Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/025—Electric or magnetic properties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • 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
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • 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
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
• • 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
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement

Definitions

• the present invention relates to a resin composition containing a polymer capable of forming an optically anisotropic molten phase (hereinafter referred to as a thermoplastic liquid crystal polymer). It also relates to a film containing the resin composition, a metal-clad laminate having a metal layer bonded to at least one surface of the film, and a circuit board having at least an insulating layer and a conductor layer containing the resin composition.
• a resin composition containing a polymer capable of forming an optically anisotropic molten phase hereinafter referred to as a thermoplastic liquid crystal polymer. It also relates to a film containing the resin composition, a metal-clad laminate having a metal layer bonded to at least one surface of the film, and a circuit board having at least an insulating layer and a conductor layer containing the resin composition.
• Patent Document 1 JP Patent No. 4639756 discloses an aromatic liquid crystal polyester that contains 40 to 74.8 mol% of repeating units derived from 2-hydroxy-6-naphthoic acid, 12.5 to 30 mol% of repeating units derived from hydroquinone or 4,4'-dihydroxybiphenyl, 12.5 to 30 mol% of repeating units derived from 2,6-naphthalenedicarboxylic acid, and 0.2 to 15 mol% of repeating units derived from terephthalic acid or 4,4'-biphenyldicarboxylic acid, the number of moles of repeating units derived from terephthalic acid or 4,4'-biphenyldicarboxylic acid being equal to or greater than the number of moles of repeating units derived from 2,6-naphthalenedicarboxylic acid, and has a flow onset
• the object of the present invention is therefore to provide a thermoplastic liquid crystal polymer resin composition that has a low dielectric tangent in the high frequency band and enables the molding of a film with reduced thickness unevenness, which is an appearance defect.
• Another object of the present invention is to provide a film containing the resin composition, a metal-clad laminate having a metal layer bonded to at least one surface of the film, and a circuit board comprising a conductor layer and an insulating layer containing the resin composition.
• a resin composition containing a thermoplastic liquid crystal polymer which has a dielectric tangent at 5 GHz in a specific range and a reduction rate of complex viscosity ⁇ * in a specific range, can be molded into a film having excellent dielectric properties in the high frequency band and reduced film thickness unevenness, and have completed the present invention.
• the repeating unit represented by the following formula (1) is 0 to 25 mol% (preferably 0.1 to 25 mol%, more preferably 1 to 20 mol%), the repeating unit
• the resin composition [Aspect 8] The resin composition according to any one of claims 1 to 7, comprising particulate matter. [Aspect 9] The resin composition according to any one of aspects 1 to 8, comprising an additive material, wherein the additive material is at least one selected from the group consisting of a thermoplastic resin, a thermosetting resin, an inorganic compound, and a liquid crystalline oligomer. The resin composition.
• a resin composition according to aspect 9, comprising, as the thermoplastic resin, at least one selected from the group consisting of an amorphous polyarylate-based resin, a polyphenylene ether-based resin, a polyphenylene sulfide-based resin, a polyetherimide-based resin, a polyethersulfone-based resin, a polycarbonate-based resin, a polyetheretherketone-based resin, and a fluorine-based resin.
• the resin composition according to aspect 9 or 10 comprising at least one selected from the group consisting of silica and titanium oxide as the inorganic compound.
• Aspect 12 The resin composition according to any one of aspects 9 to 11, comprising two or more types of inorganic particles having different median sizes.
• Aspect 13 The resin composition according to any one of aspects 9 to 12, comprising two or more types of the additive material.
• Aspect 14 A resin composition according to any one of aspects 9 to 13, wherein the weight ratio of the thermoplastic liquid crystal polymer to the additive material (thermoplastic liquid crystal polymer / additive material) is in the range of 63.0 / 37.0 to 94.9 / 5.1 (preferably 66.0 / 34.0 to 94.5 / 5.5, more preferably 72.0 / 28.0 to 93.0 / 7.0).
• Aspect 15 A film comprising the resin composition according to any one of aspects 1 to 14.
• a film according to claim 15 having a thickness of 5 to 200 ⁇ m (preferably 10 to 150 ⁇ m).
• Aspect 17 A film according to Aspect 15 or 16, wherein the coefficient of variation of thickness in the film width direction as measured by a continuous thickness meter is 1.90% or less (preferably 1.80% or less, more preferably 1.75% or less, even more preferably 1.70% or less, still more preferably 1.40% or less, and particularly preferably 1.30% or less).
• Aspect 18 A metal-clad laminate comprising the film according to any one of claims 15 to 17, and a metal layer bonded to at least one surface of the film.
• Aspect 19 A circuit board comprising at least a conductor layer and an insulating layer comprising the resin composition according to any one of aspects 1 to 14.
• the resin composition of the present invention has a low dielectric tangent in the high frequency band and can be molded into a film with reduced unevenness in film thickness.
• the film containing the resin composition of the present invention has a low dielectric tangent in the high frequency band, making it suitable for use as a circuit board material, etc.
• the resin composition includes a thermoplastic liquid crystal polymer.
• the thermoplastic liquid crystal polymer is composed of a liquid crystal polymer that can be melt molded (or a polymer that can form an optically anisotropic molten phase), and the chemical composition is not particularly limited as long as it is a liquid crystal polymer that can be melt molded, but examples thereof include thermoplastic liquid crystal polyesters and thermoplastic liquid crystal polyester amides in which amide bonds are introduced therein.
• thermoplastic liquid crystal polymer may also be a polymer in which an isocyanate-derived bond such as an imide bond, a carbonate bond, a carbodiimide bond, or an isocyanurate bond has been introduced into an aromatic polyester or an aromatic polyester amide.
• an isocyanate-derived bond such as an imide bond, a carbonate bond, a carbodiimide bond, or an isocyanurate bond has been introduced into an aromatic polyester or an aromatic polyester amide.
• the ability to form an optically anisotropic molten phase can be confirmed, for example, by placing a sample on a hot stage, heating it in a nitrogen atmosphere, and observing the light transmitted through the sample.
• thermoplastic liquid crystal polymers include the known thermoplastic liquid crystal polyesters and thermoplastic liquid crystal polyester amides derived from the compounds classified into (1) to (4) below and their derivatives. However, it goes without saying that there is an appropriate range for the combination of various raw material compounds in order to form a polymer capable of forming an optically anisotropic molten phase.
• Aromatic or aliphatic diols see Table 1 for representative examples
• Aromatic hydroxycarboxylic acids (representative examples are shown in Table 3)
• Aromatic diamines, aromatic hydroxyamines, or aromatic aminocarboxylic acids see Table 4 for representative examples.
• thermoplastic liquid crystal polymers obtained from these raw material compounds include copolymers having the repeating units shown in Tables 5 and 6.
• copolymers constituting thermoplastic liquid crystal polymers include copolymers containing repeating units derived from two or more aromatic hydroxycarboxylic acids, and copolymers containing repeating units derived from at least one aromatic hydroxycarboxylic acid, repeating units derived from at least one aromatic dicarboxylic acid, and repeating units derived from at least one aromatic diol and/or aromatic hydroxyamine.
• copolymers containing at least repeating units derived from aromatic hydroxycarboxylic acids copolymers containing at least repeating units derived from p-hydroxybenzoic acid and/or 6-hydroxy-2-naphthoic acid are preferred.
• the resin composition may contain a mixture containing two or more of these copolymers with different combinations of repeating units or different contents of repeating units.
• the thermoplastic liquid crystal polymer in the resin composition preferably contains repeating units derived from at least one aromatic hydroxycarboxylic acid, repeating units derived from at least one aromatic dicarboxylic acid, and repeating units derived from at least one aromatic diol and/or aromatic hydroxyamine.
• the repeating units constituting the thermoplastic liquid crystal polymer in the resin composition are expressed as the total repeating units of all those copolymers.
• the content of each repeating unit constituting the thermoplastic liquid crystal polymer in the resin composition is expressed as an average value calculated taking into account the combination of repeating units, the contents and molecular weights of each of the two or more copolymers.
• the thermoplastic liquid crystal polymer in the resin composition may contain, relative to the total amount of all repeating units, 0 to 25 mol% of repeating units represented by the following formula (1) (hereinafter, may be referred to as repeating units (1)), 25 to 90 mol% of repeating units represented by the following formula (2) (hereinafter, may be referred to as repeating units (2)), 0.1 to 40 mol% of repeating units represented by the following formula (3) (hereinafter, may be referred to as repeating units (3)), and 0.1 to 40 mol% of repeating units represented by the following formula (4) (hereinafter, may be referred to as repeating units (4)).
• repeating units (1) may be referred to as repeating units (1)
• repeating units (3) hereinafter, may be referred to as repeating units (3)
• repeating units (4) 0.1 to 40 mol% of repeating units represented by the following formula (4)
• Ar 1 is a 1,4-phenylene group
• Ar 2 is a 2,6-naphthylene group
• Ar 3 is at least one selected from the group consisting of a 1,4-phenylene group, a 1,3-phenylene group, and a 2,6-naphthylene group
• Ar 4 is at least one selected from the group consisting of a 1,4-phenylene group, a 1,3-phenylene group, and a 4,4'-biphenylylene group
• hydrogen atoms in the aromatic rings of Ar 1 , Ar 2 , Ar 3 , and Ar 4 may each independently be substituted with at least one selected from the group consisting of a C 1-3 alkyl group, a halogen atom, and a phenyl group.
• the content of repeating unit (1) may be preferably 0.1 to 25 mol %, more preferably 1 to 20 mol %, based on the total amount of all repeating units.
• the content of repeating unit (2) in the thermoplastic liquid crystal polymer in the resin composition may be preferably 25 to 80 mol %, more preferably 30 to 75 mol %, based on the total amount of all repeating units.
• the content of repeating unit (3) in the thermoplastic liquid crystal polymer in the resin composition may be preferably 0.1 to 37.5 mol%, more preferably 1 to 35 mol%, and even more preferably 5 to 30 mol%, based on the total amount of all repeating units.
• the content of repeating unit (4) in the thermoplastic liquid crystal polymer in the resin composition may be preferably 0.1 to 37.5 mol%, more preferably 1 to 35 mol%, and even more preferably 5 to 30 mol%, based on the total amount of all repeating units.
• the molar ratio of repeating units (3) to repeating units (4) in the thermoplastic liquid crystal polymer in the resin composition, as (3)/(4), may be 95/100 to 100/95, preferably 98/100 to 100/98, more preferably 99/100 to 100/99, and even more preferably 100/100.
• the thermoplastic liquid crystal polymer in the resin composition preferably has a naphthalene skeleton as a repeating unit from the viewpoint of reducing the dielectric tangent.
• the total amount of repeating units containing 2,6-naphthylene groups in the thermoplastic liquid crystal polymer in the resin composition may be 40 mol% or more, preferably 50 mol% or more, more preferably 60 mol% or more, based on the total amount of all repeating units.
• it may be 95 mol% or less, preferably 90 mol% or less, more preferably 85 mol% or less.
• the repeating unit (2) (a repeating unit derived from 6-hydroxy-2-naphthoic acid) and the repeating unit (3) (a repeating unit derived from 2,6-naphthalenedicarboxylic acid) in which Ar 3 is a 2,6-naphthylene group are preferable.
• each of the repeating units (1) to (4) may contain two or more kinds.
• the above content of each repeating unit represents the content of all repeating units corresponding to each repeating unit.
• the thermoplastic liquid crystal polymer in the resin composition contains two repeating units as the repeating unit (3), that is, a repeating unit in which Ar 3 is a 1,4-phenylene group and a repeating unit in which Ar 3 is a 2,6-naphthylene group
• the content of the repeating unit (3) represents the total content thereof.
• thermoplastic liquid crystal polymer in the resin composition may contain two or more types of repeating unit (3) and/or two or more types of repeating unit (4).
• thermoplastic liquid crystal polymer in the resin composition may have repeating units other than repeating units (1) to (4), but the total content of repeating units (1) to (4) relative to the total amount of all repeating units may be, for example, 95 mol% or more, preferably 98 mol% or more, more preferably 99 mol% or more, and even more preferably 100 mol%.
• Thermoplastic liquid crystal polymers can be synthesized by known polycondensation methods.
• monomers to be subjected to polycondensation various aromatic diols, aromatic dicarboxylic acids, aromatic hydroxycarboxylic acids, aromatic hydroxyamines, etc. may be used, and carboxylic acid derivatives such as acylated products of hydroxyl groups with activated terminals of these monomers, esterified products of carboxyl groups, acid halides, and acid anhydrides may also be used.
• the polycondensation may be carried out in the presence of various polymerization catalysts, such as organotin catalysts (dialkyltin oxides, etc.), antimony catalysts (antimony trioxide, etc.), titanium catalysts (titanium dioxide, etc.), alkali metal salts or alkaline earth metal salts of carboxylic acids (potassium acetate, etc.), Lewis acid salts ( BF3, etc.), and organic compound catalysts (N,N-dimethylaminopyridine, 1-methylimidazole, etc.).
• organotin catalysts dialkyltin oxides, etc.
• antimony catalysts antimony trioxide, etc.
• titanium catalysts titanium catalysts (titanium dioxide, etc.)
• alkali metal salts or alkaline earth metal salts of carboxylic acids potassium acetate, etc.
• Lewis acid salts BF3, etc.
• organic compound catalysts N,N-dimethylaminopyridine, 1-methylimidazole
• Solid-phase polymerization can be carried out by extracting the polymer obtained by the melt polymerization process, pulverizing it into powder or flakes, or granulating it in an extruder into pellets, and then heat-treating it in the solid state under vacuum or in an inert atmosphere such as nitrogen.
• the resin composition has a dielectric loss tangent of 0.0015 or less at 5 GHz and a decrease rate of the complex viscosity ⁇ * of 20% or less. Such a resin composition can be used to mold a film having excellent dielectric properties in the high frequency band and reduced unevenness in film thickness.
• the inventors have found a problem that when a conventional thermoplastic liquid crystal polymer having a low dielectric tangent in a high frequency band is molded into a film, the resulting film is likely to have uneven thickness.
• the cause of this is that the low dielectric tangent thermoplastic liquid crystal polymer in the conventional technology tends to have weak polarization in the molecular chain direction, and the liquid crystal domain, which is a region in which the molecular chain orientation and arrangement of such a thermoplastic liquid crystal polymer are aligned, is less stable under shear during film formation, which is thought to cause uneven thickness as an appearance defect of the molded film.
• thermoplastic liquid crystal polymer that exhibits a low dielectric tangent in a high frequency band are disadvantageous in film formation.
• the inventors have found that the stability of the liquid crystal domain under shear of a thermoplastic liquid crystal polymer correlates with the reduction rate of the complex viscosity ⁇ * , and have found a resin composition that can be molded into a film with low dielectric tangent in a high frequency band, high stability of the liquid crystal domain under shear, and reduced uneven thickness by controlling the reduction rate of the complex viscosity ⁇ * in a resin composition containing a thermoplastic liquid crystal polymer to a specific range.
• the resin composition may have a dielectric loss tangent at 5 GHz of preferably 0.0014 or less, more preferably 0.0013 or less, even more preferably 0.0012 or less, even more preferably 0.0011 or less, particularly preferably 0.0010 or less, and particularly preferably 0.0009 or less.
• the lower the dielectric loss tangent at 5 GHz, the better, and the lower limit is not particularly limited, but may be, for example, 0.0001 or more.
• the dielectric loss tangent of the resin composition is a value measured on a film-shaped (or sheet-shaped) sample in one direction in the plane (X direction) and in a perpendicular direction in the plane (Y direction) relative to the X direction, and calculated as the average value of the X direction and the Y direction, specifically, the value measured by the method described in the examples described later. If the target is not in the shape of a film, the sample can be prepared by molding into a film shape (for example, by heat pressing, etc.), and the dielectric loss tangent of the resin composition can be measured.
• the resin composition may have a reduction rate of complex viscosity ⁇ * of preferably 19% or less, more preferably 18% or less, even more preferably 15% or less, and even more preferably 10% or less.
• the lower limit of the reduction rate of complex viscosity ⁇ * is not particularly limited, and may be, for example, 0.1% or more, or 0.2% or more.
• the reduction rate of complex viscosity ⁇ * is a value measured by the following operation in a parallel plate measurement with a plate diameter of 25 mm and a gap distance of 0.9 mm, under the conditions of measurement temperature: endothermic peak temperature Tm 1 +20 ° C.
• thermoplastic liquid crystal polymer contained in the resin composition strain: 3.0%
• soak time at each measurement at frequencies of 1 rad / s and 100 rad / s: 0.0 seconds
• sampling interval at a frequency of 100 rad / s: 5.0 seconds / pt. That is, first, preheating is performed for 5 minutes after the temperature inside the apparatus reaches the above-mentioned measurement temperature, and then measurement is performed for 12 minutes at a frequency of 1 rad/s.
• the complex viscosity ⁇ * X at the time when the frequency is switched to 100 rad/s and the complex viscosity ⁇ * Y 7 minutes after the frequency is switched are measured, and the reduction rate of the complex viscosity ⁇ * is calculated as ( ⁇ * X - ⁇ * Y )/ ⁇ * Xx100 .
• the endothermic peak temperature Tm 1 refers to the temperature of the endothermic peak derived from the thermoplastic liquid crystal polymer contained in the resin composition, which appears when the temperature is raised from 25 ° C. to 400 ° C. at a rate of 20 ° C. / min in the differential scanning calorimetry of the resin composition.
• the "endothermic peak temperature” is the temperature at the apex of the endothermic peak.
• the endothermic peak temperature with the lowest temperature is taken as Tm 1.
• the endothermic peak temperature Tm 1 may be, for example, in the range of 260 to 370 ° C., preferably in the range of 280 to 360 ° C., more preferably in the range of 290 to 350 ° C.
• the resin composition may have a melt viscosity of 30 to 120 Pa ⁇ s measured using a capillary rheometer under the conditions of a capillary diameter of 1.0 mm, a capillary length of 20 mm, an endothermic peak temperature Tm 1 +20° C., a shear rate of 1000 sec ⁇ 1 , and a preheating time of 5 minutes.
• the melt viscosity of the resin composition may be preferably 35 to 80 Pa ⁇ s, more preferably 40 to 70 Pa ⁇ s, and even more preferably 42 to 65 Pa ⁇ s. If this value is too high, retention of the molten resin may occur in the melt molding process, and if it is too low, sufficient melt tension may not be expressed during film formation.
• the melt viscosity is a value measured by the method described in the examples described below.
• the resin composition may have a melt viscosity measured by a capillary rheometer under the conditions of a capillary diameter of 1.0 mm, a capillary length of 20 mm, an endothermic peak temperature Tm 1 +20° C., a shear rate of 1000 sec ⁇ 1 , and a preheating time of 5 minutes as X (Pa ⁇ s), and then, after leaving the resin composition at rest for 30 minutes in a barrel at the same temperature, the melt viscosity measured under the conditions of the same temperature and shear rate as Y (Pa ⁇ s), and the ratio Y/X may be 1.30 or less.
• melt viscosity ratio Y/X may be preferably 1.25 or less, more preferably 1.20 or less.
• the lower limit value of the melt viscosity ratio Y/X of the resin composition is not particularly limited, but may be, for example, 1.00 or more.
• the resin composition may have a melt tension of 0.002N or more when pulled at a take-up speed of 30 m/ min using a capillary rheometer under the conditions of a capillary diameter of 1.0 mm, a capillary length of 20 mm, a distance from the capillary outlet to the center position of the tension pulley of 200 mm, an endothermic peak temperature Tm 1 +20°C, a shear rate of 1000 sec -1 , and a preheating time of 5 minutes. If the melt tension is too low, it may lead to film formation problems in melt molding, such as draw resonance occurring during film molding using a T-die or bubbles becoming unstable during inflation molding.
• the melt tension of the resin composition may be preferably 0.003N or more, more preferably 0.004N or more.
• the upper limit of the melt tension of the resin composition is not particularly limited, but may be, for example, 0.01N or less.
• the resin composition may have a difference Tm 1 -Tm 6 between the endothermic peak temperature Tm 1 at the first heating and the endothermic peak temperature Tm 6 at the sixth heating, which is 12° C. or less, measured using a differential scanning calorimeter.
• These endothermic peak temperatures are determined by repeating six cycles of heating and cooling under the heating condition of heating from 25° C. to 400° C. at a rate of 20° C./min, holding for two minutes after reaching 400° C., and then cooling from 400° C. to 25° C. at a rate of 20° C./min, and holding for two minutes after reaching 25° C., in differential scanning calorimetry of the resin composition.
• the temperature of the endothermic peak at the first heating is Tm 1 (° C.), and the temperature of the endothermic peak at the sixth heating is Tm 6 (° C.).
• the difference in endothermic peak temperature Tm 1 -Tm 6 is an index showing how much the endothermic peak temperature, which means the melting point of the thermoplastic liquid crystal polymer, has decreased due to the thermal history caused by the temperature rise and fall cycle. If this is too large, it is expected that the thermoplastic liquid crystal polymer has undergone ester exchange due to heating, and the heat resistance tends to be poor due to the thermal history.
• the difference in endothermic peak temperature Tm 1 -Tm 6 may be preferably 10°C or less, more preferably 9°C or less, and even more preferably 8°C or less.
• the resin composition is not limited as long as the reduction rate of the dielectric loss tangent and the complex viscosity ⁇ * is within a specific range, but may contain, for example, particulate matter.
• particulate matter refers to a component that is not compatible with and is dispersed at room temperature in the matrix of the thermoplastic liquid crystal polymer having a predetermined composition (combination of repeating units and its content) contained as the main component in the resin composition.
• the shape of the particulate matter is not particularly limited, and it may be present in any particulate shape such as spherical, cylindrical, honeycomb, fibrous, or irregular. It is sufficient to confirm that the particulate matter is dispersed in the matrix of the thermoplastic liquid crystal polymer contained as the main component.
• the average particle diameter of the particulate matter may be 50 ⁇ m or less, preferably 30 ⁇ m or less, more preferably 10 ⁇ m or less, and the lower limit is not particularly limited, but may be, for example, 0.01 ⁇ m or more.
• the average particle diameter of the particulate matter is calculated as the average value of the maximum diameter of the particulate matter dispersed in the matrix by image analysis using an electron microscope (e.g., SEM).
• the particulate matter may be not only the additive material described below, but also particulate thermoplastic liquid crystal polymers having a different composition from the thermoplastic liquid crystal polymer contained as the main component.
• the term "main component" refers to the component contained in the resin composition at the highest content.
• the repeating unit and its content of the thermoplastic liquid crystal polymer in the resin composition are expressed as the average value of all repeating units and their contents of all thermoplastic liquid crystal polymers contained in the resin composition, without distinguishing between the main component and the particulate matter.
• the resin composition is not limited as long as the reduction rate of the dielectric tangent and the complex viscosity ⁇ * is within a specific range, but may contain, for example, an additive material.
• the additive material is a component other than the thermoplastic liquid crystal polymer, and may be at least one selected from the group consisting of a thermoplastic resin, a thermosetting resin, an inorganic compound, and a liquid crystal oligomer.
• the additive material is preferably at least one selected from the group consisting of a thermoplastic resin and an inorganic compound.
• Thermoplastic resins are not particularly limited as long as they are thermoplastic resins other than the above-mentioned thermoplastic liquid crystal polymers, but examples thereof include amorphous polyarylate resins, polyphenylene ether resins, polyphenylene sulfide resins, polyetherimide resins, polyethersulfone resins, polyetheretherketone resins, polycarbonate resins, and fluororesins.
• the amorphous polyarylate resins refer to amorphous aromatic polyesters obtained by polycondensation of dihydric phenols and aromatic dicarboxylic acids, and examples thereof include copolymers of bisphenol A with terephthalic acid and isophthalic acid.
• the fluororesins refer to polymers having fluorine atoms in the molecular chain, and examples thereof include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), and copolymers of tetrafluoroethylene and perfluoroalkoxyethylene (PFA). Of these thermoplastic resins, amorphous polyarylate resins, polyphenylene ether resins, and fluororesins are preferred.
• Thermosetting resins include epoxy resins, unsaturated polyester resins, thermosetting polyimide resins, bismaleimide resins, phenolic resins, melamine resins, and thermosetting polyurethane resins.
• Inorganic compounds include silica (silicon oxide), alumina (aluminum oxide), titanium oxide, zirconium oxide, silicon carbide, aluminum nitride, boron nitride, barium titanate, glass, mica, talc, etc.
• silica silicon oxide
• alumina aluminum oxide
• titanium oxide zirconium oxide
• silicon carbide aluminum nitride
• boron nitride boron nitride
• barium titanate glass
• glass mica, talc, etc.
• the inorganic compound is preferably contained as inorganic particles.
• the median diameter of the inorganic particles may be 0.01 to 10 ⁇ m, preferably 0.03 to 5 ⁇ m, and more preferably 0.05 to 1 ⁇ m.
• the median diameter of the inorganic particles refers to the particle diameter that is 50% of the cumulative value in the particle size distribution measured by a laser diffraction/scattering method.
• the resin composition may contain two or more types of inorganic particles having different median diameters.
• the inorganic particles having different median diameters may be the same type of inorganic particles having different median diameters, or may be different types of inorganic particles having different median diameters.
• Liquid crystal oligomers refer to oligomers of 10 or less that are composed of repeating units selected from the various repeating units exemplified for the thermoplastic liquid crystal polymers described above, and are produced by known polymerization methods such as polycondensation of the raw material compounds (monomers) described above.
• a 10 or less mer means that the total number of repeating units in one molecule is 10 or less.
• the resin composition may contain two or more additive materials. Two or more additive materials with different chemical structures may be used. For example, two or more of each of thermoplastic resins, thermosetting resins, inorganic compounds, and liquid crystal oligomers may be used (e.g., two or more thermoplastic resins and two or more inorganic compounds), or at least two or more selected from the group consisting of thermoplastic resins, thermosetting resins, inorganic compounds, and liquid crystal oligomers may be used (e.g., one or more thermoplastic resins and one or more inorganic compounds, one or more thermoplastic resins and one or more thermosetting resins, etc.).
• thermoplastic resins, thermosetting resins, inorganic compounds, and liquid crystal oligomers may be used (e.g., two or more thermoplastic resins and two or more inorganic compounds), or at least two or more selected from the group consisting of thermoplastic resins, thermosetting resins, inorganic compounds, and liquid crystal oligomers may be used (e.g., one or
• the resin composition can adjust the rate of decrease in dielectric tangent and complex viscosity ⁇ * depending on the additive material used and its content, but for example, the weight ratio of the thermoplastic liquid crystal polymer to the additive material (thermoplastic liquid crystal polymer/additive material) may be in the range of 63.0/37.0 to 94.9/5.1, preferably 66.0/34.0 to 94.5/5.5, more preferably 72.0/28.0 to 93.0/7.0. In this specification, when the resin composition contains two or more additive materials, this weight ratio is calculated based on the total amount of all additive materials.
• the resin composition may contain a thermoplastic liquid crystal polymer and an inorganic compound.
• the inorganic compound may be any of the inorganic compounds described above, and it is preferable to use inorganic particles, which may be at least one type selected from the group consisting of silica particles and titanium oxide particles.
• inorganic particles which may be at least one type selected from the group consisting of silica particles and titanium oxide particles.
• two or more types of inorganic particles having different median diameters may be used, and for example, the resin composition may contain silica particles and titanium oxide particles having different median diameters, or may contain two or more types of silica particles having different median diameters.
• the resin composition may contain a thermoplastic liquid crystal polymer and a thermoplastic resin.
• the thermoplastic resin may be any of the above-mentioned thermoplastic resins, and it is preferable to use at least one selected from the group consisting of amorphous polyarylate-based resins, polyphenylene ether-based resins, and fluorine-based resins.
• the resin composition may also contain a thermoplastic resin as thermoplastic resin particles, for example, fluororesin particles.
• the resin composition may contain a thermoplastic liquid crystal polymer, a thermoplastic resin, and an inorganic compound.
• the resin composition may contain at least one selected from the group consisting of an amorphous polyarylate-based resin and a polyphenylene ether-based resin as the thermoplastic resin, and may contain silica as the inorganic compound.
• the resin composition may contain two or more types of thermoplastic liquid crystal polymers having different compositions.
• the resin composition may contain a thermoplastic liquid crystal polymer as a particulate material as a component other than the thermoplastic liquid crystal polymer as the main component.
• the weight ratio of the thermoplastic liquid crystal polymer to the inorganic compound may be in the range of 66.0/34.0 to 96.0/4.0, preferably 80.0/20.0 to 94.9/5.1, and more preferably 90.0/10.0 to 94.0/6.0.
• the content of the inorganic compound in the resin composition may be 0 to 30% by weight, preferably 1 to 15% by weight, and more preferably 4.5 to 9.5% by weight, based on the weight of the solid content in the resin composition.
• the weight ratio of the thermoplastic liquid crystal polymer to the thermoplastic resin may be in the range of 60.0/40.0 to 96.0/4.0, preferably 63.0/37.0 to 94.9/5.1, and more preferably 65.0/35.0 to 94.0/6.0.
• the content of the thermoplastic resin in the resin composition may be 0 to 37% by weight, preferably 3 to 30% by weight, and more preferably 5 to 28% by weight, based on the weight of the solid content in the resin composition.
• the total content of the inorganic compound and the thermoplastic resin in the resin composition may be 4 to 37% by weight, preferably 5 to 30% by weight, and more preferably 6 to 20% by weight, based on the weight of the solids in the resin composition.
• the resin composition can be produced by mixing the above-mentioned thermoplastic liquid crystal polymer and additive materials by a known method.
• the resin composition may be produced by mixing two or more thermoplastic liquid crystal polymers having different compositions.
• these thermoplastic liquid crystal polymers may be obtained by melt polymerization, and then mixed with a thermoplastic liquid crystal polymer whose polymerization degree is adjusted by solid-phase polymerization.
• the resin composition may be produced by melt-kneading raw materials such as the above-mentioned thermoplastic liquid crystal polymer and additive materials in an extruder.
• extruder used for melt-kneading, but examples include single-screw extruders, twin-screw extruders, and multi-screw extruders.
• twin-screw extruders are preferred from the viewpoint of uniformly dispersing subcomponents (e.g., additive materials) in the resin composition.
• the L/D of the extruder is preferably 10 to 100, more preferably 15 to 80, and even more preferably 20 to 60.
• L/D is 10 or more, it becomes easier to obtain a better kneaded state.
• L/D is 100 or less, the shear heat generated during kneading can be reduced, and the thermal decomposition of each component in the resin composition can be suppressed.
• L [unit: mm] is the length of the cylinder of the extruder
• D [unit: mm] is the inner diameter of the cylinder of the extruder.
• the extruder is preferably equipped with one or more open vents.
• decomposition products and volatile components can be sucked through the open vents, improving the quality of the resin composition obtained.
• the pressure is preferably 0.1 to 90 kPa, more preferably 0.3 to 80 kPa, even more preferably 0.5 to 50 kPa, and particularly preferably 0.7 to 10 kPa.
• the pressure of the open vents to 90 kPa or less, the amount of remaining decomposition products and volatile components can be reduced.
• the productivity of the resin composition can be improved.
• a known die can be connected to the extruder depending on the shape of the desired resin composition.
• a strand die can be connected and the extruded resin composition can be cut to the desired length to obtain a granular or columnar resin composition.
• the method of feeding the raw materials for the resin composition to the extruder is not particularly limited, and all of the raw materials may be fed together from a gravimetric feeder to a raw material feed hopper, or each or some of the raw materials may be fed together to a raw material feed hopper using two or more gravimetric feeders.
• a mixer such as a known tumbler mixer or Henschel mixer.
• An example of the screw configuration of an extruder is one having a conveying section equipped with a full-flight screw segment that conveys the raw materials of the resin composition and the kneaded product, and a kneading section equipped with a kneading disk (forward, neutral, reverse, etc.) that kneads the raw materials of the resin composition and a screw segment with a reverse feed direction of the molten resin (screw segment with a reverse spiral winding direction, reverse flight).
• a conveying section equipped with a full-flight screw segment that conveys the raw materials of the resin composition and the kneaded product
• a kneading disk forward, neutral, reverse, etc.
• screw segment with a reverse feed direction of the molten resin screw segment with a reverse spiral winding direction, reverse flight.
• the conveying section is installed behind the kneading section that conveys the kneaded product of the resin composition to the die section, etc.
• the resin may be melt-kneaded while passing an inert gas through the extruder.
• a polymer filter may be installed behind the extruder to remove foreign matter.
• Examples of polymer filters include candle-type polymer filters and leaf-disk-type polymer filters.
• the above-mentioned resin composition can be suitably used for forming a film.
• the film can be produced by extruding the resin composition. Any method can be used as the extrusion molding method, but the well-known T-die method, inflation method, etc. are industrially advantageous.
• the inflation method stress is applied not only in the mechanical axis direction of the film (hereinafter abbreviated as MD direction) but also in the direction perpendicular thereto (hereinafter abbreviated as TD direction), and the film can be uniformly stretched in the MD direction and the TD direction, so that a film with controlled molecular orientation, dielectric properties, etc. in the MD direction and the TD direction can be obtained.
• the film may be stretched as necessary.
• the stretching method itself is well known, and either biaxial stretching or uniaxial stretching may be used, but biaxial stretching is preferred because it is easier to control the degree of molecular orientation.
• a well-known uniaxial stretching machine, simultaneous biaxial stretching machine, sequential biaxial stretching machine, etc. may be used.
• Extrusion molding may be accompanied by a stretching process to control the orientation.
• the molten sheet extruded from the T-die may be stretched not only in the MD direction of the thermoplastic liquid crystal polymer film, but also in both the TD direction and the MD direction simultaneously to form a film, or the molten sheet extruded from the T-die may be stretched once in the MD direction and then in the TD direction to form a film.
• a cylindrical sheet melt-extruded from a ring die may be stretched at a predetermined draw ratio (corresponding to the stretch ratio in the MD direction) and blow ratio (corresponding to the stretch ratio in the TD direction) to form a film.
• the film thus obtained is composed of the above-mentioned resin composition.
• the above-mentioned resin composition has a low reduction rate of complex viscosity ⁇ * within a specific range, so that it is possible to mold a film with high stability of liquid crystal domains under shear and reduced film thickness unevenness.
• the film may have a thickness variation coefficient of 1.90% or less in the film width direction measured with a continuous thickness meter, preferably 1.80% or less, more preferably 1.75% or less, even more preferably 1.70% or less, even more preferably 1.40% or less, and particularly preferably 1.30% or less.
• the thickness variation coefficient is calculated by the thickness standard deviation/thickness average value x 100 using the measured thickness data in the film width direction, and is measured by the method described in the examples described later.
• the thickness of the film can be set appropriately depending on the application, and can be selected from a wide range, for example, from 1 to 500 ⁇ m. However, considering that it will be used as a material for the insulating layer of a circuit board, it may be preferably 5 to 200 ⁇ m, and more preferably 10 to 150 ⁇ m.
• the film may have a melting point (Tm) in the range of 260 to 370°C, preferably in the range of 280 to 360°C, and more preferably in the range of 285 to 350°C.
• Tm melting point
• the melting point Tm of the film is determined as the temperature of the endothermic peak derived from the thermoplastic liquid crystal polymer that appears when the film sample is heated from 25°C at a rate of 20°C/min using a differential scanning calorimeter.
• the above-mentioned film can be used for a metal-clad laminate having a metal layer bonded to at least one surface thereof.
• the metal-clad laminate may be a single-sided metal-clad laminate having a metal layer on one surface of the film, or a double-sided metal-clad laminate having a metal layer on both surfaces of the film.
• the metal-clad laminate may be a laminate in which the film and the metal layer are laminated via an adhesive layer (e.g., adhesive), but from the viewpoint of reducing the thickness as a circuit board manufacturing material, it is preferable that the metal-clad laminate is a laminate in which the film and the metal layer are directly laminated without an adhesive layer.
• the metal-clad laminate may be manufactured by adhering a metal foil to the above-mentioned film by thermocompression to form a metal layer, or by forming the metal layer by sputtering, vapor deposition, electroless plating, etc., or by casting a resin composition onto the metal foil.
• the metal forming the metal layer is not particularly limited, and may be, for example, gold, silver, copper, iron, tin, nickel, aluminum, chromium, or alloy metals thereof. These metals may contain other metal species at 2000 ppm by mass or less, and unavoidable impurities may be present.
• a metal foil When a metal foil is used as the metal layer, it may be, for example, a metal foil made of the above-mentioned metals, and from the viewpoints of conductivity, ease of handling, cost, etc., copper foil or stainless steel foil is preferred. Copper foil manufactured by rolling or electrolysis can be used. In addition, the metal foil may be subjected to a surface treatment such as a roughening treatment that is usually performed, as long as it does not impair the high-frequency characteristics of the metal-clad laminate of the present invention.
• a surface treatment such as a roughening treatment that is usually performed, as long as it does not impair the high-frequency characteristics of the metal-clad laminate of the present invention.
• sputtering or vapor deposition method a process is carried out in which metal parts are brought into contact by sputtering or vapor deposition of a metal, and the two are bonded together.
• the sputtering or vapor deposition method is a well-known method in the field of circuit board manufacturing.
• metals for sputtering or vapor deposition include copper, aluminum, gold, tin, and chromium.
• Electroless plating a process is carried out in which a metal is deposited from a solution containing metal ions to bond the two together.
• Electroless plating is a well-known method in the field of manufacturing plated products on non-conductive materials (such as plastics and ceramics), and examples of metals include copper, nickel, cobalt, gold, tin, and chromium.
• Metal-clad laminates can be effectively used in parts used in the electrical and electronic fields, the office equipment and precision equipment fields, and the power semiconductor fields, for example, as circuit board materials.
• the above-mentioned resin composition can be used for a circuit board having at least an insulating layer and a conductor layer containing the resin composition.
• a circuit board can be manufactured by forming a conductor pattern on the surface of the above-mentioned film.
• a circuit board can be manufactured by wiring and circuit processing the metal layer of the above-mentioned metal-clad laminate.
• a circuit processing method a known method can be used, and for example, a circuit can be formed by etching the metal layer on the film by a subtractive method.
• the conductor layer is formed, for example, from a metal that is at least conductive, and a circuit is formed in this conductor layer using a known circuit processing method.
• the conductor forming the conductor layer may be any of a variety of conductive metals, such as gold, silver, copper, iron, tin, nickel, aluminum, chromium, or alloy metals of these.
• the circuit board can be used as various high-frequency circuit boards.
• the circuit board may also be a circuit board (or a semiconductor element mounting board) on which a semiconductor element (e.g., an IC chip) is mounted. Since the dielectric tangent of the circuit board is controlled to be low, the circuit board may be used for various transmission lines, for example, known or conventional transmission lines such as coaxial lines, strip lines, microstrip lines, coplanar lines, and parallel lines, or may be used for antennas (e.g., microwave or millimeter wave antennas).
• the circuit board may also be used for an antenna device in which an antenna and a transmission line are integrated. For example, the circuit board may be used for various sensors, particularly for on-board radar.
• Antennas include those that use millimeter waves or microwaves, such as waveguide slot antennas, horn antennas, lens antennas, printed antennas, triplate antennas, microstrip antennas, and patch antennas.
• Temperature increase conditions increase from 25°C to 400°C at a rate of 20°C/min, and hold for 2 minutes after reaching 400°C.
• Temperature decrease conditions decrease from 400°C to 25°C at a rate of 20°C/min, and hold for 2 minutes after reaching 25°C.
• a 5 GHz cavity resonator (manufactured by Kanto Electronics Application Development Co., Ltd.) was connected to a network analyzer ("E8362B" manufactured by Agilent Technology Co., Ltd.), the above sample pieces were inserted into the cavity resonator, and measurements were performed at 25°C to measure the dielectric loss tangent in the MD direction and the TD direction, and the average value thereof was calculated as the dielectric loss tangent.
• Measurement method Using a rotational rheometer (TA Instruments Japan Co., Ltd. "ARES-G2”), a measurement sample was set on a parallel plate with a plate diameter of 25 mm, and the gap distance was 0.9 mm, the measurement temperature was the endothermic peak temperature Tm 1 +20 ° C. of the resin composition obtained above, the strain was 3.0%, the soak time at each measurement at frequencies of 1 rad / s and 100 rad / s was 0.0 seconds, and the sampling interval at the measurement at a frequency of 100 rad / s was 5.0 seconds / pt. The measurement was performed by the following operation. First, the device temperature was preheated for 5 minutes after reaching the measurement temperature.
• the frequency was switched to 100 rad / s and the measurement was continued.
• the complex viscosity at the time when the frequency was switched to 100 rad/s was defined as ⁇ * X
• the complex viscosity 7 minutes after the switching was defined as ⁇ * Y .
• the reduction rate (%) of the complex viscosity ⁇ * was calculated from ( ⁇ * X - ⁇ * Y )/ ⁇ * Xx100 .
• melt viscosity was measured under the conditions of the measurement temperature and a shear rate of 1000 sec -1 , and this melt viscosity was designated as X (Pa ⁇ s).
• melt viscosity ratio Y/X was calculated.
• the sample was preheated in the barrel for 5 minutes, and then the melt tension was measured when the take-up speed was increased from 25 m/min to 50 m/min at an acceleration rate of 0.02778 m/ s2 under the conditions of the above-mentioned measurement temperature and a piston speed of 33.33 mm/min (shear rate 1000 sec-1), and the melt tension was measured when the sample was taken up at a take-up speed of 30 m/min.
• the mixture was heated with stirring and held at 145°C for 1 hour. Next, the temperature was raised from 145°C to 310°C over 3 hours and 30 minutes while distilling off the by-product acetic acid and unreacted acetic anhydride. The mixture was kept at 310° C. for 3 hours, then cooled to room temperature and pulverized in a pulverizer to obtain a powder of a thermoplastic liquid crystal polymer.
• the obtained powder was heated under a heating atmosphere. After the temperature was raised from 25 ° C to 250 ° C over 1 hour, the temperature was raised from 250 ° C to 315 ° C over 5 hours. Then, the temperature was kept at 315 ° C, and solid-state polymerization was performed until the endothermic peak temperature was 320.5 ° C, and the melt viscosity at a shear rate of 1000 s -1 at 340.5 ° C was 54 Pa ⁇ s. Thereafter, the solid-state polymerized powder was cooled, and the cooled powder was granulated at 340 ° C using a twin-screw kneading extruder to obtain pellets of thermoplastic liquid crystal polymer A.
• the mixture was heated from room temperature while stirring under a nitrogen atmosphere, and was maintained at 160°C for about 2 hours. Thereafter, the mixture was heated and maintained at 280°C for 0.5 hours, at 320°C for 1 hour, and at 360°C for 1 hour. Next, the mixture was subjected to a decompression treatment (100 Pa) until foaming ceased (30 to 120 minutes), and then the mixture was replaced with nitrogen, cooled to room temperature, and pulverized with a pulverizer to obtain a powder of thermoplastic liquid crystal polymer.
• the powder after cooling had an endothermic peak temperature of 291.1 ° C. and a melt viscosity of 55 Pa s at a shear rate of 1000 s -1 at 311.1 ° C.
• the powder after cooling was granulated at 315 ° C. using a twin-screw kneading extruder to obtain pellets of thermoplastic liquid crystal polymer B.
• the obtained powder was heated under a heating atmosphere. After the temperature was raised from 25°C to 250°C over 1 hour, the temperature was raised from 250°C to 325°C over 2 hours. Then, the temperature was kept at 325°C, and solid-state polymerization was performed until the endothermic peak temperature reached 340.0°C and the melt viscosity at a shear rate of 1000s -1 at 360.0°C was 55 Pa ⁇ s.
• the cooled powder was granulated at 360°C using a twin-screw kneading extruder to obtain pellets of thermoplastic liquid crystal polymer C.
• Silica particles A Surface-treated Adma Fine Silica SC2500-SQ” manufactured by Admatechs Co., Ltd., median diameter 0.5 ⁇ m
• Silica particles B manufactured by Admatechs Co., Ltd., median diameter 0.3 ⁇ m
• Polyphenylene ether PPE; "Zylon S201A” manufactured by Asahi Kasei Corporation
• Amorphous polyarylate PAR; "U-100” manufactured by Unitika Ltd.
• Example 1 90.9% by weight of the thermoplastic liquid crystal polymer A obtained in Reference Example 1 and 9.1% by weight of the silica particles A were melt-kneaded using a twin-screw kneading extruder at a cylinder setting temperature of 330 ° C. to prepare a resin composition.
• the analysis results of the obtained resin composition are shown in Table 7.
• the obtained resin composition was melt extruded from an annular inflation die (die diameter 46.0 mm, die slit spacing 900 ⁇ m) at a draw ratio of 2.0 and a blow ratio of 4.2 to produce a film.
• the analysis results of the obtained film are shown in Table 7.
• Examples 2 to 9, Comparative Examples 1 to 5 Resin compositions and films were prepared in the same manner as in Example 1, except that the components were used in the weight ratios shown in Table 7. The analysis results of the obtained resin compositions and films are shown in Table 7.
• the resin compositions of Examples 1 to 9 have a specific range of reduction in dielectric tangent and complex viscosity ⁇ * at 5 GHz, and therefore the films obtained by molding such resin compositions have a small coefficient of variation in thickness.
• thermoplastic liquid crystal polymer had a low dielectric tangent at 5 GHz, the rate of decrease in complex viscosity ⁇ * was high, and therefore the film obtained by molding such a thermoplastic liquid crystal polymer had a large coefficient of variation in thickness and had uneven thickness as an appearance defect.
• the resin compositions of Comparative Examples 3 and 5 had low dielectric tangents at 5 GHz, but had high rates of decrease in complex viscosity ⁇ *. Therefore, the films obtained by molding such resin compositions had large coefficients of variation in thickness and had uneven film thickness as an appearance defect.
• the resin composition of Comparative Example 4 had a low reduction rate of the complex viscosity ⁇ * , and thus the film obtained by molding this composition had a small coefficient of variation in thickness.
• the dielectric loss tangent at 5 GHz was high, and therefore the dielectric properties in the high frequency range required for various circuit boards were insufficient.
• the resin composition of the present invention has a low dielectric tangent in the high frequency band and can be molded into a film with reduced unevenness in film thickness. Therefore, the film obtained by molding the resin composition can be suitably used as a high frequency circuit board material in the electrical and electronic fields, the office equipment and precision equipment fields, the power semiconductor fields, etc.

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