WO2021112087A1 - 共重合体及びこれを含む積層体 - Google Patents

共重合体及びこれを含む積層体 Download PDF

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Publication number
WO2021112087A1
WO2021112087A1 PCT/JP2020/044699 JP2020044699W WO2021112087A1 WO 2021112087 A1 WO2021112087 A1 WO 2021112087A1 JP 2020044699 W JP2020044699 W JP 2020044699W WO 2021112087 A1 WO2021112087 A1 WO 2021112087A1
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WIPO (PCT)
Prior art keywords
mass
monomer
copolymer
olefin
aromatic
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
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PCT/JP2020/044699
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English (en)
French (fr)
Japanese (ja)
Inventor
荒井　亨
翔太 山本
西村　裕章
梓 八木
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Denka Co Ltd
Original Assignee
Denka 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
Priority to JP2021562661A priority Critical patent/JP7378494B2/ja
Priority to KR1020227018349A priority patent/KR102882289B1/ko
Priority to CN202411309385.XA priority patent/CN119161537A/zh
Priority to EP24205839.4A priority patent/EP4530315A1/en
Priority to US17/781,499 priority patent/US12091531B2/en
Priority to CN202080082954.5A priority patent/CN114746272A/zh
Application filed by Denka Co Ltd filed Critical Denka Co Ltd
Priority to EP20895908.0A priority patent/EP4071209A4/en
Publication of WO2021112087A1 publication Critical patent/WO2021112087A1/ja
Anticipated expiration legal-status Critical
Priority to JP2023185893A priority patent/JP7676503B2/ja
Priority to US18/807,116 priority patent/US20240400808A1/en
Ceased legal-status Critical Current

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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • 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
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/12—Copper
    • 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
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • 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
    • B32B2325/00—Polymers of vinyl-aromatic compounds, e.g. polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • 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
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/08—Copolymers of styrene
    • 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
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2471/12—Polyphenylene oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates

Definitions

  • the present invention relates to a copolymer and a laminate containing a resin layer containing the copolymer and a metal foil.
  • Fluorine-based resins such as perfluoroethylene have excellent characteristics of low dielectric constant, low dielectric loss and heat resistance, but molding processing and film molding are difficult and device suitability is low. In addition, there is a problem in the adhesive strength of the wiring with the copper foil.
  • substrates and insulating materials using post-curable resins such as epoxy resins, unsaturated polyester resins, polyimide resins, and phenol resins have been widely used due to their heat resistance and easy handling, but their dielectric constants and dielectric losses are high. It is relatively expensive, and improvement is desired as an insulating material for high frequencies (Patent Document 2).
  • Patent Document 3 A graft composed of olefin-based and styrene-based polymer segments, or an electrically insulating material composed of a block copolymer has been proposed (Patent Document 3).
  • This material focuses on the essential low dielectric constant and low dielectric loss of olefin and styrene hydrocarbon polymers.
  • the production method is to perform general graft polymerization on commercially available polyethylene or polypropylene in the presence of styrene monomer, divinylbenzene monomer and radical polymerization initiator. With such a method, the graft efficiency does not increase and the polymer is uniform. There is a problem that the sex is not enough.
  • the obtained polymer contains a gel, and has a problem of poor processability and filling property.
  • This material is a thermoplastic resin and does not have sufficient heat resistance, and it is necessary to add a heat-resistant resin such as 4-methyl-1-pentene. It is difficult to apply this material to a molding method in which it is applied or filled in a predetermined place and then cured.
  • Patent Document 4 describes an insulating layer made of a crosslinked structure containing a hydrocarbon compound having a plurality of aromatic vinyl groups as a crosslinked component.
  • the cured product of the present cross-linking component specifically described in the examples is rigid, and it is considered difficult to fill a large amount of the filler.
  • Patent Document 5 shows a cured product obtained from a specific polymerization catalyst and composed of an ethylene-olefin (aromatic vinyl compound) -polyene copolymer and a non-polar vinyl compound copolymer having a specific composition and composition. There is.
  • the cured product specifically described in the examples of Patent Document 5 has the characteristics of low dielectric constant and low dielectric loss tangent, but is extremely soft, and therefore improves mechanical strength such as elastic modulus at normal temperature and high temperature. It is necessary to.
  • For thin film insulating materials such as FPC and FCCL interlayer insulating materials and coverlay applications, it is preferable to improve dimensional stability such as thickness during the mounting process or during use after mounting.
  • Patent Document 6 shows a cured product obtained from the same specific polymerization catalyst and composed of an ethylene-olefin (aromatic vinyl compound) -polyene copolymer and a non-polar vinyl compound copolymer having a specific composition and composition.
  • Patent Document 7 also describes a cured product of a composition containing a similar copolymer, but the cured product of the composition specifically described in Examples has adhesion to a metal foil, particularly a copper foil. There is room for improvement.
  • the curable composition disclosed in Patent Documents 5, 6 and 7 contains a relatively large amount of monomer components (aromatic vinyl compound and aromatic polyene) and is varnish-like. Therefore, not only is there an odor, but there is also a problem that a B stage sheet (semi-cured product sheet) cannot be easily manufactured. These curable compositions have a problem that the production equipment becomes complicated.
  • the present invention can provide the following aspects.
  • the number average molecular weight of the copolymer is 5,000 or more, preferably 20,000 or more and 100,000 or less.
  • the aromatic vinyl compound monomer is an aromatic vinyl compound having 8 or more and 20 or less carbon atoms, and the content of the aromatic vinyl compound monomer unit is 10% by mass or more and less than 60% by mass.
  • the aromatic polyene is one or more selected from polyenes having a plurality of vinyl groups and / or vinylene groups in the molecule and having 5 or more and 20 or less carbon atoms, and the vinyl group and / or derived from the aromatic polyene unit.
  • the content of vinylene groups is 1.5 or more and less than 20 per number average molecular weight.
  • the olefin is one or more selected from olefins having 2 or more and 20 or less carbon atoms, and the olefin is ethylene alone, or an ⁇ -olefin monomer other than ethylene with respect to the ethylene monomer component contained in the olefin.
  • the mass ratio of the components is 1/7 or less, and the total of the olefin monomer unit, the aromatic vinyl compound monomer unit, and the aromatic polyene monomer unit is 100% by mass.
  • An olefin-aromatic vinyl compound-aromatic polyene copolymer that satisfies the following conditions (1) to (4).
  • the number average molecular weight of the copolymer is 5,000 or more, preferably 20,000 or more and 100,000 or less.
  • the aromatic vinyl compound monomer is an aromatic vinyl compound having 8 or more and 20 or less carbon atoms, and the content of the aromatic vinyl compound monomer unit is 10% by mass or more and less than 60% by mass.
  • the aromatic polyene is one or more selected from polyenes having a plurality of vinyl groups and / or vinylene groups in the molecule and having 5 or more and 20 or less carbon atoms, and the vinyl group and / or derived from the aromatic polyene unit.
  • the content of vinylene groups is 1.5 or more and less than 20 per number average molecular weight.
  • the olefin is one or more selected from olefins having 2 or more and 20 or less carbon atoms, and the olefin is ethylene alone, or an ⁇ -olefin monomer other than ethylene with respect to the ethylene monomer component contained in the olefin.
  • the mass ratio of the components is 1/7 or less, and the total of the olefin monomer unit, the aromatic vinyl compound monomer unit, and the aromatic polyene monomer unit is 100% by mass.
  • copolymer of the present invention or the resin layer containing the same and the cured product (cured product) of the laminate containing the metal foil have high adhesiveness to the metal foil and excellent low dielectric properties, and are at room temperature or high temperature. Can show high mechanical properties.
  • the term "sheet” also includes the concept of a film. Moreover, even if it is described as a film in this specification, it has the same meaning as a sheet.
  • the "resin layer” is a layer containing the composition of the present invention, and its shape is arbitrary. Generally, it is in the form of a sheet, and the size in the horizontal direction and the thickness in the vertical direction with respect to the metal foil are arbitrary.
  • the resin layer may also contain other materials contained in a known insulating layer such as a filler and a flame retardant, or may be a fiber or non-woven fabric such as glass or ceramics impregnated with a composition.
  • the shape is not limited to a sheet shape, and may be a hemispherical shape such as a potting material or a striped shape, and the shape thereof is arbitrary.
  • the metal foil is a concept including wiring of the metal, and the shape is arbitrary, and may be foil-like, linear, or dot-like.
  • the metal foil a commercially available metal foil may be used, or it may be formed through an arbitrary process such as vapor deposition or plating.
  • the numerical range in the present specification shall include the upper limit value and the lower limit value.
  • the content may be referred to as the content.
  • the laminated body refers to a body having a structure including at least the resin layer and the metal foil which are in contact with each other and adhered to each other, and the laminated form thereof is arbitrary.
  • at least the resin layer and the metal foil may be laminated in a layered manner, and the number of layers is arbitrary.
  • the resin layer and the metal leaf may be adjacent to each other, or may include another layer intervening.
  • Examples of the laminated body include CCL, FCCL, PC, FPC and the like.
  • composition may be referred to as a resin composition or a curable composition.
  • the composition of the present invention contains the olefin-aromatic vinyl compound-aromatic polyene copolymer having a certain range of composition and molecular weight range, and also includes a "hardener”, a “monomer”, and an "added resin”. , "Solar”, “filler”, “flame retardant”, “surface modifier” may contain one or more selected.
  • ⁇ Olefin-Aromatic Vinyl Compound-Aromatic Polyene Copolymer Methods for producing a general olefin-aromatic vinyl compound-aromatic polyene copolymer that can be used in the present invention are described in, for example, JP-A-2009-161743, JP-A-2010-280771 and WO00. / 37517.
  • the olefin-aromatic vinyl compound-aromatic polyene copolymer (hereinafter, may be simply referred to as "copolymer”) satisfies all of the following conditions (1) to (4).
  • the number average molecular weight of the copolymer is 5,000 or more, preferably 20,000 or more and 100,000 or less.
  • the aromatic vinyl compound monomer is an aromatic vinyl compound having 8 or more and 20 or less carbon atoms, and the content of the aromatic vinyl compound monomer unit is 10% by mass or more and less than 60% by mass.
  • the aromatic polyene is one or more selected from polyenes having a plurality of vinyl groups and / or vinylene groups in the molecule and having 5 or more and 20 or less carbon atoms, and the vinyl group and / or derived from the aromatic polyene unit.
  • the content of vinylene groups is 1.5 or more and less than 20 per number average molecular weight.
  • the olefin is one or more selected from olefins having 2 or more and 20 or less carbon atoms, and the olefin is ethylene alone, or an ⁇ -olefin monomer other than ethylene with respect to the ethylene monomer unit contained in the olefin.
  • the mass ratio of the units is 1/7 or less, and the total of the olefin monomer unit, the aromatic vinyl compound monomer unit, and the aromatic polyene monomer unit is 100% by mass.
  • the number average molecular weight of this copolymer is 5,000 or more, preferably 20,000 or more and 100,000 or less, and further preferably 30,000 or more and 100,000 or less.
  • the present olefin-aromatic vinyl compound-aromatic polyene copolymer can be obtained by copolymerizing each monomer of an olefin, an aromatic vinyl compound, and an aromatic polyene.
  • the olefin monomer unit content is preferably 35% by mass or more, and particularly preferably 45% by mass or more.
  • the total of the olefin monomer unit, the aromatic vinyl compound monomer unit, and the aromatic polyene monomer unit is 100% by mass.
  • the olefin monomer unit content is 35% by mass or more, the toughness (elongation) of the finally obtained cured product is improved, cracks during curing, impact resistance of the cured product is lowered, and heat of the cured product is reduced. No cracking occurs during the cycle test.
  • the preferable olefin monomer unit content is 90% by mass or less.
  • the olefin monomer is one or more selected from ⁇ -olefins having 2 or more and 20 or less carbon atoms and cyclic olefins having 5 or more and 20 or less carbon atoms, and substantially does not contain oxygen, nitrogen, or halogen, and is composed of carbon and hydrogen. It is a constituent compound.
  • ⁇ -olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decane, 1-dodecane, 4-methyl-1-pentene, 3,5,5. -Trimethyl-1-hexene can be exemplified.
  • Examples of the cyclic olefin having 5 or more and 20 or less carbon atoms include norbornene and cyclopentene.
  • the olefin is preferably a combination of ethylene and an ⁇ -olefin or a cyclic olefin other than ethylene, or ethylene alone.
  • the olefin is ethylene alone or the mass ratio of the ⁇ -olefin monomer component to the ethylene monomer component contained in the olefin is 1/7 or less, more preferably 1/10 or less, the obtained cured product is obtained. It is preferable because the breaking strength (breaking point strength) and breaking elongation (breaking point elongation) can be increased and the peel strength from copper foil and copper wiring can be increased.
  • the content of the ⁇ -olefin monomer unit other than ethylene contained in the copolymer is 6% by mass or less, most preferably 4% by mass or less, or the olefin is ethylene alone.
  • the peel strength from the copper foil and the copper wiring can be further increased, which is more preferable.
  • the glass transition temperature of the finally obtained cured product of ethylene- ⁇ -olefin-aromatic vinyl compound-aromatic polyene chain depends on the type and content of ⁇ -olefin. It can be freely adjusted in the range of 60 ° C to -5 ° C.
  • the aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and examples thereof include styrene, paramethylstyrene, paraisobutylstyrene, various vinylnaphthalene, and various vinylanthracene.
  • the aromatic polyene monomer is a polyene having a plurality of vinyl groups and / or vinylene groups in its molecule and having 5 or more and 20 or less carbon atoms, and preferably 8 or more and 20 or less carbon atoms.
  • the aromatic polyene monomer is preferably a polyene having a plurality of vinyl groups in the molecule and having 8 or more and 20 or less carbon atoms, and more preferably various divinylbenzenes of ortho, meta, and para, or a mixture thereof, and divinylnaphthalene.
  • a bifunctional aromatic vinyl compound described in JP-A-2004-087639, for example, 1,2-bis (vinylphenyl) ethane (abbreviation: BVPE) can also be used.
  • various divinylbenzenes of ortho, meta and para, or mixtures thereof are preferably used, and most preferably a mixture of meta and paradivinylbenzene is used.
  • divinylbenzenes are referred to as divinylbenzenes.
  • divinylbenzenes are used as the aromatic polyene, it is preferable because the curing efficiency is high and the curing is easy when the curing treatment is performed.
  • Other monomers of the above olefin, aromatic vinyl compound, and aromatic polyene include an olefin containing a polar group such as an oxygen atom and a nitrogen atom, an aromatic vinyl compound containing an oxygen atom and a nitrogen atom, or the like.
  • Aromatic polyene containing oxygen atom, nitrogen atom and the like may be contained, but the total mass of the monomer containing these polar groups is preferably 10% by mass or less of the total mass of the present composition, and is preferably 3% by mass. The following are more preferable, and it is most preferable that the monomer containing a polar group is not contained.
  • the low dielectric property low dielectric constant / low dielectric loss
  • the number average molecular weight of this copolymer is 5,000 or more, preferably 20,000 or more and 100,000 or less, and particularly preferably 30,000 or more and 100,000 or less.
  • the number average molecular weight is 5000 or more, preferably 20,000 or more, good physical properties such as high breaking point strength and high breaking point elongation can be easily imparted to the finally obtained cured product, and toughness is imparted. Easy to use and preferable.
  • the tensile breaking point elongation (tensile breaking elongation) is 30% or more.
  • the content of the aromatic vinyl compound monomer unit contained in this copolymer is 10% by mass or more and less than 60% by mass.
  • the glass transition temperature of the cured product of the finally obtained composition becomes around room temperature, and the toughness at low temperature may decrease. Alternatively, the elongation may decrease, which is not preferable.
  • the peel strength from the copper foil may be lower than that when it is less than 60% by mass.
  • the content of the aromatic vinyl compound monomer unit contained in the copolymer is particularly preferably 10% by mass or more and 55% by mass or less. If the content of the aromatic vinyl compound monomer unit is less than 10% by mass, the aromaticity of the copolymer is lowered, the compatibility with the flame retardant and the filler is deteriorated, and the flame retardant bleeds out. In some cases, the filler may not be filled. Further, when the content of the aromatic vinyl compound monomer unit is 10% by mass or more, a cured product of a composition having high peeling strength from a metal foil (particularly copper foil) or copper wiring can be obtained.
  • the content of vinyl group and / or vinylene group derived from aromatic polyene unit (hereinafter, the content may also be referred to as content) is 1.5 or more per number average molecular weight of the copolymer. Less than, preferably 3 or more and less than 20. If the number is less than 1.5, the cross-linking efficiency is low, and it may be difficult to increase the storage elastic modulus at high temperatures.
  • the content of vinyl group and / or vinylene group may be collectively referred to as "vinyl group content” below.
  • the vinyl group content derived from aromatic polyene units (divinylbenzene units) per number average molecular weight in this copolymer is a standard polystyrene-equivalent number determined by a GPC (gel permeation chromatography) method known to those skilled in the art.
  • the average molecular weight (Mn) with the vinyl group content or vinylene group content derived from the aromatic polyene unit obtained by 1 H-NMR measurement.
  • Mn average molecular weight
  • the intensity of each peak area obtained by 1 H-NMR measurement the vinyl group content derived from the aromatic polyene unit in the copolymer is 0.095% by mass, and the standard polystyrene conversion number by GPC measurement is obtained.
  • the average molecular weight is 68,000
  • the molecular weight of the vinyl group derived from the aromatic polyene unit in the number average molecular weight is 64.8, which is the product of these, and by dividing this by the formula weight 27 of the vinyl group, 2. It becomes 4.
  • the content of vinyl groups derived from aromatic polyene units per number average molecular weight in this copolymer is 2.4.
  • the attribution of peaks obtained by 1 H-NMR measurement of the copolymer is known in the literature. Further, a method for obtaining the composition of the copolymer from the comparison of the peak areas obtained by 1 1 H-NMR measurement is also known.
  • the content of the divinylbenzene unit in the copolymer is determined from the peak intensity of the vinyl group derived from the divinylbenzene unit (according to 1 H-NMR measurement). That is, from the vinyl group content derived from the divinylbenzene unit, the content of the divinylbenzene unit is determined by assuming that one vinyl group is derived from one divinylbenzene unit in the copolymer.
  • the olefin-aromatic vinyl compound-aromatic polyene copolymer as the olefin-aromatic vinyl compound-aromatic polyene copolymer, the ethylene-styrene-divinylbenzene copolymer, the ethylene-propylene-styrene-divinylbenzene copolymer, and the ethylene-1-hexene- Examples thereof include a styrene-divinylbenzene copolymer and an ethylene-1-octene-styrene-divinylbenzene copolymer.
  • the curing agent that can be used in the composition of the present invention for example, a curable resin
  • a known curing agent that can be conventionally used for polymerization or curing of aromatic polyenes and aromatic vinyl compounds.
  • examples of such a curing agent include a radical polymerization initiator, a cationic polymerization initiator, and an anionic polymerization initiator, but a radical polymerization initiator can be preferably used.
  • it is an organic peroxide-based (peroxide), azo-based polymerization initiator, or the like, and can be freely selected depending on the application and conditions. Catalogs with examples of organic peroxides can be found on the NOF website, for example.
  • Examples of the curing agent using the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanionic polymerization initiator.
  • a photopolymerization initiator can be obtained from, for example, Tokyo Chemical Industry Co., Ltd. Furthermore, it can be cured by radiation or the electron beam itself. It is also possible to carry out cross-linking and curing by thermal polymerization of the contained raw materials without containing a curing agent.
  • the amount of the curing agent used is not particularly limited, but is generally preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the composition.
  • a curing agent such as an organic peroxide-based (peroxide) or azo-based polymerization initiator
  • the curing treatment is performed at an appropriate temperature and time in consideration of its half-life.
  • the conditions in this case are arbitrary according to the curing agent, but generally, a temperature range of about 50 ° C. to 180 ° C. is suitable.
  • the monomer that can be used in the composition of the present invention is 1 to 500 parts by mass, preferably 1 to 200 parts by mass with respect to 100 parts by mass of the copolymer.
  • the amount of the monomer is 200 parts by mass or less, it is preferable that the toughness is easily imparted to the finally obtained cured product.
  • the tensile break point elongation of the cured product is 30% or more.
  • the smaller the amount of monomer, the easier it is to handle preferably 30 parts by mass or less, and particularly preferably 10 parts by mass or less with respect to 100 parts by mass of the copolymer.
  • the monomers that can be suitably used in the composition of the present invention are aromatic vinyl compound monomers, aromatic polyene monomers, and / or polar monomers, and the molecular weight thereof is preferably less than 1000. More preferably less than 500.
  • the monomer that can be suitably used in the composition of the present invention may be any monomer that can be cured by various curing agents, and is preferably a monomer that can be polymerized by a radical polymerization initiator.
  • the aromatic vinyl compound and aromatic polyene are more preferable.
  • BVPE (1,2-bis (vinylphenyl) ethane) described in JP-A-2003-212941 can also be preferably used.
  • the amount of the aromatic polyene monomer is preferably 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the copolymer.
  • a relatively small amount of polar monomer can be used for the purpose of imparting adhesiveness to other materials required as an insulating material or improving the crosslink density.
  • the above-mentioned polar monomers include various maleimides, bismaleimides, maleic anhydride, glycidyl (meth) acrylate, triallyl isocyanurate (TAIC), tri (meth) acrylic isocyanurate, and trimethylolpropane tri (meth).
  • Maleimides and bismaleimides that can be used in the present invention are described in, for example, International Publication WO2016 / 114287 and Japanese Patent Application Laid-Open No. 2008-291227, and can be purchased from, for example, Daiwa Kasei Kogyo Co., Ltd. and Designer molecules inc.
  • these maleimide group-containing compounds bismaleimides are preferable from the viewpoints of solubility in an organic solvent, high frequency characteristics, high adhesiveness to a conductor, moldability of a prepreg, and the like.
  • Equation (d1) In the formula, R 2 represents a divalent organic group having an aromatic ring.
  • Examples of the compound represented by the formula (d1) include a compound represented by the following formula (d2).
  • Equation (d2) (In the formula, R 3 represents a single bond or methylene, R 4 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer from 0 to 4.)
  • Examples of the compound represented by the formula (d2) include bismaleimide BMI-3000H (m-phenylene bismaleimide) manufactured by Daiwa Kasei Kogyo Co., Ltd.
  • Bismaleimides may be used as a polyaminobismaleimide compound.
  • the polyaminobismaleimide compound is obtained, for example, by carrying out a Michael addition reaction of a compound having two maleimide groups at the terminal and an aromatic diamine compound having two primary amino groups in the molecule.
  • a polar monomer having a polyfunctional group of two or more functional groups and bismaleimides, triallyl isocyanurate (TAIC), trimethylolpropane tri ( Meta) acrylate can be exemplified.
  • TAIC triallyl isocyanurate
  • Meta trimethylolpropane tri
  • the amount of the polar monomer used in the composition of the present invention is in the range of 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the copolymer.
  • the dielectric constant and dielectric loss tangent of the obtained cured product become low.
  • the permittivity is lower than 3.0 and the dielectric loss tangent is lower than 0.005.
  • the composition of the present invention is a single or a plurality of resins selected from hydrocarbon-based elastomers, polyphenylene ethers, and aromatic polyene-based resins based on 100 parts by mass of the copolymer contained therein (in the present specification, simply "additional resin”). ) Can preferably be contained in a total of 1 to 500 parts by mass.
  • the amount of the hydrocarbon-based elastomer used in the composition of the present invention is preferably 1 to 500 parts by mass, more preferably 1 to 200 parts by mass with respect to 100 parts by mass of the copolymer.
  • the hydrocarbon-based elastomer that can be suitably used for the composition of the present invention has a number average molecular weight of 20,000 or more, preferably 30,000 or more, and is an ethylene-based or propylene-based elastomer, a conjugated diene-based polymer, or an aromatic.
  • the number average molecular weight of the hydrocarbon-based elastomer is 1000 or more, more preferably 2000 or more, still more preferably 20,000 or more, and most preferably 30,000 or more.
  • the number average molecular weight of the hydrocarbon-based elastomer is preferably 80,000 or less, more preferably 60,000 or less.
  • the ethylene-based elastomer include ethylene- ⁇ -olefin copolymers such as an ethylene-octene copolymer and an ethylene-1-hexene copolymer, EPR, and EPDM
  • examples of the propylene-based elastomer include atactic polypropylene and low steric polymer. Examples thereof include propylene- ⁇ -olefin copolymers such as regular polypropylene and propylene-1-butene copolymers.
  • Examples of the conjugated diene polymer include polybutadiene and 1,2-polybutadiene.
  • Examples of aromatic vinyl compound-conjugated diene-based block copolymers or random copolymers, and hydrides (hydrogenates) thereof include SBS, SIS, SEBS, SEPS, SEEPS, and SEEBS.
  • the 1,2-polybutadiene that can be preferably used can be obtained, for example, as a product of JSR Corporation, or can be obtained from Nippon Soda Corporation under the product names of liquid polybutadiene: product names B-1000, 2000 and 3000. Can be done.
  • a copolymer containing a 1,2-polybutadiene structure that can be preferably used
  • "Ricon 100" manufactured by TOTAL CRAY VALLEY can be exemplified.
  • the composition of the present invention can be handled and molded in an uncured state.
  • the amount used is preferably 1 to 100 parts by mass, more preferably 1 to 30 parts by mass, and particularly preferably 1 with respect to 100 parts by mass of the copolymer. The range is from 20 parts by mass.
  • polyphenylene ether As the polyphenylene ether, a commercially available known polyphenylene ether can be used.
  • the number average molecular weight of the polyphenylene ether is arbitrary, and the number average molecular weight is preferably 10,000 or less, most preferably 5,000 or less in consideration of the molding processability of the composition.
  • the number average molecular weight is preferably 500 or more, most preferably 1000 or more. Further, in the case of addition for the purpose of curing the composition of the present invention, it is preferable that the molecular end is modified, and / or it is preferable that a plurality of functional groups are contained in one molecule.
  • the functional group examples include functional groups such as an allyl group, a vinyl group and an epoxy group, most preferably a radically polymerizable functional group, and a vinyl group, particularly a (meth) acrylic group or an aromatic vinyl group. .. That is, in the composition of the present invention, a bifunctional polyphenylene ether in which both ends of the molecular chain are modified with radically polymerizable functional groups is particularly preferable.
  • a bifunctional polyphenylene ether in which both ends of the molecular chain are modified with radically polymerizable functional groups is particularly preferable.
  • examples of such polyphenylene ethers include Noyl (registered trademark) SA9000 manufactured by SABIC, and particularly preferably bifunctional polyphenylene ether oligomer (OPE-2St) manufactured by Mitsubishi Gas Chemical Company.
  • the amount of the polyphenylene ether used in the composition of the present invention is preferably 1 to 200 parts by mass, and more preferably 30 to 100 parts by mass with respect to 100 parts by
  • the aromatic polyene-based resin includes a divinylbenzene-based reactive multi-branched copolymer (PDV) manufactured by Nittetsu Chemical & Materials Co., Ltd.
  • PDV divinylbenzene-based reactive multi-branched copolymer
  • Such PDVs are described, for example, in the literature "Synthesis of Polyfunctional Aromatic Vinyl Copolymers and Development of New IPN Type Low Dielectric Loss Materials Using It" (Honest Kawabe et al., Journal of Electronics Packaging Society, p.125, Vol.12). No. 2 (2009)).
  • an aromatic polyene polymer resin containing the above-mentioned aromatic polyene monomer as a main constituent unit can also be mentioned.
  • solvent An appropriate solvent may be added to the composition of the present invention, if necessary.
  • the amount used is not particularly limited.
  • the solvent is used to adjust the viscosity and fluidity of the composition.
  • a solvent is preferably used.
  • the amount used as a varnish is generally in the range of 50 to 1000 parts by mass with respect to 100 parts by mass of the copolymer.
  • the solvent cyclohexane, toluene, ethylbenzene, xylene, tetralin, acetone, limonene, mixed alkane, mixed aromatic solvent and the like are preferably used.
  • the amount of solvent is small, less than 1 part by mass with respect to 100 parts by mass of the copolymer of the present invention, and the formability and handling of the composition before curing as a thermoplastic resin.
  • a solvent is substantially not used. Not substantially used is preferably 5 parts by mass or less, more preferably 1 part by mass or less, and most preferably 0 parts by mass.
  • the composition of the present invention may further contain one or more selected from fillers, flame retardants, and surface modifiers with respect to the above compositions.
  • the composition of the present invention may be a matrix of cured products and may contain one or more selected from these fillers, flame retardants and surface modifiers in order to be excellent in filling properties of other materials when cured. Even after being cured, the cured product can easily exhibit impact resistance and toughness.
  • a known inorganic or organic filler can be added. These fillers are added for the purpose of controlling the coefficient of thermal expansion, controlling the thermal conductivity, and reducing the price, and the amount used thereof is arbitrary depending on the purpose.
  • a known surface modifier for example, a silane coupling agent.
  • boron nitride (BN) or silica, particularly molten silica is preferable as the inorganic filler. ..
  • the dielectric constant becomes particularly high when a large amount is added and blended. Therefore, a filler of less than 500 parts by mass, more preferably less than 400 parts by mass, is preferably used with respect to 100 parts by mass of the copolymer. Use. Further, in order to improve and improve the low dielectric property (low dielectric constant, low dielectric loss tangent), a hollow filler or a filler having a shape with many voids may be added.
  • organic filler such as high molecular weight or ultra high molecular weight polyethylene instead of the inorganic filler. It is preferable that the organic filler is crosslinked by itself from the viewpoint of heat resistance, and it is preferable that the organic filler is used in the form of fine particles or powder. These organic fillers can suppress an increase in dielectric constant and dielectric loss tangent.
  • the amount of the organic filler used is preferably 10 to 70% by volume, more preferably 30 to 50% by volume, based on 100 parts by mass of the composition.
  • the amount of the filler used is most preferably 1 part by mass or more and less than 400 parts by mass with respect to 100 parts by mass of the copolymer.
  • the composition of the present invention is mixed with a high dielectric constant insulator filler having a dielectric constant of preferably 3 to 10000, more preferably 5 to 10000 at 1 GHz and dispersed to suppress an increase in dielectric loss tangent (dielectric loss).
  • a high dielectric constant insulator filler having a dielectric constant of preferably 3 to 10000, more preferably 5 to 10000 at 1 GHz and dispersed to suppress an increase in dielectric loss tangent (dielectric loss).
  • a high dielectric constant insulator filler having a dielectric constant of preferably 3 to 10000, more preferably 5 to 10000 at 1 GHz and dispersed to suppress an increase in dielectric loss tangent (dielectric loss).
  • the high dielectric constant and low dielectric loss tangent insulating layer is suitable for applications such as capacitors, inductors for resonant circuits, filters, and antennas.
  • Examples of the high dielectric constant insulator filler used in the present invention include inorganic fillers and metal particles subjected to insulation treatment. Specific examples are known high dielectric constant inorganic fillers such as barium titanate and strontium titanate, and other examples are specifically described in, for example, Japanese Patent Application Laid-Open No. 2004-087639.
  • a known flame retardant can be added to the composition of the present invention.
  • the preferred flame retardant is a known organic phosphorus-based flame retardant such as a phosphoric acid ester or a condensate thereof, a known bromine-based flame retardant, or red phosphorus.
  • a compound having a plurality of xylenyl groups in the molecule is preferable from the viewpoint of flame retardancy and low dielectric loss tangent property.
  • antimony compounds such as antimony trioxide, antimony tetroxide, antimony pentoxide, and sodium antimonate or melamine, triaryl-1,3,5-triazine-2,3,4- Nitrogen-containing compounds such as 1H, 3H, 5H) -trione, 2,4,6-triaryloxy 1,3,5-triazine may be used.
  • the total amount of these flame-retardant agents and flame-retardant aids is usually preferably 1 to 100 parts by mass with respect to 100 parts by mass of the composition. Further, 30 to 200 parts by mass of the polyphenylene ether (PPE) -based resin having a low dielectric constant and excellent flame retardancy may be used with respect to 100 parts by mass of the flame retardant.
  • PPE polyphenylene ether
  • the composition of the present invention may contain various surface modifiers for the purpose of improving adhesion to fillers, copper plates, and wiring.
  • the amount of the surface modifier used is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the composition of the present invention other than the surface modifier.
  • Examples of the surface modifier include various silane coupling agents and titanate-based coupling agents. As various silane coupling agents and titanate-based coupling agents, one or more may be used.
  • the flame retardant, the filler, and the surface modifier are further blended.
  • the ratio By changing the ratio, the fluidization temperature of the curable resin or the composition can be adjusted according to the purpose and molding method.
  • the composition of the present invention can take the product form of "thermoplastic composition” and "varnish".
  • thermoplastic is preferably uncured, but also includes the concept of a semi-cured state (B stage sheet or the like) or a partially cured state.
  • the composition of the present invention may be a single or a plurality selected from a copolymer and a curing agent, as well as a monomer, a solvent, an additive resin, a filler, a flame retardant, and a surface modifier, if necessary. Is obtained by mixing / melting or melting, but any known method can be adopted as the method of mixing / melting / melting.
  • the composition of the present invention uses a copolymer having a molecular weight in a certain range or more.
  • a relatively small amount of monomer of a certain amount or less is contained, the properties of the thermoplastic resin can be exhibited because it mainly contains a copolymer. Therefore, under conditions that do not cause cross-linking, it can be molded into the shape of a sheet, tube, strip, pellet, etc. in a substantially uncured state by a known molding method as a thermoplastic resin, and then cross-linked (cured). Can be done.
  • the number average molecular weight of the copolymer used in the thermoplastic composition is preferably 20,000 or more and 100,000 or less, and more preferably 30,000 or more and 100,000 or less.
  • the amount of the monomer used in the thermoplastic composition of the present invention is 10 parts by mass or less with respect to 100 parts by mass of the copolymer. More preferably, 0.3 parts by mass or more is an aromatic polyene monomer such as divinylbenzene or BVPE with respect to 100 parts by mass of the copolymer. Most preferably, an aromatic polyene monomer such as divinylbenzene or BVPE is substantially used as the monomer. Furthermore, it is preferred that the thermoplastic composition or composition is substantially free of solvent. By satisfying all of these conditions, the thermoplastic composition of the present invention can be easily molded as a thermoplastic resin in an uncured state.
  • thermoplastic composition of the present invention it is as follows.
  • the hydrocarbon-based elastomer (excluding liquid resin) or polyphenylene ether is contained in a certain proportion or more as the additive resin, the molding process as a thermoplastic resin becomes easy in the same uncured state.
  • the amount of the hydrocarbon-based elastomer (excluding the liquid resin) and / or polyphenylene ether used is preferably in the range of 30 to 200 parts by mass with respect to 100 parts by mass of the copolymer.
  • the number average molecular weight of the copolymer used is preferably 5,000 or more and 100,000 or less.
  • thermoplastic composition is molded into various shapes such as a sheet in advance by utilizing its thermoplasticity at a temperature equal to or lower than the working temperature of the curing agent, and if necessary, is heated after combining a semiconductor element, wiring, or a substrate and a laminate. Can be cured and adhered.
  • thermoplastic composition is as follows.
  • Thermoplastic containing 10 parts by mass or less of a monomer with respect to 100 parts by mass of an olefin-aromatic vinyl compound-aromatic polyene copolymer satisfying the following conditions (1) to (4) and substantially free of a solvent.
  • It is a molded product or a cured product composed of the above composition.
  • the cured product refers to, for example, a cured product of a molded product.
  • the number average molecular weight of the copolymer is 20,000 or more and 100,000 or less.
  • the aromatic vinyl compound monomer is an aromatic vinyl compound having 8 or more and 20 or less carbon atoms, and the content of the aromatic vinyl compound monomer unit is 10% by mass or more and less than 60% by mass.
  • the aromatic polyene is one or more selected from polyenes having a plurality of vinyl groups and / or vinylene groups in the molecule and having 5 or more and 20 or less carbon atoms, and the vinyl group content derived from the aromatic polyene unit is The number is 1.5 or more and less than 20 per number average molecular weight.
  • the olefin is one or more selected from olefins having 2 or more and 20 or less carbon atoms, and the olefin is ethylene alone, or an ⁇ -olefin monomer other than ethylene with respect to the ethylene monomer component contained in the olefin.
  • the mass ratio of the components is 1/10 or less, more preferably the content of the ⁇ -olefin monomer component other than ethylene in the copolymer is 4% by mass or less, and the olefin monomer unit and the aromatic vinyl compound are used.
  • the total of the monomer unit and the aromatic polyene monomer unit is 100% by mass.
  • the number average molecular weight of the present copolymer may be preferably 30,000 or more and 100,000 or less.
  • it may contain one or more selected from “hardener”, “additional resin”, “filler”, “flame retardant”, and “surface modifier”.
  • the sheet may be uncured (semi-cured) to the extent that the sheet shape can be maintained, or it may be completely cured.
  • the degree of curing of the composition can be quantitatively measured by a known dynamic viscoelasticity measurement method (DMA, Dynamic Mechanical Analysis).
  • thermoplastic composition according to another preferred embodiment of the present invention is as follows. It contains 100 parts by mass of an olefin-aromatic vinyl compound-aromatic polyene copolymer satisfying the following conditions (1) to (4), and is further selected from a hydrocarbon-based elastomer, a polyphenylene ether-based resin, and an aromatic polyene-based resin. It is a molded product or a cured product composed of a thermoplastic composition containing 1 to 200 parts by mass of a total of one or more resins. (1) The number average molecular weight of the copolymer is 20,000 or more and 100,000 or less.
  • the aromatic vinyl compound monomer is an aromatic vinyl compound having 8 or more and 20 or less carbon atoms, and the content of the aromatic vinyl compound monomer unit is 10% by mass or more and less than 60% by mass.
  • the aromatic polyene is one or more selected from polyenes having a plurality of vinyl groups and / or vinylene groups in the molecule and having 5 or more and 20 or less carbon atoms, and the vinyl group content derived from the aromatic polyene unit is The number is 3 or more and less than 20 per number average molecular weight.
  • the olefin is one or more selected from olefins having 2 or more and 20 or less carbon atoms, and the olefin is ethylene alone, or an ⁇ -olefin monomer other than ethylene with respect to the ethylene monomer component contained in the olefin.
  • the mass ratio of the components is 1/10 or less, more preferably the content of the ⁇ -olefin monomer component other than ethylene in the copolymer is 4% by mass or less, and the olefin monomer unit and the aromatic vinyl compound are used.
  • the total of the monomer unit and the aromatic polyene monomer unit is 100% by mass.
  • the number average molecular weight of this copolymer is preferably 30,000 or more and 100,000 or less.
  • the molded product is a sheet, and the molded product and the cured product of the main molded product.
  • the composition of the present invention may be provided as a sheet obtained by molding a composition heated and melted at a temperature equal to or lower than the working temperature of the curing agent or the decomposition temperature by a known method.
  • the sheet may be molded by extrusion molding with a T-die, double rolls, or extrusion lamination into a base film.
  • the composition of the composition, the mass ratio of the copolymer / monomer, or the solvent, the added resin, and the flame retardant so as to melt at the working temperature of the curing agent or below the decomposition temperature and become a solid near room temperature. Make selections and adjustments.
  • the sheet in this case is substantially uncured.
  • Such a technique is a general technique used for an ethylene-vinyl acetate resin-based cross-linking sealant sheet of a solar cell (photovoltaic power generation device).
  • compositions and molded products in a semi-cured state (B stage sheet, etc.)> Further, the composition of the present invention is a molded product in a partially crosslinked state, for example, a state in which a part of the curing agent contained therein is reacted and semi-cured (so-called B stage state), for example, a sheet, a tube or the like. It is also possible to. For example, by adopting a plurality of curing agents and / or curing conditions having different curing temperatures, semi-curing can be performed, and the melt viscosity and fluidity can be controlled to achieve the B stage state.
  • the present curable resin or composition is formed into an easy-to-handle B stage sheet, which is laminated on an electronic device or a substrate and pressure-bonded, and then the second stage curing (partial curing). It is also possible to perform complete curing) to obtain the final shape.
  • the composition of the composition that is, the mass ratio of the copolymer / monomer is selected, and if necessary, a solvent, an added resin, and a flame retardant are added, and the composition further contains a curing agent such as a peroxide.
  • a curing agent such as a peroxide.
  • a known direction can be adopted.
  • peroxides having different decomposition temperatures are used in combination and treated for a predetermined time at a temperature at which only one of them substantially acts to obtain a semi-cured product sheet.
  • the composition of the present invention may be in the form of a viscous liquid varnish depending on its composition and compounding ratio. For example, it can be made into a varnish by using a sufficient amount of solvent. In particular, when used as a varnish, it is preferable to add an appropriate solvent to the composition of the present invention.
  • the solvent is used to adjust the viscosity and fluidity of the composition as a varnish.
  • a solvent having a boiling point of a certain level or higher is preferable because the thickness of the applied film becomes uniform when the boiling point under atmospheric pressure is high, that is, when the volatility is low.
  • the preferred boiling point is approximately 130 ° C. or higher and 300 ° C. or lower under atmospheric pressure.
  • xylene, mesitylene, ethylbenzene, limonene, ethylene glycol methyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether and the like are used as a solvent suitable for such a varnish.
  • the amount used is preferably in the range of 10 to 2000 parts by mass with respect to 100 parts by mass of the composition of the present invention.
  • the varnish-like composition of the present invention and a molded product thereof contain an olefin-aromatic vinyl compound-aromatic polyene copolymer satisfying the following conditions (1) to (4).
  • the number average molecular weight of the copolymer is 5,000 or more and 100,000 or less.
  • the aromatic vinyl compound monomer is an aromatic vinyl compound having 8 or more and 20 or less carbon atoms, and the content of the aromatic vinyl compound monomer unit is 10% by mass or more and less than 60% by mass.
  • the aromatic polyene is one or more selected from polyenes having a plurality of vinyl groups and / or vinylene groups in the molecule and having 5 or more and 20 or less carbon atoms, and the vinyl group content derived from the aromatic polyene unit is The number is 1.5 or more, preferably 3 or more and less than 20 per number average molecular weight.
  • the olefin is one or more selected from olefins having 2 or more and 20 or less carbon atoms, and the olefin is ethylene alone, or an ⁇ -olefin monomer other than ethylene with respect to the ethylene monomer component contained in the olefin.
  • the mass ratio of the components is 1/10 or less, more preferably the content of the ⁇ -olefin monomer component other than ethylene in the copolymer is 4% by mass or less, and the olefin monomer unit and the aromatic vinyl compound are used.
  • the total of the monomer unit and the aromatic polyene monomer unit is 100% by mass.
  • the varnish preferably has a low viscosity in order to facilitate coating and impregnation, and therefore, a more preferable number average molecular weight of the copolymer is 5,000 or more and 70,000 or less.
  • it may contain one or more selected from the above-mentioned "additional resin", “hardener”, “monomer”, “solvent”, “filler”, "flame retardant”, and "surface modifier".
  • the "monomer” used when used as a varnish using a solvent, is preferably non-volatile. Since it is non-volatile as compared with the solvent used, it is possible to prevent the monomer from volatilizing together with the solvent in the solvent removing step after coating the varnish, for example.
  • the polar monomer which is generally non-volatile, is preferable.
  • various maleimides and bismaleimides can be exemplified as the present polar monomer.
  • the varnish-like composition of the present invention can also be prepared by utilizing a polymerization solution containing the copolymer of the present invention obtained by polymerization.
  • the polymerization solution may be concentrated or treated to remove residual monomers.
  • a solvent, other resin components, various additives, etc. may be added to adjust the component concentration and solution viscosity. You can also.
  • the varnish can be, for example, applied or impregnated on a base material, and the solvent or the like can be removed by drying or the like to obtain an uncured or semi-cured molded product.
  • the present molded product has a sheet, film, or tape-like form.
  • Curing conditions temperature, temperature, of the curing agent included in the curing of the thermoplastic composition, the molded product, the composition in the semi-cured state (B stage sheet, etc.), the molded product, and the varnish-like composition and the molded product. Curing can be performed by a known method with reference to (time, pressure).
  • the curing agent used is a peroxide
  • the curing conditions can be determined with reference to the half-life temperature and the like disclosed for each peroxide.
  • the dielectric constant of the cured product obtained from the copolymer of the present invention is 3.0 or less and 2.0 or more, preferably 2.8 or less and 2.0 or more, particularly preferably 2.5 or less and 2.0 or more at 10 GHz. Is.
  • the dielectric loss tangent is 0.005 or less and 0.0003 or more, preferably 0.003 or less and 0.0005 or more.
  • These dielectric constants and dielectric loss tangents can be obtained by any method known to those skilled in the art, and can be obtained, for example, by the resonator method (cavity resonator perturbation method or balanced disk resonator method).
  • the volume resistivity of the obtained cured product is preferably 1 ⁇ 10 15 ⁇ ⁇ cm or more.
  • the cured product obtained from the composition using the copolymer is relatively soft and has impact resistance while exhibiting sufficient mechanical characteristics. It can have a feature that it can follow the thermal expansion of the base material. That is, the cured product of the present invention has a tensile elastic modulus of less than 3 GPa, 5 MPa or more, preferably 10 MPa or more, and more preferably 20 MPa or more as measured at room temperature (23 ° C.).
  • the present tensile elastic modulus may take a value of 3 GPa or more and 20 GPa or less.
  • the tensile breaking point strength is preferably less than 50 MPa, 10 MPa or more, preferably 15 MPa or more, and the tensile breaking point elongation (tensile breaking elongation) is preferably 30% or more, more preferably 50% or more.
  • the elongation at the breaking point of this tension may take a value of less than 30%.
  • the cured product of the composition of the present invention can have sufficient heat resistance for practical use.
  • the cured product of the composition of the present invention has a storage elastic modulus of 5 ⁇ 10 5 Pa or more, preferably 1 ⁇ 10 6 Pa or more, most preferably 1. A value of 2 ⁇ 10 6 Pa or more can be shown.
  • the cured product obtained from the composition of the present invention has sufficient heat resistance and high temperature for practical use even under the condition that the monomer in the composition and the aromatic polyene as a component of the monomer are suppressed to a certain ratio or less. It is possible to show the mechanical properties of. It is important to suppress the monomer and the aromatic polyene as a component of the monomer to a certain ratio or less in order to maintain the moldability as a thermoplastic resin even in the uncured state as described above. is there.
  • the uncured or semi-cured thermoplastic composition of the present invention is a metal foil for wiring (generally copper) by being cured by a heat-pressurizing treatment or the like without applying an adhesive or an adhesive treatment. Most of the foils are used, but they can be bonded to other metals such as nickel, aluminum, iron, etc. that can be used for wiring or alloys thereof.
  • a copolymer having an aromatic vinyl compound monomer unit content of 10% by mass or more is used, and the olefin is ethylene alone.
  • the mass ratio of the ⁇ -olefin monomer component other than ethylene to the ethylene monomer component contained in the olefin is 1/7 or less
  • the measurement according to the Japanese Industrial Standard (JIS) C6481: 1996 shows.
  • a peeling strength of 1.0 N / mm or more can be provided.
  • the olefin is ethylene alone, or the mass ratio of the ⁇ -olefin monomer component other than ethylene to the ethylene monomer component contained in the olefin is 1/10 or less, more preferably.
  • the peeling strength can be further improved, and for example, a peeling strength of 1.3 N / mm or more can be given. Possible and more preferred.
  • JIS Japanese Industrial Standards
  • the uncured or semi-cured thermoplastic composition of the present invention is adhered to the metal leaf for wiring by a curing treatment such as a heat-pressurizing treatment without applying an adhesive or an adhesive treatment.
  • a curing treatment such as a heat-pressurizing treatment
  • other adhesiveness-imparting measures adheres to metal foils and other members.
  • adhesive application, adhesive treatment, etc. including the addition of the above-mentioned "surface modifier" are to be implemented. It does not prevent anything.
  • the metal foil of the present invention may be any metal foil that can be used for wiring or a substrate, and for example, copper foil, aluminum foil, nickel foil, or the like is used.
  • the thickness is not particularly limited, but is generally in the range of 1 to 500 ⁇ m, preferably 5 to 100 ⁇ m.
  • a copper foil compatible with high frequency can be preferably used as the metal foil, and either rolled copper foil or electrolytic copper foil may be used.
  • the copper foil may be a copper foil having a surface roughness (maximum height) Rz specified in JIS B0601: 2001, preferably 5 ⁇ m or less, particularly preferably 3 ⁇ m or less.
  • Such copper foil can be obtained from Furukawa Electric Co., Ltd., JX Nippon Mining & Metals Co., Ltd., Mitsui Mining & Smelting Co., Ltd. and the like.
  • the composition of the present invention comprises various insulating materials for wiring, preferably wiring of high frequency signals, such as coverlays, solder resists, build-up materials, interlayer insulators, bonding sheets, interlayer adhesives, and bumps for flip chip bonders. It can be used as a sheet. Further, it can be used as an adhesive layer for a substrate / substrate such as a single-layer or multi-layer printed circuit board, a flexible printed circuit board, a CCL (copper clad laminate), or an FCCL (flexible copper clad laminate) substrate.
  • a substrate / substrate such as a single-layer or multi-layer printed circuit board, a flexible printed circuit board, a CCL (copper clad laminate), or an FCCL (flexible copper clad laminate) substrate.
  • a cured product of a laminated body can be obtained by laminating an uncured or B-stage thermoplastic composition and a metal foil by a known method, and heating and pressurizing the metal foil under appropriate conditions.
  • a varnish-like composition may be applied or coated on a metal foil, and if necessary, these may be further laminated and heated to be cured.
  • the laminate may be a laminate containing a resin layer containing an olefin-aromatic vinyl compound-aromatic polyene copolymer and a metal foil adjacent to the resin layer.
  • a solvent used for the varnish, the solvent may be removed before curing under appropriate conditions and then cured, or the solvent may be removed by heating after curing, and curing and removal of the solvent are performed at the same time. You may. These can be appropriately adjusted by selecting a solvent or monomer having an appropriate vapor pressure and a curing agent having appropriate curing conditions.
  • the laminate containing the metal foil of the present invention and its cured product are, for example, a printed circuit board, a flexible copper-clad laminate in which a copper foil is bonded to a resin sheet (film), and a flexible copper-clad laminate in which an electronic circuit is formed.
  • the metal foil or copper foil is a concept including metal wiring or copper wiring.
  • the composition of the present invention Since the composition of the present invention has high adhesive strength with metal foil, it is used for coverlays, solder resists, build-up materials, interlayer insulators, interlayer adhesives, build-up films, bonding sheets, coverlay sheets, and flip-chip bonders. Can be used as a bump sheet or potting material.
  • the uncured sheet or partially cured sheet of the composition of the present invention can be suitably used as an electrically insulating material for high frequencies. For example, it can be suitably used as a build-up film, a bonding sheet, a coverlay sheet, a bump sheet for a flip chip bonder, or an insulating layer or an adhesive layer for a substrate.
  • this composition By using this composition as a substitute for the conventionally used epoxy resin or silicone resin, it is possible to perform a curing treatment to form a cured insulating layer or a cured matrix phase having a low dielectric constant and a low dielectric loss.
  • the thickness of the sheet is generally 1 to 300 microns.
  • This sheet may contain a woven fabric such as glass cloth or ceramic fiber, or a non-woven fabric, may be impregnated, or may be multilayered with these.
  • a flexible bendable wiring that is partially or completely insulated by this sheet can be used instead of the conventional coaxial cable.
  • LCP liquid crystal polymer
  • PPE sheet polyethylene tere resin
  • fluororesin polyimide resin
  • polyimide resin etc.
  • a laminate containing a metal foil in which the cured product obtained by using the composition of the present invention is an insulating layer can be a wiring board having low dielectric loss and excellent high frequency characteristics.
  • heat resistance that can withstand solder, and some degree of softness, elongation, and impact resistance that can withstand stress due to heat cycle or thermal expansion difference are merits.
  • a cloth made of glass or quartz, a non-woven fabric, a film material, a ceramic substrate, a glass substrate, a core material such as a general-purpose resin plate such as epoxy, a general-purpose laminated plate, and a conductor foil with an insulating layer made of this cured product are laminated and pressed. It is possible to make it by.
  • a slurry or solution containing a curable composition may be applied to a core material, dried and cured to form an insulating layer.
  • the thickness of the insulating layer is generally 1 to 300 microns.
  • Such a multi-layer wiring board can be used in multiple layers or integrated.
  • the composition or copolymer of the present invention can also be cured together with an LCP (Liquid Crystal Polymer) layer under relatively mild curing conditions to provide high adhesive strength.
  • the LCP layer may be specifically an LCP sheet or a film. Therefore, for example, an LCP sheet, a metal foil, preferably a copper foil, and various laminates containing the composition of the present invention can be obtained. The number of layers of this laminate and the order of lamination are arbitrary.
  • the composition of the present invention is useful as an adhesive layer between a metal foil (copper foil) and an LCP sheet.
  • the composition of the present invention can exhibit high adhesiveness to both a metal foil and an LCP sheet.
  • adhesion between an LCP sheet and a copper foil has required heating to the melting point of LCP (approximately 280 ° C. to 330 ° C. or a temperature close to that) and crimping.
  • the composition of the present invention as an adhesive layer, it is possible to bond the LCP and the metal leaf at a lower temperature by pressure bonding substantially near the curing temperature of the composition of the present invention.
  • the low dielectric constant and the low dielectric loss tangent value of the cured product of the composition of the present invention impart usefulness as wiring for the high-frequency signal transmission of the present laminate.
  • the laminated body is a structure in which the metal wiring arranged on the LCP layer, preferably the copper wiring, is covered with the cured product layer of the composition of the present invention from the side opposite to the LCP layer side. .. It is used as a so-called coverlay on LCP board wiring.
  • the LCP refers to a thermoplastic polymer having a liquid crystal state or a property of optically birefringent when melted.
  • LCP include a lyotropic liquid crystal polymer that exhibits liquid crystallinity in a solution state and a thermotropic liquid crystal polymer that exhibits liquid crystallinity when melted.
  • the liquid crystal polymer is classified into type I, type II, and type III according to the thermal deformation temperature, and any type may be used.
  • the liquid crystal polymer include a thermoplastic aromatic liquid crystal polyester, a thermoplastic aromatic liquid crystal polyester amide in which an amide bond is introduced therein, and the like.
  • the LCP may be a polymer in which an imide bond, a carbonate bond, a carbodiimide bond, an isocyanate-derived bond such as an isocyanurate bond, or the like is further introduced into an aromatic polyester or an aromatic polyester amide.
  • a molten liquid crystal forming polyester composed of 2-hydroxy-6-naphthoic acid and para-hydroxybenzoic acid for example, an LCP resin manufactured by Ueno Fine Chemicals Industry Co., Ltd. (product number A-5000, melting point 280 ° C.) may be used.
  • the melting point of the LCP is preferably 220 to 400 ° C., more preferably 260 to 380 ° C. by the DSC method.
  • LCPs can be obtained from, for example, Ueno Fine Chemicals Industry Co., Ltd., Sumitomo Chemical Co., Ltd., and Polyplastics Co., Ltd.
  • the LCP sheet is a known LCP sheet, and its thickness is arbitrary.
  • the LCP sheet can be obtained by a known method such as a T-die extrusion method, an inflation method, or an endless belt (double belt press) method.
  • copolymers obtained in the synthetic examples and the comparative synthetic examples were analyzed by the following means.
  • the content of vinyl group units derived from ethylene, hexene, styrene, and divinylbenzene in the copolymer was determined from the peak area intensity assigned to each by 1 H-NMR measurement.
  • the sample was dissolved in weight 1,1,2,2-tetrachloroethane, and the measurement was carried out at 80 to 130 ° C.
  • the number average molecular weight (Mn) in terms of standard polystyrene was determined using GPC (gel permeation chromatography). The measurement was performed under the following conditions.
  • the molecular weight in terms of standard polystyrene is determined by the following high-temperature GPC method. .. The measurement was performed under the following conditions.
  • the DSC measurement was performed using a DSC6200 manufactured by Seiko Electronics Co., Ltd. under a nitrogen air flow. That is, using 10 mg of resin and 10 mg of ⁇ -alumina as a reference, using an aluminum pan, the temperature was raised from room temperature to 240 ° C. at a heating rate of 10 ° C./min and then cooled to -120 ° C. at 20 ° C./min. did. After that, DSC measurement was performed while raising the temperature to 240 ° C. at a heating rate of 10 ° C./min to determine the glass transition temperature.
  • the glass transition temperature referred to here is the supplementary glass transition start temperature of JIS K7121: 2012, and the gradient between the straight line extending the baseline on the low temperature side to the high temperature side and the curve of the stepwise change portion of the glass transition is maximized. It is the temperature of the intersection with the tangent line drawn at the point.
  • ⁇ Tensile test> In accordance with JIS K-6251: 2017, a film sheet with a thickness of about 1 mm is cut into a No. 2 dumbbell No. 1/2 type test piece shape, and using Orientec's Tencilon UCT-1T type, 23 ° C., tensile speed 500 mm.
  • the tensile elastic modulus, the tensile breaking point strength (breaking strength), and the tensile breaking point elongation (breaking elongation) were determined by measuring at / min.
  • ⁇ Measurement of storage elastic modulus> Using a dynamic viscoelasticity measuring device (RSA-III manufactured by Leometrics), measurement was performed in a frequency range of 1 Hz and a temperature range of ⁇ 60 ° C. to + 300 ° C. A measurement sample (3 mm ⁇ 40 mm) was cut out from a film having a thickness of about 0.1 mm to 0.3 mm and measured to determine the storage elastic modulus.
  • the main measurement parameters related to the measurement are as follows.
  • the dielectric constant and dielectric loss tangent of the cured product of the composition are 1 mm x 1.5 mm cut out from the composition sheet using the cavity resonator perturbation method (8722ES type network analyzer manufactured by Agilent Technologies, cavity resonator manufactured by Kanto Electronics Applied Development). Using a sample of ⁇ 80 mm, the value at 23 ° C. and 10 GHz was measured.
  • the raw materials are as follows. As divinylbenzene, divinylbenzene manufactured by Nittetsu Chemical & Materials Co., Ltd. (meta-para mixture, divinylbenzene purity 81%) was used.
  • the bifunctional polyphenylene ether oligomer (OPE-2St, number average molecular weight 1200, toluene solution) is made by Mitsubishi Gas Chemical Company, further diluted with toluene, further added with a large amount of methanol to precipitate methanol, air-dried, and then dried under reduced pressure. As a result, a powdered polyphenylene ether oligomer was obtained and used. This powder was used both when kneading with lavender and when making varnishes.
  • H-1041 (number average molecular weight 58000) manufactured by Asahi Kasei Chemicals Co., Ltd. was used.
  • the curing agent is Park Mill D (dicumyl peroxide), Perbutyl O (t-butylperoxy-2-ethylhexanoate) or Perhexin 25B (2,5-dimethyl-2,5-bis (t) manufactured by NOF CORPORATION. -Butyl peroxy) hexin-3) was used.
  • 1,2-polybutadiene liquid polybutadiene manufactured by Nippon Soda Corporation: product name B-3000 (number average molecular weight 3200) was used.
  • Example 1 Using a Brabender plastic coder (PL2000 type manufactured by Brabender), pre-kneaded resin P-1 (ethylene-styrene-divinylbenzene copolymer) and a monomer are added, and the rotation speed is 100 ° C. Knead at 50 times / minute for 5 minutes, and add a curing agent (Dicumyl Peroxide, Park Mill D, manufactured by Nichiyu Co., Ltd.) to 100 parts by mass of the total resin and monomer (total of raw materials other than the curing agent). 1 part by mass was added, and the mixture was kneaded under the conditions of 100 ° C. and a rotation speed of 50 times / minute for 5 minutes to prepare a composition.
  • a curing agent Dicumyl Peroxide, Park Mill D, manufactured by Nichiyu Co., Ltd.
  • the obtained curable composition is sandwiched between a mold and two Teflon (registered trademark) sheets, tightly adhered and sealed, and pressed by a heat pressing method (120 ° C., time 5 minutes, pressure 1.5 MPa) to obtain various thicknesses.
  • a sheet (uncured sheet) having a thickness (thickness of 1.0 mm, 0.5 mm, etc.) was obtained.
  • the obtained sheet was sandwiched between Teflon (registered trademark) sheets and glass plates to bring them into close contact with each other, and heat-treated at 120 ° C. for 30 minutes, 150 ° C. for 30 minutes, and then at 180 ° C. for 120 minutes to cure. After curing, the glass plate, Teflon (registered trademark) sheet and mold were removed to obtain a cured sheet of the composition of the present invention.
  • Example 2-5 The composition was prepared according to the same procedure as in Example 1 with the formulations shown in Table 2 (the formulations in the table indicate parts by mass). However, in Examples 3 and 4, the raw materials other than the curing agent were kneaded at 120 ° C. at a rotation speed of 30 times / minute for 10 minutes, then the curing agent was added, and further kneading was performed under these conditions for 5 minutes. In Example 3, perhexine 25B was used as a curing agent. An uncured sheet was obtained by press molding in the same manner as in Example 1.
  • the properties (room temperature) of the uncured sheets of Examples 1 to 5 are all soft resin-like sheets, which are easy to handle as sheets, and even if they are peeled off from the Teflon (registered trademark) sheet after pressing, the sheets themselves It had low self-adhesiveness and could be handled as a single sheet. That is, the molding process as a thermoplastic resin was easy in the uncured state. Further, Examples 3 and 4 were heat-treated at 120 ° C. for 30 minutes, 150 ° C. for 30 minutes, and then at 200 ° C. for 120 minutes to be cured. In Example 5, 1,2-polybutadiene was added before the curing agent was added.
  • Examples 8-10, Comparative Example 4 A raw material other than the curing agent was charged into a container provided with a heating / cooling jacket and a stirring blade according to the formulation shown in Table 2, and the mixture was heated to 60 ° C. and stirred to obtain a varnish-like (viscous liquid) composition. Then, a curing agent was added, and the mixture was stirred and dissolved.
  • the curing agent dicumyl peroxide was used in Examples 8 and 10, and perhexin 25B was used in Example 9. In Examples 8 and 9, 1,2-polybutadiene was added before the curing agent was added.
  • the obtained varnish-like composition is poured into a Teflon (registered trademark) mold on a Teflon (registered trademark) sheet, the solvent is blown off at a blower dryer at about 100 ° C. for 6 hours, and then the Teflon (registered trademark) mold is used. Was carefully removed to obtain a soft resin-like sheet.
  • the obtained sheet is further sandwiched between a mold and two Teflon (registered trademark) sheets, closely adhered and sealed, and pressed by a heating press method (120 ° C., time 5 minutes, pressure 1.5 MPa) to various thicknesses (thickness).
  • a sheet (uncured sheet) having a size of 1.0 mm, 0.5 mm, etc.) was obtained.
  • This sheet was easy to handle, and even if it was peeled off from the Teflon (registered trademark) sheet, the self-adhesiveness of the sheet itself was low, and it could be handled as a single sheet. That is, the molding process as a thermoplastic resin was easy in the uncured state.
  • the obtained sheet was sandwiched between Teflon (registered trademark) sheets and a glass plate and brought into close contact with each other, and Examples 8 and 9 were heat-treated at 120 ° C. for 30 minutes, 150 ° C. for 30 minutes, and then at 180 ° C. for 120 minutes to cure. It was.
  • Examples 10 and 4 were heat-treated at 120 ° C. for 30 minutes, 150 ° C. for 30 minutes, and then at 200 ° C. for 120 minutes to be cured. After curing, the glass plate, Teflon (registered trademark) sheet and mold were removed to obtain a cured sheet of the composition of the present invention.
  • the cured product of the composition sheet obtained in Examples 1 to 10 can measure the elastic modulus without melting and breaking even at 300 ° C. by viscoelastic spectrum measurement, and the storage elastic modulus at 300 ° C. (573K) is the present application.
  • the condition was 5 ⁇ 10 5 Pa or more, and substantially 1 ⁇ 10 6 Pa or more.
  • all of them showed a tensile elastic modulus of less than 3 GPa and 3 MPa or more.
  • the tensile breaking point strength was 5 MPa or more, and the tensile breaking point elongation was 50% or more.
  • the permittivity and the dielectric loss tangent also satisfy the scope of the present invention.
  • the water absorption rates of the cured films obtained in Examples 1 to 10 were all less than 0.1% by mass.
  • the cured product of the sheet obtained in Comparative Example 1 had a too low tensile elastic modulus at room temperature and a low tensile breaking point strength.
  • the sheet obtained in Comparative Example 2 had a low tensile breaking point strength.
  • the copper foil used was manufactured by Mitsui Mining & Smelting Co., Ltd. (VSP series, TQ-M7-VSP, thickness 12 ⁇ m). Copper foil was placed on the uncured sheets (thickness 0.5 mm) obtained in Examples 1 to 10 and Comparative Examples 1 to 4, and the pressure was 1.5 MPa, 120 ° C. for 30 minutes, and then 150 by a mold heating press. By heating and pressurizing at ° C. for 30 minutes and then at 180 ° C. for 120 minutes, a laminate was obtained by adhering and curing the sheet and the copper foil. The peel strength measurement with the copper foil was evaluated by 90 ° peeling according to Japanese Industrial Standards (JIS) C6481: 1996.
  • JIS Japanese Industrial Standards
  • the copper foil used was manufactured by Mitsui Mining & Smelting Co., Ltd. (VSP series, TQ-M7-VSP, thickness 12 ⁇ m, surface roughness 1.1 ⁇ m).
  • the uncured sheet (thickness 0.3 to 0.5 mm) obtained in each Example and Comparative Example (excluding Examples 6 and 7 and Comparative Examples 1 to 3) was placed on the roughened surface of the copper foil.
  • a laminate was obtained by adhering and curing the sheet and copper foil by heating and pressurizing with a mold heating press at a pressure of 5 MPa, 120 ° C. for 30 minutes, then 150 ° C. for 30 minutes, and then 180 ° C. for 120 minutes.
  • Copper foil is layered on a Teflon sheet on a glass plate with the roughened surface facing up, and a Teflon (registered trademark) mold (thickness 0.3 mm) is installed on the copper foil, and Examples 6 and 7 are installed therein.
  • the compositions obtained in Comparative Examples 1 to 3 were poured, and a Teflon sheet and a glass plate were further overlapped with each other, and a load was applied to bring them into close contact with each other. It was. After curing, the glass plate, Teflon (registered trademark) sheet and mold were removed, and a laminate was obtained by adhesively curing the sheet and copper foil.
  • the embrittlement temperature of the sample obtained by molding the compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 4 into a test piece B for embrittlement test and curing under the same conditions as the sheet is any.
  • the low temperature brittleness in Table 2 is indicated by ⁇ (Good).
  • the embrittlement temperature of the samples obtained in Comparative Examples 3 and 4 was higher than ⁇ 5 ° C.
  • the low temperature brittleness in Table 2 is indicated by ⁇ (NG).
  • a copolymer of P-8 was obtained by appropriately changing the amount of monomer, the ratio, the polymerization pressure, and the polymerization temperature with reference to the production methods of JP-A-2009-161743 and JP-A-2010-280771.
  • the total of the olefin monomer unit (ethylene), the aromatic vinyl compound monomer unit (styrene) and the aromatic polyene monomer unit (divinylbenzene) was set to 100% by mass.
  • Table 3 shows the composition of the copolymer, the number average molecular weight, and the glass transition temperature.
  • Example 11 Using P-8, a varnish using toluene as a solvent was prepared with the formulation (parts by mass) shown in Table 4, and a soft resin-like uncured sheet and a cured sheet thereof were prepared in the same manner as in Examples 8 to 10. did.
  • the polar monomer bismaleimide BMI-3000H (m-phenylene bismaleimide) manufactured by Daiwa Kasei Kogyo Co., Ltd. was used. Table 4 shows the measured values evaluated in the same manner as described above.
  • Example 12 Using P-8, a varnish using toluene as a solvent was prepared with the formulation (parts by mass) shown in Table 4, and a soft resin-like uncured sheet and a cured sheet thereof were prepared in the same manner as in Examples 8 to 10. did. However, a molten silica filler SFP-130MC manufactured by Denka Co., Ltd. was used as a raw material. 40% by volume of silica filler was used with respect to 60% by volume of the resin component. Table 4 shows the measured values evaluated in the same manner as described above.
  • Examples 13 and 14 ⁇ Evaluation as an adhesive between copper foil and LCP (liquid crystal polymer) sheet> Using the varnish obtained in Example 11 and the varnish obtained in Example 12 (however, the varnish before adding the silica filler), the adhesiveness between the copper foil and the LCP sheet was evaluated as follows.
  • the copper foil was used as the copper foil, and an LCP resin manufactured by Ueno Fine Chemicals Industry Co., Ltd. (product number A-5000, melting point 280 ° C.) was used as the LCP sheet, and the thickness was obtained by the method described in International Publication WO2020 / 153391. A 100 ⁇ m sheet was used.
  • a varnish was applied onto the LCP sheet, and the solvent was first removed by air drying at 60 ° C., and then the solvent was sufficiently removed carefully so as not to foam under normal pressure to vacuum at 60 ° C.
  • the thickness of the varnish layer after removing the solvent was about 50 ⁇ m.
  • the roughened surface of the copper foil was brought into close contact with the varnish side of the sheet from which the solvent had been removed, and heat-treated at 120 ° C. for 30 minutes, 150 ° C. for 30 minutes, and then at 180 ° C. for 120 minutes while pressurizing at 5 MPa with a vacuum press to cure.
  • the sheet was cut into a width of 10 mm and a length of 100 mm, and the peel strength measurement between the LCP sheet and the copper foil was evaluated by 90 ° peeling according to Japanese Industrial Standards (JIS) C6481: 1996.
  • JIS Japanese Industrial Standards
  • the peel strength was 1.7 N / mm.
  • the varnish obtained in Example 12 but not containing the silica filler
  • the peeled surface was observed, it was peeled at the interface between the cured product derived from varnish and the LCP sheet, so the peel strength between the LCP sheet and the cured product derived from varnish was 1.7 N / mm and 1.3 N / mm, respectively. I concluded that there is.
  • Comparative Example 5 Heat crimping was performed with a press machine under the same conditions as in Examples 11 and 12 using only the copper foil and the LCP sheet, but the two were not substantially adhered to each other.
  • the cured product obtained by curing the composition of the present invention has a high elastic modulus under excellent high temperature conditions, exhibits a specific range of elastic modulus, good breaking strength, breaking elongation, and low water absorption. , Shows low dielectric properties (low modulus, dielectric loss tangent).
  • the peeling strength with the copper foil was also practically sufficient. It shows a lower embrittlement temperature and has high cold resistance. Further, it can exhibit high peel strength with a LCP (liquid crystal polymer) sheet under relatively mild conditions. Therefore, it can be suitably used as an electrical insulating material for high frequencies.
  • the composition of the present invention in an uncured state, coverslay film, solder-resist film, build-up film, bonding sheet, coverlay sheet, bump sheet for flip chip bonder, interlayer insulating agent, and the like.
  • the composition of the present invention can be cured and used as a printed circuit board, a flexible printed circuit board, or an FCCL (flexible copper clad laminate) base material. Further, it can be used as an insulating layer for a CCL substrate and a PCB substrate.

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