Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
• • 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
• • 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
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/38—Boron-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment

Definitions

• the present invention relates to compositions and their cured products, and in particular to those that have high heat dissipation performance and excellent low dielectric properties.
• Patent Document 1 ethylene-olefin-polyene copolymers as described in Patent Document 1 have attracted attention.
• Patent Document 2 ethylene-olefin-polyene copolymers compatible with the solder reflow process by blending silica with specified physical properties as a filler.
• insulating materials used for these components must have both sufficiently high heat dissipation properties and sufficiently low dielectric tangent and dielectric constant.
• conventional insulating materials such as fluorine-based resins (perfluoroethylene, etc.), epoxy resins, unsaturated polyester resins, polyimide resins, and phenolic resins have been unable to achieve both of the physical properties mentioned above.
• the present invention aims to provide a composition, a molded body, a cured body, a laminate, a single-layer CCL, a multilayer CCL, a single-layer FCCL, or a multilayer FCCL substrate, etc., that combines high heat dissipation and low dielectric tangent and dielectric constant.
• the present invention provides the following specific aspects.
• Aspect 1 (a) an olefin-aromatic vinyl compound-aromatic polyene copolymer which satisfies all of the following conditions (i) to (iv): (i) The number average molecular weight of the copolymer is 500 or more and less than 100,000. (ii) The aromatic vinyl compound monomer unit is an aromatic vinyl compound having from 8 to 20 carbon atoms, and the content of the aromatic vinyl compound monomer unit is 70 mass% 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 monomer unit is 1.5 or more and less than 20 per number average molecular weight.
• the olefin monomer unit is one or more olefins selected from olefins having 2 to 20 carbon atoms, the content of the olefin monomer units is 30 mass% or more, and the total of the olefin monomer units, the aromatic vinyl compound monomer units, and the aromatic polyene monomer units is 100 mass%.
• the volume ratio of the component (a) to the component (b) is in the range of 98 to 15:2 to 85, a dielectric loss tangent of a cured body of the composition, measured by a split cylinder resonator method, is 2 ⁇ 10 or less at a measurement frequency of 35 to 42 GHz;
• a composition, characterized in that a cured product of the composition has a thermal conductivity of 0.6 [W/m ⁇ K] or more, as determined by a laser flash method at 23°C.
• composition of claim 1, wherein the (b) component comprises spherical boron nitride particles.
• Aspect 4 The composition according to any one of aspects 1 to 3, wherein the volume-based cumulative diameter (D50) of the component (b) measured by a laser diffraction scattering method without homogenization treatment is 35 ⁇ m or less.
• Aspect 5 The composition according to any one of aspects 2 to 4, wherein the average circularity of component (b) is 0.80 or more.
• Aspect 6 A composition according to any one of Aspects 1 to 5, wherein the component (b) has a semi-quantitative value of 0.6 or more calculated from an O 1s peak intensity measured by X-ray photoelectron spectroscopy.
• Aspect 7 The composition according to any one of Aspects 1 to 6, further comprising one or more selected from the group consisting of the following components (c) to (g): (c) a curing agent; and (d) an inorganic filler different from the component (b). (e) one or more resins different from the component (a) and selected from the group consisting of a hydrocarbon-based elastomer, a polyether-based resin, and an aromatic polyene-based resin; (f) a monomer; and (g) a solvent.
• Aspect 9 The molded article according to claim 8, which is in the form of a sheet.
• Aspect 11 The molded product according to aspect 8 or 9 or the cured product according to aspect 10, which is an electrical insulating material.
• a laminate comprising a layer comprising the composition according to any one of aspects 1 to 7 and a metal foil.
• a single layer CCL, a multilayer CCL, a single layer FCCL, or a multilayer FCCL substrate comprising the molded body according to aspect 8, 9, or 11, the cured body according to aspect 10, 11, or 13, or the laminate according to aspect 12.
• the present invention provides an insulating material that has both sufficiently high heat dissipation and sufficiently low dielectric tangent and dielectric constant.
• the olefin-aromatic vinyl compound-aromatic polyene copolymer may be abbreviated as "copolymer”.
• Numerical ranges in this specification include the upper and lower limits unless otherwise specified. For example, a numerical range of "1 to 100" includes both the lower limit "1" and the upper limit "100". The same applies to other numerical ranges.
• sheet also includes the concept of a film.
• film also includes the concept of a sheet.
• composition is characterized by comprising an olefin-aromatic vinyl compound-aromatic polyene copolymer having a certain range of composition and molecular weight as described below, and boron nitride particles (hereinafter, sometimes abbreviated as "composition").
• the composition may be moldable into a molded product (e.g., a sheet shape).
• the composition is preferably curable, and in this case, a cured product can be obtained by curing the composition under predetermined conditions.
• the cured product of the composition is preferably an electrical insulating material.
• the copolymer is characterized by satisfying all of the following conditions (i) to (iv): (i) The number average molecular weight of the copolymer may be 500 or more and less than 100,000, preferably 5,000 or more and less than 100,000, and more preferably 5,000 or more and less than 50,000. (ii)
• the aromatic vinyl compound monomer unit is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of the aromatic vinyl compound monomer unit may be 70 mass% or less, more preferably 10 mass% or more and 70 mass% or less, and even more preferably 10 mass% or more and 60 mass% 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 monomer unit may be 1.5 or more and less than 20, preferably 3 or more and less than 20, more preferably 3 or more and less than 10, per number average molecular weight.
• the olefin monomer unit is one or more selected from olefins having 2 to 20 carbon atoms, the content of the olefin monomer unit may be 30% by mass or more, preferably 30% by mass or more and 90% by mass or less, and the total content of the olefin monomer unit, the aromatic vinyl compound monomer unit and the aromatic polyene monomer unit is 100% by mass.
• This olefin-aromatic vinyl compound-aromatic polyene copolymer can be obtained, for example, by copolymerizing the monomers of an olefin, an aromatic vinyl compound, and an aromatic polyene.
• 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, and is a compound composed of carbon and hydrogen, substantially free of oxygen, nitrogen, and halogens.
• ⁇ -olefins having 2 to 20 carbon atoms include, but are not limited to, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, and 3,5,5-trimethyl-1-hexene.
• cyclic olefins having 5 to 20 carbon atoms include, but are not limited to, norbornene and cyclopentene.
• olefins that can be preferably used include, but are not limited to, a combination of ethylene with an ⁇ -olefin other than ethylene or a cyclic olefin, or ethylene alone.
• the aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms.
• aromatic vinyl compound monomers include, but are not limited to, styrene, paramethylstyrene, paraisobutylstyrene, various vinylnaphthalenes, and various vinylanthracenes.
• the aromatic polyene monomer is a polyene having 5 to 20 carbon atoms and having multiple vinyl groups and/or vinylene groups (preferably vinyl groups) in its molecule.
• the aromatic polyene monomer may preferably be a polyene having 8 to 20 carbon atoms.
• a preferred aromatic polyene monomer may be a polyene having 8 to 20 carbon atoms and having multiple vinyl groups in its molecule, more preferably a compound having an aromatic vinyl structure such as ortho-, meta-, or para-divinylbenzene or a mixture thereof, divinylnaphthalene, divinylanthracene, p-2-propenylstyrene, or p-3-butenylstyrene, which is substantially free of oxygen, nitrogen, and halogen and is composed of carbon and hydrogen.
• an aromatic vinyl structure such as ortho-, meta-, or para-divinylbenzene or a mixture thereof, divinylnaphthalene, divinylanthracene, p-2-propenylstyrene, or p-3-butenylstyrene, which is substantially free of oxygen, nitrogen, and halogen and is composed of carbon and hydrogen.
• a bifunctional aromatic vinyl compound described in JP-A-2004-087639 such as 1,2-bis(vinylphenyl)ethane (abbreviation: BVPE), may be used as the aromatic polyene monomer.
• BVPE 1,2-bis(vinylphenyl)ethane
• ortho-, meta-, and para-divinylbenzenes or mixtures thereof are preferably used, and a mixture of meta- and para-divinylbenzenes may be most preferably used.
• these divinylbenzenes may be abbreviated as divinylbenzenes (DVBs).
• VVBs divinylbenzenes
• the above olefin, aromatic vinyl compound, and aromatic polyene monomers may also contain polar groups, such as olefins containing oxygen atoms, nitrogen atoms, etc., aromatic vinyl compounds containing oxygen atoms or nitrogen atoms, or aromatic polyenes containing oxygen atoms or nitrogen atoms.
• the total mass of these monomers containing polar groups can be set appropriately depending on the desired performance and is not particularly limited, but is preferably 10 mass% or less of the total mass of the composition, more preferably 3 mass% or less, and most preferably substantially free of monomers containing polar groups. By keeping the amount of such monomers at 10 mass% or less, the low dielectric properties (low dielectric constant, low dielectric loss) of the cured body obtained by curing the composition can be further improved.
• the number average molecular weight (Mn) of the copolymer is 500 or more and less than 100,000, preferably 5,000 or more and less than 100,000, more preferably 5,000 or more and less than 50,000, and even more preferably 5,000 or more and less than 30,000. By setting it in such a range, the composition becomes less sticky in the uncured state, and the effect of improving thermoplasticity is obtained, and further, the finally obtained cured product can be easily given good physical properties such as high breaking strength and high breaking elongation. If the number average molecular weight is less than 500, the mechanical properties of the composition in the uncured stage are low and the adhesiveness is high, so that the composition may be difficult to mold as a thermoplastic resin.
• the number average molecular weight is 100,000 or more, the moldability may be reduced.
• the number average molecular weight of 500 or more and less than 100,000 means that the molecular weight in standard polystyrene equivalent obtained by GPC (gel permeation chromatography) method is within that range.
• the content of aromatic vinyl compound monomer units contained in this copolymer may be 0% by mass or more and 70% by mass or less, preferably 0% by mass or more and less than 70% by mass, and more preferably 10% by mass or more and 60% by mass or less.
• the olefin-aromatic vinyl compound-aromatic polyene copolymer also includes an embodiment in which the aromatic vinyl compound monomer units are 0% by mass. If the content of aromatic vinyl compound monomer units is more than 70% by mass, the glass transition temperature of the cured body of the final composition is near room temperature, and the toughness and elongation at low temperatures may decrease.
• the content of aromatic vinyl compound monomer units is 10% by mass or more, the aromaticity of this copolymer is improved, the compatibility with the filler is improved, and the dispersibility of boron nitride particles tends to be excellent. Furthermore, if the content of aromatic vinyl compound monomer units is 10% by mass or more, in addition to improving dispersibility, a cured body of the composition having high peel strength with copper foil or copper wiring tends to be easily obtained.
• the content of vinyl groups and/or vinylene groups derived from aromatic polyene monomer units may be 1.5 or more and less than 20, preferably 3 or more and less than 20, more preferably 3 or more and less than 10 per number average molecular weight of the copolymer.
• the content of vinyl groups and/or vinylene groups may be collectively referred to as "vinyl group content" hereinafter. If the vinyl group content is less than 1.5, the crosslinking efficiency is low, and it is difficult to obtain a cured body with sufficient crosslinking density. If the vinyl group content is increased, it tends to be easier to improve the mechanical properties of the finally obtained cured body at room temperature and high temperature.
• the vinyl group content derived from aromatic polyene monomer units (e.g., divinylbenzene units) per number average molecular weight in the present copolymer can be obtained, for example, by comparing the number average molecular weight (Mn) calculated in terms of standard polystyrene obtained by GPC (gel permeation chromatography) method known to those skilled in the art with the vinyl group content or vinylene group content derived from aromatic polyene monomer units obtained by 1 H-NMR measurement.
• Mn number average molecular weight
• the vinyl group content derived from aromatic polyene monomer units (e.g., divinylbenzene units) in the copolymer is 0.6% by mass by comparing the intensity of each peak area obtained by 1 H-NMR measurement, and the number average molecular weight in terms of standard polystyrene measured by GPC measurement is 49,000
• the molecular weight of the vinyl group derived from the aromatic polyene monomer units in the number average molecular weight is the product of these, 294, which is divided by the formula weight of the vinyl group, 130, to obtain 2.3.
• the vinyl group content derived from aromatic polyene monomer units per number average molecular weight in this copolymer is determined to be 2.3.
• the assignment of peaks obtained by 1 H-NMR measurement of the copolymer is known from literature.
• a method of determining the composition of the copolymer from a comparison of peak areas obtained by 1 H-NMR measurement is also known.
• the peak areas of 13 C-NMR spectra measured in a known quantitative mode or their ratios may be used as an auxiliary.
• the content of aromatic polyene monomer units (divinylbenzene units will be explained below, but the following explanation is not limited to the case of divinylbenzene units) in the copolymer is determined from the peak intensity (measured by 1 H-NMR) of vinyl groups derived from the divinylbenzene units. That is, the content of divinylbenzene units is determined from the content of vinyl groups derived from divinylbenzene units, assuming that one vinyl group is derived from one divinylbenzene unit in the copolymer.
• the content of the olefin monomer units is 30% by mass or more, preferably 30% by mass or more and 90% by mass or less, and more preferably 30% by mass or more and 60% by mass or less.
• the total of the olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units is 100% by mass.
• the present copolymer can be produced by copolymerizing each monomer of an aromatic vinyl compound, an aromatic polyene, and an olefin used as needed by coordination polymerization.
• a single-site coordination polymerization catalyst composed of a transition metal compound and a cocatalyst, as described in JP-A-2009-161743, JP-A-2010-280771, WO 00/37517, etc., because the present copolymer can be produced efficiently.
• Suitable olefin-aromatic polyene copolymers that do not contain aromatic vinyl compound monomer units include ethylene-divinylbenzene copolymer, ethylene-propylene-divinylbenzene copolymer, ethylene-1-butene-divinylbenzene copolymer, ethylene-1-hexene-divinylbenzene copolymer, and ethylene-1-octene-divinylbenzene copolymer.
• examples of the olefin-aromatic vinyl compound-aromatic polyene copolymer containing an aromatic vinyl compound monomer unit include ethylene-styrene-divinylbenzene copolymer, ethylene-propylene-styrene-divinylbenzene copolymer, ethylene-1-hexene-styrene-divinylbenzene copolymer, and ethylene-1-octene-styrene-divinylbenzene copolymer.
• This copolymer can be produced by the production methods described in, for example, WO 00/37517, JP 2009-161743 A, and JP 2010-280771 A.
• the composition is characterized by containing boron nitride (BN) particles.
• the boron nitride particles may include spherical boron nitride particles, scaly primary particles of boron nitride, and secondary particles which are aggregates thereof, and preferably spherical boron nitride particles can be used.
• Examples of boron nitride include hexagonal boron nitride (h-BN) and cubic boron nitride (c-BN).
• spherical means that the particles are observed as circular or rounded grain shapes when observed at 10,000 times magnification using a scanning electron microscope.
• the ratio B 1s /O 1s of the semi-quantitative value calculated from the O 1s peak intensity measured by X-ray photoelectron spectroscopy and the semi-quantitative value calculated from the B 1s peak intensity measured by X-ray photoelectron spectroscopy may be 90 or less, more preferably 85 or less, even more preferably 80 or less, even more preferably 75 or less, and particularly preferably 70 or less.
• the lower limit of the B 1s /O 1s value can be appropriately set according to the desired performance and is not particularly limited, but may be preferably 10 or more, more preferably 15 or more, and even more preferably 20 or more.
• the value of the B 1s /O 1s ratio may be in the range of 10 to 90, 15 to 85, or 20 to 80.
• the B 1s /O 1s ratio is obtained by taking the background by the Shirley method and calculating a semi-quantitative value calculated from the B 1s peak intensity and the O 1s peak intensity.
• the Shirley method is a method for determining the shape of the background to be subtracted, assuming that the inelastically scattered electrons that cause the background are not energy-dependent and that the number of inelastically scattered electrons is proportional to the peak intensity.
• the B 1s /O 1s ratio is 90 or less, the boron nitride particles have excellent dispersibility in water due to the surface state, and tend to easily obtain the effect of improving the fluidity of the composition when mixed with the copolymer.
• the B 1s /O 1s ratio of boron nitride particles can be adjusted by subjecting the raw material boron nitride particles (preferably spherical boron nitride particles) to a cavitation treatment in a liquid containing water.
• boron nitride particles preferably spherical boron nitride particles
• the aggregated state can be broken down while maintaining the shape of the primary particles, and many hydroxyl groups are introduced onto the surfaces of the broken down primary particles, making it possible to reduce the B 1s /O 1s ratio and adjust it to 90 or less. Details of the cavitation treatment will be described later.
• the semi-quantitative value calculated from the O 1s peak intensity measured by X-ray photoelectron spectroscopy is preferably 0.6 (0.60) or more, more preferably 0.65 or more, and even more preferably 0.7 (0.70) or more.
• the upper limit of the semi-quantitative value calculated from the O 1s peak intensity may be, for example, 5.0 or less, more preferably 4.0 or less, even more preferably 3.0 or less, and even more preferably 2.0 or less.
• the semi-quantitative value calculated from the O 1s peak intensity may be in the range of 0.6 (0.60) or more and 5.0 or less, 0.65 or more and 4.0 or less, or 0.7 (0.70) or more and 3.0 or less.
• the boron nitride particles have a semi-quantitative value calculated from the B 1s peak intensity measured by X-ray photoelectron spectroscopy of preferably less than 48.4 (48.40), more preferably 48.35 or less, and even more preferably 48.3 (48.30) or less.
• the boron nitride particles are preferably measured by a laser diffraction scattering method without a specific dispersion treatment, such as a homogenizer treatment (i.e., without applying an external force), with a volume-based cumulative diameter (D50) of 35 ⁇ m or less, more preferably 33 ⁇ m or less, even more preferably 32 ⁇ m or less, even more preferably 30 ⁇ m or less, and particularly preferably 28 ⁇ m or less.
• the lower limit of D50 measured without a homogenizer treatment is not particularly limited, but may be, for example, 5 ⁇ m or more, more preferably 10 ⁇ m or more, and even more preferably 15 ⁇ m or more.
• volume-based cumulative diameter refers to the particle diameter at which the cumulative value corresponds to 50% in the volume-based cumulative particle size distribution measured by a laser diffraction scattering method (refractive index: 1.7).
• the cumulative particle size distribution is represented by a distribution curve with the particle diameter ( ⁇ m) on the horizontal axis and the cumulative value (%) on the vertical axis.
• the fact that the D50 is small even without homogenization means that the particles are relatively small and that the proportion of primary particles is higher than that of secondary particles. This characteristic has the effect of improving the fluidity of compositions filled with boron nitride particles.
• the boron nitride particles according to one embodiment may be further homogenized to produce smaller particles.
• the boron nitride particles are homogenized in ethanol (conditions: 300 W, 90 sec) and then evaluated by a laser diffraction scattering method to have a volume-based cumulative diameter (D50) of preferably 0.6 (0.60) ⁇ m or less, more preferably 0.58 ⁇ m or less, and even more preferably 0.56 ⁇ m or less.
• the D50 measured after the homogenization may be, for example, 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and even more preferably 0.3 ⁇ m or more.
• the average circularity of the primary particles of the spherical boron nitride particles is preferably 0.80 or more, more preferably 0.82 or more, and even more preferably 0.84 or more.
• the upper limit of the average circularity is not particularly limited, but may be, for example, 1 or less, or 0.95 or less.
• the average circularity is in the range of 0.80 or more and 1 or less, or 0.82 or more and 0.95 or less. When the average circularity is within the above range, the effect of improving the fluidity of the composition filled with the boron nitride particles tends to be easily obtained.
• the boron nitride particles as the raw material can be produced by a known method, and are not particularly limited, but can be preferably produced as spherical boron nitride particles by the method described in International Publication No. 2015/122379.
• the spherical boron nitride particles as the raw material can be produced by reacting a boric acid ester having an ammonia/boric acid ester molar ratio of 1 to 10 with ammonia in an inert gas stream at 750° C. or higher for 30 seconds or less, followed by heat treatment at 1,000 to 1,600° C.
• boric acid ester a known one can be used, and is not particularly limited, but for example, trimethyl borate can be mentioned.
• the raw boron nitride particles can be placed in a liquid containing water (preferably pure water) and cavitation bubbles (bubbles generated by vaporization when the liquid becomes low pressure) can be generated in the liquid, and the secondary particles of the boron nitride particles can be broken down into primary particles by the expansion and contraction forces caused by the pressure difference of the generated bubbles, while at the same time changing the surface condition of the particles, such as increasing the proportion of hydroxyl groups present.
• Cavitation bubbles can be generated by causing a foaming phenomenon in the liquid using reduced pressure or ultrasound, using commercially available equipment (such as a powder suction continuous dissolution and dispersion device). It is particularly preferable to circulate the liquid during processing.
• Powder suction continuous dissolving and dispersing devices generally have a mechanism for generating a flow rate using an agitator blade, and the rotation speed of the agitator blade can be set appropriately according to the desired performance and is not particularly limited, but is preferably 2,000 to 10,000 rpm, more preferably 4,000 to 9,000 rpm, even more preferably 4,500 to 8,000 rpm, even more preferably 5,000 to 8,000 rpm, and particularly preferably 6,000 to 7,200 rpm.
• the process of generating cavitation bubbles is preferably performed 50 times or more, more preferably 100 times or more, and even more preferably 150 times or more, as the number of times of cavitation processing calculated from the rotation speed (rpm) of the stirring blade of the device and the discharge amount.
• the process of generating cavitation bubbles is easily adjusted to a B 1s / O 1s ratio of 90 or less by performing the process of generating cavitation bubbles 50 times or more.
• the B 1s / O 1s ratio tends to be smaller.
• the surface hydroxyl groups can be increased and the B 1s / O 1s ratio can be reduced.
• the composition may further include a curing agent, an inorganic filler different from the boron nitride particles, one or more resins different from the copolymer and selected from the group consisting of a hydrocarbon-based elastomer, a polyether-based resin, and an aromatic polyene-based resin, a monomer, and one or more solvents.
• a curing agent an inorganic filler different from the boron nitride particles
• one or more resins different from the copolymer selected from the group consisting of a hydrocarbon-based elastomer, a polyether-based resin, and an aromatic polyene-based resin, a monomer, and one or more solvents.
• curing agent that may be contained in the present composition, it is possible to use a known curing agent that can be used for polymerization or curing of conventional aromatic polyenes and aromatic vinyl compounds.
• curing agents include, but are not limited to, radical polymerization initiators (radical generators), cationic polymerization initiators, and anionic polymerization initiators.
• radical polymerization initiators can be used.
• organic peroxides (peroxides), azo-based polymerization initiators, etc. can be freely selected depending on the application and conditions.
• a catalog listing organic peroxides can be downloaded from the NOF Corporation website, for example, https://www.nof.co.jp/product-search/family/1020001. Organic peroxides are also listed in catalogs from Fujifilm Wako Pure Chemical Industries, Ltd. and Tokyo Chemical Industry Co., Ltd. Curing agents that can be used in this embodiment can be obtained from these companies.
• An example of an organic peroxide-based curing agent is Perhexine 25B (manufactured by NOF Corporation).
• a known photopolymerization initiator that uses light, ultraviolet light, or radiation can be used as a curing agent.
• photopolymerization initiator examples include a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanionic polymerization initiator.
• photopolymerization initiators are available from, for example, Tokyo Chemical Industry Co., Ltd.
• 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 curing agent used there are no particular restrictions on the amount of curing agent used, but generally, 0.01 to 10 parts by mass, and 0.1 to 10 parts by mass, are preferred, based on 100 parts by mass of copolymer. It is preferable that the above composition does not include the curing agent or solvent.
• a curing agent such as a peroxide or azo-based polymerization initiator
• the curing process is carried out at an appropriate temperature and time, taking into account its half-life. In this case, the conditions can be determined according to the curing agent, but generally a temperature range of about 50°C to 200°C is appropriate.
• the present composition may contain known inorganic fillers (fillers) other than the above-mentioned boron nitride particles, so long as the object of the present invention is not impaired. These fillers can be added, for example, for the purpose of controlling the thermal expansion coefficient, controlling thermal conductivity, and reducing the cost, and the amount of fillers used is arbitrary depending on the purpose.
• a known surface modifier for example, a silane coupling agent. Silica or alumina may be added as the inorganic filler.
• silica fused silica is preferable.
• Such an inorganic filler may be added in an amount of 200 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 10 parts by mass or less, based on 100 parts by mass of the present copolymer.
• a hollow filler or a filler having a shape with many voids may be added to improve and enhance low dielectric properties (low dielectric constant, low dielectric loss tangent).
• the composition may contain resins other than the copolymers described above, including hydrocarbon-based elastomers, polyether-based resins, and aromatic polyene-based resins.
• the hydrocarbon-based elastomer is preferably one or more selected from ethylene-based or propylene-based elastomers having a radical crosslinkable functional group, conjugated diene-based polymers, aromatic vinyl compound-conjugated diene-based block or random copolymers, and hydrogenated products thereof.
• the amount of the hydrocarbon-based elastomer used can be appropriately set according to the desired performance and is not particularly limited, but from the viewpoint of improving the handling and moldability of the composition in an uncured state, it is preferably added in an amount of 100 parts by mass or less, more preferably 1 to 50 parts by mass, and even more preferably 1 to 30 parts by mass, based on 100 parts by mass of the copolymer.
• the number average molecular weight of the hydrocarbon-based elastomer that can be suitably used in the composition of this embodiment is preferably, for example, 500 to 100,000, and more preferably 1,000 to 4,500.
• Examples of ethylene-based elastomers include ethylene- ⁇ -olefin copolymers such as ethylene-octene copolymer and ethylene-1-hexene copolymer, EPR, EPDM, etc.
• examples of propylene-based elastomers include atactic polypropylene, low stereoregular polypropylene, propylene- ⁇ -olefin copolymers such as propylene-1-butene copolymer, etc., but are not limited to these.
• Examples of radical crosslinkable functional groups include vinyl groups, allyl groups, ethylidene norbornene groups (units), and other functional groups normally contained in rubber raw materials such as EPDM, but are not limited to these. These radical crosslinkable soft resins may be modified by introducing functional groups with maleic anhydride or other compounds.
• Conjugated diene polymers include, but are not limited to, polybutadiene and 1,2-polybutadiene.
• aromatic vinyl compound-conjugated diene block or random copolymers and their hydrogenated products (hydrogenated products) include, but are not limited to, SBS, SIS, SEBS, SEPS, SEEPS, SEEBS, etc., which can be suitably used.
• 1,2-polybutadiene can be obtained, for example, from Nippon Soda Co., Ltd. under the product names of liquid polybutadiene: B-1000, 2000, and 3000.
• an example of a copolymer containing a 1,2-polybutadiene structure which can be suitably used is "Ricon 100" from TOTAL CRAY VALLEY.
• the above-mentioned conjugated diene polymers and their hydrogenated products may be modified, for example, by introducing functional groups with maleic anhydride or other compounds.
• the conjugated diene polymers polymers that do not contain vinylene groups in the main chain or have fewer vinylene groups are preferred.
• the vinylene groups in the main chain tend to remain in the cured product even after curing, and these vinylene groups tend to react with oxygen in the air to generate polar groups containing oxygen, which is undesirable since the dielectric constant and dielectric tangent tend to be high after high-temperature durability tests of the cured product (for example, in air at 125°C).
• 1,4-polybutadiene copolymers are not suitable as conjugated diene polymers, and 1,2-polybutadiene polymers or copolymers containing a 1,2-polybutadiene structure are preferred.
• various hydrogenated polymers in which the vinylene group has been hydrogenated and its content has been greatly reduced are preferred.
• hydrogenated polymers of conjugated diene polymers include hydrogenated SBR, SEBS, SEPS, SEEPS, SEEBS, etc., and preferably hydrogenated polymers of conjugated diene polymers having methyl-substituted styrene.
• Polyether-based resins include, but are not limited to, polyphenylene ether, polyether, etc. It is preferable that the molecular end of the polyphenylene ether having a functional group is modified with a functional group. In addition, when adding for the purpose of curing the composition of this embodiment, it is preferable that one molecule of the polyphenylene ether has multiple functional groups. For example, it is preferable to use a modified polyphenylene ether.
• the functional group include a radically polymerizable functional group, an epoxy group, and the like, and preferably a radically polymerizable functional group. As the radically polymerizable functional group, a vinyl group is preferable.
• the vinyl group one or more types selected from the group consisting of an allyl group, a (meth)acryloyl group, and an aromatic vinyl group are preferable, one or more types selected from the group consisting of a (meth)acryloyl group and an aromatic vinyl group are more preferable, and an aromatic vinyl group is most preferable.
• a bifunctional polyphenylene ether in which both ends of the molecular chain are modified with a radically polymerizable functional group is particularly preferable.
• polyphenylene ethers examples include, but are not limited to, Noryl (registered trademark) SA9000 manufactured by SABIC (modified polyphenylene ether having methacryloyl groups at both ends, number average molecular weight 2200) and bifunctional polyphenylene ether oligomer manufactured by Mitsubishi Gas Chemical Company, Inc. (OPE-2St, modified polyphenylene ether having vinylbenzyl groups at both ends, number average molecular weight 1200).
• allylated PPE manufactured by Asahi Kasei Corporation and aromatic polyethers (ELPAC HC-F series) manufactured by JSR Corporation can also be used.
• Aromatic polyene resins include divinylbenzene reactive hyperbranched copolymers (PDV or ODV) manufactured by Nippon Steel Chemical & Material Co., Ltd. Such hyperbranched copolymers are described, for example, in the literature “Synthesis of polyfunctional aromatic vinyl copolymers and development of new IPN-type low dielectric loss materials using them” (Kawabe Masanao, Journal of the Japan Institute of Electronics Packaging, p. 125, Vol. 12, No. 2 (2009)).
• the composition may further contain a monomer, and a radically polymerizable monomer is preferably used.
• the content of the monomer may be preferably 10 parts by mass or less based on 100 parts by mass of the copolymer.
• the composition may be substantially free of a monomer. When the monomer is 10 parts by mass or less, the uncured composition does not have a viscous property, and tends to be easily molded as a thermoplastic resin.
• the monomer that can be suitably used preferably has a molecular weight of less than 1000, more preferably less than 500.
• an aromatic vinyl compound monomer As the monomer, an aromatic vinyl compound monomer, an aromatic polyene monomer, and/or a polar monomer, etc., are preferably included, but are not particularly limited thereto.
• an aromatic vinyl compound and an aromatic polyene are more preferable.
• BVPE 1,2-bis(vinylphenyl)ethane
• the aromatic polyene is preferably 1 part by mass or more and 30 parts by mass or less per 100 parts by mass of the copolymer.
• polar monomer in addition, there is a tendency that a relatively small amount of polar monomer can be used for the purpose of imparting adhesion to other materials required as an insulating material or improving crosslink density.
• the polar monomer include various maleimides, bismaleimides, maleic anhydride, glycidyl (meth)acrylate, triallyl isocyanurate, tri(meth)acrylic isocyanurate, trimethylolpropane tri(meth)acrylate, etc., but are not particularly limited thereto.
• Maleimides and bismaleimides that can be used in this embodiment are described in, for example, International Publication No. 2016/114287 and JP-A No.
• an appropriate solvent may be added to the composition.
• the amount of the solvent is not particularly limited.
• the solvent is used to adjust the viscosity and fluidity of the composition.
• a solvent may be preferably used.
• the solvent a solvent having a boiling point of a certain degree or higher is preferred, since a high boiling point at atmospheric pressure, i.e., low volatility, tends to result in a uniform thickness of the applied film.
• the preferred boiling point is approximately 75°C or higher at atmospheric pressure, and more preferably 100°C or higher and 300°C or lower.
• any solvent known in the art may be used, and is not particularly limited.
• cyclohexane cyclohexanone, methyl ethyl ketone (MEK), toluene, ethylbenzene, xylene, mesitylene, tetralin, acetone, limonene, mixed alkanes, mixed aromatic solvents, etc.
• the amount of the solvent used in the composition of the present embodiment can be appropriately set depending on the desired performance, and is arbitrary. However, the amount is preferably 5 to 500 parts by mass, more preferably 10 to 300 parts by mass, and most preferably 50 to 150 parts by mass, based on 100 parts by mass of the composition.
• spherical boron nitride particles preferably spherical boron nitride particles having a B 1s /O 1s ratio of 90 or less
• the intermolecular force between the copolymer and the spherical boron nitride particles is strengthened (they are more likely to stick together).
• affinity between the surface of spherical boron nitride particles having preferred properties and the copolymer having a specific structure is particularly enhanced by ⁇ -electron interaction, resulting in a preferred synergistic effect.
• a composition that combines a copolymer satisfying all of the above conditions (i) to (iv) with spherical boron nitride particles having a B 1s /O 1s ratio of 10 to 90 and a D50 of 5 ⁇ m to 35 ⁇ m measured by a laser diffraction scattering method without homogenizer treatment can be provided as one that brings about an even better synergistic effect.
• composition and properties of the composition is characterized in that it contains the copolymer and the boron nitride particles in a volume ratio in the range of 98-15:2-85.
• the volume ratio of the copolymer to the boron nitride particles in the composition may be in the range of 90-15:10-85, more preferably in the range of 80-20:20-80, and even more preferably in the range of 75-25:25-75.
• the composition is characterized in that the dielectric tangent of the cured product is 2 ⁇ 10 ⁇ 3 or less as determined by a split cylinder resonator method at a measurement frequency of 35 to 42 GHz.
• the dielectric tangent may be 1 ⁇ 10 ⁇ 3 or less, and more preferably 8 ⁇ 10 ⁇ 4 or less.
• the dielectric constant of the cured product of this composition is preferably 4.0 or less, more preferably 3.5 or less, and even more preferably 3.0 or more and 3.5 or less.
• the thermal conductivity of the cured product of this composition is characterized by being 0.6 [W/m ⁇ K] or more as determined by the laser flash method at 23°C. In a preferred embodiment, the thermal conductivity may be 0.7 [W/m ⁇ K] or more.
• a cured product of the composition according to a preferred embodiment may have a dielectric loss tangent of 1 ⁇ 10 ⁇ 3 or less and a thermal conductivity of 0.7 [W/m ⁇ K] or more, as measured as described above, and more preferably may have a dielectric constant of 4.0 or less, a dielectric loss tangent of 1 ⁇ 10 ⁇ 3 or less, and a thermal conductivity of 0.7 [W/m ⁇ K] or more.
• the composition can be used as a base material or substrate, such as a single-layer or multi-layer printed circuit board, a flexible printed circuit board, a so-called single-layer or multi-layer CCL (copper clad laminate) board, or a single-layer or multi-layer FCCL (flexible copper clad laminate) board.
• the composition can also be used as various electrical insulating materials for wiring, preferably for wiring of high-frequency signals, such as coverlays, high-frequency transmission circuits, antennas, solder resists, build-up materials, interlayer insulating materials, bonding sheets, interlayer adhesives, and bump sheets for flip-chip bonders.
• a laminate including a layer including the above composition and a metal foil (preferably copper foil) can be provided.
• a cured product of the laminate can be provided, and the above substrate including the laminate or the cured product can be provided.
• Copolymers P1 and P2 were produced by referring to the production methods described in JP-A-2009-161743 and JP-A-2010-280771, respectively.
• Dimethylmethylenebiscyclopentadienylzirconium dichloride (structural formula (1) below) and Rac-diphenylmethylene(1-indenyl)(cyclopentadienyl)zirconium dichloride (structural formula (2) below) were used as catalysts.
• Tritium tetrakis(pentafluorophenyl)borate (TRI-FABA, manufactured by Tosoh Finechem Co., Ltd.) was used as the cocatalyst.
• Toluene was used as the solvent.
• Styrene, divinylbenzene, and ethylene were used as raw monomers, and polymerization was carried out in a 10 L polymerization vessel equipped with a stirrer and a jacket for heating and cooling.
• NMR spectrum peaks were as follows: 0.6-1.02 ppm: CH3, 3H of ⁇ -olefins other than ethylene 0.6-2.1 ppm: St + DVB + Et + CH2, 2H of ⁇ -olefins other than ethylene 5.1-5.4 ppm: CH, 1H of DVB vinyl 6.3-7.8 ppm: St aromatic ring C6H5, 5H, DVB aromatic ring C6H4, 4H
• Mn number average molecular weight
• GPC gel permeation chromatography
• Synthesis Example Production of Copolymer P3 Using the same method as above, but further incorporating 1-octene as an ⁇ -olefin as a raw material, copolymer P3, which is an ethylene-1-octene-styrene-divinylbenzene copolymer, was obtained.
• the obtained precursor of boron nitride particles was placed in a boron nitride crucible installed in a resistance heating furnace, and nitrogen gas and ammonia gas were introduced into the reaction tube at flow rates of 10 L/min and 15 L/min, respectively.
• the reaction tube was heated at 1500°C for 5 hours to obtain a second precursor.
• the obtained second precursor was placed in a boron nitride crucible and heated in an induction heating furnace in a nitrogen atmosphere at 2000°C for 5 hours to obtain raw spherical boron nitride particles.
• the volume-based cumulative diameter (D50) of the raw spherical boron nitride particles was measured by the laser diffraction scattering method and found to be 0.62 ⁇ m. The average circularity was also 0.87.
• 0.1 g of the obtained spherical boron nitride powder was dispersed in 80 mL of ethanol as a sample, and the volumetric particle size distribution was measured using a laser diffraction scattering particle size distribution analyzer (manufactured by Beckman Coulter, Inc., product name: LS-13 320) without treatment with a homogenizer.
• a refractive index of 1.359 was used for ethanol, and a refractive index of 1.7 was used for the boron nitride powder.
• the median diameter D50 of particles not treated with a homogenizer was calculated. The D50 was 25 ⁇ m.
• the obtained spherical boron nitride powder was dispersed in 80 mL of ethanol as a sample, and ultrasonic dispersion was performed for 1 minute and 30 seconds with an ultrasonic homogenizer (manufactured by Nippon Seiki Seisakusho, product name: US-300E) with the AMPLITUDE (amplitude) set to 70-80%, after which the volumetric particle size distribution was measured with a laser diffraction scattering particle size distribution measuring device (manufactured by Beckman Coulter, product name: LS-13 320).
• the median diameter D50 was calculated from the obtained volumetric particle size distribution and was found to be 0.537 ⁇ m.
• the refractive index of ethanol was 1.359
• the refractive index of the boron nitride powder was 1.7.
• Perhexyne 25B manufactured by NOF Corp.
• a curing agent 1 part by mass of Perhexyne 25B (manufactured by NOF Corp.) was added as a curing agent in an amount of 1 part by mass per 100 parts by mass of the copolymer, dissolved, stirred and mixed to obtain a varnish-like composition.
• the boron nitride powder (filler) produced above was added to the obtained varnish-like composition in the volume parts shown in the table, and mixed for 5 minutes at 1000 rpm in a Planetary Vacuum Mixer (Thinky Corporation, ARV310) to obtain the compositions according to Examples 1 to 4, respectively.
• a Planetary Vacuum Mixer Thinky Corporation, ARV310
• dielectric constant and dielectric loss tangent The dielectric constant and dielectric loss tangent of each of the cured bodies of the obtained compositions were measured by the split cylinder resonator method using an 8722ES network analyzer manufactured by Agilent Technologies and a split cylinder resonator (CR-740 40 GHz) manufactured by EM Labs, Inc., as measuring devices, and using samples of 0.2 mm x 30 mm x 40 mm cut out from the sheets, values were measured at 23°C in the measurement frequency range of 35 to 42 GHz.
• the thermal conductivity of each cured product of the obtained composition was calculated by multiplying the thermal diffusivity, specific gravity, and specific heat.
• the thermal diffusivity was measured by processing the cured sample into a width of 10 mm x 10 mm x thickness of 1 mm and using the laser flash method. The measurement temperature was 23°C.
• the measurement device used was a xenon flash analyzer (manufactured by NETZSCH, product name: LFA447 NanoFlash).
• the specific gravity was measured using the Archimedes method.
• the specific heat was measured by using a differential scanning calorimeter (manufactured by TA Instruments, product name: Q2000) in a nitrogen atmosphere, heating from room temperature to 200°C at a heating rate of 10°C/min.
• Comparative Example 1 A composition according to Comparative Example 1 was prepared in the same manner as in the above Examples, except that no filler was used. The physical properties were measured in the same manner as above (hereinafter the same).
• Comparative Example 3 A composition according to Comparative Example 3 was prepared in the same manner as in the above-mentioned Examples, except that polybutadiene (B-1000 manufactured by Nippon Soda Co., Ltd.) was used in place of the copolymer.
• polybutadiene B-1000 manufactured by Nippon Soda Co., Ltd.
• Comparative Example 4 A composition according to Comparative Example 4 was prepared in the same manner as in the above-mentioned Examples, except that a liquid epoxy resin (YDF-8170C manufactured by Nippon Steel Chemical & Material Co., Ltd.) was used in place of the copolymer.
• a liquid epoxy resin YDF-8170C manufactured by Nippon Steel Chemical & Material Co., Ltd.
• compositions and physical properties of the above examples and comparative examples are summarized in the table below.
• Each example exhibited excellent dielectric constant, dielectric tangent, thermal conductivity, and dispersibility.
• Comparative Example 1 which did not contain filler, had inferior thermal conductivity to the other Examples.

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