WO2024090112A1 - Composition de résine de carte de circuit imprimé et procédé de production de particules de poudre de résine - Google Patents

Composition de résine de carte de circuit imprimé et procédé de production de particules de poudre de résine Download PDF

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WO2024090112A1
WO2024090112A1 PCT/JP2023/035250 JP2023035250W WO2024090112A1 WO 2024090112 A1 WO2024090112 A1 WO 2024090112A1 JP 2023035250 W JP2023035250 W JP 2023035250W WO 2024090112 A1 WO2024090112 A1 WO 2024090112A1
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powder particles
resin powder
cyclic olefin
resin composition
polymer
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PCT/JP2023/035250
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English (en)
Japanese (ja)
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明 古国府
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日本ゼオン株式会社
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    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a resin composition for circuit boards and a method for producing resin powder particles, and in particular to a resin composition for circuit boards and a method for producing resin powder particles used in the resin composition for circuit boards.
  • Patent Document 1 proposes a fluororesin-containing polyimide precursor composition containing a fluororesin micropowder, a specific compound, and a polyimide precursor solution as a material for such substrates.
  • the use of the fluororesin-containing polyimide precursor composition can improve electrical properties (low dielectric constant, low dielectric loss tangent), physical properties, etc.
  • the fluorine-based resin-containing polyimide precursor composition disclosed in Patent Document 1 is not preferred because it contains a fluorine-based resin. For this reason, there is a demand for the development of substrate materials that can reduce the environmental burden.
  • the present invention aims to provide a resin composition for substrates that can reduce the environmental impact and can be used as a material for producing substrates with reduced dielectric constants, and a method for producing resin powder particles used in the resin composition for substrates.
  • the present inventors have conducted extensive research to achieve the above object.
  • the inventors have newly discovered that a composition containing resin powder particles with a halogen content of 3% by mass or less can reduce the environmental impact and can be used as a material for manufacturing substrates with a reduced dielectric constant, and have thus completed the present invention.
  • the present invention aims to advantageously solve the above-mentioned problems, and [1] the resin composition for substrates of the present invention is a resin composition for substrates containing resin powder particles having a halogen content of 3 mass% or less.
  • the above-mentioned resin composition for substrates can reduce the environmental load and can be used as a material for producing substrates having a reduced dielectric constant.
  • the "halogen content" can be measured by the method described in the Examples.
  • the resin powder particles have an average particle diameter of 30 ⁇ m or less, and the ratio of the volume of resin powder particles having a particle diameter of 70 ⁇ m or more to the total volume of the resin powder particles in the resin composition for substrates is 15% or less.
  • the resin powder particles have an average particle diameter of 20 ⁇ m or less, and the ratio of the volume of resin powder particles having a particle diameter of 70 ⁇ m or more to the total volume of the resin powder particles in the resin composition for substrates is 15% or less.
  • the term "average particle size” means a volume-weighted average diameter
  • the term “particle size” means a volume-weighted diameter.
  • the "average particle size” and the "proportion of the volume of resin powder particles having a particle size of 70 ⁇ m or more to the total volume of resin powder particles in a resin composition for substrates” can be determined by the method described in the Examples.
  • the resin powder particles are preferably particles of a cyclic olefin resin.
  • the resin powder particles are particles of a cyclic olefin resin, the heat resistance of a substrate produced using the resin composition for substrates of the present invention can be improved.
  • the resin powder particles are preferably particles of a crystalline cyclic olefin resin. If the resin powder particles are particles of a crystalline cyclic olefin resin, the heat resistance of the substrate produced using the resin composition for substrates of the present invention can be further improved.
  • the present invention also aims to solve the above-mentioned problems in an advantageous manner, and [6] the method for producing resin powder particles of the present invention is a method for producing resin powder particles, which comprises subjecting a solution containing a cyclic olefin ring-opening polymer at a solid content concentration of 10 mass% or more to a hydrogenation reaction, to obtain resin powder particles of a hydrogenated crystalline cyclic olefin ring-opening polymer having a halogen content of 3 mass% or less.
  • the above-mentioned method for producing resin powder particles it is possible to produce resin powder particles that can be suitably used in the resin composition for substrates of the present invention.
  • the present invention also aims to solve the above-mentioned problems in an advantageous manner, and [7] the method for producing resin powder particles of the present invention is a method for producing resin powder particles, which comprises a step of pulverizing a crystalline cyclic olefin ring-opening polymer hydrogenated product in a solution to obtain resin powder particles of a crystalline cyclic olefin ring-opening polymer hydrogenated product having a halogen content of 3 mass% or less.
  • the above-mentioned method for producing resin powder particles it is possible to produce resin powder particles that can be suitably used in the resin composition for substrates of the present invention.
  • the present invention it is possible to provide a resin composition for substrates which can reduce the environmental load and can be used as a material for producing substrates having a reduced dielectric constant. Furthermore, according to the present invention, it is possible to provide a method for producing resin powder particles used in the resin composition for substrates of the present invention.
  • the resin composition for substrates of the present invention is used as a material for forming a substrate, and contains resin powder particles having a halogen content of 3 mass% or less.
  • the substrate manufactured using the resin composition for substrates of the present invention has a reduced environmental load and a reduced dielectric constant, and therefore can be used for various purposes, and is particularly suitable for use as a high-frequency substrate.
  • the resin powder particles contained in the resin composition for substrates of the present invention can be manufactured, for example, by the manufacturing method of resin powder particles of the present invention.
  • the resin composition for substrates of the present invention contains resin powder particles having a halogen content of 3 mass % or less, and may optionally contain other components such as additives.
  • the resin powder particles contained in the resin composition for substrates of the present invention are resin powder particles having a halogen content of 3 mass % or less.
  • the term "resin powder particles” refers to resin particles having an average particle diameter of 500 ⁇ m or less.
  • the resin powder particles of the present invention preferably have a halogen content of 1% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.01% by mass or less.
  • the average particle size of the resin powder particles is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, and even more preferably 10 ⁇ m or less.
  • the average particle size of the resin powder particles is usually 0.3 ⁇ m or more.
  • the ratio of the volume of resin powder particles having a particle diameter of 70 ⁇ m or more to the total volume of resin powder particles in the resin composition for substrates is preferably 15% or less, more preferably 1% or less, and even more preferably 0% (i.e., the resin powder particles in the resin composition for substrates do not include resin powder particles having a particle diameter of 70 ⁇ m or more).
  • the average particle diameter of the resin powder particles is 30 ⁇ m or less, and the proportion of the volume of resin powder particles having a particle diameter of 70 ⁇ m or more to the total volume of resin powder particles in the resin composition for substrates is 15% or less. And more preferably, the average particle diameter of the resin powder particles is 20 ⁇ m or less, and the proportion of the volume of resin powder particles having a particle diameter of 70 ⁇ m or more to the total volume of resin powder particles in the resin composition for substrates is 15% or less.
  • the resin powder particles having a halogen content of 3% by mass or less are not particularly limited, but from the viewpoint of improving the heat resistance of the resulting substrate, they are preferably particles of a cyclic olefin resin, and more preferably particles of a crystalline cyclic olefin resin.
  • cyclic olefin resin refers to a polymer having an alicyclic structure in the molecule, and is obtained by polymerizing a cyclic olefin monomer, or a hydrogenated product thereof.
  • crystalline cyclic olefin resin refers to a cyclic olefin resin whose melting point can be observed by a differential scanning calorimeter (DSC).
  • Cyclic olefin resins include, for example, ring-opening polymers of cyclic olefin monomers (hereinafter also referred to as “polymer ( ⁇ )”) and their hydrogenated products, as well as addition polymers using at least one cyclic olefin monomer (hereinafter also referred to as “polymer ( ⁇ )”) and their hydrogenated products. Cyclic olefin resins can be used alone or in combination of two or more types.
  • the hydrogenation rate of the hydrogenated product is preferably 95% or more. If the hydrogenation rate is 95% or more, the resin composition for substrates has excellent resistance to heat yellowing and heat deterioration.
  • the "hydrogenation rate” refers to the hydrogenation rate with respect to all carbon-carbon unsaturated bonds contained in the hydrogenated polymer (including double bonds in the aromatic rings, when the polymer has an aromatic ring), and can be measured by a nuclear magnetic resonance (NMR) method.
  • NMR nuclear magnetic resonance
  • the cyclic olefin monomer used in the production of the polymer ( ⁇ ) and its hydrogenated product is a compound having a ring structure formed by carbon atoms and having a carbon-carbon double bond in the ring. Examples of such compounds include norbornene-based monomers.
  • a monocyclic olefin can also be used as the cyclic olefin monomer.
  • the norbornene-based monomer is a monomer that contains a norbornene ring.
  • Norbornene monomers include: Bicyclic monomers such as bicyclo[2.2.1]hept-2-ene (trivial name: norbornene), 5-ethylidene-bicyclo[2.2.1]hept-2-ene (trivial name: ethylidenenorbornene) and their derivatives (having a substituent on the ring); tricyclic monomers such as tricyclo[4.3.0.1 2,5 ]deca-3,7-diene (trivial name: dicyclopentadiene) and its derivatives; 7,8-benzotricyclo[4.3.0.1 2,5 ]deca-3-ene (trivial name: methanotetrahydrofluorene, also known as tetracyclo[7.4.0.0 2,7 .1 10,13 ]trideca-2,4,6,11-tetraene) and its derivatives, tetracycl
  • These monomers may have a substituent at any position.
  • substituents include alkyl groups such as methyl and ethyl groups; alkenyl groups such as vinyl groups; alkylidene groups such as ethylidene and propan-2-ylidene groups; aryl groups such as phenyl groups; hydroxy groups; acid anhydride groups; carboxyl groups; alkoxycarbonyl groups such as methoxycarbonyl groups; and the like.
  • monocyclic olefins examples include cyclic monoolefins such as cyclobutene, cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, cycloheptene, and cyclooctene; and cyclic diolefins such as cyclohexadiene, methylcyclohexadiene, cyclooctadiene, methylcyclooctadiene, and phenylcyclooctadiene.
  • cyclic monoolefins such as cyclobutene, cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, cycloheptene, and cyclooctene
  • cyclic diolefins such as cyclohexadiene, methylcyclohexadiene, cyclooctadiene, methylcyclo
  • cyclic olefin monomers can be used alone or in combination of two or more.
  • the polymer ( ⁇ ) may be a block copolymer or a random copolymer.
  • the polymer ( ⁇ ) can be produced according to a known method using a metathesis polymerization catalyst.
  • the metathesis polymerization catalyst is not particularly limited, and known catalysts can be used.
  • the metathesis polymerization catalyst include a catalyst system consisting of a halide, nitrate, or acetylacetone compound of a metal selected from ruthenium, rhodium, palladium, osmium, iridium, platinum, etc., and a reducing agent; a catalyst system consisting of a halide or acetylacetone compound of a metal selected from titanium, vanadium, zirconium, tungsten, and molybdenum, and an organoaluminum compound as a co-catalyst; a Schrock-type or Grubbs-type living ring-opening metathesis polymerization catalyst (JP Patent Publication 7-179575, J.
  • the amount of metathesis polymerization catalyst used may be appropriately selected depending on the polymerization conditions, etc., but is usually 0.000001 to 0.1 moles, preferably 0.00001 to 0.01 moles, per mole of cyclic olefin monomer.
  • a linear ⁇ -olefin having 4 to 40 carbon atoms such as 1-butene, 1-hexene, or 1-decene
  • the amount of the linear ⁇ -olefin added is usually 0.01 to 0.50 mol, preferably 0.03 to 0.30 mol, and more preferably 0.05 to 0.15 mol, per mol of the cyclic olefin monomer.
  • the ring-opening polymerization of the cyclic olefin monomer can be carried out in an organic solvent.
  • the organic solvent is not particularly limited as long as it is inactive in the polymerization reaction.
  • examples of the organic solvent include alkanes such as pentane, hexane, heptane, octane, nonane, and decane; cycloalkanes such as cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, cycloheptane, cyclooctane, decalin, norbornane, methylnorbornane, and ethylnorbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and cumen
  • the polymerization temperature is not particularly limited, but is usually -50 to 250°C, preferably -30 to 200°C, and more preferably -20 to 150°C.
  • the polymerization time is appropriately selected depending on the polymerization conditions, but is usually 30 minutes to 20 hours, and preferably 1 to 10 hours.
  • the polymer ( ⁇ ) obtained by the above method can be subjected to a hydrogenation reaction to obtain a hydrogenated product of the polymer ( ⁇ ).
  • the hydrogenation reaction of the polymer ( ⁇ ) can be carried out in a conventional manner by contacting the polymer ( ⁇ ) with hydrogen in the presence of a hydrogenation catalyst.
  • the hydrogenation catalyst may be a homogeneous or heterogeneous catalyst.
  • Homogeneous catalysts are easily dispersed in the hydrogenation reaction solution, so that the amount of catalyst added can be reduced.
  • homogeneous catalysts since they have sufficient activity even without high temperature and high pressure, decomposition and gelation of the polymer ( ⁇ ) and its hydrogenated product are unlikely to occur. For this reason, it is preferable to use homogeneous catalysts from the viewpoints of cost and product quality.
  • heterogeneous catalysts exhibit particularly excellent activity under high temperature and pressure conditions, and therefore can hydrogenate the polymer ( ⁇ ) in a short period of time.
  • Homogeneous catalysts include Wilkinson's complex [chlorotris(triphenylphosphine)rhodium(I)], dichlorobis(triphenylphosphine)palladium, chlorohydridocarbonyltris(triphenylphosphine)ruthenium, bis(tricyclohexylphosphine)benzylidineruthenium(IV) dichloride; catalysts consisting of combinations of transition metal compounds and alkyl metal compounds, such as combinations of cobalt acetate/triethylaluminum, nickel acetylacetonate/triisobutylaluminum, titanocene dichloride/n-butyllithium, zirconocene dichloride/sec-butyllithium, tetrabutoxytitanate/dimethylmagnesium, etc.; and the like.
  • Heterogeneous catalysts include those in which metals such as Ni, Pd, Pt, Ru, and Rh are supported on a carrier.
  • metals such as Ni, Pd, Pt, Ru, and Rh
  • an adsorbent such as alumina or diatomaceous earth as the carrier.
  • the hydrogenation reaction is usually carried out in an organic solvent.
  • organic solvent there are no particular limitations on the organic solvent, so long as it is inert to the hydrogenation reaction. Specific examples include the same organic solvents as those mentioned above as used in the ring-opening polymerization of cyclic olefin monomers.
  • the solvent used in the ring-opening polymerization reaction is usually also suitable as a solvent for the hydrogenation reaction, so that after adding a hydrogenation catalyst to the ring-opening polymerization reaction liquid, it can be subjected to the hydrogenation reaction.
  • the hydrogenation rate varies depending on the type of hydrogenation catalyst and the reaction temperature. Therefore, if the polymer ( ⁇ ) has aromatic rings, the remaining rate of aromatic rings can be controlled by selecting the hydrogenation catalyst and adjusting the reaction temperature. For example, in order to leave a certain amount of unsaturated bonds in the aromatic rings, it is sufficient to control the reaction temperature, reduce the hydrogen pressure, shorten the reaction time, etc.
  • Examples of the cyclic olefin monomer used in the synthesis of the polymer ( ⁇ ) and its hydrogenated product include the same cyclic olefin monomers as those used in the synthesis of the polymer ( ⁇ ). In the synthesis of the polymer ( ⁇ ), other monomers copolymerizable with the cyclic olefin monomer may be used as the monomer.
  • Examples of other monomers include ⁇ -olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, and 1-hexene, aromatic ring vinyl compounds, such as styrene and ⁇ -methylstyrene, and non-conjugated dienes, such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and 1,7-octadiene.
  • ⁇ -olefins are preferred, and ethylene is more preferred.
  • the other monomers may be used alone or in combination of two or more.
  • the ratio of the amounts of the cyclic olefin monomer to the other monomers used is usually 30:70 to 99:1, preferably 50:50 to 97:3, and more preferably 70:30 to 95:5, by weight (cyclic olefin monomer: other monomer).
  • the polymer ( ⁇ ) may be a block copolymer or a random copolymer.
  • the polymer ( ⁇ ) can be synthesized according to a known method using an addition polymerization catalyst.
  • the addition polymerization catalyst include vanadium-based catalysts formed from vanadium compounds and organoaluminum compounds, titanium-based catalysts formed from titanium compounds and organoaluminum compounds, and zirconium-based catalysts formed from zirconium complexes and aluminoxanes. These addition polymerization catalysts can be used alone or in combination of two or more.
  • the amount of the addition polymerization catalyst used may be appropriately selected depending on the polymerization conditions, etc., but is usually 0.000001 to 0.1 mol, preferably 0.00001 to 0.01 mol, per 1 mol of the monomer.
  • the addition polymerization of cyclic olefin monomers is usually carried out in an organic solvent.
  • organic solvent there are no particular limitations on the organic solvent, so long as it is inert to the polymerization reaction. Specific examples include the same organic solvents as those listed above for use in the ring-opening polymerization of cyclic olefin monomers.
  • the polymerization temperature is usually -50 to 250°C, preferably -30 to 200°C, and more preferably -20 to 150°C.
  • the polymerization time is selected appropriately depending on the polymerization conditions, but is usually 30 minutes to 20 hours, and preferably 1 to 10 hours.
  • the polymer ( ⁇ ) obtained by the above method can be subjected to a hydrogenation reaction to obtain a hydrogenated product of the polymer ( ⁇ ).
  • the hydrogenation reaction of the polymer ( ⁇ ) can be carried out by the same method as that described above for hydrogenating the polymer ( ⁇ ).
  • a crystalline hydrogenated cyclic olefin polymer (hereinafter, also referred to as "polymer ( ⁇ )") is preferable.
  • the polymer ( ⁇ ) is a hydrogenated product of a polymer obtained by polymerizing a cyclic olefin monomer, and has crystallinity. That is, the polymer ( ⁇ ) is a polymer whose melting point can be observed by a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the melting point of the polymer ( ⁇ ) is preferably 200°C or higher, more preferably 230 to 290°C.
  • the polymer ( ⁇ ) may be a ring-opening polymer or an addition polymer, but a ring-opening polymer (i.e., a hydrogenated product of the polymer ( ⁇ ) that has crystallinity) is preferred because it has better crystallinity.
  • a ring-opening polymer i.e., a hydrogenated product of the polymer ( ⁇ ) that has crystallinity
  • the cyclic olefin monomer used in the production of polymer ( ⁇ ) is not particularly limited, and those previously mentioned as the cyclic olefin monomers used in the production of polymer ( ⁇ ) can be used. Among them, it is preferable to use dicyclopentadiene as at least one of the cyclic olefin monomers, since it gives a polymer ( ⁇ ) with better crystallinity.
  • the content of dicyclopentadiene-derived repeating units in all repeating units of polymer ( ⁇ ) is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, and even more preferably 100% by mass.
  • Some cyclic olefin monomers have stereoisomers, endo and exo, and both can be used as monomers when producing polymer ( ⁇ ).
  • One of the isomers may be used alone, or an isomer mixture in which the endo and exo are present in any ratio may be used. Since polymer ( ⁇ ) has better crystallinity, it is preferable to increase the ratio of one of the stereoisomers.
  • the ratio of the endo isomer is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on the total isomer mixture being 100% by mass.
  • the ratio of the exo isomer is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on the total isomer mixture being 100% by mass. Since synthesis is easier, it is preferable that the ratio of the endo isomer is high in the isomer mixture.
  • the degree of syndiotactic stereoregularity (ratio of racemo-dyad) increases, the crystallinity tends to become higher.
  • the degree of stereoregularity of the polymer ( ⁇ ) is not particularly limited, but the ratio of racemo-dyads in the repeating units is preferably 60% or more, more preferably 70% or more, and particularly preferably 88% or more.
  • the ratio of the racemo dyad can be determined by measuring with 13 C-NMR spectrum analysis. Specifically, 13 C-NMR measurement is performed by applying the inverse-gated decoupling method at 200 ° C. using a mixed solvent of 1,3,5-trichlorobenzene-d3/1,2-dichlorobenzene-d4 (volume ratio 2:1) as the solvent, and the ratio of the racemo dyad can be determined from the intensity ratio of the signal at 43.35 ppm derived from the meso dyad and the signal at 43.43 ppm derived from the racemo dyad, with the peak at 127.5 ppm of 1,2-dichlorobenzene-d4 as the reference shift.
  • a polymer ( ⁇ ) having high syndiotactic stereoregularity can be obtained, for example, by ring-opening polymerization of a cyclic olefin monomer to obtain a polymer having high syndiotactic stereoregularity, and then subjecting the polymer to a hydrogenation reaction.
  • a polymer ( ⁇ ) having high syndiotactic stereoregularity can be synthesized according to the methods described in WO2012/033076, JP2014-118475A, and the like.
  • the weight average molecular weight (Mw) of the above-mentioned cyclic olefin resin is not particularly limited, but is preferably 10,000 or more and 100,000 or less, and the number average molecular weight (Mn) is preferably 3,000 or more and 800,000 or less.
  • the method for producing the resin powder particles having a halogen content of 3 mass % or less contained in the resin composition for substrates of the present invention is not particularly limited, and for example, the following methods 1) to 3) can be adopted.
  • a method for producing resin powder particles comprising the step of pulverizing a hydrogenated crystalline cyclic olefin ring-opening polymer in a solution to obtain resin powder particles of a hydrogenated crystalline cyclic olefin ring-opening polymer having a halogen content of 3 mass% or less.
  • a method for producing resin powder particles comprising dry-pulverizing a cyclic olefin resin having a halogen content of 3% by mass or less to obtain resin powder particles of the cyclic olefin resin having a halogen content of 3% by mass or less. Methods 1) to 3) will be described in detail below.
  • Method 1 a solution containing a cyclic olefin ring-opening polymer at a solid content concentration of 10% by mass or more is subjected to a hydrogenation reaction, thereby hydrogenating the cyclic olefin ring-opening polymer in the solution to obtain resin powder particles of a hydrogenated crystalline cyclic olefin ring-opening polymer having a halogen content of 3% by mass or less.
  • the polymer ( ⁇ ) described above can be used as the cyclic olefin ring-opening polymer.
  • a solution containing the cyclic olefin ring-opening polymer at a solid content concentration of 10 mass% or more for example, a solution containing the polymer ( ⁇ ), an organic solvent, a polymerization catalyst, etc. can be used.
  • the organic solvent and the polymerization catalyst the organic solvent and the polymerization catalyst used in the hydrogenation reaction of the polymer ( ⁇ ) described above can be used.
  • the method for hydrogenating the polymer ( ⁇ ) can be the same as the method described above.
  • the resin powder particles of the hydrogenated crystalline cyclic olefin ring-opening polymer having a halogen content of 3% by mass or less obtained by the above method 1) usually have an average particle size of 10 ⁇ m or less. Therefore, by the above method 1), it is possible to produce resin powder particles that can be suitably used in the resin composition for substrates of the present invention.
  • the reason why the resin powder particles of the hydrogenated crystalline cyclic olefin ring-opening polymer obtained by the above method 1) have a small particle size is not clear, but when a solution containing a cyclic olefin ring-opening polymer is subjected to a hydrogenation reaction, a hydrogenated crystalline cyclic olefin ring-opening polymer is generated in the solution.
  • the solid concentration of the ring-opening polymer of the cyclic olefin in the solution is 10% by mass or more, the solubility of the hydrogenated crystalline cyclic olefin ring-opening polymer in the solution decreases, and the hydrogenated crystalline cyclic olefin ring-opening polymer precipitates more quickly.
  • a hydrogenated crystalline cyclic olefin ring-opening polymer is pulverized in a solution to obtain resin powder particles of a hydrogenated crystalline cyclic olefin ring-opening polymer having a halogen content of 3 mass % or less.
  • the crystalline cyclic olefin ring-opening polymer hydrogenation product for example, the polymer ( ⁇ ) described above can be used.
  • the method for pulverizing the crystalline cyclic olefin ring-opening polymer hydrogenation product in the solution is not particularly limited, and a known wet pulverization method can be used. From the viewpoint of efficiently producing resin powder particles that can be suitably used in the resin composition for substrates of the present invention, in the above method 2), it is preferable to spray a solution containing the crystalline cyclic olefin ring-opening polymer hydrogenation product at high pressure and pulverize the crystalline cyclic olefin ring-opening polymer hydrogenation products by colliding them with each other.
  • the particles of the crystalline cyclic olefin ring-opening polymer hydrogenation product obtained by such pulverization are usually resin powder particles having an average particle size of 10 ⁇ m or less. Therefore, they can be suitably used as resin powder particles for the resin composition for substrates of the present invention.
  • the spray pressure is preferably 100 MPa or more from the viewpoint of uniforming the particle size of the obtained resin powder particles.
  • the above methods 1) and 2) may be carried out alone or in combination.
  • resin powder particles having a smaller average particle size can be efficiently produced.
  • the resin having a halogen content of 3% by mass or less used in the method 3) is not particularly limited, and may be, for example, the cyclic olefin resin described above, polypropylene, etc.
  • the dry grinding method is not particularly limited, and any known dry grinding method may be used.
  • the resin composition for substrates of the present invention may further contain components other than the above-mentioned resin powder particles.
  • other components include known additives such as antioxidants, ultraviolet absorbers, light stabilizers, near-infrared absorbers, colorants, plasticizers, flame retardants, and antistatic agents.
  • antioxidants such as antioxidants, ultraviolet absorbers, light stabilizers, near-infrared absorbers, colorants, plasticizers, flame retardants, and antistatic agents.
  • the content of other components in the resin composition for substrates can be appropriately determined depending on the application of the composition for substrates.
  • the method for preparing the resin composition for substrates of the present invention is not particularly limited, and for example, it can be prepared by mixing resin powder particles having a halogen content of 3 mass% or less with other components by a known method.
  • the content of resin powder particles in the resin composition for substrates is preferably 5% by mass or more, more preferably 15% by mass or more, and even more preferably 30% by mass or more, based on the total amount of the resin composition for substrates. If the content of resin powder is equal to or more than the lower limit, the resin composition for substrates of the present invention can be used more suitably as a material for manufacturing substrates for various applications.
  • the substrate produced using the resin composition for substrates of the present invention usually has a dielectric constant of 2.5 or less at a frequency of 10 GHz. Therefore, the substrate produced using the resin composition for substrates of the present invention can be used for various applications, and is particularly suitable for use as a high-frequency substrate.
  • the method for manufacturing a substrate using the resin composition for substrates of the present invention is not particularly limited, and for example, a substrate can be manufactured by pressing the resin composition for substrates of the present invention.
  • the pressing method is not particularly limited, and pressing can be performed by a known method.
  • the pressing pressure is not particularly limited, and can be adjusted according to the thickness of the substrate to be obtained.
  • ⁇ Weight average molecular weight and number average molecular weight> The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymers obtained in Examples 1, 3, 4, and 5 were determined as standard polystyrene equivalent values by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent. The GPC was measured at 40° C.
  • the measurement apparatus used was "System HLC-8320" manufactured by Tosoh Corporation, and the measurement column used was "H-type column” manufactured by Tosoh Corporation.
  • ⁇ Glass transition temperature and melting point> The sample was heated in a differential scanning calorimeter to completely melt it, then cooled to room temperature at a temperature drop rate of 10°C/min, and then differential scanning calorimetry was performed at a temperature rise rate of 10°C/min up to 350°C. From the peak at this time, the glass transition temperature (Tg) and melting point were measured.
  • the differential scanning calorimeter used was a "High Sensitivity Differential Scanning Calorimeter EXSTARX-DSC7000" manufactured by Hitachi High-Tech Science Corporation.
  • calibration was performed using indium, tin, and lead as standard substances for temperature and heat.
  • ⁇ Halogen content> The sample was placed in an aluminum ring, compressed with a press, and covered with a polypropylene (PP) film, and an X-ray fluorescence (XRF) analyzer (Rigaku Corporation, "Primus IV”) was used to perform composition analysis between elements from carbon (C) to gallium (Ga). From the results of the XRF analysis, the ratio of the total mass of fluorine (F) and chlorine (Cl) to the total mass of elements from carbon (C) to gallium (Ga) (C to Ga) [(F+Cl)/(C to Ga) x 100] was calculated, and the obtained value was taken as the halogen content (mass%).
  • XRF X-ray fluorescence
  • ⁇ Average particle size and proportion of resin powder particles with a particle size of 70 ⁇ m or more> The sample was dispersed in a dispersion medium (cyclohexane, isopropyl alcohol, or 3M's "Novec7300"), and the volume-weighted average diameter and particle size distribution of the sample were measured using a laser diffraction particle size distribution measuring device (Shimadzu Corporation's "SALD-3100"). The volume-weighted average diameter obtained was taken as the average particle diameter.
  • the proportion of samples with a volume-weighted diameter exceeding 70 ⁇ m to the entire sample was taken as the proportion of the volume of resin powder particles with a particle diameter of 70 ⁇ m or more to the total volume of resin powder particles in the resin composition for substrates.
  • ⁇ Dielectric constant> The sample was pressed at a pressure of 20 MPa or more to produce a sheet. The pressure during pressing was set to be equal to or higher than the glass transition temperature (Tg) of the sample if the sample was amorphous, or equal to or higher than the melting point of the sample if the sample was crystalline. The sheet was then cut to obtain test pieces, which were used to measure the dielectric constant at a frequency of 10 GHz by a cylindrical cavity resonator method using a network analyzer ("N5230A" manufactured by Keysight Technologies, Inc.).
  • Tg glass transition temperature
  • Example 1 Into a glass pressure-resistant reaction vessel that had been thoroughly dried and then substituted with nitrogen, 143 parts of a 70% cyclohexane solution of dicyclopentadiene (endo isomer content of 99% or more) (100 parts as the amount of dicyclopentadiene), 5.1 parts of 1-hexene, and 514 parts of cyclohexane were added, followed by adding 0.37 parts of a 19% concentration n-hexane solution of diethylaluminum ethoxide and stirring.
  • a 70% cyclohexane solution of dicyclopentadiene endo isomer content of 99% or more
  • the solution containing the obtained dicyclopentadiene ring-opening polymer was transferred to a reactor (manufactured by Sumitomo Heavy Industries, Ltd.) equipped with a stirrer and a temperature-controlled jacket, and then 167 parts of cyclohexane and 0.1 parts of chlorohydridocarbonyltris(triphenylphosphine)ruthenium were added to prepare a solution containing dicyclopentadiene ring-opening polymer at a solid content concentration of 12%. Next, while stirring the entire volume at a rotation speed of 64 rpm, a hydrogenation reaction was carried out at a hydrogen pressure of 4 MPa and a temperature of 180° C.
  • the obtained hydrogenated dicyclopentadiene ring-opening polymer particles were used as a sample, and differential scanning calorimetry was performed, and it was found that the hydrogenated dicyclopentadiene ring-opening polymer particles had crystallinity.
  • the halogen content, average particle size, proportion of resin powder particles with a particle size of 70 ⁇ m or more, and dielectric constant were also determined using the sample. The results are shown in Table 1.
  • Example 2 The slurry to which the antioxidant had been added in Example 1 was passed 30 times, calculated from the circulation time, through a ball chamber having a diameter of ⁇ 14 mm using a wet microparticulation device (manufactured by Sugino Machine, "HJP-25005"). The spray pressure was set to 200 MPa. The solvent was removed from the resulting slurry using a freeze dryer (manufactured by Nippon Techno Service, "FD0480-1601”) to obtain particles of a hydrogenated dicyclopentadiene ring-opening polymer.
  • a wet microparticulation device manufactured by Sugino Machine, "HJP-25005"
  • the spray pressure was set to 200 MPa.
  • the solvent was removed from the resulting slurry using a freeze dryer (manufactured by Nippon Techno Service, "FD0480-1601") to obtain particles of a hydrogenated dicyclopentadiene ring-opening polymer.
  • the obtained particles of hydrogenated dicyclopentadiene ring-opening polymer were used as a sample for differential scanning calorimetry, and it was found that the particles of hydrogenated dicyclopentadiene ring-opening polymer had crystallinity.
  • the same measurements as in Example 1 were also carried out using the above sample. The results are shown in Table 1.
  • Example 3 After thorough drying, a pressure-resistant glass reactor was substituted with nitrogen and 2.0 parts of a monomer mixture consisting of 25% tetracyclododecene, 70% methanotetrahydrofluorene and 25% norbornene (1% relative to the total amount of monomers used in polymerization), 1.2 parts of 1-hexene, 0.42 parts of diisopropyl ether, 0.11 parts of isobutyl alcohol, and 785 parts of cyclohexane were added, followed by adding 1.35 parts of a cyclohexane solution of triisobutylaluminum with a concentration of 20% and stirring.
  • a monomer mixture consisting of 25% tetracyclododecene, 70% methanotetrahydrofluorene and 25% norbornene (1% relative to the total amount of monomers used in polymerization)
  • the weight average molecular weight (Mw) of the ring-opening polymer (cyclic olefin ring-opening polymer) of the monomer mixture contained in the obtained polymerization reaction solution was 19,000, and the number average molecular weight (Mn) was 10,700.
  • 300 parts of the obtained polymerization reaction solution was transferred to an autoclave equipped with a stirrer, and 32 parts of cyclohexane and 3.8 parts of a diatomaceous earth supported nickel catalyst (manufactured by JGC Chemical Industries, Ltd., "T8400RL", nickel support rate 58%) were added. After replacing the atmosphere in the autoclave with hydrogen, the reaction was carried out at 190° C. under a hydrogen pressure of 4.5 MPa for 6 hours.
  • the mixture was filtered at a pressure of 0.25 MPa using a pressure filter (manufactured by Ishikawajima-Harima Heavy Industries, Ltd., "Funda Filter”) with diatomaceous earth (manufactured by Showa Chemical Industry Co., Ltd., "Radiolite (registered trademark) #500”) as a filter bed to obtain a colorless and transparent solution containing a hydrogenated cyclic olefin ring-opening polymer.
  • the hydrogenation rate of the hydrogenated cyclic olefin ring-opening polymer was 99.7%.
  • the obtained filtrate was then placed in a cylindrical concentrating dryer (Hitachi, Ltd.), and the solvent cyclohexane and other volatile components were removed under conditions of a temperature of 290°C and a pressure of 1 kPa or less, and the filtrate was extruded in a molten state into a strand shape from a die directly connected to the concentrator, cooled with water, and cut with a pelletizer (Nagata Manufacturing Co., Ltd., "OSP-2”) to obtain pellets.
  • a pelletizer Nagata Manufacturing Co., Ltd., "OSP-2
  • the obtained pellets were put into a rotor speed mill ("P-14" manufactured by Fritsch) together with liquid nitrogen and pulverized (dry pulverization) at a rotation speed of 10,000 rpm and a sieve ring mesh condition of 0.08 mm to 6.0 mm to obtain particles of a hydrogenated cyclic olefin ring-opening polymer.
  • the obtained particles of hydrogenated cyclic olefin ring-opening polymer were used as a sample for differential scanning calorimetry, and it was found that the particles of hydrogenated cyclic olefin ring-opening polymer were amorphous.
  • the same measurements as in Example 1 were performed using the above sample. The results are shown in Table 1.
  • Example 4 After thorough drying, 100 parts of tetracyclododecene, 0.42 parts of 1-hexene, and 388 parts of cyclohexane were added to a glass pressure-resistant reaction vessel substituted with nitrogen, followed by adding 0.40 parts of a 20% concentration triisobutylaluminum cyclohexane solution, 0.16 parts of n-dibutyl ether, and 0.31 parts of a 10% concentration isobutyl alcohol cyclohexane solution, and stirring. Next, 9.70 parts of a 0.65% cyclohexane solution of tungsten hexachloride was added, and the mixture was heated to 50°C to initiate a ring-opening polymerization reaction.
  • the weight average molecular weight (Mw) of the tetracyclododecene ring-opening polymer (cyclic olefin ring-opening polymer) contained in the obtained polymerization reaction solution was 36,200, and the number average molecular weight (Mn) was 23,200.
  • Mw weight average molecular weight of the tetracyclododecene ring-opening polymer contained in the obtained polymerization reaction solution was 36,200, and the number average molecular weight (Mn) was 23,200.
  • diatomaceous earth (Radiolite #300" manufactured by Showa Chemical Industry Co., Ltd.) was added as a filter aid.
  • This suspension was filtered using a leaf filter ("CFR2" manufactured by IHI Corporation) to obtain a solution containing a tetracyclododecene ring-opening polymer.
  • CFR2 leaf filter
  • the solution containing the obtained tetracyclododecene ring-opening polymer was transferred to a reactor (manufactured by Sumitomo Heavy Industries, Ltd.) equipped with a stirrer and a temperature-controlled jacket, and then 600 parts of cyclohexane and 0.1 parts of chlorohydridocarbonyltris(triphenylphosphine)ruthenium were added to obtain a solution containing tetracyclododecene ring-opening polymer at a solid content concentration of 12%.
  • the obtained particles of hydrogenated tetracyclododecene ring-opening polymer were used as a sample for differential scanning calorimetry, and it was found that the particles of hydrogenated tetracyclododecene ring-opening polymer had crystallinity.
  • the same measurements as in Example 1 were also carried out using the above sample. The results are shown in Table 1.
  • Example 5 Into a polymerization reactor whose inside had been dried and purged with nitrogen, 960 parts of toluene, 220 parts of tetracyclododecene, and 0.166 parts of 1-hexene were charged, and the solvent temperature was raised to 40° C. while stirring at a rotation speed of 300 to 350 rpm. On the other hand, 23.5 parts of toluene, 0.044 parts of rac-ethylenebis(1-indenyl)zirconium dichloride, and 6.22 parts of a 9.0% toluene solution of methylaluminoxane (manufactured by Tosoh Finechem Corporation, "TMAO-200 series”) were mixed in a glass container to obtain a catalyst solution.
  • TMAO-200 series a 9.0% toluene solution of methylaluminoxane
  • the catalyst solution was added to the reactor, and immediately thereafter, ethylene gas at 0.08 MPa was introduced into the liquid phase to initiate polymerization.
  • the position of the ethylene outlet was such that the ratio (B)/(A) of the distance (A) between the bottom of the reactor and the liquid level and the distance (B) between the ethylene outlet and the liquid level was 0.60.
  • Ethylene gas was automatically supplied when ethylene gas was consumed, so that the pressure of ethylene gas was kept constant. After 30 minutes, the introduction of ethylene gas was stopped, the pressure was released, and then 5 parts of methanol was added to terminate the polymerization reaction.
  • the resulting reaction solution was filtered through diatomaceous earth ("Radiolite (registered trademark) #800" manufactured by Showa Chemical Industry Co., Ltd.) and poured into isopropanol containing 0.05% hydrochloric acid to precipitate a polymer.
  • the precipitated polymer was separated, washed, and dried under reduced pressure at 100°C for 15 hours to obtain an ethylene-tetracyclododecene copolymer.
  • the resulting ethylene-tetracyclododecene copolymer had a weight average molecular weight (Mw) of 56,000 and a number average molecular weight (Mn) of 22,000.
  • the material obtained after removing the solvent was finely crushed and placed in a rotor speed mill (manufactured by Fritsch, model number "P-14") together with liquid nitrogen, and pulverized (dry pulverization) at a rotation speed of 10,000 rpm and a sieve ring mesh condition of 0.08 mm to 6.0 mm was performed to obtain particles of an ethylene-tetracyclododecene copolymer.
  • the obtained ethylene-tetracyclododecene copolymer particles were used as samples and measurements were carried out in the same manner as in Example 1. The results are shown in Table 1.
  • Example 6 Pellets of polypropylene (Prime Polypro) were placed in a rotor speed mill (Fritsch P-14) together with liquid nitrogen. The rotation speed was set to 10,000 rpm, and the pellets were pulverized under a sieve ring mesh condition of 0.08 to 6.0 mm to obtain polypropylene particles. The obtained polypropylene particles were used as samples and measurements were carried out in the same manner as in Example 1. The results are shown in Table 1.
  • Example 1 A commercially available polytetrafluoroethylene powder (manufactured by DuPont-Mitsui Fluorochemicals, "6-J") was used as a sample and measurements were carried out in the same manner as in Example 1. The results are shown in Table 1.
  • Crystalline DCPD refers to a crystalline hydrogenated dicyclopentadiene ring-opening polymer
  • Amorphous COP refers to a hydrogenated amorphous cyclic olefin ring-opening polymer
  • Crystalline TCD refers to a crystalline hydrogenated tetracyclododecene ring-opening polymer
  • PP indicates polypropylene
  • PTFE refers to polytetrafluoroethylene
  • PFA refers to perfluoroalkoxyalkane.
  • the particles obtained in Examples 1 to 6 are resin powder particles with a halogen content of 3% by mass or less and a low dielectric constant, and therefore by using a resin composition for substrates containing these particles, it is possible to reduce the environmental load and produce substrates with a reduced dielectric constant.
  • the present invention it is possible to provide a resin composition for substrates which can reduce the environmental load and can be used as a material for producing substrates having a reduced dielectric constant. Furthermore, according to the present invention, it is possible to provide a method for producing resin powder particles that can be suitably used in the resin composition for substrates of the present invention.

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Abstract

Le but de la présente invention est de fournir une composition de résine de carte de circuit imprimé qui peut réduire la charge environnementale et qui peut être utilisée en tant que matériau pour fabriquer des cartes de circuit imprimé dans lesquelles la constante diélectrique est réduite. La présente invention concerne une composition de résine de carte de circuit imprimé contenant des particules de poudre de résine ayant une teneur en halogène de 3 % en masse ou moins.
PCT/JP2023/035250 2022-10-27 2023-09-27 Composition de résine de carte de circuit imprimé et procédé de production de particules de poudre de résine WO2024090112A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002128875A (ja) * 2000-10-25 2002-05-09 Nippon Zeon Co Ltd 環状オレフィン開環重合体水素化物の製造方法
JP2013256596A (ja) * 2012-06-13 2013-12-26 Nippon Zeon Co Ltd 樹脂組成物及びその成形品
JP2014118475A (ja) * 2012-12-17 2014-06-30 Nippon Zeon Co Ltd 環状オレフィン開環重合体水素添加物の製造方法
JP2017195334A (ja) * 2016-04-22 2017-10-26 三菱瓦斯化学株式会社 プリント配線板用樹脂組成物、プリプレグ、レジンシート、積層板、金属箔張積層板、及びプリント配線板
JP2019023265A (ja) * 2017-07-25 2019-02-14 株式会社クラレ 樹脂組成物の製造方法
WO2022045363A1 (fr) * 2020-08-31 2022-03-03 住友化学株式会社 Film

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002128875A (ja) * 2000-10-25 2002-05-09 Nippon Zeon Co Ltd 環状オレフィン開環重合体水素化物の製造方法
JP2013256596A (ja) * 2012-06-13 2013-12-26 Nippon Zeon Co Ltd 樹脂組成物及びその成形品
JP2014118475A (ja) * 2012-12-17 2014-06-30 Nippon Zeon Co Ltd 環状オレフィン開環重合体水素添加物の製造方法
JP2017195334A (ja) * 2016-04-22 2017-10-26 三菱瓦斯化学株式会社 プリント配線板用樹脂組成物、プリプレグ、レジンシート、積層板、金属箔張積層板、及びプリント配線板
JP2019023265A (ja) * 2017-07-25 2019-02-14 株式会社クラレ 樹脂組成物の製造方法
WO2022045363A1 (fr) * 2020-08-31 2022-03-03 住友化学株式会社 Film

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