Classifications

• • 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
  • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D177/12—Polyester-amides
• • 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
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
  • C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
  • C08G69/12—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids with both amino and carboxylic groups aromatically bound
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/44—Polyester-amides
• • 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
  • 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
  • C08L21/00—Compositions of unspecified rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
  • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D153/02—Vinyl aromatic monomers and conjugated dienes
• • 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
  • H05K1/0277—Bendability or stretchability details
  • H05K1/0283—Stretchable printed circuits
• • 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
  • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
• • 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
  • H05K1/032—Organic insulating material consisting of one material
• • 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
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/01—Dielectrics
  • H05K2201/0104—Properties and characteristics in general
  • H05K2201/0133—Elastomeric or compliant polymer
• • 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
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/01—Dielectrics
  • H05K2201/0137—Materials
  • H05K2201/0141—Liquid crystal polymer [LCP]
• • 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
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/01—Dielectrics
  • H05K2201/0137—Materials
  • H05K2201/015—Fluoropolymer, e.g. polytetrafluoroethylene [PTFE]
• • 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
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
  • H05K2201/0203—Fillers and particles
  • H05K2201/0206—Materials
  • H05K2201/0209—Inorganic, non-metallic particles
• • 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
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
  • H05K2201/0203—Fillers and particles
  • H05K2201/0206—Materials
  • H05K2201/0212—Resin particles
• • 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
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
  • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates

Definitions

• the present disclosure relates to polymer compositions, polymer film precursors, polymer films, laminate precursors, and laminates.
• JP 2019-199612 A describes a resin composition comprising a styrene-based polymer, an inorganic filler, and a curing agent, in which the styrene-based polymer is an acid-modified styrene-based polymer having a carboxyl group, the inorganic filler is silica and/or aluminum hydroxide, the particle size of the inorganic filler is 1 ⁇ m or less, the content of the inorganic filler is 20 to 80 parts by mass relative to 100 parts by mass of the styrene-based polymer, and the resin composition is in the form of a film having a thickness of 25 ⁇ m.
• the resin composition satisfies the formulas (A) and (B).
• the dielectric loss tangent is 0.0001 to 0.01 at a frequency of 10 GHz and at 23° C.
• the linear expansion coefficient ⁇ 1 from 0° C. to the glass transition temperature is 100 to 500 ppm/° C.
• a copper-clad laminate is manufactured by laminating a copper foil on the surface of a polymer film.
• a wiring board is manufactured by stacking a copper-clad laminate and a wiring substrate so that the polymer film of the copper-clad laminate and the wiring substrate are in contact with each other.
• the polymer film deforms to follow the steps formed on the surface of the wiring substrate from the viewpoint of adhesion.
• wiring patterns have become finer, there is a demand for deformation that follows finer steps than before.
• Means for solving the above problems include the following aspects.
• a polymer composition comprising particles having a ratio of average particle size D90 to average particle size D50 of 2.3 or less, and a polymer having a dielectric loss tangent of 0.01 or less.
• ⁇ 4> ⁇ 4> The polymer composition according to any one of ⁇ 1> to ⁇ 3>, wherein the particles have an elastic modulus of 10 MPa or less at 160° C.
• ⁇ 5> The polymer composition according to any one of ⁇ 1> to ⁇ 4>, wherein the particles contain an organic substance as a main component.
• ⁇ 6> The polymer composition according to any one of ⁇ 1> to ⁇ 5>, wherein the particles contain a thermoplastic elastomer.
• ⁇ 7> ⁇ 6> The polymer composition according to any one of ⁇ 1> to ⁇ 6>, wherein the polymer having a dielectric tangent of 0.01 or less has a mass retention rate of 80% or more at 440°C.
• ⁇ 8> The polymer composition according to any one of ⁇ 1> to ⁇ 7>, wherein the polymer having a dielectric tangent of 0.01 or less includes an aromatic polyester amide.
• a polymer film precursor comprising particles having a ratio of average particle size D90 to average particle size D50 of 2.3 or less, and a polymer having a dielectric loss tangent of 0.01 or less.
• the polymer film precursor according to ⁇ 9> having an average particle size D90 of 20 ⁇ m or less.
• ⁇ 11> The polymer film precursor according to ⁇ 9> or ⁇ 10>, wherein the content of the particles is 40% by mass or more and less than 100% by mass with respect to the total amount of the polymer film precursor.
• ⁇ 18> The polymer film according to ⁇ 16> or ⁇ 17>, having a viscosity at 260°C of 1,000 Pa ⁇ s or more.
• layer B comprises particles having a ratio of average particle size D90 to average particle size D50 of 2.3 or less, and a polymer having a dielectric loss tangent of 0.01 or less.
• Layer B has a phase-separated structure including at least two phases, and the distribution width of the elastic modulus at 160°C is less than 100 MPa.
• a polymer composition suitable for producing a polymer film that has excellent step conformability when attached to wiring there is provided a polymer film precursor, a polymer film, a laminate precursor, and a laminate that have excellent step conformability when attached to wiring.
• the use of "to" indicating a range of values means that the values before and after it are included as the lower limit and upper limit.
• the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages.
• the upper or lower limit value of the numerical range may be replaced with a value shown in the examples.
• an "alkyl group” includes not only an alkyl group that has no substituent (an unsubstituted alkyl group) but also an alkyl group that has a substituent (a substituted alkyl group).
• (meth)acrylic is a term used as a concept including both acrylic and methacrylic
• (meth)acryloyl is a term used as a concept including both acryloyl and methacryloyl.
• the term "process" in this specification includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. Furthermore, in the present disclosure, combinations of two or more preferred aspects are more preferred aspects.
• GPC gel permeation chromatography
• the polymer composition according to the present disclosure comprises particles having a ratio of average particle size D90 to average particle size D50 (i.e., "average particle size D90/average particle size D50") of 2.3 or less, and a polymer having a dielectric loss tangent of 0.01 or less.
• the average particle size D50 indicates the average particle size of particles when the number of particles in the population of particles to be measured is 50% by volume in total.
• the average particle size D90 indicates the average particle size of particles when the number of particles in the population of particles to be measured is 90% by volume. In particles, the ratio of the average particle size D90 to the average particle size D50 being 2.3 or less means that the particle size distribution is narrow.
• the distribution width of the elastic modulus in the polymer film will be narrow. In particular, it is thought that this can suppress localized decreases in surface pressure during lamination press processing, resulting in excellent step-following properties.
• JP 2019-199612 A and JP 2022-17947 A do not mention the combination of the ratio of average particle diameter D90 to average particle diameter D50 and a polymer with a dielectric tangent of 0.01 or less.
• the polymer composition according to the present disclosure contains particles (hereinafter also referred to as "specific particles") having a ratio of average particle diameter D90 to average particle diameter D50 of 2.3 or less.
• the ratio of the average particle diameter D90 to the average particle diameter D50 is preferably greater than 1.0 and less than 2.3, more preferably greater than 1.0 and less than 2.0, and even more preferably greater than 1.0 and less than 1.8.
• the average particle size D50 is preferably 0.1 ⁇ m to 20 ⁇ m, and more preferably 1 ⁇ m to 10 ⁇ m.
• the average particle size D90 is preferably 20 ⁇ m or less, and more preferably 1 ⁇ m to 15 ⁇ m.
• the average particle size D50 and the average particle size D90 are measured using a laser diffraction/scattering type particle size distribution measuring device.
• a laser diffraction/scattering type particle size distribution measuring device For example, the LA-950V2 manufactured by HORIBA is used as the laser diffraction/scattering type particle size distribution measuring device.
• the specific particles preferably have an elastic modulus of 10 MPa or less at 160°C, more preferably 5 MPa or less, and even more preferably 1 MPa or less.
• the lower limit of the elastic modulus it is preferably 0.2 MPa, and more preferably 0.4 MPa.
• the specific particles preferably have an elastic modulus of 0.2 MPa to 10 MPa, and more preferably 0.4 MPa to 5 MPa at 160°C.
• the elastic modulus at 160°C is measured as the indentation elastic modulus using the nanoindentation method.
• the indentation elastic modulus is measured using a microhardness tester (product name "DUH-W201", manufactured by Shimadzu Corporation) at 160°C by applying a load with a Vickers indenter at a loading rate of 0.28 mN/sec, holding the maximum load of 10 mN for 10 seconds, and then unloading at a loading rate of 0.28 mN/sec.
• the specific particles may be organic particles or inorganic particles.
• the specific particles may also be composite particles containing an organic material and an inorganic material.
• the specific particles are preferably particles containing an organic material as a main component.
• the main component means a component that has the largest mass ratio among the components constituting the specific particles.
• the specific particles are preferably organic particles.
• the specific particles contain a thermoplastic elastomer.
• Thermoplastic elastomers are not particularly limited, and examples include elastomers containing repeating units derived from styrene (polystyrene-based elastomers), polyester-based elastomers, polyolefin-based elastomers, polyurethane-based elastomers, polyamide-based elastomers, polyacrylic-based elastomers, silicone-based elastomers, polyimide-based elastomers, etc.
• the thermoplastic elastomers may be hydrogenated.
• Polystyrene-based elastomers include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), polystyrene-poly(ethylene-propylene) diblock copolymers (SEP), polystyrene-poly(ethylene-propylene)-polystyrene triblock copolymers (SEPS), styrene-ethylene-butylene-styrene block copolymers (SEBS), polystyrene-poly(ethylene/ethylene-propylene)-polystyrene triblock copolymers (SEEPS), styrene-isobutylene-styrene block copolymers (SIBS), and hydrogenated versions of these.
• SBS styrene-butadiene-styrene block copolymers
• SIS
• the polymer film according to the present disclosure preferably contains a thermoplastic resin containing a structural unit derived from a monomer having an aromatic hydrocarbon group, more preferably contains a polystyrene-based elastomer, and even more preferably contains a styrene-ethylene-butylene-styrene block copolymer, or a styrene-isobutylene-styrene block copolymer, a styrene-ethylene-propylene block copolymer, a styrene-ethylene-propylene-styrene block copolymer, or a styrene-ethylene-ethylene-propylene-styrene copolymer.
• the content of the specific particles is preferably 40% by mass or more and less than 100% by mass, and more preferably 60% by mass to 85% by mass, based on the total amount of the polymer composition.
• the polymer composition according to the present disclosure comprises a polymer having a dielectric loss tangent of 0.01 or less.
• the dielectric tangent of a polymer with a dielectric tangent of 0.01 or less is preferably 0.005 or less, and more preferably greater than 0 and less than 0.003.
• the dielectric tangent is measured by the following method.
• the dielectric loss tangent is measured by a resonance perturbation method at a frequency of 10 GHz.
• a 10 GHz cavity resonator (Kanto Electronics Application Development Co., Ltd., CP531) is connected to a network analyzer (Agilent Technology, Inc., E8363B), a measurement sample is inserted into the cavity resonator, and the change in resonance frequency is measured before and after insertion for 96 hours under an environment of 25°C temperature and 60% RH.
• a polymer with a dielectric tangent of 0.01 or less has a mass retention rate of 80% or more at 440°C, and more preferably 85% or more.
• the upper limit of the mass retention rate at 440°C is, for example, 100%.
• the mass retention rate at 440° C. is measured by the following method. 5 mg of the measurement sample is added to a platinum pan, and measured using a differential thermobalance (TG-DTA) (TG-8120, manufactured by Rigaku Corporation) at a measurement temperature of 25 to 900°C and a heating rate of 10°C/min. The mass (%) at 900°C is calculated by subtracting the mass (%) at 440°C from the mass (%) at 900°C.
• TG-DTA differential thermobalance
• polymers with a dielectric tangent of 0.01 or less include liquid crystal polymers, fluororesins, polymers of compounds having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, thermoplastic resins such as polyether ether ketone, polyolefin, polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone, polyphenylene ether and modified products thereof, and polyether imide; elastomers such as copolymers of glycidyl methacrylate and polyethylene; and thermosetting resins such as phenol resins, epoxy resins, polyimides, and cyanate resins.
• thermoplastic resins such as polyether ether ketone, polyolefin, polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone, polyphenylene ether and modified products thereof, and polyether
• the polymer having a dielectric loss tangent of 0.01 or less is preferably a liquid crystal polymer, that is, the polymer composition preferably contains a liquid crystal polymer.
• the type of liquid crystal polymer is not particularly limited, and any known liquid crystal polymer can be used.
• the liquid crystal polymer may be a thermotropic liquid crystal polymer that exhibits liquid crystallinity in a molten state, or a lyotropic liquid crystal polymer that exhibits liquid crystallinity in a solution state. In the case of a thermotropic liquid crystal, it is preferable that the liquid crystal polymer melts at a temperature of 450° C. or less.
• liquid crystal polymers examples include liquid crystal polyester, liquid crystal polyester amide in which an amide bond has been introduced into liquid crystal polyester, liquid crystal polyester ether in which an ether bond has been introduced into liquid crystal polyester, and liquid crystal polyester carbonate in which a carbonate bond has been introduced into liquid crystal polyester.
• the liquid crystal polymer is preferably a polymer having an aromatic ring, and is more preferably an aromatic polyester or an aromatic polyester amide.
• the liquid crystal polymer may be a polymer in which an isocyanate-derived bond such as an imide 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 carbodiimide bond, or an isocyanurate bond has been introduced into an aromatic polyester or an aromatic polyester amide.
• liquid crystal polymer is preferably a fully aromatic liquid crystal polymer made using only aromatic compounds as raw material monomers.
• liquid crystal polymer examples include the following liquid crystal polymers. 1) A compound obtained by polycondensation of (i) an aromatic hydroxycarboxylic acid, (ii) an aromatic dicarboxylic acid, and (iii) at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxyamine, and an aromatic diamine. 2) Those obtained by polycondensation of multiple types of aromatic hydroxycarboxylic acids. 3) (i) a polycondensation product of an aromatic dicarboxylic acid and (ii) at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxyamine and an aromatic diamine.
• Polyester such as polyethylene terephthalate
• aromatic hydroxycarboxylic acid are polycondensed.
• the aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic hydroxyamine and aromatic diamine may each independently be replaced with a derivative capable of undergoing polycondensation.
• the melting point of the liquid crystal polymer is preferably 250°C or higher, more preferably 250°C to 350°C, and even more preferably 260°C to 330°C.
• the melting point is measured using a differential scanning calorimeter.
• a differential scanning calorimeter For example, it is measured using a product called "DSC-60A Plus" (manufactured by Shimadzu Corporation).
• the heating rate in the measurement is 10°C/min.
• the weight average molecular weight of the liquid crystal polymer is preferably 1,000,000 or less, more preferably 3,000 to 300,000, even more preferably 5,000 to 100,000, and particularly preferably 5,000 to 30,000.
• the liquid crystal polymer preferably contains an aromatic polyesteramide from the viewpoint of further reducing the dielectric tangent.
• An aromatic polyesteramide is a resin having at least one aromatic ring and having an ester bond and an amide bond.
• the aromatic polyesteramide is preferably a fully aromatic polyesteramide.
• the aromatic polyesteramide is preferably a crystalline polymer.
• the polymer composition preferably contains a crystalline aromatic polyesteramide.
• the aromatic polyesteramide is crystalline, the dielectric loss tangent is further reduced.
• crystalline polymer refers to a polymer that has a clear endothermic peak, not a stepwise change in endothermic amount, in differential scanning calorimetry (DSC). Specifically, for example, it means that the half-width of the endothermic peak is within 10° C. when measured at a heating rate of 10° C./min. Polymers with a half-width exceeding 10° C. and polymers without a clear endothermic peak are classified as amorphous polymers and are distinguished from crystalline polymers.
• the aromatic polyester amide preferably contains a constitutional unit represented by the following formula 1, a constitutional unit represented by the following formula 2, and a constitutional unit represented by the following formula 3. -O-Ar 1 -CO- ... Formula 1 -CO-Ar 2 -CO- ... Formula 2 —NH—Ar 3 —O— Formula 3
• Ar 1 , Ar 2 and Ar 3 each independently represent a phenylene group, a naphthylene group or a biphenylylene group.
• the structural unit represented by formula 1 will also be referred to as "unit 1", etc.
• the unit 1 can be introduced, for example, by using an aromatic hydroxycarboxylic acid as a raw material.
• the unit 2 can be introduced, for example, by using an aromatic dicarboxylic acid as a raw material.
• Unit 3 can be introduced, for example, by using an aromatic hydroxylamine as a raw material.
• aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, and aromatic hydroxylamine may each be independently replaced with a derivative capable of polycondensation.
• aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid esters and aromatic dicarboxylic acid esters by converting the carboxy group to an alkoxycarbonyl group or an aryloxycarbonyl group.
• Aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid halides and aromatic dicarboxylic acid halides by converting the carboxy groups to haloformyl groups.
• Aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced by aromatic hydroxycarboxylic acid anhydrides and aromatic dicarboxylic acid anhydrides by converting the carboxy groups to acyloxycarbonyl groups.
• polycondensable derivatives of compounds having a hydroxy group such as aromatic hydroxycarboxylic acids and aromatic hydroxyamines
• examples of polycondensable derivatives of compounds having a hydroxy group include those obtained by acylation of a hydroxy group into an acyloxy group (acylated products).
• aromatic hydroxycarboxylic acids and aromatic hydroxylamines can be replaced with their acylated counterparts by acylation of the hydroxy group to convert it to an acyloxy group.
• polycondensable derivatives of aromatic hydroxylamines include those obtained by acylation of the amino group to an acylamino group (acylated product).
• aromatic hydroxyamines can be replaced with acylated products by converting the amino group into an acylamino group through acylation.
• Ar 1 is preferably a p-phenylene group, a 2,6-naphthylene group, or a 4,4'-biphenylylene group, and more preferably a 2,6-naphthylene group.
• unit 1 is, for example, a constitutional unit derived from p-hydroxybenzoic acid.
• unit 1 is, for example, a constitutional unit derived from 6-hydroxy-2-naphthoic acid.
• Ar 1 is a 4,4'-biphenylylene group
• unit 1 is, for example, a constitutional unit derived from 4'-hydroxy-4-biphenylcarboxylic acid.
• Ar 2 is preferably a p-phenylene group, an m-phenylene group, or a 2,6-naphthylene group, and more preferably an m-phenylene group.
• unit 2 is, for example, a constitutional unit derived from terephthalic acid.
• unit 2 is, for example, a constitutional unit derived from isophthalic acid.
• Ar 2 is a 2,6-naphthylene group
• unit 2 is, for example, a constitutional unit derived from 2,6-naphthalenedicarboxylic acid.
• Ar 3 is preferably a p-phenylene group or a 4,4′-biphenylylene group, and more preferably a p-phenylene group.
• unit 3 is, for example, a constitutional unit derived from p-aminophenol.
• unit 3 is, for example, a constitutional unit derived from 4-amino-4'-hydroxybiphenyl.
• the content of units 1 is preferably 30 mol % or more, the content of units 2 is preferably 35 mol % or less, and the content of units 3 is preferably 35 mol % or less.
• the content of unit 1 is more preferably 30 mol % to 80 mol %, further preferably 30 mol % to 60 mol %, and particularly preferably 30 mol % to 40 mol %, based on the total content of unit 1, unit 2, and unit 3.
• the content of unit 2 is preferably 10 mol % to 35 mol %, more preferably 20 mol % to 35 mol %, and particularly preferably 30 mol % to 35 mol %, based on the total content of unit 1, unit 2, and unit 3.
• the content of unit 3 is preferably 10 mol % to 35 mol %, more preferably 20 mol % to 35 mol %, and particularly preferably 30 mol % to 35 mol %, based on the total content of unit 1, unit 2, and unit 3.
• the total content of each structural unit is the sum of the amounts (moles) of each structural unit, which is calculated by dividing the mass of each structural unit constituting the aromatic polyesteramide by the formula weight of the structural unit.
• the ratio of the content of unit 2 to the content of unit 3, expressed as [content of unit 2]/[content of unit 3] (mol/mol), is preferably 0.9/1 to 1/0.9, more preferably 0.95/1 to 1/0.95, and even more preferably 0.98/1 to 1/0.98.
• the aromatic polyesteramide may have two or more types of units 1 to 3, each of which is independent.
• the aromatic polyesteramide may also have other structural units in addition to units 1 to 3.
• the content of the other structural units is preferably 10 mol % or less, more preferably 5 mol % or less, based on the total content of all structural units.
• Aromatic polyesteramides are preferably produced by melt polymerizing raw material monomers that correspond to the structural units that make up the aromatic polyesteramide.
• the weight average molecular weight of the aromatic polyester amide is preferably 1,000,000 or less, more preferably 3,000 to 300,000, even more preferably 5,000 to 100,000, and particularly preferably 5,000 to 30,000.
• the polymer having a dielectric loss tangent of 0.01 or less may be a fluororesin from the viewpoints of heat resistance and mechanical strength.
• the type of fluororesin is not particularly limited, and any known fluororesin can be used.
• Fluororesins include homopolymers and copolymers that contain structural units derived from fluorinated ⁇ -olefin monomers, i.e., ⁇ -olefin monomers that contain at least one fluorine atom. Fluororesins also include copolymers that contain structural units derived from fluorinated ⁇ -olefin monomers and structural units derived from non-fluorinated ethylenically unsaturated monomers that are reactive with fluorinated ⁇ -olefin monomers.
• Fluorinated ⁇ -olefin monomers include CF 2 ⁇ CF 2 , CHF ⁇ CF 2 , CH 2 ⁇ CF 2 , CHCl ⁇ CHF, CCIF ⁇ CF 2 , CCl 2 ⁇ CF 2 , CCIF ⁇ CCIF, CHF ⁇ CCl 2 , CH 2 ⁇ CCIF, CCl 2 ⁇ CCIF, CF 3 CF ⁇ CF 2 , CF 3 CF ⁇ CHF, CF 3 CH ⁇ CF 2 , CHF 2 CH ⁇ CHF, CF 3 CF ⁇ CF 2 , and perfluoro ( alkyl having 2 to 8 carbon atoms)vinyl ethers (e.g., perfluoromethyl vinyl ether, perfluoropropyl vinyl ether, and perfluorooctyl vinyl ether ) .
• perfluoro ( alkyl having 2 to 8 carbon atoms)vinyl ethers e.g., perfluoromethyl vinyl ether, perfluoropropyl
• the fluorinated ⁇ -olefin monomer is preferably at least one monomer selected from the group consisting of tetrafluoroethylene (CF 2 ⁇ CF 2 ), chlorotrifluoroethylene (CCIF ⁇ CF 2 ), (perfluorobutyl)ethylene, vinylidene fluoride (CH 2 ⁇ CF 2 ), and hexafluoropropylene (CF 2 ⁇ CFCF 3 ).
• Non-fluorinated ethylenically unsaturated monomers include ethylene, propylene, butene, ethylenically unsaturated aromatic monomers (eg, styrene and ⁇ -methylstyrene), and the like.
• the fluorinated ⁇ -olefin monomers may be used alone or in combination of two or more kinds.
• the non-fluorinated ethylenically unsaturated monomers may be used alone or in combination of two or more kinds.
• fluororesins include polychlorotrifluoroethylene (PCTFE), poly(chlorotrifluoroethylene-propylene), poly(ethylene-tetrafluoroethylene) (ETFE), poly(ethylene-chlorotrifluoroethylene) (ECTFE), poly(hexafluoropropylene), poly(tetrafluoroethylene) (PTFE), poly(tetrafluoroethylene-ethylene-propylene), poly(tetrafluoroethylene-hexafluoropropylene) (FEP), poly(tetrafluoroethylene-propylene) (FEPM), poly(tetrafluoroethylene-perfluoropropylene vinyl ether), poly(tetrafluoroethylene-perfluoroalkyl vinyl ether) (PFA) (e.g., poly(tetrafluoroethylene-perfluoropropyl vinyl ether)), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), poly((
• the fluororesin may have a structural unit derived from fluorinated ethylene or fluorinated propylene.
• the fluororesin may be used alone or in combination of two or more kinds.
• the fluororesin is preferably FEP, PFA, ETFE, or PTFE.
• FEP is available from DuPont under the trade name TEFLON FEP, or from Daikin Industries, Ltd. under the trade name NEOFLON FEP.
• PFA is available from Daikin Industries, Ltd. under the trade name NEOFLON PFA, from DuPont under the trade name TEFLON PFA, or from Solvay Solexis under the trade name HYFLON PFA.
• the fluororesin contains PTFE.
• the PTFE may be a PTFE homopolymer, a partially modified PTFE homopolymer, or a combination containing one or both of these.
• the partially modified PTFE homopolymer preferably contains less than 1% by mass of structural units derived from comonomers other than tetrafluoroethylene, based on the total mass of the polymer.
• the fluororesin may be a crosslinkable fluoropolymer having a crosslinkable group.
• the crosslinkable fluoropolymer can be crosslinked by a conventionally known crosslinking method.
• One representative crosslinkable fluoropolymer is a fluoropolymer having (meth)acryloyloxy.
• R is an oligomer chain containing constitutional units derived from a fluorinated ⁇ -olefin monomer
• R′ is H or —CH3
• n is 1 to 4.
• R may also be a fluorine-based oligomer chain containing constitutional units derived from tetrafluoroethylene.
• a crosslinked fluoropolymer network can be formed by exposing a fluoropolymer having (meth)acryloyloxy groups to a free radical source to initiate a radical crosslinking reaction via the (meth)acryloyloxy groups on the fluororesin.
• the free radical source is not particularly limited, but a photoradical polymerization initiator or an organic peroxide are suitable. Suitable photoradical polymerization initiators and organic peroxides are well known in the art.
• Crosslinkable fluoropolymers are commercially available, for example, Viton B manufactured by DuPont.
• the polymer having a dielectric loss tangent of 0.01 or less may be a polymer of a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond.
• polymers of compounds having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond include thermoplastic resins having structural units derived from cyclic olefin monomers such as norbornene or polycyclic norbornene monomers.
• the polymer of a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be a ring-opening polymer of the above-mentioned cyclic olefin or a hydrogenated product of a ring-opening copolymer using two or more kinds of cyclic olefins, or may be an addition polymer of a cyclic olefin and an aromatic compound having an ethylenically unsaturated bond such as a chain olefin or a vinyl group.
• a polar group may be introduced into the polymer of a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond.
• the polymer of the compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be used alone or in combination of two or more types.
• the ring structure of the cyclic aliphatic hydrocarbon group may be a monocyclic ring, a condensed ring in which two or more rings are condensed, or a bridged ring.
• Examples of the ring structure of the cyclic aliphatic hydrocarbon group include a cyclopentane ring, a cyclohexane ring, a cyclooctane ring, an isoborone ring, a norbornane ring, and a dicyclopentane ring.
• the compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond is not particularly limited, and may be a (meth)acrylate compound having a cyclic aliphatic hydrocarbon group, a (meth)acrylamide compound having a cyclic aliphatic hydrocarbon group, or a vinyl compound having a cyclic aliphatic hydrocarbon group.
• a (meth)acrylate compound having a cyclic aliphatic hydrocarbon group is preferred.
• the compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be a monofunctional ethylenically unsaturated compound or a polyfunctional ethylenically unsaturated compound.
• the number of cycloaliphatic hydrocarbon groups in the compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be one or more, and may be two or more.
• the polymer of a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be a polymer obtained by polymerizing a compound having at least one type of cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, and may be a polymer of a compound having two or more types of cyclic aliphatic hydrocarbon groups and a group having an ethylenically unsaturated bond, or may be a copolymer with another ethylenically unsaturated compound that does not have a cyclic aliphatic hydrocarbon group.
• the polymer of a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond is preferably a cycloolefin polymer.
• the polymer having a dielectric loss tangent of 0.01 or less may be a polyphenylene ether.
• the polyphenylene ether preferably has an average number of phenolic hydroxyl groups at the molecular terminals per molecule (number of terminal hydroxyl groups) of 1 to 5, and more preferably 1.5 to 3, from the viewpoints of dielectric tangent and heat resistance.
• the number of terminal hydroxyl groups of polyphenylene ether can be known from, for example, the specification value of the polyphenylene ether product.
• the number of terminal hydroxyl groups is expressed, for example, as the average number of phenolic hydroxyl groups per molecule of all polyphenylene ethers present in 1 mole of polyphenylene ether.
• the polyphenylene ether may be used alone or in combination of two or more kinds.
• polyphenylene ethers examples include polyphenylene ethers made of 2,6-dimethylphenol and at least one of a difunctional phenol and a trifunctional phenol, and poly(2,6-dimethyl-1,4-phenylene oxide). More specifically, the polyphenylene ether is preferably a compound having a structure represented by the formula (PPE).
• X represents an alkylene group having 1 to 3 carbon atoms or a single bond
• m represents an integer of 0 to 20
• n represents an integer of 0 to 20
• the sum of m and n represents an integer of 1 to 30.
• the alkylene group for X may, for example, be a dimethylmethylene group.
• the weight average molecular weight (Mw) is preferably 500 to 5,000, and more preferably 500 to 3,000, from the viewpoints of heat resistance and film formability. If the polyphenylene ether is not thermally cured, the weight average molecular weight (Mw) is not particularly limited, but is preferably 3,000 to 100,000, and more preferably 5,000 to 50,000.
• Aromatic polyether ketone The polymer having a dielectric loss tangent of 0.01 or less may be an aromatic polyether ketone.
• the aromatic polyether ketone is not particularly limited, and any known aromatic polyether ketone can be used.
• the aromatic polyether ketone is preferably polyether ether ketone.
• Polyetheretherketone is a type of aromatic polyetherketone, and is a polymer in which bonds are arranged in the following order: ether bond, ether bond, and carbonyl bond. Each bond is preferably linked by a divalent aromatic group.
• the aromatic polyether ketones may be used alone or in combination of two or more kinds.
• aromatic polyetherketones examples include polyetheretherketone (PEEK) having a chemical structure represented by the following formula (P1), polyetherketone (PEK) having a chemical structure represented by the following formula (P2), polyetherketoneketone (PEKK) having a chemical structure represented by the following formula (P3), polyetheretherketoneketone (PEEKK) having a chemical structure represented by the following formula (P4), and polyetherketoneetherketoneketone (PEKEKK) having a chemical structure represented by the following formula (P5).
• n in each of formulas (P1) to (P5) is preferably 10 or more, and more preferably 20 or more.
• n is preferably 5,000 or less, and more preferably 1,000 or less. In other words, n is preferably 10 to 5,000, and more preferably 20 to 1,000.
• the content of the polymer having a dielectric tangent of 0.01 or less is preferably 0.1% by mass to 90% by mass, more preferably 1% by mass to 40% by mass, and even more preferably 3% by mass to 20% by mass, based on the total mass of the polymer composition.
• the content of the polymer having a dielectric tangent of 0.01 or less is preferably 1% by mass to 100% by mass, more preferably 5% by mass to 50% by mass, and even more preferably 10% by mass to 30% by mass, based on the total solid content of the polymer composition.
• the polymer composition according to the present disclosure may contain other additives in addition to the specific particles and the polymer having a dielectric loss tangent of 0.01.
• known additives can be used, such as a curing agent, a leveling agent, a defoaming agent, an antioxidant, an ultraviolet absorbing agent, a flame retardant, a colorant, etc.
• the polymer film precursor according to the present disclosure includes particles (specific particles) having a ratio of average particle diameter D90 to average particle diameter D50 of 2.3 or less, and a polymer having a dielectric loss tangent of 0.01 or less.
• the distribution width of the elastic modulus in the polymer film will be narrow. In particular, it is possible to suppress localized reductions in surface pressure during lamination press processing, resulting in excellent step-following properties.
• the preferred aspects of the specific particles contained in the polymer film precursor of the present disclosure and the polymer having a dielectric tangent of 0.01 or less are the same as the preferred aspects of the specific particles contained in the polymer composition of the present disclosure and the polymer having a dielectric tangent of 0.01 or less.
• the polymer film precursor according to the present disclosure may contain other additives in addition to the specific particles and the polymer having a dielectric tangent of 0.01 or less.
• Other additives include the same as other additives that may be included in the polymer compositions of the present disclosure.
• the average thickness of the polymer film precursor according to the present disclosure is not particularly limited, but from the viewpoints of dielectric tangent and step conformability, it is preferably 5 ⁇ m to 90 ⁇ m, more preferably 10 ⁇ m to 70 ⁇ m, and particularly preferably 15 ⁇ m to 50 ⁇ m.
• the average thickness of the polymer film precursor is determined by measuring any five points using an adhesive thickness meter, for example, an electronic micrometer (product name "KG3001A", manufactured by Anritsu Corporation), and averaging these measurements.
• phase-separated structure containing at least two phases, and has a distribution width of the elastic modulus at 160° C. of less than 100 MPa.
• phase-separated structure refers to a structure in which at least two parts containing different components are present in a polymer film.
• phase separation structures include a sea-island structure, a cocontinuous structure, a cylindrical structure, and a lamellar structure.
• the phase separation structure in the polymer film according to the present disclosure is preferably a sea-island structure.
• the sea-island structure refers to a structure in which one of at least two phases forms a continuous phase and the other phase exists discontinuously dispersed.
• phase-separated structure can be confirmed by using means such as morphological observation, material distribution evaluation, mechanical property distribution evaluation, etc., for the surface of the polymer film, the cross section of the polymer film, or both the surface and cross section of the polymer film.
• morphological observation is carried out using a known optical microscope.
• the observation is carried out using an electron microscope or the like.
• the material distribution evaluation is performed using infrared spectroscopy imaging.
• Raman spectroscopy imaging is used. If Raman spectroscopy imaging is not possible, X-ray photoelectron spectroscopy imaging is used. The mechanical property distribution is evaluated using an atomic force microscope or the like.
• the polymer film according to the present disclosure can be produced, for example, by heating the polymer film precursor according to the present disclosure.
• the polymer film precursor according to the present disclosure is positioned as a precursor of the polymer film according to the present disclosure.
• the first phase which is one of the at least two phases, preferably contains a polymer having a dielectric loss tangent of 0.01 or less.
• a preferred embodiment of the polymer having a dielectric loss tangent of 0.01 or less is the same as a preferred embodiment of the polymer having a dielectric loss tangent of 0.01 or less contained in the polymer composition according to the present disclosure.
• the second phase which is one of the at least two phases, preferably comprises a thermoplastic elastomer.
• a thermoplastic elastomer Preferred aspects of the thermoplastic elastomer are the same as the preferred aspects of the thermoplastic elastomer that may be included in the polymer composition according to the present disclosure.
• thermoplastic elastomer is preferably present in particulate form. Whether or not it is present in particulate form can be determined by observing a cross section of the polymer film with a scanning electron microscope (SEM).
• SEM scanning electron microscope
• the polymer film according to the present disclosure has a distribution width of the elastic modulus at 160° C. of less than 100 MPa.
• the polymer film according to the present disclosure has an elastic modulus distribution width at 160° C. of less than 100 MPa, and therefore has excellent step-following ability.
• the distribution width of the elastic modulus at 160° C. is measured by the following method. Observe in VE-AFM mode using a scanning probe microscope (product name "SPA400", manufactured by SII NanoTechnology, Inc.) and determine the average value of the storage modulus in a 15 ⁇ m square area at 160° C. The average value of the storage modulus is determined at each of five arbitrary locations within the polymer film plane, and the difference between the maximum value and the minimum value is defined as the distribution width of the elastic modulus.
• the distribution width of the elastic modulus at 160°C is preferably 10 MPa or less, more preferably 3 MPa or less, and even more preferably 1 MPa or less.
• the lower limit of the distribution width of the elastic modulus at 160°C is not particularly limited, and may be 0 MPa.
• the dielectric tangent of the polymer film according to the present disclosure is preferably 0.01 or less, more preferably 0.005 or less, and even more preferably greater than 0 and 0.003 or less.
• the polymer film according to the present disclosure preferably has a mass retention rate of 20% or more at 440°C, and more preferably 30% or more.
• the upper limit of the mass retention rate at 440°C is not particularly limited, and is, for example, 100%.
• the polymer film according to the present disclosure preferably has a viscosity of 1,000 Pa ⁇ s or more at 260°C.
• the film has excellent mechanical strength.
• a laminate having a configuration in which a layer with low gas permeability such as a metal foil is adjacent when the laminate is heated rapidly, outgas generated from inside the film remains near the film surface, causing the film material to flow and foaming near the film surface, which causes delamination. Therefore, if the viscosity of the film at high temperatures is increased, delamination is less likely to occur in a high-temperature environment. That is, the film has excellent heat resistance.
• the ratio of the average particle diameter D90 to the average particle diameter D50 is appropriately controlled, and the phase separation structure of the formed polymer film is appropriately controlled, which is effective in achieving the above-mentioned preferred viscosity and reducing the thickness of the low-viscosity region.
• the viscosity of the polymer film at 260° C. is more preferably 3,000 Pa ⁇ s or more.
• the upper limit of the viscosity is not particularly limited, but is, for example, 1,000,000 Pa ⁇ s.
• the viscosity of a polymer film at 260° C. is measured by the following method. A 1 ⁇ m thick layer is scraped off from the surface of the polymer film with a razor, and the viscosity of the surface is measured at 260° C. using a rheometer equipped with a heating unit (eg, HAAKE MARS, manufactured by Thermo Fisher Scientific Co., Ltd.).
• the polymer film may have at least one surface having a viscosity of 1,000 Pa ⁇ s or more at 260° C.
• the average thickness of the polymer film according to the present disclosure is not particularly limited, but from the viewpoints of dielectric tangent and step conformability, it is preferably 5 ⁇ m to 90 ⁇ m, more preferably 10 ⁇ m to 70 ⁇ m, and particularly preferably 15 ⁇ m to 50 ⁇ m.
• the average thickness of the polymer film is determined by measuring any five points using an adhesive film thickness meter, for example, an electronic micrometer (product name "KG3001A", manufactured by Anritsu Corporation), and averaging these values.
• the laminate precursor according to the present disclosure includes a layer A and a layer B disposed on at least one surface of the layer A, and the layer B includes particles having a ratio of an average particle size D90 to an average particle size D50 of 2.3 or less, and a polymer having a dielectric loss tangent of 0.01 or less.
• Layer B will function as a step-following layer.
• the laminate precursor according to the present disclosure has a layer A on which a layer B described below is provided. From the viewpoint of making the dielectric loss tangent of the laminate 0.01 or less, the layer A preferably contains a polymer having a dielectric loss tangent of 0.01 or less.
• Layer A may contain only one type of polymer having a dielectric tangent of 0.01 or less, or may contain two or more types. Preferred aspects of the polymer having a dielectric tangent of 0.01 or less that may be contained in layer A are similar to preferred aspects of the polymer having a dielectric tangent of 0.01 or less that is contained in the polymer composition according to the present disclosure.
• the content of the polymer having a dielectric tangent of 0.01 or less is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 20% by mass to 100% by mass, relative to the total mass of Layer A.
• Layer A may contain a filler in addition to the polymer having a dielectric tangent of 0.01 or less.
• the filler may be particulate, fibrous, inorganic, or organic.
• organic filler a known organic filler can be used.
• the organic filler material include polyethylene, polystyrene, urea-formalin filler, polyester, cellulose, acrylic resin, fluororesin, hardened epoxy resin, crosslinked benzoguanamine resin, crosslinked acrylic resin, liquid crystal polymer, and materials containing two or more of these.
• the organic filler may also be in the form of fibers such as nanofibers, or may be hollow resin particles.
• the organic filler is preferably fluororesin particles, polyester resin particles, polyethylene particles, liquid crystal polymer particles, or nanofibers of cellulose resin, more preferably polytetrafluoroethylene particles, polyethylene particles, or liquid crystal polymer particles, and particularly preferably liquid crystal polymer particles.
• the liquid crystal polymer particles are not limited, but refer to liquid crystal polymer particles obtained by polymerizing liquid crystal polymer and pulverizing it with a pulverizer or the like to obtain powdered liquid crystal.
• the liquid crystal polymer particles are preferably smaller than the thickness of each layer.
• a preferred embodiment of the liquid crystal polymer constituting the liquid crystal polymer particles is the same as a preferred embodiment of the liquid crystal polymer that can be contained in the polymer composition according to the present disclosure.
• the average particle size of the organic filler is preferably 5 nm to 20 ⁇ m, and more preferably 100 nm to 10 ⁇ m, from the viewpoint of dielectric tangent and step conformability.
• the inorganic filler a known inorganic filler can be used.
• the inorganic filler material include BN, Al2O3 , AlN, TiO2 , SiO2 , barium titanate , strontium titanate, aluminum hydroxide, calcium carbonate, and materials containing two or more of these.
• metal oxide particles or fibers are preferred, silica particles, titania particles, or glass fibers are more preferred, and silica particles or glass fibers are particularly preferred.
• the average particle size of the inorganic filler is preferably about 20% to about 40% of the thickness of the film, and may be, for example, 25%, 30%, or 35% of the thickness of the film.
• the length indicates the length in the short side direction.
• the average particle size of the inorganic filler is preferably 5 nm to 20 ⁇ m, more preferably 10 nm to 10 ⁇ m, even more preferably 20 nm to 1 ⁇ m, and particularly preferably 25 nm to 500 nm.
• the filler contained in layer A is preferably an organic filler, and more preferably liquid crystal polymer particles.
• Layer A may contain only one type of filler, or may contain two or more types of fillers.
• the content of the filler is preferably 30% by mass to 90% by mass, more preferably 50% by mass to 85% by mass, and even more preferably 60% by mass to 80% by mass, relative to the total mass of Layer A, from the viewpoints of the dielectric tangent and the step-following ability.
• Layer A may contain additives other than the above-mentioned components. Preferred aspects of other additives that may be included in Layer A are the same as preferred aspects of other additives that may be included in the polymer composition according to the present disclosure.
• the layer A may contain, as other additives, resins other than the polymer having a dielectric loss tangent of 0.01 or less.
• resins other than polymers having a dielectric tangent of 0.01 or less include thermoplastic resins other than liquid crystal polyesters, such as polypropylene, polyamide, polyesters other than liquid crystal polyesters, polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone, polyphenylene ether and modified products thereof, and polyether imide; elastomers such as copolymers of glycidyl methacrylate and polyethylene; and thermosetting resins such as phenol resins, epoxy resins, polyimide resins, and cyanate resins.
• the total content of other additives in Layer A is preferably 25 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, per 100 parts by mass of the polymer having a dielectric tangent of 0.01 or less.
• the average thickness of layer A is not particularly limited, but from the viewpoint of the dielectric tangent of the laminate and its ability to conform to unevenness, it is preferably 5 ⁇ m to 90 ⁇ m, more preferably 10 ⁇ m to 70 ⁇ m, and particularly preferably 15 ⁇ m to 50 ⁇ m.
• the method for measuring the average thickness of each layer in the laminate according to the present disclosure is as follows.
• the laminate is cut on a plane perpendicular to the surface direction of the laminate, the thickness is measured at five or more points on the cross section, and the average of these measurements is taken as the average thickness.
• the laminate precursor according to the present disclosure has a layer B on at least one surface of the layer A.
• the layer B contains specific particles and a polymer having a dielectric loss tangent of 0.01 or less.
• the preferred aspects of the specific particles contained in the laminate precursor according to the present disclosure and the polymer having a dielectric tangent of 0.01 or less are the same as the preferred aspects of the specific particles contained in the polymer composition according to the present disclosure and the polymer having a dielectric tangent of 0.01 or less.
• the polymer film precursor according to the present disclosure may contain other additives in addition to the specific particles and the polymer having a dielectric loss tangent of 0.01.
• Other additives include the same as other additives that may be included in the polymer compositions of the present disclosure.
• the average thickness of layer B is preferably 5 ⁇ m to 50 ⁇ m, more preferably 10 ⁇ m to 40 ⁇ m, and even more preferably 15 ⁇ m to 30 ⁇ m.
• the laminate precursor according to the present disclosure preferably further comprises layer C in addition to layer A and layer B, and more preferably comprises layer B, layer A, and layer C in this order.
• Layer C is preferably an adhesive layer, i.e., Layer C is preferably a surface layer (outermost layer).
• layer C contains at least one type of polymer.
• the preferred embodiment of the polymer used in layer C is the same as the preferred embodiment of the polymer used in layer A having a dielectric tangent of 0.01 or less.
• the polymer contained in layer C may be the same as or different from the polymer contained in layer A or layer B, but from the viewpoint of adhesion between layer A and layer C, it is preferable that the polymer is the same as the polymer contained in layer A.
• layer C contains an epoxy resin to bond the metal layer to layer A.
• the epoxy resin is preferably a crosslinked product of a multifunctional epoxy compound.
• a multifunctional epoxy compound is a compound having two or more epoxy groups.
• the number of epoxy groups in a multifunctional epoxy compound is preferably 2 to 4.
• layer C contains an aromatic polyester amide and an epoxy resin.
• the layer C may contain a filler.
• the preferred embodiments of the filler used in Layer C are the same as those of the filler used in Layer A.
• Layer C may contain additives other than those mentioned above. Preferred embodiments of the other additives used in Layer C are the same as those of the other additives used in Layer A, except as described below.
• the average thickness of layer C is preferably thinner than the average thickness of layer A from the viewpoints of the dielectric tangent of the laminate and adhesion to metals.
• T A /T C which is the ratio of the average thickness T A of Layer A to the average thickness T C of Layer C, is preferably greater than 1, more preferably from 2 to 100, even more preferably from 2.5 to 20, and particularly preferably from 3 to 10, from the viewpoints of the dielectric tangent of the laminate and the adhesion to the metal layer.
• T B /T C which is the ratio of the average thickness T B of Layer B to the average thickness T C of Layer C, is preferably greater than 1, more preferably from 2 to 100, even more preferably from 2.5 to 20, and particularly preferably from 3 to 10, from the viewpoints of the dielectric tangent of the laminate and the adhesion to the metal layer.
• the average thickness of layer C is preferably 0.1 ⁇ m to 20 ⁇ m, more preferably 0.5 ⁇ m to 15 ⁇ m, even more preferably 1 ⁇ m to 10 ⁇ m, and particularly preferably 2 ⁇ m to 8 ⁇ m.
• the average thickness of the laminate precursor according to the present disclosure is preferably 6 ⁇ m to 200 ⁇ m, more preferably 12 ⁇ m to 100 ⁇ m, and particularly preferably 20 ⁇ m to 80 ⁇ m, from the viewpoints of strength and electrical properties (characteristic impedance) when laminated with a metal layer.
• the average thickness of the laminate precursor is measured at any five points using an adhesive thickness gauge, such as an electronic micrometer (product name "KG3001A", manufactured by Anritsu Corporation), and the average thickness is calculated.
• an adhesive thickness gauge such as an electronic micrometer (product name "KG3001A”, manufactured by Anritsu Corporation)
• the laminate precursor according to the present disclosure preferably has a dielectric tangent of 0.01 or less, more preferably 0.005 or less, and even more preferably greater than 0 and 0.003 or less.
• the laminate according to the present disclosure includes a layer A and a layer B disposed on at least one surface of the layer A, and the layer B has a phase-separated structure including at least two phases and has a distribution width of elastic modulus of less than 100 MPa.
• the laminate according to the present disclosure can be produced, for example, by heating the laminate precursor according to the present disclosure. That is, the laminate precursor according to the present disclosure is considered as a precursor of the laminate according to the present disclosure.
• ⁇ Layer A> A preferred embodiment of the layer A in the laminate according to the present disclosure is the same as the preferred embodiment of the layer A in the laminate precursor according to the present disclosure.
• the laminate according to the present disclosure has a layer B on at least one surface of the layer A.
• the layer B is preferably a surface layer (outermost layer).
• the layer B has a phase-separated structure including at least two phases, and has a distribution width of the elastic modulus of less than 100 MPa.
• the preferred embodiment of Layer B in the laminate according to the present disclosure is the same as the preferred embodiment of the polymer film according to the present disclosure.
• the laminate according to the present disclosure preferably has a mass retention rate of 30% or more at 440°C, and more preferably 50% or more.
• the upper limit of the mass retention rate at 440°C is not particularly limited, and is, for example, 100%.
• Method for producing the laminate according to the present disclosure is not particularly limited, and known methods can be referred to.
• Suitable film-forming methods include, for example, co-casting, multi-layer coating, and co-extrusion. Among these, the co-casting method is preferred.
• the multilayer structure of the laminate is produced by the co-casting method or the multi-layer coating method
• Solvents include, for example, halogenated hydrocarbons such as dichloromethane, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, 1-chlorobutane, chlorobenzene, and o-dichlorobenzene; halogenated phenols such as p-chlorophenol, pentachlorophenol, and pentafluorophenol; ethers such as diethyl ether, tetrahydrofuran, and 1,4-dioxane; ketones such as acetone and cyclohexanone; esters such as ethyl acetate and ⁇ -butyrolactone; and ethylene carbonate.
• halogenated hydrocarbons such as dichloromethane, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, 1-
• organic solvent examples include carbonates such as propylene carbonate and propylene carbonate; amines such as triethylamine; nitrogen-containing heterocyclic aromatic compounds such as pyridine; nitriles such as acetonitrile and succinonitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, and urea compounds such as tetramethylurea; nitro compounds such as nitromethane and nitrobenzene; sulfur compounds such as dimethyl sulfoxide and sulfolane; and phosphorus compounds such as hexamethylphosphoramide and tri-n-butylphosphoric acid, and two or more of these may be used.
• carbonates such as propylene carbonate and propylene carbonate
• amines such as triethylamine
• nitrogen-containing heterocyclic aromatic compounds such as pyridine
• nitriles such as acetonitrile and succinon
• the solvent is preferably a solvent mainly composed of an aprotic compound, particularly an aprotic compound without halogen atoms, because it is less corrosive and easier to handle, and the ratio of the aprotic compound to the entire solvent is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass.
• amides such as N,N-dimethylformamide, N,N-dimethylacetamide, tetramethylurea, and N-methylpyrrolidone, or esters such as ⁇ -butyrolactone, because they easily dissolve liquid crystal polymers, and N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone are more preferable.
• a solvent mainly composed of a compound having a dipole moment of 3 to 5 is preferred because it easily dissolves the liquid crystal polymer, and the proportion of the compound having a dipole moment of 3 to 5 in the entire solvent is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass.
• the aprotic compound it is preferable to use a compound having a dipole moment of 3 to 5.
• the solvent is preferably a solvent mainly composed of a compound having a boiling point of 220° C. or lower at 1 atmospheric pressure, because it is easy to remove.
• the proportion of the compound having a boiling point of 220° C. or lower at 1 atmospheric pressure in the entire solvent is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass.
• the aprotic compound it is preferable to use a compound having a boiling point of 220° C. or lower at 1 atmospheric pressure.
• a support may be used when the laminate is produced by the above-mentioned co-casting method, multi-layer coating method, co-extrusion method, or the like.
• the support include a metal drum, a metal band, a glass plate, a resin film, and a metal foil.
• the support is preferably a metal drum, a metal band, or a resin film.
• resin films include polyimide (PI) films, and examples of commercially available products include U-PIREX S and U-PIREX R manufactured by Ube Industries, Ltd., Kapton manufactured by DuPont-Toray Co., Ltd., and IF30, IF70, and LV300 manufactured by SKC Kolon PI.
• the support may have a surface treatment layer formed on its surface so that it can be easily peeled off.
• the surface treatment layer may be made of hard chrome plating, fluororesin, or the like.
• the average thickness of the support is not particularly limited, but is preferably from 25 to 75 ⁇ m, and more preferably from 50 to 75 ⁇ m.
• the method for removing at least a portion of the solvent from the cast or applied film-like composition (coating film) is not particularly limited, and any known drying method can be used.
• the laminate according to the present disclosure can be appropriately combined with stretching in terms of controlling molecular orientation and adjusting the thermal expansion coefficient and mechanical properties.
• the stretching method is not particularly limited, and known methods can be referred to. It may be performed in a state containing a solvent or in a dry film state. Stretching in a state containing a solvent may be performed by gripping the laminate and stretching it, or it may be performed by utilizing autogenous shrinkage due to drying without stretching it. Stretching is particularly effective for the purpose of improving the breaking elongation and breaking strength when the film brittleness is reduced by the addition of inorganic fillers, etc.
• the laminate according to the present disclosure can be used for various applications, and is particularly suitable for use as a film for electronic components such as printed wiring boards, and more particularly suitable for use as a flexible printed circuit board. Moreover, the laminate according to the present disclosure can be suitably used as a liquid crystal polymer film for metal bonding.
• the aromatic polyesteramide P1a was heated from room temperature to 160°C over 2 hours and 20 minutes in a nitrogen atmosphere, then heated from 160°C to 180°C over 3 hours and 20 minutes, and held at 180°C for 5 hours to carry out solid-state polymerization, and then cooled.
• the aromatic polyesteramide P1a was then pulverized in a pulverizer to obtain a powdered aromatic polyesteramide A1b.
• the flow-initiation temperature of the aromatic polyesteramide P1b was 220°C.
• the aromatic polyester amide P1b was heated in a nitrogen atmosphere from room temperature to 180°C over 1 hour 25 minutes, then heated from 180°C to 255°C over 6 hours 40 minutes, and held at 255°C for 5 hours to carry out solid-state polymerization, and then cooled to obtain a powdered aromatic polyester amide P1.
• the flow initiation temperature of the aromatic polyesteramide P1 was 302°C.
• the melting point of the aromatic polyesteramide P1 was measured using a differential scanning calorimeter and found to be 311°C.
• the dielectric tangent of the aromatic polyesteramide P1 was 0.003.
• the solubility of the aromatic polyesteramide P1 in N-methylpyrrolidone at 140°C was 1% by mass or more.
• the mass residual rate of the aromatic polyesteramide P1 at 440°C was 93%.
• F1 Particles of styrene-isobutylene-styrene block copolymer (thermoplastic elastomer) prepared according to the following production method, elastic modulus at 160°C: 1.1 MPa
• F2 Particles of styrene-ethylene-butylene-styrene block copolymer (thermoplastic elastomer) produced according to the following production method, elastic modulus at 160°C: 0.16 MPa
• F3 Particles of styrene-ethylene-butylene-styrene block copolymer (thermoplastic elastomer) produced according to the following production method, elastic modulus at 160°C: 0.16 MPa
• SEBS product name "Tuftec M1913", manufactured by Asahi Kasei Chemicals Corporation
• the average particle size D50 and average particle size D90 of the particles F1 to F3 produced were measured using a laser diffraction/scattering type particle size distribution measuring device (product name "LA-950V2", manufactured by HORIBA).
• the average particle size D90 relative to the average particle size D50 (“D90/D50") and the average particle size D90 are shown in Table 1.
• PP-1 Liquid crystal polymer particles prepared according to the following manufacturing method
• acetic anhydride (1.08 molar equivalent relative to the hydroxyl group) was further added. Under a nitrogen gas stream, the temperature was raised from room temperature to 150°C over 15 minutes while stirring, and refluxed at 150°C for 2 hours. Next, while distilling off the by-produced acetic acid and unreacted acetic anhydride, the temperature was raised from 150°C to 310°C over 5 hours, and the polymer was taken out and cooled to room temperature. The obtained polymer was raised from room temperature to 295°C over 14 hours, and solid-phase polymerized at 295°C for 1 hour.
• liquid crystal polymer particles PP-1 After the solid-phase polymerization, the mixture was cooled to room temperature over 5 hours to obtain liquid crystal polymer particles PP-1.
• the liquid crystal polymer particles PP-1 had a median diameter (D50) of 7 ⁇ m, a dielectric dissipation factor of 0.0007, and a melting point of 334°C.
• the liquid crystal polymer particles PP-1 had a mass residual rate of 93% at 440°C.
• a solution for forming layer A a solution for forming layer B, and a solution for forming layer C were prepared.
• the polymer film was prepared using the solution for forming layer B.
• Example 1 In Examples 1 to 6, 8 to 9, and Comparative Example 1, a laminate precursor and a laminate were produced. In Example 7, a polymer film precursor and a polymer film were produced.
• a heat treatment was performed by holding at 300° C. for 2 hours, and a polymer film having a copper layer was obtained.
• the obtained solution for forming layer B was sent to a slot die coater equipped with a slide coater.
• the solution for forming layer B was applied to the obtained polymer film having a copper layer by adjusting the flow rate to the film thickness shown in Table 1.
• the solvent was removed from the coating film by drying at 40°C for 4 hours.
• a laminate precursor single-sided copper-clad multilayer film precursor having a copper layer, layer C, layer A, and layer B in this order was obtained.
• the obtained single-sided copper-clad monolayer film precursor was heated from room temperature (25° C.) to 230° C. at a rate of 1° C./min under a nitrogen atmosphere. A heat treatment was performed by holding at 230° C. for 2 hours to obtain a single-sided copper-clad monolayer film.
• the obtained single-sided copper-clad monolayer film contained a phase derived from the polymer and a phase derived from the particles, and had a sea-island structure (phase-separated structure).
• the viscosity of Layer B in Examples 1 to 6 and 8 and Comparative Example 1 at 260° C. was 140,000 Pa ⁇ s.
• the viscosity of Layer A of Examples 1 to 6 and 8 at 260° C. was 760,000 Pa ⁇ s.
• the viscosity of Layer A of Comparative Example 1 at 260° C. was 820 Pa ⁇ s.
• the viscosity of the polymer film of Example 7 at 260° C. was 760,000 Pa ⁇ s.
• thermocompression bonding machine product name "MP-SNL", manufactured by Toyo Seiki Seisakusho Co., Ltd.
• MP-SNL manufactured by Toyo Seiki Seisakusho Co., Ltd.
• the copper foils on both sides of the double-sided copper-clad laminate were etched and patterned to produce a substrate with a wiring pattern including a ground line and three pairs of signal lines on both sides of the substrate.
• the signal lines were 100 mm long, and three types of line and space (L/S) were produced: 5 ⁇ m/5 ⁇ m, 20 ⁇ m/20 ⁇ m, and 50 ⁇ m/50 ⁇ m.
• the above substrate with wiring pattern and a pair of the above single-sided copper-clad multilayer films were stacked so that layer B of the single-sided copper-clad multilayer film was in contact with the wiring pattern of the substrate with wiring pattern, forming a single-sided copper-clad multilayer film/substrate with wiring pattern/single-sided copper-clad multilayer film.
• a vacuum press was used to perform heat pressing for 1 hour at 300°C and 4 MPa to obtain a wiring board.
• Example 7 a flexible wiring board having a four-layer strip line structure with an outer layer plane (ground layer) was produced using a single-sided copper-clad monolayer film.
• the above substrate with wiring pattern and a pair of the above single-sided copper-clad single layer films were stacked together so that the film side of the single-sided copper-clad single layer film was in contact with the wiring pattern of the substrate with wiring pattern, forming a single-sided copper-clad single layer film/substrate with wiring pattern/single-sided copper-clad single layer film.
• a vacuum press was used to perform heat pressing for 1 hour at 300°C and 4 MPa to obtain a wiring board.
• the average storage modulus was calculated at any five locations on the layer B surface of the single-sided copper-clad multilayer film, and the difference between the maximum and minimum values was defined as the distribution width of the elastic modulus.
• Example 7 the average value of the storage elastic modulus was determined at any five locations within the film plane of the single-sided copper-clad monolayer film, and the difference between the maximum and minimum values was defined as the distribution width of the elastic modulus.
• Example 7 [Mass Residual Rate at 440° C.]
• the measurement samples were taken from layer B of the single-sided copper-clad multilayer film. Also, the measurement samples were taken from the film of the single-sided copper-clad multilayer film.
• Example 7 a measurement sample was taken from a single-sided copper-clad monolayer film. 5 mg of the measurement sample was added to a platinum pan, and measured using a differential thermal balance (TG-DTA) (TG-8120, manufactured by Rigaku Corporation) at a measurement temperature of 25 to 900°C and a heating rate of 10°C/min. The mass (%) at 900°C was subtracted from the mass (%) at 440°C.
• TG-DTA differential thermal balance
• the dielectric loss tangent was measured using a film obtained by removing the copper foil from each of the single-sided copper-clad monolayer film and the single-sided copper-clad multilayer film with an aqueous solution of ferric chloride, washing with pure water, and drying.
• the dielectric loss tangent was measured at a frequency of 10 GHz by a resonance perturbation method.
• a 10 GHz cavity resonator (Kanto Electronics Application Development Co., Ltd., "CP531") was connected to a network analyzer (Agilent Technology, Inc., "E8363B"), and a measurement sample was inserted into the cavity resonator.
• the dielectric loss tangent of the measurement sample was measured from the change in resonance frequency before and after insertion for 96 hours under an environment of 25°C temperature and 60% RH.
• Examples 1 to 6, 8 to 9, and Comparative Example 1 a copper foil (product name "CF-T9DA-SV-18", average thickness 18 ⁇ m, manufactured by Fukuda Metal Foil and Powder Co., Ltd.) was laminated so that the treated surface of the foil was in contact with the layer B side of the prepared single-sided copper-clad multilayer film.
• a laminator product name "Vacuum Laminator V-130", manufactured by Nikko Materials Co., Ltd.
• Example 7 a copper foil (product name "CF-T9DA-SV-18", average thickness 18 ⁇ m, manufactured by Fukuda Metal Foil and Powder Co., Ltd.) was laminated on the film side of the prepared single-sided copper-clad monolayer film so that the treated surface of the foil was in contact with the film side.
• a laminator product name "Vacuum Laminator V-130", manufactured by Nikko Materials Co., Ltd.
• Through-hole via processing was performed using a laser processing machine (UV-YAG laser Model 5330 manufactured by ESI Corporation). The via portion was cut with a microtome, and the cross section was observed under an optical microscope to measure the length of the scraped portion of the polymer film (i.e., the maximum horizontal length of the depression formed on the horizontal cut surface of the cut portion).
• Example 1 As shown in Table 1, in Examples 1 to 9, a polymer composition containing particles having a ratio of average particle diameter D90 to average particle diameter D50 of 2.3 or less and a polymer having a dielectric tangent of 0.01 or less was used, and therefore it was found that the step-following ability was excellent. On the other hand, in Comparative Example 1, no particles having a ratio of average particle diameter D90 to average particle diameter D50 of 2.3 or less were contained, and it was found that the step-following ability was poor. In addition, when the step conformability was evaluated using a wiring pattern base material in which the width of the wiring pattern was set to 100 ⁇ m and a wiring board, no gaps were observed around the wiring pattern in any of Examples 1 to 9 and Comparative Example 1.
• examples 1 to 9 were found to have excellent heat resistance.

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