Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K19/38—Polymers
  • C09K19/3804—Polymers with mesogenic groups in the main chain
  • C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
• • 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

Definitions

• the present disclosure relates to films and laminates.
• JP 2021-30631A describes a laminated film in which a liquid crystal polyester layer to which no filler is added is laminated on both sides of a filler-added layer made of a synthetic resin to which a filler is added.
• Films may be required to suppress curling.
• the present disclosure has been made in view of these circumstances, and the problem to be solved by an embodiment of the present disclosure is to provide a film with suppressed curling. Further, another problem to be solved by another embodiment of the present disclosure is to provide a laminate using the above film.
• the present disclosure includes the following aspects. ⁇ 1> It has a phase separation structure including at least two phases, and if the glass transition temperature of the first phase, which is one of the at least two phases, is Tg1, then one of the at least two phases A film in which the second phase, which is different from the first phase, does not have an inflection point of storage modulus in a temperature range of 25° C. or higher and Tg1 or lower. ⁇ 2> It has a phase separation structure including at least two phases, and if the glass transition temperature of the first phase, which is one of the at least two phases, is Tg1, then one of the at least two phases The second phase, which is different from the first phase, has a melting point higher than Tg1.
• ⁇ 3> It has a phase separation structure including at least two phases, and if the glass transition temperature of the first phase, which is one of the at least two phases, is Tg1, then one of the at least two phases
• the second phase which is different from the first phase, has a storage modulus at a temperature 25° C. higher than Tg1 that is 0.5 times or more greater than a storage modulus at a temperature 25° C. lower than Tg1.
• ⁇ 4> The film according to any one of ⁇ 1> to ⁇ 3>, wherein the second phase has a storage modulus of 10 GPa or less at 25°C.
• ⁇ 5> The film according to any one of ⁇ 1> to ⁇ 4>, which has a dielectric loss tangent of 0.010 or less.
• ⁇ 6> The film according to any one of ⁇ 1> to ⁇ 5>, which has a crystallinity of 60% or less.
• ⁇ 7> The film according to any one of ⁇ 1> to ⁇ 6>, which has a glass transition temperature of 100°C to 200°C.
• ⁇ 8> The film according to any one of ⁇ 1> to ⁇ 7>, wherein the second phase has a melting point of 500° C. or lower.
• ⁇ 9> The film according to any one of ⁇ 1> to ⁇ 8>, wherein the second phase has a dielectric loss tangent of 0.002 or less.
• ⁇ 10> The film according to any one of ⁇ 1> to ⁇ 9>, wherein the dielectric loss tangent of the second phase is lower than the dielectric loss tangent of the film.
• ⁇ 11> The film according to any one of ⁇ 1> to ⁇ 10>, wherein the second phase contains particles.
• ⁇ 12> The film according to any one of ⁇ 1> to ⁇ 11>, wherein the content of the second phase is 45% by mass or more based on the total mass of the film.
• ⁇ 13> The film according to any one of ⁇ 1> to ⁇ 12>, wherein the first phase contains a liquid crystal polymer.
• ⁇ 14> The film according to any one of ⁇ 1> to ⁇ 13>, wherein the first phase contains an aromatic polyesteramide.
• the aromatic polyester amide includes a structural unit represented by the following formula 1, a structural unit represented by the following formula 2, and a structural unit represented by the following formula 3, and the structural unit represented by the formula 1.
• the content of the structural unit represented by Formula 1 is 30 mol% to 80 mol% with respect to the total content of the structural unit represented by Formula 2, and the structural unit represented by Formula 3, and the formula
• Ar 1 , Ar 2 and Ar 3 each independently represent a phenylene group, a naphthylene group or a biphenylylene group.
• Ar 1 , Ar 2 and Ar 3 each independently represent a phenylene group, a naphthylene group or a biphenylylene group.
• a film with suppressed curl can be provided. Further, according to another embodiment of the present disclosure, a laminate using the above film can be provided.
• alkyl group includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
• process in this specification refers not only to an independent process, but also to the term “process” when the intended purpose of the process is achieved, even if the process cannot be clearly distinguished from other processes. included.
• weight average molecular weight (Mw) and number average molecular weight (Mn) in this disclosure are determined using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all product names manufactured by Tosoh Corporation).
• the molecular weight was detected using a gel permeation chromatography (GPC) analyzer using a solvent THF (tetrahydrofuran) and a differential refractometer, and was calculated using polystyrene as a standard substance.
• GPC gel permeation chromatography
• a first aspect of the film according to the present disclosure has a phase-separated structure including at least two phases, and when the glass transition temperature of the first phase is Tg1, the second phase has a temperature range of 25° C. or higher and Tg1 or lower. In other words, it is a film that does not have an inflection point in its storage modulus.
• a second aspect of the film according to the present disclosure is a film that has a phase-separated structure including at least two phases, and where the glass transition temperature of the first phase is Tg1, the second phase has a melting point higher than Tg1. .
• a third aspect of the film according to the present disclosure has a phase-separated structure including at least two phases, and when the glass transition temperature of the first phase is Tg1, the second phase is stored at a temperature 25° C. higher than Tg1.
• the film has an elastic modulus that is 0.5 times or more the storage elastic modulus at a temperature 25° C. lower than Tg1.
• the first phase is one of at least two phases
• the second phase is one of at least two phases that is different from the first phase. It is phase.
• the film according to the present disclosure may further have another phase different from the first phase and the second phase.
• cur refers to a film having an annular or arcuate shape when viewed from a direction parallel to the main surface of the film.
• the inventors of the present invention have found that by adopting the above configuration, it is possible to provide a film with suppressed curling.
• the second phase when the glass transition temperature of the first phase is Tg1, the second phase does not have an inflection point of storage modulus in a temperature range of 25° C. or higher and Tg1 or lower.
• the first phase solidifies in a temperature range of 25° C. or more and Tg1 or less, shrinkage of the second phase is suppressed, so that curling of the film is suppressed.
• the second phase when the glass transition temperature of the first phase is Tg1, the second phase has a melting point higher than Tg1.
• the second phase when the glass transition temperature of the first phase is Tg1, the second phase has a storage modulus at a temperature 25° C. higher than Tg1 and a storage modulus at a temperature 25° C. lower than Tg1.
• the ratio is 0.5 times or more.
• JP 2021-30631 A does not include any description focusing on storage modulus or melting point.
• phase separation structure The film according to the present disclosure has a phase-separated structure including at least two phases.
• phase-separated structure refers to a structure in which at least two parts containing mutually different components exist in the film.
• phase separation structure examples include a sea-island structure, a co-continuous structure, a cylinder structure, and a lamella structure.
• a sea-island structure is a structure in which one of at least two phases forms a continuous phase and the other phase exists discontinuously and dispersed (i.e., the other phase forms a dispersed phase).
• a co-continuous structure means a structure in which at least two phases both form a continuous phase.
• the cylindrical structure means a structure having a plurality of rod-shaped phases in at least one of at least two phases.
• the lamellar structure means a layered structure in which at least two phases are alternately overlapped. Both the cylindrical structure and the lamellar structure are structures in which at least two phases form a continuous phase, but they are distinguished from the co-continuous structure because they have the above-mentioned characteristics (rod-like or layer-like). .
• the phase separation structure in the film according to the present disclosure is preferably a sea-island structure.
• the first phase is preferably a continuous phase and the second phase is preferably a dispersed phase.
• phase-separated structure can be confirmed by using means such as morphology observation, material distribution evaluation, mechanical property distribution evaluation, etc. 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, or the like.
• Material distribution evaluation can be performed using imaging such as infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy.
• Mechanical property distribution evaluation can be performed using an atomic force microscope or the like.
• the film according to the present disclosure is manufactured, for example, by applying a dispersion containing a polymer and polymer particles onto a substrate, drying it, and then performing an annealing treatment. At least a portion of the polymer particles are melted by the annealing treatment, and the polymer particles are connected to each other, thereby forming a phase-separated structure including a first phase derived from the polymer and a second phase derived from the polymer particles. . Details of the method for manufacturing a film according to the present disclosure will be described later.
• the film according to the present disclosure preferably has a dielectric loss tangent of 0.010 or less, more preferably 0.005 or less, and more than 0 and 0.003 or less. More preferred.
• the dielectric loss tangent shall be measured by the following method.
• the measurement of the dielectric loss tangent is carried out using a resonance perturbation method at a frequency of 10 GHz.
• a 10 GHz cavity resonator (Kanto Electronics Application Development Co., Ltd. CP531) was connected to a network analyzer (Agilent Technology's "E8363B"), and a measurement sample (width: 2.0 mm x length: 80 mm) was inserted into the cavity resonator. Then, the dielectric loss tangent of the measurement sample is measured from the change in resonance frequency before and after insertion for 96 hours in an environment with a temperature of 25° C. and a humidity of 60% RH.
• the film according to the present disclosure preferably has a crystallinity of 80% or less, more preferably 70% or less, and even more preferably 60% or less.
• the lower limit of the degree of crystallinity is not particularly limited, and is, for example, 1%.
• crystallinity is measured by the following method.
• the film is subjected to X-ray diffraction (XRD) measurement, and the ratio of the peak area of the crystal component to the total peak area of the obtained profile is defined as the degree of crystallinity.
• XRD X-ray diffraction
• the XRD measurement shall be performed at 25°C.
• the film according to the present disclosure preferably has a glass transition temperature of 100°C to 200°C, more preferably 130°C to 200°C, and more preferably 150°C to 200°C. is even more preferable.
• the glass transition temperature is measured using a differential scanning calorimetry (DSC) device.
• DSC differential scanning calorimetry
• the average thickness of the film 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 60 ⁇ m.
• the average thickness of the film is measured at five arbitrary (random) locations using an adhesive film thickness meter, such as an electronic micrometer (product name "KG3001A", manufactured by Anritsu Corporation), and the average value and do.
• an adhesive film thickness meter such as an electronic micrometer (product name "KG3001A", manufactured by Anritsu Corporation), and the average value and do.
• the film according to the present disclosure preferably has a phase-separated structure including at least two phases, and the first phase, which is one of the at least two phases, preferably includes at least one type of polymer.
• the type of polymer is not particularly limited, and known polymers can be used.
• polymers include liquid crystal polymers, fluororesins, polymers of compounds having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, polyether ether ketone, polyolefin, polyamide, polyester, polyphenylene sulfide, and polyester.
• Thermoplastic resins such as ether ketone, polycarbonate, polyether sulfone, polyphenylene ether and its modified products, polyetherimide; Elastomers such as copolymers of glycidyl methacrylate and polyethylene; Phenol resins, epoxy resins, polyimide resins, cyanate resins, etc. Examples include thermosetting resins.
• the first phase is made of a liquid crystal polymer, a fluororesin, a polymer of a compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, and polyphenylene ether. It is preferable to contain at least one kind of polymer selected from the group consisting of a liquid crystal polymer and a fluororesin, and it is more preferable to contain at least one kind of polymer selected from the group consisting of a liquid crystal polymer and a fluororesin. From the viewpoint of film formability and mechanical strength, It is particularly preferable that a liquid crystal polymer is included, and from the viewpoint of dielectric loss tangent, it is particularly preferable that a fluororesin is included.
• liquid crystal polymer The type of liquid crystal polymer is not particularly limited, and any known liquid crystal polymer can be used. Further, the liquid crystal polymer may be a thermotropic liquid crystal polymer that exhibits liquid crystallinity in a molten state, or may be a lyotropic liquid crystal polymer that exhibits liquid crystallinity in a solution state. Further, in the case of thermotropic liquid crystal, it is preferable that the liquid crystal melts at a temperature of 450° C. or lower.
• liquid crystal polymers examples include liquid crystal polyester, liquid crystal polyester amide in which an amide bond is introduced into a liquid crystal polyester, liquid crystal polyester ether in which an ether bond is introduced into a liquid crystal polyester, and liquid crystal polyester carbonate in which a carbonate bond is introduced into a liquid crystal polyester. can be mentioned.
• the liquid crystal polymer is preferably a polymer having an aromatic ring, and more preferably an aromatic polyester or an aromatic polyester amide.
• liquid crystal polymer may be a polymer in which isocyanate-derived bonds such as imide bonds, carbodiimide bonds, and isocyanurate bonds are further introduced into aromatic polyester or aromatic polyester amide.
• liquid crystal polymer is preferably a wholly aromatic liquid crystal polymer using only aromatic compounds as raw material monomers.
• liquid crystal polymer examples include the following liquid crystal polymers. 1) (i) aromatic hydroxycarboxylic acid, (ii) aromatic dicarboxylic acid, and (iii) at least one compound selected from the group consisting of aromatic diol, aromatic hydroxyamine, and aromatic diamine; Something made by polycondensation. 2) A product obtained by polycondensing multiple types of aromatic hydroxycarboxylic acids. 3) A product obtained by polycondensing (i) 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.
• a product obtained by polycondensing (i) a polyester such as polyethylene terephthalate and (ii) an aromatic hydroxycarboxylic acid.
• a polyester such as polyethylene terephthalate
• an aromatic hydroxycarboxylic acid the aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic hydroxyamine, and aromatic diamine may each be independently replaced with a polycondensable derivative.
• aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid esters and aromatic dicarboxylic acid esters.
• aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid halides and aromatic dicarboxylic acid halides.
• aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid anhydrides and aromatic dicarboxylic acid anhydrides.
• polymerizable derivatives of compounds having hydroxy groups such as aromatic hydroxycarboxylic acids, aromatic diols, and aromatic hydroxyamines include those obtained by acylating a hydroxy group to convert it into an acyloxy group (acylated products) can be mentioned.
• aromatic hydroxycarboxylic acids, aromatic diols, and aromatic hydroxyamines can each be replaced with acylated products.
• polymerizable derivatives of compounds having an amino group such as aromatic hydroxyamines and aromatic diamines include those obtained by acylating an amino group to convert it into an acylamino group (acylated product). For example, by acylating an amino group to convert it into an acylamino group, aromatic hydroxyamine and aromatic diamine can each be replaced with an acylated product.
• the liquid crystal polymer preferably has crystallinity (for example, aromatic polyesteramide described below).
• crystallinity for example, aromatic polyesteramide described below.
• 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.
• 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, 5. 000 to 30,000 is particularly preferred.
• the liquid crystal polymer preferably contains aromatic polyesteramide from the viewpoint of further lowering the dielectric loss tangent.
• Aromatic polyester amide is a resin that has at least one aromatic ring and also has an ester bond and an amide bond.
• the aromatic polyesteramide contained in the resin layer is preferably a wholly aromatic polyesteramide.
• the aromatic polyester amide includes a structural unit represented by the following formula 1, a structural unit represented by the following formula 2, and a structural unit represented by the following 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 etc. represented by Formula 1 will also be referred to as "unit 1" etc.
• Unit 1 can be introduced, for example, by using an aromatic hydroxycarboxylic acid as a raw material.
• 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 aromatic hydroxylamine as a raw material.
• aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, and aromatic hydroxylamine may each be independently replaced with a polycondensable derivative.
• aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid esters and aromatic dicarboxylic acid esters.
• aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid halides and aromatic dicarboxylic acid halides.
• aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid anhydrides and aromatic dicarboxylic acid anhydrides.
• polycondensable derivatives of compounds having hydroxy groups such as aromatic hydroxycarboxylic acids and aromatic hydroxyamines include derivatives obtained by acylating a hydroxy group to convert it into an acyloxy group (acylated products). .
• aromatic hydroxycarboxylic acid and aromatic hydroxylamine can each be replaced with an acylated product.
• polycondensable derivatives of aromatic hydroxylamine include those obtained by acylating an amino group to convert it into an acylamino group (acylated product).
• acylated product an aromatic hydroxyamine can be replaced with an acylated product by acylating an amino group to convert it into an acylamino group.
• 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 structural unit derived from p-hydroxybenzoic acid.
• unit 1 is, for example, a structural unit derived from 6-hydroxy-2-naphthoic acid.
• Ar 1 is a 4,4'-biphenylylene group
• unit 1 is, for example, a structural unit derived from 4'-hydroxy-4-biphenylcarboxylic acid.
• Ar 2 is preferably a p-phenylene group, m-phenylene group, or 2,6-naphthylene group, and more preferably an m-phenylene group.
• unit 2 is, for example, a structural unit derived from terephthalic acid.
• unit 2 is, for example, a structural unit derived from isophthalic acid.
• Ar 2 is a 2,6-naphthylene group
• unit 2 is, for example, a structural unit derived from 2,6-naphthalene dicarboxylic acid.
• Ar 3 is preferably a p-phenylene group or a 4,4'-biphenylylene group, more preferably a p-phenylene group.
• the unit 3 is, for example, a structural unit derived from p-aminophenol.
• unit 3 is, for example, a structural unit derived from 4-amino-4'-hydroxybiphenyl.
• the content of unit 1 is preferably 30 mol% or more, and the content of unit 2 is preferably 35 mol% or less.
• the content of unit 3 is preferably 35 mol% or less.
• the content of unit 1 is more preferably 30 mol% to 80 mol%, more preferably 30 mol% to 60 mol%, based on the total content of unit 1, unit 2, and unit 3. It is preferably 30 mol% to 40 mol%.
• the content of unit 2 is preferably 10 mol% to 35 mol%, more preferably 20 mol% to 35 mol%, based on the total content of unit 1, unit 2, and unit 3. , 30 mol% to 35 mol% is particularly preferred.
• the content of unit 3 is preferably 10 mol% to 35 mol%, more preferably 20 mol% to 35 mol%, based on the total content of unit 1, unit 2, and unit 3. , 30 mol% to 35 mol% is particularly preferred.
• the total content of each structural unit is the value which totaled the substance amount (mol) of each structural unit.
• the amount of substance of each structural unit is calculated by dividing the mass of each structural unit constituting the aromatic polyesteramide by the formula weight of each structural unit.
• the ratio between the content of unit 2 and the content of unit 3 is preferably 0.9/1 to 0.9/1 when expressed as [content of unit 2]/[content of unit 3] (mol/mol).
• the ratio is 1/0.9, more preferably 0.95/1 to 1/0.95, even more preferably 0.98/1 to 1/0.98.
• the aromatic polyester amide may have two or more types of units 1 to 3, each independently. Further, the aromatic polyester amide may have other structural units other than units 1 to 3. The content of other structural units is preferably 10 mol% or less, more preferably 5 mol% or less, based on the total content of all structural units.
• the aromatic polyester amide is preferably produced by melt polymerizing raw material monomers corresponding to the structural units constituting the aromatic polyester amide.
• the first phase may contain only one type of aromatic polyester amide, or may contain two or more types of aromatic polyesteramide.
• the content of aromatic polyesteramide is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total amount of the first phase.
• the upper limit of the aromatic polyesteramide content is not particularly limited, and may be 100% by mass.
• the liquid crystal polymer is preferably produced by melt polymerizing raw material monomers corresponding to the structural units constituting it.
• Melt polymerization may be carried out in the presence of a catalyst, examples of which include metal compounds such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide, Examples include nitrogen-containing heterocyclic compounds such as 4-(dimethylamino)pyridine and 1-methylimidazole, and nitrogen-containing heterocyclic compounds are preferably used.
• the melt polymerization may be further carried out by solid phase polymerization, if necessary.
• the liquid crystal polymer has a flow start temperature of preferably 250°C or higher, more preferably 250°C or higher and 350°C or lower, and still more preferably 260°C or higher and 330°C or lower.
• a flow start temperature of the liquid crystal polymer is within the above range, the solubility, heat resistance, strength and rigidity are excellent, and the viscosity of the solution is appropriate.
• the flow start temperature is also called the flow temperature or flow temperature
• the liquid crystal polymer is melted using a capillary rheometer while increasing the temperature at a rate of 4°C/min under a load of 9.8 MPa (100 kg/cm 2 ).
• This is the temperature at which liquid crystal polymers exhibit a viscosity of 4,800 Pa ⁇ s (48,000 poise) when extruded through a nozzle with an inner diameter of 1 mm and a length of 10 mm, which is a guideline for the molecular weight of liquid crystal polymers (edited by Naoyuki Koide). , "Liquid Crystal Polymers - Synthesis, Molding, and Applications," CMC Co., Ltd., June 5, 1987, p. 95).
• the type of fluororesin is not particularly limited, and any known fluororesin can be used.
• the fluororesin examples include fluorinated ⁇ -olefin monomers, that is, homopolymers and copolymers containing structural units derived from ⁇ -olefin monomers containing at least one fluorine atom.
• the fluororesin is a copolymer containing a structural unit derived from a fluorinated ⁇ -olefin monomer and a structural unit derived from a non-fluorinated ethylenically unsaturated monomer reactive with the fluorinated ⁇ -olefin monomer. can be mentioned.
• vinyl ethers eg, perfluoromethyl vinyl ether, perfluoropropyl vinyl ether, and perfluorooctyl vinyl ether
• 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. Further, the non-fluorinated ethylenically unsaturated monomers may be used alone or in combination of two or more.
• fluororesin examples include polychlorotrifluoroethylene (PCTFE), poly(chlorotrifluoroethylene-propylene), poly(ethylene-tetrafluoroethylene) (ETFE), and poly(ethylene-chlorotrifluoroethylene) (ECTFE).
• PCTFE polychlorotrifluoroethylene
• ETFE poly(chlorotrifluoroethylene-propylene)
• ETFE poly(ethylene-tetrafluoroethylene)
• ECTFE poly(ethylene-chlorotrifluoroethylene)
• PTFE poly(tetrafluoroethylene)
• FEP
• 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.
• 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 the product name NEOFLON PFA from Daikin Industries, Ltd., the product name TEFLON (registered trademark) PFA from DuPont, or Solvay Solexis. It is available from 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 including one or both of these.
• the partially modified PTFE homopolymer contains less than 1% by weight of constitutional units derived from comonomers other than tetrafluoroethylene, based on the total weight of the polymer.
• the fluororesin may be a crosslinkable fluoropolymer having a crosslinkable group.
• the crosslinkable fluoropolymer can be crosslinked by conventionally known crosslinking methods.
• One representative crosslinkable fluoropolymer is a fluoropolymer with (meth)acryloyloxy.
• R may be a fluorine-based oligomer chain containing a structural unit derived from tetrafluoroethylene.
• Forming a crosslinked fluoropolymer network by exposing a fluoropolymer with (meth)acryloyloxy groups to a free radical source to initiate a radical crosslinking reaction via the (meth)acryloyloxy groups on the fluororesin be able to.
• the free radical source is not particularly limited, but suitable examples include photoradical polymerization initiators and organic peroxides. 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.
• Polymers of a compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond examples include thermoplastic resins having structural units derived from cyclic olefin monomers such as norbornene or polycyclic norbornene monomers. can be mentioned.
• Polymers of compounds having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond can be obtained by hydrogenation of a ring-opening polymer of the above-mentioned cyclic olefin or a ring-opening copolymer using two or more types of cyclic olefins. It may be an addition polymer of a cyclic olefin and a chain olefin or an aromatic compound having an ethylenically unsaturated bond such as a vinyl group. Further, a polar group may be introduced into the polymer of the compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond. The polymer of a compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be used alone or in combination of two or more.
• the ring structure of the cyclic aliphatic hydrocarbon group may be a single ring, a condensed ring of two or more rings, 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 cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond is not particularly limited, and includes (meth)acrylate compounds having a cycloaliphatic hydrocarbon group, (meth)acrylate compounds having a cycloaliphatic hydrocarbon group, Examples include meth)acrylamide compounds, vinyl compounds having a cyclic aliphatic hydrocarbon group, and the like. Among these, (meth)acrylate compounds having a cyclic aliphatic hydrocarbon group are preferred.
• the compound having a cycloaliphatic 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 cyclic aliphatic hydrocarbon groups in the compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be one or more, and may have two or more.
• the polymer of a compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond is obtained by polymerizing a compound having at least one kind of cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond. It may be a polymer of compounds having two or more types of cycloaliphatic hydrocarbon groups and a group having an ethylenically unsaturated bond, or it may be a polymer having no cycloaliphatic hydrocarbon groups. It may also be a copolymer with other ethylenically unsaturated compounds. Further, the polymer of a compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond is preferably a cycloolefin polymer.
• the average number of phenolic hydroxyl groups per molecule at the end of the molecule is preferably 1 to 5, and 1.5 from the viewpoint of dielectric loss tangent and heat resistance. It is more preferable that the number is 3 to 3.
• the number of terminal hydroxyl groups of polyphenylene ether can be determined, for example, from the specification value of polyphenylene ether products. Further, 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.
• One type of polyphenylene ether may be used alone, or two or more types may be used in combination.
• polyphenylene ether examples include polyphenylene ether consisting of 2,6-dimethylphenol and at least one of bifunctional phenol and trifunctional phenol, and poly(2,6-dimethyl-1,4-phenylene oxide). Can be mentioned. 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
• m and n represent The sum represents an integer from 1 to 30.
• Examples of the alkylene group in the above X include a dimethylmethylene group.
• the weight average molecular weight (Mw) of polyphenylene ether is preferably from 500 to 5,000, preferably from 500 to 3,000, from the viewpoint of heat resistance and film forming properties when it is thermally cured after film formation. It is preferable that there be. Further, in the case of not being thermally cured, it is preferably 3,000 to 100,000, and preferably 5,000 to 50,000, although it is not particularly limited.
• the aromatic polyetherketone is not particularly limited, and any known aromatic polyetherketone can be used.
• the aromatic polyetherketone is a polyetheretherketone.
• Polyetheretherketone is a type of aromatic polyetherketone, and is a polymer in which bonds are arranged in the order of ether bonds, ether bonds, and carbonyl bonds. It is preferable that each bond is connected by a divalent aromatic group.
• One type of aromatic polyetherketone may be used alone, or two or more types may be used in combination.
• aromatic polyetherketones examples include polyetheretherketone (PEEK) having a chemical structure represented by the following formula (P1), and 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 the following formula (P5) Examples include polyetherketoneetherketoneketone (PEKEKK) having the chemical structure represented by:
• 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, more preferably 1,000 or less. That is, n is preferably 10 to 5,000, more preferably 20 to 1,000.
• the first phase may contain components other than the polymer as long as the effects of the present disclosure are not significantly impaired.
• known additives can be used.
• Other components include, for example, leveling agents, antifoaming agents, antioxidants, ultraviolet absorbers, flame retardants, and colorants.
• the content of the first phase is preferably 55% by mass or less, more preferably 20% by mass to 35% by mass, based on the total mass of the film.
• the glass transition temperature (Tg1) of the first phase is preferably 100°C to 200°C, more preferably 150°C to 200°C, from the viewpoint of thermal stability of the film.
• the method for measuring glass transition temperature is as described above.
• the film according to the present disclosure has a phase-separated structure including at least two phases, and one of the at least two phases, a second phase different from the first phase, includes at least one type of polymer. is preferred.
• the second phase may satisfy any or at least one of the following conditions with respect to the glass transition temperature Tg1 of the first phase, and the type of polymer that may be included in the second phase is not particularly limited.
• the storage modulus does not have an inflection point in the temperature range of 25° C. or higher and Tg1 or lower.
• Melting point is higher than Tg1.
• the storage modulus at a temperature 25° C. higher than Tg1 is 0.5 times or more the storage modulus at a temperature 25° C. lower than Tg1.
• polymer examples include liquid crystal polymer, polyethylene, polystyrene, urea-formalin filler, polyester, cellulose, acrylic resin, fluororesin, cured epoxy resin, crosslinked benzoguanamine resin, and crosslinked acrylic resin.
• the second phase preferably has a storage modulus at 25° C. of 10 GPa or less, more preferably 3.5 GPa or less.
• the lower limit of the storage modulus is not particularly limited, and is, for example, 0.1 GPa.
• storage modulus is measured by the following method
• the film was embedded in UV resin and cut with a microtome to prepare a sample for cross-sectional evaluation.
• a scanning probe microscope product name "SPA400", manufactured by SII Nanotechnology
• the storage modulus is measured with the dispersed phase specified as the second phase.
• the second phase preferably has a melting point of 500°C or less, more preferably 400°C or less.
• the lower limit of the melting point is not particularly limited, but is preferably 300°C.
• the method for measuring the melting point is as described above.
• the second phase preferably has a dielectric loss tangent of 0.002 or less, more preferably 0.0015 or less, and even more preferably more than 0 and 0.001 or less. .
• the dielectric loss tangent of the second phase is preferably lower than that of the film.
• the second phase preferably contains particles, more preferably polymer particles.
• the fact that the second phase contains particles can be confirmed by using means such as morphology observation, material distribution evaluation, mechanical property distribution evaluation, etc. on the film surface, film cross section, or both the film surface and cross section.
• the shape of the particles is not particularly limited, and examples thereof include spherical, spindle-shaped, prismatic, cylindrical, tabular, and irregular shapes.
• the average particle diameter of the particles is preferably from 5 nm to 20 ⁇ m, more preferably from 0.1 ⁇ m to 20 ⁇ m, even more preferably from 5 ⁇ m to 20 ⁇ m, from the viewpoint of suppressing curling of the film.
• the average particle size is the particle size (D50) when the volume accumulation from the small diameter side becomes 50% in the volume-based particle size distribution. D50 can be measured using a scanning electron microscope (SEM).
• the content of the second phase is preferably 45% by mass or more, more preferably 65% by mass to 80% by mass, based on the total mass of the film.
• the second phase when the glass transition temperature of the first phase is Tg1, the second phase does not have an inflection point of storage modulus in a temperature range of 25° C. or higher and Tg1 or lower.
• the temperature indicating the inflection point of storage modulus is 25 °C or higher than Tg1.
• An inflection point is a point where the way a continuous curve curves changes, and refers to a point where the slope of the tangent to the curve changes. For example, the point where the slope of the curve changes from increasing to decreasing (or from decreasing to increasing), the point where the shape of the curve changes from concave to convex (or from convex to concave), etc.
• the temperature that indicates the inflection point of the storage modulus is a curve obtained by measuring the storage modulus by scanning the temperature from the low temperature side to the high temperature side, and plotting the temperature on the horizontal axis and the storage modulus on the vertical axis. This is the temperature at which the inflection point occurs.
• the storage modulus was measured as described above.
• the second phase has a temperature at which the inflection point of the storage modulus is higher than Tg1.
• the temperature at which the storage modulus shows an inflection point is preferably 200°C or higher, more preferably 300°C or higher.
• the upper limit of the temperature indicating the inflection point of the storage modulus is not particularly limited, and is, for example, 5000°C.
• the absolute value of the difference between the temperature indicating the inflection point of the storage modulus in the second phase and Tg1 is preferably 50°C or higher, and 150°C or higher, from the viewpoint of further suppressing curling of the film. is more preferable.
• the upper limit of the absolute value of the difference is not particularly limited, and is, for example, 5000°C.
• the second phase since the second phase does not have an inflection point of the storage modulus in the temperature range of 25°C or higher and Tg1 or lower, the first phase does not have an inflection point in the temperature range of 25°C or higher and Tg1 or lower in the film manufacturing process. During solidification, shrinkage of the second phase is suppressed, and as a result, curling of the film is suppressed.
• the second phase when the glass transition temperature of the first phase is Tg1, the second phase has a melting point higher than Tg1.
• the method for measuring the melting point is as described above.
• the absolute value of the difference between the melting point of the second phase and Tg1 is preferably 50°C or higher, more preferably 150°C or higher, from the viewpoint of further suppressing curling of the film.
• the upper limit of the absolute value of the difference is not particularly limited, and is, for example, 5000°C.
• the melting point of the second phase is higher than Tg1
• shrinkage of the second phase is suppressed when the first phase solidifies in a temperature range below Tg1 in the film manufacturing process, and as a result, the film curls are suppressed.
• the second phase has a storage modulus at a temperature 25° C. higher than Tg1 and a storage modulus at a temperature 25° C. lower than Tg1.
• the ratio is 0.5 times or more.
• the storage modulus was measured as described above.
• the ratio of the storage modulus at a temperature 25°C higher than Tg1 to the storage modulus at a temperature 25°C lower than Tg1 is preferably 0.6 times or more, and preferably 0.8 times or more. is more preferable.
• the upper limit of the ratio is not particularly limited, but is usually less than 1.0 times.
• the second phase has a small change in storage modulus at a temperature 25° C. higher than Tg1 and at a temperature 25° C. lower than Tg1. Therefore, in the film manufacturing process, when the first phase solidifies in a temperature range of Tg1 or lower, shrinkage of the second phase is suppressed, and thus curling of the film is suppressed.
• the film according to the present disclosure may have one layer, or may have two or more layers.
• the film when manufacturing a laminate described below using a film, it is preferable that the film has an adhesive layer from the viewpoint of improving the adhesion between the metal base material and the film.
• the film according to the present disclosure can be used for various purposes. Among them, the film according to the present disclosure can be suitably used as a film for electronic components such as a printed wiring board, and can be more suitably used as a flexible printed circuit board.
• the film according to the present disclosure can be suitably used as a metal adhesive film.
• the film according to the present disclosure includes, for example, a step of preparing a dispersion containing a polymer, polymer particles, and a solvent (hereinafter also referred to as a "dispersion preparation step"), a base material, and a dispersion solution formed on the base material.
• a process of producing a precursor having a cured film of a dispersion hereinafter also referred to as "precursor production process”
• precursor production process a process of annealing the precursor to form a film on a substrate
• film forming process also referred to as a “film forming process”
• a film manufactured by the film manufacturing method of the present disclosure has a phase-separated structure including at least two phases.
• a method for manufacturing a film according to the present disclosure includes a step of preparing a dispersion containing a polymer, polymer particles, and a solvent.
• the preferred embodiments of the polymer prepared in the dispersion preparation step are the same as the preferred embodiments of the polymer that may be included in the first phase.
• Preferred embodiments of the polymer contained in the polymer particles prepared in the dispersion liquid preparation step are the same as the preferred embodiments of the polymer that may be included in the second phase.
• the polymer is preferably dissolved in the solvent contained in the dispersion, and the polymer particles are preferably insoluble in the solvent contained in the dispersion.
• the polymer is preferably present in a dissolved state in the solvent, and the polymer particles are not dissolved in the solvent, but are preferably present in a particulate and dispersed state.
• Examples of the solvent contained in the dispersion include dichloromethane, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, 1-chlorobutane, chlorobenzene, o-dichlorobenzene, etc.
• Halogenated hydrocarbons 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; Ethyl acetate and ⁇ -butyrolactone esters such as ethylene carbonate, carbonates such as propylene carbonate; amines such as triethylamine; nitrogen-containing heterocyclic aromatic compounds such as pyridine; nitrites such as acetonitrile and succinonitrile; N,N-dimethylformamide, N,N-dimethyl Amides such as acetamide and N-methylpyrrolidone; urea compounds such as tetramethylurea; nitro compounds such as nitromethane and nitrobenzene; sulfur compounds such as dimethylsulfoxide and sulfolane; phospho
• the solvent is preferably a solvent whose main component is an aprotic compound, especially an aprotic compound that does not have a halogen atom, because it has low corrosivity and is easy to handle.
• the proportion of the aprotic compound in the entire solvent is preferably 50% to 100% by weight, more preferably 70% to 100% by weight, particularly preferably 90% to 100% by weight.
• the above-mentioned aprotic compound easily dissolves the liquid crystal polymer, the above-mentioned aprotic compound is an amide such as N,N-dimethylformamide, N,N-dimethylacetamide, tetramethylurea, N-methylpyrrolidone, or an ester such as ⁇ -butyrolactone. is preferred, and N,N-dimethylformamide, N,N-dimethylacetamide, or N-methylpyrrolidone is more preferred.
• a method for producing a film according to the present disclosure includes a step of producing a precursor having a base material and a cured film of a dispersion liquid formed on the base material.
• the type of base material is not particularly limited, but when it is assumed that a laminate described below (specifically, a laminate including a film and a metal layer disposed on the film) is produced, a metal base material is used. It is preferable that it is a material.
• the metal constituting the metal base material is preferably copper.
• the thickness of the base material is not particularly limited, but is preferably 1 ⁇ m to 50 ⁇ m, more preferably 5 ⁇ m to 25 ⁇ m.
• a dispersion liquid is applied onto the base material and dried.
• methods for applying the dispersion include a casting method and a coating method.
• the drying method is not particularly limited, and may be natural drying or heating drying using hot air or the like.
• the thickness of the cured film of the dispersion is not particularly limited, but is preferably from 5 ⁇ m to 200 ⁇ m, more preferably from 10 ⁇ m to 100 ⁇ m.
• a cured film of the dispersion liquid may be directly formed on the surface of the base material, or after providing another layer on the base material, a cured film of the dispersion liquid may be formed on the surface of the other layer. may be formed.
• layers include, for example, an adhesive layer and a release layer. Other layers are appropriately selected depending on the purpose.
• a method for manufacturing a film according to the present disclosure includes a step of performing an annealing treatment on a precursor to form a film on a base material.
• the cured film of the dispersion is heated to form a film.
• the temperature of the annealing treatment is preferably 100°C to 400°C. Further, it is preferable that the annealing treatment time is 0.1 minute to 10 hours.
• the temperature and time of the annealing treatment can be changed as appropriate depending on the type of polymer and polymer particles, and can also be lowered or shortened by other means such as adding a catalyst.
• the film forming step is preferably carried out under an inert gas atmosphere from the viewpoint of lowering the dielectric loss tangent.
• the laminate according to the present disclosure may be any laminate as long as it includes the film according to the present disclosure.
• the laminate according to the present disclosure preferably includes a polymer film according to the present disclosure and a layer disposed on at least one surface of the polymer film.
• the layer disposed on at least one surface of the polymer film is not particularly limited, and examples thereof include a polymer layer and a metal layer.
• the layer disposed on at least one side of the polymer film may be a coating layer.
• the layer disposed on at least one surface of the film may be disposed on the entire surface of the film, or may be disposed only on a part of the film.
• the laminate according to the present disclosure preferably includes the film according to the present disclosure and a metal layer disposed on at least one surface of the film.
• the metal layer is preferably a copper layer.
• the copper foil used to form the copper layer is preferably a rolled copper foil formed by a rolling method or an electrolytic copper foil formed by an electrolytic method, and more preferably an electrolytic copper foil.
• the surface roughness of the metal layer on the side in contact with the film is preferably 0.5 ⁇ m or less, more preferably 0.3 ⁇ m or less.
• the lower limit is not particularly limited, and is, for example, 0 ⁇ m.
• surface roughness means a value expressed in micrometers of the average value in a reference area of the absolute value of the difference in height of each measurement point with respect to the average surface.
• the surface roughness Sa of a metal layer is measured by the following method.
• a square area of 465.48 ⁇ m in length and 620.64 ⁇ m in width is measured to evaluate the surface roughness Sa of the object to be measured.
• the average thickness of the metal layer, preferably the copper layer, is not particularly limited, but is preferably 3 ⁇ m to 30 ⁇ m, more preferably 5 ⁇ m to 20 ⁇ m.
• the copper foil may be a carrier-attached copper foil that is removably formed on a support (carrier).
• carrier known carriers can be used.
• the average thickness of the carrier is not particularly limited, but is preferably 10 ⁇ m to 100 ⁇ m, more preferably 18 ⁇ m to 50 ⁇ m.
• etching for example, to form a flexible printed circuit board.
• the etching method is not particularly limited, and any known etching method can be used.
• Aromatic polyesteramide A1a is heated under a nitrogen atmosphere from room temperature to 160°C over 2 hours and 20 minutes, then from 160°C to 180°C over 3 hours and 20 minutes, and held at 180°C for 5 hours.
• aromatic polyesteramide A1b was 220°C.
• Aromatic polyesteramide A1b is heated under a nitrogen atmosphere from room temperature to 180°C over 1 hour and 25 minutes, then from 180°C to 255°C over 6 hours and 40 minutes, and held at 255°C for 5 hours.
• the mixture was cooled to obtain a powdery aromatic polyesteramide A1 (wholly aromatic polyesteramide).
• the flow initiation temperature of aromatic polyesteramide A1 was 302°C. Further, the melting point of the aromatic polyesteramide A1 was measured using a differential scanning calorimeter and was found to be 311°C.
• Method C2 Low density polyethylene particles (product name "Flow Beads CL-2080N", manufactured by Sumitomo Seika Co., Ltd.) 70 L of deionized water was charged into a 150 L stainless steel polymerization tank equipped with a stirring blade and the tank was sealed. After removing the air in the tank, 100 g of e
• a solution for forming layer B was obtained by mixing the aromatic polyesteramide A1 solution and the polymer particles so that the content of the aromatic polyesteramide A1 and the polymer particles was as shown in Table 1.
• Example 1 a resin layer consisting of layer A and layer B was formed on the copper layer.
• the precursor in which a resin layer was formed on a copper layer was annealed at 300° C. for 3 hours in a nitrogen atmosphere to obtain a laminate in which a film was formed on a copper layer.
• the layer B in the film has a phase-separated structure including at least two phases, and the phase consisting of aromatic polyesteramide A1 is the first phase, and the layer B in the film is a phase-separated structure containing at least two phases.
• a phase consisting of polyethylene was used as the second phase.
• the glass transition temperature (Tg1) of the first phase in the film was measured. Furthermore, regarding the second phase of the film, the inflection point of storage modulus, melting point, ratio P, dielectric loss tangent, and storage modulus at 25° C. were measured.
• the ratio P means the ratio of the storage modulus at a temperature 25° C. higher than Tg1 to the storage modulus at a temperature 25° C. lower than Tg1.
• the film was measured for dielectric loss tangent, crystallinity, glass transition temperature, and coefficient of linear thermal expansion (CTE). Further, the above laminate was used to evaluate curl. The measurement method and evaluation method are as follows. Note that the melting point and dielectric loss tangent of the second phase were measured by cutting out the second phase from the film.
• the glass transition temperature was measured using a differential scanning calorimetry (DSC) device (product name "DSC-60A Plus", manufactured by Shimadzu Corporation).
• DSC differential scanning calorimetry
• ⁇ Storage modulus> The above laminate was embedded in UV resin and cut with a microtome to prepare a sample for cross-sectional evaluation. Using a scanning probe microscope (product name "SPA400", manufactured by SII Nanotechnology), the cross section exposed by the cutting was observed in VE-AFM mode, and the storage modulus was measured.
• SPA400 scanning probe microscope
• ⁇ Inflection point of storage modulus> The storage modulus was measured by scanning the temperature from the low temperature side to the high temperature side, and the inflection point was calculated from the curve obtained by plotting the temperature on the horizontal axis and the storage modulus on the vertical axis.
• ⁇ Dielectric loss tangent> The measurement of the dielectric loss tangent was carried out using a resonance perturbation method at a frequency of 10 GHz.
• a 10 GHz cavity resonator (Kanto Electronics Application Development Co., Ltd. CP531) was connected to a network analyzer (Agilent Technology's "E8363B"), and a measurement sample (width: 2.0 mm x length: 80 mm) was inserted into the cavity resonator. Then, the dielectric loss tangent of the measurement sample was measured from the change in resonance frequency before and after insertion for 96 hours under an environment of temperature 25° C. and humidity 60% RH.
• ⁇ Crystallinity> The film was subjected to X-ray diffraction (XRD) measurement, and the ratio of the peak area of the crystal component to the total peak area of the obtained profile was defined as the degree of crystallinity. Note that the XRD measurement was performed at 25°C.
• CTE Cost of linear thermal expansion
• TMA thermomechanical analyzer
• a tensile load of 1 g was applied to both ends of a film with a width of 5 mm and a length of 20 mm, and the temperature was increased from 25 to 200 °C at a rate of 5 °C/min.
• the linear expansion coefficient was calculated from the slope of the TMA curve between 30° C. and 150° C. when the sample was cooled to 30° C. at a rate of 5° C./min and then raised again at a rate of 5° C./min.
• the film was a laminate with copper foil, the copper foil was etched with iron chloride and the film was taken out for measurement.
• the laminate cut into 10 cm square pieces was placed on a flat table, and a rod-shaped weight was placed on the diagonal of the surface on which the film was formed. In this state, the shape of the film was observed from a direction parallel to the main surface of the film. When the film had an arc shape, the floating height of the film was measured. The floating height is the height of the top of the film on the side where no weight is placed from the flat base.
• the evaluation criteria are as follows. A: The film has an arc shape and the floating height is 24 mm or less. B: The film has an arc shape and the floating height is more than 24 mm. C: The film is circular.
• Examples 1 and 2 have a phase-separated structure including at least two phases, and the glass transition temperature of the first phase, which is one of the at least two phases, is Tg1.
• the second phase does not have an inflection point of storage modulus in the temperature range of 25° C. or higher and Tg1 or lower.
• Example 1 and Example 2 have a phase separation structure including at least two phases, and when the glass transition temperature of the first phase, which is one of the at least two phases, is Tg1, the second phase is , the melting point is higher than Tg1.
• Example 1 and Example 2 have a phase separation structure including at least two phases, and when the glass transition temperature of the first phase, which is one of the at least two phases, is Tg1, the second phase is , the storage modulus at a temperature 25°C higher than Tg1 is 0.5 times or more the storage modulus at a temperature 25°C lower than Tg1. Therefore, in Examples 1 and 2, it was found that curling was suppressed.
• the second phase has an inflection point of storage modulus in the temperature range of 25° C. or higher and Tg1 or lower.
• the melting point of the second phase is lower than Tg1.
• the storage modulus of the second phase at a temperature 25° C. higher than Tg1 is less than 0.5 times the storage modulus at a temperature 25° C. lower than Tg1. Therefore, in Comparative Example 1, curling was confirmed.

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