WO2023033131A1 - Composition de résine, préimprégné, stratifié, film de résine, carte de circuit imprimé et boîtier de semi-conducteur - Google Patents

Composition de résine, préimprégné, stratifié, film de résine, carte de circuit imprimé et boîtier de semi-conducteur Download PDF

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WO2023033131A1
WO2023033131A1 PCT/JP2022/033057 JP2022033057W WO2023033131A1 WO 2023033131 A1 WO2023033131 A1 WO 2023033131A1 JP 2022033057 W JP2022033057 W JP 2022033057W WO 2023033131 A1 WO2023033131 A1 WO 2023033131A1
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group
resin
resin composition
carbon atoms
primary amino
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PCT/JP2022/033057
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English (en)
Japanese (ja)
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俊希 藤井
諒 下川
圭芸 日▲高▼
真 柳田
幸雄 中村
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昭和電工マテリアルズ株式会社
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Priority to JP2023545686A priority Critical patent/JPWO2023033131A1/ja
Priority to CN202280058895.7A priority patent/CN117881738A/zh
Priority to KR1020247006802A priority patent/KR20240051946A/ko
Publication of WO2023033131A1 publication Critical patent/WO2023033131A1/fr

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    • 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
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08L79/085—Unsaturated polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • 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
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • 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
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
    • 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
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement

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 characterized by containing a naphthol novolac type epoxy resin and a polyphenylene ether resin.
  • the present embodiment provides a resin composition having excellent copper foil peel strength and curability, and a prepreg, laminate, resin film, printed wiring board, and semiconductor package using the resin composition.
  • the task is to
  • thermosetting resin a thermosetting resin
  • B a polyphenylene ether-based resin
  • C an alkoxysilane compound having a primary amino group
  • D an inorganic filler
  • a resin composition containing [2] The resin composition according to [1] above, wherein (A) the thermosetting resin is one or more selected from the group consisting of epoxy resins, cyanate resins and maleimide resins.
  • thermosetting resin is a maleimide resin.
  • thermosetting resin is a maleimide resin.
  • polyphenylene ether resin has a functional group containing an ethylenically unsaturated bond.
  • functional group containing an ethylenically unsaturated bond is a (meth)acryloyl group.
  • C) the alkoxysilane compound having a primary amino group has a trialkoxysilyl group.
  • the content of (C) the alkoxysilane compound having a primary amino group is 0.1 to 10% by mass with respect to the total solid content (100% by mass) of the resin composition.
  • a printed wiring board comprising a cured product of the resin composition according to any one of [1] to [9] above.
  • the present embodiment it is possible to provide a resin composition excellent in copper foil peel strength and curability, and a prepreg, laminate, resin film, printed wiring board, and semiconductor package using the resin composition.
  • 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 alone 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 indicates 25° C. in this specification.
  • (Meth)acryloyl as used herein means “acryloyl” and the corresponding “methacryloyl”.
  • the weight average molecular weight (Mw) in this specification means a value measured in terms of polystyrene by gel permeation chromatography (GPC; Gas Permeation Chromatography). 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) a thermosetting resin; (B) a polyphenylene ether-based resin; (C) an alkoxysilane compound having a primary amino group; (D) an inorganic filler; It is a resin composition containing
  • the above components may be abbreviated as (A) component, (B) component, (C) component, (D) component, etc., and other components are also abbreviated in the same manner.
  • the resin composition of the present embodiment contains (A) a thermosetting resin and (B) a polyphenylene ether resin.
  • the (B) polyphenylene ether-based resin has a lower probability of existence of polar groups than the (A) thermosetting resin, and therefore tends to have weak intermolecular forces with other components. Therefore, it is thought that (B) the resin composition to which the polyphenylene ether-based resin is added is likely to break when a stress that peels off the copper foil is applied.
  • the resin composition of the present embodiment solves the above problem by containing (C) an alkoxysilane compound having a primary amino group.
  • the alkoxysilane compound having a primary amino group comprises a primary amino group having excellent reactivity and affinity with organic components and an alkoxysilyl group having excellent reactivity and affinity with inorganic components. have. Therefore, in the resin composition of the present embodiment containing (C) an alkoxysilane compound having a primary amino group, mainly the interfacial adhesion between the organic component and the inorganic component is strengthened, and the resin phase and (D) It is presumed that interfacial failure with the inorganic filler is less likely to occur, and the peeling strength of the copper foil is improved.
  • the resin composition of the present embodiment contains (A) a thermosetting resin.
  • the thermosetting resin may be used alone or in combination of two or more.
  • Thermosetting resins include, for example, epoxy resins, phenol resins, maleimide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, Examples include silicone resins, triazine resins, melamine resins, and the like.
  • thermosetting resin is preferably one or more selected from the group consisting of epoxy resins, cyanate resins and maleimide resins, more preferably maleimide resins, from the viewpoint of heat resistance, and N-substituted At least one selected from the group consisting of maleimide resins having one or more maleimide groups and derivatives of the maleimide resins is more preferable.
  • maleimide resin 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
  • maleimide resin a maleimide resin having one or more N-substituted maleimide groups
  • 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.
  • Examples of the divalent organic group represented by X a11 in general formula (A1-1) include a divalent group represented by general formula (A1-2) below, and general formula (A1-3) below.
  • 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 the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R a12 and R a13 in the general formula (A1-3) 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.
  • 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 the above 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 methyl group, ethyl group, n-propyl group, isopropyl group, 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 resin (A1) examples 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) is a structural unit derived from the maleimide resin (AX) and a diamine compound [hereinafter sometimes referred to as "diamine compound (a)" or “component (a)". ] and a structural unit derived from.
  • 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 one kind alone or two or more kinds.
  • 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 structural units derived from the maleimide resin (AX) in the aminomaleimide resin (A2) is within the above range, dielectric properties and film handling properties tend to be better.
  • the structural unit derived from the diamine compound (a) for example, one or both of the two amino groups possessed by the diamine compound (a) are N-substituted maleimide groups possessed by the maleimide resin (AX). Structural units obtained by Michael addition reaction can be mentioned.
  • the structural unit derived from the diamine compound (a) 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 (a) is preferably a primary amino group.
  • Examples of the structural unit derived from the diamine compound (a) having two primary amino groups include a group represented by the following general formula (a-1) and a group represented by the following general formula (a-2). etc.
  • X a21 is a divalent organic group, and * represents a binding site.
  • X a21 in the general formulas (a-1) and (a-2) above is a divalent organic group, and is a divalent organic group obtained by removing two primary amino groups from the diamine compound (a). corresponds to the base.
  • X a21 in general formulas (a-1) and (a-2) above is preferably a divalent group represented by general formula (a-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.
  • 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, na25 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.
  • the number of carbon atoms represented by X a22 in the general formula (a-3), X a23 in the general formula (a-3-1), and X a24 and X a25 in the general formula (a-3-2) is 1
  • 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 further preferably an isopropylidene group.
  • n a21 and n a22 in the general formula (a-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 of 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 (a-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 (a-3-2) is an integer of 0 to 4, and from the viewpoint of availability, preferably an integer of 0 to 2, more preferably 0 or 1, more preferably 0 is.
  • n a25 is an integer of 2 or more, the plurality of R a25 may be the same or different.
  • X a21 in the general formula (a-1) and the general formula (a-2) may be a divalent group containing a structural unit represented by the following general formula (a-4). Alternatively, it may be a divalent group represented by the following general formula (a-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 (a-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 are each independently 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 (a-4) and (a-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 methylene, ethylene and propylene.
  • 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 structural units derived from the diamine compound (a) 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.
  • the content of the structural unit derived from the diamine compound (a) 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 compound (a) 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'-d
  • the diamine compound (a) is 4,4′-diaminodiphenylmethane, 3,3′-dimethyl, and is excellent in solubility in organic solvents, reactivity, heat resistance, dielectric properties and low water absorption.
  • 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.
  • Equivalent ratio (Ta2/Ta1) is not particularly limited, but from the viewpoint of dielectric properties, heat resistance, flame retardancy and glass transition temperature, preferably 0.05 to 10, more preferably 1 to 8, even more preferably is 3-7.
  • the group derived from the —NH 2 group of the diamine compound (a) includes —NH 2 itself.
  • 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 the diamine compound (a) in an organic solvent. By reacting the maleimide resin (AX) with the diamine compound (a), an aminomaleimide resin (A2) is obtained through the Michael addition reaction between the maleimide resin (AX) and the diamine compound (a).
  • reaction catalyst When reacting the maleimide resin (AX) and the diamine compound (a), a reaction catalyst may be used as necessary.
  • the reaction catalyst include acidic catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine and tributylamine; imidazoles such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine. . These may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the amount of the reaction catalyst is not particularly limited, but from the viewpoint of reaction rate and reaction uniformity, it is preferably 0.01 to 5 parts per 100 parts by mass of the total amount of the maleimide resin (AX) and the diamine compound (a). parts by mass, more preferably 0.05 to 3 parts by mass, and still more preferably 0.1 to 2 parts by mass.
  • 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.
  • thermosetting resin ((A) content of thermosetting resin)
  • the content of (A) the thermosetting resin is not particularly limited, but is preferably 20 to 95% by mass, more preferably 50 to 90% by mass, still more preferably 70 to 85% by mass.
  • the content of the thermosetting 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 thermosetting 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.
  • 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.
  • Optional components corresponding to the resin component include (E) a styrene-based elastomer, (F) a curing accelerator, and the like, which will be described later.
  • (C) the alkoxysilane compound having a primary amino group and (D) the inorganic filler are 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 30 to 95% by mass, more preferably 50 to 90% by mass, still more preferably 70 to 80% by mass relative to the total amount (100% by mass).
  • the content of the maleimide-based resin in the thermosetting resin is not particularly limited, but is preferably 80 to 100% by mass, more than It is preferably 90 to 100% by mass, more preferably 95 to 100% by mass.
  • the content of the maleimide resin is at least the above lower limit, heat resistance, moldability, workability and conductor adhesion tend to be better.
  • the content of the maleimide resin is equal to or less than the above upper limit, the dielectric properties tend to be more favorable.
  • the polyphenylene ether-based resin is not particularly limited as long as it is a resin having a polyphenylene ether chain.
  • 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 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • n b1 represents 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.
  • nb1 represents an integer of 0 to 4, preferably 1 or 2, more preferably 2.
  • Rb1 is preferably substituted at the ortho position (based on the substitution position of the oxygen atom) on the benzene ring. 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').
  • 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 heat resistance. ] is preferable.
  • 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.
  • a group represented by the following general formula (B-2) is preferable from the viewpoint of dielectric properties.
  • R b2 represents 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.
  • Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, pentadecyl, hexadecyl, and heptadecyl groups. , methyl groups are preferred.
  • the group represented by the general formula (B-2) is preferably a (meth)acryloyl group, more preferably a methacryloyl group.
  • 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, the heat resistance tends to be better. Further, when the number of ethylenically unsaturated bond-containing groups is equal to or less than the above upper limit, moldability tends to be more favorable.
  • 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 each independently represent an integer of 0 to 4.
  • n b4 and n b5 each independently represent 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 each independently represent the ethylenically unsaturated bond-containing group.
  • nb2 and nb3 represent an integer of 0-4, preferably an integer of 0-3, 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 represent an integer of 0-20, preferably an integer of 1-20, more preferably an integer of 2-15, and still more preferably an integer 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.
  • the alkylidene group having 2 to 5 carbon atoms represented by X b1 includes, for example, an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, an 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 above 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 each independently represent a hydrogen atom or a methyl group.
  • X b2 is methylene. 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-based 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 4 to 20% by mass, still more preferably 7 to 15% 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 more favorable.
  • the alkoxysilane compound having a primary amino group is not particularly limited as long as it is a compound having an alkoxyryl group having a primary amino group.
  • the alkoxysilane compound having a primary amino group may be used alone or in combination of two or more.
  • the alkoxysilane compound having a primary amino group includes, for example, those having a monoalkoxysilyl group, a dialkoxysilyl group, a trialkoxysilyl group, etc. Among them, those having a trialkoxysilyl group things are preferred.
  • the number of carbon atoms in the alkyl group constituting the alkoxy group contained in the alkoxysilyl group is preferably 1-10, more preferably 1-5, and still more preferably 1 or 2.
  • An alkyl group constituting an alkoxy group contained in an alkoxysilyl group may be linear or branched.
  • the number of primary amino groups possessed by the alkoxysilane compound having a primary amino group is not particularly limited, but is preferably 1 to 3, more preferably 1 or 2, still more preferably 1. is.
  • (C) As the alkoxysilane compound having a primary amino group, a compound represented by the following general formula (C-1) is preferable.
  • each R c1 is independently an alkyl group having 1 to 10 carbon atoms
  • R c2 is a hydrocarbon group having 1 to 10 carbon atoms and having a primary amino group.
  • Examples of the alkyl group having 1 to 10 carbon atoms represented by R c1 in the general formula (C-1) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group. , decyl group, dodecyl group and the like.
  • the alkyl group having 1 to 10 carbon atoms may be linear or branched. Among these, a methyl group, an ethyl group, and a propyl group are preferable, and a methyl group and an ethyl group are more preferable.
  • a hydrocarbon group having 1 to 10 carbon atoms and having a primary amino group represented by R c2 in the general formula (C-1) [hereinafter sometimes referred to as a “hydrocarbon group having a primary amino group” . ] preferably has 1 to 8 carbon atoms, more preferably 2 to 7 carbon atoms, and still more preferably 3 to 6 carbon atoms.
  • a hydrocarbon group having a primary amino group may or may not have a substituent other than the primary amino group. When the hydrocarbon group having a primary amino group has a substituent other than the primary amino group, the primary amino group may be bonded to the substituent.
  • the carbon number of the substituent is also included in the number of carbon atoms.
  • hydrocarbon groups having a primary amino group examples include alkyl groups having 1 to 10 carbon atoms having a primary amino group, alkenyl groups having 1 to 10 carbon atoms having a primary amino group, primary Examples thereof include alkynyl groups having 1 to 10 carbon atoms having an amino group. Among these, an alkyl group having 1 to 10 carbon atoms and having a primary amino group is preferred.
  • the term "having a primary amino group" as used herein refers not only to the case where the primary amino group is directly bonded to a carbon atom constituting the alkyl group, alkenyl group, or alkynyl group, but also to the alkyl group.
  • a substituent containing a primary amino group may be referred to as a "primary amino group-containing group”.
  • alkyl group constituting the alkyl group having 1 to 10 carbon atoms and having a primary amino group examples include, for example, a methyl group, an ethyl group substituted with a primary amino group or a group containing a primary amino group, A propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, and the like.
  • a methyl group, an ethyl group, and a propyl group substituted by a primary amino group or a primary amino group-containing group are preferred, and substituted by a primary amino group or a primary amino group-containing group.
  • a propyl group is more preferred.
  • a propyl group substituted with a primary amino group includes, for example, a 3-aminopropyl group.
  • Examples of preferred primary amino group-containing groups include substituted amino groups having a primary amino group.
  • a substituted amino group having a primary amino group includes, for example, an amino group substituted with a hydrocarbon group having a primary amino group.
  • the hydrocarbon group having a primary amino group is preferably an alkyl group having 1 to 5 carbon atoms and having a primary amino group, more preferably an alkyl group having 2 to 4 carbon atoms and having a primary amino group. .
  • a 2-aminoethylamino group is preferred as the substituted amino group substituted with a hydrocarbon group having a primary amino group.
  • As the alkyl group having 1 to 10 carbon atoms and having a substituted amino group substituted by a hydrocarbon group having a primary amino group a 3-(2-aminoethylamino)propyl group is preferred.
  • alkoxysilane compound having a primary amino group examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3- (2-aminoethylamino)propyltriethoxysilane, N-(trimethoxysilylpropyl)melamine, N-(triethoxysilylpropyl)melamine and the like.
  • 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, and 3-(2-aminoethylamino)propyltriethoxysilane are preferred. More preferred are 3-aminopropyltriethoxysilane and 3-(2-aminoethylamino)propyltriethoxysilane.
  • the content of (C) the alkoxysilane compound having a primary amino group in the resin composition of the present embodiment is not particularly limited, but the total solid content (100 mass%) of the resin composition of the present embodiment is , preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, still more preferably 0.3 to 2% by mass, and particularly preferably 0.5 to 1% by mass.
  • the content of (C) the alkoxysilane compound having a primary amino group in the resin composition of the present embodiment is not particularly limited, but is preferably 0 with respect to 100 parts by mass of the (D) inorganic filler.
  • the component (C) may exist in a form reacted with other components.
  • the content of the component (C) in the resin composition of the present embodiment includes the amount of the reacted component (C). That is, the total amount of component (C) blended in the resin composition of the present embodiment is regarded as the content of component (C) in the resin composition of the present embodiment.
  • the resin composition of the present embodiment tends to be more excellent in low thermal expansion, heat resistance and flame retardancy.
  • An inorganic filler may be used individually by 1 type, or may be used in combination of 2 or more type.
  • inorganic fillers examples include 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 water content, dry-process silica produced by a dry method and containing almost no bound water, and the like.
  • dry process silica include crushed silica, fumed silica, fused silica, etc., depending on the production method.
  • the average particle size of the (D) inorganic filler is not particularly limited, but from the viewpoint of dispersibility and fine wiring properties of the (D) 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 (D) is defined as the particle size at the point corresponding to 50% volume when the cumulative frequency distribution curve by particle size is obtained with the total volume of the particles being 100%. 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 (D) includes, for example, a spherical shape, a crushed shape, etc., and a spherical shape is preferred.
  • the content of (D) the inorganic filler is not particularly limited, but is preferably 20 to 90% by mass, relative to the total solid content (100% by mass) of the resin composition, and more It is preferably 40 to 80% by mass, more preferably 50 to 75% by mass, and particularly preferably 55 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 better.
  • the content of the inorganic filler (D) is equal to or less than the above upper limit, moldability and conductor adhesion tend to be improved.
  • the resin composition of the present embodiment preferably further contains (E) a styrene elastomer. Since the resin composition of the present embodiment contains (E) a styrene-based elastomer, it tends to have better dielectric properties.
  • the term "elastomer” as used herein means a polymer having a glass transition temperature of 25°C or lower 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.
  • (E) As the styrene-based elastomer, one having a structural unit derived from a styrene-based compound represented by the following general formula (E-1) is preferable.
  • R e1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R e2 is an alkyl group having 1 to 5 carbon atoms
  • n e1 is an integer of 0 to 5.
  • alkyl groups having 1 to 5 carbon atoms represented by R e1 and R e2 in the general formula (E-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.
  • Alkyl groups 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 e1 in the general formula (E-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 styrene-based compound-derived structural units possessed by the styrene-based elastomer include, for example, butadiene-derived structural units, isoprene-derived structural units, maleic acid-derived structural units, and maleic anhydride-derived structural units. etc.
  • 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 (E) styrene elastomers include hydrogenated styrene-butadiene-styrene block copolymers, hydrogenated styrene-isoprene-styrene block copolymers, styrene-maleic anhydride copolymers, and the like. 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 is not particularly limited, but is preferably 5 to 60% by mass, more preferably 7 to 40% by mass, and still more preferably 10 to 20% by mass.
  • the melt flow rate (MFR) of SEBS is not particularly limited, but is preferably 0.1 to 20 g/10 min, more preferably 1 to 10 g/10 min under the measurement conditions of 230°C and a load of 2.16 kgf (21.2 N). , more preferably 3 to 7 g/10 min.
  • SEBS Commercially available products of SEBS include, for example, Tuftec (registered trademark) H series and M series manufactured by Asahi Kasei Corporation, Septon (registered trademark) series manufactured by Kuraray Co., Ltd., and Kraton (registered trademark) G manufactured by Kraton Polymer Japan Co., Ltd. polymer series and the like.
  • the weight average molecular weight (Mw) of the styrene elastomer is not particularly limited, but is preferably 10,000 to 500,000, more preferably 20,000 to 350,000, still more preferably 40,000 to 200, 000, particularly preferably 60,000 to 90,000.
  • the content of (E) the styrene-based elastomer is not particularly limited, but the total amount of resin components in the resin composition of the present embodiment (100 % by mass), preferably 1 to 30 mass %, more preferably 4 to 20 mass %, and still more preferably 7 to 15 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 (E) the styrene-based elastomer is equal to or less than the above upper limit, heat resistance and flame retardancy tend to be better.
  • the resin composition of the present embodiment preferably further contains (F) a curing accelerator.
  • the curing accelerator may be used alone or in combination of two or more.
  • Curing accelerators include, for example, amine-based curing accelerators, imidazole-based curing accelerators, phosphorus-based curing accelerators, organic metal salts, acidic catalysts, organic peroxides, and the like.
  • 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.
  • Examples of acidic catalysts include p-toluenesulfonic acid and the like.
  • Examples of organic peroxides include dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3,2,5-dimethyl-2,5-bis(t- butylperoxy)hexane, t-butylperoxyisopropylmonocarbonate, ⁇ , ⁇ '-di(t-butylperoxy)diisopropylbenzene and the like.
  • amine-based curing accelerators from the viewpoint of dielectric properties, heat resistance, adhesion to conductors, and elastic modulus, amine-based curing accelerators, imidazole-based curing accelerators, and phosphorus-based curing accelerators are preferable, and dicyandiamide, imidazole-based curing accelerators, A quaternary phosphonium compound is more preferred, and a combination thereof is even more preferred.
  • the resin composition of the present embodiment contains (F) a curing accelerator
  • its content is preferably 0.01 to 10 parts by mass, more preferably 100 parts by mass of the thermosetting resin (A) is 0.1 to 5 parts by mass, more preferably 1 to 3 parts by mass.
  • the content of the curing accelerator is at least the above lower limit, a sufficient curing acceleration effect tends to be obtained.
  • the content of (F) the curing accelerator 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 further contains 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, an organic It may contain one or more optional components selected from the group consisting of 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 gel time at 180° C. of the resin composition of the present embodiment is not particularly limited, but is preferably 150 to 350 seconds, more preferably 200 to 300 seconds, still more preferably 220 to 270 seconds.
  • the gel time is at least the above lower limit, excessive flow tends to be easily suppressed when the resin composition of the present embodiment is laminated and pressed in the form of a resin film or prepreg.
  • the gel time is equal to or less than the above upper limit, storage stability and embeddability tend to be more favorable.
  • the gel time can be measured by the method 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 can be produced, for example, by impregnating or coating a sheet-like fiber base material with the resin composition of the present embodiment, followed by B-staging. 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.
  • 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 thickness of the sheet-like fiber base material is not particularly limited, it is preferably 0.01 to 0.5 mm, more preferably 0.02 to 0.3 mm, and still more preferably 0.03 to 0.1 mm.
  • the sheet-like fiber base material may be surface-treated with a coupling agent or the like from the viewpoint of impregnating property of the resin composition, heat resistance, moisture absorption resistance and workability when laminated. It may be one subjected to fiber opening treatment.
  • 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 drying it as necessary.
  • a method for impregnating or applying the resin composition of the present embodiment to the sheet-like fiber base material for example, a hot melt method, a solvent method, or the like can be employed.
  • the hot-melt method is a method of impregnating or coating a sheet-like fiber base material with a resin composition containing no organic solvent.
  • the resin composition of the present embodiment that does not contain an organic solvent is coated once on coated paper with good releasability, and then the coated resin composition is applied to a sheet-like fiber base material.
  • a method of laminating may be mentioned.
  • Another aspect of the hot-melt method is a method in which the resin composition of the present embodiment containing no organic solvent is directly applied to a sheet-like fiber base material using a die coater or the like.
  • the solvent method is a method of impregnating or coating a sheet-like fiber base material with a resin composition containing an organic solvent.
  • a method of immersing a sheet-like fiber base material in the resin composition of the present embodiment containing an organic solvent and then drying the base material may be used.
  • the organic solvent in the resin composition can be removed and the resin composition can be B-staged.
  • the drying temperature is not particularly limited, it is preferably 50 to 200° C., more preferably 100 to 190° C., still more preferably 150 to 150° C., from the viewpoint of productivity and moderate B-stage of the resin composition of the present embodiment. 180°C.
  • the drying time is not particularly limited, but from the viewpoint of productivity and moderate B-stage of the resin composition of the present embodiment, it is preferably 1 to 30 minutes, more preferably 2 to 15 minutes, and still more preferably 3 to 30 minutes. 10 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 thickness of the prepreg of the present embodiment is not particularly limited, it is preferably 0.01 to 0.5 mm, more preferably 0.02 to 0.3 mm, and still more preferably 0.03 to 0.1 mm.
  • 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 preferably a B-staged resin composition formed by converting the resin composition of the present embodiment into a B-stage into a film.
  • 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.
  • plastic films include films of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyethylene terephthalate (hereinafter sometimes referred to as "PET"). ], polyester films such as polyethylene naphthalate; polycarbonate films, polyimide films and the like. Among these, polyethylene terephthalate film is preferable from the viewpoint of economy and handling.
  • Examples of metal foil include copper foil and aluminum foil. When a copper foil is used as the support, the copper foil can be used as a conductor layer to form a circuit. In this case, a rolled copper foil, an electrolytic copper foil, or the like can be used as the copper foil.
  • a copper foil with a carrier may be used from the viewpoint of improving workability.
  • the support may be subjected to surface treatment such as matte treatment or corona treatment. Further, the support may be subjected to release treatment with a silicone resin release agent, an alkyd resin release agent, a fluororesin release agent, or the like.
  • the thickness of the support is not particularly limited, but is preferably 10 to 150 ⁇ m, more preferably 20 to 100 ⁇ m, still more preferably 25 to 50 ⁇ m, from the viewpoints of ease of handling and economy.
  • a coating device for coating the resin varnish for example, a coating device known to those skilled in the art such as a comma coater, bar coater, kiss coater, roll coater, gravure coater and die coater can be used. These coating apparatuses may be appropriately selected according to the film thickness to be formed. Drying conditions after applying the resin varnish may be appropriately determined according to the content of the organic solvent, the boiling point, etc., and are not particularly limited. For example, in the case of a resin varnish containing 40 to 60% by mass of an aromatic hydrocarbon-based solvent, the drying temperature is not particularly limited, but the productivity and the resin composition of the present embodiment are appropriately B-staged.
  • the drying time is not particularly limited, but from the viewpoint of productivity and moderate B-stage of the resin composition of the present embodiment, it is preferably 1 to 30 minutes, more preferably 2 to 30 minutes. 15 minutes, more preferably 3 to 10 minutes.
  • the thickness of the resin film of the present embodiment can be appropriately determined according to the application of the resin film, but from the viewpoint of moldability and high-density wiring, it is preferably 5 to 150 ⁇ m, more preferably 10 to 100 ⁇ m. , more preferably 15 to 60 ⁇ m.
  • the resin film of this embodiment may have a protective film on the surface opposite to the surface on which the support is provided, from the viewpoint of preventing adhesion of foreign matter and damage.
  • the protective film is peeled off before laminating the resin film of the present embodiment on a circuit board or the like.
  • the resin film of the present embodiment is preferably used for forming an insulating layer when manufacturing a printed wiring board.
  • the resin film of the present embodiment is a layer that melts and flows when laminated on a circuit board, and plays a role of embedding the circuit board.
  • the resin film of the present embodiment flows into these holes and fills the inside of the holes.
  • 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.
  • alloys include copper-based alloys, aluminum-based alloys, and iron-based alloys.
  • Copper-based alloys include, for example, copper-nickel alloys.
  • iron-based alloys include iron-nickel alloys. Among these, copper, nickel, aluminum, and iron-nickel alloys are preferred, copper and aluminum are more preferred, and copper is even more preferred, from the viewpoint of conductivity and availability.
  • the thickness of the metal foil is not particularly limited, it is preferably 1 to 200 ⁇ m, more preferably 2 to 100 ⁇ m, still more preferably 3 to 50 ⁇ m.
  • 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.
  • the laminate of the present embodiment is obtained by curing the prepreg in a semi-cured state by this heating and pressure molding.
  • the heat and pressure molding only one prepreg may be used, or two or more prepregs may be laminated.
  • substrates on which inner layer circuits have been processed may also be molded under heat and pressure.
  • 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 heating temperature for hot-press molding is not particularly limited, but is preferably 100 to 300.degree. C., more preferably 150 to 280.degree. C., still more preferably 200 to 250.degree.
  • the heating and pressing time for the heating and pressing molding is not particularly limited, but is preferably 10 to 300 minutes, more preferably 30 to 200 minutes, still more preferably 80 to 150 minutes.
  • the pressure for hot-press molding is not particularly limited, but is preferably 1.5 to 5 MPa, more preferably 1.7 to 3 MPa, still more preferably 1.8 to 2.5 MPa. However, these conditions can be appropriately adjusted according to the type of raw material used, etc., and are not particularly limited.
  • 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 includes at least the cured prepreg of the present embodiment, the cured resin film of the present embodiment, or the laminate of the present embodiment and a conductor circuit layer.
  • the printed wiring board of the present embodiment is preferably a multilayer printed wiring board. A method for manufacturing the printed wiring board of the present embodiment using the resin film of the present embodiment will be described below.
  • the resin film of this embodiment is laminated on one side or both sides of a circuit board. Specifically, for example, after the resin film of the present embodiment is placed on a circuit board, the resin film of the present embodiment is laminated on the circuit board while being pressurized and heated by a vacuum laminator, thereby forming the resin film of the present embodiment on the circuit board. Can be stacked.
  • Circuit substrates used for printed wiring boards include, for example, glass epoxy, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc.
  • a patterned conductor layer is formed on one or both sides of the substrate. and the like. From the viewpoint of adhesiveness, the surface of the conductor layer of the circuit board may be roughened in advance by blackening treatment or the like.
  • the heating temperature for heat curing is not particularly limited, but is preferably 100 to 300.degree. C., more preferably 120 to 280.degree. C., still more preferably 150 to 250.degree.
  • the heating time for heat curing is not particularly limited, but is preferably 2 to 300 minutes, more preferably 5 to 200 minutes, still more preferably 10 to 150 minutes.
  • Drilling is a step of drilling holes in the circuit board and the formed insulating layer by, for example, a drill, laser, plasma, or a combination thereof to form via holes, through holes, and the like.
  • lasers used for drilling include carbon dioxide lasers, YAG lasers, UV lasers, excimer lasers, and the like.
  • the surface of the insulating layer may be roughened with an oxidizing agent.
  • an oxidizing agent such as a known oxidizing agent.
  • Roughening treatment and smear removal can be performed at the same time. By the roughening treatment, uneven anchors can be formed on the surface of the insulating layer to improve the adhesive strength with the conductor layer.
  • the conductor layer can be formed by plating, for example.
  • plating methods include electroless plating and electrolytic plating.
  • Metals for plating include, for example, copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and alloys containing at least one of these metal elements. Among these, copper and nickel are preferable, and copper is more preferable.
  • Methods of patterning a conductor layer to form a circuit include, for example, a subtractive method, a full additive method, a semi-additive method (SAP: semi-additive process), a modified semi-additive method (m-SAP: modified semi-additive process), etc.
  • SAP semi-additive process
  • m-SAP modified semi-additive process
  • the semiconductor package of this embodiment is a semiconductor package having the printed wiring board of this embodiment. That is, the semiconductor package of the present embodiment is a semiconductor package formed using the printed wiring board of the present embodiment, preferably the multilayer printed wiring board of the present 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.
  • a calibration curve using standard polystyrene was converted by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • GPC measurement conditions are shown below.
  • Examples 1-3, Comparative Examples 1-4 Manufacture of resin composition
  • Each component shown in Table 1 is blended according to the formulation shown in Table 1, stirred and mixed with toluene and methyl isobutyl ketone at room temperature (25 ° C.) to obtain a resin composition having a solid content concentration of 55 to 65% by mass. manufactured.
  • the unit of the compounding amount of each component is parts by mass, and in the case of solutions, it means parts by mass in terms of solid content.
  • the amount of component (C) and the component for comparison in Table 1 was such that the amount of component (C) and the component for comparison in each example would be the same number of moles.
  • a specimen was prepared by etching the copper foil of the double-sided copper-clad laminate obtained in each example into a straight line shape with a width of 5 mm.
  • the formed straight line-shaped copper foil is attached to a small desktop tester (manufactured by Shimadzu Corporation, trade name "EZ-TEST"), and is subjected to JIS C 6481: 90 at room temperature (25 ° C.) in accordance with 1996.
  • the copper foil peel strength was measured by peeling in the direction of °.
  • the pulling speed for peeling off the copper foil was 50 mm/min.
  • the resin composition obtained in each example was applied to a 38 ⁇ m thick PET film (manufactured by Teijin Limited, product name: G2-38) and then dried by heating at 170° C. for 5 minutes to obtain a B-stage resin film. was made. After the resin film was peeled off from the PET film, it was pulverized to obtain a B-stage resin powder. Using 0.1 g of the obtained resin powder as a measurement sample, the time until the resin hardens (gel time) was measured on a hot platen at 180°C. For the measurement, a gelation tester "GT-D-JIS" manufactured by Nisshin Kagaku Co., Ltd. was used.
  • 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 90 mm and a width of 70 mm. A cut piece was used as a test piece. Using this test piece, the dielectric constant and dielectric loss tangent were measured by the SPDR (split post dielectric resonators) method under the conditions of a frequency of 10 GHz and a measurement temperature of 25°C.
  • SPDR split post dielectric resonators
  • Keysight Technologies' network analyzer “E5071C” is used as the measuring instrument
  • QWED's SPDR-10GHz
  • Keysight Technologies' material measurement software "85071E” is used as the measurement program. each used.
  • (B) component polyphenylene ether resin
  • Polyphenylene ether resin polyphenylene ether having methacryloyl groups at both ends (compounds included in the general formula (B-4), weight average molecular weight (Mw) 1,700)
  • [comparative component] 3-anilinopropyltriethoxysilane/benzotriazole group-containing silane coupling agent: a compound represented by the following general formula (C'-1), manufactured by Shin-Etsu Chemical Co., Ltd., trade name "X-12-1214A" (Wherein, R represents a divalent linking group.) ⁇ melamine
  • SEBS maleic anhydride-modified hydrogenated styrene elastomer
  • the resin compositions of Examples 1 to 3 of the present embodiment are the resin compositions of Comparative Examples 1 to 4 that do not contain (C) an alkoxysilane compound having a primary amino group. It can be seen that the copper foil peeling strength is superior to that of Further, from the gel time results, the resin compositions of Examples 1 to 3 of the present embodiment are the resin composition of Comparative Example 1 that does not contain (C) an alkoxysilane compound having a primary amino group and a comparative component. It can be seen that the curability is superior to that of the material.
  • the resin composition of the present embodiment is excellent in copper foil peeling strength and curability, prepregs, laminates, printed wiring boards, semiconductor packages, etc. obtained using the resin composition are highly sensitive to high-frequency signals. It is suitable for electronic component applications that handle

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Abstract

La présente invention concerne : une composition de résine comprenant (A) une résine thermodurcissable, (B) une résine à base de polyphénylène éther, (C) un composé alcoxysilane comportant un groupe amino primaire, et (D) une charge minérale ; et un préimprégné, un stratifié, un film de résine, une carte de circuit imprimé et un boîtier de semi-conducteur, chacun obtenu à l'aide de la composition de résine.
PCT/JP2022/033057 2021-09-03 2022-09-02 Composition de résine, préimprégné, stratifié, film de résine, carte de circuit imprimé et boîtier de semi-conducteur WO2023033131A1 (fr)

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KR1020247006802A KR20240051946A (ko) 2021-09-03 2022-09-02 수지 조성물, 프리프레그, 적층판, 수지 필름, 프린트 배선판 및 반도체 패키지

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014101398A (ja) * 2012-11-16 2014-06-05 Hitachi Chemical Co Ltd 熱硬化性樹脂組成物、プリプレグ、金属張積層板及びプリント配線板
JP2017057346A (ja) * 2015-09-18 2017-03-23 日立化成株式会社 樹脂組成物、プリプレグ、積層板及び多層プリント配線板
WO2021149733A1 (fr) * 2020-01-24 2021-07-29 三菱瓦斯化学株式会社 Composition de résine, feuille de résine, préimprégné et carte de câblage imprimée

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JP5995051B2 (ja) 2012-03-08 2016-09-21 Dic株式会社 硬化性樹脂組成物、その硬化物、及びプリント配線基板

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014101398A (ja) * 2012-11-16 2014-06-05 Hitachi Chemical Co Ltd 熱硬化性樹脂組成物、プリプレグ、金属張積層板及びプリント配線板
JP2017057346A (ja) * 2015-09-18 2017-03-23 日立化成株式会社 樹脂組成物、プリプレグ、積層板及び多層プリント配線板
WO2021149733A1 (fr) * 2020-01-24 2021-07-29 三菱瓦斯化学株式会社 Composition de résine, feuille de résine, préimprégné et carte de câblage imprimée

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