Classifications

• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/12—Polymers provided for in subclasses C08C or C08F
• • 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
  • 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
  • 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
  • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material

Definitions

• the present invention relates to a varnish consisting of a copolymer and a liquid monomer component, and an insulating material that is a cured product thereof.
• Fluorine-based resins such as perfluoroethylene have excellent characteristics such as low dielectric constant, low dielectric loss, and excellent heat resistance, but they have difficulty in molding and film forming, and they also have poor adhesion to copper foil for wiring. There are also issues, making it difficult to apply to multilayer substrates.
• substrates and insulating materials using post-cured resins such as epoxy resins, unsaturated polyester resins, polyimide resins, and phenolic resins have been widely used due to their heat resistance and ease of handling, but their dielectric constant and dielectric loss are It is relatively expensive, and improvement is desired as an insulating material for high frequencies (Patent Document 1).
• hydrocarbon resins that inherently have low dielectric properties.
• hydrocarbon resin which is originally a thermoplastic resin, into a curable resin
• it is necessary to introduce a functional group but generally radicals or functional groups that react with heat have polarity, so they have low resistance to heat. Dielectric properties deteriorate.
• Patent Document 2 When attempting to introduce a functional group composed only of hydrocarbons, such as an aromatic vinyl group, intermolecular reactions between expensive hydrocarbon monomers are often used (Patent Document 2), which is not economical. There are many cases.
• Patent Document 3 describes a cured product consisting of an ethylene-olefin (aromatic vinyl compound)-aromatic polyene copolymer and a non-polar vinyl compound copolymer obtained from a specific coordination polymerization catalyst and having a specific composition and blend. body is shown.
• an ethylene-olefin (aromatic vinyl compound)-aromatic polyene copolymer and a non-polar vinyl compound copolymer obtained from a specific coordination polymerization catalyst and having a specific composition and blend. body is shown.
• only one of the two vinyl groups of aromatic polyene (divinylbenzene) is selectively copolymerized and the remaining vinyl group is preserved, so that aromatic A crosslinkable hydrocarbon copolymer macromonomer having a vinyl functional group can be obtained.
• a cured product obtained from a composition of a similar olefin-aromatic vinyl compound-aromatic polyene copolymer and auxiliary raw materials has the characteristics of a low dielectric constant and a low dielectric loss tangent (Patent Documents 4, 5) ).
• a relatively low viscosity varnish made of a relatively low molecular weight olefin-aromatic vinyl compound-aromatic polyene copolymer, an additive resin, a monomer, and a solvent is also known (Patent Document 6).
• a liquid curable resin composition comprising an olefin-aromatic vinyl compound-aromatic polyene copolymer and a nonpolar vinyl compound is also known (Patent Document 7).
• Patent Document 7 describes a varnish that does not contain a solvent, but the viscosity of the varnish is high due to the high molecular weight of the copolymer used, and in applications such as CCL, it is necessary to further improve the impregnating properties of glass cloth, etc. There's room. Further, all of the formulations exemplified in Patent Document 7 have relatively low crosslinking densities, and there is room for improvement, for example, in the elastic modulus at high temperatures.
• the present invention can provide the following aspects to address the problems that the prior art described above could not solve.
• Aspect 2 The varnish according to aspect 1, wherein the polymer compound is an olefin-aromatic vinyl compound-aromatic polyene copolymer that satisfies all of the following conditions (1) to (4).
• the number average molecular weight of the copolymer is 500 or more and 12,000 or less.
• the aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of aromatic vinyl compound monomer units is 0 to 98% by mass.
• the aromatic polyene is one or more types selected from polyenes having 5 to 20 carbon atoms and having multiple vinyl groups and/or vinylene groups in the molecule, and vinyl groups and/or derived from the aromatic polyene unit.
• the content of vinylene groups is 2 or more and 30 or less per number average molecular weight.
• It may contain one or more olefin monomer units having 2 or more carbon atoms and 20 or less carbon atoms, and when an aromatic vinyl compound monomer unit and an aromatic polyene monomer unit are present.
• the total amount of the olefin monomer units is 100% by mass.
• Aspect 3 The varnish according to aspect 2, wherein the content of the olefin-aromatic vinyl compound-aromatic polyene copolymer is in the range of 30% by mass or more and 69% by mass or less based on the total mass of the varnish.
• Aspect 4 The varnish according to any one of aspects 1 to 3, wherein the polyfunctional monomer contains divinylbenzene.
• Aspect 5 The varnish according to aspect 4, wherein the content of divinylbenzene is 30% by mass or more based on the total mass of the varnish.
• Aspect 6 The varnish according to any one of aspects 1 to 5, wherein the monomer component further includes a monofunctional monomer.
• Aspect 7 The varnish according to aspect 6, wherein the content of the monofunctional monomer is 40% by mass or less based on the total mass of the varnish.
• Aspect 8 The varnish according to aspect 6 or 7, wherein the monofunctional monomer includes one or more selected from styrene, ethylvinylbenzene, or acenaphthylene.
• Aspect 10 The cured product according to aspect 9, which is an electrically insulating material.
• a crosslinked resin matrix that is a cured product of a varnish containing an olefin-aromatic vinyl compound-aromatic polyene copolymer and a polyfunctional monomer component, A crosslinked resin matrix, wherein the crosslinked resin matrix has a storage modulus of 30 MPa or more at 280°C.
• Aspect 13 The crosslinked resin matrix according to aspect 12, wherein the crosslinked resin matrix has a storage modulus of 80 MPa or more at 25°C.
• Aspect 14 Using a balanced disk resonator, the average value of the dielectric constant measured at 23°C and a frequency of 20 to 42 GHz is 2.5 or more and 2.0 or more, and the average value of the dielectric loss tangent is 0.0012 or less and 0.0003 or more.
• Aspect 15 The crosslinked resin matrix according to any one of aspects 12 to 14, containing 99% by mass or more of carbon and hydrogen.
• Aspect 16 The crosslinked resin matrix according to any one of aspects 12 to 15, wherein the varnish is substantially free of solvent components.
• Aspect 17 The crosslinked resin matrix according to any one of aspects 12 to 15, wherein the varnish contains a solvent component.
• Aspect 18 The crosslinked resin matrix according to any one of aspects 12 to 17, wherein the olefin-aromatic vinyl compound-aromatic polyene copolymer satisfies all of the following conditions (1) to (4).
• the number average molecular weight of the copolymer is 500 or more and 12,000 or less.
• the aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of the aromatic vinyl compound monomer unit is 0 to 98% by mass.
• the aromatic polyene is one or more types selected from polyenes having 5 to 20 carbon atoms and having multiple vinyl groups and/or vinylene groups in the molecule, and vinyl groups and/or derived from the aromatic polyene unit.
• the content of vinylene groups is 2 or more and 30 or less per number average molecular weight.
• a single or plural olefin monomer unit selected from olefin monomer units having 2 to 20 carbon atoms may be included, and when an aromatic vinyl compound monomer unit and an aromatic polyene monomer unit are present.
• the total amount of the olefin monomer units is 100% by mass.
• a method for producing a cured body comprising: preparing a varnish containing an olefin-aromatic vinyl compound-aromatic polyene copolymer and a polyfunctional monomer component; A manufacturing method comprising the step of curing the varnish to obtain a cured product having a storage modulus of 30 MPa or more at 280°C.
• Aspect 20 The manufacturing method according to aspect 19, wherein the cured product has a storage modulus of 80 MPa or more at 25°C.
• Aspect 21 The manufacturing method according to aspect 19 or 20, wherein the olefin-aromatic vinyl compound-aromatic polyene copolymer satisfies all of the following conditions (1) to (4).
• the number average molecular weight of the copolymer is 500 or more and 12,000 or less.
• the aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of aromatic vinyl compound monomer units is 0 to 98% by mass.
• the aromatic polyene is one or more types selected from polyenes having 5 to 20 carbon atoms and having multiple vinyl groups and/or vinylene groups in the molecule, and vinyl groups and/or derived from the aromatic polyene unit.
• the content of vinylene groups is 2 or more and 30 or less per number average molecular weight.
• It may contain one or more olefin monomer units having 2 or more carbon atoms and 20 or less carbon atoms, and when an aromatic vinyl compound monomer unit and an aromatic polyene monomer unit are present.
• the total amount of the olefin monomer units is 100% by mass.
• the present invention it is possible to provide a cured product that has excellent low dielectric properties, exhibits high elastic modulus at room temperature and high temperature, and has high crosslink density.
• This cured product is particularly useful as an insulating component for rigid substrates.
• the varnish of the present invention can omit the step of drying the solvent, has a low viscosity and is highly suitable for processes involving impregnation, and the resulting cured product can exhibit a low dielectric loss tangent value and high high-temperature elastic modulus. Therefore, it is particularly useful as a substrate material for high frequency insulation.
• sheet also includes the concept of film. Furthermore, even though the term “film” is used in this specification, the concept of “sheet” is also included.
• the varnish according to the present invention contains a polymer compound and a monomer component that meet specific conditions, and more specifically, it does not substantially contain components other than the polymer compound and monomer component (such as a solvent component). (That is, it is preferably a varnish consisting of the polymer compound and monomer component). Therefore, in this specification, when describing an embodiment in which the present varnish can contain the polymer compound and monomer component, the content of other components is expressed as an external addition (for example, based on 100 parts by mass of the varnish). (adding some amount). In other words, only the blending ratio of the polymer compound and the monomer component (or the polyfunctional monomer that the monomer component essentially includes and the monofunctional monomer that may optionally include) shall be considered in detail.
• the content of the polyfunctional monomer may be from 31% by mass to 70% by mass, preferably from 35% by mass to 60% by mass, based on the total mass of the varnish. Further, the present varnish does not substantially contain a solvent component (detailed definition thereof will be described later).
• the polymer compound contained in the present varnish has a plurality of radical-reactive functional groups (that is, functional groups that can be crosslinked by radicals) in the molecule.
• the radical-reactive functional group include one or more of the group consisting of a vinyl group, a vinylene group, and an allyl group, with a vinyl group being particularly preferred.
• the molecular weight of the polymer compound having a radical-reactive functional group is set to a number average molecular weight (Mn) of 500 to 12,000 or 500 to 12,000, from the viewpoint of achieving a low viscosity of the varnish suitable for handling such as impregnation and coating. and preferably 500 or more and 5000 or less or 500 or more and less than 5000.
• the number average molecular weight is defined as a standard polystyrene equivalent molecular weight obtained by GPC (gel permeation chromatography).
• polymeric compounds having radically reactive functional groups include the following olefin-aromatic vinyl compound-aromatic polyene copolymers; other examples include styryl groups, (meth)acrylic groups, and allyl groups.
• polyether resins including polyphenylene ether and polyether (ketone)).
• SA9000 polyphenylene ether and polyether (ketone)
• OPE-2St polyphenylene ether and polyether (ketone)
• JSR Asahi Kasei and JSR.
• a polymer compound having a radically reactive functional group a polymer compound having a 1,2-butadiene structure in the molecule can also be used.
• polymer compounds examples include 1,2-polybutadiene from Nippon Soda Co., Ltd. and "Ricon” (trade name) from Cray Valley. Furthermore, as the polymer compound, a styrene-1,2-polybutadiene copolymer having a random or block copolymer structure can also be suitably used.
• the content of the polymer compound in the present varnish may be 30% by mass or more and 69% by mass or less, preferably 40% by mass or more and 65% by mass or less based on the total mass of the varnish.
• the monomer component contained in the present varnish may have a single monomer species or a plurality of monomer species, and is liquid at room temperature (25° C.). In other words, when there are multiple types of monomer components, the total monomer component may be liquid at room temperature. That is, when all of the constituent elements of the monomer component are independent, it does not need to be liquid at room temperature, and a portion of the monomer component that is solid at room temperature may be included.
• the molecular weight of the monomer species contained in the present monomer component is (in the case of a plurality of monomers, all) 300 or less, preferably 200 or less.
• This monomer component contains a polyfunctional monomer as an essential component, and may contain a monofunctional monomer as an optionally added component.
• the polyfunctional monomer may be more than 50% by mass and 100% by mass or less, and the remainder (if included) is the monofunctional monomer.
• the boiling point of each constituent monomer component under atmospheric pressure is preferably 130°C or higher, more preferably 150°C or higher, and most preferably 180°C or higher.
• the above monomer component has a radically reactive functional group in the molecule. Therefore, it should be noted that solvents (organic solvents) such as toluene and methysylene are not included in the monomer components.
• the polyfunctional monomer contained in the monomer component is a monomer having a molecular weight of 300 or less and having a plurality of radically reactive functional groups in the molecule. It is preferable that each of the polyfunctional monomers is liquid at room temperature (25°C), but when multiple types of polyfunctional monomers are included, it is sufficient that the entire monomer is liquid at room temperature (25°C).
• the polyfunctional monomer includes ortho, meta, or para-divinylbenzene, or a mixture thereof (excluding the case where only para-divinylbenzene is used).
• the boiling point of these divinylbenzenes under atmospheric pressure is 180°C or higher.
• examples of the polyfunctional monomer include BVPE (bisvinylphenylethane) which may contain various isomers (see, for example, JP-A No. 2003-012710).
• BVPE has a substantially boiling point of 200°C or higher.
• a method for producing BVPE which is liquid at room temperature is described in JP-A No. 2003-105036.
• the polyfunctional monomer accounts for 31% by mass or more and 70% by mass or less in the total mass of the varnish, preferably 35% by mass or more and 60% by mass or less, more preferably 35% by mass or more and 50% by mass or less. It's okay.
• a bismaleimide compound is generally not included as a polyfunctional monomer. This is because although bismaleimide compounds have a carbonyl group, which is a type of radically reactive functional group, they are solid at room temperature.
• the monofunctional monomer that the above monomer component may contain has a molecular weight of 300 or less and has one radically reactive functional group in the molecule, and is either liquid or solid at room temperature (25°C). (That is, it is sufficient if the monomer components as a whole are liquid at room temperature (25° C.)).
• Preferred monofunctional monomers include one or more selected from styrene, ethylvinylbenzene, and acenaphthylene. The boiling point of styrene under atmospheric pressure is 145°C, ethylvinylbenzene is 189°C, and acenaphthylene is 280°C.
• the blending ratio of the monofunctional monomer in the monomer component may be 50% by mass or less or less than 50% by mass.
• the monofunctional monomer may be 0% by mass or more and 40% by mass or less, 0% by mass or more and less than 40% by mass, preferably 0% by mass or more and 35% by mass or less, or 0% by mass or more. It may be less than 35% by mass, more preferably 0% by mass or more and 20% by mass or less, or 0% by mass or more and less than 20% by mass.
• the amount of the monofunctional monomer is 40% by mass or less, the elastic modulus of the resulting cured product at high temperatures tends to improve.
• the olefin-aromatic vinyl compound-aromatic polyene copolymer that can be used as the polymer compound may preferably be a copolymer that satisfies all of the following conditions (1) to (4).
• the number average molecular weight of the copolymer is 500 or more and 12,000 or less, preferably 500 or more and less than 12,000.
• the aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of aromatic vinyl compound monomer units is 0 to 98% by mass.
• the aromatic polyene monomer unit is one or more types selected from polyenes having 5 to 20 carbon atoms and having multiple vinyl groups and/or vinylene groups in the molecule, and the aromatic polyene monomer unit is The content of derived vinyl groups and/or vinylene groups is 2 or more and 30 or less, or 2 or more and less than 30, preferably 20 or less or less than 20, per number average molecular weight.
• It may contain one or more olefin monomer units having 2 or more carbon atoms and 20 or less carbon atoms, and when an aromatic vinyl compound monomer unit and an aromatic polyene monomer unit are present. The total amount of the olefin monomer units is 100% by mass.
• the number average molecular weight (Mn) of the copolymer is 500 or more and 12,000 or less, or 500 or more and less than 12,000, preferably 500 or more and 5,000 or less, or 500 or more and less than 5,000.
• the aromatic vinyl compound monomer may be an aromatic vinyl compound having 8 to 20 carbon atoms, such as styrene, paramethylstyrene, paraisobutylstyrene, various vinylnaphthalenes, and various vinylanthracenes. can.
• the olefin monomer is one or more selected from ⁇ -olefins having 2 to 20 carbon atoms and cyclic olefins having 5 to 20 carbon atoms.
• the olefin monomer is a compound that does not substantially contain oxygen, nitrogen, or halogen and is composed of carbon and hydrogen (that is, a compound that consists of 99% by mass or more of carbon and hydrogen, preferably only carbon and hydrogen) It is preferable that Examples of ⁇ -olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 3,5,5 -trimethyl-1-hexene is an example.
• cyclic olefin having 5 to 20 carbon atoms examples include norbornene and cyclopentene.
• Preferably used as the olefin are a combination of ethylene and an ⁇ -olefin or cyclic olefin other than ethylene, or ethylene alone.
• the aromatic polyene monomer is a polyene having a carbon number of 5 to 20 and having a plurality of vinyl groups and/or vinylene groups in its molecule, and preferably various divinylbenzenes such as ortho, meta, and para, or a mixture thereof. , divinylnaphthalene, divinylanthracene, p-2-propenylstyrene, p-3-butenylstyrene, and the like.
• the aromatic polyene monomer is a compound that substantially does not contain oxygen, nitrogen, or halogen and is composed of carbon and hydrogen (i.e., 99% or more by mass consists of carbon and hydrogen, preferably consists only of carbon and hydrogen). compound) is preferred.
• a difunctional aromatic vinyl compound described in JP-A No. 2004-087639 such as 1,2-bis(vinylphenyl)ethane (abbreviation: BVPE)
• BVPE 1,2-bis(vinylphenyl)ethane
• various ortho, meta, and para divinylbenzenes or mixtures thereof are preferably used, and most preferably, a mixture of meta and para divinylbenzenes is used.
• these divinylbenzenes are referred to as divinylbenzenes.
• divinylbenzenes When divinylbenzenes are used as the aromatic polyene, curing efficiency is high and curing is easy during curing treatment.
• the content of aromatic vinyl compound monomer units contained in the present copolymer may be 0% by mass or more and 98% by mass or less, more preferably 10% by mass or more and 70% by mass or less.
• the glass transition temperature of the cured product of the final composition will be lower than around room temperature, improving toughness and elongation at low temperatures. It is preferable because it can be done.
• the content of the aromatic vinyl compound monomer unit is 0% by mass or more, the aromaticity of the copolymer improves, compatibility with flame retardants and fillers improves, and bleed-out of the flame retardant can be avoided. , the effect of improving filler filling properties can be obtained.
• a cured product of the composition can be obtained which has high adhesive strength with copper foil or copper wiring.
• the content of vinyl groups and/or vinylene groups derived from aromatic polyene units is 2 to 30 or 2 to less than 30 per number average molecular weight, More preferably, the number is 20 or less or less than 20, and even more preferably 3 or more and 20 or less, or 3 or more and less than 20.
• the content of the vinyl group and/or vinylene group is 2 or more, the crosslinking efficiency is high and it is easy to obtain a cured product with sufficient crosslinking density.
• the vinyl group content derived from aromatic polyene units (divinylbenzene units) per number average molecular weight in the copolymer is the number average in terms of standard polystyrene determined by GPC (gel permeation chromatography) method known to those skilled in the art. What can be obtained by comparing the molecular weight (Mn), the composition obtained by 1 H-NMR measurement and/or 13 C-NMR measurement measured in quantitative mode, and the vinyl group content derived from aromatic polyene units. can. Such methods are obvious and known to those skilled in the art. It is also possible to use the method described in the patent documents of the prior art documents of this specification.
• the content of olefin monomer units is preferably 10% by mass or more, more preferably 20% by mass or more.
• the total of the olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units is 100% by mass.
• the content of olefin monomer units is 10% by mass or more, the toughness (elongation) and impact resistance of the finally obtained cured product will improve, and cracking during curing and heat cycle tests of the cured product will improve. Cracks are less likely to occur.
• olefin-aromatic vinyl compound-aromatic polyene copolymer examples include ethylene-styrene-divinylbenzene copolymer, ethylene-1-octene-divinylbenzene copolymer, ethylene-norbornene-divinylbenzene copolymer, and ethylene-styrene-divinylbenzene copolymer.
• the content of the olefin-aromatic vinyl compound-aromatic polyene copolymer may range from 30% by mass to 69% by mass, more preferably from 40% by mass to 65% by mass. It can be a range.
• the content of the olefin-aromatic vinyl compound-aromatic polyene copolymer is 30% by mass or more, the resulting cured product is less likely to develop brittleness, and when it is 69% by mass or less, the elastic modulus at high temperatures is It is easy to improve the characteristics, and it is possible to obtain the effect of easily satisfying the required characteristics of rigid substrates and the like.
• the monomer component contained in the present varnish may be divinylbenzene, and its content may be 30% by mass or more, or more than 30% by mass, and 69% by mass or less in the total mass of the varnish.
• the divinylbenzene content is 30% by mass or more, the viscosity of the varnish can be appropriately suppressed, and the resulting cured product can have an appropriate crosslinking density and elastic modulus in a high temperature range.
• the content of divinylbenzene is 69% by mass or less, the effect that brittleness is less likely to occur in the resulting cured product can be obtained.
• a cured product that has a sufficiently high crosslinking density, a low coefficient of linear expansion, and a high modulus of elasticity in a high temperature range, which is particularly suitable as an insulating layer of a rigid substrate.
• a cured product having a coefficient of linear expansion of 100 ppm/°C or less and a storage modulus (E') at 280°C obtained by DMA (dynamic mechanical analysis) measurement of 20 MPa or more, preferably 30 MPa or more. It becomes easy to obtain.
• the varnish may include one or more (divided) selected from (a) or (b) below.
• (a) Curing agent (b) One or more resins selected from hydrocarbon elastomers, polyether resins, and aromatic polyene resins
• curing agent that can be used in the varnish of the present invention
• curing agents include radical polymerization initiators (radical generators), cationic polymerization initiators, and anionic polymerization initiators, and preferably radical polymerization initiators can be used.
• radical polymerization initiators Radical generators
• cationic polymerization initiators cationic polymerization initiators
• anionic polymerization initiators preferably radical polymerization initiators
• More preferred are organic peroxide-based polymerization initiators, azo-based polymerization initiators, etc., which can be freely selected depending on the application and conditions. Catalogs listing organic peroxides are available on the NOF website, for example. https://www.nof.co.jp/product-search/family/1020001 It can be downloaded from.
• Organic peroxides are also described in the catalogs of Fuji Film Wako Pure Chemical Industries, Ltd. and Tokyo Kasei Kogyo Co., Ltd.
• the curing agents used in the present invention are available from these companies.
• a known photopolymerization initiator using light, ultraviolet rays, or radiation can also be used as a curing agent.
• the photopolymerization initiator include radical photopolymerization initiators, cationic photopolymerization initiators, and anionic photopolymerization initiators.
• photopolymerization initiators are available from Tokyo Chemical Industry Co., Ltd., for example.
• curing by radiation or electron beam itself is also possible. It is also possible to perform crosslinking and curing by thermal polymerization of the raw materials contained without containing a curing agent.
• the amount of the curing agent used is generally preferably 0.01 to 10 parts by weight based on 100 parts by weight of the varnish of the present invention.
• the resin composition does not contain a curing agent or a solvent.
• a curing agent such as a peroxide type (peroxide) or an azo type polymerization initiator
• the curing treatment is performed at an appropriate temperature and time, taking into account its half-life.
• the conditions in this case are arbitrary depending on the curing agent, but generally a temperature range of about 50°C to 200°C is appropriate.
• the amount of component (b) used is preferably within a range that allows the varnish of the present invention to maintain its liquid state at room temperature, preferably 20 parts by mass relative to 100 parts by mass of the varnish of the present invention. It is not more than 10 parts by mass, more preferably not more than 10 parts by mass.
• the addition of these components (b) has the effect of improving the mechanical properties at room temperature of the cured product obtained from the varnish.
• hydrocarbon elastomer that can be suitably used in the composition of the present invention preferably has a number average molecular weight of 100 or more and 100,000 or less, more preferably 1,000 or more and 4,500 or less.
• Hydrocarbon elastomers that can be suitably used in the composition of the present invention are preferably ethylene-based or propylene-based elastomers, conjugated diene-based polymers, aromatic vinyl compound-conjugated diene-based block copolymers, or One or more elastomers selected from random copolymers and hydrides thereof.
• ethylene-based elastomers include ethylene- ⁇ olefin copolymers such as ethylene-octene copolymers and ethylene-1-hexene copolymers, EPR, and EPDM.
• propylene-based elastomer include atactic polypropylene, polypropylene with low stereoregularity, and propylene- ⁇ -olefin copolymers such as propylene-1-butene copolymers.
• These hydrocarbon elastomers may be modified by introducing functional groups with maleic anhydride or other compounds.
• the composition according to another embodiment does not substantially contain a hydrocarbon elastomer containing oxygen atoms and other elements and/or other optional additive components listed below (carbon and hydrogen are 99% by mass or more). is also preferable.
• conjugated diene polymer examples include polybutadiene and 1,2-polybutadiene.
• aromatic vinyl compound-conjugated diene block copolymers or random copolymers and hydrides thereof examples include SBS, SIS, SEBS, SEPS, SEEPS, and SEEBS.
• 1,2-polybutadiene that can be suitably used is, for example, available from Nippon Soda Co., Ltd. under the product names of liquid polybutadiene: product names B-1000, 2000, and 3000.
• a copolymer containing a 1,2-polybutadiene structure that can be suitably used, "Ricon 100" manufactured by TOTAL CRAY VALLEY can be exemplified.
• conjugated diene polymers and their hydrides may be modified by introducing functional groups with maleic anhydride or other compounds.
• the resin or resins selected from these hydrocarbon elastomers should be liquid (approximately 300,000 mPa ⁇ s or less) at room temperature (25°C) to improve the handleability and moldability of the composition of the present invention in an uncured state. It is preferable from the viewpoint of processability (handling properties as a thermoplastic resin).
• polyether resin examples include polyphenylene ether and polyether.
• the polyphenylene ether having a functional group it is preferable that the molecular terminal is modified with a functional group.
• the polyphenylene ether also referred to as "polyphenylene ether resin”
• commercially available known polyphenylene ethers can be used.
• the number average molecular weight of the polyphenylene ether is arbitrary, and in consideration of the moldability of the composition, the number average molecular weight is preferably 10,000 or less, most preferably 5,000 or less. The number average molecular weight is preferably 500 or more.
• the polyether resin when added for the purpose of curing the composition of the present invention, it is preferable that the molecular terminal is modified with a functional group. Further, in the case of addition for the purpose of curing the composition of the present invention, it is preferable that one molecule has a plurality of functional groups.
• the polyether resin for example, modified polyphenylene ether is preferable.
• the functional group include radically polymerizable functional groups and epoxy groups, and preferably radically polymerizable functional groups.
• a vinyl group is preferable.
• the vinyl group is preferably one or more of the group consisting of an allyl group, a (meth)acryloyl group, and an aromatic vinyl group, more preferably one or more of the group consisting of a (meth)acryloyl group and an aromatic vinyl group.
• groups that is, in the composition of the present invention, bifunctional polyphenylene ether in which both ends of the molecular chain are modified with radically polymerizable functional groups is particularly preferred.
• Such polyphenylene ethers include SABIC's Noryl (trademark) SA9000 (modified polyphenylene ether having methacryloyl groups at both ends, number average molecular weight 2200) and Mitsubishi Gas Chemical's bifunctional polyphenylene ether oligomer (OPE-2St, both ends). Examples include modified polyphenylene ether having a vinylbenzyl group, number average molecular weight 1200), and the like. Furthermore, allylated PPE from Asahi Kasei Corporation and aromatic polyether (ELPAC HC-F series) from JSR may also be used. Among these, bifunctional polyphenylene ether oligomer (OPE-2St) manufactured by Mitsubishi Gas Chemical Co., Ltd. can be preferably used.
• the aromatic polyene resin includes divinylbenzene-based reactive hyperbranched copolymer (PDV or ODV) manufactured by Nippon Steel Chemical & Materials. Such PDV can be found in, for example, the document "Synthesis of polyfunctional aromatic vinyl copolymer and development of new IPN type low dielectric loss material using the same" (Masashi Kawabe, Electronics Packaging Society Journal p125, Vol. 12 No. 2) (2009)).
• the use of aromatic polyene resin is preferable in order to prevent a decrease in adhesiveness with other members and a decrease in toughness.
• the number average molecular weight of the aromatic polyene resin is arbitrary, and considering the moldability of the composition, the number average molecular weight is preferably 10,000 or less, most preferably 5,000 or less. The number average molecular weight is 500 or more.
• the present varnish may also contain one or more (divided) selected from the following (c) to (f). (c) polar monomer (d) filler (e) flame retardant (f) surface modifier
• the amount of the polar monomer that may be included in the varnish composition of the present invention may be 10 parts by mass or less based on 100 parts by mass of the varnish. By using an amount within this range, it is possible to prevent the dielectric constant and dielectric loss tangent of the resulting cured product from becoming too high.
• the dielectric constant is 4.0 or less, preferably 3.0 or less
• the dielectric loss tangent is 0.0. 003 or less, preferably 0.002 or less.
• the resin composition does not need to contain substantially no polar monomer.
• a polar monomer is a monomer having one or more atoms selected from oxygen, nitrogen, phosphorus, and sulfur in its molecule.
• the molecular weight of the polar monomer that can be suitably used is preferably 5,000 or less or less than 5,000, more preferably 1,000 or less or less than 1,000, and even more preferably 500 or less or less than 500.
• the polar monomer that can be suitably used in the resin composition of the present invention is preferably a polar monomer that can be polymerized with a radical polymerization initiator.
• Examples of the polar monomer include various maleimides, bismaleimides, maleic anhydride, triallylisocyanurate, glycidyl (meth)acrylate, tri(meth)acrylisocyanurate, trimethylolpropane tri(meth)acrylate, etc. It will be done.
• Maleimides and bismaleimides that can be used in the present invention are described in, for example, International Publication No. 2016/114287 and Japanese Patent Application Laid-open No. 2008-291227. You can purchase from Bismaleimide resin "SLK” manufactured by Shin-Etsu Chemical Co., Ltd. can also be used. These maleimide group-containing compounds are preferably bismaleimides from the viewpoints of solubility in organic solvents, high frequency properties, high adhesion to conductors, moldability of prepregs, and the like.
• maleimide group-containing compounds may be used as polyamino bismaleimide compounds from the viewpoints of solubility in organic solvents, high frequency properties, high adhesion to conductors, moldability of prepregs, and the like.
• a polyamino bismaleimide compound can be obtained, for example, by subjecting a compound having two terminal maleimide groups to a Michael addition reaction with 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 When attempting to obtain high crosslinking efficiency with a small amount of addition, it is preferable to use a polar monomer having a polyfunctional group of two or more functional groups. Examples of the polar monomer having a polyfunctional group of two or more functional groups include bismaleimides, triallylisocyanurate (TAIC), trimethylolpropane tri(meth)acrylate, and the like.
• ⁇ Filler> Known inorganic or organic fillers can be added as necessary. These fillers are added for the purpose of controlling the coefficient of thermal expansion, controlling thermal conductivity, and reducing costs, and the amount used is arbitrary depending on the purpose. Particularly when adding an inorganic filler, it is preferable to use a known surface modifier such as a silane coupling agent.
• a known surface modifier such as a silane coupling agent.
• one or more types of boron nitride (BN) or silica may be used as the inorganic filler.
• BN boron nitride
• silica is more preferable.
• fused silica is preferred.
• the viscosity of the varnish if a large amount is added and blended, the viscosity will increase, so it is preferably 200 parts by mass or less or less than 200 parts by mass, more preferably 100 parts by mass, based on 100 parts by mass of the varnish of the present invention. Up to or less than 100 parts by weight of filler may be used. Furthermore, a hollow filler or a filler having a shape with many voids may be added to improve the low dielectric properties (low dielectric constant, low dielectric loss tangent).
• Flame retardants can be used in the compositions of the 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 a low dielectric constant and low dielectric loss tangent.
• phosphoric acid esters compounds having a plurality of xylenyl groups in the molecule are particularly preferred from the viewpoint of flame retardancy and low dielectric loss tangent.
• antimony compounds such as antimony trioxide, antimony tetroxide, antimony pentoxide, and sodium antimonate, as well as melamine, triallyl-1,3,5-triazine-2,3,4-( Nitrogen-containing compounds such as 1H,3H,5H)-trione, 2,4,6-triaryloxy1,3,5-triazine, etc. may be added.
• the total amount of these flame retardants and flame retardant aids is usually preferably 1 to 100 parts by weight per 100 parts by weight of the varnish of the present invention.
• 30 to 200 parts by mass of the polyphenylene ether (PPE)-based resin having a low dielectric constant and excellent flame retardancy may be used per 100 parts by mass of the flame retardant.
• PPE polyphenylene ether
• the varnish of the present invention may contain a surface modifier for the purpose of improving adhesion to copper foil for wiring.
• the purpose is to increase the adhesive strength (peel strength) with the smooth surface of copper foil.
• the amount of the surface modifier used may be in the range of 0.001 to 10 parts by weight, and 0.01 to 5 parts by weight based on 100 parts by weight of the olefin-aromatic vinyl compound-aromatic polyene copolymer. The range is more preferable, and the range of 0.01 to 1 part by mass is most preferable. If the amount of the surface modifier used is 10 parts by mass or less, the dielectric constant and dielectric loss tangent value of the cured product obtained from the composition will be low.
• silane surface modifiers also known as silane coupling agents
• titanate surface modifiers also known as silane coupling agents
• isocyanate surface modifiers and the like
• silane surface modifiers are preferably used. These surface modifiers may be used singly or in combination.
• Such silane-based surface modifiers are available from Shin-Etsu Chemical Co., Ltd., Dow Corning, and Evonik.
• this varnish may contain components (a) to (f), in particular, this varnish does not substantially contain any of the components (a) to (f). is preferred. These components (a) to (f) can be used within the above ranges by those skilled in the art in the varnish, if necessary.
• the varnish contains substantially none of the components (a) to (f), and the varnish contains any of the components (a) to (f) in proportion to the varnish. It may be considered that it is possible to provide a composition comprising .
• the varnish is substantially free of solvent components.
• substantially free of solvent component means that the content of the solvent component is 2% by mass or less or less than 2% by mass, preferably 1% by mass or less or 1% by mass, based on 100 parts by mass of the varnish. %, more preferably 0.5% by mass or less or less than 0.5% by mass, more preferably substantially zero. If the varnish does not substantially contain a solvent component, it will not foam during curing, and the circuit board will not swell or bulge.
• the varnish of the present invention does not substantially contain a solvent, but can exhibit fluidity as a varnish due to the liquid monomer component, particularly the polyfunctional monomer component. In another embodiment, it is also possible to provide a varnish containing a solvent component as described below.
• the varnish of the present invention may contain additives normally used for resins, such as antioxidants, weathering agents, light stabilizers, lubricants, compatibilizers, antistatic materials, etc., to the extent that the effects and objectives of the present invention are not impaired. can be included.
• the composition and varnish of the present invention can be obtained by mixing and dissolving the various raw materials and additives described above, and any known method can be used for mixing and dissolving.
• the varnish of the present invention can exhibit a liquid state at room temperature due to the above-described structure.
• the viscosity of the present varnish is, for example, at 25° C., tens of thousands of mPa ⁇ s or less, preferably 5,000 mPa ⁇ s or less, more preferably 2,000 mPa ⁇ s or less in a state without a filler.
• the present varnish can be applied to, impregnated, filled with, or dropped onto another material by an appropriate method, and then cured under heat and pressure to form a cured product.
• the varnish of the present invention may partially contain residual monomers during polymerization as monomer components.
• the varnish of the invention can also be obtained in the following manner. That is, an olefin-aromatic vinyl compound-aromatic polyene copolymer (for example, an olefin-aromatic vinyl compound-aromatic polyene copolymer that satisfies the above conditions (1) to (4)) and a liquid state at room temperature.
• a varnish is prepared that contains a monomer component including a polyfunctional monomer, and further contains a relatively small amount of a relatively volatile solvent component.
• “relatively small amount of solvent component” refers to an amount of the solvent component that is preferably smaller than the monomer component containing the polyfunctional monomer that is liquid at room temperature.
• the term "relatively volatile solvent component” refers to a solvent component whose boiling point at atmospheric pressure is 30° C. or more, preferably 50° C. or more lower than the contained polyfunctional monomer component.
• a preferred combination is, for example, divinylbenzene as the polyfunctional monomer component and toluene as the solvent component.
• the present invention allows a varnish that is substantially free of solvent components to be obtained.
• a varnish composition substantially free of solvent can be obtained after the selective removal step of the solvent, and by curing this, the cured product of the present invention can also be obtained. That's what it means.
• the cured varnish described above can be treated as a crosslinked resin matrix.
• the crosslinked resin matrix may preferably consist essentially of carbon and hydrogen (containing 99% by mass or more of carbon and hydrogen), and more preferably may consist only of carbon and hydrogen.
• the storage modulus of the cured product or crosslinked resin matrix at 25° C. may be 80 MPa or more, more preferably 80 MPa or more and 2000 MPa or less.
• the storage elastic modulus of the cured product or crosslinked resin matrix at 280° C. may be 30 MPa or more, more preferably 30 MPa or more and 1000 MPa or less.
• a method for producing a cured product can also be provided.
• the manufacturing method includes: preparing a varnish containing an olefin-aromatic vinyl compound-aromatic polyene copolymer and a polyfunctional monomer component; A step of curing the varnish to obtain a cured body having a storage modulus of 80 MPa or more at 25°C and a storage modulus of 30 MPa or more at 280°C.
• the manufacturing method may further include a step of selectively removing the solvent component.
• the shapes of molded bodies and cured bodies obtained from the varnish of the present invention are arbitrary. For example, it can be applied to a base material, or impregnated into cloth such as glass fiber, nonwoven fabric, or porous base material, then laminated with copper foil or a substrate, coated, heated under a press, and cured. It can be a layered or multilayered substrate.
• the varnish of the present invention and the molded product obtained from the same can be cured by a known method with reference to the curing conditions (temperature, time, pressure) of the raw materials and curing agent contained.
• curing conditions can be determined with reference to the half-life temperature etc. disclosed for each peroxide.
• Curing may be done in one step or in multiple steps.
• a semi-cured molded product prepreg
• the sheet may be in a semi-cured state to the extent that it can maintain its sheet shape, or it may be completely cured after being laminated with another substrate or copper foil.
• it is possible to adjust the amount of a plurality of curing agents with different half-life temperatures and use them together, to adjust the curing time and/or curing temperature as appropriate, or to change the curing mode.
• methods include methods of changing (for example, semi-curing is carried out with light curing, main curing is carried out with peroxide, etc.).
• a conventional solvent drying process for such a semi-curing process.
• a semi-cured state can be introduced in the middle of this process to suppress varnish bleeding and uneven thickness. It is possible.
• the degree of hardening of a molded article, particularly a sheet can be quantitatively measured by a known dynamic mechanical analysis (DMA) method.
• DMA dynamic mechanical analysis
• Base material for impregnation examples include known fiber base materials for substrates such as glass fiber, polyamide fiber, and alumina fiber. The use of various coupling agents to improve compatibility with these fibers is also known. Furthermore, porous fluororesin such as PTFE can also be used.
• the cured product obtained from the varnish of the present invention is sufficiently cured, and the gel content measured according to ASTM is 90% by mass or more.
• the average dielectric constant of the cured product is preferably 3.0 or less and 2.0 or more, more preferably 2.8 or less and 2.0 or more. , most preferably 2.5 or less and 2.0 or more.
• the average dielectric loss tangent is preferably 0.0020 or less and 0.0003 or more, more preferably 0.0015 or less and 0.0003 or more, and most preferably 0.0012 or less and 0.0003 or more.
• the average dielectric constant may be 3.0 or more and 2.0 or more, and the average dielectric loss tangent may be 0.0012 or less and 0.0003 or more.
• the cured product obtained from the varnish of the present invention is particularly preferable as an electrical insulating material for high frequencies of 10 GHz or higher, for example, because of its low dielectric loss tangent value.
• the cured product obtained from the varnish of the present invention exhibits a storage modulus of 50 MPa or more, preferably 80 MPa or more at room temperature (25° C.) without containing a filler, and has sufficient strength. I can do it.
• As a substrate it is possible to further increase the storage modulus by adding a filler, but by using the cured product obtained from the varnish of the present invention, it is possible to increase the storage modulus to achieve the required elastic modulus as a substrate. It becomes possible to reduce the amount of materials used. Adding a larger amount of filler may be undesirable for those skilled in the art, as it may reduce the fluidity of the varnish, resulting in poor moldability, and particularly increases the dielectric constant Dk of the cured product. be.
• the cured product obtained from the varnish of the present invention exhibits a high temperature (280°C) storage modulus of 20 MPa or more, preferably 30 MPa or more in a state without a filler, and has sufficient strength and crosslink density. can.
• the magnitude of the storage modulus at high temperatures corresponds to the high crosslinking density, and a high crosslinking density indicates a low linear expansion coefficient of the cured product. This is considered preferable in terms of ensuring stability.
• the cured products obtained from the varnish of the present invention are particularly suitable as electrical insulating materials for high-frequency signals, and these cured products can be suitably used for CCL substrates, FCCL substrates, interlayer insulation materials, or coverlays.
• the present invention can also provide a CCL substrate, an FCCL substrate, an interlayer insulating material, or a coverlay made of the present copolymer or a composition containing the same. Since the cured product obtained from the varnish of the present invention has a high crosslinking density, it is considered to be particularly useful as an insulating material for package substrates.
• the varnish of the present invention does not substantially contain a solvent component, it can be preferably used as various coating inks, such as printer inks, particularly inkjet printers and 3D printer inks.
• printer inks particularly inkjet printers and 3D printer inks.
• photocuring UV photocuring, etc. is preferable.
• the copolymers obtained in the synthesis examples and comparative synthesis examples were analyzed by the following means.
• the content of vinyl group units derived from ethylene, 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 heavy 1,1,2,2-tetrachloroethane, and the measurement was performed at 80-130°C.
• the copolymer contained an ⁇ -olefin unit the measurement was carried out using a known method in conjunction with 13 C-NMR measurement in quantitative mode.
• the molecular weight was determined by the number average molecular weight (Mn) in terms of standard polystyrene using GPC (gel permeation chromatography). The measurements were conducted under the following conditions.
• the viscosity of the copolymer obtained in each Example and Comparative Example was determined as follows. A 50% by mass toluene solution of each copolymer was prepared and measured at 25°C using a rotary rheometer (MCR302: manufactured by Anton Paar), and the value at a shear rate of 1 sec -1 was used.
• the method for evaluating dielectric properties in a balanced disk resonator is to prepare two identical samples (3 cm in diameter and 0.2 to 0.6 mm thick), place a copper foil between them, and set them inside the resonator. , the peak resonance frequency f0 that appeared between 20 and 42 GHz, and the no-load Q and Qu were measured.
• the dielectric constant is calculated from f0, and the dielectric loss tangent (tan ⁇ ) is calculated from Qu using the analysis software (Balanced type circular disk resonator (method) calculator) attached to the resonator. The average value was calculated. The measurement temperature was 23° C. and the humidity was 50% RH.
• a dynamic viscoelasticity measurement device (TA Instruments, formerly Rheometrics RSA-G2) was used to measure at a frequency of 1 Hz while increasing the temperature from room temperature, and the storage modulus at 280°C was measured.
• a measurement sample (3 mm x 40 mm) was cut out from a film with a thickness of approximately 0.1 to 0.3 mm and measured to determine the storage modulus.
• the main measurement parameters involved in the measurement are as follows. Measurement frequency 1Hz Heating rate 3°C/min Sample measurement length 10mm Distortion 0.1%
• Polymerization was carried out to obtain a polymerization solution.
• the resulting polymer solution is poured into a sufficiently large amount of methanol little by little, stirred and decanted to obtain a copolymer.
• Spread the obtained copolymer thinly in a vat and vacuum thoroughly at room temperature. By drying, a semisolid ethylene-styrene-divinylbenzene copolymer P-1 was obtained.
• the styrene monomer used was changed to a low phenylacetylene (LPA) grade (manufactured by Denka Corporation) with a phenylacetylene content of 17 ppm, and ethylene, styrene, and divinylbenzene were copolymerized to produce P-, an ethylene-styrene-divinylbenzene copolymer.
• LPA low phenylacetylene
• Table 1 shows the composition and molecular weight of P-1 to P-4 obtained in each synthesis example.
• Divinylbenzene (DVB) is manufactured by Nippon Steel Chemical & Materials under the trade name "Divinylbenzene (96%)" (liquid at room temperature, a mixture of meta and para forms, containing 96% by mass of divinylbenzene, the remainder being ethylvinyl). benzene) was used. When 35 parts by mass of this product is used in the following example, the amount of divinylbenzene used as a compound is 33.6 parts by mass. Ethylvinylbenzene corresponds to the monofunctional monomer of the present invention. BVPE (bisvinylphenylethane) was manufactured by Changzhou Xingsheng Technology Co., Ltd.
• Example 1 Using a container equipped with a heating and cooling jacket and a stirring blade, 65 parts by mass of P-1 (ethylene-styrene-divinylbenzene copolymer) obtained in the synthesis example was added to divinylbenzene, a product manufactured by Nippon Steel Chemical & Materials Co., Ltd. The copolymer was dissolved in 35 parts by mass of divinylbenzene (96%) by heating to about 50° C. and stirring to prepare 100 parts by mass of varnish.
• P-1 ethylene-styrene-divinylbenzene copolymer
• Examples 2 to 7 A cured sheet was obtained in the same manner as in Example 1 using the formulations shown in Table 2 (units in the table are parts by mass), and physical property values were determined in the same manner.
• Example 5 and Comparative Example 2 which use styrene, low-temperature curing conditions are required to prevent evaporation of styrene, and perbutyl O (t-butylperoxy-2-ethylhexanoate) is used as the curing agent. was used. The curing conditions were 85° C. for 10 hours.
• Comparative example 1 In the same manner as in Example 1, except that a varnish-like composition was prepared by adding 3 parts by mass of toluene to the varnish, a cured sheet was prepared using the same procedure as in Example 1 and the formulation shown in Table 2 (units in the table are parts by mass). However, the resulting sheet had severe foaming and no further physical property measurements were conducted.
• Comparative example 3 A varnish-like composition was prepared using P-2, OPE-2St as an auxiliary raw material, and toluene as a solvent according to the formulation in Table 2 (units in the table are parts by mass). The composition was poured into the Teflon mold of Example 1, and dried in a vacuum dryer at 60°C overnight to remove the solvent toluene and obtain an uncured sheet. Several sheets of this sheet were stacked and placed in the same Teflon mold, degassed under reduced pressure, and further Teflon plates were stacked on top of each other, followed by curing under pressure in the same manner as in Example 1 to obtain a cured sheet.
• Table 2 shows the viscosity of the varnishes of each example and comparative example. When the viscosity of the varnish was 5000 mPa ⁇ s or less, it was written as ⁇ , and when it was higher than 5000 mPa ⁇ s, it was written as ⁇ . The viscosity of the varnishes of each example was 5000 mPa ⁇ s or less.
• the cured sheets obtained in the examples showed a high gel content and were sufficiently cured, and also exhibited a low dielectric constant and a low dielectric loss tangent value necessary for high frequency insulating materials.
• the storage modulus showed sufficient hardness (storage modulus at room temperature) as a substrate, especially a rigid substrate, and mechanical strength at high temperatures (high storage modulus at 280° C.).
• Comparative Example 1 when attempting to cure a varnish containing a solvent using a process that does not involve removing the solvent or drying as in this example, the cured sheet foams, resulting in a hardening process suitable for the substrate. Didn't get a sheet.
• Comparative Example 2 when the amount of polyfunctional monomer contained is small, the elastic modulus at high temperature does not meet the criteria of the present invention.
• Comparative Example 3 OPE-2St was used instead of divinylbenzene, a varnish was prepared using a toluene solvent, and after drying the solvent, it was cured by heating to obtain a cured sheet, but the cured sheet was not stored at 280°C.

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