Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/14—Monomers containing five or more carbon atoms
• • 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
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • 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
  • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
  • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate

Definitions

• a resin composition comprising a 3-methyl-1-butene polymer and a highly thermally conductive inorganic filler having a thermal conductivity of 20 W/m ⁇ K or more.
• the resin composition contains a 3-methyl-1-butene polymer and therefore has a low water absorption rate. Therefore, no blisters are generated when the resin composition is subjected to reflow soldering. Furthermore, even after being left to stand for 7 days in an atmosphere of 85°C and 85% RH, the resin composition has a low water absorption rate, so that the resin composition can be subjected to reflow soldering and the generation of blisters is suppressed. Furthermore, the resin composition does not require special storage conditions and has a low water absorption rate even under the above conditions, making it easy to store and manage.
• the content of structural units derived from ethylene or an ⁇ -olefin in 100 mol % of the copolymer is preferably more than 0 mol % and 20 mol % or less. From the viewpoint of flexibility and impact resistance, the content of structural units derived from ethylene or an ⁇ -olefin in 100 mol % of the copolymer is more preferably 0.1 mol % or more, and even more preferably 0.5 mol % or more.
• the content of structural units derived from 3-methyl-1-butene in 100 mol % of the copolymer is preferably 80 mol % or more and less than 100 mol %.
• the content of structural units derived from 3-methyl-1-butene in 100 mol% of the copolymer is preferably more than 50 mol%, more preferably 70 mol% or more, more preferably 85 mol% or more, even more preferably 90 mol% or more, still more preferably 92 mol% or more, and even more preferably 93 mol% or more.
• the melting point of the 3-methyl-1-butene polymer is preferably 260 to 310° C.
• the resin composition can be easily molded by injection molding or the like, and the warping, melting, and blistering of the sheet due to reflow soldering are further suppressed, that is, the reflow heat resistance is improved.
• the melting point of the 3-methyl-1-butene polymer means a peak temperature measured by using a differential scanning calorimeter to raise the temperature of a test piece (3-methyl-1-butene polymer) from 30° C. to 320° C.
• the melting point can be measured by the method described in the Examples. From the viewpoint of the balance between production efficiency and reflow heat resistance, the melting point of the 3-methyl-1-butene polymer is preferably 270 to 305°C, more preferably 280 to 305°C, and further preferably 280 to 300°C.
• the melt viscosity of the 3-methyl-1-butene polymer of the present embodiment is preferably 10 to 1,000 Pa ⁇ s.
• the melt viscosity of the 3-methyl-1-butene polymer is 10 Pa ⁇ s or more, the mechanical strength is further improved, and when the melt viscosity is 1,000 Pa ⁇ s or less, good flowability during molding is easily obtained.
• the melt viscosity of the 3-methyl-1-butene polymer is more preferably 30 to 500 Pa ⁇ s, further preferably 50 to 300 Pa ⁇ s, further more preferably 50 to 200 Pa ⁇ s, and further more preferably 70 to 150 Pa ⁇ s.
• the melt viscosity of the 3-methyl-1-butene polymer of the present embodiment means a value measured using a capillary rheometer under conditions of a barrel temperature of 320° C. and a shear rate of 1220 sec ⁇ 1 (capillary: inner diameter 1.0 mm ⁇ length 10 mm, extrusion rate 10 mm/min), and specifically, can be measured by the method described in the Examples.
• the content of the 3-methyl-1-butene polymer in 100% by mass of the resin composition is preferably 1.0 to 80.0% by mass, more preferably 3.0 to 70.0% by mass, even more preferably 5.0 to 40.0% by mass, still more preferably 5.0 to 15.0% by mass, and even more preferably 7.0 to 10.0% by mass.
• 3-Methyl-1-butene polymers have a relatively low specific gravity, which can contribute to reducing the weight of sheets.
• 3-methyl-1-butene polymers do not generate harmful gases when incinerated.
• the decomposition products in an inert atmosphere are low-molecular-weight hydrocarbons, which are suitable for chemical recycling.
• Examples of the highly thermally conductive inorganic filler include diamond, silicon carbide, titanium carbide, tungsten carbide, magnesium oxide, aluminum oxide, zinc oxide, yttrium oxide, ytterbium oxide, beryllium oxide, sialon (ceramics consisting of silicon, aluminum, oxygen, and nitrogen), boron nitride, aluminum nitride, silicon nitride, and carbon fiber.
• boron nitride, aluminum nitride, and aluminum oxide are preferred, and boron nitride is more preferred, from the viewpoint of obtaining a sheet that is relatively inexpensive, has high thermal conductivity, and has excellent mechanical properties.
• These highly thermally conductive inorganic fillers may be surface-treated with, for example, a silane coupling agent.
• a compatibilizer may be used in the resin composition to improve the dispersibility of the highly thermally conductive inorganic filler.
• the inorganic fillers may be used alone or in combination of two or more kinds.
• the content of the highly thermally conductive inorganic filler in 100 mass% of the resin composition is preferably 20.0 to 98.0 mass%, more preferably 30.0 to 96.0 mass%, more preferably 50.0 to 94.0 mass%, even more preferably 60.0 to 94.0 mass%, still more preferably 75.0 to 94.0 mass%, and even more preferably 89.0 to 92.0 mass%.
• the content of the highly thermally conductive inorganic filler in 100 volume% of the resin composition is preferably 10 to 95 volume%, more preferably 30 to 90 volume%, even more preferably 35 to 90 volume%, even more preferably 40 to 90 volume%, and still more preferably 45 to 85 volume%.
• the resin composition may contain an alkyl radical scavenger from the viewpoint of exhibiting better mechanical properties.
• alkyl radical scavenger refers to a compound having a function of reacting with an alkyl radical derived from a 3-methyl-1-butene polymer and then stabilizing the alkyl radical, thereby losing the ability to abstract hydrogen. From the viewpoint of exerting better mechanical properties, it is preferable that the alkyl radical scavenger contains at least one selected from the group consisting of an acrylphenol compound and a benzofuranone compound.
• the alkyl radical scavengers may be used alone or in combination of two or more kinds.
• alkyl group having 1 to 9 carbon atoms examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group, a 2,2-dimethylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, and an n-nonyl group.
• R1 is preferably a hydrogen atom.
• R2 is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
• R 3 , R 4 , R 5 and R 6 are each independently preferably an alkyl group having 3 to 8 carbon atoms, more preferably an alkyl group having 5 carbon atoms, and even more preferably a 1,1-dimethylpropyl group.
• acrylic phenol compound represented by general formula (I) examples include 2,4-di-t-amyl-6-[1-(3,5-di-t-amyl-2-hydroxyphenyl)ethyl]phenyl acrylate, 2,4-di-t-butyl-6-[1-(3,5-di-t-butyl-2-hydroxyphenyl)ethyl]phenyl acrylate, and 2-t-butyl-6-[(3-t-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenyl acrylate.
• alkyl radical scavenger a commercially available product may be used.
• the benzofuranone compound used in this embodiment can be represented, for example, by the following general formula (II).
• R 7 and R 8 each independently represent an alkyl group having 1 to 4 carbon atoms
• R 9 and R 10 each independently represent an alkyl group having 1 to 9 carbon atoms.
• the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
• the alkyl group having 1 to 9 carbon atoms may be linear or branched.
• alkyl group having 1 to 9 carbon atoms examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group, a 2,2-dimethylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, and an n-nonyl group.
• the content of the alkyl radical scavenger in the resin composition is preferably 0.01 to 1.00 part by mass based on 100 parts by mass of the 3-methyl-1-butene polymer.
• the content of the alkyl radical scavenger is 0.01 parts by mass or more, the physical properties of the resin composition can be more stably maintained during melt kneading of the resin composition, and molding defects caused by generation of decomposition gas during melt molding can be suppressed.
• the content of the alkyl radical scavenger is 1.00 parts by mass or less, a sheet having better mechanical properties is easily obtained.
• the alkyl radical scavenger is prevented from bleeding out, or from impairing the physical properties required for the resin composition, such as deterioration of moisture absorption and thermal conductivity.
• the content of the alkyl radical scavenger in the resin composition relative to 100 parts by mass of the 3-methyl-1-butene polymer is more preferably 0.02 parts by mass or more, and further preferably 0.05 parts by mass or more.
• the content of the alkyl radical scavenger in the resin composition relative to 100 parts by mass of the 3-methyl-1-butene polymer is more preferably 0.80 parts by mass or less, and further preferably 0.70 parts by mass or less.
• the content of the alkyl radical scavenger in the resin composition is more preferably 0.02 to 0.80 parts by mass, and further preferably 0.05 to 0.70 parts by mass, per 100 parts by mass of the 3-methyl-1-butene polymer.
• the content of the alkyl radical scavengers means the total content of the alkyl radical scavengers.
• octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate thiodiethylene-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamide], 3,3',3'',5,5',5''-hexa-t-butyl- ⁇ , ⁇ ', ⁇ ''-(mesitylene-2,4,6-triyl)tri-p-c Resole, ethylene bis(oxyethylene)bis[3-(5-t-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,6-di-t-butyl-4-[4,6-bis(oc
• phenolic antioxidants such as the "Adekastab (registered trademark) AO series” manufactured by ADEKA Corporation and the “Irganox (registered trademark) series” manufactured by BASF Japan Ltd.
• phosphorus-based antioxidant examples include 3,9-bis(2,6-di-t-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, tetrakis(2,4-di-t-butyl-phenyl)-4,4'-biphenylene phosphonite, 2,2-methylenebis(4,6-di-t-butylphenyl)octyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl ester phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis( 2,4-dicumylphenyl)pentaerythri
• phosphorus-based antioxidants such as the "ADEKA STAB (registered trademark) PEP series” and “ADEKA STAB (registered trademark) HP series” manufactured by ADEKA Corporation, the “Irgafos (registered trademark) series” manufactured by BASF Japan, and "HOSTANOX (registered trademark) P-EPQ” manufactured by Clariant.
• sulfur-based antioxidant examples include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, laurylstearyl 3,3'-thiodipropionate, pentaerythritol-tetrakis-( ⁇ -lauryl-thio-propionate), 3,9-bis(2-dodecylthioethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, and the like.
• the resin composition may contain an antioxidant other than the phenol-based antioxidant, the phosphorus-based antioxidant, and the sulfur-based antioxidant, as long as the effect of the present invention is not impaired.
• antioxidant other than the phenol-based antioxidant, the phosphorus-based antioxidant, and the sulfur-based antioxidant include an amine-based antioxidant.
• the content of the antioxidant in the resin composition relative to 100 parts by mass of the 3-methyl-1-butene polymer is preferably 0.01 parts by mass or more, more preferably 0.10 parts by mass or more, from the viewpoint of ensuring the stability of the 3-methyl-1-butene polymer, and is preferably 1.00 parts by mass or less, more preferably 0.80 parts by mass or less, from the viewpoint of the relative dielectric constant and the dielectric loss tangent, i.e., preferably 0.01 to 1.00 parts by mass, more preferably 0.10 to 0.80 parts by mass.
• the content of the antioxidants means the total content of the antioxidants.
• the resin composition may or may not contain additives other than the alkyl radical scavenger and the antioxidant.
• additives include antacids, fillers, light stabilizers, antistatic agents, flame retardants, pigments, polymerization inhibitors, heavy metal deactivators, ultraviolet absorbers, nucleating agents, clarifying agents, lubricants, fluorescent brightening agents, rust inhibitors, and sliding agents.
• the other additives may be used alone or in combination of two or more.
• the resin composition preferably contains an antacid.
• antacids include barium laurate, calcium stearate, zinc stearate, magnesium stearate, aluminum stearate, zinc oleate, magnesium 12-hydroxystearate and the like.
• the antacids may be used alone or in combination of two or more.
• the content of the antacid in the resin composition relative to 100 parts by mass of the 3-methyl-1-butene polymer can be determined appropriately, and may be, for example, 0.01 to 200 parts by mass, 0.01 to 2.0 parts by mass, or 0.01 to 1.0 parts by mass. Alternatively, it may be 0.01 to 0.5 parts by mass, or 0.01 to 0.3 parts by mass.
• antistatic agent examples include sodium alkylsulfonate, phosphonium alkylsulfonate, and fatty acid ester hydroxyamine compounds such as glycerin ester of stearic acid.
• the content of the antistatic agent in the resin composition per 100 parts by mass of the 3-methyl-1-butene polymer can be determined appropriately and may be, for example, 5 parts by mass or less.
• the resin composition may contain a filler from the viewpoint of further improving the mechanical properties of the sheet.
• the filler include fibrous compounds such as glass fibers, resin fibers, and cellulose fibers; flat compounds such as mica, talc, and montmorillonite; spherical compounds such as glass beads, shirasu balloons, and acrylic balloons; needle-shaped compounds such as acicular metal titanates, wollastonite, acicular silica, and tin oxide; powdered metal titanates, finely powdered wood chips, titanium oxide, calcium carbonate, and silica; and the like.
• These fillers may be surface-treated with, for example, a silane coupling agent.
• a compatibilizer may also be used to enhance the dispersibility of the filler.
• the "highly thermally conductive inorganic filler” is not included in the "lubricant".
• glass fibers are preferred from the viewpoint of further improving the mechanical properties of the sheet.
• the fillers may be used alone or in combination of two or more.
• the amount of filler in the resin composition relative to 100 parts by mass of the 3-methyl-1-butene polymer can be determined appropriately, and may be, for example, 0.01 to 300 parts by mass, or 0.1 to 100 parts by mass.
• the content of the ultraviolet absorber in the resin composition relative to 100 parts by mass of the 3-methyl-1-butene polymer can be determined appropriately, and may be, for example, 0.001 to 5 parts by mass, or 0.01 to 1 part by mass.
• Inorganic fine particles are generally used as the lubricant.
• examples of inorganic fine particles include oxides, hydroxides, sulfides, nitrides, halides, carbonates, sulfates, acetates, phosphates, phosphites, organic carboxylates, silicates, titanates, borates, and their hydrated compounds, composite compounds mainly composed of them, and natural minerals of elements of Groups 1, 2, 4, 6, 7, 8 to 10, 11, 12, 13, and 14 of the periodic table.
• the "highly thermally conductive inorganic filler” is not included in the "lubricant”.
• the "highly thermally conductive inorganic filler" and the "lubricant” contained in the resin composition can be distinguished from each other by, for example, incinerating the resin composition and measuring the thermal conductivity of the resulting residue.
• Inorganic fine particles include, for example, Group 1 element compounds such as lithium fluoride and borax (sodium borate hydrate); Group 2 element compounds such as magnesium carbonate, magnesium phosphate, magnesium chloride, magnesium acetate, magnesium fluoride, magnesium titanate, magnesium silicate, magnesium silicate hydrate, calcium carbonate, calcium phosphate, calcium phosphite, calcium sulfate (gypsum), calcium acetate, calcium terephthalate, calcium hydroxide, calcium silicate, calcium fluoride, calcium titanate, strontium titanate, barium titanate, zinc titanate, lanthanum titanate, bismuth titanate, lead titanate, barium carbonate, barium phosphate, barium sulfate, and barium phosphite; Examples of inorganic fine particles include Group 4 element compounds such as titanium oxide (titania), titanium monoxide, zirconium dioxide (zirconia), and zirconium monoxide; Group 6 element compounds such as molybdenum dioxide,
• the amount of lubricant in the resin composition relative to 100 parts by mass of the 3-methyl-1-butene polymer can be determined appropriately, and may be, for example, 0.001 to 5 parts by mass, or 0.005 to 3 parts by mass.
• ⁇ -olefins having 3 to 20 carbon atoms include those described in the above section on 3-methyl-1-butene polymers. These may be homopolymers or copolymers. In addition, these polyolefins may be high density or low density, and may be polymerized with at least one catalyst selected from the group consisting of a Ziegler-Natta catalyst and a metallocene catalyst.
• the resin other than the 3-methyl-1-butene polymer is preferably at least one selected from the group consisting of polyethylene or polypropylene, more preferably at least one selected from the group consisting of modified polyethylene or modified polypropylene in which polyolefin is partially oxidized and/or modified with a reactive functional group such as maleic acid, and further preferably maleic anhydride-modified polypropylene.
• the content of the vinyl acetate-ethylene copolymer and the modified polyolefin in which the polyolefin is partially oxidized and/or modified with a reactive functional group such as maleic acid in the resin composition per 100 parts by mass of the 3-methyl-1-butene polymer is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less.
• Examples of resins other than vinyl acetate-ethylene copolymers and modified polyolefins in which polyolefins are partially oxidized and/or modified with reactive functional groups such as maleic acid include polyolefins such as low-density polyethylene, high-density polyethylene, linear low-density polyethylene, very low-density polyethylene, polypropylene, syndiotactic polypropylene, polybutene, and polypentene; polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyamides such as nylon 6 and nylon 66; ethylene-ethyl acrylate copolymers, polystyrene, syndiotactic polystyrene, polyphenylene sulfide, polyphenylene ether, polycarbonate, and thermoplastic elastomers.
• polyolefins such as low-density polyethylene, high-density polyethylene, linear low-density poly
• thermoplastic elastomer examples include random or block copolymers of aromatic vinyl monomers and conjugated diene monomers, such as styrene-butadiene block copolymers, styrene-butadiene block copolymers, styrene-isoprene block copolymers, styrene-isoprene-styrene block copolymers, and styrene-butadiene random copolymers; polyisoprene rubber; polyolefin rubbers, such as ethylene-propylene copolymers, ethylene- ⁇ -olefin copolymers, and propylene- ⁇ -olefin copolymers; diene copolymers, such as ethylene-propylene-diene copolymers, ⁇ -olefin-diene copolymers, diene copolymers, isobutylene-isoprene copolymers, and isobutylene
• the melting point of the resin composition of the present embodiment is preferably 260 to 310° C. When the melting point of the resin composition is within the above range, molding can be performed more easily, and reflow heat resistance can be further improved.
• the melting point of the resin composition means a peak temperature measured by a method similar to the method for measuring the melting point of a 3-methyl-1-butene polymer, and specifically, the melting point can be measured by the method for measuring the melting point of a 3-methyl-1-butene polymer described in the Examples.
• the melting point of the resin composition is preferably 270 to 305°C, more preferably 280 to 305°C, and further preferably 280 to 300°C.
• the melting point of the resin composition of the present embodiment is almost the same as that of the 3-methyl-1-butene polymer, and therefore, in this specification, the melting point of the 3-methyl-1-butene polymer can be regarded as the melting point of the resin composition.
• the method for producing the resin composition of the present embodiment is not particularly limited as long as it can produce a resin composition containing a 3-methyl-1-butene polymer and a highly thermally conductive inorganic filler having a thermal conductivity of 20 W/m ⁇ K or more.
• the method for producing the resin composition of the present embodiment includes a step of mixing a 3-methyl-1-butene polymer with a highly thermally conductive inorganic filler having a thermal conductivity of 20 W/m ⁇ K or more.
• the method for producing the resin composition includes a step of obtaining a 3-methyl-1-butene polymer and a step of obtaining a resin composition. Details of each step can be described later in [Step of obtaining a 3-methyl-1-butene polymer] and [Step of obtaining a resin composition].
• the sheet of the present embodiment includes the resin composition of the present embodiment.
• the sheet of the present embodiment includes a 3-methyl-1-butene polymer and a highly thermally conductive inorganic filler having a thermal conductivity of 20 W/m ⁇ K or more.
• the sheet can be used for various purposes, but is preferably used for a heat dissipating circuit board.
• the sheet of the present embodiment may consist of only the resin composition, or may contain components other than the resin composition.
• the dielectric loss tangent of the sheet of this embodiment means a dielectric loss tangent measured at a specific frequency, specifically, a dielectric loss tangent measured at a frequency of 10 kHz to 300 GHz.
• the dielectric loss tangent at 10 kHz to 300 GHz is preferably 0.00010 or more, more preferably 0.00013 or more, and even more preferably 0.00015 or more. From the viewpoint of reducing transmission loss, it is preferably 0.00100 or less, more preferably 0.00080 or less, and even more preferably 0.00050 or less.
• the dielectric loss tangent at 10 kHz to 300 GHz is preferably 0.00010 to 0.00100, more preferably 0.00013 to 0.00080, and even more preferably 0.00015 to 0.00050.
• the dielectric loss tangent of the sheet at 10 kHz to 300 GHz means a value measured by a common method such as a capacitance method, a resonance method, or a frequency change method, and specifically can be measured by the method described in the Examples.
• the measurement frequency is 10 kHz to 1 GHz, it is preferable to measure by the capacitance method, and when the measurement frequency is 1 GHz to 300 GHz, it is preferable to measure by the resonance method or the frequency change method.
• the dielectric loss tangent measured by the cavity resonance method at a measurement frequency of 10 GHz is preferably 0.00010 to 0.00100, more preferably 0.00013 to 0.00080, and further preferably 0.00015 to 0.00050.
• the dielectric loss tangent measured by the frequency change method at a measurement frequency of 100 GHz is preferably 0.00010 to 0.00100, more preferably 0.00013 to 0.00080, and further preferably 0.00015 to 0.00050.
• the dielectric loss tangent measured by the frequency change method at a measurement frequency of 200 GHz is preferably 0.00010 to 0.00100, more preferably 0.00013 to 0.00080, and further preferably 0.00015 to 0.00050.
• the dielectric loss tangent of the resin composition of the present embodiment can be measured by a general method such as a capacitance method, a resonance method, and a frequency change method. Specifically, the dielectric loss tangent of the resin composition of the present embodiment can be obtained by preparing a sheet from the resin composition and measuring the dielectric loss tangent of the sheet by the method described in the examples. The preferred range of the dielectric loss tangent of the resin composition is the same as above.
• the dielectric constant of the sheet at 10 kHz to 300 GHz means a value measured by a common method such as a capacitance method, a resonance method, or a frequency change method, and specifically can be measured by the method described in the Examples.
• a common method such as a capacitance method, a resonance method, or a frequency change method
• the relative dielectric constant as measured by a cavity resonance method at a measurement frequency of 10 GHz is preferably 0.5 to 5.0, more preferably 1.5 to 4.0, and further preferably 2.0 to 3.5.
• the relative dielectric constant as measured by a frequency change method at a measurement frequency of 100 GHz is preferably 0.5 to 5.0, more preferably 1.5 to 4.0, and further preferably 2.0 to 3.5.
• the relative dielectric constant as measured by a frequency change method at a measurement frequency of 200 GHz is preferably 0.5 to 5.0, more preferably 1.5 to 4.0, and even more preferably 2.0 to 3.5.
• the dielectric constant of the resin composition of the present embodiment can be measured by a general method such as a capacitance method, a resonance method, and a frequency change method. Specifically, the dielectric constant of the resin composition of the present embodiment can be obtained by preparing a sheet from the resin composition by the method described in the examples and measuring the dielectric constant of the sheet. The preferred range of the dielectric constant of the resin composition is the same as described above.
• the method for producing the sheet of the present embodiment is not particularly limited as long as it is a method for producing the above-mentioned sheet.
• the sheet production method preferably includes a step of obtaining a 3-methyl-1-butene polymer and a step of forming a resin composition to obtain a sheet.
• a resin composition is obtained by blending other components such as additives in addition to the 3-methyl-1-butene polymer, it is preferable to go through a step of obtaining a resin composition described later.
• the sheet production method includes a step of obtaining a 3-methyl-1-butene polymer, a step of obtaining a resin composition, and a step of forming the resin composition to obtain a sheet.
• the step of obtaining a 3-methyl-1-butene polymer is not particularly limited as long as it is a step of obtaining a 3-methyl-1-butene polymer.
• the method of obtaining a 3-methyl-1-butene polymer is not particularly limited, and the polymer can be produced using a known catalyst such as a Ziegler-Natta catalyst and a metallocene catalyst.
• the step of obtaining a 3-methyl-1-butene polymer is a step of preparing a raw material containing 3-methyl-1-butene and polymerizing the raw material to obtain a 3-methyl-1-butene polymer.
• the method of obtaining a 3-methyl-1-butene polymer is, for example, as described in JP-A-61-103910, in which 3-methyl-1-butene is homopolymerized in the presence of a catalyst, or 3-methyl-1-butene is copolymerized with ethylene or the above-mentioned ⁇ -olefin to obtain a powder.
• the raw material contains at least 3-methyl-1-butene and may further contain a catalyst.
• the raw material contains at least 3-methyl-1-butene and ethylene or the above-mentioned ⁇ -olefin, and may further contain a catalyst.
• the stereoregularity of the 3-methyl-1-butene polymer may be isotactic or syndiotactic.
• the step of obtaining a resin composition is a step of obtaining a resin composition by blending and mixing other components such as additives in addition to the 3-methyl-1-butene polymer. Specifically, it is a step of obtaining a resin composition containing a 3-methyl-1-butene polymer and a highly thermally conductive inorganic filler having a thermal conductivity of 20 W/m ⁇ K or more. A resin composition is obtained by mixing a 3-methyl-1-butene polymer and a highly thermally conductive inorganic filler having a thermal conductivity of 20 W/m ⁇ K or more.
• the mixing method is not particularly limited, and a method of melt-kneading using a twin-screw kneading extruder or the like can be used.
• each raw material may be dry-blended before melt-kneading.
• additives examples include those similar to those described in the above [Resin composition], and in addition to the highly thermally conductive inorganic filler, examples of the additives include alkyl radical scavengers, antioxidants, antacids, fillers, light stabilizers, antistatic agents, flame retardants, pigments, polymerization inhibitors, heavy metal deactivators, ultraviolet absorbers, nucleating agents, clarifying agents, lubricants, fluorescent brightening agents, rust inhibitors, and sliding agents.
• melt kneading are not particularly limited, but it is preferable to perform melt kneading by injecting an inert gas into the inside of a melt kneader, or by degassing the inside of the melt kneader under reduced pressure.
• melt and knead the resin composition in an inert atmosphere or in a low-oxygen state.
• the "low oxygen state” refers to a state in which the oxygen concentration is lower than that before the degassing by depressurizing the inside of the melt kneader. Alternatively, it refers to a state in which the oxygen concentration is lower than that before the injection of an inert gas such as nitrogen gas.
• the oxygen concentration inside the melt kneader is preferably 5% or less, more preferably 2% or less, and further preferably 1% or less.
• the oxygen concentration is measured using an oxygen concentration meter such as a diaphragm-type galvanic type.
• the method of injecting an inert gas into the melt kneader to melt and knead may be, for example, to inject each component into the melt kneader while injecting an inert gas into the melt kneader to perform melt kneading, or to inject an inert gas into the melt kneader after injecting each component into the melt kneader to perform melt kneading.
• the inert gas may be continuously injected into the melt kneader during melt kneading. The method of injecting the inert gas can be carried out depending on the equipment provided in each melt kneader.
• the inert gas may be injected from a gas supply section such as an inert gas provided in the melt kneader, from a supply section for each component provided in the melt kneader, or from a gas vent vent provided in the melt kneader.
• a gas supply section such as an inert gas provided in the melt kneader
• the inert gas can be injected into the entire area from the inert gas supply section to the heating section where melting and kneading are performed, and melting and kneading can be performed.
• the inert gas include nitrogen gas, helium gas, neon gas, argon gas, krypton gas, and carbon dioxide gas. From the viewpoints of availability and versatility, nitrogen gas is preferred.
• the melt kneader may be a single-screw extruder, multi-screw extruder, kneader, Banbury mixer, or the like, which is equipped with equipment capable of melt kneading by injecting an inert gas into the melt kneader, or equipment capable of melt kneading by depressurizing and degassing the inside of the melt kneader.
• the melt-kneading time can be adjusted depending on the size of the kneading device, etc. For example, it may be 1 to 15 minutes, but is not limited to this numerical range of melt-kneading time.
• the "melt-kneading time” refers to the time the mixer is rotating in a batch kneader, and the residence time of the raw materials in the device in the case of a continuous extrusion kneader.
• the rotation speed of the mixer during melt kneading may be 80 rpm or more, or 100 rpm or more, and may be 300 rpm or less, or 250 rpm or less.
• the resin composition is removed from the melt-kneader and cooled.
• the step of obtaining a sheet is a step of obtaining a sheet by molding a resin composition.
• the molding method is not particularly limited, and a method suitable for the shape of the sheet may be used.
• the resin composition of the present embodiment is thermoplastic and can be melt molded. Therefore, injection molding, extrusion molding, compressed air molding, heat press molding, etc. can be used. Among these, extrusion molding is preferred from the viewpoint of obtaining a molded product with excellent ease of manufacture and dimensional accuracy.
• the thickness of the sheet may be 0.01 to 5.0 mm, may be 0.05 to 2.0 mm, or may be 0.1 to 1.0 mm.
• the circuit board of this embodiment includes the sheet of this embodiment and a circuit in contact with one surface of the sheet.
• the circuit board of this embodiment may further include a metal foil in contact with the other surface of the sheet, or may include a circuit board in contact with the other surface of the sheet. More specifically, the circuit board of this embodiment may include the sheet of this embodiment, a circuit on one surface of the sheet, and a metal foil or another circuit board on the other surface of the sheet.
• the method for producing the circuit board of the present embodiment is not particularly limited, and the circuit board can be produced by a known method.
• the circuit board can be produced by forming a circuit by removing a part of the metal foil of the metal foil-coated substrate of the present embodiment.
• the circuit board of the present embodiment is preferably a heat dissipating circuit board.
• the heat dissipating circuit board is a circuit board in which the thermal conductivity of the sheet used at 25°C is preferably 0.5 W/m ⁇ K or more, more preferably 0.6 W/m ⁇ K or more, more preferably 1.0 W/m ⁇ K or more, even more preferably 2.0 W/m ⁇ K or more, and even more preferably 5.0 W/m ⁇ K or more.
• the thermal conductivity of the sheet be equal to or more than the above lower limit, good heat dissipation can be obtained when used as a circuit board.
• a calibration curve was prepared from the ratio of the peak area of 1,461 cm -1 bending vibration derived from the main chain methylene group of the 3-methyl-1-butene homopolymer to the peak area of 727 cm -1 bending vibration derived from the side chain methylene group of the homopolymer of ⁇ -olefin (1-decene), and the addition ratio of each polymer (3-methyl-1-butene copolymer and ⁇ -olefin).
• the IR measurement was carried out on the 3-methyl-1-butene copolymer obtained in the Production Examples, and the measured value (peak area ratio) was inserted into the calibration curve to determine the content ratio of the structural unit derived from ⁇ -olefin (1-decene) other than 3-methyl-1-butene.
• test pieces The 3-methyl-1-butene polymer and the resin composition used in the examples and comparative examples were press-molded at a press temperature of 320° C. and a press pressure of 1.8 MPa to prepare test pieces (length: 40 mm, width: 10 mm, thickness: 4 mm). The specific gravity of the test pieces was measured in accordance with JIS K 7112:1999, Method A.
• the resin compositions prepared in the examples and comparative examples were injection molded at a cylinder temperature of 320° C. and a mold temperature of 180° C. to prepare test pieces (length: 30 mm, width: 1.5 mm, thickness: 1 mm).
• the relative dielectric constant and dielectric loss tangent at a measurement frequency of 10 GHz were measured using a PNA series network analyzer "Keysight E8361A" (manufactured by Agilent Technologies) by a perturbation type cavity resonance method.
• the resin compositions prepared in the examples and comparative examples were injection molded to prepare test pieces (length: 40 mm, width: 40 mm, thickness: 0.5 mm).
• test pieces were used to measure the relative dielectric constant and the dielectric loss tangent at a measurement frequency of 100 GHz by a frequency change method using a millimeter wave module (manufactured by Virginia Diodes Inc., WR10 67 GHz-115 GHz). Further, the resin compositions prepared in the examples and comparative examples were injection molded to prepare test pieces (length: 40 mm, width: 40 mm, thickness: 0.5 mm). The relative dielectric constant and dielectric loss tangent of the test pieces were measured at a measurement frequency of 200 GHz by a frequency change method using a vector network analyzer (Anritsu ME7838G 70 kHz-220 GHz).
• a test piece in which at least one of warping, melting, and blisters was observed was rated as B, and a test piece in which none of the warping, melting, and blisters was observed was rated as A.
• Reflow temperature profile The temperature was raised from 25° C. to 150° C. over 60 seconds, then raised to 180° C. over 80 seconds, and further raised to 280° C. over 60 seconds, and held at 280° C. for 10 seconds. Then, air cooling was performed.
• Thermal conductivity Measurement samples were cut out to a size of 10 mm square from the 0.5 mm thick sheets prepared in the Examples and Comparative Examples, and a thin layer of laser light absorption spray (Fine Chemical Japan's Blackguard Spray FC-153) was applied to both sides and dried. Thereafter, the thermal diffusivity a (mm 2 /sec) in the sheet thickness direction at a measurement temperature of 25°C was measured by the laser flash method using a xenon flash analyzer (NETZSCH's LFA447 NanoFlash300). The measurement was performed on five points cut out from the same sheet, and the arithmetic average value was calculated, and this arithmetic average value was used to calculate the thermal conductivity.
• NETZSCH's LFA447 NanoFlash300 a xenon flash analyzer
• the specific heat c was calculated using a differential scanning calorimeter (TA Instruments, “DSC25”) in accordance with heat flux differential scanning calorimetry according to JIS K 7123:1987.
• ⁇ is the specific gravity measured by the above method.
• the composition of the obtained titanium catalyst component was 4.0 mass % titanium, 56.0 mass % chlorine, 17.0 mass % magnesium, 10.4 mass % ethyl benzoate, and 12.6 mass % of the hydrocarbon solvent consisting of decane and hexane.
• copolymer (A) which is a copolymer of 3-methyl-1-butene and 1-decene.
• the copolymer (A) thus obtained was subjected to the above-mentioned measurements, and found to have a melting point of 286° C., a melt viscosity of 104 Pa ⁇ s, and a specific gravity of 0.89.
• the content of structural units derived from the comonomer 1-decene in the copolymer (A) was 1.1 mol %.
• Example 1 (Resin composition) The components shown in Table 1 were dry-blended in the mixing ratio shown in Table 1, and then melt-kneaded using a small kneader "Micro 15 Compounder” (manufactured by DSMXplore) to obtain a pellet-shaped resin composition (M1). Details of the various components in Table 1 are as follows.
• Phenolic antioxidant pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], trade name "AO-60", manufactured by ADEKA Corporation
• Phosphorus antioxidant PEP-36: 3,9-bis (2,6-di-t-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, trade name "PEP-36", manufactured by ADEKA Corporation
• Alkyl radical scavenger Sumilizer (registered trademark) GS): acrylic phenol compound, 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate, trade name "Sumilizer (registered trademark) GS", manufactured by Sumi
• the content (volume %) of the highly thermally conductive inorganic filler in the resin composition shown in Table 1 was calculated using the amount and specific gravity of the 3-methyl-1-butene polymer and highly thermally conductive inorganic filler added to the resin composition. Note that components other than the 3-methyl-1-butene polymer and highly thermally conductive inorganic filler in the resin composition were not taken into account in the calculation because their amounts added were small.
• the obtained resin composition (M1) was extruded under a nitrogen atmosphere at a resin temperature of 320° C. using an extrusion molding machine "Twin-screw kneading extruder KZW15-45" (manufactured by Technovel Co., Ltd.) to obtain a sheet having a size of 80 mm square and a thickness of 0.5 mm.
• Metal foil substrate After the surface of the obtained sheet was subjected to plasma treatment, copper foil having a thickness of 35 ⁇ m was placed on each side of the sheet, and these were hot-pressed at 300° C. and 70 kgf/cm 2 to produce a copper pressure-bonded sheet (metal foil substrate).
• a sheet containing a resin composition containing the 3-methyl-1-butene polymer of this embodiment has high thermal conductivity, a low dielectric constant and a low dielectric tangent, and is capable of being reflow soldered. Therefore, the industrial usefulness of the sheet of this embodiment is extremely high.

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• 2023
  • 2023-12-27 JP JP2024567915A patent/JPWO2024143449A1/ja active Pending
  • 2023-12-27 WO PCT/JP2023/046868 patent/WO2024143449A1/ja not_active Ceased
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