WO2023090351A1 - Resin composition, prepreg, laminated board, resin film, printed wiring board, and semiconductor package - Google Patents

Resin composition, prepreg, laminated board, resin film, printed wiring board, and semiconductor package Download PDF

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Publication number
WO2023090351A1
WO2023090351A1 PCT/JP2022/042516 JP2022042516W WO2023090351A1 WO 2023090351 A1 WO2023090351 A1 WO 2023090351A1 JP 2022042516 W JP2022042516 W JP 2022042516W WO 2023090351 A1 WO2023090351 A1 WO 2023090351A1
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group
resin composition
resin
carbon atoms
maleimide
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PCT/JP2022/042516
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French (fr)
Japanese (ja)
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諒 下川
俊希 藤井
真 柳田
圭芸 日▲高▼
幸雄 中村
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株式会社レゾナック
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Priority to JP2023562371A priority Critical patent/JPWO2023090351A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present embodiment relates to resin compositions, prepregs, laminates, resin films, printed wiring boards, and semiconductor packages.
  • Patent Document 1 the object is to provide a curable resin composition that can be applied to the insulating layer of a printed wiring board, and the resulting cured product has a low relative dielectric constant and dielectric loss tangent and is excellent in heat resistance.
  • a curable resin composition containing a naphthol novolac type epoxy resin and a polyphenylene ether resin is disclosed.
  • the insulating layer is treated with an aqueous solution of an oxidizing agent for the purpose of removing residual components after drilling the insulating layer or roughening the surface for improving the adhesion between the insulating layer and the conductor layer.
  • Desmear processing is performed by According to the studies of the present inventors, when an insulating layer formed from a resin composition containing a thermosetting resin and polyphenylene ether is subjected to desmear treatment, a particle having a diameter exceeding about 0.5 ⁇ m is formed on the surface of the insulating layer. It has been found that pitting may occur.
  • the present embodiment provides a resin composition capable of forming a cured product in which the occurrence of depressions on the surface after desmear treatment is suppressed, a prepreg, a laminate, a resin film using the resin composition,
  • An object of the present invention is to provide a printed wiring board and a semiconductor package.
  • the present embodiment relates to the following [1] to [13].
  • [1] (A) one or more selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of the maleimide resins; (B) a polyphenylene ether resin having a functional group containing an ethylenically unsaturated bond; (C) a styrene-based elastomer having a weight average molecular weight (Mw) of more than 10,000 and less than 100,000; (D) an organic peroxide; A resin composition containing [2] The resin composition according to [1] above, wherein the component (B) has a functional group containing an ethylenically unsaturated bond at its end.
  • a printed wiring board comprising a cured product of the resin composition according to any one of [1] to [8] above.
  • a resin composition capable of forming a cured product in which the occurrence of depressions on the surface after desmearing is suppressed, a prepreg, a laminate, a resin film, a printed wiring board, and a semiconductor package using the resin composition can be provided.
  • a numerical range indicated using “to” indicates a range including the numerical values before and after “to” as the minimum and maximum values, respectively.
  • the notation of a numerical range “X to Y” means a numerical range that is greater than or equal to X and less than or equal to Y.
  • the description "X or more” in this specification means X and a numerical value exceeding X.
  • the description “Y or less” in this specification means Y and a numerical value less than Y.
  • the lower and upper limits of any numerical range recited herein are optionally combined with the lower or upper limits of other numerical ranges, respectively. In the numerical ranges described herein, the lower or upper limit of the numerical range may be replaced with the values shown in the examples.
  • each component and material exemplified in this specification may be used singly or in combination of two or more unless otherwise specified.
  • the content of each component in the resin composition refers to the content of the plurality of substances present in the resin composition when there are multiple substances corresponding to each component in the resin composition, unless otherwise specified. means the total amount of
  • solid content means components other than the solvent, including those that are liquid at room temperature, starch syrup, and wax.
  • room temperature means 25°C.
  • (Meth)acryloyl as used herein means “acryloyl” and the corresponding “methacryloyl”.
  • the weight average molecular weight (Mw) in this specification means a value measured by gel permeation chromatography (GPC; Gel Permeation Chromatography) in terms of polystyrene. Specifically, the weight average molecular weight (Mw) in this specification can be measured by the method described in Examples.
  • the resin composition of this embodiment is (A) one or more selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of the maleimide resins; (B) a polyphenylene ether resin having a functional group containing an ethylenically unsaturated bond; (C) a styrene-based elastomer having a weight average molecular weight (Mw) of more than 10,000 and less than 100,000; (D) an organic peroxide; It is a resin composition containing
  • maleimide resin having one or more N-substituted maleimide groups and derivatives of the maleimide resin
  • (A) maleimide resin or "(A) component ”
  • (B) the polyphenylene ether-based resin having a functional group containing an ethylenically unsaturated bond may be simply referred to as "(B) polyphenylene ether-based resin” or "(B) component".
  • (C) a styrene-based elastomer having a weight average molecular weight (Mw) of more than 10,000 and less than 100,000 may be simply referred to as "(C) styrene-based elastomer” or "(C) component”.
  • (D) organic peroxide may be called "(D)component.”
  • the reason why the resin composition of the present embodiment can form a cured product in which the occurrence of depressions on the surface after desmear treatment is suppressed is presumed as follows.
  • a conventional polyphenylene ether is blended with (A) a maleimide resin
  • the compatibility between the two decreases as the curing of the maleimide resin (A) progresses due to the difference in polarity between the two, and the cured product lacks homogeneity. It is presumed that there was an insufficient area and this was the cause of the depression.
  • the resin composition of the present embodiment uses, as the component (B), a polyphenylene ether-based resin having a functional group containing an ethylenically unsaturated bond that is reactive with the maleimide-based resin (A), Furthermore, it also contains (D) an organic peroxide. Therefore, (B) the polyphenylene ether-based resin is mixed with (A) the maleimide-based resin using (D) an organic peroxide as a polymerization initiator before the compatibility decreases with the progress of curing of the (A) maleimide-based resin. It is considered that the reaction becomes easier and the homogeneity of the cured product is improved.
  • the resin composition of the present embodiment further contains a styrene-based elastomer having a weight average molecular weight (Mw) of more than 10,000 and less than 100,000 as component (C).
  • component (C) has an excellent balance of physical properties such as dielectric properties, heat resistance and Young's modulus.
  • the component (C) has a weight average molecular weight (Mw) of more than 10,000, so that the fluidity of the resin composition during heating is moderately suppressed, resulting in excellent moldability and a weight average molecular weight (Mw) of When Mw) is less than 100,000, compatibility with other resins tends to be excellent.
  • the (C) styrene-based elastomer also loses compatibility with the (A) maleimide-based resin as the curing of the (A) maleimide-based resin progresses.
  • the (C) styrene-based elastomer since the (C) styrene-based elastomer has excellent affinity with the (B) polyphenylene ether-based resin, the (B) polyphenylene ether-based resin tends to be homogeneously present in the resin composition of the present embodiment.
  • (C) It is thought that the compatibility of the styrene-based elastomer became less likely to decrease.
  • the resin composition of the present embodiment suppresses the formation of depressions on the surface of the cured product after desmearing, and thus the cured product is preferably a resin composition that undergoes desmearing. It is more preferable that the cured product is a resin composition for a printed wiring board which is subjected to desmear treatment.
  • the resin composition of the present embodiment will be described below in order.
  • the maleimide resin is one or more selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of the maleimide resins.
  • the maleimide-based resin may be used singly or in combination of two or more.
  • maleimide resin having one or more N-substituted maleimide groups may be referred to as "maleimide resin (AX)” or “(AX) component”.
  • a maleimide resin derivative having one or more N-substituted maleimide groups is sometimes referred to as a “maleimide resin derivative (AY)” or “(AY) component”.
  • the maleimide resin (AX) is not particularly limited as long as it has one or more N-substituted maleimide groups.
  • the maleimide resin (AX) is preferably an aromatic maleimide resin having two or more N-substituted maleimide groups from the viewpoint of conductor adhesion and heat resistance, and an aromatic bismaleimide having two N-substituted maleimide groups. Resin is more preferred.
  • aromatic maleimide resin means a compound having an N-substituted maleimide group directly bonded to an aromatic ring.
  • aromatic bismaleimide resin as used herein means a compound having two N-substituted maleimide groups directly bonded to an aromatic ring.
  • aromatic polymaleimide resin as used herein means a compound having 3 or more N-substituted maleimide groups directly bonded to an aromatic ring.
  • aliphatic maleimide resin as used herein means a compound having an N-substituted maleimide group directly bonded to an aliphatic hydrocarbon.
  • maleimide resin (AX) a maleimide resin represented by the following general formula (A1-1) [hereinafter referred to as "maleimide resin (A1)"] is preferable.
  • X a11 is a divalent organic group.
  • X a11 in general formula (A1-1) above is a divalent organic group.
  • the divalent organic group represented by X a11 in the general formula (A1-1) includes, for example, a divalent group represented by the following general formula (A1-2), and a divalent group represented by the following general formula (A1-3).
  • a divalent group represented by is mentioned.
  • 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.
  • Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R a11 in the general formula (A1-2) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl t-butyl group, n-pentyl group and other alkyl groups having 1 to 5 carbon atoms; alkenyl groups having 2 to 5 carbon atoms and alkynyl groups having 2 to 5 carbon atoms.
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms may be linear or branched.
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group.
  • Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.
  • n a11 in the general formula (A1-2) is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, still more preferably 0, from the viewpoint of availability. When n a11 is an integer of 2 or more, the plurality of R a11 may be the same or different.
  • R a12 and R a13 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom;
  • X a12 is an alkylene group having 1 to 5 carbon atoms;
  • n a12 and n a13 are an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, or a divalent group represented by the following general formula (A1-3-1). , each independently an integer from 0 to 4. * represents a binding site.)
  • Examples of aliphatic hydrocarbon groups having 1 to 5 carbon atoms represented by R a12 and R a13 in general formula (A1-3) include methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl. alkyl groups having 1 to 5 carbon atoms such as isobutyl group, t-butyl group and n-pentyl group; alkenyl groups having 2 to 5 carbon atoms and alkynyl groups having 2 to 5 carbon atoms.
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms may be linear or branched.
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group or an ethyl group.
  • Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.
  • Examples of the alkylene group having 1 to 5 carbon atoms represented by X a12 in the general formula (A1-3) include methylene group, 1,2-dimethylene group, 1,3-trimethylene group and 1,4-tetramethylene group, 1,5-pentamethylene group, and the like.
  • the alkylene group having 1 to 5 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and still more preferably a methylene group.
  • the alkylidene group having 2 to 5 carbon atoms represented by X a12 in the general formula (A1-3) includes, for example, an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopentylidene group. etc.
  • an alkylidene group having 2 to 4 carbon atoms is preferred, an alkylidene group having 2 or 3 carbon atoms is more preferred, and an isopropylidene group is even more preferred.
  • n a12 and n a13 in general formula (A1-3) are each independently an integer of 0 to 4.
  • n a12 or n a13 is an integer of 2 or more
  • the plurality of R a12s or the plurality of R a13s may be the same or different.
  • the divalent group represented by general formula (A1-3-1) represented by X a12 in general formula (A1-3) is as follows.
  • R a14 and R a15 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom;
  • X a13 is an alkylene group having 1 to 5 carbon atoms; an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond,
  • n a14 and n a15 are each independently an integer of 0 to 4. * represents a bonding site.
  • Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R a14 and R a15 in the general formula (A1-3-1) include methyl group, ethyl group, n-propyl group, isopropyl group, n C1-5 alkyl groups such as -butyl group, isobutyl group, t-butyl group and n-pentyl group; C2-5 alkenyl groups and C2-5 alkynyl groups.
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms may be linear or branched.
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group.
  • Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.
  • alkylene group having 1 to 5 carbon atoms represented by X a13 in the general formula (A1-3-1) examples include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4- A tetramethylene group, a 1,5-pentamethylene group and the like can be mentioned.
  • the alkylene group having 1 to 5 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and still more preferably a methylene group.
  • Examples of the alkylidene group having 2 to 5 carbon atoms represented by X a13 in the general formula (A1-3-1) include ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentyl A lidene group and the like can be mentioned.
  • an alkylidene group having 2 to 4 carbon atoms is preferred, an alkylidene group having 2 or 3 carbon atoms is more preferred, and an isopropylidene group is even more preferred.
  • X a13 in the general formula (A1-3-1) is preferably an alkylidene group having 2 to 5 carbon atoms, more preferably an alkylidene group having 2 to 4 carbon atoms, and further an isopropylidene group. preferable.
  • n a14 and n a15 in the general formula (A1-3-1) are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, and more It is preferably 0 or 1, more preferably 0.
  • n a14 or n a15 is an integer of 2 or more, the plurality of R a14s or the plurality of R a15s may be the same or different.
  • an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, and an alkylidene group having 2 to 5 carbon atoms, represented by the general formula (A1-3-1) is preferred, an alkylene group having 1 to 5 carbon atoms is more preferred, and a methylene group is even more preferred.
  • n a16 is an integer of 0 to 10. * represents a binding site.
  • n a16 in general formula (A1-4) is preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and still more preferably an integer of 0 to 3, from the viewpoint of availability.
  • n a17 is a number from 0 to 5. * represents a binding site.
  • R a16 and R a17 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
  • n a18 is an integer of 1 to 8. * represents a bonding site.
  • Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R a16 and R a17 in the general formula (A1-6) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. alkyl groups having 1 to 5 carbon atoms such as isobutyl group, t-butyl group and n-pentyl group; alkenyl groups having 2 to 5 carbon atoms and alkynyl groups having 2 to 5 carbon atoms.
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms may be linear or branched.
  • n a18 in general formula (A1-6) is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1.
  • n a18 is an integer of 2 or more, the plurality of R a16 or the plurality of R a17 may be the same or different.
  • maleimide resins (A1) include aromatic bismaleimide resins, aromatic polymaleimide resins, and aliphatic maleimide resins.
  • Specific examples of the maleimide resin (A1) 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'-diphenylmethane bismaleimide, bis(4-maleimide phenyl)ether, bis(4-maleimidophenyl)sulfone
  • maleimide resin derivative (AY) As the maleimide resin derivative (AY), an aminomaleimide resin having a structural unit derived from the maleimide resin (AX) and a structural unit derived from a diamine compound [hereinafter referred to as "aminomaleimide resin (A2)" or “(A2) component ” may be called. ] is preferable.
  • aminomaleimide resin (A2) has structural units derived from the maleimide resin (AX) and structural units derived from the diamine compound.
  • the structural unit derived from the maleimide resin (AX) for example, among the N-substituted maleimide groups possessed by the maleimide resin (AX), at least one N-substituted maleimide group undergoes a Michael addition reaction with an amino group possessed by the diamine compound.
  • a structural unit consisting of The structural unit derived from the maleimide resin (AX) contained in the aminomaleimide resin (A2) may be of one type alone or of two or more types.
  • the content of structural units derived from the maleimide resin (AX) in the aminomaleimide resin (A2) is not particularly limited, but is preferably 5 to 95% by mass, more preferably 30 to 93% by mass, and still more preferably 60 to 90%. % by mass.
  • the content of the structural unit derived from the maleimide resin (AX) in the aminomaleimide resin (A2) is within the above range, the dielectric properties and the handleability of the resin film tend to be better.
  • the structural unit derived from the diamine compound for example, one or both of the two amino groups of the diamine compound undergo a Michael addition reaction with an N-substituted maleimide group of the maleimide resin (AX).
  • AX N-substituted maleimide group of the maleimide resin
  • the structural unit derived from the diamine compound contained in the aminomaleimide resin (A2) may be of one type alone or of two or more types.
  • the amino group of the diamine compound is preferably a primary amino group.
  • Examples of the structural unit derived from the diamine compound having two primary amino groups include a group represented by the following general formula (A2-1), a group represented by the following general formula (A2-2), and the like. be done.
  • X a21 is a divalent organic group, and * represents a binding site.
  • X a21 in general formulas (A2-1) and (A2-2) above is a divalent organic group and corresponds to a divalent group obtained by removing two primary amino groups from a diamine compound. do.
  • X a21 in general formulas (A2-1) and (A2-2) above is preferably a divalent group represented by general formula (A2-3) below.
  • R a21 and R a22 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group or a halogen atom. an alkylene group having up to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a fluorenylene group, a single bond, or the following general formula (A2-3-1) or the following It is a divalent group represented by the general formula (A2-3-2), n a21 and n a22 are each independently an integer of 0 to 4. * represents a binding site.)
  • R a23 and R a24 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom;
  • X a23 is an alkylene group having 1 to 5 carbon atoms; an alkylidene group, a m-phenylenediisopropylidene group, a p-phenylenediisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond,
  • n a23 and n a24 are each independently , an integer from 0 to 4. * represents a binding site.
  • R a25 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom;
  • X a24 and X a25 each independently represent an alkylene group having 1 to 5 carbon atoms; is an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond,
  • n a25 is an integer of 0 to 4. * represents a bonding site.
  • 1 to 5 aliphatic hydrocarbon groups include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group and the like. to 5 alkyl groups; alkenyl groups having 2 to 5 carbon atoms; and alkynyl groups having 2 to 5 carbon atoms.
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms may be linear or branched.
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group or an ethyl group.
  • Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.
  • X a22 in the general formula (A2-3), X a23 in the general formula (A2-3-1), and X a24 and X a25 in the general formula (A2-3-2) have 1 carbon atoms.
  • the alkylene group of 1 to 5 include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group and the like.
  • the alkylene group having 1 to 5 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and still more preferably a methylene group.
  • alkylidene groups of 2 to 5 include ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group and the like.
  • the alkylidene group having 2 to 5 carbon atoms is preferably an alkylidene group having 2 to 4 carbon atoms, more preferably an alkylidene group having 2 or 3 carbon atoms, and still more preferably an isopropylidene group.
  • n a21 and n a22 in the general formula (A2-3) are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 3, more preferably It is an integer from 0 to 2, more preferably 0 or 2.
  • n a21 or n a22 is an integer of 2 or more, the plurality of R a21s or the plurality of R a22s may be the same or different.
  • n a23 and n a24 in the general formula (A2-3-1) are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, and more It is preferably 0 or 1, more preferably 0.
  • n a23 or n a24 is an integer of 2 or more, the plurality of R a23s or the plurality of R a24s may be the same or different.
  • n a25 in the general formula (A2-3-2) is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, more preferably 0 from the viewpoint of availability is.
  • n a25 is an integer of 2 or more, a plurality of R a25 may be the same or different.
  • X a21 in general formulas (A2-1) and (A2-2) above may be a divalent group containing a structural unit represented by general formula (A2-4) below. Alternatively, it may be a divalent group represented by the following general formula (A2-5).
  • R a26 and R a27 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a phenyl group or a substituted phenyl group. * represents a bonding site.
  • R a26 and R a27 are the same as those in the above general formula (A2-4), R a28 and R a29 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a phenyl group or a substituted phenyl group, X a26 and X a27 each independently represent a divalent organic group, and n a26 is an integer of 2 to 100. * represents a binding site.
  • Examples of aliphatic hydrocarbon groups having 1 to 5 carbon atoms represented by R a26 to R a29 in general formulas (A2-4) and (A2-5) include methyl group, ethyl group, n-propyl group, C1-5 alkyl groups such as isopropyl group, n-butyl group, isobutyl group, t-butyl group and n-pentyl group; C2-5 alkenyl groups, C2-5 alkynyl groups, etc. mentioned.
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms may be linear or branched.
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group.
  • Substituents possessed by the phenyl groups in the substituted phenyl groups represented by R a26 to R a29 include the aforementioned aliphatic hydrocarbon groups having 1 to 5 carbon atoms.
  • Examples of the divalent organic group represented by X a26 and X a27 include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, —O—, and a divalent linking group in which these are combined.
  • Examples of the alkylene group include alkylene groups having 1 to 10 carbon atoms such as a methylene group, ethylene group and 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 phenylene group and naphthylene group.
  • Xa26 and Xa27 are preferably an alkylene group or an arylene group, more preferably an alkylene group.
  • n a26 is an integer of 2-100, preferably an integer of 2-50, more preferably an integer of 3-40, and still more preferably an integer of 5-30.
  • n a26 is an integer of 2 or more
  • the plurality of R a26 or the plurality of R a27 may be the same or different.
  • the content of the structural unit derived from the diamine compound in the aminomaleimide resin (A2) is not particularly limited, but is preferably 5 to 95% by mass, more preferably 7 to 70% by mass, and still more preferably 10 to 40% by mass. be.
  • the content of the structural unit derived from the diamine compound in the aminomaleimide resin (A2) is within the above range, dielectric properties, heat resistance, flame retardancy and glass transition temperature tend to be better.
  • diamine compounds examples 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'-diaminodipheny
  • diamine compounds are 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4, 3,3'-dimethyl-4, 4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-[1,3-phenylene Bis(1-methylethylidene)]bisaniline and 4,4′-[1,4-phenylenebis(1-methylethylidene)]bisaniline are preferred, and 3,3′-diethyl-4,4′-diaminodiphenylmethane is more preferred. preferable.
  • a silicone compound having two primary amino groups is preferable.
  • the silicone compound having two primary amino groups a silicone compound having primary amino groups at both terminals is preferable.
  • the primary amino group equivalent weight of the silicone 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 g/mol. ⁇ 1,000 g/mol.
  • the ratio (Ta2/Ta1) is not particularly limited, it is preferably from 0.05 to 10, more preferably from 1 to 8, and still more preferably from 3 to 3, from the viewpoint of dielectric properties, heat resistance, flame retardancy and glass transition temperature.
  • the group derived from the —NH 2 group of the diamine compound includes —NH 2 itself. Further, the group derived from the N-substituted maleimide group of the maleimide resin (AX) includes the N-substituted maleimide group itself.
  • the weight average molecular weight (Mw) of the aminomaleimide resin (A2) is not particularly limited, but is preferably 400 to 10,000, more preferably 1,000 to 5,000, still more preferably 1,000 to 5,000, from the viewpoint of handleability and moldability. is 1,500 to 4,000, particularly preferably 2,000 to 3,000.
  • the aminomaleimide resin (A2) can be produced, for example, by reacting the maleimide resin (AX) with a diamine compound in an organic solvent. By reacting the maleimide resin (AX) with the diamine compound, an aminomaleimide resin (A2) is obtained through the Michael addition reaction between the maleimide resin (AX) and the diamine compound.
  • a reaction catalyst may be used as necessary.
  • 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 viewpoint of workability such as reaction rate and suppression of gelation of the product during the reaction. °C.
  • the reaction time of the Michael addition reaction is preferably 0.5 to 10 hours, more preferably 1 to 8 hours, still more preferably 2 to 6 hours, from the viewpoint of productivity and sufficient progress of the reaction.
  • these reaction conditions are not particularly limited and can be appropriately adjusted depending on the type of raw material used.
  • the content of (A) the maleimide-based resin is not particularly limited, but is preferably 20 ⁇ 95% by mass, more preferably 50 to 90% by mass, still more preferably 70 to 85% by mass.
  • the content of the maleimide-based resin is at least the above lower limit, heat resistance, moldability, workability, and conductor adhesion tend to be better. Further, when the content of (A) the maleimide resin is equal to or less than the above upper limit, the dielectric properties tend to be more favorable.
  • the term "resin component” means a resin and a compound that forms a resin through a curing reaction.
  • resin component means a resin and a compound that forms a resin through a curing reaction.
  • (A) maleimide-based resin, (B) polyphenylene ether-based resin, (C) styrene-based elastomer, and (D) organic peroxide correspond to resin components.
  • the resin composition of the present embodiment contains, as optional components, a resin or a compound that forms a resin by a curing reaction in addition to the above components, these optional components are also included in the resin component.
  • the optional component corresponding to the resin component include (F) a curing accelerator other than the organic peroxide, which will be described later.
  • the (E) inorganic filler is not included in the resin component.
  • the total content of the resin components in the resin composition of the present embodiment is not particularly limited, but from the viewpoint of low thermal expansion, heat resistance, flame retardancy and conductor adhesion, the solid content of the resin composition of the present embodiment It is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and still more preferably 30 to 50% by mass relative to the total amount (100% by mass).
  • the polyphenylene ether-based resin is not particularly limited as long as it is a resin having a functional group containing a polyphenylene ether chain and an ethylenically unsaturated bond.
  • the resin composition of the present embodiment tends to easily obtain excellent dielectric properties by containing (B) a polyphenylene ether-based resin.
  • the polyphenylene ether-based resin may be used alone or in combination of two or more.
  • the polyphenylene ether-based resin has a phenylene ether bond, and preferably has a structural unit represented by the following general formula (B-1).
  • R b1 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • n b1 is an integer of 0 to 4.
  • Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b1 in the general formula (B-1) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group, t-butyl group, n-pentyl group and the like.
  • the aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group.
  • n b1 is an integer of 0 to 4, preferably 1 or 2, more preferably 2;
  • the substitution position of R b1 is preferably the ortho position on the benzene ring with respect to the substitution position of the oxygen atom.
  • n b1 is an integer of 2 or more, a plurality of R b1 may be the same or different.
  • the structural unit represented by the above general formula (B-1) is preferably a structural unit represented by the following general formula (B-1').
  • the polyphenylene ether-based resin has a functional group containing an ethylenically unsaturated bond [hereinafter sometimes referred to as an "ethylenically unsaturated bond-containing group” from the viewpoint of suppressing the generation of depressions after desmear treatment. ].
  • ethylenically unsaturated bond means a carbon-carbon double bond capable of an addition reaction, and does not include a double bond of an aromatic ring.
  • Ethylenically unsaturated bond-containing groups include, for example, vinyl group, allyl group, 1-methylallyl group, isopropenyl group, 2-butenyl group, 3-butenyl group, styryl group, maleimide group, the following general formula (B-2 ) and the like.
  • R b2 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • the alkyl group having 1 to 20 carbon atoms represented by R b2 may be a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group, preferably a straight-chain alkyl group.
  • the number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-5, still more preferably 1-3, and particularly preferably 1.
  • alkyl group examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, pentadecyl group, hexadecyl group and heptadecyl group. Among them, a methyl group is preferred.
  • the group represented by the above general formula (B-2) in which R b2 is a hydrogen atom corresponds to an acryloyl group
  • the group represented by the above general formula (B-2) in which R b2 is a methyl group corresponds to a methacryloyl group.
  • the ethylenically unsaturated bond-containing group possessed by the polyphenylene ether-based resin is preferably a group represented by the general formula (B-2) from the viewpoint of dielectric properties, and (meth) An acryloyl group is more preferred, and a methacryloyl group is even more preferred.
  • the number of ethylenically unsaturated bond-containing groups that the polyphenylene ether-based resin has in one molecule is not particularly limited, but is preferably 1 to 5, more preferably 2 to 3, and still more preferably 2. be.
  • the number of ethylenically unsaturated bond-containing groups is at least the above lower limit, heat resistance tends to be better.
  • the number of ethylenically unsaturated bond-containing groups is equal to or less than the above upper limit, it tends to be easier to suppress the occurrence of depressions after the desmear treatment.
  • the polyphenylene ether-based resin preferably has ethylenically unsaturated bond-containing groups at its terminals, more preferably at both terminals.
  • the polyphenylene ether-based resin may have an ethylenically unsaturated bond-containing group in addition to the terminal, but preferably has an ethylenically unsaturated bond-containing group only at the terminal.
  • Polyphenylene ether-based resin is preferably a compound represented by the following general formula (B-3) from the viewpoint of dielectric properties.
  • R b1 and n b1 are as described in the general formula (B-1) above.
  • R b3 and R b4 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen
  • n b2 and n b3 are each independently an integer of 0 to 4.
  • n b4 and n b5 are each independently an integer of 0 to 20, and the sum of n b4 and n b5 is , an integer of 1 to 30.
  • X b1 is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond.
  • Yb1 and Yb2 are each independently the above ethylenically unsaturated bond-containing group.
  • n b2 and n b3 are integers from 0 to 4, preferably integers from 0 to 3, more preferably 2 or 3.
  • nb2 or nb3 is an integer of 2 or more
  • the plurality of Rb3 's or the plurality of Rb4 's may be the same or different.
  • nb4 and nb5 are integers of 0-20, preferably integers of 1-20, more preferably integers of 2-15, and even more preferably integers of 3-10.
  • nb4 or nb5 is an integer of 2 or more
  • the plurality of nb1 may be the same or different.
  • the sum of n b4 and n b5 is an integer of 1-30, preferably an integer of 2-25, more preferably an integer of 5-20, and still more preferably an integer of 7-15.
  • Examples of the alkylene group having 1 to 5 carbon atoms represented by X b1 in the general formula (B-3) include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group and a 1,4-tetramethylene group. group, 1,5-pentamethylene group, and the like.
  • Examples of the alkylidene group having 2 to 5 carbon atoms represented by X b1 include ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group and the like.
  • an isopropylidene group is preferable from the viewpoint of dielectric properties.
  • Preferred embodiments of the ethylenically unsaturated bond-containing groups represented by Yb1 and Yb2 are as described above.
  • the compound represented by the general formula (B-3) is preferably a compound represented by the following general formula (B-4).
  • n b4 and n b5 are as described in the general formula (B-3) above.
  • R b5 and R b6 are each independently a hydrogen atom or a methyl group.
  • X b2 is methylene. group or isopropylidene group.
  • the weight average molecular weight (Mw) of the polyphenylene ether resin 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, especially It is preferably 1,200 to 2,500.
  • the weight average molecular weight (Mw) of the polyphenylene ether-based resin is at least the above lower limit, there is a tendency to easily obtain a cured product having excellent dielectric properties of the polyphenylene ether and excellent heat resistance. Further, when the weight average molecular weight (Mw) of the (B) polyphenylene ether resin is equal to or less than the above upper limit, moldability tends to be more favorable.
  • the method for synthesizing the polyphenylene ether-based resin is not particularly limited, and a known method for synthesizing and modifying a polyphenylene ether can be applied.
  • the content of (B) the polyphenylene ether-based resin in the resin composition of the present embodiment is not particularly limited, but is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, still more preferably 10 to 20% by mass.
  • the content of the polyphenylene ether-based resin is at least the above lower limit, the dielectric properties tend to be more favorable.
  • the content of the (B) polyphenylene ether-based resin is equal to or less than the above upper limit, heat resistance, moldability, and workability tend to be improved.
  • the styrene elastomer is not particularly limited as long as it has a weight average molecular weight (Mw) of more than 10,000 and less than 100,000.
  • Mw weight average molecular weight
  • the resin composition of the present embodiment tends to easily obtain excellent dielectric properties by containing (C) the styrene-based elastomer.
  • elastomer as used herein means a polymer having a glass transition temperature of 25°C or less as measured by differential scanning calorimetry according to JIS K 6240:2011.
  • Styrene-based elastomers may be used singly or in combination of two or more.
  • (C) As the styrene-based elastomer, one having a structural unit derived from a styrene-based compound represented by the following general formula (C-1) is preferable.
  • R c1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R c2 is an alkyl group having 1 to 5 carbon atoms
  • n c1 is an integer of 0 to 5.
  • alkyl groups having 1 to 5 carbon atoms represented by R c1 and R c2 in the general formula (C-1) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group, t-butyl group, n-pentyl group and the like.
  • the alkyl group having 1 to 5 carbon atoms may be linear or branched. Among these, an alkyl group having 1 to 3 carbon atoms is preferred, an alkyl group having 1 or 2 carbon atoms is more preferred, and a methyl group is even more preferred.
  • n c1 in the general formula (C-1) is an integer of 0 to 5, preferably an integer of 0 to 2, more preferably 0 or 1, still more preferably 0.
  • the styrene-based elastomer may contain structural units other than structural units derived from styrene-based compounds.
  • structural units other than structural units derived from styrene compounds that may be contained in the styrene elastomer (C) include structural units derived from butadiene, structural units derived from isoprene, structural units derived from maleic acid, and structural units derived from maleic anhydride. Structural units and the like can be mentioned.
  • the butadiene-derived structural unit and the isoprene-derived structural unit may be hydrogenated. When hydrogenated, structural units derived from butadiene become structural units in which ethylene units and butylene units are mixed, and structural units derived from isoprene become structural units in which ethylene units and propylene units are mixed.
  • Examples of (C) styrene elastomers include hydrogenated styrene-butadiene-styrene block copolymers, hydrogenated styrene-isoprene-styrene block copolymers, and styrene-maleic anhydride copolymers. be done. Hydrogenated products of styrene-butadiene-styrene block copolymers are SEBS obtained by completely hydrogenating the carbon-carbon double bonds in the butadiene block, and SBBS obtained by partially hydrogenating a heavy bond can be mentioned.
  • complete hydrogenation in SEBS usually means that the hydrogenation rate of the entire carbon-carbon double bond is 90% or more, may be 95% or more, or may be 99% or more. It may be 100%.
  • the partial hydrogenation rate in SBBS is, for example, 60 to 85% with respect to the entire carbon-carbon double bond.
  • a hydrogenated styrene-isoprene-styrene block copolymer is obtained as SEPS by hydrogenating the polyisoprene portion.
  • SEBS and SEPS are preferred, and SEBS is more preferred, from the viewpoint of dielectric properties, conductor adhesion, heat resistance, glass transition temperature and low thermal expansion.
  • the content of structural units derived from styrene compounds is not particularly limited, but is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and still more preferably 30 to 60% by mass.
  • the melt flow rate (MFR) of the styrene elastomer is not particularly limited, but is preferably 0.1 to 20 g/10 min, more preferably 1 to 10 g/10 min, more preferably 3 to 7 g/10 min.
  • Examples of commercially available styrene-based elastomers include SEBS, Tuftec (registered trademark) H series and M series manufactured by Asahi Kasei Corporation, Septon (registered trademark) series manufactured by Kuraray Co., Ltd., and Kraton Polymer Japan Co., Ltd. Kraton (registered trademark) G polymer series manufactured by the company and the like can be mentioned.
  • the weight average molecular weight (Mw) of the styrene-based elastomer is more than 10,000 and less than 100,000, preferably 15,000 to 98,000, more preferably 30,000 to 95,000, even more preferably is 50,000 to 93,000, more preferably 70,000 to 92,000, particularly preferably 80,000 to 90,000.
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) of the styrene-based elastomer (C) is at least the above lower limit, the fluidity of the resin composition during heating is moderately suppressed, so that moldability tends to be excellent.
  • compatibility with other resins tends to be excellent.
  • the content of (C) the styrene-based elastomer in the resin composition of the present embodiment is not particularly limited, but is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and even more preferably 5 to 10% by mass.
  • the content of the styrene-based elastomer is at least the above lower limit, dielectric properties and flexibility tend to be better.
  • the content of (C) the styrene-based elastomer is equal to or less than the above upper limit, heat resistance and flame retardancy tend to be better.
  • Organic peroxide is not particularly limited as long as it is an organic compound containing a peroxide bond (--O--O--).
  • Organic peroxides may be used singly or in combination of two or more.
  • the one-hour half-life temperature of the organic peroxide is not particularly limited, but is preferably 100 to 200°C, more preferably 120 to 170°C, and still more preferably 130 to 150°C.
  • the 1-hour half-life temperature of the organic peroxide is at least the above lower limit, the progress of unintended reactions during storage tends to be suppressed.
  • the content of (D) the organic peroxide is equal to or less than the above upper limit, the occurrence of depressions after the desmear treatment tends to be more easily suppressed.
  • the 1-hour half-life temperature of the organic peroxide is obtained by decomposing the (D) organic peroxide in the solvent under a plurality of temperature conditions, determining the decomposition rate constants at each temperature, and calculating these decomposition rate constants. It can be calculated by Arrhenius plotting.
  • the 1-hour half-life temperature in the present embodiment is the 1-hour half-life temperature measured under the condition that the concentration of (D) organic peroxide is 0.1 mol/L in benzene.
  • Organic peroxides include, for example, 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(t-butylperoxy)butane, 2,2-di(4,4- di-t-butylperoxycyclohexyl)propane, peroxyketals such as 1,1-di(t-amylperoxy)cyclohexane; hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide; t - Alkyl peroxides such as butyl peroxyacetate and t-amyl peroxy isononanoate; t-butyl cumyl peroxide, di-t-butyl peroxide, dicumyl peroxide, di-t-hexyl peroxide, 1 , 3-bis(2-t-butylperoxyisopropyl)benzene and other dialkyl peroxides; t-butylperoxyacetate
  • the content of (D) organic peroxide in the resin composition of the present embodiment is not particularly limited, but is preferably is 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 0.5 to 2 parts by mass.
  • (D) When the content of the organic peroxide is at least the above lower limit, the occurrence of depressions after desmear treatment tends to be more easily suppressed. Further, when the content of (D) the organic peroxide is equal to or less than the above upper limit, the reaction rate becomes moderate, and the homogeneity of the cured product tends to be easily improved.
  • Inorganic fillers include, for example, silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, silicon aluminum oxide, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, silicon carbide and the like.
  • silica, alumina, mica, and talc are preferred, and silica and alumina are more preferred, from the viewpoint of low thermal expansion, heat resistance, and flame retardancy.
  • Silica includes, for example, precipitated silica produced by a wet method and having a high moisture content, and dry-process silica produced by a dry method and containing almost no bound water.
  • dry process silica include crushed silica, fumed silica, fused silica, etc., depending on the production method.
  • the average particle size of the (E) inorganic filler is not particularly limited, but from the viewpoint of dispersibility and fine wiring properties of the (E) inorganic filler, it is preferably 0.01 to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m. , more preferably 0.2 to 1 ⁇ m, particularly preferably 0.3 to 0.8 ⁇ m.
  • the average particle size of the inorganic filler (E) is the total volume of the particles as 100%, and when the cumulative frequency distribution curve by the particle size is obtained, the particle size of the point corresponding to 50% of the volume. That is.
  • the average particle size of the inorganic filler can be measured, for example, with a particle size distribution analyzer using a laser diffraction scattering method.
  • the shape of the inorganic filler includes, for example, a spherical shape, a crushed shape, etc., and a spherical shape is preferred.
  • ((E) content of inorganic filler When the resin composition of the present embodiment contains (E) an inorganic filler, the content is not particularly limited, but is preferably 30 to 90 with respect to the total solid content (100% by mass) of the resin composition. % by mass, more preferably 40 to 80% by mass, and even more preferably 50 to 70% by mass.
  • the content of the inorganic filler is at least the above lower limit, low thermal expansion, heat resistance and flame retardancy tend to be more favorable.
  • the content of (E) the inorganic filler is equal to or less than the above upper limit, moldability and conductor adhesiveness tend to be more favorable.
  • the resin composition of the present embodiment preferably further contains (F) a curing accelerator other than the organic peroxide.
  • (F) Curing accelerators other than organic peroxides may be used alone or in combination of two or more.
  • Curing accelerators other than organic peroxides include, for example, amine-based curing accelerators, imidazole-based curing accelerators, phosphorus-based curing accelerators, organic metal salts, and acidic catalysts.
  • imidazole-based curing accelerators are not classified as amine-based curing accelerators.
  • amine curing accelerators include amine compounds having primary to tertiary amines such as triethylamine, pyridine, tributylamine and dicyandiamide; quaternary ammonium compounds.
  • imidazole-based curing accelerators examples include imidazole compounds such as methylimidazole, phenylimidazole and 2-undecylimidazole; isocyanate masked imidazoles such as addition reaction products of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole; mentioned.
  • phosphorus curing accelerators include tertiary phosphines such as triphenylphosphine; quaternary phosphonium compounds such as tri-n-butylphosphine addition reaction product of p-benzoquinone.
  • Organic metal salts include, for example, carboxylates of manganese, cobalt, zinc and the like.
  • acidic catalysts examples include p-toluenesulfonic acid and the like.
  • acidic catalysts examples include p-toluenesulfonic acid and the like.
  • amine-based curing accelerators examples include amine-based curing accelerators, imidazole-based curing accelerators, and phosphorus-based curing accelerators are preferable.
  • Class phosphonium compounds are more preferred, and it is even more preferred to use them in combination.
  • the content thereof is preferably 0.01 to 10 parts per 100 parts by mass of the maleimide resin (A). parts by mass, more preferably 0.1 to 7 parts by mass, and even more preferably 1 to 5 parts by mass.
  • the content of the curing accelerator (F) other than the organic peroxide is at least the above lower limit, a sufficient curing acceleration effect tends to be obtained.
  • the content of (F) the curing accelerator other than the organic peroxide is equal to or less than the above upper limit, the storage stability tends to be more favorable.
  • the resin composition of the present embodiment may further contain a resin material other than the above components, a flame retardant, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a coloring agent, a lubricant, and a silane. It may contain one or more optional components selected from the group consisting of coupling agents, organic solvents and additives other than these. Each of the above optional components may be used alone or in combination of two or more. The content of the above optional components in the resin composition of the present embodiment is not particularly limited, and may be used as necessary within a range that does not impair the effects of the present embodiment. Moreover, the resin composition of the present embodiment may not contain any of the above optional components depending on the desired performance.
  • the resin composition of this embodiment can be produced by mixing the components described above.
  • each component When mixing each component, each component may be dissolved or dispersed while stirring.
  • Conditions such as the order of mixing raw materials, mixing temperature, and mixing time are not particularly limited, and may be arbitrarily set according to the type of raw materials.
  • the relative dielectric constant (Dk) at 10 GHz of the cured product of the resin composition of the present embodiment is not particularly limited, but from the viewpoint of low transmission loss, it is preferably 3.8 or less, more preferably 3.6 or less, and further Preferably it is 3.4 or less.
  • the dielectric constant (Dk) of the cured product is preferably as small as possible, and the lower limit thereof is not particularly limited. It may be 4 or more, or 2.6 or more.
  • the conditions for obtaining a cured product from the resin composition of the present embodiment can be the conditions described in Examples.
  • the dielectric loss tangent (Df) at 10 GHz of the cured product of the resin composition of the present embodiment is not particularly limited, but from the viewpoint of low transmission loss, it is preferably 0.0040 or less, more preferably 0.0035 or less, and further preferably is 0.0030 or less.
  • the dielectric loss tangent (Df) of the cured product is preferably as small as possible, and the lower limit thereof is not particularly limited. or more, or 0.0020 or more.
  • the relative permittivity (Dk) and dielectric loss tangent (Df) are values based on the cavity resonator perturbation method, more specifically, values measured by the method described in Examples.
  • the conditions for obtaining a cured product from the resin composition of the present embodiment can be the conditions described in Examples.
  • the prepreg of the present embodiment is a prepreg containing the resin composition of the present embodiment or a semi-cured material of the resin composition. That is, the prepreg of this embodiment is a prepreg formed using the resin composition of this embodiment.
  • the prepreg of the present embodiment preferably contains a B-staged resin composition obtained by converting the resin composition of the present embodiment into a B-stage, and a sheet-like fiber base material.
  • the prepreg of the present embodiment is preferably obtained by impregnating or coating a sheet-like fiber base material with the resin composition of the present embodiment, followed by B-stage.
  • B-staging is to bring the material into a B-stage state defined in JIS K 6900:1994, and is also called semi-curing.
  • sheet-like fiber base material contained in the prepreg of the present embodiment for example, known sheet-like fiber base materials used for various laminates for electrical insulating materials can be used.
  • materials for the sheet-like fiber substrate 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 fabrics, non-woven fabrics, robinks, chopped strand mats, surfacing mats, and the like.
  • the prepreg of the present embodiment can be produced, for example, by impregnating or applying the resin composition of the present embodiment to a sheet-like fiber base material, and then B-stages the resin composition by heating and drying.
  • the temperature and time of heat drying are not particularly limited, but from the viewpoint of productivity and moderate B-stage of the resin composition of the present embodiment, for example, 50 to 200 ° C., 1 to 30 minutes. .
  • the concentration of solids derived from the resin composition in the prepreg of the present embodiment is not particularly limited. More preferably 25 to 80 mass %, still more preferably 30 to 75 mass %.
  • the resin film of the present embodiment is a resin film containing the resin composition of the present embodiment or a semi-cured product of the resin composition. That is, the resin film of this embodiment is a resin film formed using the resin composition of this embodiment.
  • the resin film of the present embodiment is a film made from the resin composition of the present embodiment or a B-staged resin composition obtained by converting the resin composition of the present embodiment into a B-stage.
  • the resin film of the present embodiment can be produced, for example, by applying the resin composition of the present embodiment containing an organic solvent, ie, a resin varnish, to a support, followed by heating and drying. Examples of the support include plastic films, metal foils, release papers and the like.
  • the temperature and time of heat drying are not particularly limited, but from the viewpoint of productivity and moderate B-stage of the resin composition of the present embodiment, it can be 50 to 200 ° C. and 1 to 30 minutes.
  • the resin film of the present embodiment is preferably used for forming an insulating layer when manufacturing a printed wiring board.
  • the laminated board of this embodiment is a laminated board having a cured product of the prepreg of this embodiment. That is, the laminate of this embodiment is a laminate formed using the prepreg of this embodiment.
  • the laminate of the present embodiment preferably contains the cured prepreg of the present embodiment and metal foil.
  • a laminate having metal foil is sometimes referred to as a metal-clad laminate.
  • the metal of the metal foil is not particularly limited, and examples thereof include copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and alloys containing one or more of these metal elements. are mentioned.
  • the laminate of the present embodiment can be produced, for example, by placing a metal foil on one side or both sides of the prepreg of the present embodiment, followed by heating and pressure molding. Normally, the laminate of the present embodiment is obtained by curing the B-staged prepreg by this heat and pressure molding. In the heat and pressure molding, only one prepreg may be used, or two or more prepregs may be laminated.
  • heat-press molding for example, a multi-stage press, a multi-stage vacuum press, continuous molding, an autoclave molding machine, etc. can be used.
  • the conditions for the heat and pressure molding are not particularly limited, but can be, for example, a temperature of 100 to 300° C., a time of 10 to 300 minutes, and a pressure of 1.5 to 5 MPa.
  • the printed wiring board of this embodiment is a printed wiring board having a cured product of the resin composition of this embodiment.
  • the printed wiring board of the present embodiment is, for example, a printed wiring board formed 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. be.
  • the printed wiring board of the present embodiment includes at least a cured product of the resin composition of the present embodiment and a conductor circuit layer, a cured product of the prepreg of the present embodiment, and a cured product of the resin film of the present embodiment.
  • the method for manufacturing the printed wiring board of the present embodiment preferably includes a step of subjecting the insulating material containing the cured product of the resin composition of the present embodiment to desmear treatment.
  • a desmearing method a known method can be applied.
  • the printed wiring board of the present embodiment can be manufactured by forming a conductive circuit on the insulating material subjected to the desmear treatment by a known method.
  • a multilayer printed wiring board can also be manufactured by applying a multilayer adhesion process, if necessary.
  • the conductor circuit can be formed by appropriately performing, for example, drilling, metal plating, etching of metal foil, or the like.
  • the semiconductor package of this embodiment is a semiconductor package having the printed wiring board of this embodiment. That is, the semiconductor package of this embodiment is a semiconductor package formed using the printed wiring board of this embodiment.
  • the semiconductor package of this embodiment can be manufactured, for example, by mounting a semiconductor chip, a memory, etc. on the printed wiring board of this embodiment by a known method.
  • the weight average molecular weight (Mw) was measured by the following method. Conversion was performed from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). Calibration curve, 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, product name] and approximated by a cubic equation. GPC measurement conditions are shown below.
  • Examples 1 and 2 Comparative Example 1 (Manufacture of resin composition)
  • Each component shown in Table 1 was blended according to the formulation shown in Table 1, and stirred and mixed with 58 parts by mass of toluene and 10 parts by mass of methyl isobutyl ketone at room temperature (25 ° C.) to obtain a solid content concentration of 55 to 65.
  • a mass % resin composition was produced.
  • the unit of the compounding amount of each component is parts by mass, and in the case of a solution, it means parts by mass in terms of solid content.
  • a double-sided copper-clad laminate (thickness: 0.23 mm) was manufactured by placing in contact with the prepreg and heat-pressing molding under the conditions of a temperature of 230° C., a pressure of 3.0 MPa, and a time of 90 minutes.
  • the copper foil was removed from the double-sided copper-clad laminate obtained in each example by immersing it in a copper etching solution to obtain a cured prepreg.
  • the test piece was desmeared by performing the following (1) to (4) in order.
  • (1) After being immersed in a swelling liquid (manufactured by Atotech Japan Co., Ltd., trade name "Swelling Dip Securigant P", an aqueous solution of glycol ethers and sodium hydroxide) at 70°C for 5 minutes, it was washed with water.
  • An ion milling device (manufactured by Hitachi High-Technologies Co., Ltd., trade name: E-3500) was applied to the test piece after the desmear treatment with an acceleration voltage of 6 kV, a discharge voltage of 4 kV, and an Ar gas flow rate of 1.80 cm 3 /min. , a processing width of 500 ⁇ m, and a processing time of 6 hours. Then, using a scanning electron microscope (SEM) (manufactured by Hitachi High-Technologies Co., Ltd., trade name: SV-4700), the above test was performed under the conditions of secondary electron mode, acceleration voltage of 20 kV, and observation magnification of 5,000 times. A cross-section of the piece was observed.
  • SEM scanning electron microscope
  • the test piece has a composite layer consisting of a glass cloth and a cured product of the resin composition, and a cured resin consisting only of a cured product of the resin composition on both sides of the composite layer. It was confirmed that it has a material layer.
  • the test pieces having dents dents were observed on the surface of the cured resin layer, that is, on the surface of the cured resin layer that was in contact with the copper foil before removal.
  • FIG. 1 shows a schematic cross-sectional view of a test piece 10 for explaining a method of calculating the existence ratio (%) of depressions in the test piece after desmear treatment.
  • an area S1 surrounded by a dotted line is an area when it is assumed that the test piece 10 does not have a depression.
  • a region S2 is a region of the depression 3 with a size exceeding 0.5 ⁇ m.
  • the size of the recess 3 here means the length of a straight line connecting both ends of the recess represented by D in the enlarged view of FIG.
  • the existence ratio (%) of depressions was calculated as the ratio of the total area of the region S2 to the area of the region S1 (S2 ⁇ 100/S1).
  • a specimen was prepared by etching the copper foil of the double-sided copper-clad laminate obtained in each example into a straight line with a width of 3 mm.
  • the formed straight line-shaped copper foil is attached to a small desktop tester (manufactured by Shimadzu Corporation, trade name "EZ-TEST"), and the copper foil is pulled by peeling it off in a 90 ° direction at room temperature (25 ° C.).
  • the peel strength was measured.
  • the pulling speed for peeling off the copper foil was 50 mm/min.
  • the outer layer copper foil of the double-sided copper-clad laminate obtained in each example was removed by immersion in a copper etching solution (10% by mass ammonium persulfate solution, manufactured by Mitsubishi Gas Chemical Co., Ltd.) to a length of 60 mm and a width of 2 mm. A cut piece was used as a test piece. Using the test piece, the dielectric constant (Dk) and dielectric loss tangent (Df) were measured by the cavity resonator perturbation method.
  • a cavity resonator is "CP129” (10 GHz band resonator) manufactured by Kanto Denshi Applied Development Co., Ltd., and a measurement program is "CPMA-V2". each used. The measurement was performed under conditions of a frequency of 10 GHz and a measurement temperature of 25°C.
  • SEBS maleic anhydride-modified hydrogenated styrene elastomer (SEBS), acid value 10 mgCH3ONa /g, styrene content 45% by mass, weight average molecular weight (Mw) 86,000
  • the resin composition of the present embodiment can form a cured product in which the occurrence of depressions on the surface after desmear treatment is suppressed, prepregs, laminates, printed wiring boards, and semiconductors obtained using the resin composition Packages and the like are particularly suitable for electronic component applications that handle high-frequency signals.

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Abstract

Provided is a resin composition that contains: (A) at least one type selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of said maleimide resins, (B) a poly(phenylene ether) resin having a functional group that includes an ethylenically unsaturated bond, (C) a styrene-based elastomer having a weight average molecular weight (Mw) of more than 10,000 and less than 100,000, and (D) an organic peroxide. Also provided are a prepreg, a laminated board, a resin film, a printed wiring board and a semiconductor package that are obtained using said resin composition.

Description

樹脂組成物、プリプレグ、積層板、樹脂フィルム、プリント配線板及び半導体パッケージResin compositions, prepregs, laminates, resin films, printed wiring boards and semiconductor packages
　本実施形態は、樹脂組成物、プリプレグ、積層板、樹脂フィルム、プリント配線板及び半導体パッケージに関する。 The present embodiment relates to resin compositions, prepregs, laminates, resin films, printed wiring boards, and semiconductor packages.
　携帯電話に代表される移動体通信機器、その基地局装置、サーバー、ルーター等のネットワークインフラ機器、大型コンピューターなどの電子機器では、使用する信号の高速化及び大容量化が年々進んでいる。これに伴い、これらの電子機器に搭載するプリント配線板の基板材料には、高周波信号の伝送損失を低減できる誘電特性［以下、「高周波特性」と称する場合がある。］、すなわち、低比誘電率及び低誘電正接が求められている。
　近年、上述した電子機器の他にも、自動車、交通システム関連等のＩＴＳ（Intelligent　Transport　Systems）分野及び室内の近距離通信分野でも、高周波無線信号を扱う新規システムの実用化又は実用計画が進んでいる。そのため、今後、これらの分野で使用するプリント配線板に対しても、高周波特性に優れる基板材料の必要性が高まると予想される。 2. Description of the Related Art Mobile communication devices such as mobile phones, network infrastructure devices such as base stations, servers and routers, and electronic devices such as large computers use signals with higher speeds and larger capacities year by year. Along with this, substrate materials for printed wiring boards mounted in these electronic devices have dielectric properties capable of reducing transmission loss of high frequency signals [hereinafter sometimes referred to as "high frequency properties". ], that is, a low dielectric constant and a low dielectric loss tangent are required.
In recent years, in addition to the above-mentioned electronic devices, in the field of ITS (Intelligent Transport Systems) such as those related to automobiles and traffic systems, and in the field of indoor short-distance communication, new systems that handle high-frequency wireless signals have been put to practical use or planned for practical use. there is Therefore, it is expected that there will be an increasing need for substrate materials with excellent high-frequency characteristics for printed wiring boards used in these fields in the future.
　特許文献１には、プリント配線板の絶縁層に適用できる樹脂組成物として、得られる硬化物の比誘電率と誘電正接が低く、耐熱性にも優れる硬化性樹脂組成物を提供することを課題とする、ナフトールノボラック型エポキシ樹脂とポリフェニレンエーテル樹脂とを含有する硬化性樹脂組成物が開示されている。 In Patent Document 1, the object is to provide a curable resin composition that can be applied to the insulating layer of a printed wiring board, and the resulting cured product has a low relative dielectric constant and dielectric loss tangent and is excellent in heat resistance. A curable resin composition containing a naphthol novolac type epoxy resin and a polyphenylene ether resin is disclosed.
特開２０１３－１８５０８０号公報JP 2013-185080 A
　ところで、プリント配線板の製造工程において、絶縁層の穴あけ加工後の残渣成分の除去、或いは、絶縁層と導体層との接着性向上のための表面粗化を目的として、絶縁層を酸化剤水溶液によって処理するデスミア処理が行われている。
　本発明者等の検討によると、熱硬化性樹脂とポリフェニレンエーテルを含有する樹脂組成物から形成された絶縁層をデスミア処理すると、絶縁層の表面に、直径が約０．５μｍを超える大きさの窪みが発生する場合があることが判明している。 By the way, in the manufacturing process of a printed wiring board, the insulating layer is treated with an aqueous solution of an oxidizing agent for the purpose of removing residual components after drilling the insulating layer or roughening the surface for improving the adhesion between the insulating layer and the conductor layer. Desmear processing is performed by
According to the studies of the present inventors, when an insulating layer formed from a resin composition containing a thermosetting resin and polyphenylene ether is subjected to desmear treatment, a particle having a diameter exceeding about 0.5 μm is formed on the surface of the insulating layer. It has been found that pitting may occur.
　本実施形態は、このような現状に鑑み、デスミア処理後の表面における窪みの発生が抑制された硬化物を形成可能な樹脂組成物、該樹脂組成物を用いたプリプレグ、積層板、樹脂フィルム、プリント配線板及び半導体パッケージを提供することを課題とする。 In view of the current situation, the present embodiment provides a resin composition capable of forming a cured product in which the occurrence of depressions on the surface after desmear treatment is suppressed, a prepreg, a laminate, a resin film using the resin composition, An object of the present invention is to provide a printed wiring board and a semiconductor package.
　本発明者等は、上記課題を解決するために鋭意研究を重ねた結果、下記の本実施形態によって、上記課題を解決できることを見出した。
　すなわち、本実施形態は、下記［１］～［１３］に関するものである。
［１］（Ａ）Ｎ－置換マレイミド基を１個以上有するマレイミド樹脂及び該マレイミド樹脂の誘導体からなる群から選択される１種以上と、
　（Ｂ）エチレン性不飽和結合を含む官能基を有するポリフェニレンエーテル系樹脂と、
　（Ｃ）重量平均分子量（Ｍｗ）が１０，０００超、１００，０００未満であるスチレン系エラストマーと、
　（Ｄ）有機過酸化物と、
　を含有する樹脂組成物。
［２］前記（Ｂ）成分が、前記エチレン性不飽和結合を含む官能基を末端に有する、上記［１］に記載の樹脂組成物。
［３］前記（Ｂ）成分が有するエチレン性不飽和結合を含む官能基が、（メタ）アクリロイル基である、上記［１］又は［２］に記載の樹脂組成物。
［４］前記（Ｂ）成分の重量平均分子量（Ｍｗ）が、５００～７，０００である、上記［１］～［３］のいずれかに記載の樹脂組成物。
［５］前記（Ｄ）成分の１時間半減期温度が、１００～２００℃である、上記［１］～［４］のいずれかに記載の樹脂組成物。
［６］前記（Ｄ）成分の含有量が、前記（Ａ）成分と前記（Ｂ）成分の総量１００質量部に対して、０．０１～１０質量部である、上記［１］～［５］のいずれかに記載の樹脂組成物。
［７］さらに、（Ｅ）無機充填材を含有する、上記［１］～［６］のいずれかに記載の樹脂組成物。
［８］さらに、（Ｆ）有機過酸化物以外の硬化促進剤を含有する、上記［１］～［７］のいずれかに記載の樹脂組成物。
［９］上記［１］～［８］のいずれかに記載の樹脂組成物又は前記樹脂組成物の半硬化物を含有するプリプレグ。
［１０］上記［９］に記載のプリプレグの硬化物を有する積層板。
［１１］上記［１］～［８］のいずれかに記載の樹脂組成物又は前記樹脂組成物の半硬化物を含有する樹脂フィルム。
［１２］上記［１］～［８］のいずれかに記載の樹脂組成物の硬化物を有するプリント配線板。
［１３］上記［１２］に記載のプリント配線板を有する半導体パッケージ。 The present inventors have made intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by the present embodiment described below.
That is, the present embodiment relates to the following [1] to [13].
[1] (A) one or more selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of the maleimide resins;
(B) a polyphenylene ether resin having a functional group containing an ethylenically unsaturated bond;
(C) a styrene-based elastomer having a weight average molecular weight (Mw) of more than 10,000 and less than 100,000;
(D) an organic peroxide;
A resin composition containing
[2] The resin composition according to [1] above, wherein the component (B) has a functional group containing an ethylenically unsaturated bond at its end.
[3] The resin composition according to [1] or [2] above, wherein the ethylenically unsaturated bond-containing functional group of component (B) is a (meth)acryloyl group.
[4] The resin composition according to any one of [1] to [3] above, wherein the weight average molecular weight (Mw) of component (B) is 500 to 7,000.
[5] The resin composition according to any one of [1] to [4] above, wherein the component (D) has a one-hour half-life temperature of 100 to 200°C.
[6] The above [1] to [5], wherein the content of the component (D) is 0.01 to 10 parts by mass with respect to the total amount of the component (A) and the component (B) of 100 parts by mass. ] The resin composition according to any one of the above.
[7] The resin composition according to any one of [1] to [6] above, further comprising (E) an inorganic filler.
[8] The resin composition according to any one of [1] to [7] above, further comprising (F) a curing accelerator other than an organic peroxide.
[9] A prepreg containing the resin composition according to any one of [1] to [8] or a semi-cured product of the resin composition.
[10] A laminate having a cured product of the prepreg according to [9] above.
[11] A resin film containing the resin composition according to any one of [1] to [8] or a semi-cured product of the resin composition.
[12] A printed wiring board comprising a cured product of the resin composition according to any one of [1] to [8] above.
[13] A semiconductor package having the printed wiring board according to [12] above.
　本実施形態によると、デスミア処理後の表面における窪みの発生が抑制された硬化物を形成可能な樹脂組成物、該樹脂組成物を用いたプリプレグ、積層板、樹脂フィルム、プリント配線板及び半導体パッケージを提供することができる。 According to the present embodiment, a resin composition capable of forming a cured product in which the occurrence of depressions on the surface after desmearing is suppressed, a prepreg, a laminate, a resin film, a printed wiring board, and a semiconductor package using the resin composition can be provided.
窪みの存在比率の算出方法を説明するための断面模式図である。It is a cross-sectional schematic diagram for demonstrating the calculation method of the existence ratio of a hollow.
　本明細書において、「～」を用いて示された数値範囲は、「～」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。
　例えば、数値範囲「Ｘ～Ｙ」（Ｘ、Ｙは実数）という表記は、Ｘ以上、Ｙ以下である数値範囲を意味する。そして、本明細書における「Ｘ以上」という記載は、Ｘ及びＸを超える数値を意味する。また、本明細書における「Ｙ以下」という記載は、Ｙ及びＹ未満の数値を意味する。
　本明細書中に記載されている数値範囲の下限値及び上限値は、それぞれ他の数値範囲の下限値又は上限値と任意に組み合わせられる。
　本明細書中に記載されている数値範囲において、その数値範囲の下限値又は上限値は、実施例に示されている値に置き換えてもよい。 In this specification, a numerical range indicated using "to" indicates a range including the numerical values before and after "to" as the minimum and maximum values, respectively.
For example, the notation of a numerical range “X to Y” (X and Y are real numbers) means a numerical range that is greater than or equal to X and less than or equal to Y. And the description "X or more" in this specification means X and a numerical value exceeding X. In addition, the description “Y or less” in this specification means Y and a numerical value less than Y.
The lower and upper limits of any numerical range recited herein are optionally combined with the lower or upper limits of other numerical ranges, respectively.
In the numerical ranges described herein, the lower or upper limit of the numerical range may be replaced with the values shown in the examples.
　本明細書に例示する各成分及び材料は、特に断らない限り、１種を単独で使用してもよいし、２種以上を組み合わせて用いてもよい。
　本明細書において、樹脂組成物中の各成分の含有量は、樹脂組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、樹脂組成物中に存在する当該複数の物質の合計量を意味する。 Each component and material exemplified in this specification may be used singly or in combination of two or more unless otherwise specified.
In the present specification, the content of each component in the resin composition refers to the content of the plurality of substances present in the resin composition when there are multiple substances corresponding to each component in the resin composition, unless otherwise specified. means the total amount of
　本明細書において「固形分」とは、溶媒以外の成分を意味し、室温で液状、水飴状及びワックス状のものも含む。ここで、本明細書において室温とは２５℃を意味する。 As used herein, the term "solid content" means components other than the solvent, including those that are liquid at room temperature, starch syrup, and wax. Here, in this specification, room temperature means 25°C.
　本明細書における「（メタ）アクリロイル」とは「アクリロイル」及びそれに対応する「メタクリロイル」を意味する。 "(Meth)acryloyl" as used herein means "acryloyl" and the corresponding "methacryloyl".
　本明細書における重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ；Gel　Permeation　Chromatography）によってポリスチレン換算にて測定された値を意味する。具体的には、本明細書における重量平均分子量（Ｍｗ）は、実施例に記載の方法によって測定することができる。 The weight average molecular weight (Mw) in this specification means a value measured by gel permeation chromatography (GPC; Gel Permeation Chromatography) in terms of polystyrene. Specifically, the weight average molecular weight (Mw) in this specification can be measured by the method described in Examples.
　本明細書に記載されている作用機序は推測であって、本実施形態の効果を奏する機序を限定するものではない。 The mechanism of action described in this specification is a guess, and does not limit the mechanism that produces the effects of this embodiment.
　本明細書の記載事項を任意に組み合わせた態様も本実施形態に含まれる。 Aspects in which the items described in this specification are arbitrarily combined are also included in the present embodiment.
［樹脂組成物］
　本実施形態の樹脂組成物は、
　（Ａ）Ｎ－置換マレイミド基を１個以上有するマレイミド樹脂及び該マレイミド樹脂の誘導体からなる群から選択される１種以上と、
　（Ｂ）エチレン性不飽和結合を含む官能基を有するポリフェニレンエーテル系樹脂と、
　（Ｃ）重量平均分子量（Ｍｗ）が１０，０００超、１００，０００未満であるスチレン系エラストマーと、
　（Ｄ）有機過酸化物と、
　を含有する樹脂組成物である。 [Resin composition]
The resin composition of this embodiment is
(A) one or more selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of the maleimide resins;
(B) a polyphenylene ether resin having a functional group containing an ethylenically unsaturated bond;
(C) a styrene-based elastomer having a weight average molecular weight (Mw) of more than 10,000 and less than 100,000;
(D) an organic peroxide;
It is a resin composition containing
　なお、以下の説明において、Ｎ－置換マレイミド基を１個以上有するマレイミド樹脂及び該マレイミド樹脂の誘導体からなる群から選択される１種以上を「（Ａ）マレイミド系樹脂」又は「（Ａ）成分」と称する場合がある。
　また、（Ｂ）エチレン性不飽和結合を含む官能基を有するポリフェニレンエーテル系樹脂を、単に「（Ｂ）ポリフェニレンエーテル系樹脂」又は「（Ｂ）成分」と称する場合がある。
　また、（Ｃ）重量平均分子量（Ｍｗ）が１０，０００超、１００，０００未満であるスチレン系エラストマーを、単に「（Ｃ）スチレン系エラストマー」又は「（Ｃ）成分」と称する場合がある。
　また、（Ｄ）有機過酸化物を「（Ｄ）成分」と称する場合がある。 In the following description, one or more selected from the group consisting of a maleimide resin having one or more N-substituted maleimide groups and derivatives of the maleimide resin is referred to as "(A) maleimide resin" or "(A) component ” may be called.
Moreover, (B) the polyphenylene ether-based resin having a functional group containing an ethylenically unsaturated bond may be simply referred to as "(B) polyphenylene ether-based resin" or "(B) component".
Also, (C) a styrene-based elastomer having a weight average molecular weight (Mw) of more than 10,000 and less than 100,000 may be simply referred to as "(C) styrene-based elastomer" or "(C) component".
Moreover, (D) organic peroxide may be called "(D)component."
　本実施形態の樹脂組成物が、デスミア処理後の表面における窪みの発生が抑制された硬化物を形成可能である理由については、以下の通り推測される。
　従来のポリフェニレンエーテルを（Ａ）マレイミド系樹脂に配合する場合、両者の極性の違いによって、（Ａ）マレイミド系樹脂の硬化が進行するにつれて両者の相容性は低下し、硬化物は均質性が十分でない領域が生じ、これが窪みの要因になっていたものと推測される。
　これに対して、本実施形態の樹脂組成物は、（Ｂ）成分として、（Ａ）マレイミド系樹脂との反応性を有するエチレン性不飽和結合を含む官能基を有するポリフェニレンエーテル系樹脂を用い、更に、（Ｄ）有機過酸化物も含有する。そのため、（Ｂ）ポリフェニレンエーテル系樹脂は（Ａ）マレイミド系樹脂の硬化の進行に伴い相容性が低下する前に、（Ｄ）有機過酸化物を重合開始剤として（Ａ）マレイミド系樹脂と反応し易くなり、硬化物の均質性が向上したものと考えられる。
　また、本実施形態の樹脂組成物は、さらに、（Ｃ）成分として、重量平均分子量（Ｍｗ）が１０，０００超、１００，０００未満であるスチレン系エラストマーを含有するものである。（Ｃ）成分は、誘電特性、耐熱性、ヤング率等の物理特性のバランスに優れる。特に、（Ｃ）成分は、重量平均分子量（Ｍｗ）が１０，０００超であることによって、加熱時における樹脂組成物の流動性が適度に抑制されるため成形性に優れると共に、重量平均分子量（Ｍｗ）が１００，０００未満であることによって、他の樹脂との相容性にも優れる傾向にある。しかし、該（Ｃ）スチレン系エラストマーも、（Ａ）マレイミド系樹脂の硬化の進行に伴い（Ａ）マレイミド系樹脂との相容性は低下すると考えられる。
　一方で、（Ｃ）スチレン系エラストマーは、（Ｂ）ポリフェニレンエーテル系樹脂との親和性に優れるため、（Ｂ）ポリフェニレンエーテル系樹脂が均質に存在し易くなった本実施形態の樹脂組成物においては、（Ｃ）スチレン系エラストマーの相容性も低下し難くなったものと考えられる。その結果、得られる硬化物全体の均質性が向上し、デスミア処理後の表面における窪みの発生が抑制されたと考えられる。
　上記の通り、本実施形態の樹脂組成物は、硬化物をデスミア処理した後の表面における窪みの発生が抑制されるものであるため、硬化物がデスミア処理される樹脂組成物であることが好ましく、硬化物がデスミア処理される、プリント配線板用の樹脂組成物であることがより好ましい。
　以下、本実施形態の樹脂組成物が含有し得る各成分について順に説明する。 The reason why the resin composition of the present embodiment can form a cured product in which the occurrence of depressions on the surface after desmear treatment is suppressed is presumed as follows.
When a conventional polyphenylene ether is blended with (A) a maleimide resin, the compatibility between the two decreases as the curing of the maleimide resin (A) progresses due to the difference in polarity between the two, and the cured product lacks homogeneity. It is presumed that there was an insufficient area and this was the cause of the depression.
On the other hand, the resin composition of the present embodiment uses, as the component (B), a polyphenylene ether-based resin having a functional group containing an ethylenically unsaturated bond that is reactive with the maleimide-based resin (A), Furthermore, it also contains (D) an organic peroxide. Therefore, (B) the polyphenylene ether-based resin is mixed with (A) the maleimide-based resin using (D) an organic peroxide as a polymerization initiator before the compatibility decreases with the progress of curing of the (A) maleimide-based resin. It is considered that the reaction becomes easier and the homogeneity of the cured product is improved.
The resin composition of the present embodiment further contains a styrene-based elastomer having a weight average molecular weight (Mw) of more than 10,000 and less than 100,000 as component (C). Component (C) has an excellent balance of physical properties such as dielectric properties, heat resistance and Young's modulus. In particular, the component (C) has a weight average molecular weight (Mw) of more than 10,000, so that the fluidity of the resin composition during heating is moderately suppressed, resulting in excellent moldability and a weight average molecular weight (Mw) of When Mw) is less than 100,000, compatibility with other resins tends to be excellent. However, it is thought that the (C) styrene-based elastomer also loses compatibility with the (A) maleimide-based resin as the curing of the (A) maleimide-based resin progresses.
On the other hand, since the (C) styrene-based elastomer has excellent affinity with the (B) polyphenylene ether-based resin, the (B) polyphenylene ether-based resin tends to be homogeneously present in the resin composition of the present embodiment. , (C) It is thought that the compatibility of the styrene-based elastomer became less likely to decrease. As a result, the homogeneity of the resulting cured product as a whole was improved, and the occurrence of depressions on the surface after desmear treatment was suppressed.
As described above, the resin composition of the present embodiment suppresses the formation of depressions on the surface of the cured product after desmearing, and thus the cured product is preferably a resin composition that undergoes desmearing. It is more preferable that the cured product is a resin composition for a printed wiring board which is subjected to desmear treatment.
Each component that can be contained in the resin composition of the present embodiment will be described below in order.
＜（Ａ）マレイミド系樹脂＞
　（Ａ）マレイミド系樹脂は、Ｎ－置換マレイミド基を１個以上有するマレイミド樹脂及び該マレイミド樹脂の誘導体からなる群から選択される１種以上である。
　（Ａ）マレイミド系樹脂は、１種を単独で用いても、２種以上を組み合わせて用いてもよい。 <(A) Maleimide resin>
(A) The maleimide resin is one or more selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of the maleimide resins.
(A) The maleimide-based resin may be used singly or in combination of two or more.
　なお、以下の説明で、Ｎ－置換マレイミド基を１個以上有するマレイミド樹脂を「マレイミド樹脂（ＡＸ）」又は「（ＡＸ）成分」と称する場合がある。
　また、Ｎ－置換マレイミド基を１個以上有するマレイミド樹脂の誘導体を「マレイミド樹脂誘導体（ＡＹ）」又は「（ＡＹ）成分」と称する場合がある。 In the following description, the maleimide resin having one or more N-substituted maleimide groups may be referred to as "maleimide resin (AX)" or "(AX) component".
A maleimide resin derivative having one or more N-substituted maleimide groups is sometimes referred to as a “maleimide resin derivative (AY)” or “(AY) component”.
（マレイミド樹脂（ＡＸ））
　マレイミド樹脂（ＡＸ）は、Ｎ－置換マレイミド基を１個以上有するマレイミド樹脂であれば特に限定されない。
　マレイミド樹脂（ＡＸ）は、導体接着性及び耐熱性の観点から、Ｎ－置換マレイミド基を２個以上有する芳香族マレイミド樹脂であることが好ましく、Ｎ－置換マレイミド基を２個有する芳香族ビスマレイミド樹脂であることがより好ましい。
　なお、本明細書中、「芳香族マレイミド樹脂」とは、芳香環に直接結合するＮ－置換マレイミド基を有する化合物を意味する。また、本明細書中、「芳香族ビスマレイミド樹脂」とは、芳香環に直接結合するＮ－置換マレイミド基を２個有する化合物を意味する。また、本明細書中、「芳香族ポリマレイミド樹脂」とは、芳香環に直接結合するＮ－置換マレイミド基を３個以上有する化合物を意味する。また、本明細書中、「脂肪族マレイミド樹脂」とは、脂肪族炭化水素に直接結合するＮ－置換マレイミド基を有する化合物を意味する。 (Maleimide resin (AX))
The maleimide resin (AX) is not particularly limited as long as it has one or more N-substituted maleimide groups.
The maleimide resin (AX) is preferably an aromatic maleimide resin having two or more N-substituted maleimide groups from the viewpoint of conductor adhesion and heat resistance, and an aromatic bismaleimide having two N-substituted maleimide groups. Resin is more preferred.
As used herein, the term "aromatic maleimide resin" means a compound having an N-substituted maleimide group directly bonded to an aromatic ring. Further, the term "aromatic bismaleimide resin" as used herein means a compound having two N-substituted maleimide groups directly bonded to an aromatic ring. Further, the term "aromatic polymaleimide resin" as used herein means a compound having 3 or more N-substituted maleimide groups directly bonded to an aromatic ring. Further, the term "aliphatic maleimide resin" as used herein means a compound having an N-substituted maleimide group directly bonded to an aliphatic hydrocarbon.
　マレイミド樹脂（ＡＸ）としては、下記一般式（Ａ１－１）で表されるマレイミド樹脂［以下、「マレイミド樹脂（Ａ１）」と称する］が好ましい。 As the maleimide resin (AX), a maleimide resin represented by the following general formula (A1-1) [hereinafter referred to as "maleimide resin (A1)"] is preferable.
Figure JPOXMLDOC01-appb-C000001
（式中、Ｘａ１１は２価の有機基である。）
Figure JPOXMLDOC01-appb-C000001
(In the formula, X a11 is a divalent organic group.)
　上記一般式（Ａ１－１）中のＸａ１１は、２価の有機基である。
　上記一般式（Ａ１－１）中のＸａ１１が表す２価の有機基としては、例えば、下記一般式（Ａ１－２）で表される２価の基、下記一般式（Ａ１－３）で表される２価の基、下記一般式（Ａ１－４）で表される２価の基、下記一般式（Ａ１－５）で表される２価の基、下記一般式（Ａ１－６）で表される２価の基等が挙げられる。 X a11 in general formula (A1-1) above is a divalent organic group.
The divalent organic group represented by X a11 in the general formula (A1-1) includes, for example, a divalent group represented by the following general formula (A1-2), and a divalent group represented by the following general formula (A1-3). A divalent group represented by the following general formula (A1-4), a divalent group represented by the following general formula (A1-5), a divalent group represented by the following general formula (A1-6) A divalent group represented by is mentioned.
Figure JPOXMLDOC01-appb-C000002
（式中、Ｒａ１１は、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。ｎａ１１は０～４の整数である。＊は結合部位を表す。）
Figure JPOXMLDOC01-appb-C000002
(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.)
　上記一般式（Ａ１－２）中のＲａ１１が表す炭素数１～５の脂肪族炭化水素基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基等の炭素数１～５のアルキル基；炭素数２～５のアルケニル基、炭素数２～５のアルキニル基などが挙げられる。炭素数１～５の脂肪族炭化水素基は、直鎖状又は分岐鎖状のいずれであってもよい。該炭素数１～５の脂肪族炭化水素基としては、炭素数１～３の脂肪族炭化水素基が好ましく、炭素数１～３のアルキル基がより好ましく、メチル基がさらに好ましい。
　ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。
　上記一般式（Ａ１－２）中のｎａ１１は０～４の整数であり、入手容易性の観点から、好ましくは０～２の整数、より好ましくは０又は１、さらに好ましくは０である。
　ｎａ１１が２以上の整数である場合、複数のＲａ１１同士は、同一であってもよいし、異なっていてもよい。 Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R a11 in the general formula (A1-2) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl t-butyl group, n-pentyl group and other alkyl groups having 1 to 5 carbon atoms; alkenyl groups having 2 to 5 carbon atoms and alkynyl groups having 2 to 5 carbon atoms. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be linear or branched. The aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group.
Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.
n a11 in the general formula (A1-2) is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, still more preferably 0, from the viewpoint of availability.
When n a11 is an integer of 2 or more, the plurality of R a11 may be the same or different.
Figure JPOXMLDOC01-appb-C000003
（式中、Ｒａ１２及びＲａ１３は、各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。Ｘａ１２は炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボニルオキシ基、ケト基、単結合、又は下記一般式（Ａ１－３－１）で表される２価の基である。ｎａ１２及びｎａ１３は、各々独立に、０～４の整数である。＊は結合部位を表す。）
Figure JPOXMLDOC01-appb-C000003
(In the formula, R a12 and R a13 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; X a12 is an alkylene group having 1 to 5 carbon atoms; n a12 and n a13 are an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, or a divalent group represented by the following general formula (A1-3-1). , each independently an integer from 0 to 4. * represents a binding site.)
　上記一般式（Ａ１－３）中のＲａ１２及びＲａ１３が表す炭素数１～５の脂肪族炭化水素基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基等の炭素数１～５のアルキル基；炭素数２～５のアルケニル基、炭素数２～５のアルキニル基などが挙げられる。炭素数１～５の脂肪族炭化水素基は、直鎖状又は分岐鎖状のいずれであってもよい。該炭素数１～５の脂肪族炭化水素基としては、炭素数１～３の脂肪族炭化水素基が好ましく、炭素数１～３のアルキル基がより好ましく、メチル基、エチル基がさらに好ましい。
　ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。 Examples of aliphatic hydrocarbon groups having 1 to 5 carbon atoms represented by R a12 and R a13 in general formula (A1-3) include methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl. alkyl groups having 1 to 5 carbon atoms such as isobutyl group, t-butyl group and n-pentyl group; alkenyl groups having 2 to 5 carbon atoms and alkynyl groups having 2 to 5 carbon atoms. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be linear or branched. The aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group or an ethyl group.
Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.
　上記一般式（Ａ１－３）中のＸａ１２が表す炭素数１～５のアルキレン基としては、例えば、メチレン基、１，２－ジメチレン基、１，３－トリメチレン基、１，４－テトラメチレン基、１，５－ペンタメチレン基等が挙げられる。該炭素数１～５のアルキレン基としては、炭素数１～３のアルキレン基が好ましく、炭素数１又は２のアルキレン基がより好ましく、メチレン基がさらに好ましい。 Examples of the alkylene group having 1 to 5 carbon atoms represented by X a12 in the general formula (A1-3) include methylene group, 1,2-dimethylene group, 1,3-trimethylene group and 1,4-tetramethylene group, 1,5-pentamethylene group, and the like. The alkylene group having 1 to 5 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and still more preferably a methylene group.
　上記一般式（Ａ１－３）中のＸａ１２が表す炭素数２～５のアルキリデン基としては、例えば、エチリデン基、プロピリデン基、イソプロピリデン基、ブチリデン基、イソブチリデン基、ペンチリデン基、イソペンチリデン基等が挙げられる。これらの中でも、炭素数２～４のアルキリデン基が好ましく、炭素数２又は３のアルキリデン基がより好ましく、イソプロピリデン基がさらに好ましい。 The alkylidene group having 2 to 5 carbon atoms represented by X a12 in the general formula (A1-3) includes, for example, an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopentylidene group. etc. Among these, an alkylidene group having 2 to 4 carbon atoms is preferred, an alkylidene group having 2 or 3 carbon atoms is more preferred, and an isopropylidene group is even more preferred.
　上記一般式（Ａ１－３）中のｎａ１２及びｎａ１３は、各々独立に、０～４の整数である。
　ｎａ１２又はｎａ１３が２以上の整数である場合、複数のＲａ１２同士又は複数のＲａ１３同士は、それぞれ同一であってもよいし、異なっていてもよい。 n a12 and n a13 in general formula (A1-3) are each independently an integer of 0 to 4.
When n a12 or n a13 is an integer of 2 or more, the plurality of R a12s or the plurality of R a13s may be the same or different.
　上記一般式（Ａ１－３）中のＸａ１２が表す一般式（Ａ１－３－１）で表される２価の基は以下のとおりである。 The divalent group represented by general formula (A1-3-1) represented by X a12 in general formula (A1-3) is as follows.
Figure JPOXMLDOC01-appb-C000004
（式中、Ｒａ１４及びＲａ１５は、各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。Ｘａ１３は炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボニルオキシ基、ケト基又は単結合である。ｎａ１４及びｎａ１５は、各々独立に、０～４の整数である。＊は結合部位を表す。）
Figure JPOXMLDOC01-appb-C000004
(wherein R a14 and R a15 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; X a13 is an alkylene group having 1 to 5 carbon atoms; an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond, n a14 and n a15 are each independently an integer of 0 to 4. * represents a bonding site. )
　上記一般式（Ａ１－３－１）中のＲａ１４及びＲａ１５が表す炭素数１～５の脂肪族炭化水素基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基等の炭素数１～５のアルキル基；炭素数２～５のアルケニル基、炭素数２～５のアルキニル基などが挙げられる。炭素数１～５の脂肪族炭化水素基は、直鎖状又は分岐鎖状のいずれであってもよい。該炭素数１～５の脂肪族炭化水素基としては、炭素数１～３の脂肪族炭化水素基が好ましく、炭素数１～３のアルキル基がより好ましく、メチル基がさらに好ましい。
　ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。 Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R a14 and R a15 in the general formula (A1-3-1) include methyl group, ethyl group, n-propyl group, isopropyl group, n C1-5 alkyl groups such as -butyl group, isobutyl group, t-butyl group and n-pentyl group; C2-5 alkenyl groups and C2-5 alkynyl groups. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be linear or branched. The aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group.
Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.
　上記一般式（Ａ１－３－１）中のＸａ１３が表す炭素数１～５のアルキレン基としては、例えば、メチレン基、１，２－ジメチレン基、１，３－トリメチレン基、１，４－テトラメチレン基、１，５－ペンタメチレン基等が挙げられる。該炭素数１～５のアルキレン基としては、炭素数１～３のアルキレン基が好ましく、炭素数１又は２のアルキレン基がより好ましく、メチレン基がさらに好ましい。 Examples of the alkylene group having 1 to 5 carbon atoms represented by X a13 in the general formula (A1-3-1) include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4- A tetramethylene group, a 1,5-pentamethylene group and the like can be mentioned. The alkylene group having 1 to 5 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and still more preferably a methylene group.
　上記一般式（Ａ１－３－１）中のＸａ１３が表す炭素数２～５のアルキリデン基としては、例えば、エチリデン基、プロピリデン基、イソプロピリデン基、ブチリデン基、イソブチリデン基、ペンチリデン基、イソペンチリデン基等が挙げられる。これらの中でも、炭素数２～４のアルキリデン基が好ましく、炭素数２又は３のアルキリデン基がより好ましく、イソプロピリデン基がさらに好ましい。 Examples of the alkylidene group having 2 to 5 carbon atoms represented by X a13 in the general formula (A1-3-1) include ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentyl A lidene group and the like can be mentioned. Among these, an alkylidene group having 2 to 4 carbon atoms is preferred, an alkylidene group having 2 or 3 carbon atoms is more preferred, and an isopropylidene group is even more preferred.
　上記一般式（Ａ１－３－１）中のＸａ１３としては、上記選択肢の中でも、炭素数２～５のアルキリデン基が好ましく、炭素数２～４のアルキリデン基がより好ましく、イソプロピリデン基がさらに好ましい。 Among the above options, X a13 in the general formula (A1-3-1) is preferably an alkylidene group having 2 to 5 carbon atoms, more preferably an alkylidene group having 2 to 4 carbon atoms, and further an isopropylidene group. preferable.
　上記一般式（Ａ１－３－１）中のｎａ１４及びｎａ１５は、各々独立に、０～４の整数であり、入手容易性の観点から、いずれも、好ましくは０～２の整数、より好ましくは０又は１、さらに好ましくは０である。
　ｎａ１４又はｎａ１５が２以上の整数である場合、複数のＲａ１４同士又は複数のＲａ１５同士は、それぞれ同一であってもよいし、異なっていてもよい。 n a14 and n a15 in the general formula (A1-3-1) are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, and more It is preferably 0 or 1, more preferably 0.
When n a14 or n a15 is an integer of 2 or more, the plurality of R a14s or the plurality of R a15s may be the same or different.
　上記一般式（Ａ１－３）中のＸａ１２としては、上記選択肢の中でも、炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基、上記一般式（Ａ１－３－１）で表される２価の基が好ましく、炭素数１～５のアルキレン基がより好ましく、メチレン基がさらに好ましい。 As X a12 in the general formula (A1-3), among the above options, an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, and an alkylidene group having 2 to 5 carbon atoms, represented by the general formula (A1-3-1) is preferred, an alkylene group having 1 to 5 carbon atoms is more preferred, and a methylene group is even more preferred.
Figure JPOXMLDOC01-appb-C000005
（式中、ｎａ１６は０～１０の整数である。＊は結合部位を表す。）
Figure JPOXMLDOC01-appb-C000005
(Wherein, n a16 is an integer of 0 to 10. * represents a binding site.)
　上記一般式（Ａ１－４）中のｎａ１６は、入手容易性の観点から、好ましくは０～５の整数、より好ましくは０～４の整数、さらに好ましくは０～３の整数である。 n a16 in general formula (A1-4) is preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and still more preferably an integer of 0 to 3, from the viewpoint of availability.
Figure JPOXMLDOC01-appb-C000006
（式中、ｎａ１７は０～５の数である。＊は結合部位を表す。）
Figure JPOXMLDOC01-appb-C000006
(Wherein, n a17 is a number from 0 to 5. * represents a binding site.)
Figure JPOXMLDOC01-appb-C000007
（式中、Ｒａ１６及びＲａ１７は、各々独立に、水素原子又は炭素数１～５の脂肪族炭化水素基である。ｎａ１８は１～８の整数である。＊は結合部位を表す。）
Figure JPOXMLDOC01-appb-C000007
(In the formula, R a16 and R a17 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. n a18 is an integer of 1 to 8. * represents a bonding site. )
　上記一般式（Ａ１－６）中のＲａ１６及びＲａ１７が表す炭素数１～５の脂肪族炭化水素基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基等の炭素数１～５のアルキル基；炭素数２～５のアルケニル基、炭素数２～５のアルキニル基などが挙げられる。炭素数１～５の脂肪族炭化水素基は、直鎖状又は分岐鎖状のいずれであってもよい。
　上記一般式（Ａ１－６）中のｎａ１８は、１～８の整数であり、好ましくは１～５の整数、より好ましくは１～３の整数、さらに好ましくは１である。ｎａ１８が２以上の整数である場合、複数のＲａ１６同士又は複数のＲａ１７同士は、それぞれ同一であってもよいし、異なっていてもよい。 Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R a16 and R a17 in the general formula (A1-6) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. alkyl groups having 1 to 5 carbon atoms such as isobutyl group, t-butyl group and n-pentyl group; alkenyl groups having 2 to 5 carbon atoms and alkynyl groups having 2 to 5 carbon atoms. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be linear or branched.
n a18 in general formula (A1-6) is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1. When n a18 is an integer of 2 or more, the plurality of R a16 or the plurality of R a17 may be the same or different.
　マレイミド樹脂（Ａ１）としては、例えば、芳香族ビスマレイミド樹脂、芳香族ポリマレイミド樹脂、脂肪族マレイミド樹脂等が挙げられる。
　マレイミド樹脂（Ａ１）の具体例としては、Ｎ，Ｎ’－エチレンビスマレイミド、Ｎ，Ｎ’－ヘキサメチレンビスマレイミド、Ｎ，Ｎ’－（１，３－フェニレン）ビスマレイミド、Ｎ，Ｎ’－［１，３－（２－メチルフェニレン）］ビスマレイミド、Ｎ，Ｎ’－［１，３－（４－メチルフェニレン）］ビスマレイミド、Ｎ，Ｎ’－（１，４－フェニレン）ビスマレイミド、ビス（４－マレイミドフェニル）メタン、ビス（３－メチル－４－マレイミドフェニル）メタン、３，３’－ジメチル－５，５’－ジエチル－４，４’－ジフェニルメタンビスマレイミド、ビス（４－マレイミドフェニル）エーテル、ビス（４－マレイミドフェニル）スルホン、ビス（４－マレイミドフェニル）スルフィド、ビス（４－マレイミドフェニル）ケトン、ビス（４－マレイミドシクロヘキシル）メタン、１，４－ビス（４－マレイミドフェニル）シクロヘキサン、１，４－ビス（マレイミドメチル）シクロヘキサン、１，４－ビス（マレイミドメチル）ベンゼン、１，３－ビス（４－マレイミドフェノキシ）ベンゼン、１，３－ビス（３－マレイミドフェノキシ）ベンゼン、ビス［４－（３－マレイミドフェノキシ）フェニル］メタン、ビス［４－（４－マレイミドフェノキシ）フェニル］メタン、１，１－ビス［４－（３－マレイミドフェノキシ）フェニル］エタン、１，１－ビス［４－（４－マレイミドフェノキシ）フェニル］エタン、１，２－ビス［４－（３－マレイミドフェノキシ）フェニル］エタン、１，２－ビス［４－（４－マレイミドフェノキシ）フェニル］エタン、２，２－ビス［４－（３－マレイミドフェノキシ）フェニル］プロパン、２，２－ビス［４－（４－マレイミドフェノキシ）フェニル］プロパン、２，２－ビス［４－（３－マレイミドフェノキシ）フェニル］ブタン、２，２－ビス［４－（４－マレイミドフェノキシ）フェニル］ブタン、２，２－ビス［４－（３－マレイミドフェノキシ）フェニル］－１，１，１，３，３，３－ヘキサフルオロプロパン、２，２－ビス［４－（４－マレイミドフェノキシ）フェニル］－１，１，１，３，３，３－ヘキサフルオロプロパン、４，４－ビス（３－マレイミドフェノキシ）ビフェニル、４，４－ビス（４－マレイミドフェノキシ）ビフェニル、ビス［４－（３－マレイミドフェノキシ）フェニル］ケトン、ビス［４－（４－マレイミドフェノキシ）フェニル］ケトン、ビス（４－マレイミドフェニル）ジスルフィド、ビス［４－（３－マレイミドフェノキシ）フェニル］スルフィド、ビス［４－（４－マレイミドフェノキシ）フェニル］スルフィド、ビス［４－（３－マレイミドフェノキシ）フェニル］スルホキシド、ビス［４－（４－マレイミドフェノキシ）フェニル］スルホキシド、ビス［４－（３－マレイミドフェノキシ）フェニル］スルホン、ビス［４－（４－マレイミドフェノキシ）フェニル］スルホン、ビス［４－（３－マレイミドフェノキシ）フェニル］エーテル、ビス［４－（４－マレイミドフェノキシ）フェニル］エーテル、１，４－ビス［４－（４－マレイミドフェノキシ）－α，α－ジメチルベンジル］ベンゼン、１，３－ビス［４－（４－マレイミドフェノキシ）－α，α－ジメチルベンジル］ベンゼン、１，４－ビス［４－（３－マレイミドフェノキシ）－α，α－ジメチルベンジル］ベンゼン、１，３－ビス［４－（３－マレイミドフェノキシ）－α，α－ジメチルベンジル］ベンゼン、１，４－ビス［４－（４－マレイミドフェノキシ）－３，５－ジメチル－α，α－ジメチルベンジル］ベンゼン、１，３－ビス［４－（４－マレイミドフェノキシ）－３，５－ジメチル－α，α－ジメチルベンジル］ベンゼン、１，４－ビス［４－（３－マレイミドフェノキシ）－３，５－ジメチル－α，α－ジメチルベンジル］ベンゼン、１，３－ビス［４－（３－マレイミドフェノキシ）－３，５－ジメチル－α，α－ジメチルベンジル］ベンゼン、ポリフェニルメタンマレイミド、ビフェニルアラルキル型マレイミド等が挙げられる。これらの中でも、２，２－ビス［４－（４－マレイミドフェノキシ）フェニル］プロパンが好ましい。 Examples of maleimide resins (A1) include aromatic bismaleimide resins, aromatic polymaleimide resins, and aliphatic maleimide resins.
Specific examples of the maleimide resin (A1) 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'-diphenylmethane bismaleimide, bis(4-maleimide phenyl)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-maleimide phenoxy)-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, polyphenylmethane maleimide, biphenylaralkyl type maleimide and the like. Among these, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane is preferred.
（マレイミド樹脂誘導体（ＡＹ））
　マレイミド樹脂誘導体（ＡＹ）としては、上記したマレイミド樹脂（ＡＸ）由来の構造単位とジアミン化合物由来の構造単位とを有するアミノマレイミド樹脂［以下、「アミノマレイミド樹脂（Ａ２）」又は「（Ａ２）成分」と称する場合がある。］が好ましい。 (Maleimide resin derivative (AY))
As the maleimide resin derivative (AY), an aminomaleimide resin having a structural unit derived from the maleimide resin (AX) and a structural unit derived from a diamine compound [hereinafter referred to as "aminomaleimide resin (A2)" or "(A2) component ” may be called. ] is preferable.
〔アミノマレイミド樹脂（Ａ２）〕
　アミノマレイミド樹脂（Ａ２）は、マレイミド樹脂（ＡＸ）由来の構造単位とジアミン化合物由来の構造単位とを有する。 [Aminomaleimide resin (A2)]
The aminomaleimide resin (A2) has structural units derived from the maleimide resin (AX) and structural units derived from the diamine compound.
《マレイミド樹脂（ＡＸ）由来の構造単位》
　マレイミド樹脂（ＡＸ）由来の構造単位としては、例えば、マレイミド樹脂（ＡＸ）が有するＮ－置換マレイミド基のうち、少なくとも１つのＮ－置換マレイミド基が、ジアミン化合物が有するアミノ基とマイケル付加反応してなる構造単位が挙げられる。
　アミノマレイミド樹脂（Ａ２）中に含まれるマレイミド樹脂（ＡＸ）由来の構造単位は、１種単独であってもよく、２種以上であってもよい。 <<Structural Unit Derived from Maleimide Resin (AX)>>
As the structural unit derived from the maleimide resin (AX), for example, among the N-substituted maleimide groups possessed by the maleimide resin (AX), at least one N-substituted maleimide group undergoes a Michael addition reaction with an amino group possessed by the diamine compound. A structural unit consisting of
The structural unit derived from the maleimide resin (AX) contained in the aminomaleimide resin (A2) may be of one type alone or of two or more types.
　アミノマレイミド樹脂（Ａ２）中におけるマレイミド樹脂（ＡＸ）由来の構造単位の含有量は、特に限定されないが、好ましくは５～９５質量％、より好ましくは３０～９３質量％、さらに好ましくは６０～９０質量％である。
　アミノマレイミド樹脂（Ａ２）中におけるマレイミド樹脂（ＡＸ）由来の構造単位の含有量が上記範囲内であると、誘電特性及び樹脂フィルムとした場合の取り扱い性がより良好になる傾向にある。 The content of structural units derived from the maleimide resin (AX) in the aminomaleimide resin (A2) is not particularly limited, but is preferably 5 to 95% by mass, more preferably 30 to 93% by mass, and still more preferably 60 to 90%. % by mass.
When the content of the structural unit derived from the maleimide resin (AX) in the aminomaleimide resin (A2) is within the above range, the dielectric properties and the handleability of the resin film tend to be better.
《ジアミン化合物由来の構造単位》
　ジアミン化合物由来の構造単位としては、例えば、ジアミン化合物が有する２個のアミノ基のうち、一方又は両方のアミノ基が、マレイミド樹脂（ＡＸ）が有するＮ－置換マレイミド基とマイケル付加反応してなる構造単位が挙げられる。
　アミノマレイミド樹脂（Ａ２）中に含まれるジアミン化合物由来の構造単位は、１種単独であってもよく、２種以上であってもよい。 <<Structural unit derived from diamine compound>>
As the structural unit derived from the diamine compound, for example, one or both of the two amino groups of the diamine compound undergo a Michael addition reaction with an N-substituted maleimide group of the maleimide resin (AX). structural units.
The structural unit derived from the diamine compound contained in the aminomaleimide resin (A2) may be of one type alone or of two or more types.
　ジアミン化合物が有するアミノ基は第１級アミノ基であることが好ましい。
　第１級アミノ基を２個有するジアミン化合物由来の構造単位としては、例えば、下記一般式（Ａ２－１）で表される基、下記一般式（Ａ２－２）で表される基等が挙げられる。 The amino group of the diamine compound is preferably a primary amino group.
Examples of the structural unit derived from the diamine compound having two primary amino groups include a group represented by the following general formula (A2-1), a group represented by the following general formula (A2-2), and the like. be done.
Figure JPOXMLDOC01-appb-C000008
（式中、Ｘａ２１は２価の有機基であり、＊は結合部位を表す。）
Figure JPOXMLDOC01-appb-C000008
(In the formula, X a21 is a divalent organic group, and * represents a binding site.)
　上記一般式（Ａ２－１）及び上記一般式（Ａ２－２）中のＸａ２１は２価の有機基であり、ジアミン化合物から２個の第１級アミノ基を除いた２価の基に相当する。 X a21 in general formulas (A2-1) and (A2-2) above is a divalent organic group and corresponds to a divalent group obtained by removing two primary amino groups from a diamine compound. do.
　上記一般式（Ａ２－１）及び上記一般式（Ａ２－２）中のＸａ２１は、下記一般式（Ａ２－３）で表される２価の基であることが好ましい。 X a21 in general formulas (A2-1) and (A2-2) above is preferably a divalent group represented by general formula (A2-3) below.
Figure JPOXMLDOC01-appb-C000009
（式中、Ｒａ２１及びＲａ２２は、各々独立に、炭素数１～５の脂肪族炭化水素基、炭素数１～５のアルコキシ基、水酸基又はハロゲン原子である。Ｘａ２２は、炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボニルオキシ基、ケト基、フルオレニレン基、単結合、又は下記一般式（Ａ２－３－１）若しくは下記一般式（Ａ２－３－２）で表される２価の基である。ｎａ２１及びｎａ２２は、各々独立に、０～４の整数である。＊は結合部位を表す。）
Figure JPOXMLDOC01-appb-C000009
(In the formula, R a21 and R a22 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group or a halogen atom. an alkylene group having up to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a fluorenylene group, a single bond, or the following general formula (A2-3-1) or the following It is a divalent group represented by the general formula (A2-3-2), n a21 and n a22 are each independently an integer of 0 to 4. * represents a binding site.)
Figure JPOXMLDOC01-appb-C000010
（式中、Ｒａ２３及びＲａ２４は、各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。Ｘａ２３は炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基、ｍ－フェニレンジイソプロピリデン基、ｐ－フェニレンジイソプロピリデン基、エーテル基、スルフィド基、スルホニル基、カルボニルオキシ基、ケト基又は単結合である。ｎａ２３及びｎａ２４は、各々独立に、０～４の整数である。＊は結合部位を表す。）
Figure JPOXMLDOC01-appb-C000010
(In the formula, R a23 and R a24 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; X a23 is an alkylene group having 1 to 5 carbon atoms; an alkylidene group, a m-phenylenediisopropylidene group, a p-phenylenediisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond, n a23 and n a24 are each independently , an integer from 0 to 4. * represents a binding site.)
Figure JPOXMLDOC01-appb-C000011
（式中、Ｒａ２５は、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。Ｘａ２４及びＸａ２５は、各々独立に、炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボニルオキシ基、ケト基又は単結合である。ｎａ２５は０～４の整数である。＊は結合部位を表す。）
Figure JPOXMLDOC01-appb-C000011
(In the formula, R a25 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; X a24 and X a25 each independently represent an alkylene group having 1 to 5 carbon atoms; is an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond, n a25 is an integer of 0 to 4. * represents a bonding site.)
　上記一般式（Ａ２－３）、上記一般式（Ａ２－３－１）及び上記一般式（Ａ２－３－２）中のＲａ２１、Ｒａ２２、Ｒａ２３、Ｒａ２４及びＲａ２５が表す炭素数１～５の脂肪族炭化水素基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基等の炭素数１～５のアルキル基；炭素数２～５のアルケニル基、炭素数２～５のアルキニル基などが挙げられる。炭素数１～５の脂肪族炭化水素基は、直鎖状又は分岐鎖状のいずれであってもよい。該炭素数１～５の脂肪族炭化水素基としては、炭素数１～３の脂肪族炭化水素基が好ましく、炭素数１～３のアルキル基がより好ましく、メチル基、エチル基がさらに好ましい。
　ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。 Number of carbon atoms represented by R a21 , R a22 , R a23 , R a24 and R a25 in general formula (A2-3), general formula (A2-3-1) and general formula (A2-3-2) Examples of 1 to 5 aliphatic hydrocarbon groups include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group and the like. to 5 alkyl groups; alkenyl groups having 2 to 5 carbon atoms; and alkynyl groups having 2 to 5 carbon atoms. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be linear or branched. The aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group or an ethyl group.
Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.
　上記一般式（Ａ２－３）中のＸａ２２、上記一般式（Ａ２－３－１）中のＸａ２３並びに上記一般式（Ａ２－３－２）中のＸａ２４及びＸａ２５が表す炭素数１～５のアルキレン基としては、例えば、メチレン基、１，２－ジメチレン基、１，３－トリメチレン基、１，４－テトラメチレン基、１，５－ペンタメチレン基等が挙げられる。該炭素数１～５のアルキレン基としては、炭素数１～３のアルキレン基が好ましく、炭素数１又は２のアルキレン基がより好ましく、メチレン基がさらに好ましい。 X a22 in the general formula (A2-3), X a23 in the general formula (A2-3-1), and X a24 and X a25 in the general formula (A2-3-2) have 1 carbon atoms. Examples of the alkylene group of 1 to 5 include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group and the like. The alkylene group having 1 to 5 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and still more preferably a methylene group.
　上記一般式（Ａ２－３）中のＸａ２２、上記一般式（Ａ２－３－１）中のＸａ２３、並びに上記一般式（Ａ２－３－２）中のＸａ２４及びＸａ２５が表す炭素数２～５のアルキリデン基としては、例えば、エチリデン基、プロピリデン基、イソプロピリデン基、ブチリデン基、イソブチリデン基、ペンチリデン基、イソペンチリデン基等が挙げられる。該炭素数２～５のアルキリデン基としては、炭素数２～４のアルキリデン基が好ましく、炭素数２又は３のアルキリデン基がより好ましく、イソプロピリデン基がさらに好ましい。 Number of carbon atoms represented by X a22 in general formula (A2-3), X a23 in general formula (A2-3-1), and X a24 and X a25 in general formula (A2-3-2) Examples of alkylidene groups of 2 to 5 include ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group and the like. The alkylidene group having 2 to 5 carbon atoms is preferably an alkylidene group having 2 to 4 carbon atoms, more preferably an alkylidene group having 2 or 3 carbon atoms, and still more preferably an isopropylidene group.
　上記一般式（Ａ２－３）中のｎａ２１及びｎａ２２は、各々独立に、０～４の整数であり、入手容易性の観点から、いずれも、好ましくは０～３の整数、より好ましくは０～２の整数、さらに好ましくは０又は２である。
　ｎａ２１又はｎａ２２が２以上の整数である場合、複数のＲａ２１同士又は複数のＲａ２２同士は、それぞれ同一であってもよいし、異なっていてもよい。 n a21 and n a22 in the general formula (A2-3) are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 3, more preferably It is an integer from 0 to 2, more preferably 0 or 2.
When n a21 or n a22 is an integer of 2 or more, the plurality of R a21s or the plurality of R a22s may be the same or different.
　上記一般式（Ａ２－３－１）中のｎａ２３及びｎａ２４は、各々独立に、０～４の整数であり、入手容易性の観点から、いずれも、好ましくは０～２の整数、より好ましくは０又は１、さらに好ましくは０である。
　ｎａ２３又はｎａ２４が２以上の整数である場合、複数のＲａ２３同士又は複数のＲａ２４同士は、それぞれ同一であってもよいし、異なっていてもよい。 n a23 and n a24 in the general formula (A2-3-1) are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, and more It is preferably 0 or 1, more preferably 0.
When n a23 or n a24 is an integer of 2 or more, the plurality of R a23s or the plurality of R a24s may be the same or different.
　上記一般式（Ａ２－３－２）中のｎａ２５は、０～４の整数であり、入手容易性の観点から、好ましくは０～２の整数、より好ましくは０又は１、さらに好ましくは０である。
　ｎａ２５が２以上の整数である場合、複数のＲａ２５同士は、それぞれ同一であってもよいし、異なっていてもよい。 n a25 in the general formula (A2-3-2) is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, more preferably 0 from the viewpoint of availability is.
When n a25 is an integer of 2 or more, a plurality of R a25 may be the same or different.
　また、上記一般式（Ａ２－１）及び上記一般式（Ａ２－２）中のＸａ２１は、下記一般式（Ａ２－４）で表される構造単位を含有する２価の基であってもよく、下記一般式（Ａ２－５）で表される２価の基であってもよい。 Further, X a21 in general formulas (A2-1) and (A2-2) above may be a divalent group containing a structural unit represented by general formula (A2-4) below. Alternatively, it may be a divalent group represented by the following general formula (A2-5).
Figure JPOXMLDOC01-appb-C000012
（式中、Ｒａ２６及びＲａ２７は、各々独立に、炭素数１～５の脂肪族炭化水素基、フェニル基又は置換フェニル基である。＊は結合部位を表す。）
Figure JPOXMLDOC01-appb-C000012
(In the formula, R a26 and R a27 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a phenyl group or a substituted phenyl group. * represents a bonding site.)
Figure JPOXMLDOC01-appb-C000013
（式中、Ｒａ２６及びＲａ２７は、上記一般式（Ａ２－４）中のものと同じであり、Ｒａ２８及びＲａ２９は、各々独立に、炭素数１～５の脂肪族炭化水素基、フェニル基又は置換フェニル基である。Ｘａ２６及びＸａ２７は、各々独立に、２価の有機基であり、ｎａ２６は、２～１００の整数である。＊は結合部位を表す。）
Figure JPOXMLDOC01-appb-C000013
(Wherein, R a26 and R a27 are the same as those in the above general formula (A2-4), R a28 and R a29 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a phenyl group or a substituted phenyl group, X a26 and X a27 each independently represent a divalent organic group, and n a26 is an integer of 2 to 100. * represents a binding site.)
　上記一般式（Ａ２－４）及び（Ａ２－５）中のＲａ２６～Ｒａ２９が表す炭素数１～５の脂肪族炭化水素基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基等の炭素数１～５のアルキル基；炭素数２～５のアルケニル基、炭素数２～５のアルキニル基などが挙げられる。炭素数１～５の脂肪族炭化水素基は、直鎖状又は分岐鎖状のいずれであってもよい。該炭素数１～５の脂肪族炭化水素基としては、炭素数１～３の脂肪族炭化水素基が好ましく、炭素数１～３のアルキル基がより好ましく、メチル基がさらに好ましい。
　Ｒａ２６～Ｒａ２９が表す置換フェニル基におけるフェニル基が有する置換基としては、上記した炭素数１～５の脂肪族炭化水素基が挙げられる。 Examples of aliphatic hydrocarbon groups having 1 to 5 carbon atoms represented by R a26 to R a29 in general formulas (A2-4) and (A2-5) include methyl group, ethyl group, n-propyl group, C1-5 alkyl groups such as isopropyl group, n-butyl group, isobutyl group, t-butyl group and n-pentyl group; C2-5 alkenyl groups, C2-5 alkynyl groups, etc. mentioned. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be linear or branched. The aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group.
Substituents possessed by the phenyl groups in the substituted phenyl groups represented by R a26 to R a29 include the aforementioned aliphatic hydrocarbon groups having 1 to 5 carbon atoms.
　Ｘａ２６及びＸａ２７が表す２価の有機基としては、例えば、アルキレン基、アルケニレン基、アルキニレン基、アリーレン基、－Ｏ－又はこれらが組み合わされた２価の連結基等が挙げられる。
　上記アルキレン基としては、例えば、メチレン基、エチレン基、プロピレン基等の炭素数１～１０のアルキレン基が挙げられる。
　上記アルケニレン基としては、例えば、炭素数２～１０のアルケニレン基が挙げられる。
　上記アルキニレン基としては、例えば、炭素数２～１０のアルキニレン基が挙げられる。
　上記アリーレン基としては、例えば、フェニレン基、ナフチレン基等の炭素数６～２０のアリーレン基が挙げられる。
　これらの中でも、Ｘａ２６及びＸａ２７としては、アルキレン基、アリーレン基が好ましく、アルキレン基がより好ましい。 Examples of the divalent organic group represented by X a26 and X a27 include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, —O—, and a divalent linking group in which these are combined.
Examples of the alkylene group include alkylene groups having 1 to 10 carbon atoms such as a methylene group, ethylene group and 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 phenylene group and naphthylene group.
Among these, Xa26 and Xa27 are preferably an alkylene group or an arylene group, more preferably an alkylene group.
　ｎａ２６は、２～１００の整数であり、好ましくは２～５０の整数、より好ましくは３～４０の整数、さらに好ましくは５～３０の整数である。ｎａ２６が２以上の整数である場合、複数のＲａ２６同士又は複数のＲａ２７同士は、それぞれ同一であってもよいし、異なっていてもよい。 n a26 is an integer of 2-100, preferably an integer of 2-50, more preferably an integer of 3-40, and still more preferably an integer of 5-30. When n a26 is an integer of 2 or more, the plurality of R a26 or the plurality of R a27 may be the same or different.
　アミノマレイミド樹脂（Ａ２）中におけるジアミン化合物由来の構造単位の含有量は、特に限定されないが、好ましくは５～９５質量％、より好ましくは７～７０質量％、さらに好ましくは１０～４０質量％である。
　アミノマレイミド樹脂（Ａ２）中におけるジアミン化合物由来の構造単位の含有量が上記範囲内であると、誘電特性、耐熱性、難燃性及びガラス転移温度がより良好になる傾向にある。 The content of the structural unit derived from the diamine compound in the aminomaleimide resin (A2) is not particularly limited, but is preferably 5 to 95% by mass, more preferably 7 to 70% by mass, and still more preferably 10 to 40% by mass. be.
When the content of the structural unit derived from the diamine compound in the aminomaleimide resin (A2) is within the above range, dielectric properties, heat resistance, flame retardancy and glass transition temperature tend to be better.
　ジアミン化合物としては、例えば、４，４’－ジアミノジフェニルメタン、３，３’－ジメチル－４，４’－ジアミノジフェニルメタン、３，３’－ジエチル－４，４’－ジアミノジフェニルメタン、４，４’－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルスルホン、３，３’－ジアミノジフェニルスルホン、４，４’－ジアミノジフェニルケトン、４，４’－ジアミノビフェニル、３，３’－ジメチル－４，４’－ジアミノビフェニル、２，２’－ジメチル－４，４’－ジアミノビフェニル、３，３’－ジヒドロキシベンジジン、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）プロパン、３，３’－ジメチル－５，５’－ジエチル－４，４’－ジアミノジフェニルメタン、２，２－ビス（４－アミノフェニル）プロパン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン、１，３－ビス（３－アミノフェノキシ）ベンゼン、１，３－ビス（４－アミノフェノキシ）ベンゼン、１，４－ビス（４－アミノフェノキシ）ベンゼン、４，４’－ビス（４－アミノフェノキシ）ビフェニル、１，３－ビス〔１－［４－（４－アミノフェノキシ）フェニル］－１－メチルエチル〕ベンゼン、１，４－ビス〔１－［４－（４－アミノフェノキシ）フェニル］－１－メチルエチル〕ベンゼン、４，４’－［１，３－フェニレンビス（１－メチルエチリデン）］ビスアニリン、４，４’－［１，４－フェニレンビス（１－メチルエチリデン）］ビスアニリン、３，３’－［１，３－フェニレンビス（１－メチルエチリデン）］ビスアニリン、ビス［４－（４－アミノフェノキシ）フェニル］スルホン、ビス［４－（３－アミノフェノキシ）フェニル］スルホン、９，９－ビス（４－アミノフェニル）フルオレン等の芳香族ジアミン化合物；第１級アミノ基を２個有するシリコーン化合物などが挙げられる。
　なお、本明細書中、「芳香族ジアミン化合物」とは、芳香環に直接結合するアミノ基を２個有する化合物を意味する。 Examples of diamine compounds 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( aromatic diamine compounds such as 4-aminophenyl)fluorene; and silicone compounds having two primary amino groups.
As used herein, the term "aromatic diamine compound" means a compound having two amino groups directly bonded to an aromatic ring.
　これらの中でも、ジアミン化合物は、有機溶媒への溶解性、反応性、耐熱性、誘電特性及び低吸水性に優れるという観点から、４，４’－ジアミノジフェニルメタン、３，３’－ジメチル－４，４’－ジアミノジフェニルメタン、３，３’－ジエチル－４，４’－ジアミノジフェニルメタン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン、４，４’－［１，３－フェニレンビス（１－メチルエチリデン）］ビスアニリン、及び４，４’－［１，４－フェニレンビス（１－メチルエチリデン）］ビスアニリンが好ましく、３，３’－ジエチル－４，４’－ジアミノジフェニルメタンがより好ましい。また、低熱膨張性の観点からは、第１級アミノ基を２個有するシリコーン化合物が好ましい。 Among them, diamine compounds are 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4, 3,3'-dimethyl-4, 4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-[1,3-phenylene Bis(1-methylethylidene)]bisaniline and 4,4′-[1,4-phenylenebis(1-methylethylidene)]bisaniline are preferred, and 3,3′-diethyl-4,4′-diaminodiphenylmethane is more preferred. preferable. Moreover, from the viewpoint of low thermal expansion, a silicone compound having two primary amino groups is preferable.
　第１級アミノ基を２個有するシリコーン化合物としては、第１級アミノ基を両末端に有するシリコーン化合物が好ましい。
　第１級アミノ基を２個有するシリコーン化合物の第１級アミノ基当量は、特に限定されないが、好ましくは３００～２，０００ｇ／ｍｏｌ、より好ましくは４００～１，５００ｇ／ｍｏｌ、さらに好ましくは５００～１，０００ｇ／ｍｏｌである。 As the silicone compound having two primary amino groups, a silicone compound having primary amino groups at both terminals is preferable.
The primary amino group equivalent weight of the silicone 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 g/mol. ~1,000 g/mol.
　アミノマレイミド樹脂（Ａ２）中における、ジアミン化合物の－ＮＨ２基由来の基の合計当量（Ｔａ２）と、マレイミド樹脂（ＡＸ）のＮ－置換マレイミド基由来の基の合計当量（Ｔａ１）との当量比（Ｔａ２／Ｔａ１）は、特に限定されないが、誘電特性、耐熱性、難燃性及びガラス転移温度の観点から、好ましくは０．０５～１０、より好ましくは１～８、さらに好ましくは３～７である。なお、上記ジアミン化合物の－ＮＨ２基由来の基とは、－ＮＨ２自体も含めるものとする。また、上記マレイミド樹脂（ＡＸ）のＮ－置換マレイミド基由来の基とは、Ｎ－置換マレイミド基自体も含めるものとする。 The equivalent of the total equivalent weight (Ta2) of the groups derived from the —NH 2 groups of the diamine compound in the aminomaleimide resin (A2) and the total equivalent weight (Ta1) of the groups derived from the N-substituted maleimide groups of the maleimide resin (AX) Although the ratio (Ta2/Ta1) is not particularly limited, it is preferably from 0.05 to 10, more preferably from 1 to 8, and still more preferably from 3 to 3, from the viewpoint of dielectric properties, heat resistance, flame retardancy and glass transition temperature. 7. The group derived from the —NH 2 group of the diamine compound includes —NH 2 itself. Further, the group derived from the N-substituted maleimide group of the maleimide resin (AX) includes the N-substituted maleimide group itself.
　アミノマレイミド樹脂（Ａ２）の重量平均分子量（Ｍｗ）は、特に限定されないが、取り扱い性及び成形性の観点から、好ましくは４００～１０，０００、より好ましくは１，０００～５，０００、さらに好ましくは１，５００～４，０００、特に好ましくは２，０００～３，０００である。 The weight average molecular weight (Mw) of the aminomaleimide resin (A2) is not particularly limited, but is preferably 400 to 10,000, more preferably 1,000 to 5,000, still more preferably 1,000 to 5,000, from the viewpoint of handleability and moldability. is 1,500 to 4,000, particularly preferably 2,000 to 3,000.
（アミノマレイミド樹脂（Ａ２）の製造方法）
　アミノマレイミド樹脂（Ａ２）は、例えば、マレイミド樹脂（ＡＸ）とジアミン化合物とを有機溶媒中で反応させることによって製造することができる。
　マレイミド樹脂（ＡＸ）とジアミン化合物とを反応させることによって、マレイミド樹脂（ＡＸ）とジアミン化合物とがマイケル付加反応してなるアミノマレイミド樹脂（Ａ２）が得られる。
　マレイミド樹脂（ＡＸ）とジアミン化合物とを反応させる際には、必要に応じて反応触媒を使用してもよい。 (Method for producing aminomaleimide resin (A2))
The aminomaleimide resin (A2) can be produced, for example, by reacting the maleimide resin (AX) with a diamine compound in an organic solvent.
By reacting the maleimide resin (AX) with the diamine compound, an aminomaleimide resin (A2) is obtained through the Michael addition reaction between the maleimide resin (AX) and the diamine compound.
When reacting the maleimide resin (AX) and the diamine compound, a reaction catalyst may be used as necessary.
　マイケル付加反応の反応温度は、反応速度等の作業性、反応中における生成物のゲル化抑制などの観点から、好ましくは５０～１６０℃、より好ましくは６０～１５０℃、さらに好ましくは７０～１４０℃である。
　マイケル付加反応の反応時間は、生産性及び十分に反応を進行させるという観点から、好ましくは０．５～１０時間、より好ましくは１～８時間、さらに好ましくは２～６時間である。
　但し、これらの反応条件は、使用する原料の種類等に応じて適宜調整することができ、特に限定されない。 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 viewpoint of workability such as reaction rate and suppression of gelation of the product during the reaction. °C.
The reaction time of the Michael addition reaction is preferably 0.5 to 10 hours, more preferably 1 to 8 hours, still more preferably 2 to 6 hours, from the viewpoint of productivity and sufficient progress of the reaction.
However, these reaction conditions are not particularly limited and can be appropriately adjusted depending on the type of raw material used.
（（Ａ）マレイミド系樹脂の含有量）
　本実施形態の樹脂組成物において、（Ａ）マレイミド系樹脂の含有量は、特に限定されないが、本実施形態の樹脂組成物中の樹脂成分の総量（１００質量％）に対して、好ましくは２０～９５質量％、より好ましくは５０～９０質量％、さらに好ましくは７０～８５質量％である。
　（Ａ）マレイミド系樹脂の含有量が上記下限値以上であると、耐熱性、成形性、加工性及び導体接着性がより良好になり易い傾向にある。また、（Ａ）マレイミド系樹脂の含有量が上記上限値以下であると、誘電特性がより良好になり易い傾向にある。 (Content of (A) maleimide resin)
In the resin composition of the present embodiment, the content of (A) the maleimide-based resin is not particularly limited, but is preferably 20 ~95% by mass, more preferably 50 to 90% by mass, still more preferably 70 to 85% by mass.
(A) When the content of the maleimide-based resin is at least the above lower limit, heat resistance, moldability, workability, and conductor adhesion tend to be better. Further, when the content of (A) the maleimide resin is equal to or less than the above upper limit, the dielectric properties tend to be more favorable.
　ここで、本明細書において、「樹脂成分」とは、樹脂及び硬化反応によって樹脂を形成する化合物を意味する。
　例えば、本実施形態の樹脂組成物においては、（Ａ）マレイミド系樹脂、（Ｂ）ポリフェニレンエーテル系樹脂、（Ｃ）スチレン系エラストマー及び（Ｄ）有機過酸化物が樹脂成分に相当する。
　本実施形態の樹脂組成物が、任意成分として、上記成分以外に樹脂又は硬化反応によって樹脂を形成する化合物を含有する場合、これらの任意成分も樹脂成分に含まれる。樹脂成分に相当する任意成分としては、後述する、（Ｆ）有機過酸化物以外の硬化促進剤等が挙げられる。
　一方、（Ｅ）無機充填材は、樹脂成分には含まれないものとする。 As used herein, the term "resin component" means a resin and a compound that forms a resin through a curing reaction.
For example, in the resin composition of the present embodiment, (A) maleimide-based resin, (B) polyphenylene ether-based resin, (C) styrene-based elastomer, and (D) organic peroxide correspond to resin components.
When the resin composition of the present embodiment contains, as optional components, a resin or a compound that forms a resin by a curing reaction in addition to the above components, these optional components are also included in the resin component. Examples of the optional component corresponding to the resin component include (F) a curing accelerator other than the organic peroxide, which will be described later.
On the other hand, the (E) inorganic filler is not included in the resin component.
　本実施形態の樹脂組成物中における樹脂成分の合計含有量は、特に限定されないが、低熱膨張性、耐熱性、難燃性及び導体接着性の観点から、本実施形態の樹脂組成物の固形分総量（１００質量％）に対して、好ましくは１０～７０質量％、より好ましくは２０～６０質量％、さらに好ましくは３０～５０質量％である。 The total content of the resin components in the resin composition of the present embodiment is not particularly limited, but from the viewpoint of low thermal expansion, heat resistance, flame retardancy and conductor adhesion, the solid content of the resin composition of the present embodiment It is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and still more preferably 30 to 50% by mass relative to the total amount (100% by mass).
＜（Ｂ）ポリフェニレンエーテル系樹脂＞
　（Ｂ）ポリフェニレンエーテル系樹脂は、ポリフェニレンエーテル鎖及びエチレン性不飽和結合を含む官能基を有する樹脂であれば特に限定されない。
　本実施形態の樹脂組成物は、（Ｂ）ポリフェニレンエーテル系樹脂を含有することによって、優れた誘電特性が得られ易い傾向にある。
　（Ｂ）ポリフェニレンエーテル系樹脂は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 <(B) Polyphenylene ether resin>
(B) The polyphenylene ether-based resin is not particularly limited as long as it is a resin having a functional group containing a polyphenylene ether chain and an ethylenically unsaturated bond.
The resin composition of the present embodiment tends to easily obtain excellent dielectric properties by containing (B) a polyphenylene ether-based resin.
(B) The polyphenylene ether-based resin may be used alone or in combination of two or more.
　（Ｂ）ポリフェニレンエーテル系樹脂は、フェニレンエーテル結合を有するものであり、下記一般式（Ｂ－１）で表される構造単位を有することが好ましい。 (B) The polyphenylene ether-based resin has a phenylene ether bond, and preferably has a structural unit represented by the following general formula (B-1).
Figure JPOXMLDOC01-appb-C000014
（式中、Ｒｂ１は、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。ｎｂ１は、０～４の整数である。）
Figure JPOXMLDOC01-appb-C000014
(In the formula, R b1 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. n b1 is an integer of 0 to 4.)
　上記一般式（Ｂ－１）中のＲｂ１が表す炭素数１～５の脂肪族炭化水素基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基等が挙げられる。該脂肪族炭化水素基は、炭素数１～３の脂肪族炭化水素基が好ましく、炭素数１～３のアルキル基がより好ましく、メチル基がさらに好ましい。
　ｎｂ１は０～４の整数であり、好ましくは１又は２、より好ましくは２である。なお、ｎｂ１が１又は２である場合、Ｒｂ１の置換位置は、酸素原子の置換位置を基準として、ベンゼン環上のオルト位に置換していることが好ましい。また、ｎｂ１が２以上の整数である場合、複数のＲｂ１同士は同一であっても異なっていてもよい。
　上記一般式（Ｂ－１）で表される構造単位は、下記一般式（Ｂ－１’）で表される構造単位であることが好ましい。 Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b1 in the general formula (B-1) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group, t-butyl group, n-pentyl group and the like. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group.
n b1 is an integer of 0 to 4, preferably 1 or 2, more preferably 2; When n b1 is 1 or 2, the substitution position of R b1 is preferably the ortho position on the benzene ring with respect to the substitution position of the oxygen atom. Further, when n b1 is an integer of 2 or more, a plurality of R b1 may be the same or different.
The structural unit represented by the above general formula (B-1) is preferably a structural unit represented by the following general formula (B-1').
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　（Ｂ）ポリフェニレンエーテル系樹脂は、デスミア処理後の窪みの発生を抑制するという観点から、エチレン性不飽和結合を含む官能基［以下、「エチレン性不飽和結合含有基」と称する場合がある。］を有するものである。
　なお、本明細書において、「エチレン性不飽和結合」とは、付加反応が可能な炭素－炭素二重結合を意味し、芳香環の二重結合は含まないものとする。 (B) The polyphenylene ether-based resin has a functional group containing an ethylenically unsaturated bond [hereinafter sometimes referred to as an "ethylenically unsaturated bond-containing group" from the viewpoint of suppressing the generation of depressions after desmear treatment. ].
As used herein, the term "ethylenically unsaturated bond" means a carbon-carbon double bond capable of an addition reaction, and does not include a double bond of an aromatic ring.
　エチレン性不飽和結合含有基としては、例えば、ビニル基、アリル基、１－メチルアリル基、イソプロペニル基、２－ブテニル基、３－ブテニル基、スチリル基、マレイミド基、下記一般式（Ｂ－２）で表される基等が挙げられる。 Ethylenically unsaturated bond-containing groups include, for example, vinyl group, allyl group, 1-methylallyl group, isopropenyl group, 2-butenyl group, 3-butenyl group, styryl group, maleimide group, the following general formula (B-2 ) and the like.
Figure JPOXMLDOC01-appb-C000016
（式中、Ｒｂ２は、水素原子又は炭素数１～２０のアルキル基である。）
Figure JPOXMLDOC01-appb-C000016
(In the formula, R b2 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)
　Ｒｂ２が表す炭素数１～２０のアルキル基は、直鎖状アルキル基、分岐鎖状アルキル基又は環状アルキル基のいずれであってもよく、直鎖状アルキル基であることが好ましい。
　上記アルキル基の炭素数は、好ましくは１～１０、より好ましくは１～５、さらに好ましくは１～３、特に好ましくは１である。
　上記アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、デシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基等が挙げられ、これらの中でも、メチル基が好ましい。
　なお、Ｒｂ２が水素原子である上記一般式（Ｂ－２）で表される基は、アクリロイル基に相当し、Ｒｂ２がメチル基である上記一般式（Ｂ－２）で表される基は、メタクリロイル基に相当する。 The alkyl group having 1 to 20 carbon atoms represented by R b2 may be a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group, preferably a straight-chain alkyl group.
The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-5, still more preferably 1-3, 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 and heptadecyl group. Among them, a methyl group is preferred.
The group represented by the above general formula (B-2) in which R b2 is a hydrogen atom corresponds to an acryloyl group, and the group represented by the above general formula (B-2) in which R b2 is a methyl group. corresponds to a methacryloyl group.
　以上の中でも、（Ｂ）ポリフェニレンエーテル系樹脂が有するエチレン性不飽和結合含有基は、誘電特性の観点から、上記一般式（Ｂ－２）で表される基であることが好ましく、（メタ）アクリロイル基であることがより好ましく、メタクリロイル基であることがさらに好ましい。 Among the above, (B) the ethylenically unsaturated bond-containing group possessed by the polyphenylene ether-based resin is preferably a group represented by the general formula (B-2) from the viewpoint of dielectric properties, and (meth) An acryloyl group is more preferred, and a methacryloyl group is even more preferred.
　（Ｂ）ポリフェニレンエーテル系樹脂が１分子中に有するエチレン性不飽和結合含有基の数は、特に限定されないが、好ましくは１～５個、より好ましくは２～３個、さらに好ましくは２個である。
　エチレン性不飽和結合含有基の数が上記下限値以上であると、耐熱性がより良好になり易い傾向にある。また、エチレン性不飽和結合含有基の数が上記上限値以下であると、デスミア処理後の窪みの発生をより抑制し易い傾向にある。 (B) The number of ethylenically unsaturated bond-containing groups that the polyphenylene ether-based resin has in one molecule is not particularly limited, but is preferably 1 to 5, more preferably 2 to 3, and still more preferably 2. be.
When the number of ethylenically unsaturated bond-containing groups is at least the above lower limit, heat resistance tends to be better. Moreover, when the number of ethylenically unsaturated bond-containing groups is equal to or less than the above upper limit, it tends to be easier to suppress the occurrence of depressions after the desmear treatment.
　（Ｂ）ポリフェニレンエーテル系樹脂は、エチレン性不飽和結合含有基を末端に有することが好ましく、両末端に有することがより好ましい。
　（Ｂ）ポリフェニレンエーテル系樹脂は、末端以外にもエチレン性不飽和結合含有基を有していてもよいが、末端のみにエチレン性不飽和結合含有基を有することが好ましい。 (B) The polyphenylene ether-based resin preferably has ethylenically unsaturated bond-containing groups at its terminals, more preferably at both terminals.
(B) The polyphenylene ether-based resin may have an ethylenically unsaturated bond-containing group in addition to the terminal, but preferably has an ethylenically unsaturated bond-containing group only at the terminal.
　（Ｂ）ポリフェニレンエーテル系樹脂は、誘電特性の観点から、下記一般式（Ｂ－３）で表される化合物であることが好ましい。 (B) Polyphenylene ether-based resin is preferably a compound represented by the following general formula (B-3) from the viewpoint of dielectric properties.
Figure JPOXMLDOC01-appb-C000017
（式中、Ｒｂ１及びｎｂ１は、上記一般式（Ｂ－１）における説明の通りである。Ｒｂ３及びＲｂ４は、各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。ｎｂ２及びｎｂ３は、各々独立に、０～４の整数である。ｎｂ４及びｎｂ５は、各々独立に、０～２０の整数であり、ｎｂ４及びｎｂ５の合計は、１～３０の整数である。Ｘｂ１は、炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボニルオキシ基、ケト基又は単結合である。Ｙｂ１及びＹｂ２は、各々独立に、上記エチレン性不飽和結合含有基である。）
Figure JPOXMLDOC01-appb-C000017
(In the formula, R b1 and n b1 are as described in the general formula (B-1) above. R b3 and R b4 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen n b2 and n b3 are each independently an integer of 0 to 4. n b4 and n b5 are each independently an integer of 0 to 20, and the sum of n b4 and n b5 is , an integer of 1 to 30. X b1 is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. Yb1 and Yb2 are each independently the above ethylenically unsaturated bond-containing group.)
　上記一般式（Ｂ－３）中のＲｂ３及びＲｂ４が表す炭素数１～５の脂肪族炭化水素基についての説明は、上記一般式（Ｂ－１）中のＲｂ１が表す炭素数１～５の脂肪族炭化水素基についての説明と同じである。
　ｎｂ２及びｎｂ３は、０～４の整数であり、好ましくは０～３の整数、より好ましくは２又は３である。ｎｂ２又はｎｂ３が２以上の整数である場合、複数のＲｂ３同士又は複数のＲｂ４同士は、それぞれ同一であっても異なっていてもよい。
　ｎｂ４及びｎｂ５は、０～２０の整数であり、好ましくは１～２０の整数、より好ましくは２～１５の整数、さらに好ましくは３～１０の整数である。ｎｂ４又はｎｂ５が２以上の整数である場合、複数のｎｂ１同士は、同一であっても異なっていてもよい。
　ｎｂ４及びｎｂ５の合計は、１～３０の整数であり、好ましくは２～２５の整数、より好ましくは５～２０の整数、さらに好ましくは７～１５の整数である。 The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b3 and R b4 in the general formula ( B-3) is described as follows: The explanation is the same as for the aliphatic hydrocarbon group of 1 to 5.
n b2 and n b3 are integers from 0 to 4, preferably integers from 0 to 3, more preferably 2 or 3. When nb2 or nb3 is an integer of 2 or more, the plurality of Rb3 's or the plurality of Rb4 's may be the same or different.
nb4 and nb5 are integers of 0-20, preferably integers of 1-20, more preferably integers of 2-15, and even more preferably integers of 3-10. When nb4 or nb5 is an integer of 2 or more, the plurality of nb1 may be the same or different.
The sum of n b4 and n b5 is an integer of 1-30, preferably an integer of 2-25, more preferably an integer of 5-20, and still more preferably an integer of 7-15.
　上記一般式（Ｂ－３）中のＸｂ１が表す炭素数１～５のアルキレン基としては、例えば、メチレン基、１，２－ジメチレン基、１，３－トリメチレン基、１，４－テトラメチレン基、１，５－ペンタメチレン基等が挙げられる。
　Ｘｂ１が表す炭素数２～５のアルキリデン基としては、例えば、エチリデン基、プロピリデン基、イソプロピリデン基、ブチリデン基、イソブチリデン基、ペンチリデン基、イソペンチリデン基等が挙げられる。
　Ｘｂ１が表す基の中でも、誘電特性の観点から、イソプロピリデン基が好ましい。
　Ｙｂ１及びＹｂ２が表すエチレン性不飽和結合含有基の好ましい態様については上記した通りである。
　上記一般式（Ｂ－３）で表される化合物は、誘電特性の観点から、下記一般式（Ｂ－４）で表される化合物であることが好ましい。 Examples of the alkylene group having 1 to 5 carbon atoms represented by X b1 in the general formula (B-3) include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group and a 1,4-tetramethylene group. group, 1,5-pentamethylene group, and the like.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by X b1 include ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group and the like.
Among the groups represented by Xb1 , an isopropylidene group is preferable from the viewpoint of dielectric properties.
Preferred embodiments of the ethylenically unsaturated bond-containing groups represented by Yb1 and Yb2 are as described above.
From the viewpoint of dielectric properties, the compound represented by the general formula (B-3) is preferably a compound represented by the following general formula (B-4).
Figure JPOXMLDOC01-appb-C000018
（式中、ｎｂ４及びｎｂ５は、上記一般式（Ｂ－３）における説明の通りである。Ｒｂ５及びＲｂ６は、各々独立に、水素原子又はメチル基である。Ｘｂ２は、メチレン基又はイソプロピリデン基である。）
Figure JPOXMLDOC01-appb-C000018
(Wherein, n b4 and n b5 are as described in the general formula (B-3) above. R b5 and R b6 are each independently a hydrogen atom or a methyl group. X b2 is methylene. group or isopropylidene group.)
〔（Ｂ）ポリフェニレンエーテル系樹脂の重量平均分子量（Ｍｗ）〕
　（Ｂ）ポリフェニレンエーテル系樹脂の重量平均分子量（Ｍｗ）は、特に限定されないが、好ましくは５００～７，０００、より好ましくは８００～５，０００、さらに好ましくは１，０００～３，０００、特に好ましくは１，２００～２，５００である。
　（Ｂ）ポリフェニレンエーテル系樹脂の重量平均分子量（Ｍｗ）が上記下限値以上であると、ポリフェニレンエーテルの優れた誘電特性を有し、かつ耐熱性に優れる硬化物が得られ易い傾向にある。また、（Ｂ）ポリフェニレンエーテル系樹脂の重量平均分子量（Ｍｗ）が上記上限値以下であると、成形性がより良好になり易い傾向にある。 [(B) Weight average molecular weight (Mw) of polyphenylene ether resin]
(B) The weight average molecular weight (Mw) of the polyphenylene ether resin 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, especially It is preferably 1,200 to 2,500.
(B) When the weight average molecular weight (Mw) of the polyphenylene ether-based resin is at least the above lower limit, there is a tendency to easily obtain a cured product having excellent dielectric properties of the polyphenylene ether and excellent heat resistance. Further, when the weight average molecular weight (Mw) of the (B) polyphenylene ether resin is equal to or less than the above upper limit, moldability tends to be more favorable.
　（Ｂ）ポリフェニレンエーテル系樹脂の合成方法は、公知のポリフェニレンエーテルの合成方法及び変性方法を適用することができ、特に限定されるものではない。 (B) The method for synthesizing the polyphenylene ether-based resin is not particularly limited, and a known method for synthesizing and modifying a polyphenylene ether can be applied.
（（Ｂ）ポリフェニレンエーテル系樹脂の含有量）
　本実施形態の樹脂組成物中における（Ｂ）ポリフェニレンエーテル系樹脂の含有量は、特に限定されないが、本実施形態の樹脂組成物中の樹脂成分の総量（１００質量％）に対して、好ましくは１～３０質量％、より好ましくは５～２５質量％、さらに好ましくは１０～２０質量％である。
　（Ｂ）ポリフェニレンエーテル系樹脂の含有量が、上記下限値以上であると、誘電特性がより良好になり易い傾向にある。また、（Ｂ）ポリフェニレンエーテル系樹脂の含有量が、上記上限値以下であると、耐熱性、成形性及び加工性がより良好になり易い傾向にある。 (Content of (B) polyphenylene ether resin)
The content of (B) the polyphenylene ether-based resin in the resin composition of the present embodiment is not particularly limited, but is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, still more preferably 10 to 20% by mass.
(B) When the content of the polyphenylene ether-based resin is at least the above lower limit, the dielectric properties tend to be more favorable. Moreover, when the content of the (B) polyphenylene ether-based resin is equal to or less than the above upper limit, heat resistance, moldability, and workability tend to be improved.
＜（Ｃ）スチレン系エラストマー＞
　（Ｃ）スチレン系エラストマーは、重量平均分子量（Ｍｗ）が１０，０００超、１００，０００未満であるスチレン系エラストマーであれば特に限定されない。
　本実施形態の樹脂組成物は、（Ｃ）スチレン系エラストマーを含有することによって、優れた誘電特性が得られ易い傾向にある。
　なお、ここでの「エラストマー」とは、ＪＩＳ　Ｋ　６２４０：２０１１に従って示差走査熱量測定で測定したガラス転移温度が２５℃以下である高分子を意味する。
　（Ｃ）スチレン系エラストマーは、１種を単独で用いても、２種以上を組み合わせて用いてもよい。 <(C) Styrene-based elastomer>
(C) The styrene elastomer is not particularly limited as long as it has a weight average molecular weight (Mw) of more than 10,000 and less than 100,000.
The resin composition of the present embodiment tends to easily obtain excellent dielectric properties by containing (C) the styrene-based elastomer.
The term "elastomer" as used herein means a polymer having a glass transition temperature of 25°C or less as measured by differential scanning calorimetry according to JIS K 6240:2011.
(C) Styrene-based elastomers may be used singly or in combination of two or more.
　（Ｃ）スチレン系エラストマーとしては、下記一般式（Ｃ－１）で表されるスチレン系化合物由来の構造単位を有するものが好ましい。 (C) As the styrene-based elastomer, one having a structural unit derived from a styrene-based compound represented by the following general formula (C-1) is preferable.
Figure JPOXMLDOC01-appb-C000019
（式中、Ｒｃ１は水素原子又は炭素数１～５のアルキル基であり、Ｒｃ２は、炭素数１～５のアルキル基である。ｎｃ１は、０～５の整数である。）
Figure JPOXMLDOC01-appb-C000019
(In the formula, R c1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R c2 is an alkyl group having 1 to 5 carbon atoms, and n c1 is an integer of 0 to 5.)
　上記一般式（Ｃ－１）中のＲｃ１及びＲｃ２が表す炭素数１～５のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基等が挙げられる。炭素数１～５のアルキル基は、直鎖状又は分岐鎖状のいずれであってもよい。これらの中でも、炭素数１～３のアルキル基が好ましく、炭素数１又は２のアルキル基がより好ましく、メチル基がさらに好ましい。
　上記一般式（Ｃ－１）中のｎｃ１は、０～５の整数であり、好ましくは０～２の整数、より好ましくは０又は１、さらに好ましくは０である。 Examples of alkyl groups having 1 to 5 carbon atoms represented by R c1 and R c2 in the general formula (C-1) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group, t-butyl group, n-pentyl group and the like. The alkyl group having 1 to 5 carbon atoms may be linear or branched. Among these, an alkyl group having 1 to 3 carbon atoms is preferred, an alkyl group having 1 or 2 carbon atoms is more preferred, and a methyl group is even more preferred.
n c1 in the general formula (C-1) is an integer of 0 to 5, preferably an integer of 0 to 2, more preferably 0 or 1, still more preferably 0.
　（Ｃ）スチレン系エラストマーは、スチレン系化合物由来の構造単位以外の構造単位を含有していてもよい。
　（Ｃ）スチレン系エラストマーが含有し得るスチレン系化合物由来の構造単位以外の構造単位としては、例えば、ブタジエン由来の構造単位、イソプレン由来の構造単位、マレイン酸由来の構造単位、無水マレイン酸由来の構造単位等が挙げられる。
　上記ブタジエン由来の構造単位及び上記イソプレン由来の構造単位は、水素添加されていてもよい。水素添加されている場合、ブタジエン由来の構造単位はエチレン単位とブチレン単位とが混合した構造単位となり、イソプレン由来の構造単位はエチレン単位とプロピレン単位とが混合した構造単位となる。 (C) The styrene-based elastomer may contain structural units other than structural units derived from styrene-based compounds.
Examples of structural units other than structural units derived from styrene compounds that may be contained in the styrene elastomer (C) include structural units derived from butadiene, structural units derived from isoprene, structural units derived from maleic acid, and structural units derived from maleic anhydride. Structural units and the like can be mentioned.
The butadiene-derived structural unit and the isoprene-derived structural unit may be hydrogenated. When hydrogenated, structural units derived from butadiene become structural units in which ethylene units and butylene units are mixed, and structural units derived from isoprene become structural units in which ethylene units and propylene units are mixed.
　（Ｃ）スチレン系エラストマーとしては、例えば、スチレン－ブタジエン－スチレンブロック共重合体の水素添加物、スチレン－イソプレン－スチレンブロック共重合体の水素添加物、スチレン－無水マレイン酸共重合体等が挙げられる。
　スチレン－ブタジエン－スチレンブロック共重合体の水素添加物は、ブタジエンブロック中の炭素－炭素二重結合を完全水添してなるＳＥＢＳと、ブタジエンブロック中の１，２－結合部位の炭素－炭素二重結合を部分水添してなるＳＢＢＳが挙げられる。なお、ＳＥＢＳにおける完全水添とは、通常、全体の炭素－炭素二重結合の水添率が、９０％以上であり、９５％以上であってもよく、９９％以上であってもよく、１００％であってもよい。また、ＳＢＢＳにおける部分水添率は、例えば、全体の炭素－炭素二重結合に対して６０～８５％である。スチレン－イソプレン－スチレンブロック共重合体の水素添加物は、ポリイソプレン部が水素添加され、ＳＥＰＳとして得られる。
　これらの中でも、誘電特性、導体接着性、耐熱性、ガラス転移温度及び低熱膨張性の観点から、ＳＥＢＳ、ＳＥＰＳが好ましく、ＳＥＢＳがより好ましい。 Examples of (C) styrene elastomers include hydrogenated styrene-butadiene-styrene block copolymers, hydrogenated styrene-isoprene-styrene block copolymers, and styrene-maleic anhydride copolymers. be done.
Hydrogenated products of styrene-butadiene-styrene block copolymers are SEBS obtained by completely hydrogenating the carbon-carbon double bonds in the butadiene block, and SBBS obtained by partially hydrogenating a heavy bond can be mentioned. In addition, complete hydrogenation in SEBS usually means that the hydrogenation rate of the entire carbon-carbon double bond is 90% or more, may be 95% or more, or may be 99% or more. It may be 100%. Also, the partial hydrogenation rate in SBBS is, for example, 60 to 85% with respect to the entire carbon-carbon double bond. A hydrogenated styrene-isoprene-styrene block copolymer is obtained as SEPS by hydrogenating the polyisoprene portion.
Among these, SEBS and SEPS are preferred, and SEBS is more preferred, from the viewpoint of dielectric properties, conductor adhesion, heat resistance, glass transition temperature and low thermal expansion.
　上記ＳＥＢＳにおいて、スチレン系化合物由来の構造単位の含有率［以下、「スチレン含有率」と称する場合がある。］は、特に限定されないが、好ましくは５～８０質量％、より好ましくは１０～７０質量％、さらに好ましくは３０～６０質量％である。 In the above SEBS, the content of structural units derived from styrene compounds [hereinafter sometimes referred to as "styrene content". ] is not particularly limited, but is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and still more preferably 30 to 60% by mass.
　（Ｃ）スチレン系エラストマーのメルトフローレート（ＭＦＲ）は、特に限定されないが、２３０℃、荷重２．１６ｋｇｆ（２１．２Ｎ）の測定条件では、好ましくは０．１～２０ｇ／１０ｍｉｎ、より好ましくは１～１０ｇ／１０ｍｉｎ、さらに好ましくは３～７ｇ／１０ｍｉｎである。 (C) The melt flow rate (MFR) of the styrene elastomer is not particularly limited, but is preferably 0.1 to 20 g/10 min, more preferably 1 to 10 g/10 min, more preferably 3 to 7 g/10 min.
　（Ｃ）スチレン系エラストマーの市販品としては、例えば、ＳＥＢＳである、旭化成株式会社製のタフテック（登録商標）Ｈシリーズ、Ｍシリーズ、株式会社クラレ製のセプトン（登録商標）シリーズ、クレイトンポリマージャパン株式会社製のクレイトン（登録商標）Ｇポリマーシリーズ等が挙げられる。 (C) Examples of commercially available styrene-based elastomers include SEBS, Tuftec (registered trademark) H series and M series manufactured by Asahi Kasei Corporation, Septon (registered trademark) series manufactured by Kuraray Co., Ltd., and Kraton Polymer Japan Co., Ltd. Kraton (registered trademark) G polymer series manufactured by the company and the like can be mentioned.
　（Ｃ）スチレン系エラストマーの重量平均分子量（Ｍｗ）は、１０，０００超、１００，０００未満であり、好ましくは１５，０００～９８，０００、より好ましくは３０，０００～９５，０００、さらに好ましくは５０，０００～９３，０００、よりさらに好ましくは７０，０００～９２，０００、特に好ましくは８０，０００～９０，０００である。
　（Ｃ）スチレン系エラストマーの重量平均分子量（Ｍｗ）が上記下限値以上であると、加熱時における樹脂組成物の流動性が適度に抑制されるため成形性に優れる傾向にある。また、（Ｃ）スチレン系エラストマーの重量平均分子量（Ｍｗ）が上記上限値以下であると、他の樹脂との相容性に優れる傾向にある。 (C) The weight average molecular weight (Mw) of the styrene-based elastomer is more than 10,000 and less than 100,000, preferably 15,000 to 98,000, more preferably 30,000 to 95,000, even more preferably is 50,000 to 93,000, more preferably 70,000 to 92,000, particularly preferably 80,000 to 90,000.
When the weight average molecular weight (Mw) of the styrene-based elastomer (C) is at least the above lower limit, the fluidity of the resin composition during heating is moderately suppressed, so that moldability tends to be excellent. Further, when the weight average molecular weight (Mw) of (C) the styrene-based elastomer is equal to or less than the upper limit, compatibility with other resins tends to be excellent.
（（Ｃ）スチレン系エラストマーの含有量）
　本実施形態の樹脂組成物中における（Ｃ）スチレン系エラストマーの含有量は、特に限定されないが、本実施形態の樹脂組成物中の樹脂成分の総量（１００質量％）に対して、好ましくは１～３０質量％、より好ましくは３～２０質量％、さらに好ましくは５～１０質量％である。
　（Ｃ）スチレン系エラストマーの含有量が上記下限値以上であると、誘電特性及び柔軟性がより良好になり易い傾向にある。また、（Ｃ）スチレン系エラストマーの含有量が上記上限値以下であると、耐熱性及び難燃性がより良好になり易い傾向にある。 (Content of (C) styrene-based elastomer)
The content of (C) the styrene-based elastomer in the resin composition of the present embodiment is not particularly limited, but is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and even more preferably 5 to 10% by mass.
(C) When the content of the styrene-based elastomer is at least the above lower limit, dielectric properties and flexibility tend to be better. Moreover, when the content of (C) the styrene-based elastomer is equal to or less than the above upper limit, heat resistance and flame retardancy tend to be better.
＜（Ｄ）有機過酸化物＞
　（Ｄ）有機過酸化物としては、ペルオキシド結合（－Ｏ－Ｏ－）を含む有機化合物であれば特に限定されない。
　（Ｄ）有機過酸化物は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 <(D) Organic Peroxide>
(D) The organic peroxide is not particularly limited as long as it is an organic compound containing a peroxide bond (--O--O--).
(D) Organic peroxides may be used singly or in combination of two or more.
　（Ｄ）有機過酸化物の１時間半減期温度は、特に限定されないが、好ましくは１００～２００℃、より好ましくは１２０～１７０℃、さらに好ましくは１３０～１５０℃である。
　（Ｄ）有機過酸化物の１時間半減期温度が上記下限値以上であると、保存中における意図しない反応の進行を抑制し易い傾向にある。また、（Ｄ）有機過酸化物の含有量が上記上限値以下であると、デスミア処理後の窪みの発生をより抑制し易い傾向にある。
　（Ｄ）有機過酸化物の１時間半減期温度は、溶媒中の（Ｄ）有機過酸化物を複数の温度条件で分解反応させて各温度における分解速度定数を求め、これらの分解速度定数をアレニウスプロットすることによって算出できる。なお、本実施形態の１時間半減期温度は、ベンゼン中、（Ｄ）有機過酸化物の濃度０．１ｍｏｌ／Ｌの条件下で測定された１時間半減期温度である。 (D) The one-hour half-life temperature of the organic peroxide is not particularly limited, but is preferably 100 to 200°C, more preferably 120 to 170°C, and still more preferably 130 to 150°C.
(D) When the 1-hour half-life temperature of the organic peroxide is at least the above lower limit, the progress of unintended reactions during storage tends to be suppressed. Moreover, when the content of (D) the organic peroxide is equal to or less than the above upper limit, the occurrence of depressions after the desmear treatment tends to be more easily suppressed.
(D) The 1-hour half-life temperature of the organic peroxide is obtained by decomposing the (D) organic peroxide in the solvent under a plurality of temperature conditions, determining the decomposition rate constants at each temperature, and calculating these decomposition rate constants. It can be calculated by Arrhenius plotting. The 1-hour half-life temperature in the present embodiment is the 1-hour half-life temperature measured under the condition that the concentration of (D) organic peroxide is 0.1 mol/L in benzene.
　（Ｄ）有機過酸化物としては、例えば、１，１－ジ（ｔ－ブチルパーオキシ）シクロヘキサン、２，２－ジ（ｔ－ブチルパーオキシ）ブタン、２，２－ジ（４，４－ジ－ｔ－ブチルパーオキシシクロヘキシル）プロパン、１，１－ジ（ｔ－アミルパーオキシ）シクロヘキサン等のパーオキシケタール類；クメンハイドロパーオキサイド、ｔ－ブチルハイドロパーオキサイド等のハイドロパーオキサイド類；ｔ－ブチルパーオキシアセテート、ｔ－アミルパーオキシイソノナノエート等のアルキルパーオキサイド類；ｔ－ブチルクミルパーオキサイド、ジ－ｔ－ブチルパーオキサイド、ジクミルパーオキサイド、ジ－ｔ－ヘキシルパーオキサイド、１，３－ビス（２－ｔ－ブチルパーオキシイソプロピル）ベンゼン等のジアルキルパーオキサイド類；ｔ－ブチルパーオキシアセテート、ｔ－ブチルパーオキシベンゾエート、ｔ－ブチルパーオキシイソプロピルモノカーボネート等のパーオキシエステル類；ｔ－ブチルパーオキシイソプロピルカーボネート、ポリエーテルテトラキス（ｔ－ブチルパーオキシカーボネート）等のパーオキシカーボネート類；ジベンゾイルパーオキサイド等のジアシルパーオキサイド類などが挙げられる。これらの中でも、適度な１時間半減期温度を有し、取り扱い性に優れるという観点から、１，３－ビス（２－ｔ－ブチルパーオキシイソプロピル）ベンゼン、ジクミルパーオキサイドが好ましい。 (D) Organic peroxides include, for example, 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(t-butylperoxy)butane, 2,2-di(4,4- di-t-butylperoxycyclohexyl)propane, peroxyketals such as 1,1-di(t-amylperoxy)cyclohexane; hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide; t - Alkyl peroxides such as butyl peroxyacetate and t-amyl peroxy isononanoate; t-butyl cumyl peroxide, di-t-butyl peroxide, dicumyl peroxide, di-t-hexyl peroxide, 1 , 3-bis(2-t-butylperoxyisopropyl)benzene and other dialkyl peroxides; t-butylperoxyacetate, t-butylperoxybenzoate, t-butylperoxyisopropyl monocarbonate and other peroxyesters peroxycarbonates such as t-butylperoxyisopropyl carbonate and polyether tetrakis(t-butylperoxycarbonate); and diacyl peroxides such as dibenzoyl peroxide. Among these, 1,3-bis(2-t-butylperoxyisopropyl)benzene and dicumyl peroxide are preferable from the viewpoint of having an appropriate 1-hour half-life temperature and excellent handleability.
（（Ｄ）有機過酸化物の含有量）
　本実施形態の樹脂組成物中における（Ｄ）有機過酸化物の含有量は、特に限定されないが、（Ａ）マレイミド系樹脂及び（Ｂ）ポリフェニレンエーテル系樹脂の総量１００質量部に対して、好ましくは０．０１～１０質量部、より好ましくは０．１～５質量部、さらに好ましくは０．５～２質量部である。
　（Ｄ）有機過酸化物の含有量が上記下限値以上であると、デスミア処理後の窪みの発生をより抑制し易い傾向にある。また、（Ｄ）有機過酸化物の含有量が上記上限値以下であると、反応速度が適度になり、硬化物の均質性を高め易くなる傾向にある。 ((D) content of organic peroxide)
The content of (D) organic peroxide in the resin composition of the present embodiment is not particularly limited, but is preferably is 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 0.5 to 2 parts by mass.
(D) When the content of the organic peroxide is at least the above lower limit, the occurrence of depressions after desmear treatment tends to be more easily suppressed. Further, when the content of (D) the organic peroxide is equal to or less than the above upper limit, the reaction rate becomes moderate, and the homogeneity of the cured product tends to be easily improved.
＜（Ｅ）無機充填材＞
　本実施形態の樹脂組成物は、（Ｅ）無機充填材を含有することによって、より優れた低熱膨張性、耐熱性及び難燃性が得られ易い傾向にある。
　（Ｅ）無機充填材は、１種を単独で用いても、２種以上を組み合わせて用いてもよい。 <(E) Inorganic filler>
By containing (E) the inorganic filler, the resin composition of the present embodiment tends to be more excellent in low thermal expansion, heat resistance and flame retardancy.
(E) Inorganic fillers may be used singly or in combination of two or more.
　（Ｅ）無機充填材としては、例えば、シリカ、アルミナ、酸化チタン、マイカ、ベリリア、チタン酸バリウム、チタン酸カリウム、チタン酸ストロンチウム、チタン酸カルシウム、炭酸アルミニウム、水酸化マグネシウム、水酸化アルミニウム、ケイ酸アルミニウム、炭酸カルシウム、ケイ酸カルシウム、ケイ酸マグネシウム、窒化ケイ素、窒化ホウ素、クレー、タルク、ホウ酸アルミニウム、炭化ケイ素等が挙げられる。これらの中でも、低熱膨張性、耐熱性及び難燃性の観点から、シリカ、アルミナ、マイカ、タルクが好ましく、シリカ、アルミナがより好ましい。
　シリカとしては、例えば、湿式法で製造され含水率の高い沈降シリカ、乾式法で製造され結合水等をほとんど含まない乾式法シリカ等が挙げられる。乾式法シリカとしては、さらに、製造法の違いによって、例えば、破砕シリカ、フュームドシリカ、溶融シリカ等が挙げられる。 (E) Inorganic fillers include, for example, silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, silicon aluminum oxide, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, silicon carbide and the like. Among these, silica, alumina, mica, and talc are preferred, and silica and alumina are more preferred, from the viewpoint of low thermal expansion, heat resistance, and flame retardancy.
Silica includes, for example, precipitated silica produced by a wet method and having a high moisture content, and dry-process silica produced by a dry method and containing almost no bound water. Examples of dry process silica include crushed silica, fumed silica, fused silica, etc., depending on the production method.
　（Ｅ）無機充填材の平均粒子径は、特に限定されないが、（Ｅ）無機充填材の分散性及び微細配線性の観点から、好ましくは０．０１～２０μｍ、より好ましくは０．１～１０μｍ、さらに好ましくは０．２～１μｍ、特に好ましくは０．３～０．８μｍである。
　なお、本明細書において、（Ｅ）無機充填材の平均粒子径は、粒子の全体積を１００％として粒子径による累積度数分布曲線を求めたとき、体積５０％に相当する点の粒子径のことである。（Ｅ）無機充填材の平均粒子径は、例えば、レーザー回折散乱法を用いた粒度分布測定装置等で測定することができる。
　（Ｅ）無機充填材の形状としては、例えば、球状、破砕状等が挙げられ、球状であることが好ましい。 The average particle size of the (E) inorganic filler is not particularly limited, but from the viewpoint of dispersibility and fine wiring properties of the (E) inorganic filler, it is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm. , more preferably 0.2 to 1 μm, particularly preferably 0.3 to 0.8 μm.
In this specification, the average particle size of the inorganic filler (E) is the total volume of the particles as 100%, and when the cumulative frequency distribution curve by the particle size is obtained, the particle size of the point corresponding to 50% of the volume. That is. (E) The average particle size of the inorganic filler can be measured, for example, with a particle size distribution analyzer using a laser diffraction scattering method.
(E) The shape of the inorganic filler includes, for example, a spherical shape, a crushed shape, etc., and a spherical shape is preferred.
（（Ｅ）無機充填材の含有量）
　本実施形態の樹脂組成物が（Ｅ）無機充填材を含有する場合、その含有量は、特に限定されないが、樹脂組成物の固形分総量（１００質量％）に対して、好ましくは３０～９０質量％、より好ましくは４０～８０質量％、さらに好ましくは５０～７０質量％である。
　（Ｅ）無機充填材の含有量が上記下限値以上であると、低熱膨張性、耐熱性及び難燃性がより良好になり易い傾向にある。また、（Ｅ）無機充填材の含有量が上記上限値以下であると、成形性及び導体接着性がより良好になり易い傾向にある。 ((E) content of inorganic filler)
When the resin composition of the present embodiment contains (E) an inorganic filler, the content is not particularly limited, but is preferably 30 to 90 with respect to the total solid content (100% by mass) of the resin composition. % by mass, more preferably 40 to 80% by mass, and even more preferably 50 to 70% by mass.
(E) When the content of the inorganic filler is at least the above lower limit, low thermal expansion, heat resistance and flame retardancy tend to be more favorable. Moreover, when the content of (E) the inorganic filler is equal to or less than the above upper limit, moldability and conductor adhesiveness tend to be more favorable.
＜（Ｆ）有機過酸化物以外の硬化促進剤＞
　本実施形態の樹脂組成物は、樹脂組成物の硬化反応をより促進させるという観点から、さらに、（Ｆ）有機過酸化物以外の硬化促進剤を含有することが好ましい。
　（Ｆ）有機過酸化物以外の硬化促進剤は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 <(F) Curing accelerator other than organic peroxide>
From the viewpoint of further promoting the curing reaction of the resin composition, the resin composition of the present embodiment preferably further contains (F) a curing accelerator other than the organic peroxide.
(F) Curing accelerators other than organic peroxides may be used alone or in combination of two or more.
　（Ｆ）有機過酸化物以外の硬化促進剤としては、例えば、アミン系硬化促進剤、イミダゾール系硬化促進剤、リン系硬化促進剤、有機金属塩、酸性触媒等が挙げられる。なお、本実施形態において、イミダゾール系硬化促進剤は、アミン系硬化促進剤に分類しないものとする。
　アミン系硬化促進剤としては、例えば、トリエチルアミン、ピリジン、トリブチルアミン、ジシアンジアミド等の第１級～第３級アミンを有するアミン化合物；第４級アンモニウム化合物などが挙げられる。
　イミダゾール系硬化促進剤としては、例えば、メチルイミダゾール、フェニルイミダゾール、２－ウンデシルイミダゾール等のイミダゾール化合物；ヘキサメチレンジイソシアネート樹脂と２－エチル－４－メチルイミダゾールの付加反応物等のイソシアネートマスクイミダゾールなどが挙げられる。
　リン系硬化促進剤としては、例えば、トリフェニルホスフィン等の第３級ホスフィン；ｐ－ベンゾキノンのトリ－ｎ－ブチルホスフィン付加反応物等の第４級ホスホニウム化合物などが挙げられる。
　有機金属塩としては、例えば、マンガン、コバルト、亜鉛等のカルボン酸塩などが挙げられる。
　酸性触媒としては、例えば、ｐ－トルエンスルホン酸等が挙げられる。
　これらの中でも、誘電特性、耐熱性、導体接着性及び弾性率の観点から、アミン系硬化促進剤、イミダゾール系硬化促進剤、リン系硬化促進剤が好ましく、ジシアンジアミド、イミダゾール系硬化促進剤、第４級ホスホニウム化合物がより好ましく、これらを併用することがさらに好ましい。 (F) Curing accelerators other than organic peroxides include, for example, amine-based curing accelerators, imidazole-based curing accelerators, phosphorus-based curing accelerators, organic metal salts, and acidic catalysts. In this embodiment, imidazole-based curing accelerators are not classified as amine-based curing accelerators.
Examples of amine curing accelerators include amine compounds having primary to tertiary amines such as triethylamine, pyridine, tributylamine and dicyandiamide; quaternary ammonium compounds.
Examples of imidazole-based curing accelerators include imidazole compounds such as methylimidazole, phenylimidazole and 2-undecylimidazole; isocyanate masked imidazoles such as addition reaction products of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole; mentioned.
Examples of phosphorus curing accelerators include tertiary phosphines such as triphenylphosphine; quaternary phosphonium compounds such as tri-n-butylphosphine addition reaction product of p-benzoquinone.
Organic metal salts include, for example, carboxylates of manganese, cobalt, zinc and the like.
Examples of acidic catalysts include p-toluenesulfonic acid and the like.
Among these, from the viewpoint of dielectric properties, heat resistance, conductor adhesiveness and elastic modulus, amine-based curing accelerators, imidazole-based curing accelerators, and phosphorus-based curing accelerators are preferable. Class phosphonium compounds are more preferred, and it is even more preferred to use them in combination.
　本実施形態の樹脂組成物が（Ｆ）有機過酸化物以外の硬化促進剤を含有する場合、その含有量は、（Ａ）マレイミド系樹脂１００質量部に対して、好ましくは０．０１～１０質量部、より好ましくは０．１～７質量部、さらに好ましくは１～５質量部である。
　（Ｆ）有機過酸化物以外の硬化促進剤の含有量が、上記下限値以上であると、十分な硬化促進効果が得られ易い傾向にある。また、（Ｆ）有機過酸化物以外の硬化促進剤の含有量が、上記上限値以下であると、保存安定性がより良好になり易い傾向にある。 When the resin composition of the present embodiment contains (F) a curing accelerator other than an organic peroxide, the content thereof is preferably 0.01 to 10 parts per 100 parts by mass of the maleimide resin (A). parts by mass, more preferably 0.1 to 7 parts by mass, and even more preferably 1 to 5 parts by mass.
When the content of the curing accelerator (F) other than the organic peroxide is at least the above lower limit, a sufficient curing acceleration effect tends to be obtained. Moreover, when the content of (F) the curing accelerator other than the organic peroxide is equal to or less than the above upper limit, the storage stability tends to be more favorable.
＜その他の成分＞
　本実施形態の樹脂組成物は、さらに必要に応じて、上記各成分以外の樹脂材料、難燃剤、酸化防止剤、熱安定剤、帯電防止剤、紫外線吸収剤、顔料、着色剤、滑剤、シランカップリング剤、有機溶媒及びこれら以外の添加剤からなる群から選択される１種以上の任意成分を含有していてもよい。
　上記の任意成分は、各々について、１種を単独で使用してもよく、２種以上を組み合わせて用いてもよい。
　本実施形態の樹脂組成物中における上記の任意成分の含有量は特に限定されず、必要に応じて、本実施形態の効果を阻害しない範囲で使用すればよい。
　また、本実施形態の樹脂組成物は、所望する性能に応じて、上記の任意成分を含有しないものであってもよい。 <Other ingredients>
If necessary, the resin composition of the present embodiment may further contain a resin material other than the above components, a flame retardant, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a coloring agent, a lubricant, and a silane. It may contain one or more optional components selected from the group consisting of coupling agents, organic solvents and additives other than these.
Each of the above optional components may be used alone or in combination of two or more.
The content of the above optional components in the resin composition of the present embodiment is not particularly limited, and may be used as necessary within a range that does not impair the effects of the present embodiment.
Moreover, the resin composition of the present embodiment may not contain any of the above optional components depending on the desired performance.
＜樹脂組成物の製造方法＞
　本実施形態の樹脂組成物は、上記各成分を混合することによって製造することができる。
　各成分を混合する際には、各成分は撹拌しながら溶解又は分散させてもよい。また、原料を混合する順序、混合温度、混合時間等の条件は、特に限定されず、原料の種類等に応じて任意に設定すればよい。 <Method for producing resin composition>
The resin composition of this embodiment can be produced by mixing the components described above.
When mixing each component, each component may be dissolved or dispersed while stirring. Conditions such as the order of mixing raw materials, mixing temperature, and mixing time are not particularly limited, and may be arbitrarily set according to the type of raw materials.
＜硬化物の比誘電率（Ｄｋ）＞
　本実施形態の樹脂組成物の硬化物の１０ＧＨｚにおける比誘電率（Ｄｋ）は、特に限定されないが、低伝送損失性の観点から、好ましくは３．８以下、より好ましくは３．６以下、さらに好ましくは３．４以下である。上記硬化物の比誘電率（Ｄｋ）は小さい程好ましく、その下限値に特に制限はないが、他の物性とのバランスを考慮して、例えば、２．３以上であってもよく、２．４以上であってもよく、２．６以上であってもよい。
　本実施形態の樹脂組成物から硬化物を得る条件は実施例に記載の条件とすることができる。 <Dielectric constant (Dk) of cured product>
The relative dielectric constant (Dk) at 10 GHz of the cured product of the resin composition of the present embodiment is not particularly limited, but from the viewpoint of low transmission loss, it is preferably 3.8 or less, more preferably 3.6 or less, and further Preferably it is 3.4 or less. The dielectric constant (Dk) of the cured product is preferably as small as possible, and the lower limit thereof is not particularly limited. It may be 4 or more, or 2.6 or more.
The conditions for obtaining a cured product from the resin composition of the present embodiment can be the conditions described in Examples.
＜硬化物の誘電正接（Ｄｆ）＞
　本実施形態の樹脂組成物の硬化物の１０ＧＨｚにおける誘電正接（Ｄｆ）は、特に限定されないが、低伝送損失性の観点から、好ましくは０．００４０以下、より好ましくは０．００３５以下、さらに好ましくは０．００３０以下である。上記硬化物の誘電正接（Ｄｆ）は小さい程好ましく、その下限値に特に制限はないが、他の物性とのバランスを考慮して、例えば、０．００１０以上であってもよく、０．００１５以上であってもよく、０．００２０以上であってもよい。
　上記の比誘電率（Ｄｋ）及び誘電正接（Ｄｆ）は、空洞共振器摂動法に準拠した値であり、より詳細には、実施例に記載する方法によって測定された値である。
　本実施形態の樹脂組成物から硬化物を得る条件は実施例に記載の条件とすることができる。 <Dielectric loss tangent (Df) of cured product>
The dielectric loss tangent (Df) at 10 GHz of the cured product of the resin composition of the present embodiment is not particularly limited, but from the viewpoint of low transmission loss, it is preferably 0.0040 or less, more preferably 0.0035 or less, and further preferably is 0.0030 or less. The dielectric loss tangent (Df) of the cured product is preferably as small as possible, and the lower limit thereof is not particularly limited. or more, or 0.0020 or more.
The relative permittivity (Dk) and dielectric loss tangent (Df) are values based on the cavity resonator perturbation method, more specifically, values measured by the method described in Examples.
The conditions for obtaining a cured product from the resin composition of the present embodiment can be the conditions described in Examples.
［プリプレグ］
　本実施形態のプリプレグは、本実施形態の樹脂組成物又は前記樹脂組成物の半硬化物を含有するプリプレグである。
　すなわち、本実施形態のプリプレグは、本実施形態の樹脂組成物を用いて形成されたプリプレグである。
　本実施形態のプリプレグは、本実施形態の樹脂組成物をＢステージ化してなるＢステージ化樹脂組成物と、シート状繊維基材と、を含有することが好ましい。
　本実施形態のプリプレグは、本実施形態の樹脂組成物をシート状繊維基材に含浸又は塗工した後、Ｂステージ化することによって得られるものであることが好ましい。なお、本明細書においてＢステージ化とは、ＪＩＳ　Ｋ　６９００：１９９４にて定義されるＢステージの状態にすることであり、半硬化とも称される。 [Prepreg]
The prepreg of the present embodiment is a prepreg containing the resin composition of the present embodiment or a semi-cured material of the resin composition.
That is, the prepreg of this embodiment is a prepreg formed using the resin composition of this embodiment.
The prepreg of the present embodiment preferably contains a B-staged resin composition obtained by converting the resin composition of the present embodiment into a B-stage, and a sheet-like fiber base material.
The prepreg of the present embodiment is preferably obtained by impregnating or coating a sheet-like fiber base material with the resin composition of the present embodiment, followed by B-stage. In this specification, B-staging is to bring the material into a B-stage state defined in JIS K 6900:1994, and is also called semi-curing.
　本実施形態のプリプレグが含有するシート状繊維基材としては、例えば、各種の電気絶縁材料用積層板に用いられている公知のシート状繊維基材を使用することができる。
　シート状繊維基材の材質としては、例えば、Ｅガラス、Ｄガラス、Ｓガラス、Ｑガラス等の無機物繊維；ポリイミド、ポリエステル、テトラフルオロエチレン等の有機繊維；これらの混合物などが挙げられる。これらのシート状繊維基材は、例えば、織布、不織布、ロービンク、チョップドストランドマット、サーフェシングマット等の形状を有する。 As the sheet-like fiber base material contained in the prepreg of the present embodiment, for example, known sheet-like fiber base materials used for various laminates for electrical insulating materials can be used.
Examples of materials for the sheet-like fiber substrate 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 fabrics, non-woven fabrics, robinks, chopped strand mats, surfacing mats, and the like.
　本実施形態のプリプレグは、例えば、本実施形態の樹脂組成物を、シート状繊維基材に含浸又は塗布してから、加熱乾燥によりＢステージ化することによって製造することができる。
　加熱乾燥の温度及び時間は、特に限定されないが、生産性及び本実施形態の樹脂組成物を適度にＢステージ化させるという観点から、例えば、５０～２００℃、１～３０分間とすることができる。 The prepreg of the present embodiment can be produced, for example, by impregnating or applying the resin composition of the present embodiment to a sheet-like fiber base material, and then B-stages the resin composition by heating and drying.
The temperature and time of heat drying are not particularly limited, but from the viewpoint of productivity and moderate B-stage of the resin composition of the present embodiment, for example, 50 to 200 ° C., 1 to 30 minutes. .
　本実施形態のプリプレグ中の樹脂組成物由来の固形分濃度は、特に限定されないが、積層板とした際に、より良好な成形性が得られ易いという観点から、好ましくは２０～９０質量％、より好ましくは２５～８０質量％、さらに好ましくは３０～７５質量％である。 The concentration of solids derived from the resin composition in the prepreg of the present embodiment is not particularly limited. More preferably 25 to 80 mass %, still more preferably 30 to 75 mass %.
［樹脂フィルム］
　本実施形態の樹脂フィルムは、本実施形態の樹脂組成物又は前記樹脂組成物の半硬化物を含有する樹脂フィルムである。
　すなわち、本実施形態の樹脂フィルムは、本実施形態の樹脂組成物を用いて形成された樹脂フィルムである。
　本実施形態の樹脂フィルムは、本実施形態の樹脂組成物又は本実施形態の樹脂組成物をＢステージ化してなるＢステージ化樹脂組成物をフィルム状にしたものである。
　本実施形態の樹脂フィルムは、例えば、有機溶媒を含有する本実施形態の樹脂組成物、つまり樹脂ワニスを支持体に塗布してから、加熱乾燥させることによって製造することができる。
　支持体としては、例えば、プラスチックフィルム、金属箔、離型紙等が挙げられる。
　加熱乾燥の温度及び時間は、特に限定されないが、生産性及び本実施形態の樹脂組成物を適度にＢステージ化させるという観点から、５０～２００℃、１～３０分間とすることができる。 [Resin film]
The resin film of the present embodiment is a resin film containing the resin composition of the present embodiment or a semi-cured product of the resin composition.
That is, the resin film of this embodiment is a resin film formed using the resin composition of this embodiment.
The resin film of the present embodiment is a film made from the resin composition of the present embodiment or a B-staged resin composition obtained by converting the resin composition of the present embodiment into a B-stage.
The resin film of the present embodiment can be produced, for example, by applying the resin composition of the present embodiment containing an organic solvent, ie, a resin varnish, to a support, followed by heating and drying.
Examples of the support include plastic films, metal foils, release papers and the like.
The temperature and time of heat drying are not particularly limited, but from the viewpoint of productivity and moderate B-stage of the resin composition of the present embodiment, it can be 50 to 200 ° C. and 1 to 30 minutes.
　本実施形態の樹脂フィルムは、プリント配線板を製造する場合において、絶縁層を形成するために用いられることが好ましい。 The resin film of the present embodiment is preferably used for forming an insulating layer when manufacturing a printed wiring board.
［積層板］
　本実施形態の積層板は、本実施形態のプリプレグの硬化物を有する積層板である。
　すなわち、本実施形態の積層板は、本実施形態のプリプレグを用いて形成された積層板である。
　本実施形態の積層板は、本実施形態のプリプレグの硬化物と金属箔とを含有することが好ましい。
　なお、金属箔を有する積層板は、金属張積層板と称されることもある。 [Laminate]
The laminated board of this embodiment is a laminated board having a cured product of the prepreg of this embodiment.
That is, the laminate of this embodiment is a laminate formed using the prepreg of this embodiment.
The laminate of the present embodiment preferably contains the cured prepreg of the present embodiment and metal foil.
A laminate having metal foil is sometimes referred to as a metal-clad laminate.
　金属箔の金属としては、特に限定されず、例えば、銅、金、銀、ニッケル、白金、モリブデン、ルテニウム、アルミニウム、タングステン、鉄、チタン、クロム、これらの金属元素を１種以上含有する合金等が挙げられる。 The metal of the metal foil is not particularly limited, and examples thereof include copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and alloys containing one or more of these metal elements. are mentioned.
　本実施形態の積層板は、例えば、本実施形態のプリプレグの片面又は両面に金属箔を配置してから、加熱加圧成形することによって製造することができる。
　通常、この加熱加圧成形によって、Ｂステージ化されたプリプレグを硬化させて本実施形態の積層板が得られる。
　加熱加圧成形する際、プリプレグは１枚のみを用いてもよいし、２枚以上のプリプレグを積層させてもよい。
　加熱加圧成形は、例えば、多段プレス、多段真空プレス、連続成形、オートクレーブ成形機等を使用することができる。
　加熱加圧成形の条件は、特に限定されないが、例えば、温度１００～３００℃、時間１０～３００分間、圧力１．５～５ＭＰａとすることができる。 The laminate of the present embodiment can be produced, for example, by placing a metal foil on one side or both sides of the prepreg of the present embodiment, followed by heating and pressure molding.
Normally, the laminate of the present embodiment is obtained by curing the B-staged prepreg by this heat and pressure molding.
In the heat and pressure molding, only one prepreg may be used, or two or more prepregs may be laminated.
For heat-press molding, for example, a multi-stage press, a multi-stage vacuum press, continuous molding, an autoclave molding machine, etc. can be used.
The conditions for the heat and pressure molding are not particularly limited, but can be, for example, a temperature of 100 to 300° C., a time of 10 to 300 minutes, and a pressure of 1.5 to 5 MPa.
［プリント配線板］
　本実施形態のプリント配線板は、本実施形態の樹脂組成物の硬化物を有するプリント配線板である。
　本実施形態のプリント配線板は、例えば、本実施形態のプリプレグ、本実施形態の樹脂フィルム及び本実施形態の積層板からなる群から選択される１種以上を用いて形成されたプリント配線板である。
　本実施形態のプリント配線板は、少なくとも、本実施形態の樹脂組成物の硬化物と導体回路層とを含むものであり、本実施形態のプリプレグの硬化物、本実施形態の樹脂フィルムの硬化物又は本実施形態の積層板と導体回路層とを含むものが好ましい。
　本実施形態のプリント配線板の製造方法は、本実施形態の樹脂組成物の硬化物を含む絶縁材料に対して、デスミア処理を施す工程を含むことが好ましい。デスミア処理の方法としては、公知の方法を適用することができる。
　デスミア処理を施した絶縁材料に対して、公知の方法によって、導体回路形成を行うことで、本実施形態のプリント配線板を製造することができる。また、さらに必要に応じて多層化接着加工を施すことによって、多層プリント配線板を製造することもできる。導体回路は、例えば、穴開け加工、金属めっき加工、金属箔のエッチング等を適宜施すことで形成することができる。 [Printed wiring board]
The printed wiring board of this embodiment is a printed wiring board having a cured product of the resin composition of this embodiment.
The printed wiring board of the present embodiment is, for example, a printed wiring board formed 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. be.
The printed wiring board of the present embodiment includes at least a cured product of the resin composition of the present embodiment and a conductor circuit layer, a cured product of the prepreg of the present embodiment, and a cured product of the resin film of the present embodiment. Alternatively, it is preferable to include the laminated plate of the present embodiment and a conductor circuit layer.
The method for manufacturing the printed wiring board of the present embodiment preferably includes a step of subjecting the insulating material containing the cured product of the resin composition of the present embodiment to desmear treatment. As a desmearing method, a known method can be applied.
The printed wiring board of the present embodiment can be manufactured by forming a conductive circuit on the insulating material subjected to the desmear treatment by a known method. Moreover, a multilayer printed wiring board can also be manufactured by applying a multilayer adhesion process, if necessary. The conductor circuit can be formed by appropriately performing, for example, drilling, metal plating, etching of metal foil, or the like.
［半導体パッケージ］
　本実施形態の半導体パッケージは、本実施形態のプリント配線板を有する半導体パッケージである。
　すなわち、本実施形態の半導体パッケージは、本実施形態のプリント配線板を用いて形成された半導体パッケージである。
　本実施形態の半導体パッケージは、例えば、本実施形態のプリント配線板に、公知の方法によって、半導体チップ、メモリ等を搭載することによって製造することができる。 [Semiconductor package]
The semiconductor package of this embodiment is a semiconductor package having the printed wiring board of this embodiment.
That is, the semiconductor package of this embodiment is a semiconductor package formed using the printed wiring board of this embodiment.
The semiconductor package of this embodiment can be manufactured, for example, by mounting a semiconductor chip, a memory, etc. on the printed wiring board of this embodiment by a known method.
　以下、実施例を挙げて、本実施形態を具体的に説明する。ただし、本実施形態は以下の実施例に限定されるものではない。 The present embodiment will be specifically described below with reference to examples. However, this embodiment is not limited to the following examples.
　なお、各例において、重量平均分子量（Ｍｗ）は以下の方法によって測定した。
　ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により、標準ポリスチレンを用いた検量線から換算した。検量線は、標準ポリスチレン：ＴＳＫｓｔａｎｄａｒｄ　ＰＯＬＹＳＴＹＲＥＮＥ（Ｔｙｐｅ；Ａ－２５００、Ａ－５０００、Ｆ－１、Ｆ－２、Ｆ－４、Ｆ－１０、Ｆ－２０、Ｆ－４０）［東ソー株式会社製、商品名］を用いて３次式で近似した。ＧＰＣの測定条件を、以下に示す。
装置：
　ポンプ：Ｌ－６２００型［株式会社日立ハイテクノロジーズ製］
　検出器：Ｌ－３３００型ＲＩ［株式会社日立ハイテクノロジーズ製］
　カラムオーブン：Ｌ－６５５Ａ－５２［株式会社日立ハイテクノロジーズ製］
　カラム：ガードカラム；ＴＳＫ　Ｇｕａｒｄｃｏｌｕｍｎ　ＨＨＲ－Ｌ＋カラム；ＴＳＫｇｅｌ　Ｇ４０００ＨＨＲ＋ＴＳＫｇｅｌ　Ｇ２０００ＨＨＲ（すべて東ソー株式会社製、商品名）
　カラムサイズ：６．０×４０ｍｍ（ガードカラム）、７．８×３００ｍｍ（カラム）
溶離液：テトラヒドロフラン
試料濃度：３０ｍｇ／５ｍＬ
注入量：２０μＬ
流量：１．００ｍＬ／分
測定温度：４０℃ In addition, in each example, the weight average molecular weight (Mw) was measured by the following method.
Conversion was performed from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). Calibration curve, 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, product name] and approximated by a cubic equation. GPC measurement conditions are shown below.
Device:
Pump: L-6200 type [manufactured by Hitachi High-Technologies Corporation]
Detector: L-3300 type 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 x 40 mm (guard column), 7.8 x 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
［製造例１：アミノマレイミド樹脂の製造］
　温度計、攪拌装置、還流冷却管付き水分定量器の付いた加熱及び冷却可能な容積５リットルの反応容器に、２，２－ビス［４－（４－マレイミドフェノキシ）フェニル］プロパン１００質量部と、両末端に第１級アミノ基を有するシリコーン化合物（第１級アミノ基当量７５０ｇ／ｍｏｌ）５．６質量部と、３，３’－ジエチル－４，４’－ジアミノジフェニルメタン７．９質量部と、プロピレングリコールモノメチルエーテル１７１質量部と、を投入し、還流させながら２時間反応させた。これを還流温度にて３時間かけて濃縮し、固形分濃度が６５質量％のアミノマレイミド樹脂の溶液を製造した。得られたアミノマレイミド樹脂の重量平均分子量（Ｍｗ）は、約２，７００であった。 [Production Example 1: Production of aminomaleimide resin]
100 parts by mass of 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane and , 5.6 parts by mass of a silicone compound having primary amino groups at both ends (primary amino group equivalent: 750 g/mol) and 7.9 parts by mass of 3,3'-diethyl-4,4'-diaminodiphenylmethane and 171 parts by mass of propylene glycol monomethyl ether were added and reacted for 2 hours while refluxing. This was concentrated at reflux temperature over 3 hours to produce a solution of aminomaleimide resin with a solid content concentration of 65% by mass. The weight average molecular weight (Mw) of the obtained aminomaleimide resin was about 2,700.
実施例１及び２、比較例１
（樹脂組成物の製造）
　表１に記載の各成分を表１に記載の配合組成に従って配合し、トルエン５８質量部及びメチルイソブチルケトン１０質量部と共に、室温（２５℃）で撹拌及び混合して、固形分濃度５５～６５質量％の樹脂組成物を製造した。なお、表１中、各成分の配合量の単位は質量部であり、溶液の場合は、固形分換算の質量部を意味する。 Examples 1 and 2, Comparative Example 1
(Manufacture of resin composition)
Each component shown in Table 1 was blended according to the formulation shown in Table 1, and stirred and mixed with 58 parts by mass of toluene and 10 parts by mass of methyl isobutyl ketone at room temperature (25 ° C.) to obtain a solid content concentration of 55 to 65. A mass % resin composition was produced. In addition, in Table 1, the unit of the compounding amount of each component is parts by mass, and in the case of a solution, it means parts by mass in terms of solid content.
（両面銅張積層板の製造）
　上記で得た樹脂組成物を、厚さ０．０８ｍｍのガラスクロス（ＮＥガラス、日東紡績株式会社製）に塗工した後、１８０℃で５分間加熱乾燥して、樹脂組成物由来の固形分含有量が約６０質量％のプリプレグを作製した。このプリプレグを２枚重ね、その上下に、厚さ１２μｍの銅箔（三井金属株式会社製、商品名「３ＥＣ－Ｍ３－ＶＬＰ－１２」、Ｍ面のＲｚ：３．０μｍ）を、Ｍ面がプリプレグに接するように配置し、温度２３０℃、圧力３．０ＭＰａ、時間９０分間の条件で加熱加圧成形して、両面銅張積層板（厚さ：０．２３ｍｍ）を製造した。 (Manufacturing of double-sided copper-clad laminate)
After coating the resin composition obtained above on a glass cloth (NE glass, manufactured by Nitto Boseki Co., Ltd.) having a thickness of 0.08 mm, it is dried by heating at 180 ° C. for 5 minutes, and the solid content derived from the resin composition. A prepreg with a content of about 60% by mass was produced. Two sheets of this prepreg are stacked, and a copper foil with a thickness of 12 μm (manufactured by Mitsui Kinzoku Co., Ltd., trade name “3EC-M3-VLP-12”, Rz of M surface: 3.0 μm) is placed on the top and bottom. A double-sided copper-clad laminate (thickness: 0.23 mm) was manufactured by placing in contact with the prepreg and heat-pressing molding under the conditions of a temperature of 230° C., a pressure of 3.0 MPa, and a time of 90 minutes.
［評価方法］
　各例で得られた両面銅張積層板を用いて、下記方法に従って各評価を行った。結果を表１に示す。 [Evaluation method]
Using the double-sided copper-clad laminate obtained in each example, each evaluation was performed according to the following methods. Table 1 shows the results.
（窪みの存在比率の測定）
　各例で得た両面銅張積層板を銅エッチング液に浸漬することにより銅箔を取り除いて得たプリプレグの硬化物を４０ｍｍ×４０ｍｍに切り出したものを試験片とした。
　該試験片に対して以下に示す（１）～（４）を順に行ってデスミア処理した。
（１）膨潤液（アトテックジャパン株式会社製、商品名「スエリングディップ・セキュリガントＰ」、グリコールエーテル類、水酸化ナトリウムの水溶液）に７０℃で５分間浸漬した後、水洗。
（２）粗化液（アトテックジャパン株式会社製、商品名「コンセントレート・コンパクトＰ」、ＫＭｎＯ４：６０ｇ／Ｌ、ＮａＯＨ：４０ｇ／Ｌの水溶液）に８０℃で５分間浸漬した後、水洗。
（３）中和液（アトテックジャパン株式会社製、「リダクションショリューシン・セキュリガントＭＶ」、硫酸の水溶液）に４０℃で５分間浸漬した後、水洗。
（４）８０℃で１０分間乾燥 (Measurement of existence ratio of depressions)
The copper foil was removed from the double-sided copper-clad laminate obtained in each example by immersing it in a copper etching solution to obtain a cured prepreg.
The test piece was desmeared by performing the following (1) to (4) in order.
(1) After being immersed in a swelling liquid (manufactured by Atotech Japan Co., Ltd., trade name "Swelling Dip Securigant P", an aqueous solution of glycol ethers and sodium hydroxide) at 70°C for 5 minutes, it was washed with water.
(2) After being immersed in a roughening solution (manufactured by Atotech Japan Co., Ltd., product name "Concentrate Compact P", KMnO 4 : 60 g/L, NaOH: 40 g/L aqueous solution) at 80°C for 5 minutes, washed with water.
(3) After being immersed in a neutralizing solution (manufactured by Atotech Japan Co., Ltd., "Reduction Shoryusin Securigant MV", an aqueous solution of sulfuric acid) at 40°C for 5 minutes, it was washed with water.
(4) Dry at 80°C for 10 minutes
　上記デスミア処理後の試験片に対して、イオンミリング装置（株式会社日立ハイテクノロジーズ製、商品名：Ｅ－３５００）を用いて、加速電圧６ｋＶ、放電電圧４ｋＶ、Ａｒガス流量１．８０ｃｍ３／ｍｉｎ、加工幅５００μｍ、加工時間６時間の条件で断面形成を行った。次いで、走査型電子顕微鏡（ＳＥＭ）（株式会社日立ハイテクノロジーズ製、商品名：ＳＶ－４７００）を用いて、二次電子モード、加速電圧２０ｋＶ、観察倍率５，０００倍の条件にて、上記試験片の断面を観察した。 An ion milling device (manufactured by Hitachi High-Technologies Co., Ltd., trade name: E-3500) was applied to the test piece after the desmear treatment with an acceleration voltage of 6 kV, a discharge voltage of 4 kV, and an Ar gas flow rate of 1.80 cm 3 /min. , a processing width of 500 μm, and a processing time of 6 hours. Then, using a scanning electron microscope (SEM) (manufactured by Hitachi High-Technologies Co., Ltd., trade name: SV-4700), the above test was performed under the conditions of secondary electron mode, acceleration voltage of 20 kV, and observation magnification of 5,000 times. A cross-section of the piece was observed.
　得られた試験片の断面ＳＥＭ像から、該試験片は、ガラスクロスと樹脂組成物の硬化物とからなる複合層と、該複合層の両面に、樹脂組成物の硬化物のみからなる樹脂硬化物層と、を有するものであることが確認された。そして、窪みを有する試験片については、上記樹脂硬化物層の表面、すなわち、取り除く前の銅箔と接していた樹脂硬化物層の表面において、窪みが観察された。
　図１に、デスミア処理後の試験片における窪みの存在比率（％）の算出方法を説明するための試験片１０の断面模式図を示す。図１の試験片１０は、ガラスクロスと樹脂組成物の硬化物とからなる複合層１の両面に、樹脂組成物の硬化物のみからなる樹脂硬化物層２を有する。図１中、点線で囲まれた領域Ｓ１は、試験片１０において窪みが存在しないと仮定した場合の領域である。また、図１中、領域Ｓ２は、大きさが０．５μｍを超える窪み３の領域である。なお、ここでの窪み３の大きさとは、図１の拡大図においてＤで表される窪みの両端部を結ぶ直線の長さを意味する。
　窪みの存在比率（％）は、上記領域Ｓ１の面積に対する領域Ｓ２の総面積の比率（Ｓ２×１００／Ｓ１）として算出した。 From the cross-sectional SEM image of the obtained test piece, the test piece has a composite layer consisting of a glass cloth and a cured product of the resin composition, and a cured resin consisting only of a cured product of the resin composition on both sides of the composite layer. It was confirmed that it has a material layer. As for the test pieces having dents, dents were observed on the surface of the cured resin layer, that is, on the surface of the cured resin layer that was in contact with the copper foil before removal.
FIG. 1 shows a schematic cross-sectional view of a test piece 10 for explaining a method of calculating the existence ratio (%) of depressions in the test piece after desmear treatment. A test piece 10 in FIG. 1 has cured resin layers 2 made of only a cured resin composition on both sides of a composite layer 1 made of a glass cloth and a cured resin composition. In FIG. 1, an area S1 surrounded by a dotted line is an area when it is assumed that the test piece 10 does not have a depression. Further, in FIG. 1, a region S2 is a region of the depression 3 with a size exceeding 0.5 μm. The size of the recess 3 here means the length of a straight line connecting both ends of the recess represented by D in the enlarged view of FIG.
The existence ratio (%) of depressions was calculated as the ratio of the total area of the region S2 to the area of the region S1 (S2×100/S1).
（銅箔引き剥がし強さの測定）
　各例で得た両面銅張積層板の銅箔をエッチングによって３ｍｍ幅の直線ライン状に加工したものを試験片とした。形成した直線ライン状の銅箔を小型卓上試験機（株式会社島津製作所製、商品名「ＥＺ－ＴＥＳＴ」）に取り付け、室温（２５℃）にて、９０°方向に引き剥がすことによって銅箔引き剥がし強さを測定した。なお、銅箔を引き剥がす際の引っ張り速度は５０ｍｍ／ｍｉｎとした。 (Measurement of copper foil peel strength)
A specimen was prepared by etching the copper foil of the double-sided copper-clad laminate obtained in each example into a straight line with a width of 3 mm. The formed straight line-shaped copper foil is attached to a small desktop tester (manufactured by Shimadzu Corporation, trade name "EZ-TEST"), and the copper foil is pulled by peeling it off in a 90 ° direction at room temperature (25 ° C.). The peel strength was measured. The pulling speed for peeling off the copper foil was 50 mm/min.
（比誘電率（Ｄｋ）及び誘電正接（Ｄｆ）の測定）
　各例で得た両面銅張積層板の外層銅箔を、銅エッチング液（過硫酸アンモニウムの１０質量％溶液、三菱ガス化学株式会社製）に浸漬することによって除去し、長さ６０ｍｍ、幅２ｍｍに切り出したものを試験片とした。該試験片を用いて、空洞共振器摂動法によって比誘電率（Ｄｋ）及び誘電正接（Ｄｆ）を測定した。測定器にはアジレントテクノロジー社製のベクトル型ネットワークアナライザ「Ｎ５２２７Ａ」、空洞共振器には株式会社関東電子応用開発製の「ＣＰ１２９」（１０ＧＨｚ帯共振器）、測定プログラムには「ＣＰＭＡ－Ｖ２」をそれぞれ使用した。測定は、周波数１０ＧＨｚ、測定温度２５℃の条件下で行った。 (Measurement of dielectric constant (Dk) and dielectric loss tangent (Df))
The outer layer copper foil of the double-sided copper-clad laminate obtained in each example was removed by immersion in a copper etching solution (10% by mass ammonium persulfate solution, manufactured by Mitsubishi Gas Chemical Co., Ltd.) to a length of 60 mm and a width of 2 mm. A cut piece was used as a test piece. Using the test piece, the dielectric constant (Dk) and dielectric loss tangent (Df) were measured by the cavity resonator perturbation method. A vector network analyzer "N5227A" manufactured by Agilent Technologies Inc. is used as the measuring instrument, a cavity resonator is "CP129" (10 GHz band resonator) manufactured by Kanto Denshi Applied Development Co., Ltd., and a measurement program is "CPMA-V2". each used. The measurement was performed under conditions of a frequency of 10 GHz and a measurement temperature of 25°C.
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000020
　なお、表１における各材料の詳細は、以下の通りである。
［（Ａ）成分］
・マレイミド系樹脂：製造例１で得たアミノマレイミド樹脂 Details of each material in Table 1 are as follows.
[(A) component]
- Maleimide resin: aminomaleimide resin obtained in Production Example 1
［（Ｂ）成分］
・メタクリロイル基を有するポリフェニレンエーテル系樹脂：両末端にメタクリロイル基を有するポリフェニレンエーテル（重量平均分子量（Ｍｗ）１，７００） [(B) Component]
- Polyphenylene ether resin having a methacryloyl group: polyphenylene ether having methacryloyl groups at both ends (weight average molecular weight (Mw) 1,700)
［（Ｃ）成分］
・ＳＥＢＳ：無水マレイン酸変性水添スチレン系エラストマー（ＳＥＢＳ）、酸価１０ｍｇＣＨ３ＯＮａ／ｇ、スチレン含有率４５質量％、重量平均分子量（Ｍｗ）８６，０００ [(C) component]
SEBS: maleic anhydride-modified hydrogenated styrene elastomer (SEBS), acid value 10 mgCH3ONa /g, styrene content 45% by mass, weight average molecular weight (Mw) 86,000
［（Ｄ）成分］
・１，３－ビス（２－ｔ－ブチルパ－オキシイソプロピル）ベンゼン（１時間半減期温度１３７．７℃）
・ジクミルパーオキサイド（１時間半減期温度１３５．７℃） [(D) Component]
・1,3-bis(2-t-butylperoxyisopropyl)benzene (1 hour half-life temperature 137.7°C)
・Dicumyl peroxide (1 hour half-life temperature 135.7°C)
［（Ｅ）成分］
・シリカ：平均粒子径０．５μｍの球状溶融シリカ [(E) component]
・Silica: spherical fused silica with an average particle size of 0.5 μm
［（Ｆ）成分］
・ｐ－ベンゾキノンのトリ－ｎ－ブチルホスフィン付加反応物
・ジシアンジアミド [(F) Component]
・Tri-n-butylphosphine addition reaction product of p-benzoquinone ・Dicyandiamide
　表１に示した結果から、本実施形態の実施例１及び２の樹脂組成物から形成された硬化物は、（Ｄ）有機過酸化物を含有しない比較例１の樹脂組成物よりも、デスミア処理後の窪みの発生が抑制されたものであることが分かる。 From the results shown in Table 1, the cured products formed from the resin compositions of Examples 1 and 2 of the present embodiment are more desmeared than the resin composition of Comparative Example 1 (D) containing no organic peroxide. It can be seen that the formation of depressions after the treatment was suppressed.
　本実施形態の樹脂組成物は、デスミア処理後の表面における窪みの発生が抑制された硬化物を形成可能であるため、該樹脂組成物を用いて得られるプリプレグ、積層板、プリント配線板、半導体パッケージ等は、特に高周波信号を扱う電子部品用途に好適である。 Since the resin composition of the present embodiment can form a cured product in which the occurrence of depressions on the surface after desmear treatment is suppressed, prepregs, laminates, printed wiring boards, and semiconductors obtained using the resin composition Packages and the like are particularly suitable for electronic component applications that handle high-frequency signals.
１　複合層
２　樹脂硬化物層
３　窪み
１０　試験片
Ｓ１　窪みが存在しないと仮定した場合の領域
Ｓ２　大きさが０．５μｍを超える窪み３の領域
Ｄ　窪みの大きさ

  1 Composite layer 2 Resin cured material layer 3 Hollow 10 Specimen S1 Region S2 when it is assumed that no hollow exists Region D of hollow 3 with a size exceeding 0.5 μm Size of hollow

Claims (13)

  1. 　（Ａ）Ｎ－置換マレイミド基を１個以上有するマレイミド樹脂及び該マレイミド樹脂の誘導体からなる群から選択される１種以上と、
    　（Ｂ）エチレン性不飽和結合を含む官能基を有するポリフェニレンエーテル系樹脂と、
    　（Ｃ）重量平均分子量（Ｍｗ）が１０，０００超、１００，０００未満であるスチレン系エラストマーと、
    　（Ｄ）有機過酸化物と、
    　を含有する樹脂組成物。     (A) one or more selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of the maleimide resins;
    (B) a polyphenylene ether-based resin having a functional group containing an ethylenically unsaturated bond;
    (C) a styrene-based elastomer having a weight average molecular weight (Mw) of more than 10,000 and less than 100,000;
    (D) an organic peroxide;
    A resin composition containing
  2. 　前記（Ｂ）成分が、前記エチレン性不飽和結合を含む官能基を末端に有する、請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein the component (B) has a functional group containing the ethylenically unsaturated bond at its end.
  3. 　前記（Ｂ）成分が有するエチレン性不飽和結合を含む官能基が、（メタ）アクリロイル基である、請求項１又は２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the ethylenically unsaturated bond-containing functional group of component (B) is a (meth)acryloyl group.
  4. 　前記（Ｂ）成分の重量平均分子量（Ｍｗ）が、５００～７，０００である、請求項１又は２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the weight average molecular weight (Mw) of component (B) is 500 to 7,000.
  5. 　前記（Ｄ）成分の１時間半減期温度が、１００～２００℃である、請求項１又は２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the one-hour half-life temperature of component (D) is 100 to 200°C.
  6. 　前記（Ｄ）成分の含有量が、前記（Ａ）成分と前記（Ｂ）成分の総量１００質量部に対して、０．０１～１０質量部である、請求項１又は２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the content of component (D) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (B). thing.
  7. 　さらに、（Ｅ）無機充填材を含有する、請求項１又は２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, further comprising (E) an inorganic filler.
  8. 　さらに、（Ｆ）有機過酸化物以外の硬化促進剤を含有する、請求項１又は２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, further comprising (F) a curing accelerator other than an organic peroxide.
  9. 　請求項１又は２に記載の樹脂組成物又は前記樹脂組成物の半硬化物を含有するプリプレグ。 A prepreg containing the resin composition according to claim 1 or 2 or a semi-cured product of the resin composition.
  10. 　請求項９に記載のプリプレグの硬化物を有する積層板。 A laminate having a cured product of the prepreg according to claim 9.
  11. 　請求項１又は２に記載の樹脂組成物又は前記樹脂組成物の半硬化物を含有する樹脂フィルム。 A resin film containing the resin composition according to claim 1 or 2 or a semi-cured product of the resin composition.
  12. 　請求項１又は２に記載の樹脂組成物の硬化物を有するプリント配線板。 A printed wiring board comprising a cured product of the resin composition according to claim 1 or 2.
  13. 　請求項１２に記載のプリント配線板を有する半導体パッケージ。

          A semiconductor package comprising the printed wiring board according to claim 12 .
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