[go: up one dir, main page]

WO2020096036A1 - Composition de résine, pré-imprégné, stratifié, film de résine, carte de circuit imprimé multicouche, et carte de circuit imprimé multicouche pour radar à ondes millimétriques - Google Patents

Composition de résine, pré-imprégné, stratifié, film de résine, carte de circuit imprimé multicouche, et carte de circuit imprimé multicouche pour radar à ondes millimétriques Download PDF

Info

Publication number
WO2020096036A1
WO2020096036A1 PCT/JP2019/043832 JP2019043832W WO2020096036A1 WO 2020096036 A1 WO2020096036 A1 WO 2020096036A1 JP 2019043832 W JP2019043832 W JP 2019043832W WO 2020096036 A1 WO2020096036 A1 WO 2020096036A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
component
resin composition
mass
polyphenylene ether
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/043832
Other languages
English (en)
Japanese (ja)
Inventor
彩 笠原
智彦 小竹
藤本　大輔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Priority to CN201980073342.7A priority Critical patent/CN112969749B/zh
Priority to JP2020555619A priority patent/JP7501368B2/ja
Priority to KR1020217004912A priority patent/KR20210090605A/ko
Publication of WO2020096036A1 publication Critical patent/WO2020096036A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • 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
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; 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
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • 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
    • 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
    • H05K1/036—Multilayers with layers of different types
    • 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
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • 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
    • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons

Definitions

  • the present invention relates to a resin composition, a prepreg, a laminate, a resin film, a multilayer printed wiring board and a multilayer printed wiring board for millimeter wave radar.
  • a polyphenylene ether (PPE) resin has been used as a heat-resistant thermoplastic polymer having excellent high-frequency characteristics for a printed wiring board that requires low transmission loss.
  • PPE polyphenylene ether
  • a method of using polyphenylene ether and a thermosetting resin in combination has been proposed.
  • a resin composition containing a polyphenylene ether and an epoxy resin see, for example, Patent Document 1
  • a resin composition containing a polyphenylene ether and a cyanate resin having a low dielectric constant among thermosetting resins for example, patents Reference 2 and the like are disclosed.
  • Patent Documents 1 and 2 are inadequate in terms of high-frequency characteristics in the GHz range, adhesiveness with conductors, low coefficient of thermal expansion, flame retardance, and polyphenylene ether and thermosetting properties.
  • the low compatibility with the resin may reduce the heat resistance.
  • a resin having particularly good compatibility and having dielectric properties in a high frequency band, high adhesion with a conductor, excellent heat resistance, high glass transition temperature, low thermal expansion coefficient and high flame retardancy is composed of a polyphenylene ether derivative (A) having an N-substituted maleimide structure-containing group and a structural unit represented by the following general formula in one molecule, an epoxy resin, a cyanate resin and a maleimide compound.
  • a resin composition containing one or more thermosetting resins (B) selected from the group and a styrene-based thermoplastic elastomer (C) has been proposed (see, for example, Patent Document 3).
  • each R 1 is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • X is an integer of 0 to 4.
  • JP 58-069046 A Japanese Patent Publication No. 61-018937 International Publication No. 2016/175326
  • the resin composition described in Patent Document 3 certainly has excellent dielectric properties in the high frequency band, but there is room for further improvement in heat resistance. Furthermore, in recent years, the 10 GHz band, which can be used for a fifth generation mobile communication system (5G) antenna that uses radio waves in the frequency band of over 6 GHz and a millimeter-wave radar that uses radio waves in the frequency band of 30 to 300 GHz, is also available. It has been earnestly desired to develop a resin composition having further improved dielectric properties.
  • 5G fifth generation mobile communication system
  • the present invention provides a resin composition having excellent heat resistance and capable of exhibiting excellent dielectric properties in a high frequency band of 10 GHz or higher, a prepreg, a laminate, and a resin film using the resin composition.
  • An object of the present invention is to provide a multilayer printed wiring board and a multilayer printed wiring board for millimeter wave radar.
  • the present inventors have conducted extensive studies to solve the above problems, and a polyphenylene ether derivative containing a specific molecular structure, and one or more selected from the group consisting of a specific maleimide compound and its derivative, It was found that a resin composition containing a specific cross-linking agent is excellent in heat resistance and exhibits excellent dielectric properties in a high frequency band of 10 GHz band or higher, and has completed the present invention. That is, the present invention relates to the following [1] to [15].
  • a resin composition comprising: [2] The resin composition according to the above [1], wherein the component (C) has the two or more ethylenically unsaturated bonds as a vinyl group.
  • the content of the component (C) is 5 to 60 parts by mass with respect to 100 parts by mass as the total of the resin components in the resin composition, according to any one of the above [1] to [5].
  • Resin composition. [7] The resin composition according to any one of the above [1] to [6], wherein the component (A) includes a structure represented by the following general formula (a1-1). (In the formula, R a1 is an ethylenically unsaturated bond-containing group having 2 to 10 carbon atoms. N1 is 1 or 2, n2 is 0 or 1. * represents a bonding position to another structure.
  • a multilayer printed wiring board containing at least one member selected from the group consisting of the prepreg according to [11] above, the laminate according to [12] above and the resin film according to [13] above. .. [15] A millimeter-wave radar including one or more selected from the group consisting of the prepreg described in [11] above, the laminated plate described in [12] above, and the resin film described in [13] above. Multilayer printed wiring board.
  • a resin composition having excellent heat resistance and capable of exhibiting excellent dielectric properties (low dielectric constant and low dielectric loss tangent) in a high frequency band of 10 GHz or higher a prepreg using the resin composition, and a resin It is possible to provide a film, a laminated board, a multilayer printed wiring board and a multilayer printed wiring board for millimeter wave radar.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
  • the lower limit value and the upper limit value of the numerical range are arbitrarily combined with the lower limit value and the upper limit value of the other numerical range.
  • each component and material exemplified in the present specification may be used alone or in combination of two or more unless otherwise specified.
  • the content of each component in the composition is the total amount of the plurality of substances present in the composition, unless a plurality of substances corresponding to each component are present in the composition.
  • Means The present invention also includes an embodiment in which the items described in this specification are arbitrarily combined.
  • the resin composition of the present embodiment (A) Polyphenylene ether derivative having an ethylenically unsaturated bond-containing group [Hereinafter, it may be simply referred to as polyphenylene ether derivative (A) or component (A). ]When, (B) One or more selected from the group consisting of maleimide compounds having two or more N-substituted maleimide groups and derivatives thereof [hereinafter, may be simply referred to as maleimide compound (B) or component (B). ]When, (C) Crosslinking agent having two or more ethylenically unsaturated bonds [Hereinafter, it may be simply referred to as "crosslinking agent (C) or component (C)". ]When, It is a resin composition containing. Hereinafter, each component will be described in detail in order.
  • the polyphenylene ether derivative (A) has an ethylenically unsaturated bond-containing group.
  • ethylenically unsaturated bond-containing group means a substituent containing a carbon-carbon double bond capable of addition reaction, and does not include a double bond of an aromatic ring. To do.
  • the position of the ethylenically unsaturated bond-containing group is not particularly limited and may be, for example, at one end of the component (A) or at both ends.
  • the component (A) may be a mixture of a polyphenylene ether derivative having an ethylenically unsaturated bond-containing group at one end and a polyphenylene ether derivative having an ethylenically unsaturated bond-containing group at both ends, but at least, It is preferable to contain a polyphenylene ether derivative having an ethylenically unsaturated bond-containing group at one end, and it is more preferable to use the polyphenylene ether derivative itself having an ethylenically unsaturated bond-containing group at one end.
  • the content of the polyphenylene ether derivative having an ethylenically unsaturated bond-containing group at one end in the component (A) May be 30% by mass or more, 45% by mass or more, 55% by mass or more, 70% by mass or more, or 90% by mass or more. Well, it may be substantially 100% by mass.
  • Examples of the ethylenically unsaturated bond-containing group contained in the component (A) include unsaturated aliphatic hydrocarbon groups such as vinyl group, isopropenyl group, allyl group, 1-methylallyl group and 3-butenyl group; maleimide group, Examples thereof include a substituent containing a hetero atom such as a (meth) acryloyl group.
  • unsaturated aliphatic hydrocarbon group or a maleimide group is preferable, an allyl group or a maleimide group is more preferable, and an allyl group is further preferable, from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher.
  • a maleimide group, a (meth) acryloyl group, and the like partially have an unsaturated aliphatic hydrocarbon group, but when viewed as a whole, the unsaturated aliphatic carbon group is present.
  • a group that cannot be called a hydrogen group is not included in the above "unsaturated aliphatic hydrocarbon group”.
  • a polyphenylene ether derivative having an unsaturated aliphatic hydrocarbon group as an ethylenically unsaturated bond-containing group may be simply referred to as polyphenylene ether derivative (A1) or (A1) component).
  • a polyphenylene ether derivative having a maleimide group as an ethylenically unsaturated bond-containing group hereinafter, may be simply referred to as polyphenylene ether derivative (A2) or (A2) component).
  • the component (A1) is a polyphenylene ether derivative having an unsaturated aliphatic hydrocarbon group as an ethylenically unsaturated bond-containing group.
  • the number of unsaturated aliphatic hydrocarbon groups contained in one molecule of the component (A1) is preferably 2 or more, more preferably 4 or more from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher.
  • the upper limit value is not particularly limited, and may be 8 or less, or 6 or less.
  • the number of unsaturated aliphatic hydrocarbon groups which the component (A1) has at one end is preferably 2 or more, more preferably 4 or more from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher.
  • the upper limit value is not particularly limited, and may be 8 or less, or 6 or less. It is most preferable that both the number of unsaturated aliphatic hydrocarbon groups contained in the component (A1) and the number of unsaturated aliphatic hydrocarbon groups contained in one end of the component (A1) are four.
  • the component (A1) preferably includes a structure represented by the following general formula (a1-1) from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher.
  • each R a1 independently represents an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms.
  • N1 is 1 or 2
  • n2 is 0 or 1. * Indicates the bonding position to another structure.
  • Examples of the unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms represented by R a1 in the general formula (a1-1) include a vinyl group, an isopropenyl group, an allyl group, a 1-methylallyl group, and 3-butenyl. Groups and the like. Among these, an unsaturated aliphatic hydrocarbon group having 2 to 5 carbon atoms is preferable, and an allyl group is more preferable, from the viewpoint of dielectric characteristics in a high frequency band of 10 GHz or higher.
  • the component (A1) includes a structure represented by the following general formula (a1-2) from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher.
  • R a2 and R a3 are each independently an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. * Represents a bonding position to another structure.
  • Examples of the unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms represented by R a2 and R a3 in the general formula (a1-2) include the same ones as R a1 in the general formula (a1-1). , The same is preferable.
  • the component (A1) more preferably contains a structure represented by any one of the following general formulas (a1-3) to (a1-5) from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher, and It is more preferable to include a structure represented by general formula (a1-5).
  • R a4 is an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. * Represents a bonding position to another structure.
  • R a5 and R a6 are each independently an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms.
  • X a1 is a divalent fatty acid having 1 to 6 carbon atoms. It is a group hydrocarbon group. * Indicates a bonding position to another structure.
  • R a7 to R a10 are each independently an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms.
  • X a2 is a divalent organic group. Shows the binding position to other structures.
  • Examples of the unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms represented by R a4 to R a10 in the general formulas (a1-3) to (a1-5) include R a1 in the general formula (a1-1).
  • Examples of the divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms represented by X a1 in the general formula (a1-4) include, for example, alkylene having 1 to 6 carbon atoms such as methylene group, ethylene group and trimethylene group. Group; examples thereof include an alkylidene group having 2 to 6 carbon atoms such as isopropylidene group.
  • the divalent organic group represented by X a2 in the above general formula (a1-5) is an aliphatic hydrocarbon group which may partially contain a hetero atom, or a divalent organic group which partially contains a hetero atom.
  • the hetero atom include an oxygen atom, a nitrogen atom and a sulfur atom.
  • the divalent organic group represented by X a2 is preferably a group containing no heteroatom, an aliphatic hydrocarbon group containing no heteroatom, or an alicyclic carbon group containing no heteroatom.
  • a hydrogen group is more preferable, and a group consisting of a combination of an aliphatic hydrocarbon group containing no hetero atom and an alicyclic hydrocarbon group containing no hetero atom is further preferable.
  • more preferable embodiments are the following formulas from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher. It is a structure represented by (a1-3 ′), (a1-4 ′) or (a1-5 ′). Among these, the structure represented by the following formula (a1-4 ′) or (a1-5 ′) is more preferable from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher, and the following formula (a1-5 ′) The structure represented by is more preferable. (In the formula, X a2 is the same as X a2 in the general formula (a1-5) above. * Represents a bonding position to another structure.)
  • each R a11 independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • N3 is an integer of 0 to 4.
  • R a11 in the general formula (a-1) is each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group and the like.
  • the aliphatic hydrocarbon group an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • R a11 is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
  • n3 is an integer of 0 to 4, may be an integer of 1 or 2, and may be 2.
  • R a11 may be substituted at the ortho position on the benzene ring (provided that the substitution position of the oxygen atom is the reference).
  • the plurality of R a11 's may be the same or different.
  • the structural unit represented by the general formula (a-1) may be specifically a structural unit represented by the following general formula (a-1 ′).
  • the component (A1) may contain a polyphenylene ether derivative represented by any one of the following general formulas (a1-6) to (a1-8), and in particular, the following general formula (a1-7) or (a1) It preferably contains a polyphenylene ether derivative represented by -8), and more preferably contains a polyphenylene ether derivative represented by the following general formula (a1-8).
  • X a2 is the same as X a2 in the above general formula (a1-5) .n4 ⁇ n6 are each independently an integer of 1 to 200.
  • n4 to n6 are each independently an integer of 1 to 200, and the phase of the resin composition and the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher. From the viewpoint of compatibility, it may be an integer of 1 or more, an integer of 10 or more, an integer of 20 or more, or an integer of 25 or more. From the same viewpoint, n4 to n6 may each independently be an integer of 150 or less, an integer of 120 or less, or an integer of 100 or less. Any of the above general formulas (a1-6) to (a1-8) may be a mixture of polyphenylene ether derivatives having different values of n4 to n6, and usually tends to be a mixture.
  • the number average molecular weight of the polyphenylene ether derivative (A1) is preferably 1,000 to 25,000.
  • the number average molecular weight of the polyphenylene ether derivative (A1) is 1,000 or more, the dielectric properties in the high frequency band of 10 GHz or more tend to be more favorable, and when it is 25,000 or less, the resin composition Has a good compatibility, and tends to be difficult to separate even if it is left for a long time.
  • the number average molecular weight of the polyphenylene ether derivative (A1) is more preferably 2,000 to 20,000, further preferably 3,000 to 10,000, and particularly preferably 4,000 to 6,000. is there.
  • the number average molecular weight is a value converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC), and more specifically, determined by the measuring method described in Examples. It is a value.
  • a phenol compound having a structure represented by any one of the above general formulas (a1-1) to (a1-5) [hereinafter, may be abbreviated as unsaturated aliphatic hydrocarbon group-containing phenol compound (1). . ]
  • a polyphenylene ether having a number average molecular weight of 3,000 to 30,000 [hereinafter, may be abbreviated as raw material polyphenylene ether].
  • the polyphenylene ether derivative (A1) can be produced by reducing the molecular weight of the polyphenylene ether.
  • a raw material polyphenylene ether which has been already polymerized and produced is mixed with an unsaturated aliphatic hydrocarbon group-containing phenol compound (1), and a reaction catalyst described later is added if necessary.
  • the oxy radical of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) attacks the carbon atom to which the oxygen atom in the raw material polyphenylene ether is bonded, and the OC bond is broken there, resulting in a low molecular weight. It is a reaction that changes.
  • the attacked oxy radical of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) is bonded to the carbon atom whose bond has been broken, and is incorporated into the structure of the polyphenylene ether.
  • a known method can be used and applied as the redistribution reaction.
  • the molecular weight of the polyphenylene ether derivative (A1) can be controlled by the amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) used, and the larger the amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) used is (
  • the component A1) has a low molecular weight. That is, the amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) used may be appropriately adjusted so that the finally produced component (A1) has a number average molecular weight within a suitable range.
  • the amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) to be used is not particularly limited, but for example, the amount of the raw material polyphenylene ether to be reacted with the unsaturated aliphatic hydrocarbon group-containing phenol compound (1)
  • the number average molecular weight is 3,000 to 30,000
  • the hydroxyl group of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) is 1 to 10 mol, preferably 2 to 6 mol per 1 mol of the starting polyphenylene ether.
  • the component (A1) having a number average molecular weight within the preferable range described above can be obtained.
  • the organic solvent used in the production process of the polyphenylene ether derivative (A1) is not particularly limited, but examples thereof include alcohols such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl.
  • Ketones such as isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and mesitylene; esters such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate; N, N-dimethylformamide, N, N-dimethyl Examples thereof include nitrogen-containing compounds such as acetamide and N-methyl-2-pyrrolidone. These may be used alone or in combination of two or more.
  • a reaction catalyst can be used as necessary, as described above.
  • this reaction catalyst include organic peroxides such as t-butylperoxyisopropyl monocarbonate and manganese naphthenate and manganese octylate from the viewpoint of obtaining a component (A1) having a stable and reproducible number average molecular weight. It is preferable to use the carboxylic acid metal salt in combination.
  • the amount of the reaction catalyst used is not particularly limited.
  • the raw material polyphenylene ether to be reacted with the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) is used for organic peroxide.
  • the amount may be 0.5 to 5 parts by mass, and the carboxylic acid metal salt may be 0.05 to 0.5 parts by mass.
  • the unsaturated aliphatic hydrocarbon group-containing phenol compound (1), the raw material polyphenylene ether having the number average molecular weight of 3,000 to 30,000, an organic solvent and, if necessary, a predetermined amount of a reaction catalyst are charged in a reactor, and heated and kept warm.
  • the polyphenylene ether derivative (A1) is obtained by reacting with stirring.
  • the reaction temperature and reaction time in this step can be adjusted according to known reaction conditions during redistribution reaction, and may be appropriately adjusted, but in view of workability and gelation suppression, and the desired number average molecular weight (A1). From the viewpoint of obtaining the component), the reaction temperature may be 70 to 110 ° C. and the reaction time may be 1 to 8 hours.
  • reaction concentration Concentration of solid content in the reaction in the manufacturing process of component (A1) [hereinafter also referred to as reaction concentration. ] Is not particularly limited, but may be, for example, 10 to 60% by mass, or 20 to 50% by mass.
  • reaction concentration is 10% by mass or more, the reaction rate does not become too slow, which tends to be more advantageous in terms of manufacturing cost, and when the reaction concentration is 60% by mass or less, better solubility tends to be obtained.
  • the solution viscosity is low, the stirring efficiency is good, and gelation tends to be difficult.
  • the solution of the polyphenylene ether derivative (A1) produced as described above may be concentrated to remove a part of the organic solvent, or may be diluted with an additional organic solvent, if necessary.
  • the resin composition of the present embodiment tends to have better dielectric properties in a high frequency band of 10 GHz or higher than the resin composition containing the raw material polyphenylene ether instead of the component (A1).
  • the component (A2) is a polyphenylene ether derivative having a maleimide group as an ethylenically unsaturated bond-containing group, and the number of maleimide groups in one molecule is preferably from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher.
  • the number may be 1 or more, 5 or less, 3 or less, or 2 or less.
  • the component (A2) is a nitrogen atom of two maleimide groups from the viewpoint of high-frequency characteristics (low dielectric constant, low dielectric loss tangent), adhesion with conductors, heat resistance, glass transition temperature, thermal expansion coefficient and flame retardancy.
  • Those having a structure derived from bismaleimide in which they are bonded to each other via an organic group are preferable, and those having a group represented by the following general formula (a2-1) are more preferable.
  • R a12 is each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • M1 is an integer of 0 to 4.
  • X a3 is represented by the following general formula (a2-2). ), (A2-3), (a2-4) or (a2-5).
  • Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R a12 include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group. Groups and the like.
  • the aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms or a methyl group.
  • examples of the halogen atom represented by R a12 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • R a12 may be an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
  • m1 is an integer of 0 to 4, may be an integer of 0 to 2, and may be 0.
  • a plurality of R a12 's may be the same or different.
  • the divalent group represented by general formula (a2-2), (a2-3), (a2-4) or (a2-5) represented by X a3 is as follows.
  • R a13 is each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • M2 is an integer of 0 to 4.
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R a13 are the same as those described for R a12 .
  • m2 is an integer of 0 to 4, and from the viewpoint of easy availability, it may be an integer of 0 to 2, 0 or 1, or 0.
  • a plurality of R a13 's may be the same or different.
  • R a14 and R a15 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • X a4 is an alkylene group having 1 to 5 carbon atoms, or an alkyl group having 2 to 5 carbon atoms.
  • 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 (a2-3-1), m3 and m4 are each independently.
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R a14 and R a15 the same ones as in the case of R a12 can be mentioned.
  • the aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a methyl group, an ethyl group, or an ethyl group.
  • Examples of the alkylene group having 1 to 5 carbon atoms represented by X a4 include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, and 1,5-pentamethylene group. Is mentioned.
  • the alkylene group is an alkylene group having 1 to 3 carbon atoms from the viewpoints of high-frequency characteristics (low dielectric constant, low dielectric loss tangent), adhesion with conductors, heat resistance, glass transition temperature, thermal expansion coefficient and flame retardancy. Or may be a methylene group.
  • Examples of the alkylidene group having 2 to 5 carbon atoms represented by X a4 include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopentylidene group.
  • an isopropylidene group may be used from the viewpoints of high-frequency characteristics (low dielectric constant, low dielectric loss tangent), adhesion with conductors, heat resistance, glass transition temperature, coefficient of thermal expansion, and flame retardancy.
  • X a4 may be an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms.
  • m3 and m4 are each independently an integer of 0 to 4, and from the viewpoint of easy availability, each may be an integer of 0 to 2, or 0 or 2.
  • m3 or m4 is an integer of 2 or more, the plurality of R a14 s or the plurality of R a15 s may be the same or different.
  • the divalent group represented by the general formula (a2-3-1) represented by X a4 is as follows.
  • R a16 and R a17 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • X a5 is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, or an ether group.
  • M5 and m6 are each independently an integer of 0 to 4.
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R a16 and R a17 are the same as those described for R a14 and R a15 .
  • Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X a5 include the same ones as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X a4. Be done.
  • X a5 an alkylidene group having 2 to 5 carbon atoms may be selected from the above options.
  • m5 and m6 are integers of 0 to 4, and from the viewpoint of easy availability, each may be an integer of 0 to 2, 0 or 1, or 0.
  • the plurality of R a16 s or the plurality of R a17 s may be the same or different.
  • m7 is an integer of 0 to 10.
  • m7 may be an integer of 0 to 5 or 0 to 3 from the viewpoint of easy availability.
  • R a18 and R a19 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
  • M8 is an integer of 1 to 8.
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R a18 and R a19 are the same as those described for R a12 .
  • m8 is an integer of 1 to 8, may be an integer of 1 to 3, and may be 1.
  • X a3 in the group represented by the general formula (a2-1) is high frequency characteristics (low dielectric constant, low dielectric loss tangent), adhesiveness with a conductor, heat resistance, glass transition temperature, thermal expansion coefficient, and From the viewpoint of flame retardancy, a group represented by any of the following formulas is preferable.
  • the component (A2) is preferably a polyphenylene ether derivative represented by the following general formula (a2-6).
  • a2-6 a polyphenylene ether derivative represented by the following general formula (a2-6).
  • X a3 , R a11 , R a12 , n3 and m1 are as defined above.
  • M9 is an integer of 1 or more.
  • m9 may be an integer of 1 to 300, an integer of 10 to 250, an integer of 30 to 200, or an integer of 50 to 150.
  • the component (A2) is more preferably a polyphenylene ether derivative represented by any of the following general formulas.
  • m9 is the same as m9 in the general formula (a2-6).
  • the component (A2) is preferably a polyphenylene ether derivative represented by the general formula (a2-7) from the viewpoint of inexpensive raw materials, and has the above general formula from the viewpoint of excellent dielectric properties and low water absorption.
  • the polyphenylene ether derivative represented by (a2-8) is preferable, and the polyphenylene ether represented by the above general formula (a2-9) is preferable from the viewpoint of excellent adhesiveness to a conductor and mechanical properties (elongation, breaking strength, etc.). Derivatives are preferred. Therefore, one kind of the polyphenylene ether derivative represented by any of the general formulas (a2-7) to (a2-9) can be used alone or in combination of two or more kinds according to the desired characteristics. ..
  • the number average molecular weight of the component (A2) is preferably 4,000 to 12,000, more preferably 5,000 to 10,000, and still more preferably 6,000 to 8,000.
  • Mn Number average molecular weight
  • the number average molecular weight of the component (A2) is 4,000 or more, a better glass transition temperature tends to be obtained, and when it is 12,000 or less, a better moldability tends to be obtained.
  • the component (A2) can be obtained, for example, by the following production method.
  • an aminophenol compound represented by the following general formula (a2-10) [hereinafter, may be abbreviated as aminophenol compound (AP).
  • polyphenylene ether having a number average molecular weight of 15,000 to 25,000 is subjected to a well-known redistribution reaction in an organic solvent to reduce the molecular weight of the polyphenylene ether to 1 molecule in one molecule.
  • Polyphenylene ether compound (A ′′) having a primary amino group hereinafter, sometimes simply referred to as polyphenylene ether compound (A ′′).
  • the component (A2) can be produced by subjecting [] to a Michael addition reaction.
  • aminophenol compound (AP) examples include o-aminophenol, m-aminophenol, p-aminophenol and the like.
  • m-aminophenol and p-aminophenol are preferable from the viewpoint of the reaction yield when producing the polyphenylene ether compound (A ′′) and the heat resistance of the resin composition, prepreg and laminate.
  • p-aminophenol is more preferable.
  • the molecular weight of the polyphenylene ether compound (A ′′) can be controlled by the amount of the aminophenol compound (AP) used, and the higher the amount of the aminophenol compound (AP) used, the lower the molecular weight of the polyphenylene ether compound (A ′′). It That is, the amount of the aminophenol compound (AP) used may be appropriately adjusted so that the finally produced component (A2) has a number average molecular weight in a suitable range.
  • the blending amount of the aminophenol compound (AP) is not particularly limited, but for example, when the number average molecular weight of the polyphenylene ether to be reacted with the aminophenol compound (AP) is 15,000 to 25,000.
  • the component (A2) having a number average molecular weight of 4,000 to 12,000 can be obtained by using the polyphenylene ether in an amount of 0.5 to 6 parts by mass with respect to 100 parts by mass of the polyphenylene ether.
  • Aminophenol compound (AP), polyphenylene ether having the above number average molecular weight of 15,000 to 25,000, an organic solvent and, if necessary, a reaction catalyst in a predetermined amount are charged in a reactor, and the reaction is carried out with heating, heat retention and stirring to obtain polyphenylene ether.
  • the compound (A ′′) is obtained.
  • known reaction conditions for redistribution reaction can be applied, and they are the same as those in the above-mentioned method for producing the component (A1).
  • the suitable aspect of the organic solvent used in the said manufacturing process, a reaction catalyst, and its usage amount is the same as the case of the manufacturing method of (A1) component.
  • the solution of the polyphenylene ether compound (A ′′) produced as described above may be continuously supplied as it is to the next step of producing the polyphenylene ether derivative (A2). At this time, the solution of the polyphenylene ether compound (A ′′) may be cooled, or the reaction temperature of the next step may be adjusted. If necessary, this solution may be concentrated to remove a part of the organic solvent or may be diluted by adding an organic solvent.
  • Examples of the bismaleimide compound (BM) used when producing the component (A2) include, for example, bis (4-maleimidophenyl) methane, polyphenylmethanemaleimide, bis (4-maleimidophenyl) ether, and bis (4-maleimide).
  • bis (4-maleimidophenyl) methane is preferable from the viewpoint of obtaining a polyphenylene ether derivative containing the above general formula (a2-7) and being inexpensive, and containing the above general formula (a2-8).
  • the amount of the bismaleimide compound (BM) used is determined by the amount of the aminophenol compound (AP) used.
  • the equivalent ratio (Tb1 / Ta1) of the —NH 2 group equivalent (Ta1) of the aminophenol compound (AP) and the maleimide group equivalent (Tb1) of the bismaleimide compound (BM) is preferably 2 to 6, and 2 to 4 is preferable. More preferable.
  • a reaction catalyst can be used in the Michael addition reaction when producing the component (A2).
  • the reaction catalyst is not particularly limited, but examples thereof include acidic catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine and tributylamine; imidazole compounds such as methylimidazole and phenylimidazole; phosphorus-based catalysts such as triphenylphosphine. And so on. These may be used alone or in combination of two or more.
  • the amount of the reaction catalyst blended is not particularly limited, but is, for example, 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyphenylene ether compound (A ′′).
  • a component (A2) is obtained by charging the bismaleimide compound (BM) and, if necessary, a reaction catalyst and the like into a solution of a polyphenylene ether compound (A ′′) in a predetermined amount, and subjecting the mixture to a Michael addition reaction with heating, heat retention, and stirring. Be done.
  • the reaction conditions in this step may be, for example, a reaction temperature of 50 to 160 ° C. and a reaction time of 1 to 10 hours.
  • the reaction concentration (solid content concentration) and the solution viscosity can be adjusted by adding or concentrating the organic solvent as described above.
  • the organic solvents exemplified in the production process of the polyphenylene ether compound (A ′′) can be applied, and these may be used alone or in combination of two or more. Good.
  • methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, N, N-dimethylformamide, and N, N-dimethylacetamide may be selected from the viewpoint of solubility.
  • the reaction concentration (solid content concentration) in the manufacturing process of the component (A2) and the polyphenylene ether compound (A ′′) is not particularly limited, but may be 10 to 60% by mass in each of the manufacturing processes. It may be 20 to 50% by mass. When the reaction concentration is 10% by mass or more, the reaction rate does not become too slow, and the production cost tends to be more advantageous. When the reaction temperature is 60% by mass or less, better solubility tends to be obtained. Further, the solution viscosity is low, the stirring efficiency is good, and gelation tends to be less.
  • thermosetting resins for example, , A solution viscosity suitable for the production of prepreg, a solution concentration), etc., and may be concentrated by removing a part or all of the organic solvent in the solution, or may be diluted by adding an organic solvent.
  • the organic solvent to be added is not particularly limited, and one or more kinds of organic solvents described above can be applied.
  • the formation of the polyphenylene ether compounds (A ′′) and (A2) components obtained by the above-mentioned production process can be confirmed by taking out a small amount of a sample after the completion of each process and performing a GPC measurement and an IR measurement.
  • the polyphenylene ether compound (A ′′) has a lower molecular weight than the polyphenylene ether having a number average molecular weight of 15,000 to 25,000, and the peak of the aminophenol compound (AP) as a raw material disappears according to GPC measurement. It can be confirmed from the IR measurement that the desired polyphenylene ether compound (A ′′) is produced by the appearance of primary amino groups at 3300 to 3500 cm ⁇ 1 .
  • the maleimide compound (B) is at least one selected from the group consisting of maleimide compounds having two or more N-substituted maleimide groups and derivatives thereof.
  • the maleimide compound (B) does not include the polyphenylene ether derivative (A).
  • the maleimide compound (B) does not contain the structural unit represented by the general formula (a-1), and does not contain a polyphenylene ether skeleton.
  • Examples of the "derivative thereof” include addition reaction products of the maleimide compound having two or more N-substituted maleimide groups and an amine compound such as a diamine compound (b2) described later.
  • the maleimide compound (B) has two or more N-substituted maleimide groups from the viewpoint of solubility in an organic solvent, compatibility, adhesion with a conductor, and dielectric properties in a high frequency band of 10 GHz or higher.
  • a maleimide compound derivative is preferable, and a maleimide compound (b1) having two or more N-substituted maleimide groups [hereinafter, may be simply referred to as maleimide compound (b1) or (b1) component).
  • the polyamino bismaleimide compound which has the structural unit derived from and the structural unit derived from the diamine compound (b2) [Hereinafter, it may be abbreviated as a polyamino bismaleimide compound (B1) or (B1) component. ] Is more preferable.
  • the structural unit derived from the component (b1) and the structural unit derived from the component (b2) may be one kind or a combination of two or more kinds.
  • component (b1) are not particularly limited as long as they are maleimide compounds having two or more N-substituted maleimide groups, and examples thereof include bis (4-maleimidophenyl) methane, polyphenylmethanemaleimide, bis (4- Maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, m -Aromatic maleimide compounds such as phenylene bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane; 1,6-bismaleimide- (2,2,4-trimethyl) hexane, pyrrolilonic acid binder
  • Examples include aliphatic maleimide compounds such as long-chain alkyl bismaleimide.
  • aromatic maleimide compounds are preferable from the viewpoint of adhesiveness to conductors and mechanical properties, and 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 3,3′-dimethyl-5, More preferred is 5'-diethyl-4,4'-diphenylmethane bismaleimide.
  • Examples of the structural unit derived from the component (b1) include one or more selected from the group consisting of a group represented by the following general formula (b1-1) and a group represented by the following general formula (b1-2). Be done. (In the formula, X b1 represents a divalent organic group, and * represents a bonding position to another structure.)
  • X b1 in the general formulas (b1-1) and (b1-2) is a divalent organic group and corresponds to the residue of the component (b1).
  • the residue of the component (b1) refers to the structure of the part excluding the functional group used for the bond, that is, the maleimide group, from the component (b1).
  • Examples of the divalent organic group represented by X b1 include groups represented by general formula (b1-3), (b1-4), (b1-5) or (b1-6) shown below.
  • each of R b1 is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • P1 is an integer of 0 to 4.
  • Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b1 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group. Groups and the like.
  • the aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms or a methyl group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • p1 is an integer of 0 to 4, and from the viewpoint of easy availability, it may be an integer of 0 to 2, 0 or 1, or 0.
  • p1 is an integer of 2 or more, a plurality of R b1 's may be the same or different.
  • R b2 and R b3 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • X b2 is an alkylene group having 1 to 5 carbon atoms, or an alkyl group having 2 to 5 carbon atoms.
  • p2 and p3 are each independently Is an integer of 0 to 4.
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R b2 and R b3 the same ones as in the case of R b1 can be mentioned.
  • the aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a methyl group, an ethyl group, or an ethyl group.
  • alkylene group having 1 to 5 carbon atoms represented by X b2 examples include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, and 1,5-pentamethylene group. Is mentioned.
  • the alkylene group is an alkylene group having 1 to 3 carbon atoms from the viewpoints of high-frequency characteristics (low dielectric constant, low dielectric loss tangent), adhesion with conductors, heat resistance, glass transition temperature, thermal expansion coefficient and flame retardancy. Or may be a methylene group.
  • Examples of the alkylidene group having 2 to 5 carbon atoms represented by X b2 include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopentylidene group.
  • an isopropylidene group may be used from the viewpoints of high-frequency characteristics (low dielectric constant, low dielectric loss tangent), adhesion with conductors, heat resistance, glass transition temperature, coefficient of thermal expansion, and flame retardancy.
  • X b2 may be an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms.
  • p2 and p3 are each independently an integer of 0 to 4, and from the viewpoint of easy availability, each may be an integer of 0 to 2 or 0 or 2.
  • p2 or p3 is an integer of 2 or more
  • the plurality of R b2 s or the plurality of R b3 s may be the same or different.
  • the divalent group represented by the general formula (b1-4-1) represented by X b2 is as follows.
  • R b4 and R b5 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • X b3 is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group.
  • P4 and p5 are each independently an integer of 0 to 4.
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R b4 and R b5 are the same as those described for R b1 .
  • Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X b3 include the same ones as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X b2.
  • an alkylidene group having 2 to 5 carbon atoms may be selected from the above options.
  • p4 and p5 are integers of 0 to 4, and from the viewpoint of easy availability, each may be an integer of 0 to 2, 0 or 1, or 0.
  • the plurality of R b4 s or the plurality of R b5 s may be the same or different.
  • p6 is an integer of 0 to 10.
  • p6 may be an integer of 0 to 5 or an integer of 0 to 3.
  • R b6 and R b7 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
  • P7 is an integer of 1 to 8.
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R b6 and R b7 are the same as those described for R b1 .
  • p7 is an integer of 1 to 8, may be an integer of 1 to 3, and may be 1.
  • X b1 in the above general formulas (b1-1) and (b1-2) is adhesiveness with a conductor, heat resistance, glass transition temperature, thermal expansion coefficient, flame retardancy, and high frequency band of 10 GHz or higher.
  • a divalent group represented by any of the following formulas (X b1 -1) to (X b1 -3) is preferable, and a divalent group represented by the following formula (X b1 -3) More preferably, it is a divalent group.
  • both X b1 include a group represented by the following formula (X b1 -1) and a group represented by the following formula (X b1 -3).
  • Or may have both a group represented by the following formula (X b1 -2) and a group represented by the following formula (X b1 -3) as X b1. .. (The wavy line indicates the bonding position with the nitrogen atom in the maleimide group.)
  • the total content of the structural units derived from the component (b1) in the maleimide compound (B) is preferably 5 to 95% by mass, more preferably 30 to 93% by mass, further preferably 60 to 90% by mass, and particularly preferably It is 75 to 90% by mass.
  • the content of the structural unit derived from the component (b1) is within the above range, the dielectric property in the high frequency band of 10 GHz band or higher tends to be better, and the good film handling property tends to be obtained.
  • the component (b2) is not particularly limited as long as it is a compound having two amino groups.
  • Examples of the component (b2) include 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, 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'
  • 4,4′-diaminodiphenylmethane and 4,4′-diamino are preferable as they are excellent in solubility in an organic solvent, reactivity with the component (b1), and heat resistance.
  • the component (b2) is 3,3′-dimethyl-5,5′-diethyl-4,4′-diaminodiphenylmethane from the viewpoint of excellent dielectric properties and low water absorption in the high frequency band of 10 GHz or higher. Is preferred.
  • the component (b2) is preferably 2,2-bis [4- (4-aminophenoxy) phenyl] propane from the viewpoint of excellent mechanical properties such as high adhesion to conductors, elongation, and breaking strength.
  • the component (b2) is 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisaniline, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)].
  • Bisaniline is preferred.
  • the structural unit derived from the component (b2) is, for example, one or more selected from the group consisting of a group represented by the following general formula (b2-1) and a group represented by the following general formula (b2-2). Is mentioned.
  • X b4 represents a divalent organic group, and * represents a bonding position to another structure.
  • X b4 in the general formulas (b2-1) and (b2-2) is a divalent organic group and corresponds to the residue of the component (b2).
  • the residue of the component (b2) refers to the structure of the portion excluding the functional group provided for binding, that is, the amino group, from the component (b2).
  • X b4 in the general formula (b2-1) and the general formula (b2-2) is preferably a divalent group represented by the following general formula (b2-3).
  • R b11 and R b12 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.
  • X b5 is a carbon number of 1 To 5 alkylene group, 2 to 5 carbon alkylidene group, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group, fluorenylene group, single bond, or the following general formula (b2-3-1) or ( b2-3-2), which is a divalent group.
  • p8 and p9 are each independently an integer of 0 to 4.
  • R b13 and R b14 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • X b6 is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, m- It is a 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, and p10 and p11 are each independently an integer of 0 to 4.
  • R b15 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • X b7 and X b8 each independently represent an alkylene group having 1 to 5 carbon atoms or isopropylidene.
  • P12 is an integer of 0 to 4.
  • the aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms, or may be a methyl group or an ethyl group.
  • the alkylidene groups of to 5 are explained in the same manner as in the case of X b2 in the above general formula (b1-4).
  • the alkylene group having 1 to 5 carbon atoms represented by X b7 and X b8 in the general formula (b2-3-2) is explained in the same manner as in the case of X b2 in the general formula (b1-4).
  • p8 and p9 are integers of 0 to 4, and from the viewpoint of easy availability, both may be integers of 0 to 2 or 0 or 2.
  • p10 and p11 are integers of 0 to 4, and from the viewpoint of easy availability, each may be an integer of 0 to 2, 0 or 1, or 0.
  • p12 is an integer of 0 to 4, and may be an integer of 0 to 2 or 0 from the viewpoint of easy availability.
  • the total content of the structural units derived from the component (b2) in the maleimide compound (B) is preferably 5 to 95% by mass, more preferably 7 to 70% by mass, further preferably 10 to 40% by mass, particularly preferably It is 10 to 25% by mass.
  • the total content of the structural units derived from the component (b2) is within the above range, excellent dielectric properties in a high frequency band of 10 GHz band or higher and better heat resistance, flame retardancy and glass transition temperature can be obtained. There is a tendency.
  • the content ratio of the structural unit derived from the component (b1) and the structural unit derived from the component (b2) in the maleimide compound (B) is calculated from the —NH 2 group derived from the component (b2) in the maleimide compound (B).
  • the equivalent ratio (Ta2 / Ta1) between the total equivalent (Ta2) of the group (including —NH 2 ) and the total equivalent (Ta1) of the group (including the maleimide group) derived from the maleimide group derived from the component (b1) is The content ratio is preferably 0.05 to 10, and more preferably 1 to 5.
  • the maleimide compound (B) is represented by the following general formula (b2) from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher, the solubility in an organic solvent, the high adhesion to a conductor, the moldability of a resin film, and the like. It is preferable to contain a polyamino bismaleimide compound represented by -4).
  • the component (B1) can be produced, for example, by reacting the component (b1) with the component (b2) in an organic solvent.
  • a reaction catalyst may be used, if necessary.
  • the reaction catalyst include, but are not limited to, acidic catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine and tributylamine; imidazoles such as methylimidazole and phenylimidazole; triphenylphosphine and the like.
  • Examples of the phosphorus-based catalysts include These may be used alone or in combination of two or more.
  • the amount of the reaction catalyst blended is not particularly limited, but may be, for example, 0.01 to 5 parts by mass based on 100 parts by mass of the total amount of the components (b1) and (b2).
  • the polyamino bismaleimide compound is obtained by charging a predetermined amount of the component (b1), the component (b2) and, if necessary, other components into a synthetic kettle and subjecting the component (b1) and the component (b2) to a Michael addition reaction.
  • the reaction conditions in this step are not particularly limited, but the reaction temperature is preferably 50 to 160 ° C., and the reaction time is preferably 1 to 10 hours from the viewpoints of workability such as reaction rate and suppression of gelation. .. Further, in this step, the solid content concentration and solution viscosity of the reaction raw material can be adjusted by adding or concentrating the organic solvent.
  • the solid content concentration of the reaction raw material is not particularly limited, but is, for example, preferably 10 to 90% by mass, more preferably 20 to 80% by mass.
  • the solid content concentration of the reaction raw material is 10% by mass or more, the reaction rate does not become too slow, and the production cost tends to be advantageous. Further, when the solid content concentration of the reaction raw material is 90% by mass or less, better solubility is obtained, stirring efficiency is improved, and gelation tends to be difficult.
  • the number average molecular weight of the polyamino bismaleimide compound (B1) thus obtained is not particularly limited, but is preferably 400 to 10,000, more preferably 500 to 5,000, further preferably 600 to 2,000, particularly preferably It is 700 to 1,500.
  • the weight average molecular weight of the polyamino bismaleimide compound (B1) is measured by gel permeation chromatography (GPC) in terms of polystyrene.
  • the content of the component (A) is not particularly limited, but from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher, the total amount of the resin components in the resin composition is 100 parts by mass. On the other hand, it is preferably 1 part by mass or more, more preferably 1 to 20 parts by mass, further preferably 2 to 10 parts by mass, particularly preferably 3 to 7 parts by mass.
  • the “resin component” refers to the component (A), the component (B), the component (C), and the component (D) optionally used.
  • the “resin component” refers to the component (A), the component (B) and the component (C), and the resin composition contains the component (D).
  • the “resin component” includes the component (A), the component (B), the component (C) and the component (D).
  • the content of the component (B) is not particularly limited, but from the viewpoint of dielectric properties and moldability in a high frequency band of 10 GHz or higher, it is preferably 10 with respect to 100 parts by mass of the resin components in the resin composition. To 90 parts by mass, more preferably 20 to 80 parts by mass, further preferably 30 to 70 parts by mass, and particularly preferably 35 to 60 parts by mass.
  • the content ratio of the component (A) and the component (B) [(A) / (B)] is not particularly limited, but the mass ratio is preferably 1/99 to 80/20, more preferably 3/97 to 75. / 25, more preferably 5/95 to 70/30, even more preferably 5/95 to 50/50, particularly preferably 5/95 to 20/80, most preferably 5/95 to 15/85.
  • the content ratio [(A) / (B)] is 1/99 or more, excellent dielectric properties tend to be obtained in a high frequency band of 10 GHz or more, and when it is 80/20 or less, heat resistance, Moldability and workability tend to be excellent.
  • the cross-linking agent (C) is a cross-linking agent having two or more ethylenically unsaturated bonds.
  • the resin composition of the present embodiment is particularly excellent in heat resistance and dielectric properties. The factor is not clear, but it is expected as follows.
  • the polyphenylene ether derivative (A) contained in the resin composition of the present embodiment has an ethylenically unsaturated bond as a reactive group, and reacts with the components (A) or with the component (B) to form a cured product. I will get it.
  • the component (A) is a polymer
  • miscibility with other components may not be sufficiently obtained, and the ethylenically unsaturated bond as a reaction point may be present at a part of the end of the molecular chain. Due to the presence, it may not be possible to obtain sufficient reactivity with other reactive groups.
  • the cross-linking agent (C) by applying the cross-linking agent (C), the ethylenically unsaturated bond (derived from the cross-linking agent (C)) is generated in the vicinity of the ethylenically unsaturated bond of the component (A).
  • the ethylenically unsaturated bond contained in the component (C) is, for example, an unsaturated aliphatic hydrocarbon group such as vinyl group, isopropenyl group, allyl group, 1-methylallyl group, 3-butenyl group; maleimide group, (meth) It is an unsaturated bond contained in a substituent containing a hetero atom such as an acryloyl group.
  • the component (C) preferably has an ethylenically unsaturated bond as the unsaturated aliphatic hydrocarbon group, and more preferably has a vinyl group, from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher. More preferable.
  • the number of ethylenically unsaturated bonds contained in the molecule of the component (C) is preferably 3 or more, more preferably 5 or more, and further preferably 10 or more from the viewpoint of obtaining excellent heat resistance.
  • component (C) examples include 1,2,4-trivinylcyclohexane, 1,4-butanediol divinyl ether, nonanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, triethylene glycol divinyl ether.
  • a polymer having two or more ethylenically unsaturated bonds as a vinyl group is preferable, and a 1,2-vinyl group is preferable. More preferred are polybutadiene having two or more groups and a butadiene-styrene copolymer having two or more 1,2-vinyl groups, and even more preferred is polybutadiene having two or more 1,2-vinyl groups.
  • polybutadiene when only describing as "polybutadiene", it means a butadiene homopolymer. That is, as the component (C), a butadiene homopolymer having two or more 1,2-vinyl groups is preferable.
  • the component (C) one type may be used alone, or two or more types may be used in combination.
  • the component (C) is a polybutadiene having two or more 1,2-vinyl groups
  • the content of the structural unit having a 1,2-vinyl structure [below the total structural units derived from butadiene constituting the polybutadiene] , Vinyl group content may be abbreviated. ] Is preferably 50 mol% or more, more preferably 60 mol% or more, further preferably 70 mol% or more, particularly preferably 80 mol% or more, and most preferably 85 mol% or more.
  • the polybutadiene having two or more 1,2-vinyl groups is preferably a 1,2-polybutadiene homopolymer.
  • the number average molecular weight of a polymer having two or more ethylenically unsaturated bonds is compatible with other resins, dielectric properties, low thermal expansion and heat resistance. From this point of view, it is preferably 500 to 10,000, more preferably 800 to 5,000, and further preferably 1,000 to 3,500. From the viewpoint of compatibility, it may be 3,000 or less, or 2,500 or less.
  • the number average molecular weight of a polymer having two or more ethylenically unsaturated bonds can be measured by the method described in Examples.
  • the content of the component (C) is not particularly limited, but from the viewpoint of obtaining excellent heat resistance and the viewpoint of dielectric characteristics in a high frequency band of 10 GHz band or higher, It is preferably 5 to 60 parts by mass, more preferably 7 to 40 parts by mass, still more preferably 10 to 30 parts by mass, and particularly preferably 13 to 20 parts by mass, based on 100 parts by mass of the total of the resin components.
  • the resin composition of the present embodiment may further contain other components.
  • a styrene-based thermoplastic elastomer (D) [hereinafter, may be abbreviated as a component (D). ]
  • Inorganic filler (E) [Hereinafter, it may be abbreviated as a component (E). ]
  • a hardening accelerator (F) [Hereinafter, it may be abbreviated as a component (F).
  • a flame retardant (G) [Hereinafter, it may be abbreviated as a component (G). ]
  • the resin composition of the present embodiment does not contain one or more selected from the component (D), the component (E), the component (F) and the component (G) depending on the desired performance. You may. Hereinafter, these components will be described in detail.
  • thermoplastic elastomer (D) By including the styrene-based thermoplastic elastomer (D) in the resin composition of the present embodiment, dielectric properties in a high frequency band of 10 GHz or higher, moldability, adhesiveness with a conductor, solder heat resistance, glass transition temperature, The thermal expansion coefficient and flame retardancy are good, and the balance between them tends to be good.
  • R d1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R d2 is an alkyl group having 1 to 5 carbon atoms
  • k is an integer of 0 to 5.
  • Examples of the alkyl group having 1 to 5 carbon atoms represented by R d1 and R d2 include a methyl group, an ethyl group, and an n-propyl group, and may be an alkyl group having 1 to 3 carbon atoms. It may be a group.
  • k may be an integer of 0 to 2, may be 0 or 1, and may be 0.
  • Examples of the structural unit other than the structural unit derived from the styrene compound included in the component (D) include a structural unit derived from butadiene, a structural unit derived from isoprene, a structural unit derived from maleic acid, a structural unit derived from maleic anhydride, and the like. .
  • the component (D) one type may be used alone, or two or more types may be used in combination.
  • the butadiene-derived structural unit and the isoprene-derived structural unit may be hydrogenated. When hydrogenated, the structural unit derived from butadiene is a structural unit in which ethylene units and butylene units are mixed, and the structural unit derived from isoprene is a structural unit in which ethylene units and propylene units are mixed.
  • component (D) hydrogenation of a styrene-butadiene-styrene block copolymer is carried out from the viewpoints of dielectric properties in a high frequency band of 10 GHz or higher, adhesiveness with a conductor, heat resistance, glass transition temperature and coefficient of thermal expansion.
  • SEBS, SBBS a hydrogenated product of styrene-isoprene-styrene block copolymer
  • SMA styrene-maleic anhydride copolymer
  • SEBS butadiene-styrene block copolymer
  • SEPS styrene-isoprene-styrene block copolymer
  • SEBS block copolymer hydrogenated product
  • the content of the structural unit derived from styrene [hereinafter, may be abbreviated as styrene content]. ] Is preferably 5 to 80% by mass, more preferably 10 to 75% by mass from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher, adhesiveness with a conductor, heat resistance, glass transition temperature and coefficient of thermal expansion. %, More preferably 15 to 70% by mass, and particularly preferably 20 to 50% by mass.
  • the melt flow rate (MFR) of SEBS is not particularly limited, but may be 0.1 to 20 g / 10 min under the measurement conditions of 230 ° C.
  • the weight average molecular weight (Mw) of the component (D) is not particularly limited, but is preferably 12,000 to 1,000,000, more preferably 30,000 to 500,000, further preferably 50,000 to 120, 000, particularly preferably 70,000 to 100,000.
  • the weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) in terms of polystyrene.
  • the content of the component (D) is not particularly limited, but the dielectric characteristics in a high frequency band of 10 GHz band or higher and the adhesiveness with the conductor. From the viewpoint of heat resistance, glass transition temperature and coefficient of thermal expansion, it is preferably 5 to 60 parts by mass, more preferably 10 to 55 parts by mass, based on 100 parts by mass of the total of the components (A) to (D). It is preferably 15 to 50 parts by mass, particularly preferably 20 to 45 parts by mass, most preferably 25 to 40 parts by mass.
  • the content of the component (D) is 5 parts by mass or more, the dielectric properties and moisture absorption resistance in a high frequency band of 10 GHz or more tend to be better, and when it is 60 parts by mass or less, heat resistance , Moldability, processability and flame retardancy tend to be better.
  • the component (E) is not particularly limited, but examples thereof include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, and hydroxide. Examples thereof include magnesium, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay (calcined clay and the like), talc, aluminum borate, silicon carbide and the like.
  • silica, alumina, mica, and talc are preferable, silica and alumina are more preferable, and silica is further preferable, from the viewpoints of thermal expansion coefficient, elastic modulus, heat resistance and flame retardancy.
  • examples of silica include precipitated silica having a high water content produced by a wet method, and dry method silica produced by a dry method and containing almost no bound water, and the like. Examples thereof include crushed silica, fumed silica, and fused silica (fused spherical silica).
  • the shape and particle size of the inorganic filler (E) are also not particularly limited.
  • the particle size is preferably 0.01 to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m.
  • the particle size refers to the average particle size, and is the particle size at a point corresponding to 50% volume when a cumulative frequency distribution curve based on the particle size is obtained with the total volume of the particles being 100%.
  • the particle size of the inorganic filler (E) can be measured with a particle size distribution measuring device or the like using a laser diffraction scattering method.
  • the content of the component (E) in the resin composition is not particularly limited, but the thermal expansion coefficient, elastic modulus, heat resistance and difficulty From the viewpoint of flammability, it is preferably 5 to 70 parts by mass, more preferably 15 to 65 parts by mass, still more preferably 20 to 60 parts by mass, particularly preferably 100 parts by mass of the resin components in the resin composition. Is 30 to 55 parts by weight, and most preferably 40 to 50 parts by weight.
  • a coupling agent may be optionally used in combination for the purpose of improving the dispersibility of the component (E) and the adhesion between the component (E) and the organic component in the resin composition. May be.
  • the coupling agent is not particularly limited, and for example, a silane coupling agent or a titanate coupling agent can be appropriately selected and used.
  • the coupling agents may be used alone or in combination of two or more.
  • the amount of the coupling agent used is not particularly limited, and may be, for example, 0.1 to 5 parts by mass, or 0.5 to 3 parts by mass, relative to 100 parts by mass of the component (E). ..
  • ком ⁇ онент (E) When a coupling agent is used, a so-called integral blending treatment method may be used in which the component (E) is added to the resin composition and then the coupling agent is added. A method of using an inorganic filler whose surface is treated with a dry agent or a wet agent is preferable. By adopting this method, the characteristics of the component (E) can be more effectively exhibited.
  • the component (E) is used as a slurry in which the component (E) is previously dispersed in an organic solvent for the purpose of improving the dispersibility of the component (E) in the resin composition.
  • the organic solvent used when making the component (E) into a slurry is not particularly limited, but for example, the organic solvent exemplified in the above-mentioned manufacturing process of the component (A1) can be applied. These may be used alone or in combination of two or more. Of these, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are preferable from the viewpoint of dispersibility.
  • the solid content (nonvolatile content) concentration of the slurry is not particularly limited, but from the viewpoint of the sedimentation and dispersibility of the inorganic filler (E), it is, for example, 50 to 80% by mass, and 60 to 80% by mass. It may be.
  • the curability of the resin composition is improved, and dielectric properties, heat resistance, and adhesion to a conductor in a high frequency band of 10 GHz band or higher, The elastic modulus and the glass transition temperature tend to be improved.
  • the component (F) include acidic catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, pyridine and tributylamine; methylimidazole, phenylimidazole, isocyanate mask imidazole (eg hexamethylene diisocyanate resin and 2-ethylamine).
  • Imidazole compounds such as addition reaction products of 4-methylimidazole); tertiary amine compounds; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine; dicumyl peroxide, 2,5-dimethyl-2, 5-bis (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, ⁇ , ⁇ '-bis ( t-butylperoxy) diisopropylben Organic peroxides such emissions; manganese, cobalt, etc. carboxylates of zinc, and the like.
  • these may be used alone or in combination of two or more.
  • they may be imidazole compounds, organic peroxides and carboxylates, and heat resistance, glass transition temperature, elastic modulus and thermal expansion coefficient. Therefore, the imidazole compound and the organic peroxide or carboxylate may be used in combination.
  • the organic peroxides ⁇ , ⁇ ′-bis (t-butylperoxy) diisopropylbenzene may be selected, and among the carboxylates, manganese naphthenate may be selected.
  • the content of the component (F) is not particularly limited, but for example, relative to 100 parts by mass of the total amount of the resin components in the resin composition. It is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, further preferably 0.1 to 6 parts by mass, particularly preferably 0.5 to 5 parts by mass. When the content of the component (F) is within the above range, better heat resistance and storage stability tend to be obtained.
  • the flame retardancy of the resin composition tends to be improved by incorporating the flame retardant (G) into the resin composition of the present embodiment.
  • the component (G) include phosphorus-based flame retardants, metal hydrates, halogen-based flame retardants and the like. From the viewpoint of environmental problems, phosphorus-based flame retardants and metal hydrates may be used.
  • the flame retardant (G) one type may be used alone, or two or more types may be used in combination. Further, a flame retardant aid may be contained if necessary.
  • the phosphorus-based flame retardant is not particularly limited as long as it contains a phosphorus atom among those generally used as a flame retardant, and may be an inorganic phosphorus-based flame retardant or an organic-based flame retardant. It may be a phosphorus-based flame retardant. From the viewpoint of environmental problems, those containing no halogen atom are preferable. From the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher, adhesiveness with a conductor, heat resistance, glass transition temperature, coefficient of thermal expansion and flame retardancy, an organic phosphorus-based flame retardant may be used.
  • inorganic phosphorus-based flame retardants include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as phosphoramide. Phosphoric acid; phosphine oxide and the like.
  • organic phosphorus flame retardant include aromatic phosphoric acid ester, 1-substituted phosphonic acid diester, 2-substituted phosphinic acid ester, 2-substituted phosphinic acid metal salt, organic nitrogen-containing phosphorus compound, cyclic organic phosphorus compound, and the like. Is mentioned.
  • aromatic phosphoric acid ester compounds and metal salts of disubstituted phosphinic acids are preferable.
  • the metal salt may be any one of a lithium salt, a sodium salt, a potassium salt, a calcium salt, a magnesium salt, an aluminum salt, a titanium salt and a zinc salt, or may be an aluminum salt.
  • aromatic phosphates are preferable.
  • aromatic phosphoric acid ester examples include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol bis (diphenyl phosphate), 1,3 -Phenylene bis (di-2,6-xylenyl phosphate), bisphenol A-bis (diphenyl phosphate), 1,3-phenylene bis (diphenyl phosphate), etc. may be mentioned.
  • Examples of mono-substituted phosphonic acid diesters include divinyl phenylphosphonate, diallyl phenylphosphonate, and bis (1-butenyl) phenylphosphonate.
  • Examples of the 2-substituted phosphinic acid ester include phenyl diphenylphosphinate and methyl diphenylphosphinate.
  • Examples of the metal salt of disubstituted phosphinic acid include a metal salt of dialkylphosphinic acid, a metal salt of diallylphosphinic acid, a metal salt of divinylphosphinic acid, a metal salt of diarylphosphinic acid, and the like.
  • metal salts may be any of lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt and zinc salt, and aluminum salt may be selected.
  • organic nitrogen-containing phosphorus compounds include phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicresylphosphazene; melamine phosphate; melamine pyrophosphate; melamine polyphosphate; melam polyphosphate.
  • cyclic organic phosphorus compound examples include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10- Examples thereof include phosphaphenanthrene-10-oxide.
  • aromatic phosphoric acid esters and disubstituted phosphines are preferable, and aluminum salts of 1,3-phenylenebis (di-2,6-xylenyl phosphate) and dialkylphosphinic acid are preferable.
  • metal hydrates include aluminum hydroxide hydrate and magnesium hydroxide hydrate. These may be used alone or in combination of two or more.
  • the metal hydroxide may be an inorganic filler, but a material capable of imparting flame retardancy is classified as a flame retardant.
  • -Halogen flame retardant- Examples of halogen-based flame retardants include chlorine-based flame retardants and bromine-based flame retardants. Examples of the chlorine-based flame retardant include chlorinated paraffin and the like.
  • the content of the phosphorus-based flame retardant in the resin composition is not particularly limited. However, for example, it is preferably 0.2 to 5 parts by mass, more preferably 0.3 to 4 parts by mass, and even more preferably 0.3 to 4 parts by mass in terms of phosphorus atom with respect to 100 parts by mass as the total of the resin components in the resin composition. 0.5 to 3 parts by mass.
  • the phosphorus atom content is 0.2 parts by mass or more, better flame retardancy tends to be obtained, and when the phosphorus atom content is 5 parts by mass or less, better moldability, high adhesion with a conductor, Excellent heat resistance and high glass transition temperature tend to be obtained.
  • thermoplastic resin other than the above components a resin material such as an elastomer, and a coupling agent, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet ray.
  • An absorber, a pigment, a colorant, a flame retardant aid, a lubricant and the like can be appropriately selected and contained. These may be used alone or in combination of two or more. Further, the amount of these used is not particularly limited, and may be used within a range that does not impair the effects of the present invention.
  • the resin composition of the present embodiment may contain an organic solvent from the viewpoint of facilitating the handling by diluting and facilitating the production of a prepreg described later.
  • the resin composition containing an organic solvent is generally referred to as a resin varnish or a varnish.
  • the organic solvent is not particularly limited, but examples thereof include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; tetrahydrofuran. Etc.
  • ether solvents such as; toluene, xylene, mesitylene etc. aromatic solvents; dimethylformamide, dimethylacetamide, N-methylpyrrolidone etc. nitrogen atom containing solvents; dimethyl sulfoxide etc. sulfur atom containing solvents; ⁇ -butyrolactone etc. esters
  • system solvents include system solvents.
  • alcohol solvents, ketone solvents, and nitrogen atom-containing solvents are preferable, ketone solvents are more preferable, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are more preferable, and methyl ethyl ketone is particularly preferable, from the viewpoint of solubility.
  • the organic solvent may be used alone or in combination of two or more.
  • the resin composition of the present embodiment contains an organic solvent
  • its solid content concentration is, for example, 30 to 90% by mass, 35 to 80% by mass, or 40 to 60% by mass. Good.
  • the handling becomes easy, the impregnation into the substrate and the appearance of the prepreg produced are good, and the solid content of the resin in the prepreg described below. It tends to be easier to adjust the concentration, and it becomes easier to manufacture a prepreg having a desired thickness.
  • the resin composition of the present embodiment is prepared by mixing the component (A), the component (B), the component (C), and other components which are optionally used in combination by a known method to obtain the resin composition of the present embodiment. Obtainable. At this time, each component may be dissolved or dispersed while stirring. Conditions such as mixing order, temperature, time, etc. are not particularly limited and can be set arbitrarily.
  • the resin composition of the present embodiment has good compatibility, and there is a tendency that precipitates do not occur even if left for one day. Further, in a more excellent compatibility mode, there is a tendency that precipitates do not occur even if left for one week (however, phase separation may occur), and in a more excellent compatibility mode, Even if left for one week, there is a tendency that phase separation does not occur.
  • the dielectric constant (Dk) at 10 GHz of the cured product of the resin composition of the present embodiment is preferably 3.0 or less, and more preferably It is 2.8 or less.
  • the dielectric constant (Dk) is preferably as small as possible, and the lower limit thereof is not particularly limited, but in consideration of the balance with other physical properties, for example, it may be 2.4 or more, and 2.6 or more. You may.
  • the dielectric loss tangent (Df) at 10 GHz of the cured product of the resin composition of the present embodiment is preferably 0.0055 or less, more preferably It is 0.0050 or less, more preferably 0.0045 or less, particularly preferably 0.0035 or less, and most preferably 0.0030 or less.
  • the dielectric loss tangent (Df) is preferably as small as possible, and the lower limit thereof is not particularly limited, but in consideration of the balance with other physical properties, it may be, for example, 0.0015 or more, and 0.0020 or more. Or may be 0.0023 or more.
  • the dielectric constant (Dk) and the dielectric loss tangent (Df) are values based on the cavity resonator perturbation method, and more specifically, values measured by the method described in Examples. Further, in this specification, the term “dielectric constant” simply means the relative dielectric constant.
  • the present invention also provides a prepreg containing the resin composition of the present embodiment and a sheet-shaped fiber-reinforced base material.
  • the prepreg is formed by using the resin composition of the present embodiment and a sheet-shaped fiber-reinforced base material.
  • the sheet-shaped fiber-reinforced base material is impregnated or coated with the resin composition of the present embodiment and dried. Can be obtained.
  • the prepreg of the present embodiment can be produced by heating and drying in a drying oven at a temperature of 80 to 200 ° C. for 1 to 30 minutes and semi-curing (B-stage). it can.
  • the amount of the resin composition used can be determined so that the solid content concentration derived from the resin composition in the prepreg after drying is 30 to 90% by mass. When the solid content concentration is within the above range, a better moldability tends to be obtained when the laminate is used.
  • the sheet-shaped fiber-reinforced base material of the prepreg known materials used for various laminated plates for electrical insulating materials are used.
  • the material of the sheet-like reinforcing base material include inorganic fibers such as E glass, D glass, S glass, and Q glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and a mixture thereof.
  • These sheet-like reinforcing base materials have, for example, woven cloth, non-woven cloth, robink, chopped strand mat, surfacing mat and the like.
  • the thickness of the sheet-shaped fiber-reinforced base material is not particularly limited, and for example, one having a thickness of 0.02 to 0.5 mm can be used. Further, from the viewpoints of impregnation of the resin composition, heat resistance when formed into a laminated plate, moisture absorption resistance, and processability, those surface-treated with a coupling agent or the like, and those mechanically opened. Can be used.
  • the following hot melt method or solvent method can be adopted.
  • the hot melt method does not contain an organic solvent in the resin composition, and (1) a method in which a coated paper having good releasability from the resin composition is once coated and then laminated on a sheet-shaped reinforcing substrate, or (2) A method in which a sheet-shaped reinforcing base material is directly coated with a die coater.
  • the solvent method a resin composition is allowed to contain an organic solvent, a sheet-like reinforcing base material is immersed in the obtained resin composition, the sheet-like reinforcing base material is impregnated with the resin composition, and then dried. Is the way.
  • the present invention also provides a resin film containing the resin composition of this embodiment.
  • the resin film can be produced by applying a resin composition containing an organic solvent, that is, a resin varnish to a support and heating and drying.
  • the support include polyolefin films such as polyethylene, polypropylene and polyvinyl chloride; polyester films such as polyethylene terephthalate (hereinafter also referred to as “PET”) and polyethylene naphthalate; various plastics such as polycarbonate films and polyimide films. Examples include films.
  • PET polyethylene terephthalate
  • plastics such as polycarbonate films and polyimide films. Examples include films.
  • a metal foil such as a copper foil or an aluminum foil, a release paper, etc. may be used as the support.
  • the support may be subjected to surface treatment such as matte treatment and corona treatment. Further, the support may be subjected to a release treatment with a silicone resin-based release agent, an alkyd resin-based release agent, a fluororesin-based release agent, or the like.
  • the thickness of the support is not particularly limited, but is preferably 10 to 150 ⁇ m, more preferably 25 to 50 ⁇ m.
  • the method of applying the resin varnish to the support is not particularly limited, and for example, a coating device known to those skilled in the art such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, or a die coater can be used. These coating devices may be appropriately selected depending on the film thickness.
  • the drying temperature and the drying time may be appropriately determined according to the amount of the organic solvent used, the boiling point of the organic solvent used, and the like.
  • a resin film can be suitably formed by drying at 50 to 150 ° C. for about 3 to 10 minutes.
  • a laminated plate containing the prepreg of the present embodiment and a metal foil It is also possible to manufacture a laminated plate containing the prepreg of the present embodiment and a metal foil. Specifically, a metal foil is arranged on one side or both sides of one prepreg of this embodiment, or a metal foil is arranged on one side or both sides of a prepreg obtained by stacking two or more prepregs of this embodiment, Then, a laminate can be obtained by heat-pressing. A laminate having a metal foil is sometimes called a metal-clad laminate.
  • the metal of the metal foil is not particularly limited as long as it is used for electrical insulating materials, but from the viewpoint of conductivity, copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium.
  • the conditions of the heat and pressure molding are not particularly limited, but for example, the temperature can be 100 to 300 ° C., the pressure can be 0.2 to 10 MPa, and the time can be 0.1 to 5 hours. Further, the heat and pressure molding may be carried out by using a vacuum press or the like for holding the vacuum state for 0.5 to 5 hours.
  • the multilayer printed wiring board of the present embodiment contains at least one selected from the group consisting of the prepreg of the present embodiment, the resin film of the present embodiment, and the laminated plate of the present embodiment.
  • the multilayer printed wiring board of the present embodiment is perforated by a known method using at least one 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. It can be manufactured by carrying out processing, metal plating processing, circuit forming processing such as etching of metal foil, and multilayer adhesion processing.
  • the resin composition, prepreg, laminate, resin film and multilayer printed wiring board of the present embodiment can be suitably used for electronic devices handling high frequency signals of 10 GHz or higher.
  • the multilayer printed wiring board is useful as a multilayer printed wiring board for millimeter wave radar.
  • the number average molecular weight was measured by the following procedure. (Measurement method of number average molecular weight) The number average molecular weight was converted from the calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve is based on standard polystyrene: TSKstandard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, It was approximated by a cubic equation using the product name]. The measurement conditions of GPC are shown below.
  • reaction solution taken out a small amount of methanol / benzene mixed solvent (weight ratio 1: 1) was added dropwise, was subjected to FT-IR measurement of solids were purified by reprecipitation, 3,400 cm -1 vicinity of The appearance of peaks derived from primary amino groups was confirmed.
  • reaction concentration is 30% by mass
  • reaction concentration is 30% by mass
  • the above resin powder was put into a Teflon (registered trademark) sheet that was die-cut into a size of 1 mm thick x 50 mm long x 35 mm wide, and 18 ⁇ m thick low profile copper foil (Furukawa Electric Co., Ltd. Company-made, trade name: BF-ANP18) is placed so that the M-side is in contact with the charged resin powder, and heated and pressed under the conditions of a temperature of 230 ° C., a pressure of 2.0 MPa, and a time of 120 minutes to obtain a resin composition.
  • the product was cured to prepare a resin plate with double-sided copper foil (thickness of resin plate: 1 mm).
  • the thermal expansion coefficient (plate thickness direction, temperature range: 30 to 120 ° C) and glass transition temperature (Tg) were measured using a 5 mm square test piece obtained by etching the copper foil on both sides of a resin plate with double-sided copper foil, and then using a thermomechanical machine. It measured according to IPC (The Institute for Interconnecting and Packaging Electronic Circuits) standard with the measuring device (TMA) [made by TA Instruments Japan, Inc., Q400 (model number)].
  • each material in Table 3 is as follows.
  • Kraton (registered trademark) G1652 hydrogenated styrene thermoplastic elastomer (SEBS), melt flow rate 5.0 g / 10 min, styrene content 30%, hydrogenation rate 100% (trade name of Kraton Polymer Japan Co., Ltd.)
  • OP-935 Aluminum salt of dialkylphosphinic acid, metal salt of disubstituted phosphinic acid, phosphorus content: 23.5 mass% (Clariant, trade name) 1,3-phenylene bis (di2,6-xylenyl phosphate), phosphorus content: 9.0% by mass
  • the resin composition of the present invention has good compatibility, and a laminate produced from the resin composition has excellent heat resistance and dielectric properties particularly in a high frequency band of 10 GHz band or higher, and therefore has a frequency higher than 6 GHz. It is useful for a fifth generation mobile communication system (5G) antenna that uses radio waves in the band and a multilayer printed wiring board used for a millimeter wave radar that uses radio waves in the frequency band of 30 to 300 GHz.
  • 5G fifth generation mobile communication system

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne une composition de résine qui comprend (A) un dérivé de polyphénylène éther possédant un groupe comprenant une liaison éhtyléniquement insaturée, (B) un élément ou plus choisi dans un groupe constitué d'un composé maléimide ayant deux groupes maléimide N-substitué ou plus et d'un dérivé de ce composé, et (C) un agent de réticulation possédant deux liaisons éhtyléniquement insaturées ou plus. L'invention concerne également un pré-imprégné mettant en œuvre cette composition de résine, un stratifié, un film de résine, une carte de circuit imprimé multicouche et une carte de circuit imprimé multicouche pour radar à ondes millimétriques.
PCT/JP2019/043832 2018-11-08 2019-11-08 Composition de résine, pré-imprégné, stratifié, film de résine, carte de circuit imprimé multicouche, et carte de circuit imprimé multicouche pour radar à ondes millimétriques Ceased WO2020096036A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201980073342.7A CN112969749B (zh) 2018-11-08 2019-11-08 树脂组合物、预浸料、层叠板、树脂膜、多层印刷布线板和毫米波雷达用多层印刷布线板
JP2020555619A JP7501368B2 (ja) 2018-11-08 2019-11-08 樹脂組成物、プリプレグ、積層板、樹脂フィルム、多層プリント配線板及びミリ波レーダー用多層プリント配線板
KR1020217004912A KR20210090605A (ko) 2018-11-08 2019-11-08 수지 조성물, 프리프레그, 적층판, 수지 필름, 다층 프린트 배선판 및 밀리파 레이더용 다층 프린트 배선판

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-210912 2018-11-08
JP2018210912 2018-11-08

Publications (1)

Publication Number Publication Date
WO2020096036A1 true WO2020096036A1 (fr) 2020-05-14

Family

ID=70612093

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/043832 Ceased WO2020096036A1 (fr) 2018-11-08 2019-11-08 Composition de résine, pré-imprégné, stratifié, film de résine, carte de circuit imprimé multicouche, et carte de circuit imprimé multicouche pour radar à ondes millimétriques

Country Status (5)

Country Link
JP (1) JP7501368B2 (fr)
KR (1) KR20210090605A (fr)
CN (1) CN112969749B (fr)
TW (1) TWI834753B (fr)
WO (1) WO2020096036A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020117651A (ja) * 2019-01-28 2020-08-06 Ｍｃｐｐイノベーション合同会社 ミリ波モジュール及びその構成部品
JP2020169273A (ja) * 2019-04-03 2020-10-15 日立化成株式会社 樹脂組成物、プリプレグ、積層板、多層プリント配線板及び半導体パッケージ
TWI739443B (zh) * 2020-05-26 2021-09-11 台光電子材料股份有限公司 樹脂組合物及其製品
CN113969051A (zh) * 2020-07-23 2022-01-25 南亚塑胶工业股份有限公司 高频基板用树脂组合物及金属积层板
JP2022056768A (ja) * 2020-09-30 2022-04-11 リンテック株式会社 電磁波吸収体
JP7209070B1 (ja) 2021-08-02 2023-01-19 南亞塑膠工業股▲分▼有限公司 低誘電ゴム樹脂材料及び低誘電金属基板
WO2023013650A1 (fr) * 2021-08-05 2023-02-09 旭化成株式会社 Élément d'antenne
US20230128476A1 (en) * 2021-10-25 2023-04-27 Nan Ya Plastics Corporation Resin material and metal substrate
JP2024002870A (ja) * 2022-06-24 2024-01-11 南亞塑膠工業股▲分▼有限公司 ゴム樹脂材料及び金属基板
WO2024048055A1 (fr) * 2022-08-31 2024-03-07 ナミックス株式会社 Composition de résine, film adhésif, feuille de liaison pour adhérence intercouche, et composition de résine pour boîtier de semi-conducteur muni d'une antenne
JP2024074743A (ja) * 2022-11-21 2024-05-31 南亞塑膠工業股▲分▼有限公司 樹脂組成物
JP2024091236A (ja) * 2022-12-23 2024-07-04 南亞塑膠工業股▲分▼有限公司 樹脂組成物

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08208774A (ja) * 1995-02-03 1996-08-13 Asahi Chem Ind Co Ltd 強靱な難燃性ポリフェニレンエーテル系樹脂組成物
WO2002018493A1 (fr) * 2000-08-30 2002-03-07 Asahi Kasei Kabushiki Kaisha Composition de resine durcissable
JP2008095061A (ja) * 2006-02-17 2008-04-24 Hitachi Chem Co Ltd セミｉｐｎ型複合体の熱硬化性樹脂組成物並びにこれを用いたワニス、プリプレグ及び金属張積層板
JP2017071689A (ja) * 2015-10-07 2017-04-13 日立化成株式会社 樹脂組成物、プリプレグ、積層板、多層プリント配線板及び多層プリント配線板の製造方法
JP2018123230A (ja) * 2017-01-31 2018-08-09 三井化学株式会社 樹脂組成物およびその架橋体
JP2018131519A (ja) * 2017-02-15 2018-08-23 三菱瓦斯化学株式会社 樹脂組成物、樹脂シート及びプリント配線板

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5869046A (ja) 1981-10-21 1983-04-25 旭化成株式会社 積層板及びその成形法
JPS6118937A (ja) 1984-07-06 1986-01-27 Mitsubishi Electric Corp 工業用テレビカメラの照明装置
TWI441866B (zh) * 2006-02-17 2014-06-21 Hitachi Chemical Co Ltd A thermosetting resin composition of a semi-IPN type composite and a varnish, a prepreg and a metal laminate
JP5093059B2 (ja) * 2008-11-06 2012-12-05 日立化成工業株式会社 樹脂組成物、プリプレグ、積層板及びプリント基板
JP2011001473A (ja) * 2009-06-19 2011-01-06 Hitachi Chem Co Ltd 電子部品用絶縁材料
JP2011132481A (ja) * 2009-12-25 2011-07-07 Sumitomo Rubber Ind Ltd 高減衰組成物
JP5672788B2 (ja) * 2010-06-16 2015-02-18 日立化成株式会社 ポリアゾメチンを有するビスマレイミド誘導体とその製造方法、並びに熱硬化性樹脂組成物、プリプレグ及び積層板
WO2014181456A1 (fr) * 2013-05-10 2014-11-13 株式会社 日立製作所 Composition isolante, produit traité thermiquement et fil isolé associé
CN104031385B (zh) * 2014-06-19 2016-05-18 苏州生益科技有限公司 一种高频用树脂组合物及其半固化片和层压板
JP6468021B2 (ja) 2015-03-20 2019-02-13 株式会社リコー 立体造形用粉末材料、及び立体造形用材料セット、並びに、立体造形物、立体造形物の製造方法及び製造装置
TWI589628B (zh) * 2015-12-09 2017-07-01 中山台光電子材料有限公司 樹脂組合物
JP2019035035A (ja) * 2017-08-17 2019-03-07 堺化学工業株式会社 熱硬化性樹脂組成物及び熱硬化性樹脂
TWI740485B (zh) * 2020-05-04 2021-09-21 台灣中油股份有限公司 寡聚（2,6-二甲基苯醚）、其製備方法與固化物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08208774A (ja) * 1995-02-03 1996-08-13 Asahi Chem Ind Co Ltd 強靱な難燃性ポリフェニレンエーテル系樹脂組成物
WO2002018493A1 (fr) * 2000-08-30 2002-03-07 Asahi Kasei Kabushiki Kaisha Composition de resine durcissable
JP2008095061A (ja) * 2006-02-17 2008-04-24 Hitachi Chem Co Ltd セミｉｐｎ型複合体の熱硬化性樹脂組成物並びにこれを用いたワニス、プリプレグ及び金属張積層板
JP2017071689A (ja) * 2015-10-07 2017-04-13 日立化成株式会社 樹脂組成物、プリプレグ、積層板、多層プリント配線板及び多層プリント配線板の製造方法
JP2018123230A (ja) * 2017-01-31 2018-08-09 三井化学株式会社 樹脂組成物およびその架橋体
JP2018131519A (ja) * 2017-02-15 2018-08-23 三菱瓦斯化学株式会社 樹脂組成物、樹脂シート及びプリント配線板

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020117651A (ja) * 2019-01-28 2020-08-06 Ｍｃｐｐイノベーション合同会社 ミリ波モジュール及びその構成部品
JP2020169273A (ja) * 2019-04-03 2020-10-15 日立化成株式会社 樹脂組成物、プリプレグ、積層板、多層プリント配線板及び半導体パッケージ
JP7272068B2 (ja) 2019-04-03 2023-05-12 株式会社レゾナック 樹脂組成物、プリプレグ、積層板、多層プリント配線板及び半導体パッケージ
TWI739443B (zh) * 2020-05-26 2021-09-11 台光電子材料股份有限公司 樹脂組合物及其製品
CN113969051A (zh) * 2020-07-23 2022-01-25 南亚塑胶工业股份有限公司 高频基板用树脂组合物及金属积层板
JP2022022090A (ja) * 2020-07-23 2022-02-03 南亞塑膠工業股▲分▼有限公司 高周波基板用樹脂組成物及び金属積層板
JP7209764B2 (ja) 2020-07-23 2023-01-20 南亞塑膠工業股▲分▼有限公司 高周波基板用樹脂組成物及び金属積層板
JP2022056768A (ja) * 2020-09-30 2022-04-11 リンテック株式会社 電磁波吸収体
JP7457621B2 (ja) 2020-09-30 2024-03-28 リンテック株式会社 電磁波吸収体
JP7209070B1 (ja) 2021-08-02 2023-01-19 南亞塑膠工業股▲分▼有限公司 低誘電ゴム樹脂材料及び低誘電金属基板
JP2023021885A (ja) * 2021-08-02 2023-02-14 南亞塑膠工業股▲分▼有限公司 低誘電ゴム樹脂材料及び低誘電金属基板
US11859083B2 (en) 2021-08-02 2024-01-02 Nan Ya Plastics Corporation Low-dielectric rubber resin material and low-dielectric metal substrate
JP7232383B1 (ja) * 2021-08-05 2023-03-02 旭化成株式会社 アンテナ部材
US12057627B1 (en) 2021-08-05 2024-08-06 Asahi Kasei Kabushiki Kaisha Antenna member
WO2023013650A1 (fr) * 2021-08-05 2023-02-09 旭化成株式会社 Élément d'antenne
JP2023064041A (ja) * 2021-10-25 2023-05-10 南亞塑膠工業股▲分▼有限公司 樹脂材料及び金属基板
US20230128476A1 (en) * 2021-10-25 2023-04-27 Nan Ya Plastics Corporation Resin material and metal substrate
JP2024002870A (ja) * 2022-06-24 2024-01-11 南亞塑膠工業股▲分▼有限公司 ゴム樹脂材料及び金属基板
JP7617880B2 (ja) 2022-06-24 2025-01-20 南亞塑膠工業股▲分▼有限公司 ゴム樹脂材料及び金属基板
WO2024048055A1 (fr) * 2022-08-31 2024-03-07 ナミックス株式会社 Composition de résine, film adhésif, feuille de liaison pour adhérence intercouche, et composition de résine pour boîtier de semi-conducteur muni d'une antenne
JP2024074743A (ja) * 2022-11-21 2024-05-31 南亞塑膠工業股▲分▼有限公司 樹脂組成物
JP7507274B2 (ja) 2022-11-21 2024-06-27 南亞塑膠工業股▲分▼有限公司 樹脂組成物
US12398226B2 (en) 2022-11-21 2025-08-26 Nan Ya Plastics Corporation Resin composition
JP2024091236A (ja) * 2022-12-23 2024-07-04 南亞塑膠工業股▲分▼有限公司 樹脂組成物

Also Published As

Publication number Publication date
JP7501368B2 (ja) 2024-06-18
CN112969749A (zh) 2021-06-15
JPWO2020096036A1 (ja) 2021-10-21
CN112969749B (zh) 2024-02-02
TW202035562A (zh) 2020-10-01
KR20210090605A (ko) 2021-07-20
TWI834753B (zh) 2024-03-11

Similar Documents

Publication Publication Date Title
JP7501368B2 (ja) 樹脂組成物、プリプレグ、積層板、樹脂フィルム、多層プリント配線板及びミリ波レーダー用多層プリント配線板
JP6079930B2 (ja) Ｎ−置換マレイミド基を有するポリフェニレンエーテル誘導体、並びにそれを用いた熱硬化性樹脂組成物、樹脂ワニス、プリプレグ、金属張積層板、及び多層プリント配線板
JP7298623B2 (ja) 樹脂組成物、樹脂組成物の硬化物、プリプレグ、積層板、樹脂フィルム、多層プリント配線板、ミリ波レーダー用多層プリント配線板及びポリフェニレンエーテル誘導体
JP6705446B2 (ja) 熱硬化性樹脂組成物、プリプレグ、積層板及び多層プリント配線板
JP6863126B2 (ja) 樹脂組成物、プリプレグ、積層板、多層プリント配線板及び半導体パッケージ
JP7484909B2 (ja) マレイミド樹脂組成物、プリプレグ、積層板、樹脂フィルム、多層プリント配線板及び半導体パッケージ
JPWO2016175326A1 (ja) 樹脂組成物、プリプレグ、積層板及び多層プリント配線板
JP7631673B2 (ja) 樹脂組成物、プリプレグ、積層板、樹脂フィルム、多層プリント配線板及び半導体パッケージ
JP7552037B2 (ja) 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、半導体パッケージ及び樹脂組成物の製造方法
JP7272068B2 (ja) 樹脂組成物、プリプレグ、積層板、多層プリント配線板及び半導体パッケージ
KR20230108275A (ko) 말레이미드 수지 조성물, 프리프레그, 적층판, 수지 필름, 프린트 배선판 및 반도체 패키지
JP7106819B2 (ja) 樹脂ワニス、樹脂組成物、プリプレグ、積層板、多層プリント配線板及び樹脂ワニスの保存方法
JP2021187889A (ja) 熱硬化性樹脂組成物、プリプレグ、積層板、多層プリント配線板及び半導体パッケージ
JP2017066280A (ja) 熱硬化性樹脂組成物とその製造方法、並びに前記熱硬化性樹脂組成物を有するプリプレグ、金属張積層板、及び多層プリント配線板
JP2020169274A (ja) 樹脂組成物、プリプレグ、積層板、多層プリント配線板及び半導体パッケージ
JP2020169276A (ja) 樹脂組成物、プリプレグ、積層板、多層プリント配線板及び半導体パッケージ
TW202229442A (zh) 馬來醯亞胺樹脂組成物、預浸體、積層板、樹脂薄膜、印刷線路板及半導體封裝體
WO2024111380A1 (fr) Composition de résine, film de résine, préimprégné, stratifié, carte de circuit imprimé et boîtier de semi-conducteur
JP2020169275A (ja) 樹脂組成物、プリプレグ、積層板、多層プリント配線板及び半導体パッケージ
WO2024237106A1 (fr) Composition de résine, film de résine, préimprégné, stratifié, carte de circuit imprimé et boîtier de semi-conducteur
CN118742612A (zh) 树脂组合物、预浸料、层叠板、树脂膜、印刷布线板和半导体封装体
TW202227558A (zh) 馬來醯亞胺樹脂組成物、預浸體、樹脂薄膜、積層板、印刷線路板及半導體封裝體
JP2020169277A (ja) 樹脂組成物、プリプレグ、積層板、多層プリント配線板及び半導体パッケージ

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19883068

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020555619

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19883068

Country of ref document: EP

Kind code of ref document: A1

WWR Wipo information: refused in national office

Ref document number: 1020217004912

Country of ref document: KR

WWR Wipo information: refused in national office

Ref document number: 1020217004912

Country of ref document: KR

WWC Wipo information: continuation of processing after refusal or withdrawal

Ref document number: 1020217004912

Country of ref document: KR