Classifications

• • 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
  • H01B3/448—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 from other vinyl compounds
• • 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
  • C08F212/00—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
  • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
  • C08F212/36—Divinylbenzene
• • 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
  • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
  • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
• • 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
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
  • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
  • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
• • 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
  • C08F212/00—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
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
  • C08F212/08—Styrene
• • 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
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• • 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
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

• the present invention relates to a copolymer, a method for producing the copolymer, and a cured body containing the copolymer.
• substrates and insulating materials made of post-curing resins such as epoxy resin, unsaturated polyester resin, polyimide resin, and phenol resin have been widely used due to their heat resistance and ease of handling, but their dielectric constant and dielectric loss are relatively high, and improvements are needed as insulating materials for high frequencies (Patent Document 1).
• thermoplastic resin cyclic olefin-based (co)polymers with high glass transition temperatures (Tg) have been proposed as the main insulating material as a thermoplastic resin (Patent Documents 2 and 3).
• Tg glass transition temperatures
• crosslinkable (curable) resins are preferable in consideration of process compatibility and process window.
• a hydrocarbon-based resin which is originally a thermoplastic resin, into a curable resin, it is necessary to introduce a crosslinkable functional group, but functional groups that react to radicals or heat generally have polarity, which deteriorates the low dielectric properties.
• Patent Document 4 When attempting to introduce a functional group composed only of hydrocarbons, such as an aromatic vinyl group, in many cases an intermolecular reaction between expensive hydrocarbon-based raw materials is utilized (Patent Document 4), which is often not economical.
• Patent Document 5 shows a cured body obtained from a specific coordination polymerization catalyst and consisting of an ethylene-olefin (aromatic vinyl compound)-aromatic polyene copolymer and a non-polar vinyl compound copolymer having a specific composition and formulation.
• the olefin-aromatic vinyl compound-aromatic polyene copolymer specifically described is relatively soft, and in order to harden it, it is necessary to blend a large amount of other crosslinkable hard resins or inorganic fillers.
• the known crosslinkable hard resins have insufficient low dielectric properties, and there is a problem that the low dielectric properties of the cured body decrease when a large amount is blended.
• the dielectric constant of the obtained cured body becomes high, especially because inorganic fillers generally have a high dielectric constant.
• Aspect 5 The copolymer according to any one of Aspects 1 to 4, which, when cured alone, exhibits a dielectric constant of less than 3.5 and a dielectric loss tangent of less than 0.001 at a measurement frequency of 40 GHz.
• Aspect 8 The copolymer according to any one of Aspects 1 to 7, wherein when cured alone, the cured product has a storage modulus of 5 MPa or more as measured at 280° C.
• the aromatic polyene unit is one or more selected from polyenes having 5 to 20 carbon atoms and having a plurality of vinyl groups and/or vinylene groups in the molecule, and the content of the vinyl groups and/or vinylene groups derived from the aromatic polyene monomer unit is 2 to 30 per number average molecular weight.
• the total content of ⁇ -olefin units, cyclic olefin units, and aromatic polyene units is 100 mass%.
• the copolymer according to aspect 2 which satisfies all of the following (1) to (6): (1) The number average molecular weight of the copolymer is 500 or more and 100,000 or less. (2) The ⁇ -olefin unit is an ⁇ -olefin having 2 to 20 carbon atoms. (3) The aromatic vinyl compound unit is an aromatic vinyl compound having 8 to 20 carbon atoms. (4) The cyclic olefin unit is a cyclic olefin monomer unit having from 10 to 30 carbon atoms, and the content thereof is from 30% by mass to 99% by mass.
• Aspect 14 A method for producing the copolymer according to any one of Aspects 1 to 13, comprising copolymerizing monomers of an ⁇ -olefin, a cyclic olefin, and an aromatic polyene, and optionally an aromatic vinyl compound, by coordination polymerization using a coordination polymerization catalyst.
• the aromatic polyene unit is one or more selected from polyenes having 5 to 20 carbon atoms and having a plurality of vinyl groups and/or vinylene groups in the molecule, and the content of the vinyl groups and/or vinylene groups derived from the aromatic polyene monomer unit is 2 to 30 per number average molecular weight.
• the total content of ⁇ -olefin units, cyclic olefin units, and aromatic polyene units is 100 mass%.
• a cured product of a composition comprising a resin component, a curing agent, a monomer, a solvent, and one or more additive components selected from the group consisting of a filler,
• the cured body has a dielectric constant of 3.5 or less and a dielectric tangent of 0.0015 or less at a measurement frequency of 40 GHz.
• An ⁇ -olefin-cyclic olefin-aromatic vinyl compound-aromatic polyene copolymer that satisfies all of the following (1) to (6); (1) The number average molecular weight of the copolymer is 500 or more and 100,000 or less. (2) The ⁇ -olefin unit is an ⁇ -olefin having 2 to 20 carbon atoms. (3) The aromatic vinyl compound unit is an aromatic vinyl compound having 8 to 20 carbon atoms. (4) The cyclic olefin unit is a cyclic olefin monomer unit having from 10 to 30 carbon atoms, and the content thereof is from 30% by mass to 99% by mass.
• the aromatic polyene unit is one or more selected from polyenes having 5 to 20 carbon atoms and having a plurality of vinyl groups and/or vinylene groups in the molecule, and the content of the vinyl groups and/or vinylene groups derived from the aromatic polyene monomer unit is 2 to 30 per number average molecular weight.
• the total content of ⁇ -olefin units, cyclic olefin units, aromatic vinyl compound units, and aromatic polyene units is 100 mass %.
• a method for producing a cured product comprising the step of polymerizing at least the copolymer according to any one of Aspects 1 to 13 with a radical polymerization initiator that does not contain oxygen atoms or nitrogen atoms in its structure and is composed only of carbon atoms and hydrogen atoms.
• the ⁇ -olefin unit is an ⁇ -olefin having 2 to 20 carbon atoms.
• the aromatic vinyl compound unit is an aromatic vinyl compound having 8 to 20 carbon atoms.
• the cyclic olefin unit is a cyclic olefin monomer having from 10 to 30 carbon atoms which may have an aromatic ring, and the content thereof is from 30% by mass to 99% by mass.
• the content of aromatic polyene monomer units in the copolymer is arbitrary, but is preferably less than 40% by mass, more preferably less than 30% by mass. At such a content, the number of crosslinking groups is appropriately suppressed, and the effect of improving the stability during copolymer production and the stability during curing is obtained.
• Suitable ⁇ -olefin-cyclic olefin-aromatic vinyl compound-aromatic polyene copolymers include one or more of the group consisting of propylene-norbornene-styrene-divinylbenzene copolymer, 1-hexene-norbornene-styrene-divinylbenzene copolymer, 1-octene-norbornene-styrene-divinylbenzene copolymer, ethylene-norbornene-ethylvinylbenzene-divinylbenzene copolymer, propylene-styrene-norbornene-divinylbenzene copolymer, 1-hexenestyrene-styrene-norbornene-divinylbenzene copolymer, and 1-octene-norbornene-styrene-divin
• copolymers in which the above-mentioned norbornene is replaced with dimethanooctahydronaphthalene (DMON), trimethanododecahydroanthracene (TMDA), phenylnorbornene (5-phenylbicyclo[2.2.1]hept-2-ene), or methylphenylnorbornene (5-methyl-5-phenylbicyclo[2.2.1]hept-2-ene) are also suitable examples of copolymers of the present invention.
• conjugated diene polymer examples include polybutadiene and 1,2-polybutadiene.
• aromatic vinyl compound-conjugated diene block or random copolymer and their hydrogenated products (hydrogenated products) examples include SBS, SIS, SEBS, SEPS, SEEPS, SEEBS, and the like.
• 1,2-polybutadiene that can be suitably used is available, for example, as a product of JSR Corporation, and is also available from Nippon Soda Co., Ltd. under the product names of liquid polybutadiene: B-1000, 2000, and 3000.
• Another olefin-aromatic vinyl compound-aromatic polyene copolymer not containing a cyclic olefin that can be used in the present invention is an olefin-aromatic vinyl compound-aromatic polyene copolymer that satisfies all of the following (A) to (E).
• (A) The number average molecular weight of the copolymer is 500 or more and 100,000 or less.
• the aromatic polyene monomer unit is one or more selected from polyenes having 5 to 20 carbon atoms and having a plurality of vinyl groups and/or vinylene groups in the molecule, and the content of the vinyl groups and/or vinylene groups derived from the aromatic polyene unit per number average molecular weight is 2 to 30. The content of the vinyl groups and/or vinylene groups derived from the aromatic polyene unit per number average molecular weight may be 2 to less than 30.
• the total of the olefin monomer units, the aromatic vinyl compound monomer units, and the aromatic polyene monomer units is 100 mass %. Details of the ⁇ -olefin, aromatic vinyl compound, and aromatic polyene monomers are as described above.
• Organic peroxides are also described in the catalogs of Fujifilm Wako Pure Chemical Industries, Ltd. and Tokyo Chemical Industry Co., Ltd.
• the curing agent used in the present invention can be obtained from these companies.
• a hydrocarbon-based radical polymerization initiator that does not contain oxygen atoms or nitrogen atoms in the structure, i.e., composed only of carbon atoms and hydrogen atoms, such as 2,3-dimethyl-2,3-diphenylbutane, can also be suitably used.
• the amount of curing agent used there are no particular restrictions on the amount of curing agent used, but generally, 0.01 to 10 parts by mass per 100 parts by mass of the composition (preferably excluding the curing agent and solvent) is preferred.
• the curing process should be carried out at an appropriate temperature and time, taking into account its half-life.
• the conditions can be determined according to the curing agent, but generally a temperature range of about 50°C to 180°C is appropriate.
• the amount of the monomer that may be contained in the composition of the present invention is arbitrary, but is preferably 300 parts by weight or less per 100 parts by weight of the copolymer.
• the composition may not substantially contain a monomer.
• the amount is preferably 1 part by weight or more, more preferably 5 parts by weight or more.
• the monomer is 30 parts by weight or less, the uncured composition is less likely to have a viscous property, and molding processing as a thermoplastic resin becomes easier.
• the content of the easily volatile monomer is below a certain level, odor at the uncured stage does not become a problem.
• the monomer that can be suitably 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 the aromatic vinyl compound monomers described above, the aromatic polyene monomers described above, the aromatic vinylene monomers described below, and/or the polar monomers described below.
• a monomer that can be polymerized by a radical polymerization initiator is preferred, and one or more of the group consisting of aromatic vinyl compounds and aromatic polyenes is more preferred.
• BVPE 1,2-bis(vinylphenyl)ethane described in JP-A-2003-212941 can also be suitably used.
• polar monomer A relatively small amount of polar monomer can be used for the purpose of imparting adhesion to other materials required as an insulating material.
• the polar monomer include various maleimides, bismaleimides, maleic anhydride, glycidyl (meth)acrylate, triallyl isocyanurate, tri(meth)acrylic isocyanurate, trimethylolpropane tri(meth)acrylate, etc.
• Maleimides and bismaleimides that can be used in the present invention are described in, for example, International Publication No. 2016/114287 and can be purchased, for example, from Daiwa Kasei Co., Ltd.
• maleimide group-containing compounds may be used as polyamino bismaleimide compounds from the viewpoints of solubility in organic solvents, high frequency characteristics, high adhesion to conductors, moldability of prepregs, etc.
• the polyamino bismaleimide compound can be obtained, for example, by subjecting a compound having two maleimide groups at the terminals to a Michael addition reaction with an aromatic diamine compound having two primary amino groups in the molecule.
• a polar monomer having a multifunctional group of two or more functional groups examples include bismaleimides, triallyl isocyanurate (TAIC), and trimethylolpropane tri(meth)acrylate.
• the amount of polar monomer that may be contained in the composition may be in the range of 0.1 to 30 parts by mass, preferably 0.1 to 10 parts by mass, per 100 parts by mass of the copolymer. By using 30 parts by mass or less, the dielectric constant and dielectric dissipation factor of the obtained cured body are reduced. For example, in a preferred embodiment, it is possible to suppress the dielectric constant of the cured body of the copolymer to 3.5 or less and the dielectric dissipation factor to 1.2 ⁇ 10 ⁇ 3 or less.
• solvent An appropriate solvent may be added to the composition of the present invention as necessary.
• the solvent is used to adjust the viscosity and fluidity of the composition.
• a volatile one is preferable, and for example, cyclohexane, toluene, ethylbenzene, acetone, isopropanol, etc. are used.
• 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 degree or more is preferable, because if the boiling point is high under atmospheric pressure, that is, if the volatility is low, the thickness of the applied film becomes uniform.
• the amount of the solvent used is preferably in the range of 10 to 2000 parts by mass, more preferably 5 to 500 parts by mass, and even more preferably 10 to 300 parts by mass, per 100 parts by mass of the composition of the present invention.
• the solvent is preferably removed by drying treatment or the like before curing the composition.
• inorganic or organic fillers may be added. These fillers are added for the purpose of controlling the thermal expansion coefficient, controlling the thermal conductivity, reducing the cost, etc., and the amount of the fillers added may be arbitrary depending on the purpose.
• the composition of the present invention can contain a large amount of inorganic fillers, and the amount that can be added can reach 2000 parts by mass per 100 parts by mass of copolymer.
• a known surface modifier such as a silane coupling agent.
• boron nitride (BN) is preferable as the inorganic filler.
• the dielectric constant becomes particularly high when a large amount is added, it is preferable to use less than 500 parts by mass, more preferably less than 400 parts by mass of fillers per 100 parts by mass of copolymer. Furthermore, in order to improve and enhance low dielectric properties (low dielectric constant, low dielectric loss tangent), hollow fillers or fillers with many voids may be added.
• organic fillers such as high molecular weight polyethylene, ultra-high molecular weight polyethylene, polystyrene, styrene-divinylbenzene copolymer, or fluororesins can be used.
• Fluororesins may be any known resin containing fluorine, such as PTFE (polytetrafluoroethylene) or PFA (perfluoroalkoxyalkane), and an example of such a resin is Fluon+ (registered trademark) EA-2000 from AGC.
• an organic filler When the melting point or glass transition temperature of an organic filler is lower than the solder reflow temperature of 290°C, it is preferable from the viewpoint of heat resistance that the organic filler itself is crosslinked, and it is preferable to mix it in the form of fine particles or powder. These organic fillers can also suppress increases in the dielectric constant and dielectric tangent.
• the high dielectric constant, low dielectric tangent insulating layer is suitable for applications such as capacitors, inductors for resonant circuits, filters, and antennas.
• Examples of the high dielectric constant insulating filler used in the present invention include inorganic fillers or metal particles that have been 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, JP-A-2004-087639.
• 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, per 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 coupling agents. The various silane coupling agents and titanate coupling agents may be used singly or in combination.
• the flow temperature of the curable resin or composition can be adjusted to suit the purpose and molding method by changing the compounding ratio of the "resin component,” “curing agent,” “monomer,” “solvent,” “filler,” or “other additives.”
• the composition of the present invention can take the product form of a "thermoplastic composition,” a “semi-cured state (such as a B-stage sheet),” or a “varnish.”
• composition of the present invention is obtained by mixing, dissolving or melting one or more of the following selected from the group consisting of "resin components”, “curing agents”, “monomers”, “solvents”, “fillers” and “other additives”.
• general additives added to ordinary resins such as lubricants, stabilizers, antioxidants, weather resistance agents, UV absorbers, etc., can be used to the extent that the object of the present invention is not hindered. Any known method can be used for mixing, dissolving and melting these.
• the preferred embodiment of the present composition is as follows.
• the resin component contains a certain proportion or more of the above-mentioned hydrocarbon elastomer, polyether resin, olefin-aromatic vinyl compound-aromatic polyene copolymer not containing cyclic olefin, or aromatic polyene resin, excluding resins that are liquid at room temperature
• the composition can be easily molded as a thermoplastic resin in an uncured state.
• the thermoplastic composition described above can be molded into various shapes such as a sheet in advance at or below the action temperature of the curing agent, and can be laminated and combined with a semiconductor element, wiring, or substrate as necessary, and then heated to cure and bond.
• the sheet is processed through various processing and assembly steps, and finally treated at a temperature and time above the action temperature or decomposition temperature of the curing agent to completely cure.
• This method is a common technique used for ethylene-vinyl acetate resin-based crosslinked sealant sheets for solar cells (photovoltaic power generation devices).
• the composition of the present invention can be made into a viscous liquid varnish depending on its composition and blending ratio.
• a sufficient amount of solvent and/or an appropriate amount of liquid monomer can be used to make the composition into a varnish.
• 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 a high boiling point under atmospheric pressure, i.e., low volatility, leads to a uniform thickness of the applied film.
• the composition can be cured by a known method, taking into consideration the curing conditions (temperature, time, pressure) of the curing agent contained therein.
• the curing conditions can be determined by taking into consideration the half-life temperature and the like disclosed for each peroxide.
• the dielectric constant and dielectric loss tangent of the cured body obtained from the composition of the present invention are measured by a known resonator method. In this specification, the resonator method is performed at a measurement frequency of 40 GHz.
• the dielectric constant of the cured body is 3.5 or less, preferably 3.5 or less and 2.0 or more, particularly preferably 3.0 or less and 2.0 or more.
• the dielectric loss tangent of the cured body is 0.0015 or less, may be 0.0002 or more and 0.0015 or less, preferably 0.0005 or more and 0.0010 or less.
• the volume resistivity of the cured body is preferably 1 x 1015 ⁇ cm or more.
• the storage modulus of the cured product measured at high temperature (280° C.) is preferably 1 MPa or more but 1 GPa or less, more preferably 5 MPa or more but 1 GPa or less, and even more preferably 10 MPa or more but 1 GPa or less.
• Those skilled in the art can determine the compositional formulation having the above physical property parameters and prepare a cured product by referring to the information described in this specification and known documents.
• the cured product obtained from the composition of the present invention can exhibit practically sufficient heat resistance and mechanical properties at high temperatures even under conditions in which the monomer in the composition and the aromatic polyene as a component of the monomer are suppressed to a certain ratio or less.
• a and B are each independently a group selected from an unsubstituted or substituted cyclopentaphenanthryl group, an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted cyclopentadienyl group, or an unsubstituted or substituted indenyl group.
• Y is a methylene group, a silylene group, an ethylene group, a germylene group, or a boron residue having a bond with A and B and hydrogen or a hydrocarbon group having 1 to 15 carbon atoms (which may contain 1 to 3 nitrogen, oxygen, sulfur, phosphorus, or silicon atoms) as a substituent.
• a and B in the above general formula (1) may each independently be a group selected from an unsubstituted or substituted cyclopentadienyl group or an unsubstituted or substituted indenyl group, and it is particularly preferable to use a transition metal compound having both an unsubstituted or substituted cyclopentadienyl group and an unsubstituted or substituted indenyl group.
• an uncured ⁇ -olefin-cyclic olefin-aromatic polyene copolymer or ⁇ -olefin-cyclic olefin-aromatic vinyl compound-aromatic polyene copolymer can be provided in which the total metal content derived from the catalyst and co-catalyst is 1000 ppm or less, preferably 750 ppm or less, and most preferably 500 ppm or less.
• the molecular weight was determined by GPC (gel permeation chromatography) using the number average molecular weight (Mn) converted to standard polystyrene. The measurement was performed under the following conditions.
• the raw material divinylbenzene (DVB) was "Divinylbenzene (96%)" (liquid at room temperature, a mixture of meta and para isomers containing 96% by mass of divinylbenzene, the remainder being ethylvinylbenzene) manufactured by Nippon Steel Chemical & Material Co., Ltd.
• the raw material was norbornene (75% concentration, toluene solution) manufactured by Maruzen Petrochemical Co., Ltd., which was added with a small amount of triisobutylaluminum (TIBA) and stirred at room temperature, then distilled and purified under nitrogen.
• TIBA triisobutylaluminum
• the inside of the polymerization vessel was thoroughly dried and replaced with nitrogen, and 3 kg of toluene, 1 kg of norbornene as a pure content, and 180 g of divinylbenzene as a pure content were charged, and about 20 L of dry nitrogen was bubbled in at an internal temperature of 50°C. Thereafter, the inside of the polymerization vessel was replaced with ethylene gas, TIBA (manufactured by Kanto Chemical Co., Ltd.) was added in an amount of 5 mmol in terms of the number of moles of aluminum and stirred, and MMAO (modified MAO) (manufactured by Toso Finechem Co., Ltd.) in an amount of 50 mmol in terms of aluminum was further added and stirred.
• TIBA manufactured by Kanto Chemical Co., Ltd.
• MMAO modified MAO
• the internal temperature was stabilized at 60° C., and the internal pressure of the polymerization vessel was increased to 0.4 MPaG (gauge) by supplying ethylene and stabilized. Then, from a catalyst tank installed on the polymerization vessel, 100 ⁇ mol of rac diphenylmethylene (1-indenyl) (cyclopentadienyl) zirconium dichloride (see formula (2) below for the structure) as a catalyst and 100 g of a toluene solution containing 2 mmol of TIBA were added to the polymerization vessel to initiate polymerization. The ethylene consumed in the polymerization was gradually replenished, and the polymerization was continued while maintaining the internal temperature at 60°C and the internal pressure at 0.4 MPaG.
• Example 2 Preparation of copolymer P-2 Polymerization was carried out in the same manner as in the synthesis of P-1, except that the amount of norbornene used was changed to 1.4 kg in terms of pure content, and the polymerization was terminated when the amount of ethylene consumed reached 100 g, thereby obtaining an ethylene-norbornene-divinylbenzene copolymer, P-2.
• Example 3 Production of copolymer P-3> Polymerization was carried out in the same manner as in the synthesis of P-1, except that the amounts of the raw materials were changed to 2 kg of toluene, 2 kg of norbornene as a pure content, 300 g of divinylbenzene as a pure content, and 100 mmol of MMAO (modified MAO) manufactured by Toso Finechem Co., Ltd., in terms of aluminum. Furthermore, the catalyst used was changed to 200 ⁇ mol of dimethylmethylenebis(cyclopentadienyl)zirconium dichloride (see the following formula (3) for its structure) and 100 g of a toluene solution containing 4 mmol of TIBA. The polymerization was terminated when the amount of ethylene consumed reached 150 g, thereby obtaining an ethylene-norbornene-divinylbenzene copolymer, P-3.
• MMAO modified MAO
• Example 4 Production of copolymer P-4> As in the synthesis of P-3, dimethylmethylenebis(cyclopentadienyl)zirconium dichloride was used as a catalyst, but MMAO was not used as a cocatalyst, and instead, tritium tetrakis(pentafluorophenyl)borate (manufactured by Toso Finechem Co., Ltd.) was used.
• Table 1 shows the composition, molecular weight, gel content, glass transition temperature, storage modulus at 25°C, dielectric properties, and metal content of the copolymers P-5 to P-9. It can be seen that copolymers P-5 to P-9 obtained using a boron compound as a promoter exhibit high glass transition temperatures in the uncured state, high storage modulus (25°C), and extremely low dielectric constant and dielectric tangent values.
• Copolymers obtained by using DMON or MPNB as the cyclic olefin can provide a high glass transition temperature even with a relatively small molar content of DMON or MPNB. That is, the DMON content of P-6 is 52 mol% in terms of molar content, and the MPNB content of P-7 is 46 mol%, which is a lower molar content than the norbornene content of P-5 of 74 mol%, but the glass transition temperature is 198°C for P-6 and 186°C for P-7, which is almost the same as 190°C for P-5.

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