Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D177/12—Polyester-amides
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • 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
  • 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
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D153/02—Vinyl aromatic monomers and conjugated dienes
  • C09D153/025—Vinyl aromatic monomers and conjugated dienes modified
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
  • H05K1/036—Multilayers with layers of different types
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/01—Dielectrics
  • H05K2201/0137—Materials
  • H05K2201/0145—Polyester, e.g. polyethylene terephthalate [PET], polyethylene naphthalate [PEN]
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/01—Dielectrics
  • H05K2201/0183—Dielectric layers
  • H05K2201/0195—Dielectric or adhesive layers comprising a plurality of layers, e.g. in a multilayer structure

Definitions

• This disclosure relates to polymer films and laminates.
• Copper-clad laminates are preferably used as components constituting circuit boards, and films are preferably used to manufacture copper-clad laminates.
• WO 2022/202789 describes a polymer film that contains a polymer and a filler and has a phase-separated structure containing at least two phases, each of which has an elastic modulus of 0.01 GPa or more.
• JP 2019-199612 A describes a resin composition containing a styrene-based polymer, an inorganic filler, and a curing agent, in which the styrene-based polymer is an acid-modified styrene-based polymer having a carboxy group, the inorganic filler is silica and/or aluminum hydroxide, the particle size of the inorganic filler is 1 ⁇ m or less, and the content of the inorganic filler is 20 to 80 parts by mass per 100 parts by mass of the styrene-based polymer.
• 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).
• the problem that one embodiment of the present disclosure aims to solve is to provide a polymer film and laminate that have excellent step conformability and heat resistance.
• Means for solving the above problems include the following aspects. ⁇ 1>
• the material A is liquid at 260° C.
• the material B is solid at 260° C.
• Material A and material B are phase-separated.
• the ratio of the total length of the phase separation interface between material A and material B to the length in a direction perpendicular to the thickness direction of the polymer film at a thickness of 50 ⁇ m is 2 or more
• the elastic modulus at 160°C is 0.60 MPa or less
• ⁇ 2> One of material A and material B forms a continuous phase and the other forms a dispersed phase, The polymer film according to ⁇ 1>, wherein the dispersed phase has an average length in the minor axis direction of 5 ⁇ m or less.
• ⁇ 3> One of material A and material B forms a continuous phase and the other forms a dispersed phase, The polymer film according to ⁇ 1> or ⁇ 2>, wherein the dispersed phase has an average length in the major axis direction of 10 ⁇ m or less.
• ⁇ 4> The polymer film according to any one of ⁇ 1> to ⁇ 3>, wherein the material A is an elastomer containing a structural unit derived from styrene.
• the material A is at least one selected from the group consisting of a styrene-ethylene-butylene-styrene block copolymer, a styrene-isobutylene-styrene block copolymer, a styrene-ethylene-propylene-styrene copolymer, a styrene-isoprene-styrene block copolymer, and hydrogenated products thereof.
• ⁇ 6> ⁇ 5> The polymer film according to any one of ⁇ 1> to ⁇ 5>, wherein the material B contains an aromatic polyester amide.
• Layer B comprises material A which is liquid at 260°C and material B which is solid at 260°C, wherein materials A and B are phase-separated, and in a cross section along the thickness direction of layer B, the ratio of the total length of the phase-separation interface between materials A and B to the length in a direction perpendicular to the thickness direction of layer B at a thickness of 50 ⁇ m is 2 or more, the elastic modulus at 160°C is 0.60 MPa or less, and the dielectric tangent is 0.01 or less.
• a polymer film and laminate with excellent step conformability and heat resistance are provided.
• 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).
• (meth)acrylic is a term used as a concept including both acrylic and methacrylic
• (meth)acryloyl is a term used as a concept including both acryloyl and methacryloyl.
• the term "process" in this specification includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. Furthermore, in the present disclosure, combinations of two or more preferred aspects are more preferred aspects.
• GPC gel permeation chromatography
• the average particle size (e.g., D50) of the particles in this disclosure is measured using a laser diffraction/scattering type particle size distribution analyzer.
• a laser diffraction/scattering type particle size distribution analyzer For example, HORIBA's LA-950V2 is used as the laser diffraction/scattering type particle size distribution analyzer.
• the polymer film according to the present disclosure comprises material A which is liquid at 260°C and material B which is solid at 260°C, wherein material A and material B are phase-separated, and in a cross section along the thickness direction of the polymer film, the ratio of the total length of the phase-separation interface between material A and material B to the length in a direction perpendicular to the thickness direction of the polymer film at a thickness of 50 ⁇ m is 2 or more, the elastic modulus at 160°C is 0.60 MPa or less, and the dielectric tangent is 0.01 or less.
• the polymer film is heated at a high temperature (e.g., 260°C), during which the water present in the polymer film becomes supersaturated and diffuses, which is thought to generate bubble nuclei.
• a high temperature e.g., 260°C
• Material A and material B are phase-separated, and when the ratio of the total length of the phase-separation interface between material A and material B to the length in the direction perpendicular to the thickness direction of the polymer film at a thickness of 50 ⁇ m in a cross section along the thickness direction of the polymer film is 2 or more, the growth of bubbles is suppressed, and therefore peeling between the polymer film and the metal layer is suppressed. In other words, the heat resistance is excellent.
• the elastic modulus at 160° C. is 0.60 MPa or less, the polymer film has excellent conformability to unevenness.
• WO 2022/202789 and JP 2019-199612 A do not include any description that focuses on the length of the phase separation interface in a cross section along the thickness direction of the polymer film.
• the polymer film according to the present disclosure includes a material A that is liquid at 260° C.
• Material A may be a low molecular weight compound or a high molecular weight compound, so long as it is liquid at 260° C.
• the material A may be of only one type, or of two or more types. The fact that it is liquid at 260°C can be confirmed by the fact that the viscosity when heated to 260°C is 100,000 Pa ⁇ s or less.
• material A is a thermoplastic resin, a thermoplastic elastomer, an uncured or semi-cured thermosetting resin, or an uncured or semi-cured thermosetting elastomer.
• thermoplastic elastomers examples include elastomers containing structural units derived from styrene (polystyrene-based elastomers), polyester-based elastomers, polyolefin-based elastomers, polyurethane-based elastomers, polyamide-based elastomers, polyacrylic-based elastomers, silicone-based elastomers, polyimide-based elastomers, etc.
• the thermoplastic elastomer may be a hydrogenated product.
• Polystyrene-based elastomers include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), polystyrene-poly(ethylene-propylene) diblock copolymers (SEP), polystyrene-poly(ethylene-propylene)-polystyrene triblock copolymers (SEPS), styrene-ethylene-butylene-styrene block copolymers (SEBS), and polystyrene-poly(ethylene/ethylene-propylene)-polystyrene triblock copolymers (SEEPS), styrene-isobutylene-styrene block copolymers (SIBS), as well as hydrogenated versions of these.
• SBS styrene-butadiene-styrene block copolymers
• material A is preferably a thermoplastic elastomer, more preferably an elastomer containing a structural unit derived from styrene, and even more preferably at least one selected from the group consisting of styrene-ethylene-butylene-styrene block copolymer, styrene-isobutylene-styrene block copolymer, styrene-ethylene-propylene-styrene copolymer, styrene-isoprene-styrene block copolymer, and hydrogenated products thereof.
• the content of material A is preferably 40% by mass to 95% by mass, and more preferably 60% by mass to 90% by mass, relative to the total mass of the polymer film.
• the weight average molecular weight of material A is preferably 1,000 or more, more preferably 10,000 or more, and even more preferably 30,000 or more.
• the upper limit of the weight average molecular weight is, for example, 1,000,000.
• material A is preferably used as a powder. More preferably, the method of converting material A into a powder includes a swelling step of swelling material A with a liquid medium, and a grinding step of grinding the swollen material A.
• 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.
• 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 material A 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 grinding the swollen material A is not particularly limited, and examples include a combination of a mortar and pestle, 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.
• material A 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 material A in an environment with a temperature of -50°C or lower before grinding it.
• the polymer film according to the present disclosure includes a material B that is solid at 260° C.
• Material B may be a low molecular weight compound or a high molecular weight compound, so long as it is solid at 260° C.
• the material B may be one type or two or more types. The fact that it is a solid at 260°C can be confirmed by the fact that the elastic modulus when heated to 260°C is 0.1 MPa or more.
• Examples of material B include liquid crystal polymers, fluororesins, polymers of compounds having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, polyphenylene ether and its modified products, aromatic polyether ketone, phenolic resins, epoxy resins, polyimides, cyanate resins, bismaleimide resins, triazine resins, and other thermosetting resins.
• material B contains a liquid crystal polymer.
• the type of liquid crystal polymer is not particularly limited, and any known liquid crystal polymer can be used.
• the liquid crystal polymer may be a thermotropic liquid crystal polymer that exhibits liquid crystallinity in a molten state, or a lyotropic liquid crystal polymer that exhibits liquid crystallinity in a solution state. In the case of a thermotropic liquid crystal, it is preferable that the liquid crystal polymer melts at a temperature of 450° C. or less.
• liquid crystal polymers examples include liquid crystal polyester, liquid crystal polyester amide in which an amide bond has been introduced into liquid crystal polyester, liquid crystal polyester ether in which an ether bond has been introduced into liquid crystal polyester, and liquid crystal polyester carbonate in which a carbonate bond has been introduced into liquid crystal polyester.
• the liquid crystal polymer is preferably a polymer having an aromatic ring, and is more preferably an aromatic polyester or an aromatic polyester amide.
• the liquid crystal polymer may be a polymer in which an isocyanate-derived bond such as an imide bond, a carbodiimide bond, or an isocyanurate bond has been introduced into an aromatic polyester or an aromatic polyester amide.
• an isocyanate-derived bond such as an imide bond, a carbodiimide bond, or an isocyanurate bond has been introduced into an aromatic polyester or an aromatic polyester amide.
• liquid crystal polymer is preferably a fully aromatic liquid crystal polymer made using only aromatic compounds as raw material monomers.
• liquid crystal polymer examples include the following liquid crystal polymers. 1) A compound obtained by polycondensation of (i) an aromatic hydroxycarboxylic acid, (ii) an aromatic dicarboxylic acid, and (iii) at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxyamine, and an aromatic diamine. 2) Those obtained by polycondensation of multiple types of aromatic hydroxycarboxylic acids. 3) (i) a polycondensation product of an aromatic dicarboxylic acid and (ii) at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxyamine and an aromatic diamine.
• Polyester such as polyethylene terephthalate
• aromatic hydroxycarboxylic acid are polycondensed.
• the aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic hydroxyamine and aromatic diamine may each independently be replaced with a derivative capable of undergoing polycondensation.
• the melting point of the liquid crystal polymer is preferably greater than 260°C, more preferably greater than 260°C and less than 350°C, and even more preferably greater than 260°C and less than 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 material B preferably contains a crystalline aromatic polyester amide.
• the dielectric loss tangent is further reduced.
• crystalline polymer refers to a polymer that has a clear endothermic peak, not a stepwise change in endothermic amount, in differential scanning calorimetry (DSC). Specifically, for example, it means that the half-width of the endothermic peak is within 10°C when measured at a heating rate of 10°C/min. Polymers with a half-width exceeding 10°C and polymers without a clear endothermic peak are classified as amorphous polymers and are distinguished from crystalline polymers.
• the aromatic polyester amide preferably contains a constitutional unit represented by the following formula 1, a constitutional unit represented by the following formula 2, and a constitutional unit represented by the following formula 3. -O-Ar 1 -CO-...Formula 1 -CO-Ar 2 -CO- ...Formula 2 —NH—Ar 3 —O— Formula 3
• Ar 1 , Ar 2 and Ar 3 each independently represent a phenylene group, a naphthylene group or a biphenylylene group.
• the structural unit represented by formula 1 will also be referred to as "unit 1", etc.
• the unit 1 can be introduced, for example, by using an aromatic hydroxycarboxylic acid as a raw material.
• the unit 2 can be introduced, for example, by using an aromatic dicarboxylic acid as a raw material.
• Unit 3 can be introduced, for example, by using an aromatic hydroxylamine as a raw material.
• aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, and aromatic hydroxylamine may each be independently replaced with a derivative capable of polycondensation.
• aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid esters and aromatic dicarboxylic acid esters by converting the carboxy group to an alkoxycarbonyl group or an aryloxycarbonyl group.
• Aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid halides and aromatic dicarboxylic acid halides by converting the carboxy groups to haloformyl groups.
• Aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced by aromatic hydroxycarboxylic acid anhydrides and aromatic dicarboxylic acid anhydrides by converting the carboxy groups to acyloxycarbonyl groups.
• polycondensable derivatives of compounds having a hydroxy group such as aromatic hydroxycarboxylic acids and aromatic hydroxyamines
• examples of polycondensable derivatives of compounds having a hydroxy group include those obtained by acylation of a hydroxy group into an acyloxy group (acylated products).
• aromatic hydroxycarboxylic acids and aromatic hydroxylamines can be replaced with their acylated counterparts by acylation of the hydroxy group to convert it to an acyloxy group.
• polycondensable derivatives of aromatic hydroxylamines include those obtained by acylation of the amino group to an acylamino group (acylated product).
• aromatic hydroxyamines can be replaced with acylated products by converting the amino group into an acylamino group through acylation.
• Ar 1 is preferably a p-phenylene group, a 2,6-naphthylene group, or a 4,4'-biphenylylene group, and more preferably a 2,6-naphthylene group.
• unit 1 is, for example, a constitutional unit derived from p-hydroxybenzoic acid.
• unit 1 is, for example, a constitutional unit derived from 6-hydroxy-2-naphthoic acid.
• Ar 1 is a 4,4'-biphenylylene group
• unit 1 is, for example, a constitutional unit derived from 4'-hydroxy-4-biphenylcarboxylic acid.
• Ar 2 is preferably a p-phenylene group, an m-phenylene group, or a 2,6-naphthylene group, and more preferably an m-phenylene group.
• unit 2 is, for example, a constitutional unit derived from terephthalic acid.
• unit 2 is, for example, a constitutional unit derived from isophthalic acid.
• Ar 2 is a 2,6-naphthylene group
• unit 2 is, for example, a constitutional unit derived from 2,6-naphthalenedicarboxylic acid.
• Ar 3 is preferably a p-phenylene group or a 4,4′-biphenylylene group, and more preferably a p-phenylene group.
• unit 3 is, for example, a constitutional unit derived from p-aminophenol.
• unit 3 is, for example, a constitutional unit derived from 4-amino-4'-hydroxybiphenyl.
• the content of units 1 is preferably 30 mol % or more, the content of units 2 is preferably 35 mol % or less, and the content of units 3 is preferably 35 mol % or less.
• the content of unit 1 is more preferably 30 mol % to 80 mol %, further preferably 30 mol % to 60 mol %, and particularly preferably 30 mol % to 40 mol %, based on the total content of unit 1, unit 2, and unit 3.
• the content of unit 2 is preferably 10 mol % to 35 mol %, more preferably 20 mol % to 35 mol %, and particularly preferably 30 mol % to 35 mol %, based on the total content of unit 1, unit 2, and unit 3.
• the content of unit 3 is preferably 10 mol % to 35 mol %, more preferably 20 mol % to 35 mol %, and particularly preferably 30 mol % to 35 mol %, based on the total content of unit 1, unit 2, and unit 3.
• the total content of each structural unit is the sum of the amounts (moles) of each structural unit, which is calculated by dividing the mass of each structural unit constituting the aromatic polyesteramide by the formula weight of each 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.
• -Fluorine resin- Material B may be a fluororesin from the viewpoints of heat resistance and mechanical strength.
• the type of fluororesin is not particularly limited, and any known fluororesin can be used.
• Fluororesins include homopolymers and copolymers that contain structural units derived from fluorinated ⁇ -olefin monomers, i.e., ⁇ -olefin monomers that contain at least one fluorine atom. Fluororesins also include copolymers that contain structural units derived from fluorinated ⁇ -olefin monomers and structural units derived from non-fluorinated ethylenically unsaturated monomers that are reactive with fluorinated ⁇ -olefin monomers.
• Fluorinated ⁇ -olefin monomers include CF 2 ⁇ CF 2 , CHF ⁇ CF 2 , CH 2 ⁇ CF 2 , CHCl ⁇ CHF, CCIF ⁇ CF 2 , CCl 2 ⁇ CF 2 , CCIF ⁇ CCIF, CHF ⁇ CCl 2 , CH 2 ⁇ CCIF , CCl 2 ⁇ CCIF, CF 3 CF ⁇ CF 2 , CF 3 CF ⁇ CHF , CF 3 CH ⁇ CF 2 , CF 3 CH ⁇ CH 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
• 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.
• Material B may be a polymer of a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond.
• polymers of compounds having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond include thermoplastic resins having structural units derived from cyclic olefin monomers such as norbornene or polycyclic norbornene monomers.
• the polymer of a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be a ring-opening polymer of the above-mentioned cyclic olefin or a hydrogenated product of a ring-opening copolymer using two or more kinds of cyclic olefins, or may be an addition polymer of a cyclic olefin and an aromatic compound having an ethylenically unsaturated bond such as a chain olefin or a vinyl group.
• a polar group may be introduced into the polymer of a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond.
• the polymer of the compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be used alone or in combination of two or more types.
• the ring structure of the cyclic aliphatic hydrocarbon group may be a monocyclic ring, a condensed ring in which two or more rings are condensed, or a bridged ring.
• Examples of the ring structure of the cyclic aliphatic hydrocarbon group include a cyclopentane ring, a cyclohexane ring, a cyclooctane ring, an isophorone 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.
• Polyphenylene ether- Material B may be a polyphenylene ether.
• the polyphenylene ether preferably has an average number of phenolic hydroxyl groups at the molecular terminals per molecule (number of terminal hydroxyl groups) of 1 to 5, and more preferably 1.5 to 3, from the viewpoints of dielectric tangent and heat resistance.
• the number of terminal hydroxyl groups of polyphenylene ether can be known from, for example, the specification value of the polyphenylene ether product.
• the number of terminal hydroxyl groups is expressed, for example, as the average number of phenolic hydroxyl groups per molecule of all polyphenylene ethers present in 1 mole of polyphenylene ether.
• the polyphenylene ether may be used alone or in combination of two or more kinds.
• polyphenylene ethers examples include polyphenylene ethers made of 2,6-dimethylphenol and at least one of a difunctional phenol and a trifunctional phenol, and poly(2,6-dimethyl-1,4-phenylene oxide). More specifically, the polyphenylene ether is preferably a compound having a structure represented by the formula (PPE).
• X represents an alkylene group having 1 to 3 carbon atoms or a single bond
• m represents an integer of 0 to 20
• n represents an integer of 0 to 20
• the sum of m and n represents an integer of 1 to 30.
• the alkylene group for X may, for example, be a dimethylmethylene group.
• the weight average molecular weight (Mw) is preferably 500 to 5,000, and more preferably 500 to 3,000, from the viewpoints of heat resistance and film formability. If the polyphenylene ether is not thermally cured, the weight average molecular weight (Mw) is not particularly limited, but is preferably 3,000 to 100,000, and more preferably 5,000 to 50,000.
• Aromatic polyether ketone - Material B 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.
• material B may be in a particulate form.
• material B may be organic particles or inorganic particles.
• the polymer film contains particulate material B, it preferably also contains material B that is not particulate.
• resins constituting the organic particles include polyethylene, polystyrene, urea-formaldehyde filler, polyester, cellulose, acrylic resin, fluororesin, cured epoxy resin, crosslinked benzoguanamine resin, crosslinked acrylic resin, and liquid crystal polymer.
• the resins constituting the organic particles may be one type or two or more types.
• the organic particles may also be fibrous, such as nanofibers, or hollow resin particles.
• the organic particles are preferably fluororesin particles, polyester resin particles, polyethylene particles, liquid crystal polymer particles, or nanofibers of cellulose resin, more preferably polytetrafluoroethylene particles, polyethylene particles, or liquid crystal polymer particles, and particularly preferably liquid crystal polymer particles.
• the liquid crystal polymer particles refer to, but are not limited to, a powdered liquid crystal obtained by polymerizing a liquid crystal polymer and pulverizing it with a pulverizer or the like.
• the preferred embodiments of the liquid crystal polymer constituting the liquid crystal polymer particles are the same as the preferred embodiments of the liquid crystal polymer described above.
• the average particle size of the organic particles is preferably 5 nm to 20 ⁇ m, and more preferably 100 nm to 10 ⁇ m, from the viewpoint of dielectric tangent and step conformability.
• Examples of compounds constituting the inorganic particles include BN, Al2O3 , AlN, TiO2 , SiO2 , barium titanate , strontium titanate, aluminum hydroxide, and calcium carbonate.
• the compounds constituting the inorganic particles may be one type or two or more types.
• metal oxide particles or fibers are preferred as inorganic particles, silica particles, titania particles, or glass fibers are more preferred, and silica particles or glass fibers are particularly preferred.
• the average particle size of the inorganic particles 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.
• material A and material B may contain a foaming agent that disappears when heated or that decomposes when heated to release a gas.
• the foaming agent may be an organic foaming agent or an inorganic foaming agent.
• organic foaming agents examples include particles containing acrylic resin as a main component, particles containing ethyl cellulose resin as a main component, particles containing butyral resin as a main component, nitrosamine compounds such as dinitrosopentamethylenetetramine (DPT), azo compounds such as azodicarbonamide (ADCA), and hydrazine compounds such as 4,4'-oxybisbenzenesulfonylhydrazide (OBSH) and hydrazodicarbonamide (HDCA).
• DPT dinitrosopentamethylenetetramine
• ADCA azo compounds
• hydrazine compounds such as 4,4'-oxybisbenzenesulfonylhydrazide (OBSH) and hydrazodicarbonamide (HDCA).
• inorganic foaming agents examples include bicarbonates such as sodium bicarbonate; carbonates; and combinations of bicarbonates and organic acid salts such as sodium citrate.
• the content of material B is preferably 5% by mass to 60% by mass, and more preferably 10% by mass to 40% by mass, relative to the total mass of the polymer film.
• the polymer film according to the present disclosure may contain other additives in addition to material A and material B.
• known additives can be used, such as a curing agent, a leveling agent, a defoaming agent, an antioxidant, an ultraviolet absorbing agent, a flame retardant, a colorant, etc.
• material A and material B are phase-separated. Whether or not phase separation has occurred can be determined by cutting out a cross section along the thickness direction of the polymer film with a microtome and observing it with an optical microscope. If sufficient contrast cannot be obtained with an optical microscope, it can also be determined by observing the elastic modulus distribution with a DFM.
• the ratio of the total length of the phase separation interface between material A and material B to the length in the direction perpendicular to the thickness direction of the polymer film at a thickness of 50 ⁇ m is 2 or more.
• the above ratio is preferably 20 or more, and more preferably 40 or more.
• the phase separation interface refers to the interface formed between material A and material B.
• the total length of the phase separation interface is measured by the following method.
• one of material A and material B forms a continuous phase and the other forms a dispersed phase.
• the average length of the dispersed phase in the minor axis direction is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less.
• the lower limit of the average length in the minor axis direction is not particularly limited, but is, for example, 0.1 ⁇ m.
• the dispersed phase preferably has an average length in the major axis direction of 10 ⁇ m or less, more preferably 5 ⁇ m or less.
• the lower limit of the average length in the major axis direction is not particularly limited, but is, for example, 0.5 ⁇ m.
• the length in the long axis direction means the length of the longest part of one of the dispersed phases separated into island-like phases.
• the length in the short axis direction means the length of the shortest part in the direction perpendicular to the long axis direction.
• the average length in the minor axis direction of the dispersed phase is 5 ⁇ m or less, the growth of bubbles is further suppressed when the polymer film is heated at a high temperature (e.g., 260°C), and peeling between the polymer film and the metal layer is further suppressed.
• a high temperature e.g., 260°C
• the average length in the long axis direction of the dispersed phase is 10 ⁇ m or less, the growth of bubbles is further suppressed when the polymer film is heated at a high temperature (e.g., 260°C), and peeling between the polymer film and the metal layer is further suppressed.
• a high temperature e.g., 260°C
• the polymer film according to the present disclosure has an elastic modulus of 0.60 MPa or less, preferably 0.50 MPa or less, and more preferably 0.49 MPa or less at 160° C.
• the lower limit of the elastic modulus at 160° C. is not particularly limited, but is, for example, 0.20 MPa.
• the elastic modulus at 160°C is 0.60 MPa or less, so the polymer film has excellent step conformability.
• 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) is prepared by cutting the surface of a polymer film with a microtome. 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 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 polymer film according to the present disclosure has a dielectric dissipation factor of 0.01 or less, preferably 0.005 or less, and more preferably 0.003 or less.
• the lower limit of the dielectric dissipation factor is not particularly limited, but is, for example, 0.0005.
• the dielectric loss tangent is measured by the following method.
• the dielectric loss tangent is measured by a resonance perturbation method at a frequency of 10 GHz.
• a 10 GHz cavity resonator (Kanto Electronics Application Development Co., Ltd., CP531) is connected to a network analyzer (Agilent Technology, Inc., E8363B), a polymer film is inserted into the cavity resonator, and the dielectric loss tangent is measured from the change in resonance frequency before and after insertion for 96 hours under an environment of 25°C temperature and 60% RH.
• the average thickness of the polymer film according to the present disclosure is not particularly limited, but from the viewpoint of dielectric tangent and step conformability, it is preferably 5 ⁇ m to 90 ⁇ m, more preferably 10 ⁇ m to 70 ⁇ m, and particularly preferably 15 ⁇ m to 50 ⁇ m.
• the average thickness of the polymer film is measured at any five points using an adhesive film thickness meter, such as an electronic micrometer (product name "KG3001A", manufactured by Anritsu Corporation), and the average value is calculated.
• an adhesive film thickness meter such as an electronic micrometer (product name "KG3001A", manufactured by Anritsu Corporation)
• the laminate according to the present disclosure includes a layer A and a layer B disposed on at least one surface of layer A.
• Layer B includes a material A that is liquid at 260°C and a material B that is solid at 260°C, where materials A and B are phase-separated, and in a cross section along the thickness direction of layer B, at a thickness of 50 ⁇ m, the ratio of the total length of the phase-separation interface between materials A and B to the length in a direction perpendicular to the thickness direction of layer B is 2 or more, the elastic modulus at 160°C is 0.60 MPa or less, and the dielectric loss tangent is 0.01 or less.
• the laminate according to the present disclosure has a layer A on which a layer B described below is provided. From the viewpoint of making the dielectric loss tangent of the laminate 0.01 or less, the layer A preferably contains a polymer having a dielectric loss tangent of 0.01 or less.
• Layer A may contain only one type of polymer with a dielectric tangent of 0.01 or less, or may contain two or more types.
• the dielectric tangent of a polymer having a dielectric tangent of 0.01 or less is preferably 0.005 or less, from the viewpoint of the dielectric tangent of the laminate, and more preferably is greater than 0 and less than 0.003.
• polymers with a dielectric tangent of 0.01 or less include liquid crystal polymers, fluororesins, polymers of compounds having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, thermoplastic resins such as polyether ether ketone, polyolefin, polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone, polyphenylene ether and modified products thereof, and polyether imide; elastomers such as copolymers of glycidyl methacrylate and polyethylene; and thermosetting resins such as phenol resins, epoxy resins, polyimides, and cyanate resins.
• thermoplastic resins such as polyether ether ketone, polyolefin, polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone, polyphenylene ether and modified products thereof, and polyether
• the polymer having a dielectric tangent of 0.01 or less is preferably a liquid crystal polymer. That is, it is preferable that layer A contains a liquid crystal polymer.
• the preferred embodiment of the liquid crystal polymer is the same as the preferred embodiment of the liquid crystal polymer that may be contained in the above-mentioned polymer film.
• Layer A may contain a filler in addition to the polymer having a dielectric tangent of 0.01 or less.
• the filler may be particulate or fibrous, and may be inorganic or organic particles. Specific examples of inorganic and organic particles are as described above.
• the filler contained in layer A is preferably an organic particle, and more preferably a liquid crystal polymer particle, from the viewpoints of the dielectric tangent, heat resistance, and step conformability of the laminate.
• Layer A may contain only one type of filler, or may contain two or more types of fillers.
• the content of the filler is preferably 30% by mass to 95% by mass, more preferably 50% by mass to 90% by mass, and particularly preferably 60% by mass to 80% by mass, relative to the total mass of Layer A, from the viewpoints of the dielectric tangent, heat resistance, and step-following ability of the laminate.
• Layer A may contain additives other than the above-mentioned components. Preferred aspects of other additives that may be contained in Layer A are the same as preferred aspects of other additives that may be contained in the polymer film according to the present disclosure.
• the layer A may contain, as other additives, a resin other than the polymer having a dielectric loss tangent of 0.01 or less.
• resins other than polymers having a dielectric tangent of 0.01 or less include thermoplastic resins other than liquid crystal polyesters, such as polypropylene, polyamide, polyesters other than liquid crystal polyesters, polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone, polyphenylene ether and modified products thereof, and polyether imide; elastomers such as copolymers of glycidyl methacrylate and polyethylene; and thermosetting resins such as phenol resins, epoxy resins, polyimide resins, and cyanate resins.
• the total content of other additives in Layer A is preferably 25 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, per 100 parts by mass of the polymer having a dielectric tangent of 0.01 or less.
• the average thickness of layer A is not particularly limited, but from the viewpoint of the dielectric tangent, heat resistance, and suppression of wiring distortion of the laminate, it is preferably 5 ⁇ m to 90 ⁇ m, more preferably 10 ⁇ m to 70 ⁇ m, and particularly preferably 15 ⁇ m to 50 ⁇ m.
• the method for measuring the average thickness of each layer in the laminate according to the present disclosure is as follows.
• the laminate is cut on a plane perpendicular to the surface direction of the laminate, the thickness is measured at five or more points on the cross section, and the average of these measurements is taken as the average thickness.
• the dielectric tangent of layer A is preferably 0.01 or less, more preferably 0.005 or less, and even more preferably greater than 0 and 0.003 or less.
• the laminate according to the present disclosure has a layer B on at least one surface of the layer A.
• Layer B includes a material A that is liquid at 260° C. and a material B that is solid at 260° C., where materials A and B are phase-separated, and in a cross section along the thickness direction of layer B, the ratio of the total length of the phase-separation interface between materials A and B to the length in a direction perpendicular to the thickness direction of layer B at a thickness of 50 ⁇ m is 2 or more, the elastic modulus at 160° C. is 0.60 MPa or less, and the dielectric loss tangent is 0.01 or less.
• material A and material B contained in the laminate according to the present disclosure are the same as the preferred aspects of material A and material B contained in the polymer film according to the present disclosure.
• Material A that is liquid at 260°C preferably has an elastic modulus of 0.10 MPa or less at 260°C
• material B that is solid at 260°C preferably has an elastic modulus of more than 0.10 MPa at 260°C.
• the preferred aspect of the ratio of the total length of the phase separation interface between material A and material B to the length in the direction perpendicular to the thickness direction of layer B at a thickness of 50 ⁇ m in a cross section along the thickness direction of layer B is the same as the preferred aspect of the ratio of the total length of the phase separation interface between material A and material B to the length in the direction perpendicular to the thickness direction of the polymer film according to the present disclosure at a thickness of 50 ⁇ m in a cross section along the thickness direction of the polymer film.
• layer B may contain other additives.
• Other additives include the same as other additives that may be included in the polymer films according to the present disclosure.
• the average thickness of layer B is preferably 5 ⁇ m to 50 ⁇ m, more preferably 10 ⁇ m to 40 ⁇ m, and even more preferably 15 ⁇ m to 30 ⁇ m.
• the laminate according to the present disclosure preferably further comprises layer C in addition to layer A and layer B, and more preferably comprises layer B, layer A, and layer C in this order.
• Layer C is preferably an adhesive layer, i.e., Layer C is preferably a surface layer (outermost layer).
• layer C contains at least one type of polymer.
• the preferred embodiment of the polymer used in layer C is the same as the preferred embodiment of the polymer used in layer A having a dielectric tangent of 0.01 or less.
• the polymer contained in layer C may be the same as or different from the polymer contained in layer A or layer B, but from the viewpoint of adhesion between layer A and layer C, it is preferable that the polymer is the same as the polymer contained in layer A.
• layer C contains an epoxy resin to bond the metal layer to layer A.
• the epoxy resin is preferably a crosslinked product of a multifunctional epoxy compound.
• a multifunctional epoxy compound is a compound having two or more epoxy groups.
• the number of epoxy groups in a multifunctional epoxy compound is preferably 2 to 4.
• layer C contains an aromatic polyester amide and an epoxy resin.
• the layer C may contain a filler.
• the preferred embodiments of the filler used in Layer C are the same as those of the filler used in Layer A.
• Layer C may contain additives other than those mentioned above. Preferred embodiments of the other additives used in Layer C are the same as those of the other additives used in Layer A, except as described below.
• the average thickness of layer C is preferably thinner than the average thickness of layer A from the viewpoints of the dielectric tangent of the laminate and adhesion to metals.
• T A /T C which is the ratio of the average thickness T A of Layer A to the average thickness T C of Layer C, is preferably greater than 1, more preferably from 2 to 100, even more preferably from 2.5 to 20, and particularly preferably from 3 to 10, from the viewpoints of the dielectric tangent of the laminate and the adhesion to the metal layer.
• T B /T C which is the ratio of the average thickness T B of Layer B to the average thickness T C of Layer C, is preferably greater than 1, more preferably from 2 to 100, even more preferably from 2.5 to 20, and particularly preferably from 3 to 10, from the viewpoints of the dielectric tangent of the laminate and the adhesion to the metal layer.
• the average thickness of layer C is preferably 0.1 ⁇ m to 20 ⁇ m, more preferably 0.5 ⁇ m to 15 ⁇ m, even more preferably 1 ⁇ m to 10 ⁇ m, and particularly preferably 2 ⁇ m to 8 ⁇ m.
• the average thickness of the laminate according to the present disclosure is preferably 6 ⁇ m to 200 ⁇ m, more preferably 12 ⁇ m to 100 ⁇ m, and particularly preferably 20 ⁇ m to 80 ⁇ m, from the viewpoints of strength and electrical properties (characteristic impedance) when laminated with a metal layer.
• the average thickness of the laminate is measured at any five points using an adhesive thickness gauge, such as an electronic micrometer (product name "KG3001A", manufactured by Anritsu Corporation), and the average value is calculated.
• an adhesive thickness gauge such as an electronic micrometer (product name "KG3001A”, manufactured by Anritsu Corporation)
• the laminate according to the present disclosure preferably has a dielectric tangent of 0.01 or less, more preferably 0.005 or less, and even more preferably greater than 0 and 0.003 or less.
• Method for producing the laminate according to the present disclosure is not particularly limited, and known methods can be referred to.
• Suitable film-forming methods include, for example, co-casting, multi-layer coating, and co-extrusion. Among these, the co-casting method is preferred.
• the multilayer structure of the laminate is produced by the co-casting method or the multi-layer coating method
• Solvents include, for example, halogenated hydrocarbons such as dichloromethane, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, 1-chlorobutane, chlorobenzene, and o-dichlorobenzene; halogenated phenols such as p-chlorophenol, pentachlorophenol, and pentafluorophenol; ethers such as diethyl ether, tetrahydrofuran, and 1,4-dioxane; ketones such as acetone and cyclohexanone; esters such as ethyl acetate and ⁇ -butyrolactone; and ethylene carbonate.
• halogenated hydrocarbons such as dichloromethane, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, 1-
• organic solvent examples include carbonates such as propylene carbonate and propylene carbonate; amines such as triethylamine; nitrogen-containing heterocyclic aromatic compounds such as pyridine; nitriles such as acetonitrile and succinonitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, and urea compounds such as tetramethylurea; nitro compounds such as nitromethane and nitrobenzene; sulfur compounds such as dimethyl sulfoxide and sulfolane; and phosphorus compounds such as hexamethylphosphoramide and tri-n-butylphosphoric acid, and two or more of these may be used.
• carbonates such as propylene carbonate and propylene carbonate
• amines such as triethylamine
• nitrogen-containing heterocyclic aromatic compounds such as pyridine
• nitriles such as acetonitrile and succinon
• the solvent is preferably a solvent mainly composed of an aprotic compound, particularly an aprotic compound without halogen atoms, because it is less corrosive and easier to handle, and the proportion of the aprotic compound 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.
• 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.
• a protic compound a compound having a dipole moment of 3 to 5 is preferably used.
• a solvent mainly composed of a compound having a boiling point of 220° C. or lower at 1 atmospheric pressure is preferred because it is easy to remove, and the proportion of the compound having a boiling point of 220° C. or lower at 1 atmospheric pressure in the entire solvent is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass.
• the aprotic compound it is preferable to use a compound having a boiling point of 220° C. or lower at 1 atmospheric pressure.
• a support may be used when the laminate is produced by the co-casting method, multi-layer coating method, co-extrusion method, or the like.
• the support include a metal drum, a metal band, a glass plate, a resin film, and a metal foil.
• the support is preferably a metal drum, a metal band, or a resin film.
• resin films include polyimide (PI) films, and examples of commercially available products include U-PIREX S and U-PIREX R manufactured by Ube Industries, Ltd., Kapton manufactured by DuPont-Toray Co., Ltd., and IF30, IF70, and LV300 manufactured by SKC Kolon PI.
• the support may have a surface treatment layer formed on its surface so that it can be easily peeled off.
• the surface treatment layer may be made of hard chrome plating, fluororesin, or the like.
• the average thickness of the support is not particularly limited, but is preferably from 25 ⁇ m to 75 ⁇ m, and more preferably from 50 ⁇ m to 75 ⁇ m.
• the method for removing at least a portion of the solvent from the cast or applied film-like composition (coating film) is not particularly limited, and any known drying method can be used.
• the laminate according to the present disclosure can be appropriately combined with stretching in terms of controlling molecular orientation and adjusting the thermal expansion coefficient and mechanical properties.
• the stretching method is not particularly limited, and known methods can be referred to. It may be performed in a state containing a solvent or in a dry film state. Stretching in a state containing a solvent may be performed by gripping the laminate and stretching it, or it may be performed by utilizing autogenous shrinkage due to drying without stretching it. Stretching is particularly effective for the purpose of improving the breaking elongation and breaking strength when the film brittleness is reduced by the addition of inorganic fillers, etc.
• the laminate according to the present disclosure can be used for various applications, and among others, can be suitably used as a film for electronic components such as printed wiring boards, and can be even more suitably used as a flexible printed circuit board. Moreover, the laminate according to the present disclosure can be suitably used as a liquid crystal polymer film for metal bonding.
• the aromatic polyesteramide P1a was heated 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 tangent of the aromatic polyesteramide P1 was 0.003.
• 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.
• the obtained liquid crystal polyester was pulverized using a jet mill ("KJ-200" manufactured by Kurimoto Iron Works, Ltd.) to obtain liquid crystal polymer particles F1.
• the liquid crystal polymer particles F1 had a median diameter (D50) of 7 ⁇ m, a dielectric loss tangent of 0.0007, and a melting point of 334° C.
• ⁇ Copper foil> M1 Product name "CF-T9DA-SV-18", manufactured by Fukuda Metal Foil & Powder Co., Ltd., copper foil with a 3 ⁇ m thick polymer layer formed on the treated surface with an average thickness of 18 ⁇ m by the following method - Formation of polymer layer - 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 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).
• a solution for forming layer A and a solution for forming layer B were prepared to produce a polymer film and a laminate.
• the polymer film was produced using the solution for forming layer B.
• the solution for forming Layer B was applied onto a support (product name "Nitoflon #900UL", manufactured by Nitto Denko Corporation, average thickness 50 ⁇ m).
• the coating was dried at 40° C. for 4 hours to remove the solvent from the coating, and a polymer film having a support was obtained.
• the 160° C. elastic modulus, and the dielectric tangent a sample was used which had been peeled off from the support, and further subjected to a heat treatment in which the temperature was raised from room temperature (25° C.) to 300° C. at a rate of 1° C./min in a nitrogen atmosphere and maintained at 300° C. for 2 hours, after which the support was peeled off.
• an LCP film product name "Vextar CTQ", manufactured by Kuraray Co., Ltd., average thickness 50 ⁇ m
• the treated side of the copper foil described in Table 1 was laminated at 300° C. using a thermocompression bonding machine to obtain a polymer film having a copper layer (single-sided copper-clad laminate).
• thermocompression bonding machine product name "MP-SNL", manufactured by Toyo Seiki Seisakusho Co., Ltd.
• MP-SNL manufactured by Toyo Seiki Seisakusho Co., Ltd.
• 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 and the substrate were stacked in this order so that the treated surface of the copper foil was in contact with the substrate.
• a laminator product name "Vacuum Laminator V-130", manufactured by Nikko Materials Co., Ltd.
• the prepared substrate having a wiring pattern was superimposed on the layer B side of the prepared single-sided copper-clad laminate, and hot pressed at 160° C. and 4 MPa for 1 hour to obtain a wiring board.
• 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 double-sided copper-clad laminate was etched to expose layer B.
• the modulus of elasticity in the exposed area was then measured as the indentation modulus using a nanoindentation method.
• the indentation modulus was measured using a microhardness tester (product name "DUH-W201", manufactured by Shimadzu Corporation) by applying a load with a Vickers indenter at a loading rate of 0.28 mN/s, holding the maximum load of 10 mN for 10 seconds, and then unloading at a loading rate of 0.28 mN/s.
• the copper foil of the double-sided copper-clad laminate was removed with an aqueous solution of ferric chloride, washed with pure water, and dried to obtain a polymer film, which was then used for the measurement.
• the dielectric loss tangent was measured at a frequency of 10 GHz by a resonance perturbation method.
• a 10 GHz cavity resonator (Kanto Electronics Application Development Co., Ltd., "CP531") was connected to a network analyzer (Agilent Technology, Inc., "E8363B”), and the polymer film was inserted into the cavity resonator.
• the dielectric loss tangent of the polymer film was measured from the change in resonance frequency before and after insertion for 96 hours under an environment of 25°C temperature and 60% RH.
• the prepared double-sided copper-clad laminate was cut into a size of 30 mm x 30 mm to prepare an evaluation sample.
• the evaluation sample was treated for 168 hours in a thermohygrostat at a temperature of 85°C and a relative humidity of 85%.
• the evaluation sample was then placed in an oven set at 260°C and heated for 15 minutes.
• the evaluation sample after heating was cut with a razor, and the cross section was observed with an optical microscope to evaluate the state of peeling.
• B Peeling was observed between Layer B and the copper foil with a width of 0.5 mm or less.
• C Peeling was observed between layer B and the copper foil with a width of more than 0.5 mm and 1 mm or less.
• D Peeling was observed between layer B and the copper foil with a width of more than 1 mm.
• Examples 1 to 12 contain material A, which is liquid at 260°C, and material B, which is solid at 260°C, and material A and material B are phase-separated.
• the ratio of the total length of the phase-separated interface between material A and material B to the length in the direction perpendicular to the thickness direction of the polymer film at a thickness of 50 ⁇ m is 2 or more
• the elastic modulus at 160°C is 0.60 MPa or less
• the dielectric dissipation factor is 0.01 or less, so that the film has excellent step conformability and heat resistance.

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