 to 35% by mass, more preferably 3 to 30% by mass, still more preferably 5 to 20% by mass, and particularly preferably 5 to 15% by mass, based on the total amount of the resin components in the resin composition. When the content of the component (D) is at least the lower limit value, a more excellent dielectric tangent (Df) tends to be obtained, and when it is at most the upper limit value, good heat resistance, moldability, processability, and flame retardancy tend to be obtained.

[0110] <Curing accelerator (E)> By further containing a curing accelerator as the component (E), the resin composition of the present embodiment has improved curability and tends to obtain more excellent high-frequency characteristics, heat resistance, adhesiveness to a conductor, elastic modulus, and glass transition temperature. When the resin composition of the present embodiment contains the curing accelerator (E), a suitable curing accelerator (E) may be appropriately selected according to the type of the thermosetting resin (B) component used. The curing accelerator (E) may be used alone or in combination of two or more.

[0111] Examples of the component (E) include amine-based curing accelerators, imidazole-based curing accelerators, phosphorus-based curing accelerators, organic metal salts, acidic catalysts, organic peroxides, and the like. In the present embodiment, imidazole-based curing accelerators are not classified as amine-based curing accelerators. Examples of the amine-based curing accelerators include amine compounds having primary to tertiary amines such as triethylamine, pyridine, tributylamine, dicyandiamide, and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane; quaternary ammonium compounds, and the like. Examples of the imidazole-based curing accelerators include imidazole compounds such as methylimidazole, phenylimidazole, 2-undecylimidazole, and isocyanate-masked imidazole (for example, an addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole). Examples of the phosphorus-based curing accelerator include tertiary phosphines such as triphenylphosphine; and quaternary phosphonium compounds such as the addition reaction product of tri-n-butylphosphine and p-benzoquinone. Examples of the organometallic salts include carboxylates of manganese, cobalt, zinc, and the like. Examples of the acidic catalyst include p-toluenesulfonic acid. Examples of the organic peroxide include dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexine-3, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, α,α'-di(t-butylperoxy)diisopropylbenzene, and the like. Among these, from the viewpoint of obtaining more excellent high-frequency characteristics, heat resistance, adhesion to a conductor, elastic modulus, and glass transition temperature, imidazole-based curing accelerators and phosphorus-based curing accelerators are preferable, imidazole-based curing accelerators and quaternary phosphonium compounds are more preferable, and it is even more preferable to use them in combination. Also, a mode of using an imidazole-based curing accelerator, a quaternary phosphonium compound, and an organic peroxide in combination is also preferable.

[0112] (Content of component (E)) When the resin composition of the present embodiment contains component (E), the content of component (E) is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.05 to 6% by mass, still more preferably 0.1 to 4% by mass, particularly preferably 0.5 to 4% by mass, most preferably 1.0 to 4% by mass, and may be 1.5 to 3.5% by mass, based on the total amount of the resin components in the resin composition. When the content of the curing accelerator (E) is within the above range, better high-frequency characteristics, heat resistance, storage stability, and moldability tend to be obtained.

[0113] [Flame retardant (F)] From the viewpoint of flame retardancy, the resin composition of the present embodiment may further contain a flame retardant as component (F). Examples of the flame retardant include phosphorus-based flame retardants, metal hydrates, halogen-based flame retardants, etc. Among these, from the perspective of environmental issues, phosphorus-based flame retardants and metal hydrates are preferred. The phosphorus-based flame retardant may be an inorganic phosphorus-based flame retardant, but from the perspectives of high-frequency characteristics, adhesion to conductors, heat resistance, glass transition temperature, low thermal expansion, and flame retardancy, an organic phosphorus-based flame retardant is preferred. Examples of the organic phosphorus-based flame retardants include phosphazene compounds, phosphate ester compounds, phosphaphenanthrene compounds, etc. Among these, from the perspective of flame retardancy, phosphazene compounds and phosphaphenanthrene compounds are preferred; from the perspectives of low thermal expansion and high-frequency characteristics, phosphaphenanthrene compounds are more preferred; and from the perspective of glass transition temperature, phosphazene compounds are more preferred.

[0114] (Phosphazene compound) The phosphazene compound preferably has a structural unit represented by the following general formula (F-1).

[0115] [Chemical formula] (In the formula, R f1 and R f2 each independently represent an organic group having 1 to 20 carbon atoms.)

[0116] The organic groups having 1 to 20 carbon atoms represented by R f1 and R f2 in the general formula (F-1) include aliphatic hydrocarbon groups having 1 to 20 carbon atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms, etc.

[0117] R f1 and R f2 Examples of the aliphatic hydrocarbon groups having 1 to 20 carbon atoms, which are the organic groups having 1 to 20 carbon atoms represented by them, include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, etc. The aliphatic hydrocarbon group may be linear, branched, or cyclic. Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, 2-ethylhexyl group, cyclohexyl group and the like. Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl group, propenyl, butenyl group and the like. Examples of the alkynyl group having 2 to 20 carbon atoms include 2-propynyl group, 3-butynyl group and the like. The aliphatic hydrocarbon group having 1 to 20 carbon atoms may or may not have a substituent. Examples of the substituent include hydroxyl group, carboxy group, halogen atom, aromatic hydrocarbon group, acyl group, alkoxy group, a group formed by linking these substituents and the like. When the aliphatic hydrocarbon group has a substituent, the number of carbon atoms includes the number of carbon atoms of the substituent.

[0118] R f1 and R f2 The number of carbon atoms of the aromatic hydrocarbon group having 6 to 20 carbon atoms, which is an example of the organic group having 1 to 20 carbon atoms represented by R and R, is preferably 6 to 15, more preferably 6 to 10. Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl group, naphthyl group, biphenyl group, anthranyl group and the like. The aromatic hydrocarbon group having 6 to 20 carbon atoms may or may not have a substituent. Examples of the substituent include hydroxyl group, carboxy group, halogen atom, aliphatic hydrocarbon group, acyl group, alkoxy group, cyano group, a group formed by linking these substituents and the like. The substituent is preferably a cyano group. When the aromatic hydrocarbon group has a substituent, the number of carbon atoms includes the number of carbon atoms of the substituent. Among these, the organic group having 1 to 20 carbon atoms represented by R and R is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an unsubstituted phenyl group or a phenyl group having a substituent, and still more preferably an unsubstituted phenyl group or a cyanophenyl group. f1 and R f2 The number of carbon atoms of the aromatic hydrocarbon group having 6 to 20 carbon atoms, which is an example of the organic group having 1 to 20 carbon atoms represented by R and R, is preferably 6 to 15, more preferably 6 to 10.

[0119] The phosphazene compound may be a chain phosphazene compound or a cyclic phosphazene compound, but a cyclic phosphazene compound is preferred. As the cyclic phosphazene compound, the phosphazene compound represented by the following general formula (F-2-1) is preferred, and the phosphazene compound represented by the following general formula (F-2-2) is more preferred.

[0120] [Chemical formula] (In the formula, Ar f1 and Ar f2 each independently represents an aromatic hydrocarbon group having 6 to 20 carbon atoms. n f1 represents an integer of 3 to 20.) [Chemical formula] (In the formula, Ar f3 to Ar f8 each independently represents an aromatic hydrocarbon group having 6 to 20 carbon atoms.)

[0121] Regarding the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by Ar f1 and Ar f2 in the general formula (F-2-1), and the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by Ar f3 to Ar f8 in the general formula (F-2-2), the description is the same as that of the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R f8 and R f9 in the general formula (F-1). n f1 in the general formula (F-2-1) represents an integer of 3 to 20, preferably an integer of 3 to 10, more preferably an integer of 3 to 5, and even more preferably 3.

[0122] (Phosphate ester compound) As the phosphate compound, an aromatic phosphate is preferable. The aromatic phosphate is a phosphate having an aromatic hydrocarbon group. Specific examples of the phosphate compound include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, 1,3-phenylene-bis(di-2,6-dimethylphenyl phosphate), 1,3-phenylene-bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), 1,4-phenylene-bis(di-2,6-dimethylphenyl phosphate), 4,4'-biphenylene-bis(di-2,6-dimethylphenyl phosphate), bisphenol A-poly(phenyl phosphate), 4,4'-biphenol-poly(cresyl phosphate), bisphenol A-poly(cresyl phosphate), 4,4'-biphenol-poly(2,6-xylenyl phosphate), bisphenol A-poly(2,6-xylenyl phosphate), and the like.

[0123] (Phosphaphenanthrene compound) Examples of phosphaphenanthrene include 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide, 9,10-dihydro-10-(2,5-dihydroxyphenyl)-9-oxa-10-phosphaphenanthrene 10-oxide, 9,10-dihydro-10-benzyl-9-oxa-10-phosphaphenanthrene 10-oxide, and the like.

[0124] When the resin composition of the present embodiment contains a flame retardant (F), the content of the flame retardant (F) is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, and still more preferably 1.5 to 12% by mass with respect to the total solid content of the resin composition. When the content of the flame retardant (F) is equal to or higher than the lower limit value, the flame retardancy and low thermal expansion tend to be better. Also, when the content of the flame retardant (F) is equal to or lower than the upper limit value, the high-frequency characteristics tend to be better.

[0125] <Other components> The resin composition of the present embodiment may further contain, as necessary, one or more optional components such as resin materials other than the above components, flame retardant aids, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, silane coupling agents, etc. Regarding each of the above optional components, one kind may be used alone, or two or more kinds may be used in combination. Examples of the resin material other than the above components include thermosetting resins other than maleimide compounds. The thermosetting resin preferably contains one or more selected from the group consisting of epoxy resins, phenolic resins, polyimide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, and melamine resins.

[0126] When the resin composition of the present embodiment contains the above optional components, the content thereof is not particularly limited, but may be 0.01% by mass or more, 0.1% by mass or more, 0.5% by mass or more, 30% by mass or less, 10% by mass or less, 5% by mass or less, or 1% by mass or less, respectively, based on the total amount of the resin components. Also, the resin composition of the present embodiment may not contain the above optional components depending on the desired performance.

[0127] The total content of components (A) to (B) in the resin composition of the present embodiment is not particularly limited, but is preferably 15 to 100% by mass, more preferably 20 to 80% by mass, still more preferably 25 to 55% by mass, and particularly preferably 30 to 50% by mass, based on the total amount of the solid components in the resin composition.

[0128] (Organic solvent) The resin composition of the present embodiment may be a resin composition containing an organic solvent, so-called resin varnish, from the viewpoints of facilitating handling and facilitating the production of a prepreg described later. Examples of the organic solvent include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, and mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfur atom-containing solvents such as dimethyl sulfoxide; and ester solvents such as γ-butyrolactone. These organic solvents may be used alone or in combination of two or more.

[0129] When the resin composition of the present embodiment contains an organic solvent, its content is not particularly limited, but the amount that makes the solid content concentration of the resin composition of the present embodiment 30 to 90% by mass is preferable, the amount that makes it 40 to 80% by mass is more preferable, and the amount that makes it 50 to 70% by mass is even more preferable. When the content of the organic solvent is within the above range, the handleability of the resin composition becomes easy, and the impregnation property into the base material and the appearance of the prepreg to be produced become good. Furthermore, it becomes easy to adjust the solid content concentration of the resin in the prepreg described later, and the production of a prepreg having a desired thickness tends to be easier.

[0130] <Low coefficient of thermal expansion> The coefficient of thermal expansion when the resin composition of the present embodiment is made into a test piece by the method described in the examples described later is not particularly limited, but from the viewpoint of suppressing the warpage of the printed wiring board and the semiconductor package, it is preferably 12.0 ppm / °C or less, more preferably 11.0 ppm / °C or less, and can also be 10.0 ppm / °C or less. The smaller the coefficient of thermal expansion, the more preferable, and its lower limit value is not particularly limited, but it may be 7.0 ppm / °C or more, 8.5 ppm / °C or more, or 9.0 ppm / °C or more. That is, the coefficient of thermal expansion can be 7.0 to 12.0 ppm / °C.

[0131] <High-frequency characteristics> When the resin composition of this embodiment is made into a test piece by the method described in the examples described later, the dielectric constant (Dk) at 10 GHz is not particularly limited, but is preferably 3.7 or less, more preferably 3.6 or less. The smaller the dielectric constant (Dk), the better, and the lower limit thereof is not particularly limited, but may be 2.5 or more, may be 3.0 or more, or may be 3.3 or more. That is, the dielectric constant (Dk) can be 2.5 to 3.7. When the resin composition of this embodiment is made into a test piece by the method described in the examples described later, the dielectric tangent (Df) at 10 GHz is not particularly limited, but is preferably 0.0035 or less, more preferably 0.0034 or less, even more preferably 0.0033 or less, and can also be 0.0032 or less. The smaller the dielectric tangent (Df), the better, and the lower limit thereof is not particularly limited, but may be 0.0020 or more, may be 0.0025 or more, or may be 0.0027 or more. That is, the dielectric tangent (Df) can be 0.0020 to 0.0035. The dielectric constant (Dk) and the dielectric tangent (Df) are values compliant with SPDR (Split post dielectric resonators), and more specifically, are values measured by the method described in the examples. In the present disclosure, when simply referring to the dielectric constant, it means the relative dielectric constant.

[0132] The resin composition of this embodiment can be produced by mixing the components (A) to (B) and other components as necessary by a known method. At this time, each component may be dissolved or dispersed while stirring in the organic solvent. Conditions such as the mixing order, temperature, and time are not particularly limited and can be arbitrarily set.

[0133] [Resin film] The resin film of this embodiment is a resin film containing the resin composition of this embodiment or a semi-cured product of the resin composition. The resin film of this embodiment can be manufactured, for example, by applying a resin composition containing an organic solvent, that is, a resin varnish, to a support, heating and drying it, and semi-curing (B-staging) it as necessary. The thickness of the resin film is not particularly limited, but is preferably 1 to 100 μm, more preferably 3 to 70 μm, and even more preferably 5 to 35 μm. Examples of the support include plastic films, metal foils, release papers, and the like. The drying temperature and drying time may be appropriately determined according to the amount of the organic solvent used and the boiling point of the organic solvent used. However, the resin film can be preferably formed by drying at 50 to 200 °C for about 1 to 10 minutes.

[0134] [Prepreg] The prepreg of this embodiment is a prepreg containing one or more selected from the group consisting of the resin composition of this embodiment, a semi-cured product of the resin composition, the resin film of this embodiment, and a semi-cured product of the resin film. More specifically, the prepreg of this embodiment contains one or more selected from the group consisting of the resin composition of this embodiment, a semi-cured product of the resin composition, the resin film of this embodiment, and a semi-cured product of the resin film, and a sheet-like fiber base material. The prepreg is formed using the resin composition of this embodiment or the resin film and a sheet-like fiber base material. For example, it can be obtained by impregnating the sheet-like fiber base material with the resin composition of this embodiment or the resin film, followed by heating and drying and semi-curing (B-staging) as necessary. More specifically, for example, the prepreg of this embodiment can be manufactured by heating and drying in a drying furnace at 80 to 200 °C for 1 to 30 minutes to semi-cure (B-stage). Here, in the present disclosure, B-staging means bringing it into the state of B-stage defined in JIS K6900 (1994). The amount of the resin composition used can be appropriately determined for the purpose of making the solid content concentration derived from the resin composition in the prepreg after drying 30 to 90% by mass. By setting the solid content concentration within the above range, better moldability tends to be obtained when a laminated board is formed.

[0135] As the sheet-like fiber base material of the prepreg, known materials used for various laminated boards for electrical insulation materials are used. Examples of the material of the sheet-like fiber base material include inorganic fibers such as E glass, D glass, S glass, and Q glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and mixtures thereof. These sheet-like fiber base materials have shapes such as woven fabric, non-woven fabric, roving, chopped strand mat, or surfacing mat. The thickness of the sheet-like fiber base material is not particularly limited, and may be 1 to 100 μm, may be 3 to 90 μm, may be 5 to 85 μm, may be 15 to 85 μm, may be 25 to 80 μm, or may be 40 to 80 μm.

[0136] [Laminated board] The laminated board of this embodiment is a laminated board having one or more selected from the group consisting of a cured product of the resin composition of this embodiment, a cured product of the resin film of this embodiment, and a cured product of the prepreg of this embodiment, and a metal foil. The embodiment of the laminated board of this embodiment can be manufactured, for example, by disposing a metal foil on one or both sides of one resin film of this embodiment, or by disposing a metal foil on one or both sides of a laminate obtained by stacking two or more resin films of this embodiment, and then performing heat and pressure molding. In the laminated board obtained by this manufacturing method, the resin film of this embodiment is C-staged. Another embodiment of the laminate of the present embodiment can be manufactured, for example, by disposing metal foil on one or both sides of one prepreg of the present embodiment, or on one or both sides of a laminate obtained by stacking two or more prepregs of the present embodiment, and then performing heat and pressure molding. In the laminate obtained by this manufacturing method, the prepreg of the present embodiment is in a C-stage state. In the present disclosure, C-staging means bringing it into the state of the C-stage defined in JIS K6900 (1994). Note that a laminate having a metal foil may also be referred to as a metal-clad laminate. The metal of the metal foil is not particularly limited, but from the viewpoint of conductivity, it may be copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing one or more of these metal elements. Copper and aluminum are preferred, and copper is more preferred. The method for carrying out the heat and pressure molding is not particularly limited, but examples thereof include a method carried out under the conditions of a temperature of 100 to 300°C, a pressure of 0.2 to 10 MPa, and a time of 0.1 to 5 hours. Further, for the heat and pressure molding, a method of maintaining a vacuum state for 0.5 to 5 hours using a vacuum press or the like can be adopted.

[0137] [Printed Wiring Board] The printed wiring board of the present embodiment has a cured product of the resin composition of the present embodiment. Further, it can also be said that the printed wiring board of the present embodiment is a printed wiring board having one or more selected from the group consisting of a cured product of the thermosetting resin composition of the present embodiment, a cured product of the resin film of the present embodiment, a cured product of the prepreg of the present embodiment, and the laminate of the present embodiment. The printed wiring board of the present embodiment can be manufactured by performing circuit formation processing such as drilling, metal plating, and etching of metal foil by a known method using one or more selected from the group consisting of the prepreg of the present embodiment, the resin film of the present embodiment, and the laminate of the present embodiment. Further, a multilayer printed wiring board can also be manufactured by performing multilayer bonding processing as needed. In the printed wiring board of the present embodiment, the prepreg of the present embodiment and the resin film of the present embodiment are in a C-stage state.

[0138] [Semiconductor Package] The semiconductor package of the present embodiment is a semiconductor package having the printed wiring board of the present embodiment and a semiconductor element. The semiconductor package of the present embodiment can be manufactured by mounting a semiconductor element such as a semiconductor chip or a memory on a predetermined position of the printed wiring board of the present embodiment.

[0139] The resin composition, resin film, prepreg, laminate, printed wiring board, and semiconductor package of the present embodiment can be suitably used in electronic devices that handle high-frequency signals of 10 GHz or higher. In particular, the printed wiring board is useful as a printed wiring board for millimeter-wave radar.

[0140] As described above, the preferred embodiments have been described, but these are examples for the explanation of the present disclosure, and the scope of the present disclosure is not intended to be limited only to these embodiments. The present disclosure includes various aspects different from the above embodiments without departing from the gist thereof.

Examples

[0141] Hereinafter, the present embodiment will be described more specifically with reference to examples. However, the present disclosure is not limited to the following examples.

[0142] In each example, the weight average molecular weight (Mw) was measured by the following method. It was converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve was approximated by a cubic equation using standard polystyrene: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, trade name]. The measurement conditions of GPC are shown below. Apparatus: Pump: Model L-6200 [manufactured by Hitachi High-Technologies Corporation] Detector: Model L-3300 RI [manufactured by Hitachi High-Technologies Corporation] Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Corporation] Column: Guard column; TSK Guardcolumn HHR-L + Column; TSKgel G4000HHR + TSKgel G2000HHR (all manufactured by Tosoh Corporation, trade name) Column size: 6.0 × 40 mm (guard column), 7.8 × 300 mm (column) Eluent: Tetrahydrofuran Sample concentration: 30 mg / 5 mL Injection volume: 20 μL Flow rate: 1.00 mL / min Measurement temperature: 40 °C

[0143] [Production Example 1: Production of Modified Maleimide Resin ((A1) Component)] Into a 5 L reaction vessel equipped with a thermometer, a stirrer, and a water quantifier with a reflux condenser, which can be heated and cooled, 100 parts by mass of 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 5.6 parts by mass of a siloxane compound having amino groups at both ends (functional group equivalent weight 750 g / mol), 7.9 parts by mass of 3,3'-diethyl-4,4'-diaminodiphenylmethane, and 171 parts by mass of propylene glycol monomethyl ether were charged and reacted for 2 hours while refluxing. This was concentrated over 3 hours at the reflux temperature to obtain a solution containing a modified maleimide resin [referred to as modified maleimide resin (A1-1)] with a solid content concentration of 65% by mass. The weight average molecular weight (Mw) of the obtained modified maleimide resin (A1-1) was approximately 2,700.

[0144] [Examples 1-2, Comparative Examples 1-3] (Preparation of Resin Composition) Each component described in Table 1 was stirred and mixed at room temperature together with toluene according to the compounding composition described in Table 1 to prepare a resin composition (resin varnish) having a solid content concentration of 55 to 65% by mass. The units of the numerical values described in the compounding composition of Table 1 are parts by mass, and in the case of a solution or dispersion, they mean parts by mass in terms of solid content. (Manufacture of Double-Sided Copper-Clad Laminate) The resin composition obtained above was applied to a glass cloth having a thickness of 70 μm, and then dried by heating at 130 °C for 5 minutes to prepare a prepreg having a solid content concentration derived from the resin composition of about 60% by mass. Four sheets of this prepreg were stacked, and copper foils having a thickness of 12 μm (manufactured by Mitsui Mining & Smelting Co., Ltd., trade name: "3EC-M3-VLP-12", Rz of M surface (mat surface): 3.0 μm) were placed above and below so that the M surface was in contact with the prepreg. This laminate was heat-pressed and molded under the conditions of a temperature of 240 °C, a pressure of 3.0 MPa, and a time of 90 minutes to manufacture a double-sided copper-clad laminate (thickness: 0.43 mm).

[0145] [Evaluation Method] Using the double-sided copper-clad laminates obtained in each example, each evaluation was carried out according to the following method. The results are shown in Table 1.

[0146] (1. Coefficient of Thermal Expansion and 2. Glass Transition Temperature) After removing the copper foils on both sides of the double-sided copper-clad laminate obtained in each example by etching, a test piece of 4.5 mm × 30 mm was cut out. After installing a jig so that the distance between the chucks on the test piece was 20 mm, using a thermomechanical analyzer (TMA) (manufactured by TA Instruments Japan Co., Ltd., trade name: Q400), in accordance with the IPC (The Institute for Interconnecting and Packaging Electronic Circuits) standard, in the tensile load mode, the coefficient of thermal expansion and the glass transition temperature of the test piece were measured. More specifically, measurements were taken twice under the conditions of a load of 5 g and a heating rate of 10 °C / min within the temperature range of 30 to 260 °C. The coefficient of thermal expansion was taken as the average coefficient of thermal expansion in the second measurement, and the glass transition temperature was also adopted as the glass transition temperature obtained from the second measurement. Note that the coefficient of thermal expansion is the linear coefficient of thermal expansion in the length direction of the test piece.

[0147] (3. High-frequency characteristics) The outer copper foil of the double-sided copper-clad laminate obtained in each example was removed by immersing it in a copper etching solution (a 10 mass% solution of ammonium persulfate, manufactured by Mitsubishi Gas Chemical Company, Inc.), and the one cut into a length of 90 mm and a width of 70 mm was used as a test piece. Using this test piece, the dielectric constant (Dk) and dielectric loss tangent (Df) were measured at a frequency of 10 GHz and a measurement temperature of 25 °C by the SPDR (Split post dielectric resonators) method. The dielectric constant should be 3.7 or less, and the dielectric loss tangent should be 0.0035 or less. Note that a network analyzer "E5071C" manufactured by Keysight Technologies was used as the measuring instrument, "SPDR-10GHz" of QWED was used as the dielectric constant measurement jig, and material measurement software "85071E" manufactured by Keysight Technologies was used as the measurement program.

[0148] (4. Copper foil peel strength) Using the double-sided copper-clad laminate obtained in each example, after processing it into a 3-mm-wide straight line by etching and drying it at 105 °C for 1 hour, it was used as a test piece. Next, using a small bench-top testing machine (manufactured by Shimadzu Corporation, product name: EZ-Test), the peel strength was measured when the copper foil, which is the straight line of the test piece, was peeled off in the 90° direction at a speed of 50 mm / min. The copper foil peel strength should be 0.50 kN / m or more.

[0149] (5. Heat resistance, heat and moisture resistance) The double-sided copper-clad laminate obtained in each example was cut into a size of 50 mm square, leaving half copper on only one surface, and the other surface was immersed in a copper etching solution to remove all the copper to produce a semi-copper-attached evaluation substrate. After performing the following operation (A) or (B) on the obtained semi-copper-attached evaluation substrate, the appearance of the semi-copper-attached evaluation substrate was visually observed to confirm the presence or absence of swelling. (A) It was immersed in a solder bath at 288 °C for 20 seconds. (B) The semi-copper-attached evaluation substrate was processed in an apparatus for pressure cooker test (PCT) (manufactured by Hirayama Seisakusho Co., Ltd.) under the conditions of 121 °C and 2.2 atmospheres for 1 to 5 hours, and then immersed in a solder bath at 288 °C for 20 seconds.

[0150]

Table 1

[0151] In addition, the abbreviations of each material in Table 1 are as follows. [Maleimide compound (A)] (A1) · Modified maleimide resin (A1-1) manufactured in Production Example 1 (A2) · Polymaleimide resin "MIR-3000" (manufactured by Nippon Kayaku Co., Ltd.), which is a compound represented by the general formula (A2-1), and X A2-1 is such that in the general formula (A2-2), X A2-2 and X A2-3 are methylene groups and Ar A2-2 corresponds to a divalent hydrocarbon group in which is 4,4'-biphenylene group.

[0152] [Component (B)] · Polyphenylene ether derivative having an ethylenically unsaturated bond-containing group: Polyphenylene ether having methacryloyl groups at both ends (weight average molecular weight (Mw) = 1,700)

[0153] [Component (C)] · Silica: Spherical fused silica, average particle diameter: 0.5 μm, 70 mass% slurry (solvent: methyl isobutyl ketone)

[0154] [Component (D)] · Maleic anhydride-modified SEBS: "Tuftec (registered trademark) M1913" (manufactured by Asahi Kasei Corporation), acid value 10 mg CH3ONa / g, styrene content 30%, weight average molecular weight (Mw) = 86,000

[0155] [Component (E)] · Curing accelerator E-1: α,α'-bis(t-butylperoxy) diisopropylbenzene · Curing accelerator E-2: 2-undecylimidazole · Curing accelerator E-3: p-benzoquinone tri-n-butylphosphine addition reaction product

[0156] [Component (F)] · Flame retardant F-1: Rabitol (registered trademark) FP-110 (manufactured by Fushimi Pharmaceutical Co., Ltd.), phosphazene compound (see the following structural formula) [Chemical formula] · Flame retardant F-2: 9,10-dihydro-10-benzyl-9-oxa-10-phosphaphenanthrene 10-oxide (see the following structural formula) [Chemical formula]

[0157] As is clear from the results shown in Table 1, the double-sided copper-clad laminates of Examples 1 to 2 produced using the resin composition of this embodiment had improved low thermal expansibility compared to the double-sided copper-clad laminates of Examples 1 to 3. Further, the double-sided copper-clad laminates of Examples 1 to 2 had good high-frequency characteristics, good copper foil peel strength, and good heat resistance (and moisture absorption heat resistance). Also, the double-sided copper-clad laminate of Example 1 had a higher glass transition temperature compared to the double-sided copper-clad laminates of Comparative Examples 1 and 3, and the double-sided copper-clad laminate of Example 2 had a higher glass transition temperature compared to the double-sided copper-clad laminate of Comparative Example 2.

Claims

1. A resin composition containing a maleimide compound (A) and a polyphenylene ether derivative (B) having an ethylenically unsaturated bond-containing group, wherein the component (A) includes a resin (A1) containing a structure derived from a maleimide resin (ai) having one or more N-substituted maleimide groups and a structure derived from an amine compound (aii) having one or more amino groups, and a maleimide resin (A2) having three or more N-substituted maleimide groups.

2. The resin composition according to claim 1, wherein in the component (A1), the maleimide resin (ai) having one or more N-substituted maleimide groups is a bismaleimide resin having two N-substituted maleimide groups or a polymaleimide resin having three or more N-substituted maleimide groups.

3. The resin composition according to claim 1, wherein in the component (A1), the amine compound (aii) having one or more amino groups includes a siloxane compound having one or more amino groups.

4. The resin composition according to claim 1, wherein the component (A2) is a maleimide resin having three or more N-substituted maleimide groups bonded to an aromatic ring.

5. The resin composition according to claim 1, wherein the component (A2) is a maleimide resin represented by the following general formula (A2-1). 【Chemical 1】 (wherein X Ａ１ is a divalent hydrocarbon group having 1 to 20 carbon atoms, and n Ａ１ is an integer of 2 to 5.)

6. The resin composition according to claim 1, wherein the content ratio [(A1) / (A2)] (mass ratio) of the component (A1) to the component (A2) is 10 / 90 to 90 / 10.

7. The resin composition according to claim 1, wherein the component (B) is a polyphenylene ether derivative having an ethylenically unsaturated bond-containing group at the terminal.

8. The resin composition according to claim 1, wherein in the component (B), the ethylenically unsaturated bond-containing group is an unsaturated aliphatic hydrocarbon group or a group containing a hetero atom and the unsaturated hydrocarbon group.

9. The resin composition according to claim 1, further containing an inorganic filler (C).

10. The resin composition according to claim 1, further containing an elastomer (D).

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

12. The resin composition according to claim 1, further containing a flame retardant (F).

13. The resin composition according to claim 12, wherein the flame retardant (F) includes a phosphazene compound.

14. A resin film containing the resin composition according to claim 1 or a semi-cured product of the resin composition.

15. A prepreg containing the resin composition according to Claim 1 or a semi-cured product of the resin composition.

16. A laminate having a cured product of the resin composition according to Claim 1 and a metal foil.

17. A printed wiring board having a cured product of the resin composition according to Claim 1.

18. A semiconductor package having the printed wiring board according to Claim 17 and a semiconductor element.

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