Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • 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
  • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
  • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/022—Mechanical properties
• • 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
  • 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
• • 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
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/22—Secondary treatment of printed circuits
  • H05K3/28—Applying non-metallic protective coatings

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.
• International Publication No. 2022/202789 discloses a polymer film that includes a polymer and a filler and has a phase-separated structure including at least two phases, and each of the at least two phases has an elastic modulus of 0.01 GPa or more.
• JP 2019-199612 A discloses an adhesive film containing a resin composition containing a styrene-based polymer, an inorganic filler, and a curing agent.
• 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 conform to 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.
• the dielectric tangent is 0.01 or less,
• the surface elastic modulus at 160°C is 10 MPa or less, and
• the surface viscosity at 260°C is 1,000 Pa ⁇ s or more;
• a polymer and an elastomer are included,
• ⁇ 3> The polymer film according to ⁇ 2> above, wherein a coverage of a surface of at least one of the polymer films with the elastomer is less than 100%.
• ⁇ 4> The polymer film according to ⁇ 3> above, wherein the coverage is 30% to 80%.
• ⁇ 5> The polymer film according to any one of ⁇ 2> to ⁇ 4> above, wherein the phase separation structure is a cocontinuous structure, a sea-island structure, a cylindrical structure, or a lamellar structure.
• ⁇ 6> The polymer film according to any one of the above ⁇ 2> to ⁇ 5>, wherein a content of the elastomer in any one of the at least two phases is 20 volume% or more with respect to a total volume of the any one of the phases.
• ⁇ 7> The polymer film according to any one of ⁇ 2> to ⁇ 6> above, wherein the polymer includes a liquid crystal polymer.
• ⁇ 8> The polymer film according to any one of ⁇ 2> to ⁇ 7> above, wherein the polymer contains an aromatic polyester amide.
• ⁇ 9> A laminate having a layer B on at least one surface of a layer A, the elastic modulus at 160°C of the surface of the layer B opposite to the layer A side is 10 MPa or less, the viscosity at 260°C of the surface of the layer B opposite to the layer A side is 1,000 Pa s or more, and the dielectric loss tangent of the laminate is 0.01 or less; Laminate.
• the layer B contains a polymer and an elastomer and has a phase-separated structure containing at least two phases.
• ⁇ 11> The laminate according to ⁇ 10> above, wherein a coverage of a surface of Layer B opposite to Layer A with the elastomer is less than 100%.
• ⁇ 12> The laminate according to ⁇ 11>, wherein the coverage is 30% to 80%.
• ⁇ 13> A metal-attached laminate comprising the polymer film according to any one of the above ⁇ 1> to ⁇ 8> or the laminate according to any one of the above ⁇ 9> to ⁇ 12>, and a metal layer or metal wiring disposed on at least one surface of the polymer film or the laminate.
• 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 3,000 or more and a glass transition temperature of higher than 25°C.
• an "elastomer” is a compound having a weight average molecular weight of 3,000 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 has a dielectric loss tangent of 0.01 or less, a surface elastic modulus at 160°C of 10 MPa or less, and a surface viscosity at 260°C of 1,000 Pa ⁇ s or more.
• 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.
• the amount of deformation of Layer B due to press pressure becomes larger than that of other layers that are harder than Layer B, which is presumably why the conformability to unevenness is improved.
• the polymer film according to the present disclosure has excellent mechanical strength because the viscosity of the surface at 260°C is 1,000 Pa ⁇ s or more.
• the surface 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 0.3 MPa to 4 MPa.
• the surface elastic modulus of a polymer film at 160° C. is measured by the following method.
• the polymer film is cut out to prepare an evaluation sample (length 2 mm x width 2 mm).
• the indentation modulus of elasticity at 160° C. is measured using a microhardness tester equipped with a Vickers indenter (for example, product name “DUH-W201” manufactured by Shimadzu Corporation) by nanoindentation method.
• the polymer film may have an elastic modulus of 10 MPa or less on at least one surface.
• the elastic modulus of the polymer film at 160°C is preferably 50 MPa to 2,000 MPa, more preferably 70 MPa to 1,500 MPa, and even more preferably 150 MPa to 950 MPa.
• the surface viscosity of the polymer film at 260°C is preferably 5,000 Pa ⁇ s or more, preferably 10,000 Pa ⁇ s or more, more preferably 30,000 Pa ⁇ s or more, even more preferably 50,000 Pa ⁇ s or more, and particularly preferably 70,000 Pa ⁇ s or more.
• the upper limit of the viscosity may be set to 200,000 or less.
• the surface 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 surface elastic modulus at 160°C and the surface viscosity at 260°C of the aforementioned polymer film it is preferable to adjust the surface elastic modulus at 160°C and the surface viscosity at 260°C of the aforementioned polymer film to fall within a preferred range.
• the surface elastic modulus at 160°C is 0.3 MPa to 5 MPa and the surface viscosity at 260°C is 50,000 Pa ⁇ s or more, and it is even more preferable that the surface elastic modulus at 160°C is 0.3 MPa to 4 MPa and the surface viscosity at 260°C is 70,000 Pa ⁇ s or more.
• 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 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 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 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 on 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, etc.
• 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, etc.
• the phase separation structure can be formed using polymers, elastomers, etc., as described below.
• the polymer film of the present disclosure may contain a polymer, which may 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, polyetheretherketone, polyolefin, polyamide, polyester, polyphenylene sulfide, polyetherketone, polycarbonate, polyethersulfone, polyphenylene ether and modified products thereof, and polyetherimide; and thermosetting resins such as phenolic 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 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 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 13 mass% or more, even more preferably 15 mass% to 60 mass%, and particularly preferably 18 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 an elastomer.
• the elastomer include styrene-based elastomers, polyester-based elastomers, polyolefin-based elastomers, polyurethane-based elastomers, polyamide-based elastomers, polyacrylic-based elastomers, silicone-based elastomers, polyimide-based elastomers, etc.
• 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 weight average molecular weight of the elastomer is preferably from 10,000 to 500,000, more preferably from 30,000 to 300,000, and even more preferably from 50,000 to 200,000.
• Mw weight average molecular weight
• the molecular weight is expressed as a weight average molecular weight (Mw), which is measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent.
• the content of the elastomer 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 coverage of the surface of at least one of the polymer films by the elastomer is preferably less than 100%, more preferably 30% to 80%, and even more preferably 30% to 70%, from the viewpoints of conformability to unevenness and heat resistance.
• the coverage is determined by scraping off 1 ⁇ m of the surface of the polymer film with a razor and analyzing it with a Fourier transform infrared spectrophotometer (FT-IR).
• FT-IR Fourier transform infrared spectrophotometer
• TOF-SIMS time-of-flight secondary ion mass spectrometry
• the polymer film can be produced by removing the metal layer or the like from the metal-attached laminate described below by etching, and the above-mentioned coverage can also be adjusted by changing the production conditions of the metal-attached laminate. For example, it can be adjusted by changing the thermocompression bonding conditions of the metal layer or metal wiring on the polymer film surface. Specifically, the coverage can be reduced by setting the thermocompression bonding temperature or pressure to a high value or time to a long value.
• the content of the elastomer contained in any of the at least two phases is preferably 20 volume % or more, and more preferably 30 volume % or more, relative to the total volume of any of the phases.
• the content of the elastomer contained in any of the phases is, for example, 80 volume %.
• the above content is evaluated by cutting the cross section of the film with a microtome and observing the morphology using an optical microscope.
• the composition of each phase is determined separately using another method such as FT-IR.
• the elastomer is preferably used as a powder in the production of the polymer film. More preferably, the method of converting the elastomer into a powder includes a swelling step in which the elastomer is swelled with a liquid medium, and a grinding step in which the swollen elastomer is ground.
• the liquid medium used in the swelling process is not particularly limited as long as it is a compound that is liquid at 25°C. Furthermore, when the swelling process is carried out under heated conditions, a compound that becomes liquid at the heated temperature can be used.
• liquid media include water and organic solvents. There may be only one type of liquid medium, or two or more types.
• Organic solvents include, for example, alcohols, ketones, alkyl halides, amides, sulfoxides, heterocyclic compounds, hydrocarbons, esters, and ethers.
• the absolute value of the difference between the solubility parameter of the liquid medium and the solubility parameter of the polymer having a weight average molecular weight of 1000 or more is preferably 5 MPa 1/2 to 10 MPa 1/2 , and more preferably 6 MPa 1/2 to 8 MPa 1/2 .
• the solubility parameter of the liquid media shall be the weighted average value.
• the solubility parameter used is the Hansen solubility parameter.
• the Hansen solubility parameter is a solubility parameter introduced by Hildebrand, which is divided into three components, a dispersion term ⁇ d, a polar term ⁇ p, and a hydrogen bond term ⁇ h, and expressed in a three-dimensional space.
• the solubility parameter is expressed as ⁇ (unit: MPa 1/2 ), and a value calculated using the following formula is used.
• ⁇ (MPa) 1/2 ( ⁇ d 2 + ⁇ p 2 + ⁇ h 2 ) 1/2
• the dispersion term ⁇ d, polar term ⁇ p, and hydrogen bond term ⁇ h have been extensively investigated by Hansen and his successors, and are described in detail in Polymer Handbook (fourth edition), VII-698 to 711. Details of the Hansen solubility parameters are described in the literature "Hansen Solubility Parameters; A Users Handbook (CRC Press, 2007)" written by Charles M. Hansen.
• the solubility parameter of a polymer can be calculated from the molecular structure of the polymer by the Hoy method described in Polymer Handbook (fourth edition).
• the swelling degree of the swollen elastomer is preferably 1% to 1000%, more preferably 50% to 500%, and even more preferably 100% to 250%.
• the temperature of the liquid medium is not particularly limited as long as it is a temperature at which the liquid medium is in a liquid state, and is preferably, for example, 10°C to 60°C.
• the means for pulverizing the swollen elastomer is not particularly limited, and examples include a mortar and pestle combination and a grinder (e.g., a ball mill, a bead mill, a roller mill, a jet mill, a hammer mill, an attritor, etc.).
• a grinder e.g., a ball mill, a bead mill, a roller mill, a jet mill, a hammer mill, an attritor, etc.
• the elastomer After swelling the elastomer, it may be ground at room temperature, but from the standpoint of obtaining a powder with a smaller particle size, it is preferable to cool the swollen elastomer in an environment with a temperature of -50°C or less before grinding it.
• the temperature at which the swollen elastomer is cooled is preferably lower than the melting point of the liquid medium, and more preferably at least 10°C lower than the melting point of the liquid medium. Specifically, the temperature at which the swollen elastomer is cooled is more preferably -80°C or lower, and even more preferably -100°C or lower.
• 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 preferably has at least one of an epoxy group and a maleimide 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, and may be an inorganic filler or an organic filler. From the viewpoints of the dielectric loss tangent, heat resistance, and step conformability of the polymer film, the filler is preferably an inorganic filler.
• 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.
• 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.
• 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, antioxidants, leveling agents, antifoaming agents, ultraviolet absorbing agents, flame retardants, colorants, 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 elastic modulus at 160° C. of the surface of the layer B opposite to the layer A side is 10 MPa or less, and the viscosity at 260° C. of the surface of the layer B opposite to the layer A side is 1,000 Pa s or more,
• the laminate has a dielectric loss tangent of 0.01 or less.
• 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 elastomers, curing agents, cured products of thermoplastic resins and curing agents, fillers, other additives, etc. These are as described for the polymer film, and will not be described here.
• the elastic modulus at 160° C. of the surface of the layer A is measured by the following method.
• the polymer film is embedded in ultraviolet-curing (UV) resin and cut in the thickness direction with a microtome to prepare a sample (length 2 mm x width 2 mm) for cross-sectional evaluation.
• the indentation modulus of elasticity at 160° C. is measured using a microhardness tester equipped with a Vickers indenter (for example, product name “DUH-W201” manufactured by Shimadzu Corporation) by nanoindentation method.
• the elastic modulus of the layer A at 160° C. is preferably 50 MPa to 2,000 MPa, more preferably 70 MPa to 1,500 MPa, and even more preferably 150 MPa to 950 MPa.
• 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 at 160° C. of the surface of the layer B opposite to the layer A side is preferably 0.1 MPa to 8 MPa, more preferably 0.3 MPa to 5 MPa, and even more preferably 0.3 MPa to 4 MPa.
• the elastic modulus at 160° C. of the surface of the layer B opposite to the layer A side is measured by the following method.
• the laminate is cut out to prepare a sample for evaluation.
• the laminate was a laminate including a metal layer
• at least the metal foil on the Layer B side was removed by a known wet etching method using an aqueous solution of ferric chloride or the like, and the surface of Layer B revealed after washing with pure water and drying was used as an evaluation sample (length 2 mm ⁇ width 2 mm).
• the indentation modulus at 160°C of the surface of layer B on the side opposite to layer A of the evaluation sample is measured using a microhardness tester equipped with a Vickers indenter (for example, product name "DUH-W201" manufactured by Shimadzu Corporation).
• the elastic modulus of layer B at 160°C is preferably 0.1 MPa to 8 MPa, more preferably 0.3 MPa to 5 MPa, and even more preferably 0.3 MPa to 4 MPa.
• the elastic modulus of Layer B at 160° C. is measured by the following method.
• the polymer film is embedded in ultraviolet-curing (UV) resin and cut in the thickness direction with a microtome to prepare a sample (length 2 mm x width 2 mm) for cross-sectional evaluation.
• UV ultraviolet-curing
• the indentation modulus of elasticity at 160° C. is measured using a microhardness tester equipped with a Vickers indenter (for example, product name “DUH-W201” manufactured by Shimadzu Corporation) by nanoindentation method.
• the layer B is required to have an elastic modulus at 160° C. of at most 10 MPa.
• the viscosity at 260°C of the surface of layer B opposite to layer A is preferably 5,000 Pa ⁇ s or more, preferably 10,000 Pa ⁇ s or more, more preferably 30,000 Pa ⁇ s or more, even more preferably 50,000 Pa ⁇ s or more, and particularly preferably 70,000 Pa ⁇ s or more.
• the upper limit of the viscosity may be set to 200,000 or less.
• the viscosity at 260° C. of the surface of the layer B opposite to the layer A side is measured by the following method.
• the laminate is a laminate having a metal layer
• at least the metal foil on the Layer B side is removed by a known wet etching method using an aqueous solution of ferric chloride or the like, and after washing with pure water, the surface of Layer B revealed by drying is scraped off with a razor, and the viscosity at 260°C is measured using a rheometer equipped with a heating unit (e.g., HAAKE MARS, manufactured by Thermo Fisher Scientific K.K.).
• a heating unit e.g., HAAKE MARS, manufactured by Thermo Fisher Scientific K.K.
• 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.
• the layer B may contain an elastomer.
• the elastomer is as described in the polymer film, and the preferred type, content, etc. of the elastomer are not described here.
• Layer B may contain a curing agent, a cured product of a thermoplastic resin and a curing agent, a filler, other additives, etc. These are as described in the polymer film, and the description thereof will be omitted here.
• Layer B preferably has the above-mentioned phase-separated structure.
• the ratio of the elastomers present, a/b is preferably 100/0 to 60/40, more preferably 100/0 to 70/30, and particularly preferably 100/0. In other words, it is particularly preferable that only one of the two phases contains the elastomer.
• the content of the elastomer contained in any one of the at least two phases is preferably 20% by volume or more, and more preferably 30% by volume or more, based on the total volume of any one of the phases, from the viewpoints of dielectric loss tangent, heat resistance, and step conformability.
• the upper limit of the content of the elastomer contained in any one of the phases is not particularly limited, and is, for example, 80% by volume.
• the coverage of the surface of Layer B opposite Layer A with the elastomer is preferably less than 100%, more preferably 30% to 80%, and even more preferably 30% to 70%, from the viewpoints of step conformability and heat resistance.
• the coverage is determined by analyzing the surface of Layer B by time-of-flight secondary ion mass spectrometry (TOF-SIMS).
• TOF-SIMS time-of-flight secondary ion mass spectrometry
• the coverage is measured after removing the support by etching or the like.
• the above coverage is measured by preparing a cross-sectional sample in the thickness direction of the laminate using a microtome and observing, using an optical microscope or a scanning electron microscope, the surface of Layer B opposite to Layer A.
• cross-sectional samples are prepared at any five positions, and the average value thereof is taken as the coverage.
• the average thickness of Layer B 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 ratio of the average thickness of layer B to the average thickness of the laminate is preferably 0.2 or more, more preferably 0.3 or more, even more preferably 0.4 or more, and particularly preferably 0.5 or more.
• 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 1.0 kN/m or more, more preferably 1.3 kN/m to 10 kN/m, and even more preferably 1.5 kN/m to 8 kN/m.
• the peel strength at 290° 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 thermocompression bonding temperature is preferably 170° C. to 300° C., more preferably 200° C. to 280° C., and even more preferably 210° C. to 270° C.
• the pressure in the thermocompression bonding is preferably 1 MPa to 15 MPa, more preferably 2 MPa to 10 MPa, and even more preferably 3 MPa to 8 MPa.
• the time for the thermocompression bonding is preferably 10 minutes to 300 minutes, more preferably 30 minutes to 240 minutes, and even more preferably 45 minutes to 180 minutes.
• 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 P1a was heated in a nitrogen atmosphere from room temperature to 160°C over 2 hours and 20 minutes, 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 P1b was then pulverized in a pulverizer to obtain a powdered aromatic polyesteramide P1b.
• 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 loss tangent of the aromatic polyester amide P1 was 0.005.
• F-1 Liquid crystal polymer particles prepared according to the following manufacturing method
• F-2 hydrogenated styrene-ethylene-butylene-styrene block copolymer particles, frozen and crushed Tuftec M1913 manufactured by Asahi Kasei Chemicals Corporation (average particle size 5.0 ⁇ m (D50))
• F-3 hydrogenated styrene-isobutylene-styrene block copolymer particles, frozen and crushed SIBSTAR 103T-UL manufactured by Kaneka Corporation (average particle size 5.0 ⁇ m (D50)
• F-4 Hydrogenated styrene-isobutylene-styrene block copolymer (product name "SIBSTAR103T-UL", manufactured by Kaneka Corporation) swollen with N-methylpyrrolidone, frozen and ground, average particle size 5.0 ⁇ m (D50)
• 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-state polymerized at 295° C. for 1 hour. After the solid-state polymerization, the mixture was cooled to room temperature over 5 hours.
• F-1 (LCP particles) had a median diameter (D50) of 7 ⁇ m, a dielectric loss tangent of 0.0007, and a melting point of 334° C.
• solution for layer C - 8 parts by mass of aromatic polyesteramide P1 was added to 92 parts by mass of N-methylpyrrolidone and stirred at 140° C. for 4 hours in a nitrogen atmosphere to obtain a solution of aromatic polyesteramide P1 (solid content concentration: 8% by mass).
• a solution for layer C was prepared by mixing 9.96 parts by mass of the aromatic polyesteramide P1 solution with 0.04 parts by mass of an aminophenol-type epoxy resin (product name "jER630", manufactured by Mitsubishi Chemical Corporation).
• thermocompression bonding machine product name "MP-SNL", manufactured by Toyo Seiki Seisakusho Co., Ltd.
• the first metal layer and the second metal layer were etched from the double-sided copper-clad laminate with an aqueous solution of ferric chloride, washed with pure water, and then dried.
• 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.
• ⁇ Surface coverage rate>> The first metal layer and the second metal layer were etched from the double-sided copper-clad laminate with an aqueous solution of ferric chloride, washed with pure water, and then dried. The surface of layer B of the removed laminate was scraped off by 1 ⁇ m with a razor and analyzed with a Fourier transform infrared spectrophotometer (FT-IR) to determine the coverage of layer B by the elastomer. The coverage was measured on the surface on the second metal layer side. The results are shown in Table 2.
• FT-IR Fourier transform infrared spectrophotometer
• the flexible wiring board was cut with a microtome, and the cross section was observed with an optical microscope and evaluated based on the following evaluation criteria. The results are shown in Table 2. (Evaluation criteria) A: No distortion was observed in the signal line and the ground line. B: No distortion was observed in the signal line, but distortion was observed in the ground line. C: Distortion was observed in one pair of signal lines. D: Distortion was observed in two or three pairs of signal lines.

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