Classifications

• • 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
• • 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
• • 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
• • 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
  • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
  • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
• • 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
  • C08G63/78—Preparation processes
  • C08G63/80—Solid-state polycondensation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/38—Boron-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • 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
  • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
• • 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
  • C08L53/005—Modified block copolymers
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/12—Polyester-amides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K19/38—Polymers
  • C09K19/3804—Polymers with mesogenic groups in the main chain
  • C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
• • 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
• • 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
  • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
  • C08J2377/12—Polyester-amides
• • 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
  • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/38—Boron-containing compounds
  • C08K2003/382—Boron-containing compounds and nitrogen
  • C08K2003/385—Binary compounds of nitrogen with boron
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
• • 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
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
  • C09K2219/03—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used in the form of films, e.g. films after polymerisation of LC precursor

Definitions

• This disclosure relates to polymer films, laminates and metal laminates.
• Copper-clad laminates are preferably used as components for circuit boards, and polymer films are preferably used to manufacture copper-clad laminates.
• JP 2022-126429 A describes a polymer film having a layer A and a layer B provided on at least one surface of the layer A, in which the layer A contains a polymer having a dielectric tangent of 0.01 or less, and the layer B has a moisture permeability of 100 g/( m2 ⁇ day) or less at a temperature of 40° C. and a relative humidity of 90%.
• 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.
• a polymer film having excellent step conformability to a wiring substrate is used for a copper-clad laminate, delamination may occur during the reflow soldering process performed when mounting electronic components. For this reason, there has been a demand for a material that has both step conformability to a wiring substrate and excellent adhesion during reflow soldering (i.e., excellent heat resistance).
• An object of one embodiment of the present disclosure is to provide a polymer film that is excellent in step conformability and heat resistance.
• Another problem to be solved by another embodiment of the present disclosure is to provide a laminate and a laminate with metal that are excellent in step conformability and heat resistance.
• Means for solving the above problems include the following aspects.
• ⁇ 1> Contains a polymer, has an elastic modulus of 10 MPa or less at 160°C, The elastic modulus at 260°C is 0.1 MPa or more, The equilibrium moisture absorption rate at 85° C. and a relative humidity of 85% is 2.5% by mass or less; The dielectric tangent is 0.01 or less.
• ⁇ 2> The polymer film according to ⁇ 1> above, wherein the polymer comprises a liquid crystal polymer.
• ⁇ 3> The polymer film according to ⁇ 1> or ⁇ 2> above, wherein the polymer comprises an aromatic polyester amide.
• ⁇ 4> The polymer film according to any one of ⁇ 1> to ⁇ 3> above, comprising a thermoplastic resin containing a structural unit based on a monomer having an aromatic hydrocarbon group.
• ⁇ 5> A curing agent, or at least one of the cured product of the curing agent and the thermoplastic resin, The polymer film according to the above item ⁇ 4>, wherein the curing agent has at least one of an epoxy group and a maleimide group.
• ⁇ 6> The polymer film according to any one of ⁇ 1> to ⁇ 5> above, further comprising at least one inorganic filler selected from the group consisting of silica, aluminum hydroxide, and boron nitride.
• the layer B contains a polymer and has an elastic modulus of 10 MPa or less at 160° C. and an elastic modulus of 0.1 MPa or more at 260° C.;
• the laminate has an equilibrium moisture absorption rate of 2.5% by mass or less at 85° C. and a relative humidity of 85%, and a dielectric loss tangent of 0.01 or less.
• ⁇ 8> The laminate according to ⁇ 7> above, wherein a ratio of the elastic modulus of the Layer A at 160°C to the elastic modulus of the Layer B at 160°C is 50 or more.
• ⁇ 9> The laminate according to the above ⁇ 7> or ⁇ 8>, wherein the polymer comprises a liquid crystal polymer.
• the polymer comprises an aromatic polyesteramide.
• ⁇ 11> The laminate according to any one of the above ⁇ 7> to ⁇ 10>, comprising a thermoplastic resin containing a structural unit based on a monomer having an aromatic hydrocarbon group.
• ⁇ 12> A composition comprising at least one of a curing agent and a cured product of the curing agent and the thermoplastic resin, The laminate according to the above-mentioned ⁇ 11>, wherein the curing agent has at least one of an epoxy group and a maleimide group.
• the laminate further comprises a Layer C, The laminate according to any one of ⁇ 7> to ⁇ 13> above, comprising the Layer B, the Layer A, and the Layer C in this order.
• a metal-attached laminate comprising the polymer film according to any one of the above ⁇ 1> to ⁇ 6> or the laminate according to any one of the above ⁇ 7> to ⁇ 14>, and a metal layer or metal wiring disposed on at least one surface of the polymer film or the laminate.
• ⁇ 16> The metal-attached laminate according to ⁇ 15> above, wherein a peel strength between the polymer film or the laminate and the metal layer or the metal wiring at 260° C. is 0.02 kN/m or more.
• a polymer film having excellent step conformability and heat resistance can be provided. Furthermore, according to another embodiment of the present disclosure, it is possible to provide a laminate and a laminate with metal that are excellent in step conformability and heat resistance.
• 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 substituents (unsubstituted alkyl groups) but also an alkyl group that has a substituent (substituted alkyl groups).
• 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.
• the weight average molecular weight (Mw) and number average molecular weight (Mn) in the present disclosure are molecular weights detected by a gel permeation chromatography (GPC) analyzer using columns of TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all product names manufactured by Tosoh Corporation) in a differential refractometer using THF (tetrahydrofuran) as a solvent, and converted using polystyrene as a standard substance.
• a "polymer” is a compound having a weight average molecular weight of 3000 or more and a glass transition temperature of higher than 25°C.
• an "elastomer” is a compound having a weight average molecular weight of 3000 or more and a glass transition temperature of 25° C. or less.
• the glass transition temperature is measured by differential scanning calorimetry (DSC).
• DSC differential scanning calorimetry
• the glass transition temperature can be measured using a product named "DSC-60A Plus” (manufactured by Shimadzu Corporation). The temperature rise rate in the measurement is 10°C/min.
• the polymer film according to the present disclosure contains a polymer, and has an elastic modulus of 10 MPa or less at 160° C. and an elastic modulus of 0.1 MPa or more at 260° C., an equilibrium moisture absorption rate of 2.5 mass% or less at 85° C. and a relative humidity of 85%, and a dielectric loss tangent of 0.01 or less.
• the present inventors have found that the above-mentioned structure makes it possible to provide a polymer film having excellent step conformability and heat resistance.
• the elastic modulus of Layer B at 160°C is 10 MPa or less, and it is presumed that this allows the layer to deform to conform to the shape of the steps when laminated by hot pressing, thereby improving the step-following ability.
• the polymer film according to the present disclosure has an equilibrium moisture absorption rate of 2.5% by mass or less at 85° C. and a relative humidity of 85%, so it is less susceptible to moisture absorption and less susceptible to delamination due to heating. In other words, it has excellent heat resistance.
• the elastic modulus of the polymer film at 160°C is preferably 0.1 MPa to 8 MPa, more preferably 0.3 MPa to 5 MPa, and even more preferably 0.5 MPa to 4 MPa.
• the elastic modulus of a polymer film at 160° C. is measured by the following method. First, a film cross-section sample (length 2 mm ⁇ width 2 mm) was prepared by obliquely cutting with a microtome so that the cross-section had a size of 50 ⁇ m. Next, the 160°C elastic modulus of the film cross-section sample is measured as the indentation elastic modulus using a nanoindentation method.
• the indentation elastic modulus is measured by applying a load at a loading rate of 0.5 mN/sec with a Vickers indenter using a microhardness tester (for example, product name "DUH-W201" manufactured by Shimadzu Corporation), holding the maximum load of 10 mN for 10 seconds, and then unloading at a loading rate of 0.5 mN/sec.
• a microhardness tester for example, product name "DUH-W201" manufactured by Shimadzu Corporation
• the elastic modulus at 160°C of the layer B in the laminate described below is measured by etching the support and then obliquely cutting the cross section of Layer B with a microtome to 50 ⁇ m to prepare a film cross section sample (length 2 mm ⁇ width 2 mm).
• the elastic modulus of the polymer film at 260°C is preferably 10 MPa to 0.1 MPa, more preferably 9.5 MPa to 0.1 MPa, and even more preferably 1.5 MPa to 0.1 MPa.
• the elastic modulus of a polymer film at 260° C. is measured by the following method. First, a film cross-section sample (length 2 mm ⁇ width 2 mm) was prepared by obliquely cutting with a microtome so that the cross-section had a size of 50 ⁇ m. Next, the 260°C elastic modulus of the film cross-section sample is measured as the indentation elastic modulus using a nanoindentation method.
• the indentation elastic modulus is measured by applying a load with a Vickers indenter at a loading rate of 0.28 mN/sec using a microhardness tester (for example, product name "DUH-W201" manufactured by Shimadzu Corporation), holding the maximum load of 10 mN for 10 seconds, and then unloading at a loading rate of 0.28 mN/sec.
• a microhardness tester for example, product name "DUH-W201" manufactured by Shimadzu Corporation
• the elastic modulus at 260°C of the layer B in the laminate described below is measured by etching the support and then obliquely cutting the cross section of Layer B with a microtome to 50 ⁇ m to prepare a film cross section sample (length 2 mm ⁇ width 2 mm).
• the equilibrium moisture absorption rate of the polymer film at 85°C and a relative humidity of 85% is preferably 2.2% by mass or less, more preferably 1.5% by mass or less, even more preferably 0.8% by mass or less, particularly preferably 0.5% by mass or less, and most preferably 0.25% by mass or less.
• the lower limit of the equilibrium moisture absorption rate may be 0% by mass.
• the equilibrium moisture absorption rate is measured as follows.
• the polymer film is left to stand at a temperature of 85°C and a relative humidity of 85% for 24 hours to reach equilibrium, after which the Karl Fischer moisture content of 0.1 g of the sample is measured at a temperature of 150°C using a Karl Fischer moisture measuring apparatus and an attached moisture vaporizer.
• the moisture absorption rate is calculated by dividing the measured moisture amount by the mass of the laminate x 100 (%).
• “CA-03", “VA-05” or the like manufactured by Mitsubishi Chemical Corporation
• the parallel moisture absorption rate of the laminate described later is measured by leaving the laminate instead of the polymer film.
• the dielectric tangent of the polymer film is preferably 0.005 or less, and more preferably greater than 0 and 0.003 or less.
• 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 e.g., "CP531” manufactured by Kanto Electronics Application Development Co., Ltd.
• a network analyzer e.g., "E8363B” manufactured by Agilent Technology Co., Ltd.
• a polymer film is inserted into the cavity resonator
• the dielectric loss tangent is measured from the change in the resonance frequency before and after insertion for 96 hours in an environment of a temperature of 25°C and a humidity of 60% RH.
• the dielectric loss tangent of the laminate described below is measured by inserting the laminate in place of the polymer film.
• the average thickness of the polymer film is preferably 5 ⁇ m to 90 ⁇ m, more preferably 10 ⁇ m to 70 ⁇ m, and even more preferably 15 ⁇ m to 50 ⁇ m.
• the method for measuring the average thickness is as follows.
• the polymer film is cut in a plane perpendicular to the plane direction of the polymer film, the thickness is measured at five or more points on the cross section, and the average value of the measurements is taken as the average thickness.
• the average thickness of each layer in the laminate described below is determined by cutting the laminate in a plane perpendicular to the plane direction, measuring the thickness at five or more points on each cross section, and averaging the measurements.
• the polymer film according to the present disclosure preferably has a phase-separated structure containing at least two phases.
• phase-separated structure refers to a structure in which at least two parts containing different components are present in a polymer film or layer.
• phase separation structures include an island-in-the-sea structure, a cocontinuous structure, a cylindrical structure, and a lamellar structure.
• An island-in-the-sea structure means a structure in which one of at least two phases forms a continuous phase and the other phase is present in a discontinuously dispersed state.
• a cocontinuous structure means a structure in which at least two phases both form continuous phases.
• a cylindrical structure means a structure in which at least one of at least two phases has multiple rod-shaped phases, which are the other phase.
• a lamellar structure means a layered structure in which at least two phases are alternately stacked. Both the cylindrical structure and the lamellar structure are structures in which at least two phases both form continuous phases, but are distinguished from the cocontinuous structure because they have the above-mentioned characteristics (rod-shaped or layered).
• the polymer film according to the present disclosure preferably has a phase separation structure in which at least two phases each form a continuous phase.
• the phase separation structure in the polymer film according to the present disclosure is preferably a co-continuous structure, a cylindrical structure, or a lamellar structure.
• phase separation structure can be confirmed by using means such as morphological observation, material distribution evaluation, and mechanical property distribution evaluation for the film surface, film cross section, or both the film surface and cross section.
• Morphological observation can be performed using a known optical microscope, electron microscope, or the like.
• Material distribution evaluation can be performed using imaging such as infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy.
• Mechanical property distribution evaluation can be performed using an atomic force microscope, or the like.
• whether or not the polymer film has a phase-separated structure can be confirmed by performing differential scanning calorimetry (DSC) on the entire surface. Specifically, when a glass transition temperature (Tg) below room temperature (25° C.) and a Tg above room temperature are detected, it can be determined that the polymer film has a phase separation.
• DSC differential scanning calorimetry
• the phase separation structure can be formed from at least one of a polymer described below, a thermoplastic resin such as an elastomer, and a cured product of a thermoplastic resin and a curing agent.
• the polymer examples include thermoplastic resins such as liquid crystal polymers, fluororesins, polymers of compounds having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, polyether ether ketone, polyolefin, polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone, polyphenylene ether and modified products thereof, and polyether imide; and thermosetting resins such as phenol resins, epoxy resins, polyimides, and cyanate resins.
• the polymer preferably includes a liquid crystal polymer from the viewpoint of decreasing the dielectric loss tangent.
• 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 polyester amide is preferably a crystalline polymer.
• the polymer film according to the present disclosure preferably contains a crystalline aromatic polyester amide.
• the aromatic polyester amide contained in the film 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.
• Formula 2 -NH-Ar3-O- ...
• Ar1, Ar2, and Ar3 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.
• Ar1 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.
• Ar1 is a 4,4'-biphenylylene group
• unit 1 is, for example, a constitutional unit derived from 4'-hydroxy-4-biphenylcarboxylic acid.
• Ar2 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.
• Ar2 is a 2,6-naphthylene group
• unit 2 is, for example, a constitutional unit derived from 2,6-naphthalenedicarboxylic acid.
• Ar3 is preferably a p-phenylene group or a 4,4'-biphenylylene group, and more preferably a p-phenylene group.
• unit 2 is, for example, a constitutional unit derived from p-aminophenol.
• unit 2 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 may contain 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 suitable examples include a photoradical polymerization initiator or an organic peroxide. Suitable photoradical polymerization initiators and organic peroxides are well known in the art.
• Crosslinkable fluoropolymers are commercially available, such as Viton B manufactured by DuPont.
• the polymer may include 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. Among them, a (meth)acrylate compound having a cyclic aliphatic hydrocarbon group is preferably used.
• 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 may include 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 is, for example, 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 polymer content relative to the total mass of the polymer film is preferably 10 mass% or more, more preferably 15 mass% or more, even more preferably 20 mass% to 60 mass%, and particularly preferably 20 mass% to 40 mass%.
• the content of the liquid crystal polymer relative to the total mass of the polymer is preferably 50 mass% or more, more preferably 70 mass% or more, even more preferably 90 mass% or more, and may be 100 mass%.
• the polymer film preferably contains a thermoplastic resin containing a structural unit derived from a monomer having an aromatic hydrocarbon group, and more preferably contains a polystyrene-based elastomer.
• styrene-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 products thereof.
• SBS styrene-butadiene-styrene block copolymers
• SIS poly
• the content of the above-mentioned thermoplastic resin relative to the total mass of the polymer film is preferably 40% by mass to 85% by mass, more preferably 40% by mass to 80% by mass, and even more preferably 60% by mass to 80% by mass.
• the polymer film preferably contains at least one of a curing agent and a cured product of the thermoplastic resin and the curing agent.
• the curing agent may be a compound having a maleimide group, an allyl group, a vinyl group, an epoxy group, an oxetanyl group, a cyanate group, a benzoxazine group, or the like.
• the thermosetting compound preferably has at least one group selected from the group consisting of a maleimide group, an allyl group, a vinyl group, a cyanate group, and a benzoxazine group, and from the viewpoint of heat resistance, it is more preferable for the thermosetting compound to contain a resin having at least one group selected from the group consisting of a maleimide group and an epoxy group.
• the content of the hardener relative to the total mass of the polymer film is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and even more preferably 5% by mass to 13% by mass.
• the polymer film preferably contains a filler.
• the filler may be particulate or fibrous.
• the filler may be inorganic or organic. From the viewpoints of the dielectric loss tangent, heat resistance, and step conformability of the polymer film, the filler is preferably inorganic.
• 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-based resin particles, polyethylene particles, liquid crystal polymer particles, or nanofibers of cellulose-based resin, more preferably polytetrafluoroethylene particles, polyethylene particles, or liquid crystal polymer particles, and particularly preferably liquid crystal polymer particles.
• the liquid crystal polymer particles refer to, but are not limited to, liquid crystal polymers polymerized and pulverized with a pulverizer or the like to form powdered liquid crystal. It is preferable that the liquid crystal polymer particles are smaller than the thickness of each layer.
• 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 the dielectric tangent, heat resistance, and step conformability of the polymer film.
• the inorganic filler a known inorganic filler can be used.
• inorganic filler materials include boron nitride (BN), Al 2 O 3 , aluminum nitride (AlN), TiO 2 , silica (SiO 2 ), barium titanate, strontium titanate, aluminum hydroxide, calcium carbonate, and materials containing two or more of these.
• the inorganic filler is preferably at least one selected from the group consisting of silica, aluminum hydroxide, and boron nitride.
• the average particle size of the inorganic filler is preferably about 20% to about 40% of the thickness of Layer A, and may be selected to be, for example, 25%, 30%, or 35% of the thickness of Layer A. In the case where the particles or fibers are flat, the average particle size indicates the length in the direction of the short side. Moreover, from the viewpoints of the dielectric tangent, heat resistance, and step conformability of the polymer film, 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 polymer film may contain only one type of filler, or may contain two or more types of fillers.
• the content of the filler is preferably 3 mass % to 25 mass %, more preferably 5 mass % to 23 mass %, and even more preferably 10 mass % to 20 mass %, relative to the total mass of the polymer film, from the viewpoints of the dielectric tangent, heat resistance, and step-following ability of the polymer film.
• the polymer film may contain other additives in addition to the above-mentioned components.
• known additives can be used, specifically, for example, a leveling agent, a defoaming agent, an antioxidant, an ultraviolet absorbing agent, a flame retardant, a colorant, etc.
• the laminate according to the present disclosure is a laminate having a layer B on at least one surface of a layer A, the layer B including a polymer and having an elastic modulus of 10 MPa or less at 160° C. and an elastic modulus of 0.1 MPa or more at 260° C.;
• the laminate has an equilibrium moisture absorption rate of 2.5 mass % or less at 85° C. and a relative humidity of 85%, and a dielectric loss tangent of 0.01 or less.
• the equilibrium moisture absorption rate of the laminate at 85°C and a relative humidity of 85% is preferably 2.2% by mass or less, more preferably 1.5% by mass or less, even more preferably 0.8% by mass or less, particularly preferably 0.5% by mass or less, and most preferably 0.25% by mass or less.
• the above equilibrium moisture absorption rate may be 0% by mass.
• the dielectric tangent of the laminate is preferably 0.005 or less, and more preferably greater than 0 and 0.003 or less.
• the layer A may contain a polymer.
• the polymer is as described in the polymer film, and the preferred type, content, etc. of the polymer are not described here.
• Layer A may contain a thermoplastic resin containing a structural unit derived from a monomer having an aromatic hydrocarbon group, a curing agent, a cured product of the thermoplastic resin and the curing agent, a filler, other additives, etc. These are as described for the polymer film, and will not be described here.
• the average thickness of layer A is not particularly limited, but from the viewpoints of dielectric tangent, heat resistance, 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 elastic modulus of layer A at 160° C. is preferably 50 MPa to 2000 MPa, more preferably 70 MPa to 1500 MPa, and even more preferably 150 MPa to 950 MPa.
• the ratio of the elastic modulus of Layer A at 160°C to the elastic modulus of Layer B at 160°C is preferably 50 or more, more preferably 100 or more, even more preferably 200 or more, and particularly preferably 1000 or more. The upper limit of the ratio may be 2000.
• the elastic modulus of Layer A at 160° C. is measured by the following method.
• the polymer film or laminate is obliquely cut with a microtome so that the cross section of layer A is 50 ⁇ m to prepare a cross-sectional sample (length 2 mm ⁇ width 2 mm).
• the indentation modulus at 160° C. is measured using a microhardness tester equipped with a Vickers indenter (product name “DUH-W201”, manufactured by Shimadzu Corporation) using a nanoindentation method.
• the layer B may contain a polymer.
• the polymer is as described in the polymer film, and the preferred type, content, etc. of the polymer are not described here.
• Layer B may contain a thermoplastic resin containing a structural unit derived from a monomer having an aromatic hydrocarbon group, a curing agent, a cured product of the thermoplastic resin and the curing agent, a filler, other additives, etc. These are as described in the polymer film, and will not be described here.
• the elastic modulus at 160° C., the elastic modulus at 260° C., the equilibrium moisture absorption rate at 85° C. and a relative humidity of 85%, the dielectric tangent, the average thickness, etc. of Layer B are similar to those of the polymer film, and therefore are not described here. Moreover, it is preferable that Layer B has the above-mentioned phase-separated structure.
• the laminate according to the present disclosure may have a layer C, and may have a layer B, a layer A, and a layer C in this order.
• Layer C is preferably an adhesive layer and is also preferably a surface layer (outermost layer).
• Layer C may contain a polymer.
• the polymer is as described in the polymer film, and preferred types are not described here.
• the polymer content relative to the total mass of layer C is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 99.8% by mass, and even more preferably 70% by mass to 99.7% by mass.
• Layer C may contain a thermoplastic resin containing a structural unit derived from a monomer having an aromatic hydrocarbon group, a curing agent, a cured product of the thermoplastic resin and the curing agent, a filler, other additives, etc. These are as described for the polymer film, and will not be described here.
• the average thickness of layer C is not particularly limited, but from the viewpoints of dielectric tangent, heat resistance, and step conformability, it is preferably 0.1 ⁇ m to 10 ⁇ m, more preferably 0.5 ⁇ m to 8 ⁇ m, and particularly preferably 1 ⁇ m to 5 ⁇ m.
• the method for producing the laminate according to the present disclosure is not particularly limited, and any known film-forming method can be used.
• 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 film is produced by the 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 resin film 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 film 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 adding an inorganic filler or the like.
• the polymer films and laminates according to the present disclosure can be used for various applications, and among others, can be suitably used as films for electronic components such as printed wiring boards, and can be even more suitably used for flexible printed circuit boards. Furthermore, the polymer film and laminate according to the present disclosure can be suitably used as a liquid crystal polymer film and laminate for metal bonding.
• the metal-attached laminate according to the present disclosure includes a polymer film according to the present disclosure or a laminate according to the present disclosure, and a metal layer or metal wiring disposed on at least one surface of the polymer film or the laminate.
• the metal layer or metal wiring may be made of a conventionally known material, and is preferably made of silver or copper, and more preferably made of copper.
• Metal layers or metal wiring may be disposed on both sides of the polymer film or the laminate.
• the two metal layers or metal wiring may be metal layers or metal wirings of the same material, thickness and shape, or metal layers or metal wirings of different materials, thicknesses and shapes. From the viewpoint of characteristic impedance adjustment, the two metal layers or metal wirings may be metal layers or metal wirings of different materials and thicknesses.
• the metal layer is a rolled metal foil formed by a rolling method, or an electrolytic metal foil formed by an electrolytic method.
• the peel strength at 260°C between the polymer film or laminate and the metal layer or metal wiring is preferably 0.02 kN/m or more, more preferably 0.05 kN/m or more, and even more preferably 0.08 kN/m or more.
• the upper limit of the peel strength may be 3 kN/m.
• the peel strength at 260° C. between a polymer film or laminate and a metal layer or metal wiring is measured by the following method.
• a peel test piece having a width of 1.0 cm is prepared from a laminate (laminate with metal) of a polymer film or laminate and a metal layer or metal wiring, and the peel test piece is fixed to a flat plate with double-sided adhesive tape.
• the strength (kN/m) is measured when peeled at a speed of 50 mm/min by the 180° method in accordance with JIS C 5016 (1994).
• the average thickness of the metal layer is not particularly limited, but is preferably 2 ⁇ m to 20 ⁇ m, more preferably 3 ⁇ m to 18 ⁇ m, and even more preferably 5 ⁇ m to 12 ⁇ m.
• the copper foil may be a carrier-attached copper foil that is formed releasably on a support (carrier).
• the carrier may be a known one.
• the average thickness of the carrier is not particularly limited, but is preferably 10 ⁇ m to 100 ⁇ m, and more preferably 18 ⁇ m to 50 ⁇ m.
• the average thickness of layer B is preferably greater than the average thickness of the metal in order to suppress distortion of the metal wiring when bonded to the metal wiring.
• the metal layer may be a metal layer having a circuit pattern. It is also preferable to process the metal layer into a desired circuit pattern, for example, by etching, to form a flexible printed circuit board. There are no particular limitations on the etching method, and any known etching method can be used.
• the metal-attached laminate according to the present disclosure can be produced by using a metal layer or metal wiring as the support in the laminate production method according to the present disclosure.
• a metal layer or metal wiring may be provided by thermocompression bonding or the like on the surface of the laminate opposite to the side on which the support is provided.
• the polymers and additives (components other than polymers) used to form each layer of the laminate, as well as the copper foil, are detailed below.
• Aromatic polyesteramide P1 synthesized according to the following synthesis method (referred to as "P1" in Table 1).
• the aromatic polyesteramide A1a 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 A1b was then pulverized in a pulverizer to obtain a powdered aromatic polyesteramide A1b.
• the flow-initiation temperature of the aromatic polyesteramide A1b was 220°C.
• the aromatic polyester amide A1b 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 solubility of the aromatic polyesteramide P1 in N-methylpyrrolidone at 140° C. was 1 mass% or more.
• ODPA 4,4'-oxydiphthalic anhydride
• PMDA pyromellitic dianhydride
• BAPP 2,2-bis[4-(4-aminophenoxy)phenyl]propane
• BAPB 4,4'-bis(4-aminophenoxy)biphenyl
• acetic anhydride 1.6 mol per mol of amic acid units in the polyamic acid PA-A
• isoquinoline 0.5 mol per mol of amic acid units in the polyamic acid PA-A
• DMF the total mass of acetic anhydride, isoquinoline, and DMF was 45% of the polyamic acid PA-A
• PI-A polyimide precursor
• SEBS Hydrogenated styrene-ethylene-butylene-styrene block copolymer
• Liquid crystal polymer particles PP-1 synthesized according to the following synthesis method (referred to as "PP-1" in Table 1).
• 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 heated from room temperature to 295°C over 14 hours, and solid-phase polymerized at 295°C for 1 hour.
• 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.
• Elastomer particles PP-2 (referred to as "PP-2” in Table 1): Hydrogenated styrene-ethylene-butylene-styrene block copolymer (SEBS, product name “Tuftec M1913", manufactured by Asahi Kasei Chemicals Corporation) frozen and ground (average particle size 5.0 ⁇ m (D50)); Thermoplastic resin/elastomer particles PP-3 (referred to as “PP-3” in Table 1): Hydrogenated styrene-isobutylene-styrene block copolymer particles, frozen and ground SIBSTAR 103T-UL manufactured by Kaneka Corporation (average particle size 5.0 ⁇ m (D50)); Thermoplastic resin/curing agent C1 (referred to as "C1” in Table 1): jER YX8800, manufactured by Mitsubishi Chemical Corporation; Condensation polycondensation type epoxy resin/curing agent C2 (referred to as "C2” in Table 1): Maleimide curing agent; Cur
• Silica particles A1 (referred to as “A1” in Table 1): SC2050-MB, manufactured by Admatechs Co., Ltd..
• Aluminum hydroxide particles A2 (referred to as “A2” in Table 1): AO-502, manufactured by Admatechs Co., Ltd..
• Boron nitride particles A3 (referred to as “A3” in Table 1): HP40MF100, manufactured by Mizushima Ferroalloy Co., Ltd.
• Copper foil M1 (referred to as "M1" in Table 1): CF-T9DA-SV-18, manufactured by Fukuda Metal Foil & Powder Co., Ltd., average thickness 18 ⁇ m
• Copper foil M2 (referred to as “M2” in Table 1): MT18FL, manufactured by Mitsui Mining & Smelting Co., Ltd., average thickness 1.5 ⁇ m
• Copper foil M3 (referred to as "M3” in Table 1): CF-T4X-SV-18, manufactured by Fukuda Metal Foil and Powder Co., Ltd., average thickness 18 ⁇ m
• thermocompression bonder product name "MP-SNL", manufactured by Toyo Seiki Seisakusho Co., Ltd.
• MP-SNL manufactured by Toyo Seiki Seisakusho Co., Ltd.
• thermocompression bonding machine product name "MP-SNL", manufactured by Toyo Seiki Seisakusho Co., Ltd.
• MP-SNL manufactured by Toyo Seiki Seisakusho Co., Ltd.
• Example 12 to 17 Fabrication of single-sided copper-clad laminate -
• the obtained solution for layer B was sent to a slot die coater equipped with a slide coater, and applied in a one-layer configuration (layer B) on the treated surface of the copper foil (first metal layer) shown in Table 1, adjusting the flow rate so that the thickness after drying would be the average thickness shown in Table 1.
• the solvent was removed from the coating film by drying at 40°C for 4 hours. Further, the temperature was raised from room temperature to 300°C at a rate of 1°C/min under a nitrogen atmosphere, and a heat treatment was performed by holding at that temperature for 2 hours to obtain a laminate (single-sided copper-clad laminate) having a first metal layer (copper layer).
• thermocompression bonder product name "MP-SNL", manufactured by Toyo Seiki Seisakusho Co., Ltd.
• MP-SNL manufactured by Toyo Seiki Seisakusho Co., Ltd.
• the indentation elastic modulus was measured by applying a load at a loading rate of 0.5 mN/sec with a Vickers indenter using a microhardness tester (product name "DUH-W201", manufactured by Shimadzu Corporation), holding the maximum load of 10 mN for 10 seconds, and then unloading at a loading rate of 0.5 mN/sec.
• the results are shown in Table 2.
• the first and second metal layers were etched from a double sided copper clad laminate.
• the dielectric loss tangent of the laminate taken out was measured by the following method. The results are shown in Table 1.
• the dielectric constant was measured by a resonance perturbation method at a frequency of 10 GHz.
• a 10 GHz cavity resonator (CP531, manufactured by Kanto Electronics Application Development Co., Ltd.) was connected to a network analyzer (E8363B, manufactured by Agilent Technology), and the laminate was inserted into the cavity resonator.
• the laminate dielectric loss tangent was measured from the change in resonance frequency before and after insertion for 96 hours under an environment of a temperature of 25° C. and a humidity of 60% RH. The results are shown in Table 2.
• the first and second metal layers were etched from a double sided copper clad laminate.
• the equilibrium moisture absorption rate of the laminate at 85° C. and a relative humidity of 85% was measured by the following method. The results are shown in Table 2.
• the laminate was left for 24 hours under constant temperature and humidity conditions of 85°C and 85% relative humidity to reach equilibrium, and then 0.1 g of the sample was used to measure the Karl Fischer moisture content at 150°C using a Karl Fischer moisture meter and an attached moisture vaporizer (both manufactured by Mitsubishi Chemical).
• the moisture absorption rate was calculated by measuring the amount of moisture, dividing the mass of the laminate, and multiplying the mass by 100 (%).
• a laminator (product name "Vacuum Laminator V-130", manufactured by Nikko Materials Co., Ltd.), lamination was performed for 1 minute under conditions of 140°C and a lamination pressure of 0.4 MPa to obtain a precursor of a double-sided copper foil laminate.
• the obtained precursor of the double-sided copper-clad laminate was subjected to thermocompression bonding for 10 minutes under conditions of 300° C. and 4.5 MPa using a thermocompression bonding machine (product name "MP-SNL”, manufactured by Toyo Seiki Seisakusho Co., Ltd.), to produce a double-sided copper-clad laminate.
• MP-SNL manufactured by Toyo Seiki Seisakusho Co., Ltd.
• the copper foils on both sides of the double-sided copper-clad laminate were roughened, and a dry film resist was attached to the copper foil.
• the copper foil was exposed to light, developed, etched, and the dry film was removed to leave a wiring pattern.
• a substrate A with a wiring pattern was produced, which had a line/space of 100 ⁇ m/100 ⁇ m including a ground line and three pairs of signal lines on both sides of the substrate.
• the length of the signal line was 50 mm, and the width was set so that the characteristic impedance was 50 ⁇ .
• substrate B having wiring pattern--- A copper foil (product name "MT18FL”, average thickness 1.5 ⁇ m, with carrier copper foil (thickness 18 ⁇ m), manufactured by Mitsui Mining & Smelting Co., Ltd.) and a liquid crystal polymer film (product name "CTQ-50", average thickness 50 ⁇ m, manufactured by Kuraray Co., Ltd.) were prepared as a substrate.
• the copper foil, the substrate, and the copper foil were stacked in this order so that the treated surface of the copper foil was in contact with the substrate.
• thermocompression bonding machine product name "MP-SNL”, manufactured by Toyo Seiki Seisakusho Co., Ltd.
• the substrate of the single-sided copper-clad laminate and the carrier copper foil on the opposite side were peeled off, and the exposed 1.5 ⁇ m copper foil was surface roughened and a dry film resist was attached.
• the wiring pattern was exposed and developed, and the area where the resist pattern was not arranged was plated. Furthermore, the dry film resist was peeled off, and the copper exposed by the peeling process was removed by flash etching to produce a substrate B with a wiring pattern having a line/space of 20 ⁇ m/20 ⁇ m.
• a wiring pattern-bearing substrate A or a wiring pattern-bearing substrate B was superimposed on the layer A side of the single-sided copper-clad laminate prepared in the examples and comparative examples, and a wiring board was obtained by performing a heat press for 1 hour under conditions of 160°C and 4 MPa.
• the obtained wiring board had a wiring pattern (ground line and signal line) embedded therein, and when substrate A with a wiring pattern was used, the thickness of the wiring pattern was 18 ⁇ m, and when substrate B with a wiring pattern was used, the thickness of the wiring pattern was 12 ⁇ m.
• the wiring board was cut in the thickness direction with a microtome, and the cross section was observed with an optical microscope.
• the length L of the gap between the resin layer and the wiring pattern in the in-plane direction was measured.
• the average value at 10 points was calculated, and the step conformability was evaluated based on the following evaluation criteria.
• the results are shown in Table 2. (Evaluation criteria) A: No gaps were found. B: L was less than 1 ⁇ m. C:L was 1 ⁇ m or more.

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