WO2021112088A1 - 硬化性組成物及びその硬化体 - Google Patents

硬化性組成物及びその硬化体 Download PDF

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Publication number
WO2021112088A1
WO2021112088A1 PCT/JP2020/044700 JP2020044700W WO2021112088A1 WO 2021112088 A1 WO2021112088 A1 WO 2021112088A1 JP 2020044700 W JP2020044700 W JP 2020044700W WO 2021112088 A1 WO2021112088 A1 WO 2021112088A1
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WIPO (PCT)
Prior art keywords
mass
aromatic
less
vinyl compound
copolymer
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/JP2020/044700
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
荒井　亨
翔太 山本
西村　裕章
梓 八木
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.)
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 KR1020227018345A priority Critical patent/KR102878844B1/ko
Priority to US17/782,000 priority patent/US12104047B2/en
Priority to EP20897253.9A priority patent/EP4071210B1/en
Priority to JP2021562662A priority patent/JP7465894B2/ja
Priority to KR1020257035880A priority patent/KR20250156858A/ko
Priority to CN202080083049.1A priority patent/CN114729163B/zh
Application filed by Denka Co Ltd filed Critical Denka Co Ltd
Priority to EP22202823.5A priority patent/EP4141065B1/en
Publication of WO2021112088A1 publication Critical patent/WO2021112088A1/ja
Anticipated expiration legal-status Critical
Priority to JP2023170371A priority patent/JP7654738B2/ja
Priority to JP2024059153A priority patent/JP2024071737A/ja
Priority to US18/799,459 priority patent/US20240400807A1/en
Ceased legal-status Critical Current

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    • 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
    • B32B2307/732—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 compositions.
  • sheet also includes the concept of a film. Moreover, even if it is described as a film in this specification, it also includes the concept of a sheet.
  • 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 and polypropylene in the presence of styrene monomer, divinylbenzene monomer and radical polymerization initiator. Such a method does not increase the graft efficiency and the polymer. There is a problem that the uniformity is not sufficient.
  • 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 having a specific composition and composition, that is, an ethylene-olefin (aromatic vinyl compound) -polyene copolymer and a non-polar vinyl compound copolymer.
  • 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 having a specific composition and composition of an ethylene-olefin (aromatic vinyl compound) -polyene copolymer and a non-polar vinyl compound copolymer.
  • the cured product of the composition specifically described in the examples has room for improvement in adhesion to a metal foil, particularly a copper foil, and low temperature characteristics.
  • 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.
  • Patent Documents 5, 6 and 7 show 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 having a specific composition and composition. ing. These curable compositions contain a relatively large amount of monomeric components (aromatic vinyl compounds and aromatic polyenes) and are varnish-like. Therefore, not only is there an odor, but there is also a problem that the B stage sheet (semi-cured sheet) cannot be easily manufactured. These curable compositions have a problem that the production equipment becomes complicated.
  • thermoplastic composition that can be easily molded nor a cured product having excellent low dielectric properties and high mechanical strength (elastic modulus, etc.) at room temperature and high temperature has been obtained. , The provision is desired.
  • the present invention can provide the following aspects.
  • 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 0% by mass or more and 70% by mass or less.
  • 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 total of the olefin monomer unit, the aromatic vinyl compound monomer unit, and the aromatic polyene monomer unit is 100% by mass. Is.
  • Olefin-aromatic vinyl compound-aromatic polyene copolymer satisfying the following conditions (1) to (4), hydrocarbon-based elastomer, polyphenylene ether, olefin-aromatic vinyl compound-aromatic polyene copolymer oligomer, and A cured product obtained from a composition containing an additive resin, which is one or more selected from the group consisting of aromatic polyene resins, and has a storage elasticity at 300 ° C. of 5 ⁇ 10 5 Pa or more, preferably 1 ⁇ 10 6 An electrically insulating material having a dielectric constant of Pa or more, 23 ° C.
  • 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 0% by mass or more and 70% by mass or less.
  • 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 total of the olefin monomer unit, the aromatic vinyl compound monomer unit, and the aromatic polyene monomer unit is 100% by mass. Is.
  • the curable composition of the present invention has properties as a thermoplastic resin. Further, the cured product obtained by curing the curable composition has excellent low dielectric properties and high mechanical strength (elastic modulus, etc.) at room temperature and high temperature.
  • an olefin-aromatic vinyl compound-aromatic polyene copolymer may be simply referred to as a copolymer.
  • the numerical range in the present specification shall include the upper limit value and the lower limit value.
  • 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. Further, in the present specification, the cured product has the same meaning as the cured product. In the present specification, the content may be referred to as the content.
  • composition may be referred to as a resin composition or a curable resin composition.
  • the composition of the present invention contains the olefin-aromatic vinyl compound-aromatic polyene copolymer having the above-mentioned composition and molecular weight range.
  • the composition further comprises a predetermined amount of one or more "added resins".
  • the present composition may also contain a "monomer” and a "curing agent” described later.
  • ⁇ 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" in the present specification) satisfies all of the following conditions (1) to (4).
  • the number average molecular weight of the copolymer is 5,000 or more and 100,000 or less, preferably 20,000 or more and 100,000 or less, and more preferably 30,000 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 0% by mass or more and 70% by mass or less.
  • 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, preferably 1.5 or more and less than 7, and more preferably 2 or more and less than 5.
  • the olefin is one or more selected from olefins having 2 or more and 20 or less carbon atoms, and the total of the olefin monomer unit, the aromatic vinyl compound monomer unit, and the aromatic polyene monomer unit is 100% by mass. Is.
  • 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 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 mass ratio of ethylene alone or ⁇ -olefin / ethylene other than ethylene contained is 1/7 or less, more preferably 1/10 or less, the peel strength of the obtained cured product from the copper foil or copper wiring is increased. Can be preferred.
  • 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 ethylene- ⁇ -olefin-aromatic vinyl compound-aromatic polyene chain of the finally obtained cured product depends on the type and content of the ⁇ -olefin. It can be freely adjusted in the range of ⁇ 60 ° C. to ⁇ 5 ° C., preferably ⁇ 50 ° C. to ⁇ 10 ° 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 and 100,000 or less, preferably 20,000 or more and 100,000 or less, and more preferably 30,000 or more and 100,000 or less. By setting it in such a range, even if the added resin is added in the uncured state, it becomes less sticky, the effect of improving the thermoplasticity can be obtained, and the finally obtained cured product has high breaking point strength. , Good physical properties such as high breaking point elongation can be easily imparted. If the number average molecular weight is less than 5000, the mechanical properties of the composition at the uncured stage are low and the adhesiveness is high, so that the composition may be difficult to be molded as a thermoplastic resin.
  • the content of the aromatic vinyl compound monomer unit contained in this copolymer is 0% by mass or more and 70% by mass or less, preferably 10% by mass or more and 60% by mass or less, and more preferably 10% by mass or more and 55% by mass or less. is there. If the content of the aromatic vinyl compound monomer unit is greater than 70% by mass, the glass transition temperature of the cured product of the finally obtained composition will be around room temperature, and the toughness and elongation at low temperatures will decrease. There are cases.
  • the content of the aromatic vinyl compound monomer unit is 10% by mass or more, the aromaticity of the copolymer is improved, the compatibility with the flame retardant and the filler is improved, and the flame retardant does not bleed out. Can be filled with filler. 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 peel strength from the copper foil or copper wiring can be obtained.
  • the content of vinyl group and / or vinylene group derived from aromatic polyene unit is 1.5 or more and less than 20 per number average molecular weight, preferably 2 or more and less than 20, more preferably 3. More than 10 pieces.
  • the content of vinyl group and / or vinylene group may be collectively referred to as "vinyl group content" below. If the number is less than 1.5, the cross-linking efficiency is low, and it becomes difficult to obtain a cured product having a sufficient cross-linking density. When the vinyl group content is increased, it becomes easy to improve the mechanical properties of the finally obtained cured product at normal temperature and high temperature.
  • the vinyl group content derived from the aromatic polyene unit per number average molecular weight in this copolymer is the standard polystyrene-equivalent number average molecular weight (Mn) obtained by a GPC (gel permeation chromatography) method known to those skilled in the art. It can be obtained by comparing with the vinyl group content and the vinylene group content derived from the aromatic polymer unit obtained by 1 H-NMR measurement. As an example, by comparing 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.
  • Mn polystyrene-equivalent number average molecular weight obtained by a GPC (gel permeation chromatography) method known to those skilled in the art. It can be obtained by comparing with the vinyl group content and the vinylene group content derived from the aromatic polymer unit obtained by 1 H-NMR measurement
  • 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. That is, 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 content of the olefin monomer unit is preferably 30% 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 30% 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 cracks occur during the cycle test.
  • the preferable olefin monomer unit content is 90% by mass or less.
  • an ethylene-divinylbenzene copolymer and an ethylene-propylene-divinylbenzene copolymer are suitable as an olefin-aromatic polyene copolymer that does not contain an aromatic vinyl compound monomer unit.
  • Examples thereof include coalescence, ethylene-1-butene-divinylbenzene copolymer, ethylene-1-hexene-divinylbenzene copolymer, and ethylene-1-octene-divinylbenzene copolymer.
  • examples of the olefin-aromatic vinyl compound-aromatic polyene copolymer containing an aromatic vinyl compound monomer unit include an ethylene-styrene-divinylbenzene copolymer and an ethylene-propylene-styrene-divinyl.
  • examples thereof include a benzene copolymer, an ethylene-1-hexene-styrene-divinylbenzene copolymer, and an ethylene-1-octene-styrene-divinylbenzene copolymer.
  • the composition of the present invention is a single material selected from a hydrocarbon-based elastomer, a polyphenylene ether, an olefin-aromatic vinyl compound-aromatic polyene copolymer oligomer, and an aromatic polyene-based resin with respect to 100 parts by mass of the contained copolymer.
  • a plurality of resins can be contained, preferably in a total of 1 to 500 parts by mass, and more preferably in a total of 1 to 300 parts by mass.
  • polyphenylene ether and / or a hydrocarbon-based elastomer may be particularly preferably used.
  • conjugated diene-based polymers are preferable.
  • conjugated diene-based polymers 1,2-polybutadiene is preferable.
  • polyphenylene ether and / or 1,2-polybutadiene By using polyphenylene ether and / or 1,2-polybutadiene, the amount of the monomer used can be reduced, and for example, a suitable cured product of the present invention can be obtained without using a monomer.
  • 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.
  • Hydrocarbon-based elastomers that can be suitably used in the compositions of the present invention are ethylene-based and propylene-based elastomers, conjugated diene-based polymers, aromatic vinyl compounds-conjugated diene-based block copolymers, and random copolymers. , And one or more elastomers selected from these hydrides (hydrocarbonates).
  • 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 amount used is preferably in the range of 1 to 30 parts by mass, particularly preferably 1 to 20 parts by mass with respect to 100 parts by mass of the copolymer.
  • 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.
  • examples of such polyphenylene ethers include SABIC's Noryl (trademark) SA9000 and the like, and particularly preferably, a bifunctional polyphenylene ether oligomer (OPE-2St) manufactured by Mitsubishi Gas Chemical Company, Inc. can be used.
  • 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 10 to 100 parts by mass with respect to 100 parts by mass of the copolymer.
  • an olefin-aromatic vinyl compound-aromatic polyene copolymer oligomer can also be added to the curing of the present invention, and particularly preferably, an olefin-aromatic satisfying the following conditions (1A) to (4A).
  • a vinyl compound-aromatic polyene copolymer oligomer can also be added.
  • the olefin-aromatic vinyl compound-aromatic polyene copolymer oligomer referred to here excludes the above-mentioned olefin-aromatic vinyl compound-aromatic polyene copolymer satisfying the above conditions (1) to (4).
  • the number average molecular weight of the copolymerization oligomer is 500 or more and less than 5000.
  • 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 0% by mass or more and 70% by mass or less.
  • 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 per number average molecular weight.
  • the olefin is one or more selected from olefins having 2 or more and 20 or less carbon atoms, the olefin monomer unit content is 30% by mass or more, and the olefin monomer unit and the aromatic vinyl compound monomer are used.
  • the total of the unit and the aromatic polyene monomer unit is 100% by mass.
  • the amount of the olefin-aromatic vinyl compound-aromatic polyene copolymer oligomer used in the composition of the present invention is preferably in the range of 1 to 49 parts by mass with respect to 100 parts by mass of the copolymer. Further, from the viewpoint of handleability and molding processability of the composition of the present invention in an uncured state, it is preferably 1 to 30 parts by mass, particularly preferably 1 to 20 parts by mass with respect to 100 parts by mass of the copolymer. The range.
  • the definitions and methods of olefin, aromatic vinyl compound, aromatic polyene, number average molecular weight, and vinyl group content are the same as in the case of the above-mentioned copolymer.
  • the method for determining the number average molecular weight of the copolymerized oligomer is as follows. For the molecular weight, the number average molecular weight (Mn) in terms of standard polystyrene was determined using GPC (gel permeation chromatography). The measurement can be performed under the following conditions.
  • the aromatic polyene-based resin includes a divinylbenzene-based reactive multi-branched copolymer (PDV) manufactured by Nittetsu Chemical & Materials Co., Ltd.
  • PDVs divinylbenzene-based reactive multi-branched copolymer
  • Such PDVs are described, for example, in the document "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, p125, 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.
  • a known curing agent that can be conventionally used for polymerization of aromatic polyenes and aromatic vinyl compounds, or curing can be used.
  • 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 amount of the monomer that the composition of the present invention may contain is arbitrary, but is preferably 10 parts by mass or less with respect to 100 parts by mass of the copolymer. It should be noted that the present composition does not have to contain substantially no monomer. When the amount of the monomer is 10 parts by mass or less, the uncured composition does not have a viscous property, and the molding process as a thermoplastic resin becomes easy. Further, when the content of the amount of easily volatile monomers is below a certain level, the odor at the uncured stage does not become a problem.
  • the monomer preferably used in the composition of the present invention preferably has a molecular weight of less than 1000, more preferably less than 500.
  • 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.
  • the monomer a monomer that can be polymerized with a radical polymerization initiator is preferable, and the aromatic vinyl compound and the 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 aromatic polyene 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.
  • Examples of the above-mentioned polar monomer include various maleimides, bismaleimides, maleic anhydride, glycidyl (meth) acrylate, triallyl isocyanurate, tri (meth) acrylic isocyanurate, trimethylolpropane tri (meth) acrylate and the like.
  • 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.
  • 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.
  • the bismaleimides represented by the following formula (B-1) are preferable.
  • R represents an alkylene group having 5 or more carbon atoms
  • L represents a single bond or a divalent linking group. R and L may each have an independent substituent.
  • the maleimides represented by the formula (B-1) are preferably represented by the following formula (B-2).
  • R' represents an alkylene group having 5 or more carbon atoms which may independently have a substituent
  • A may have an independent substituent.
  • n represents an integer from 1 to 10.
  • Examples of maleimides represented by the formula (B-2) include compounds represented by the following formula (B-3).
  • n represents an integer from 1 to 10.
  • 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 such as bismaleimides, triallyl isocyanurate (TAIC), and trimethylolpropane tri (TAIC).
  • TAIC triallyl isocyanurate
  • TAIC trimethylolpropane tri
  • the amount of the polar monomer that the composition may contain 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.
  • solvent An appropriate solvent may be added to the composition of the present invention, if necessary.
  • the solvent is used to adjust the viscosity and fluidity of the composition.
  • the solvent is preferably volatile, and for example, cyclohexane, toluene, ethylbenzene, acetone, isopropanol and the like are used.
  • the amount used is preferably 10 parts by mass or less with respect to 100 parts by mass of the copolymer of the present invention from the viewpoint of moldability and handling of the composition before curing as a thermoplastic resin, and during and after curing. From the viewpoint of removing the above, it is more preferable that the solvent is practically 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.
  • an appropriate 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 100 ° C. or higher, preferably 130 ° C. or higher and 300 ° C. or lower under atmospheric pressure.
  • toluene, 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.
  • 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 comprises one or more selected from these fillers, flame retardants and surface modifiers in order to be a matrix of cured products and to have excellent 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.
  • the composition of the present invention can contain a particularly large amount of an inorganic filler, and the usable amount thereof can reach 2000 parts by mass with respect to 100 parts by mass of the copolymer.
  • a known surface modifier for example, a silane coupling agent.
  • the dielectric constant may be particularly high if a large amount is added and blended. Therefore, the dielectric constant is preferably less than 500 parts by mass, more preferably less than 400 parts by mass with respect to 100 parts by mass of the copolymer. Use a filler. 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 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 an insulating 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 used in the composition of the present invention.
  • Preferred flame retardants are known organic phosphorus-based flame retardants such as phosphoric acid esters or condensates thereof, known bromine-based flame retardants, and red phosphorus from the viewpoint of maintaining low dielectric constant and low dielectric loss tangent.
  • phosphoric acid esters 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-triariroxy 1,3,5-triazine may be added.
  • the total amount of these flame retardants 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 blended 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 composition ratio of the copolymer, monomer, additive resin, and solvent of the composition may be changed within the above range, or further, the flame retardant, filler, and surface modifier may be used.
  • 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”, “semi-cured state (B stage sheet or the like)", and "varnish".
  • 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 / dissolving or melting, but any known method can be adopted as the method of mixing, dissolving and melting.
  • the composition of the present invention uses a copolymer having a molecular weight in a certain range or more and contains the predetermined additive resin, it exhibits the properties of a thermoplastic resin. 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 term "sheet” also includes the concept of a film. Moreover, even if it is described as a film in this specification, it also includes the concept of a sheet.
  • the preferable embodiment of this composition is as follows.
  • One or more resins selected from the above hydrocarbon-based elastomers, polyphenylene ethers, olefins-aromatic vinyl compounds-aromatic polyene copolymer oligomers, or aromatic polyene-based resins, excluding resins that are liquid at room temperature, are fixed.
  • the molding process as a thermoplastic resin becomes easy in the uncured state as well.
  • the hydrocarbon-based elastomer (excluding liquid resin) and / or polyphenylene ether can be added in the range of 30 to 200 parts by mass with respect to 100 parts by mass of the copolymer.
  • the added resin When the added resin is liquid at room temperature, it can be added in the range of preferably 1 to 30 parts by mass, particularly preferably 1 to 20 parts by mass with respect to 100 parts by mass of the copolymer.
  • the amount of the monomer that can be used in the present thermoplastic composition is preferably 10 parts by mass or less with respect to 100 parts by mass of the copolymer.
  • the number average molecular weight of the copolymer used is 5,000 or more and 100,000 or less, preferably 20,000 or more and 100,000 or less, and more preferably 30,000 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.
  • 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. Select and adjust.
  • 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).
  • 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. Can be partially cured, adjusted to a sheet shape (B stage state), molded and assembled, and then heated under pressure to be completely cured.
  • 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 sheet.
  • the molded product may be a sheet.
  • 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).
  • the composition of the present invention may be in the form of a viscous liquid varnish depending on its composition and compounding ratio.
  • it can be made into a varnish by using a sufficient amount of solvent and / or by using an appropriate amount of a liquid monomer.
  • 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 it has a merit that 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 100 ° C. or higher, preferably 130 ° C. or higher and 300 ° C. or lower under atmospheric pressure.
  • a solvent suitable for such a varnish xylene, mesitylene, ethylbenzene, limonene, ethylene glycol methyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether and the like are used.
  • 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 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.
  • the composition can be cured by a known method with reference to the curing conditions (temperature, time, pressure) of the contained curing agent.
  • 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 composition 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 there.
  • 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, 3 MPa or more, preferably 5 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, 3 MPa or more, more preferably 5 MPa or more, and the tensile breaking point elongation is preferably 30% or more and less than 300%, further preferably 50% or more and less than 250%.
  • 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 at 300 ° C. of 5 ⁇ 10 5 Pa or more, preferably 1 ⁇ 10 6 Pa or more. it can.
  • Those skilled in the art can easily prepare a cured product by determining the composition of the composition having the above physical characteristics parameters with reference to the information described in the present specification and publicly known materials.
  • 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 and the aromatic polyene as a component of the monomer in the composition 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.
  • 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 electrically insulating layer or an adhesive layer of a base material / 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) base material.
  • coverlays 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 electrically insulating layer or an adhesive layer of a base material / substrate such as a single-layer or multi-layer printed circuit board, a flexible printed circuit board, a CCL (copper
  • 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.
  • 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.
  • It is used as a substitute for the conventionally used epoxy resin or silicone resin sheets, and can be cured to form a cured insulating layer or cured matrix phase having a low dielectric constant and 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 in which a part or the whole is insulated by this sheet can be used instead of the conventional coaxial cable.
  • LCP liquid crystal polymer
  • PPE sheet polyethylene sheet
  • fluororesin or polyimide resin
  • B stage sheet coverlay sheet
  • a multilayer wiring board in which the cured product obtained by using the composition of the present invention is an insulating layer can be a wiring board having little 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 an epoxy, a core material such as a general-purpose laminated plate, and a conductor foil with an insulating layer made of this cured product are laminated and pressed.
  • a slurry or solution containing the present composition may be applied to the 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 cured product obtained by curing a particularly varnish-like composition of the present invention can be suitably used as an electrically insulating material as described above, and in particular, a potting material, a surface coating agent, a coverlay, a solder resist, a build-up material, etc.
  • an underfill material filling insulation, interlayer insulation, interlayer adhesive, or as a cured product, as a printed circuit board, flexible printed circuit board, FCCL (flexible copper clad laminate) base material, or as a build-up film, bonding sheet, coverlay sheet , Can be used as an electrically insulating material, particularly as an electrically insulating material for high frequencies, as a cured body of a bump sheet for a flip tip bonder.
  • the present invention contains an olefin-aromatic vinyl compound-aromatic polyene copolymer, has a storage elastic modulus of 5 ⁇ 10 5 Pa or more at 300 ° C., and has a dielectric constant of 2.5 ° C. at 23 ° C. and 10 GHz. It is an electrically insulating material having a dielectric loss tangent of 0.003 or less and 0.0005 or more.
  • the uncured or semi-cured thermoplastic composition of the present invention can be adhered to a metal leaf for wiring, particularly a copper foil, by heat and pressure treatment without applying an adhesive or adhering treatment. ..
  • the copper foil is a concept including copper wiring, and its shape is arbitrary.
  • the olefin-aromatic vinyl compound-aromatic polyene copolymer preferably when a copolymer having an aromatic vinyl compound content of 10% by mass or more is used, and / or whether the olefin is ethylene alone or not.
  • 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, and the measurement according to the Japanese Industrial Standards (JIS) C6481: 1996 is 1 N / mm.
  • JIS Japanese Industrial Standards
  • the above peeling strength can be given. Furthermore, it is more preferable to give a peel strength of 1.3 N / mm or more.
  • the olefin is ethylene alone, or the olefin monomer component other than ethylene is 1/10 or less of the ethylene monomer component contained in the olefin, and most preferably the copolymer.
  • the peeling strength can be further improved.
  • JIS Japanese Industrial Standards
  • the olefin-aromatic vinyl compound-aromatic polyene copolymer satisfying the following conditions (1) to (4), and a monomer based on 100 parts by mass of the present copolymer.
  • a curable composition containing more than 0 parts by mass and 10 parts by mass or less, wherein the monomer is selected from the group consisting of an aromatic vinyl compound monomer, an aromatic polyene monomer, and a polar monomer.
  • a curable composition which is one or more of the above can also be provided.
  • the number average molecular weight of the copolymer is 5,000 or more and 100,000 or less.
  • the aromatic vinyl compound monomer in the copolymer 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 0% by mass or more and 70% by mass or less.
  • 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 total of the olefin monomer unit, the aromatic vinyl compound monomer unit, and the aromatic polyene monomer unit is 100% by mass. Is.
  • the monomer may be a polar monomer.
  • a cured product obtained by curing the curable composition, and has a storage elastic modulus at 300 ° C. of 5 ⁇ 10 5 Pa or more, preferably 1 ⁇ 10 6 Pa or more, and a dielectric constant of 23 ° C. and 10 GHz.
  • An electrically insulating material having a dielectric constant contact of 2.5 or less and 2.0 or more and a dielectric loss tangent of 0.003 or less and 0.0005 or more can also be provided.
  • the present curable composition is the same as the curable composition containing the olefin-aromatic vinyl compound-aromatic polyene copolymer and the resin (hereinafter, simply referred to as the composition with the resin), the solvent and the curing agent.
  • the present curable composition can be molded into various shapes including a sheet such as a composition with the resin by taking advantage of thermoplasticity.
  • the present curable composition can be used as a varnish together with a solvent in the same manner as the composition with the resin.
  • the present invention is a cured product obtained by curing the present curable composition, and can exhibit various physical properties similar to those of the cured product of the composition with the resin.
  • the present curable composition can be a laminate containing a layer containing the curable composition and a copper foil in the same manner as the composition with the resin, and the present laminate can be cured to obtain a cured product. You can also
  • the composition according to the above-described embodiment of the present invention, or the composition according to another embodiment, is also cured together with the 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 particularly 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 body 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.
  • the 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. When the melting point is within the above range, a film or sheet having excellent extrusion moldability and heat resistance can be obtained.
  • Such 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 by 1 H-NMR from the peak area intensity assigned to each.
  • 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. (When the number average molecular weight is 1000 or more) Column: TSK-GEL Multipore HXL-M ⁇ 7.8 ⁇ 300 mm (manufactured by Tosoh Corporation) was used by connecting two in series. Column temperature: 40 ° C Solvent: THF Liquid flow rate: 1.0 ml / min. Detector: RI detector (differential refractive index detector)
  • 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.
  • ⁇ 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, and the tensile breaking point elongation were determined by measuring at / min.
  • 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.
  • ⁇ Measurement of storage elastic modulus and crosslink density> 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.
  • a cavity resonator perturbation method (8722ES type network analyzer manufactured by Agilent Technologies, cavity resonator manufactured by Kanto Electronics Applied Development Co., Ltd.) was used, and a 1 mm ⁇ 1.5 mm ⁇ 80 mm sample cut out from a sheet was used. Values at ° C. and 10 GHz were measured.
  • the raw materials are as follows. As divinylbenzene, divinylbenzene (meth, paramixture, divinylbenzene purity 81%) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. was used.
  • the bifunctional polyphenylene ether oligomer (OPE-2St, number average molecular weight 1200) is obtained by diluting a toluene solution product manufactured by Mitsubishi Gas Chemical Company with toluene, adding a large amount of methanol to precipitate methanol, air-drying, and then drying under reduced pressure. By doing so, a powdered polyphenylene ether oligomer was obtained and used.
  • Tough Tech H-1041 (number average molecular weight 58000) manufactured by Asahi Kasei Chemicals Co., Ltd. was used.
  • 1,2-polybutadiene liquid polybutadiene manufactured by Nippon Soda Corporation: product name B-3000 (number average molecular weight 3200) was used.
  • the curing agent is NOF Corporation's Dikmyl Peroxide (trade name "Park Mill D") or 2,5-dimethyl-2,5-bis (t-butylperoxy) hexin-3 (trade name "Perhexin 25B”). ) was used.
  • Example 1 Composition of resin P-1 (ethylene-styrene-divinylbenzene copolymer) and the monomers and resins shown in Table 2 that have been kneaded in advance using a Brabender plastic coder (PL2000 type manufactured by Brabender). Add the product (the composition in the table indicates the part by mass), knead at 120 ° C. at a rotation speed of 30 times / minute for 10 minutes, and add a curing agent (dicumyl peroxide, manufactured by Nichiyu Co., Ltd.) to the resin in a single amount. 1 part by mass was added to 100 parts by mass of the body composition and kneaded under the present conditions for 5 minutes to prepare a composition.
  • a curing agent dicumyl peroxide, manufactured by Nichiyu Co., Ltd.
  • the obtained composition is sandwiched between a mold and two Teflon (registered trademark) sheets, closely sealed, and pressed by a heating press method (120 ° C., time 5 minutes, pressure 5 MPa) to various thicknesses (thickness 1).
  • a sheet (uncured sheet) of (0.0 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 film-like cured product of the composition of the present invention.
  • Example 2 Comparative Example 1
  • 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). It was press-molded and cured in the same manner as in Example 1. However, in Example 5, raw materials other than the curing agent were kneaded at 100 ° C. and a rotation speed of 50 times / minute for 10 minutes, then a curing agent (dicumyl peroxide) was added, and further kneading was performed under these conditions for 5 minutes. However, in Example 4, perhexine 25B was used as a curing agent. In Examples 3, 4, and 7, which will be described later, 1,2-polybutadiene was added before the curing agent was added.
  • Table 2 the formulations in the table indicate parts by mass
  • the properties (room temperature) of the compositions of Examples 1 to 6 and Comparative Example 1 before curing are soft resin-like and semi-hard resin-like sheets, which are easy to handle as sheets and obtained after pressing with Teflon. (Registered trademark) Even if it was peeled off from the sheet, the self-adhesiveness of the sheet itself was low, and it could be handled as a single sheet. In the examples satisfying the preferable conditions of the present invention, the molding process as a thermoplastic resin was easy in an uncured state.
  • Examples 7-8, Comparative Examples 2-4 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. Dicumyl peroxide was used as the curing agent. The obtained varnish-like composition is poured into a Teflon (registered trademark) mold on a Teflon (registered trademark) sheet, and the solvent is sufficiently blown off at about 100 ° C. in a blower dryer and then under reduced pressure, and then Teflon.
  • Teflon registered trademark
  • Teflon registered trademark
  • 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 heat-treated at 120 ° C. for 30 minutes, 150 ° C. for 30 minutes, and then at 200 ° C. for 120 minutes to cure. After curing, the glass plate, Teflon (registered trademark) sheet and mold were removed to obtain a cured product sheet of the composition of the present invention.
  • the cured products of the sheets obtained in Examples 1 to 8 can be measured for elastic modulus without melt fracture even at 300 ° C. by viscoelastic spectrum measurement, and the storage elastic modulus at 300 ° C. (573K) is 5 ⁇ 10 5 It was more than Pa. Further, the cross-linking densities determined from the storage elasticity at 300 ° C. (573K) are all higher than 3 ⁇ 10 -5 mol / cm 3 , indicating that the cross-linking is sufficiently progressing. In addition, 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 less than 50 MPa, and the tensile breaking point elongation was 50% or more and less than 250%.
  • the permittivity and the dielectric loss tangent also satisfy the scope of the present invention.
  • the water absorption rates of the cured product sheets obtained in Examples 1 to 8 were all less than 0.1% by mass, and the volume resistivity was 1 ⁇ 10 15 ⁇ ⁇ cm or more.
  • the cured sheets obtained in Examples 1 to 8 have a dielectric constant of 2.5 or less and 2.0 or more and a dielectric loss tangent of 0.003 or less and 0.0005 or more measured at 10 GHz, and have good low dielectric properties. Indicated.
  • the cured product of the sheet obtained in Comparative Example 1 does not satisfy the conditions of the present invention in terms of storage elastic modulus at 300 ° C. and cross-linking density.
  • the sheet obtained in Comparative Example 2 had a large number of cracks and was unsuitable for use as an insulating material, and various physical properties were not measured. Since the sheets obtained in Comparative Examples 3 and 4 did not satisfy the preferable ranges of the dielectric constant and the dielectric loss tangent of the present invention, no other evaluation was carried out.
  • Example 1 ⁇ Peeling strength of copper foil from roughened surface>
  • the copper foil used was manufactured by Mitsui Mining & Smelting Co., Ltd. (VSP series, TQ-M7-VSP, thickness 12 ⁇ m).
  • the composition of Example 1 was placed on an uncured sheet having a thickness of 0.3 mm obtained by press molding at 120 ° C., 5 MPa for 2 minutes so that the roughened surface of the copper foil was in contact with the sheet, and the thickness was 0.3 mm.
  • the sheet and the copper foil were adhesively cured by heating and pressurizing with a heating press using a mold at a pressure of 5 MPa, 120 ° C. for 30 minutes, then 150 ° C. for 30 minutes, and then 200 ° C. for 120 minutes.
  • the peel strength measurement with the copper foil was evaluated by 90 ° peeling according to Japanese Industrial Standards (JIS) C6481: 1996. As a result, the peel strength was 2.3 N / mm. Similarly, the composition of Example 4 was measured for peel strength from the copper foil and found to be 1.5 N / mm.
  • MMAO-3A toluene solution manufactured by Fine Chem Co., Ltd. cyclohexane was used as a solvent, and styrene, divinylbenzene, and ethylene were used as raw materials, and the amount of monomer, ratio, polymerization pressure, and polymerization temperature were appropriately changed to carry out polymerization.
  • 1-Isopropanol was added to the obtained polymerization solution, and then a large amount of methanol was added in the presence of a polymerization inhibitor to recover the copolymerized oligomer.
  • the copolymerized oligomer O-1 was vacuum dried at 50 ° C. for 2 days and nights.
  • a copolymer of P-5 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, the aromatic vinyl compound monomer unit, and the aromatic polyene monomer unit was set to 100% by mass.
  • Table 3 shows the compositions of the obtained O-1 and P-5, the number average molecular weight, and the glass transition temperature.
  • BMI-1500 manufactured by Designer Molecules Inc was used.
  • Examples 9 and 10 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 4, 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. Perhexin 25B was used as the curing agent. The obtained varnish-like composition was poured into a Teflon (registered trademark) mold on a Teflon (registered trademark) sheet, and the solvent was sufficiently blown off at about 60 ° C. in a blower dryer and then under reduced pressure.
  • Teflon registered trademark
  • Teflon registered trademark
  • the obtained sheet was sandwiched between Teflon (registered trademark) sheets and a mirror-surfaced metal plate and brought into close contact with each other by applying a load, and heat-treated at 120 ° C. for 30 minutes, 150 ° C. for 30 minutes, and then at 200 ° C. for 120 minutes to cure. After curing, the metal plate, Teflon (registered trademark) sheet and mold were removed to obtain a cured product sheet of the composition of the present invention.
  • Example 11 Silica filler (50% by volume of silica filler with respect to 50% by volume of resin component) was added to the varnish-like composition obtained in the same manner as in Examples 9 and 10 and further stirred, and the obtained slurry-like varnish was further fluffed.
  • Stir with Tori Rentaro manufactured by Shinky
  • the obtained sheet was sandwiched between Teflon (registered trademark) sheets and a mirror-surfaced metal plate and brought into close contact with each other by applying a load, and heat-treated at 120 ° C.
  • Examples 12 and 13 ⁇ Evaluation as an adhesive between copper foil and LCP (liquid crystal polymer) sheet> Using the varnishes obtained in Examples 9 and 10, 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.
  • 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 30 ⁇ 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
  • Comparative Example 5 Heat crimping was performed with a press machine under the same conditions as in the examples using only the copper foil and the LCP sheet, but the two did not substantially adhere to each other.
  • divinylbenzene divinylbenzene (meth, paramixture, divinylbenzene purity 81%) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. was used.
  • BVPE 1,2-bis (vinylphenyl) ethane
  • 1,2-PBd B-3000 manufactured by Nippon Soda Co., Ltd. was used.
  • bifunctional polyphenylene ether oligomer OPE-2St, number average molecular weight 1200
  • a toluene solution product manufactured by Mitsubishi Gas Chemical Company is further diluted with toluene, a large amount of methanol is added, methanol precipitation is performed, air drying is performed, and the pressure is reduced.
  • SEBS H-1041 manufactured by Asahi Kasei Chemicals Co., Ltd. was used.
  • NOF Corporation's Dikmyl Peroxide (Park Mill D) was used.
  • Table 6 shows the formulations and the like of each Example and Comparative Example.
  • Example 1a Using a Brabender plastic coder (PL2000 type manufactured by Brabender), the pre-kneaded copolymer P-1a (ethylene-styrene-divinylbenzene copolymer) and the monomer were added, and the temperature was adjusted to 100 ° C. Knead at a rotation speed of 50 times / minute for 5 minutes, and further add 1 part by mass of a curing agent (dicumyl peroxide, manufactured by Nichiyu Co., Ltd.) to 100 parts by mass of the total of the copolymer and the monomer to 100 ° C. A composition was prepared by kneading under the conditions of a rotation speed of 50 times / minute for 5 minutes.
  • a curing agent dicumyl peroxide
  • the obtained composition is sandwiched between a mold and two Teflon (registered trademark) sheets, closely sealed, and pressed by a heating press method (120 ° C., time 5 minutes, pressure 5 MPa) to various thicknesses (thickness 1).
  • a sheet (uncured sheet) of (0.0 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 film-like cured product of the composition of the present invention.
  • Example 2a-4a Comparative Examples 1a-2a
  • the composition was prepared according to the same procedure as in Example 1a with the formulations shown in Table 6 (the formulations in the table indicate parts by mass). It was press-molded and cured in the same manner as in Example 1a.
  • the properties (room temperature) of the compositions of Examples 1a to 4a before curing are soft resin-like and semi-hard resin-like sheets, which are easy to handle as sheets, and are Teflon (registered trademark) sheets after pressing. Even if it was peeled off from the sheet, the self-adhesiveness of the sheet itself was low, and it could be handled as a single sheet.
  • the molding process as a thermoplastic resin was easy in an uncured state.
  • Comparative Examples 1a and 2a the raw materials were kneaded in advance by stirring at about 60 ° C. using a glass container equipped with a stirrer and a hot water jacket, a curing agent was added, and kneading was further carried out under these conditions for 10 minutes. It was press-molded and cured in the same manner as in Example 1a.
  • the properties (room temperature) of the compositions obtained in both Comparative Examples 1a and 1a and 2a before curing were semi-solid and viscous resin-like.
  • release sheet Teflon (registered trademark) sheet
  • the cured products of the composition sheets obtained in Examples 1a to 4a can be measured for elastic modulus without melt fracture even at 300 ° C. by viscoelastic spectrum measurement, and the storage elastic modulus at 300 ° C. (573K) is 5 ⁇ . was 10 5 Pa or more. Further, the cross-linking densities obtained from the storage elastic modulus at 300 ° C. (573K) are all higher than 3 ⁇ 10 -5 mol / cm 3 , indicating that the cross-linking is sufficiently progressing. In addition, 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 less than 50 MPa, and the tensile breaking point elongation was 50% or more and less than 250%.
  • 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 1a to 4a were all less than 0.1% by mass, and the volume resistivity was 1 ⁇ 10 15 ⁇ ⁇ cm or more.
  • the cured products of the sheets obtained in Comparative Examples 1a and 2a have too low tensile elastic modulus at room temperature, and the storage elastic modulus at 300 ° C. and the crosslink density do not satisfy the conditions of the present invention.
  • Example 1a The composition of Example 1a was press-molded at 120 ° C., 5 MPa for 2 minutes and placed on an uncured sheet having a thickness of 0.3 mm so that the roughened surface of the copper foil was brought into contact with the sheet, and the thickness was 0.3 mm.
  • the sheet and the copper foil were adhesively cured by heating and pressurizing with a heating press using a mold at a pressure of 5 MPa, 120 ° C. for 30 minutes, then 150 ° C. for 30 minutes, and then 180 ° C. for 120 minutes.
  • the peel strength measurement with the copper foil was evaluated by 90 ° peeling according to Japanese Industrial Standards (JIS) C6481: 1996. As a result, the peel strength was 1.7 N / mm.
  • the cured product obtained by curing the composition of the present invention has excellent low dielectric properties and electrical insulation properties, exhibits a specific range of elastic modulus, heat resistance, and water resistance, and exhibits at normal temperature and high temperature range.
  • the peeling strength with the copper foil was also practically sufficient.
  • it can exhibit high peel strength with a LCP (liquid crystal polymer) sheet under relatively mild conditions.
  • This curable composition can exhibit a solid state that can be molded into a film, and exhibits thermoplasticity that can be melted by heating under curing conditions, molded into various shapes, and cured. Therefore, it is easy to mold into various shapes including a sheet, and then heat curing can be performed.
  • the cured product can be suitably used as an electrically insulating material particularly for high frequencies.
  • This cured product can be suitably used as a thin film electrical insulating material and a high frequency electrical insulating material.
  • the present invention has a low content of a monomer component in the composition, and it is possible that the composition is substantially free of the monomer component.
  • the composition of the present invention can be used as a coverlay film, a solder resist film, a build-up film, a bonding sheet, a coverlay sheet, a bump sheet for a flip chip bonder, an interlayer insulating agent, and an interlayer adhesive in an uncured state. ..
  • the present invention can be used as a printed circuit board, a flexible printed circuit board, a CCL (copper clad laminate) base material, and an FCCL (flexible copper clad laminate) base material. Further, it can be used as an insulating layer for a substrate.

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022014599A1 (https=) * 2020-07-15 2022-01-20
WO2022054885A1 (ja) * 2020-09-11 2022-03-17 デンカ株式会社 組成物及びその硬化体
WO2023063357A1 (ja) 2021-10-14 2023-04-20 デンカ株式会社 絶縁層を含む多層構造体
JPWO2023140262A1 (https=) * 2022-01-19 2023-07-27
WO2023164430A1 (en) * 2022-02-22 2023-08-31 AGC Multi Material America, Inc. Curable compositions
WO2023190602A1 (ja) 2022-03-28 2023-10-05 デンカ株式会社 組成物
JP2024064932A (ja) * 2022-10-27 2024-05-14 南亞塑膠工業股▲分▼有限公司 樹脂組成物
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WO2024143509A1 (ja) 2022-12-27 2024-07-04 デンカ株式会社 共重合体、その製造方法及び共重合体を含む硬化体
JP2024180228A (ja) * 2023-06-14 2024-12-26 南亞塑膠工業股▲分▼有限公司 樹脂組成物
JP2025009689A (ja) * 2023-06-28 2025-01-20 南亞塑膠工業股▲分▼有限公司 樹脂組成物
WO2025028516A1 (ja) 2023-08-02 2025-02-06 デンカ株式会社 未硬化シート及びその硬化体
WO2025041755A1 (ja) * 2023-08-23 2025-02-27 デンカ株式会社 組成物、成形体及び硬化体、並びに、積層体
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JP2025081230A (ja) * 2023-10-12 2025-05-27 李長榮化學工業股▲ふん▼有限公司 ポリマー複合体、その使用、低誘電樹脂組成物、プリプレグ、および金属箔積層板
WO2026009901A1 (ja) * 2024-07-03 2026-01-08 デンカ株式会社 低誘電放熱材料

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5231272A (en) 1975-09-02 1977-03-09 Kanda Tekko Kk Method to form drop-out preventive angle for speed-change gear fitted to automobiles
JPH06192392A (ja) 1992-12-24 1994-07-12 Sumitomo Bakelite Co Ltd 低誘電率熱硬化性樹脂組成物
JPH0940709A (ja) 1995-07-31 1997-02-10 Denki Kagaku Kogyo Kk エチレン−芳香族ビニル化合物共重合体の製造方法
JPH1160645A (ja) 1997-08-27 1999-03-02 Tdk Corp 耐熱性低誘電性高分子材料ならびにそれを用いたフィルム、基板、電子部品および耐熱性樹脂成形品
WO2000037517A1 (en) 1998-12-22 2000-06-29 Denki Kagaku Kogyo Kabushiki Kaisha Cross-copolymerized olefin/styrene/diene copolymer, process for the production of the same and uses thereof
JP2003212941A (ja) 2002-01-21 2003-07-30 Hitachi Ltd 低誘電正接化方法及びそれを用いた低誘電正接樹脂組成物及び電気部品
JP2004087639A (ja) 2002-08-26 2004-03-18 Hitachi Ltd 低誘電正接絶縁材料を用いた高周波用電子部品
JP2005089631A (ja) * 2003-09-18 2005-04-07 Umg Abs Ltd 熱可塑性樹脂組成物およびその成形品
JP2006176708A (ja) * 2004-12-24 2006-07-06 Denki Kagaku Kogyo Kk 樹脂組成物
JP2008291227A (ja) 2007-04-26 2008-12-04 Hitachi Chem Co Ltd セミｉｐｎ型複合体の熱硬化性樹脂を含有する樹脂ワニスの製造方法、並びにこれを用いたプリント配線板用樹脂ワニス、プリプレグ及び金属張積層板
JP2009161743A (ja) 2007-12-10 2009-07-23 Denki Kagaku Kogyo Kk 後硬化性樹脂組成物及びそれを用いた高周波用電気絶縁材料
JP2010280771A (ja) 2009-06-03 2010-12-16 Denki Kagaku Kogyo Kk 後硬化性樹脂組成物及びそれを用いた電気絶縁材料
JP2010280860A (ja) 2009-06-08 2010-12-16 Denki Kagaku Kogyo Kk 高充填樹脂組成物
JP2012102173A (ja) * 2010-11-08 2012-05-31 Denki Kagaku Kogyo Kk 難燃性樹脂組成物
WO2015050080A1 (ja) * 2013-10-03 2015-04-09 株式会社クラレ 熱可塑性液晶ポリマーフィルム、回路基板、およびそれらの製造方法
WO2016114287A1 (ja) 2015-01-13 2016-07-21 日立化成株式会社 フレキシブルプリント配線板用樹脂フィルム、樹脂付き金属箔、カバーレイフィルム、ボンディングシート及びフレキシブルプリント配線板
WO2020153391A1 (ja) 2019-01-25 2020-07-30 デンカ株式会社 両面金属張積層体とその製造方法、絶縁フィルムおよび電子回路基板

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51109134A (ja) * 1975-03-20 1976-09-27 Obayashi Constr Co Ltd Atsukishiirudoshikitonnerukutsusakukojini okeru tatekoteishobansetsuchihoho
JPS51124187A (en) 1975-04-23 1976-10-29 Nippon Telegr & Teleph Corp <Ntt> Preparation of polyethylene having low dielectric loss
US6265493B1 (en) 1999-07-21 2001-07-24 The Penn State Research Foundation Polyolefin graft copolymers derived from linear copolymers of alpha-olefins and divinylbenzene having narrow molecular weight and composition distributions and process for preparing same
JP2002265721A (ja) * 2001-03-07 2002-09-18 Denki Kagaku Kogyo Kk 重合体組成物
JP4750300B2 (ja) * 2001-03-12 2011-08-17 電気化学工業株式会社 ヒートシール用フィルム
EP2022806B1 (en) 2006-05-29 2011-11-30 Denki Kagaku Kogyo Kabushiki Kaisha Process for production of cross copolymers, cross copolymers obtained by the process, and use thereof
BRPI0911051A2 (pt) * 2008-04-15 2015-12-29 Denki Kagaku Kogyo Kk composição de resina termoplástica.
JP2010013575A (ja) * 2008-07-04 2010-01-21 Denki Kagaku Kogyo Kk 耐摩耗性、耐熱性、シボ保持性に優れた熱可塑性樹脂組成物及びその表皮シート
JP2011074187A (ja) 2009-09-30 2011-04-14 Denki Kagaku Kogyo Kk 易架橋性熱可塑性樹脂
KR20110060645A (ko) 2009-11-30 2011-06-08 성균관대학교산학협력단 지중 차수벽 및 이의 시공방법
JP2011207936A (ja) * 2010-03-29 2011-10-20 Denki Kagaku Kogyo Kk 表皮材用シ−ト
CN104663007B (zh) * 2012-09-20 2017-10-24 株式会社可乐丽 电路基板及其制造方法
JP2015032639A (ja) 2013-07-31 2015-02-16 日立化成株式会社 先塗布型熱硬化性アンダーフィル組成物、電子部品装置及び電子部品装置の製造方法
WO2015072466A1 (ja) * 2013-11-12 2015-05-21 電気化学工業株式会社 熱可塑性エラストマー樹脂組成物
CN106459327A (zh) * 2014-05-15 2017-02-22 电化株式会社 交联共聚物和其制造方法
JP6332458B2 (ja) 2014-07-31 2018-05-30 東亞合成株式会社 接着剤層付き積層体、並びに、これを用いたフレキシブル銅張積層板及びフレキシブルフラットケーブル
DE112016004386T5 (de) * 2015-09-28 2018-06-07 Denka Company Limited Kreuz-Copolymere sowie Herstellungsverfahren dafür
US20190077893A1 (en) * 2015-12-25 2019-03-14 Denka Company Limited Cross-copolymer and medical single-layer tube including same
CN106928446B (zh) * 2015-12-30 2019-08-13 台光电子材料(昆山)有限公司 改质聚苯醚树脂、其制备方法及树脂组合物
JP6995534B2 (ja) 2016-08-31 2022-01-14 日鉄ケミカル＆マテリアル株式会社 可溶性多官能ビニル芳香族共重合体、その製造方法、硬化性樹脂組成物及びその硬化物
JP6561153B2 (ja) 2017-02-20 2019-08-14 株式会社有沢製作所 樹脂組成物、接着フィルム、カバーレイフィルム、積層板、樹脂付き銅箔及び樹脂付き銅張り積層板
CN109385018A (zh) 2017-08-04 2019-02-26 广东生益科技股份有限公司 一种热固性树脂组合物及使用其制作的半固化片与覆金属箔层压板
CN109385021A (zh) 2017-08-04 2019-02-26 广东生益科技股份有限公司 一种热固性树脂组合物及使用其制作的半固化片与覆金属箔层压板
JP7465894B2 (ja) * 2019-12-03 2024-04-11 デンカ株式会社 硬化性組成物及びその硬化体
CN118599040A (zh) 2020-07-15 2024-09-06 电化株式会社 组合物及固化体

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5231272A (en) 1975-09-02 1977-03-09 Kanda Tekko Kk Method to form drop-out preventive angle for speed-change gear fitted to automobiles
JPH06192392A (ja) 1992-12-24 1994-07-12 Sumitomo Bakelite Co Ltd 低誘電率熱硬化性樹脂組成物
JPH0940709A (ja) 1995-07-31 1997-02-10 Denki Kagaku Kogyo Kk エチレン−芳香族ビニル化合物共重合体の製造方法
JPH1160645A (ja) 1997-08-27 1999-03-02 Tdk Corp 耐熱性低誘電性高分子材料ならびにそれを用いたフィルム、基板、電子部品および耐熱性樹脂成形品
WO2000037517A1 (en) 1998-12-22 2000-06-29 Denki Kagaku Kogyo Kabushiki Kaisha Cross-copolymerized olefin/styrene/diene copolymer, process for the production of the same and uses thereof
JP2003212941A (ja) 2002-01-21 2003-07-30 Hitachi Ltd 低誘電正接化方法及びそれを用いた低誘電正接樹脂組成物及び電気部品
JP2004087639A (ja) 2002-08-26 2004-03-18 Hitachi Ltd 低誘電正接絶縁材料を用いた高周波用電子部品
JP2005089631A (ja) * 2003-09-18 2005-04-07 Umg Abs Ltd 熱可塑性樹脂組成物およびその成形品
JP2006176708A (ja) * 2004-12-24 2006-07-06 Denki Kagaku Kogyo Kk 樹脂組成物
JP2008291227A (ja) 2007-04-26 2008-12-04 Hitachi Chem Co Ltd セミｉｐｎ型複合体の熱硬化性樹脂を含有する樹脂ワニスの製造方法、並びにこれを用いたプリント配線板用樹脂ワニス、プリプレグ及び金属張積層板
JP2009161743A (ja) 2007-12-10 2009-07-23 Denki Kagaku Kogyo Kk 後硬化性樹脂組成物及びそれを用いた高周波用電気絶縁材料
JP2010280771A (ja) 2009-06-03 2010-12-16 Denki Kagaku Kogyo Kk 後硬化性樹脂組成物及びそれを用いた電気絶縁材料
JP2010280860A (ja) 2009-06-08 2010-12-16 Denki Kagaku Kogyo Kk 高充填樹脂組成物
JP2012102173A (ja) * 2010-11-08 2012-05-31 Denki Kagaku Kogyo Kk 難燃性樹脂組成物
WO2015050080A1 (ja) * 2013-10-03 2015-04-09 株式会社クラレ 熱可塑性液晶ポリマーフィルム、回路基板、およびそれらの製造方法
WO2016114287A1 (ja) 2015-01-13 2016-07-21 日立化成株式会社 フレキシブルプリント配線板用樹脂フィルム、樹脂付き金属箔、カバーレイフィルム、ボンディングシート及びフレキシブルプリント配線板
WO2020153391A1 (ja) 2019-01-25 2020-07-30 デンカ株式会社 両面金属張積層体とその製造方法、絶縁フィルムおよび電子回路基板

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
M. KAWABE ET AL.: "Synthesis of polyfunctional aromatic vinyl copolymers and development of novel IPN-type low dielectric loss material using the same", JOURNAL OF THE JAPAN INSTITUTE OF ELECTRONICS PACKAGING, vol. 12, no. 2, 2009, pages 125

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US12359049B2 (en) 2020-09-11 2025-07-15 Denka Company Limited Composition and cured product thereof
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