WO2022138665A1 - Film polymère, stratifié et son procédé de production - Google Patents

Film polymère, stratifié et son procédé de production Download PDF

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Publication number
WO2022138665A1
WO2022138665A1 PCT/JP2021/047403 JP2021047403W WO2022138665A1 WO 2022138665 A1 WO2022138665 A1 WO 2022138665A1 JP 2021047403 W JP2021047403 W JP 2021047403W WO 2022138665 A1 WO2022138665 A1 WO 2022138665A1
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Prior art keywords
polymer film
polymer
curable compound
layer
group
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PCT/JP2021/047403
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English (en)
Japanese (ja)
Inventor
泰行 佐々田
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富士フイルム株式会社
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Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to KR1020237019478A priority Critical patent/KR20230107302A/ko
Priority to JP2022571517A priority patent/JPWO2022138665A1/ja
Priority to CN202180084326.5A priority patent/CN116600986A/zh
Publication of WO2022138665A1 publication Critical patent/WO2022138665A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42—Plated through-holes or plated via connections
    • H05K3/429—Plated through-holes specially for multilayer circuits, e.g. having connections to inner circuit layers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards

Definitions

  • the present disclosure relates to a polymer film, a laminate, and a method for producing the same.
  • a liquid crystal polyester film containing at least liquid crystal polyester has a first degree of orientation with respect to a first direction parallel to the main surface of the liquid crystal polyester film.
  • the degree of orientation is defined as the degree of orientation in a second direction parallel to the main surface and orthogonal to the first direction
  • the first degree of orientation and the second degree of orientation are used.
  • the liquid crystal polyester having a first degree of orientation / second degree of orientation which is a ratio to the degree of orientation, of 0.95 or more and 1.04 or less, and is measured by a wide-angle X-ray scattering method in a direction parallel to the main surface.
  • a liquid crystal polyester film having a third degree of orientation of 60.0% or more is described.
  • Patent Document 2 describes a resin layer containing a polymer and a curable compound and having excellent adhesion to a metal layer, and a laminate for a high-frequency circuit laminated with a metal foil.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2020-26474
  • Patent Document 2 International Publication No. 2019/054334
  • An object to be solved by the embodiment of the present invention is to provide a polymer film having excellent ability to suppress wiring distortion at the time of bonding wiring. Further, an object to be solved by the embodiment of the present invention is to provide a laminate using the above polymer film and a method for producing the same.
  • the means for solving the above problems include the following aspects.
  • ⁇ 1> A polymer film containing a polymer having a dielectric loss tangent of 0.01 or less and a curable compound, wherein the curable compound is an oligomer or a polymer and contains a curable compound A.
  • ⁇ 2> A polymer film containing a liquid crystal polymer and a curable compound, wherein the curable compound is an oligomer or a polymer and contains a curable compound A.
  • ⁇ 3> The polymer film according to ⁇ 1> or ⁇ 2>, wherein the content of the curable compound A is higher on the surface than on the inside of the polymer film.
  • ⁇ 4> The polymer film according to ⁇ 1>, wherein the polymer having a dielectric loss tangent of 0.01 or less is a liquid crystal polymer.
  • ⁇ 5> The invention according to any one of ⁇ 1> to ⁇ 4>, wherein the polymer having a dielectric loss tangent of 0.01 or less or the liquid crystal polymer has a melting point Tm or a 5% by mass weight loss temperature Td of 200 ° C. or higher.
  • ⁇ 6> The polymer film according to any one of ⁇ 1> to ⁇ 5>, wherein the curable compound A has a weight average molecular weight of 10,000 or less.
  • the polymer film contains particles and contains particles.
  • ⁇ 8> The polymer film according to any one of ⁇ 1> to ⁇ 7>, wherein the polymer film contains a curing inhibitor.
  • the polymer having a dielectric loss tangent of 0.01 or less or the liquid crystal polymer contains a liquid crystal polymer having a structural repeating unit represented by any of the formulas (1) to (3) ⁇ 1> to ⁇ 8>
  • Ar 1 represents a phenylene group, a naphthylene group or a biphenylylene group
  • Ar 2 and Ar 3 independently represent a phenylene group, a naphthylene group, a biphenylylene group or the following formula (4).
  • Ar 4 and Ar 5 independently represent a phenylene group or a naphthylene group, and Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group or an alkylene group.
  • Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group or an alkylene group.
  • the film is 0.1 to 10. the film.
  • ⁇ 12> It has a layer A and a layer B provided on at least one surface of the layer A.
  • ⁇ 13> The polymer film according to any one of ⁇ 1> to ⁇ 12>, which is a base film.
  • ⁇ 14> Further having layer C The polymer film according to ⁇ 13>, which has the layer B, the layer A, and the layer C in this order.
  • ⁇ 15> The polymer film according to any one of ⁇ 1> to ⁇ 14>, which is a bonding sheet.
  • ⁇ 16> A laminate having the polymer film according to any one of ⁇ 1> to ⁇ 15> and a metal layer or metal wiring arranged on at least one surface of the polymer film.
  • ⁇ 17> The laminate according to ⁇ 16>, which has a metal layer or metal wiring, the polymer film, and the metal layer or metal wiring in this order.
  • ⁇ 18> The laminate according to ⁇ 16> or ⁇ 17>, which contains a cured product obtained by curing the curable compound A.
  • ⁇ 19> The polymer film according to any one of ⁇ 1> to ⁇ 15>, the metal layer or the metal wiring, the polymer film according to any one of ⁇ 1> to ⁇ 15>, and the metal layer.
  • a method for manufacturing a laminated body which comprises a bonding step of bonding a metal layer or a metal wiring to a film to form a laminated body in this order.
  • a partial curing step of forming the curable compound A by curing a part of the curable compound, a metal layer or a metal wiring on the film In a polymer film containing a liquid crystal polymer and a curable compound, a partial curing step of forming the curable compound A by curing a part of the curable compound, a metal layer or a metal wiring on the film.
  • a method for manufacturing a laminated body which comprises a bonding step of forming a laminated body by bonding in this order.
  • ⁇ 24> The method for producing a laminate according to any one of ⁇ 21> to ⁇ 23>, wherein the layer containing the curable compound A has a loss tangent of 0.1 or more at 300 ° C.
  • ⁇ 25> The method for producing a laminated body according to any one of ⁇ 21> to ⁇ 24>, wherein the bonding pressure in the bonding step is 0.1 MPa or more.
  • the content of the curable compound A is any one of ⁇ 21> to ⁇ 25>, which is 30% by mass to 100% by mass with respect to the total mass of the curable compound.
  • a method for producing a laminated body which comprises a through hole forming step of forming a through hole in a layer containing the curable compound A in the laminated body in this order.
  • ⁇ 29> The method for producing a laminate according to ⁇ 27> or ⁇ 28>, which comprises a post-curing step of curing the curable compound A after the through-hole forming step.
  • ⁇ 30> The method for producing a laminate according to any one of ⁇ 21> to ⁇ 29>, wherein the metal in the metal layer or the metal wiring is copper or silver.
  • the embodiment of the present invention it is possible to provide a polymer film having excellent ability to suppress wiring distortion at the time of bonding wiring. Further, according to another embodiment of the present invention, it is possible to provide a laminate using the above polymer film and a method for producing the same.
  • the notation that does not describe substitution or non-substitution includes those having no substituent as well as those having a substituent.
  • the "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).
  • (meth) acrylic is a term used in a concept that includes both acrylic and methacrylic
  • (meth) acryloyl is a term that is used as a concept that includes both acryloyl and methacrylic. Is.
  • the term "process” in the present specification is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” will be used as long as the intended purpose of the process is achieved. included.
  • “% by mass” and “% by weight” are synonymous, and “parts by mass” and “parts by weight” are synonymous.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • the first embodiment of the polymer film according to the present disclosure comprises a polymer having a dielectric loss tangent of 0.01 or less and a curable compound, wherein the curable compound comprises a curable compound A which is an oligomer or a polymer. ..
  • the second embodiment of the polymer film according to the present disclosure comprises a liquid crystal polymer and a curable compound, and the curable compound comprises a curable compound A which is an oligomer or a polymer.
  • polymer film according to the present disclosure refers to both the first embodiment and the second embodiment.
  • the present inventor has found that when a conventional polymer film is bonded to a wiring (particularly a metal wiring), the wiring is often distorted due to the stress at the time of bonding. As a result of diligent studies by the present inventor, it has been found that by adopting the above configuration, it is possible to provide a polymer film having excellent ability to suppress wiring distortion at the time of wiring bonding. The detailed mechanism by which the above effect is obtained is unknown, but it is presumed as follows. By containing the curable compound A which is an oligomer or a polymer as the curable compound, only a part of the curable compound is cured in a half-cured state (also referred to as "semi-cured state" or "B stage state").
  • the polymer film according to the present disclosure can be further strengthened after being bonded by curing the curable compound A.
  • the polymer film according to the present disclosure contains a curable compound, and the curable compound contains a curable compound A which is an oligomer or a polymer.
  • the curable compound in the present disclosure is a compound having a curable group, and may be any of a monomer, an oligomer, and a polymer.
  • the curable compound A is an oligomer or a polymer, and is preferably a polymer from the viewpoint of mechanical strength.
  • the oligomer is a polymer having a weight average molecular weight of 1,000 or more and less than 2,000
  • the polymer is a polymer having a polymerization average molecular weight of 2,000 or more.
  • the curable compound A is preferably an oligomer or polymer having a weight average molecular weight of 1,000 or more, and has a weight average molecular weight of 2, from the viewpoint of adhesion to a metal foil or metal wiring and uneven distribution. It is more preferably a polymer of 000 or more, further preferably a polymer having a weight average molecular weight of 3,000 or more and 200,000 or less, and a polymer having a weight average molecular weight of 5,000 or more and 100,000 or less. Especially preferable. Further, the weight average molecular weight of the curable compound A is preferably 100,000 or less, more preferably 50,000 or less, and particularly preferably 10,000 or less, from the viewpoint of suppressing wiring strain. preferable.
  • the polymer film according to the present disclosure preferably has a higher content of the curable compound A on the surface than on the inside of the polymer film.
  • the surface of the polymer film refers to the outer surface of the polymer film (the surface in contact with air or the substrate), in the range of 3 ⁇ m in the depth direction from the most surface, or with respect to the thickness of the entire polymer film from the most surface. Of the range of 10% or less, the smaller one is defined as the "surface".
  • the inside of the polymer film refers to a part other than the surface of the polymer film, that is, the inner surface of the polymer film (the surface not in contact with air or the substrate), and is not limited, but ⁇ from the center in the thickness direction of the polymer film. Of the range of 1.5 ⁇ m or the range of ⁇ 5% of the total thickness from the center in the thickness direction of the polymer film, the smaller numerical value is defined as “inside”.
  • the polymer film according to the present disclosure preferably contains particles, and preferably contains the curable compound inside or on the surface of the particles. Examples of the particles include microcapsules or microgels having the curable compound inside or on the surface. Among them, microcapsules or microgels having the above-mentioned curable compound inside are preferably mentioned. Further, the particles are preferably organic resin particles.
  • the number of curable groups in the curable compound may be 1 or more, may be 2 or more, but is preferably 2 or more. Further, the curable compound may have only one type of curable group or may have two or more types of curable groups.
  • the curable group is not particularly limited as long as it can be cured, but for example, an ethylenically unsaturated group, an epoxy group, an oxetanyl group, an isocyanate group, an acid anhydride group, a carbodiimide group, an N-hydroxyester group, and the like.
  • examples thereof include a glyoxal group, an imide ester group, an alkyl halide group, a thiol group, a hydroxy group, a carboxy group, an amino group, an amide group, an aldehyde group, a sulfonic acid group and the like.
  • an ethylenically unsaturated group is preferable as the curable group.
  • thermosetting resin examples include epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, and silicone. Examples thereof include resins, triazine resins and melamine resins. Further, the thermosetting resin is not particularly limited to these, and known thermosetting resins can be used. These thermosetting resins can be used alone or in combination of two or more. Further, as the curable compound A, a commercially available thermosetting resin-containing adhesive can also be used.
  • the curable compound A a curable compound obtained by half-curing a monomer is preferably mentioned.
  • the monomer is preferably an ethylenically unsaturated compound, more preferably a polyfunctional ethylenic compound.
  • the ethylenically unsaturated compound include (meth) acrylate compound, (meth) acrylamide compound, (meth) acrylic acid, styrene compound, vinyl acetate compound, vinyl ether compound, and olefin compound. Of these, (meth) acrylate compounds are preferred.
  • the molecular weight of the monomer is preferably 50 or more and less than 1,000, more preferably 100 or more and less than 1,000, and the molecular weight is 200, from the viewpoint of adhesion to the metal foil or metal wiring. It is particularly preferable that it is 800 or more and 800 or less.
  • the polymer film according to the present disclosure preferably contains a polymerization initiator.
  • the polymerization initiator is preferably a thermal polymerization initiator or a photopolymerization initiator.
  • the thermal polymerization initiator or the photopolymerization initiator known ones can be used.
  • the thermal polymerization initiator include thermal radical generators. Specific examples thereof include peroxide initiators such as benzoyl peroxide and azobisisobutyronitrile, and azo-based initiators.
  • the photopolymerization initiator include photoradical generators.
  • aromatic ketones (b) onium salt compounds, (c) organic peroxides, (d) thio compounds, (e) hexaarylbiimidazole compounds, (f) ketooxime ester compounds.
  • G borate compound, (h) azinium compound, (i) active ester compound, (j) compound having a carbon halogen bond, (k) pyridium compound and the like.
  • the polymerization initiator only one kind may be added, or two or more kinds may be used in combination.
  • the content of the polymerization initiator is preferably 0.01% by mass to 30% by mass, more preferably 0.05% by mass to 25% by mass, and 0.1% by mass to 20% by mass, based on the total mass of the curable compound. % Is more preferable.
  • the polymer film may contain only one type of curable compound, that is, only one type of curable compound A, or may contain two or more types of curable compound. Further, the polymer film may contain only one type of curable compound A, or may contain two or more types of the curable compound A.
  • the content of the curable compound in the polymer film is preferably 0.1% by mass to 70% by mass with respect to the total mass of the polymer film from the viewpoint of the dielectric positive contact of the polymer film and the ability to suppress wiring strain. It is more preferably 1% by mass to 60% by mass, further preferably 5% by mass to 60% by mass, and particularly preferably 10% by mass to 55% by mass.
  • the content of the curable compound A in the polymer film shall be 0.1% by mass to 70% by mass with respect to the total mass of the polymer film from the viewpoint of dielectric positive contact of the polymer film and suppression of wiring strain. , 1% by mass to 60% by mass, more preferably 5% by mass to 60% by mass, and particularly preferably 10% by mass to 55% by mass.
  • the content of the curable compound A in the polymer film is preferably 30% by mass to 100% by mass, preferably 50% by mass or more, based on the total mass of the curable compound from the viewpoint of suppressing wiring strain. It is more preferably 100% by mass, and particularly preferably 70% by mass to 100% by mass.
  • the first embodiment of the polymer film according to the present disclosure comprises a polymer having a dielectric loss tangent of 0.01 or less.
  • the dielectric loss tangent of the polymer having a dielectric loss tangent of 0.01 or less is preferably 0.005 or less, preferably 0.004 or less, from the viewpoint of the dielectric loss tangent of the polymer film and the adhesion to the metal foil or metal wiring. Is more preferable, and more than 0 and 0.003 or less are particularly preferable.
  • the polymer having a dielectric loss tangent of 0.01 or less may have a curable group, but it is assumed that the polymer is different from the curable compound A.
  • the curable compound A preferably has a dielectric loss tangent of more than 0.01, and is preferably not a liquid crystal polymer.
  • the method for measuring the dielectric loss tangent in the present disclosure shall be the following method.
  • the permittivity measurement is carried out by the resonance perturbation method at a frequency of 10 GHz.
  • a 10 GHz cavity resonator (CP531 manufactured by Kanto Electronics Applied Development Co., Ltd.) is connected to a network analyzer (“E8633B” manufactured by Agent Technology), and a polymer film, polymer or sample of each layer (width: 2 mm ⁇ length) is connected to the cavity resonator. (S: 80 mm) is inserted, and the dielectric constant and dielectric tangent of the polymer film or each layer are measured from the change in the resonance frequency before and after the insertion for 96 hours under a temperature of 25 ° C.
  • the measurement of the dielectric loss tangent of the polymer in the present disclosure shall be carried out according to the above-mentioned method for measuring the dielectric loss tangent using a sample obtained by identifying or isolating the chemical structure of the polymer constituting each layer and measuring the polymer as a powder. do.
  • the weight average molecular weight Mw of the polymer having a dielectric loss tangent of 0.01 or less is preferably 1,000 or more, more preferably 2,000 or more, and particularly preferably 5,000 or more. Further, the weight average molecular weight Mw of the polymer having a dielectric loss tangent of 0.005 or less is preferably 1,000,000 or less, more preferably 300,000 or less, and more preferably less than 100,000. Especially preferable.
  • the melting point Tm or 5% by mass weight loss temperature Td of the polymer having a dielectric loss tangent of 0.01 or less is 200 ° C. or higher from the viewpoint of the dielectric loss tangent of the polymer film, the adhesion to the metal foil or the metal wiring, and the heat resistance. It is preferably 250 ° C. or higher, more preferably 280 ° C. or higher, and particularly preferably 300 ° C. or higher and 420 ° C. or lower.
  • the melting point Tm in the present disclosure shall be measured using a differential scanning calorimetry (DSC) device. That is, 5 mg of a sample is placed in a DSC measuring pan, and the peak temperature of the endothermic peak that appears when the temperature is raised from 30 ° C.
  • DSC differential scanning calorimetry
  • the 5% by mass weight loss temperature Td in the present disclosure shall be measured by using a thermogravimetric analysis (TGA) apparatus. That is, the weight of the sample placed in the measurement pan is set as the initial value, and the temperature when the weight is reduced by 5% by mass with respect to the initial value due to the temperature rise is set as the 5% by mass weight loss temperature Td.
  • TGA thermogravimetric analysis
  • the glass transition temperature Tg of the polymer having a dielectric positive contact of 0.01 or less is preferably 150 ° C. or higher from the viewpoint of the dielectric positive contact of the polymer film, the adhesion to the metal foil or the metal wiring, and the heat resistance. It is more preferably 200 ° C. or higher, and particularly preferably 200 ° C. or higher and lower than 280 ° C.
  • the glass transition temperature Tg in the present disclosure shall be measured using a differential scanning calorimetry (DSC) device.
  • the type of polymer having a dielectric loss tangent of 0.01 or less is not particularly limited, and known polymers can be used.
  • the polymer having a dielectric positive contact of 0.01 or less include a liquid crystal polymer, a fluoropolymer, a polymer of a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, an aromatic polyether ketone, and a polyolefin.
  • thermoplastic resins such as polyetherimide; elastomers such as copolymers of glycidyl methacrylate and polyethylene; phenolic resins, Examples thereof include thermocurable resins such as epoxy resins, polyimide resins, and cyanate resins.
  • thermocurable resins such as epoxy resins, polyimide resins, and cyanate resins.
  • liquid crystal polymers, fluoropolymers, cyclic aliphatic hydrocarbon groups, and groups having an ethylenically unsaturated bond from the viewpoints of dielectric positive contact of polymer films, adhesion to metal foils or metal wiring, and heat resistance.
  • a liquid crystal polymer is particularly preferable from the viewpoint of the dielectric positive contact of the polymer film, and a fluoropolymer is preferable from the viewpoint of heat resistance and mechanical strength.
  • a second embodiment of the polymer film according to the present disclosure comprises a liquid crystal polymer.
  • the polymer having a dielectric loss tangent of 0.01 or less is preferably a liquid crystal polymer from the viewpoint of the dielectric loss tangent of the polymer film.
  • the type of liquid crystal polymer used in the present disclosure is not particularly limited, and known liquid crystal polymers can be used.
  • the liquid crystal polymer may be a thermotropic liquid crystal polymer that exhibits liquid crystal properties in a molten state, or may be a riotropic liquid crystal polymer that exhibits liquid crystal properties in a solution state.
  • the liquid crystal is melted at a temperature of 450 ° C. or lower.
  • the liquid crystal polymer include liquid crystal polyester, liquid crystal polyester amide having an amide bond introduced into the liquid crystal polyester, liquid crystal polyester ether having an ether bond introduced into the liquid crystal polyester, and liquid crystal polyester carbonate having a carbonate bond introduced into the liquid crystal polyester.
  • the liquid crystal polymer is preferably a polymer having an aromatic ring, and more preferably an aromatic polyester or an aromatic polyester amide, from the viewpoint of liquid crystal property and linear expansion coefficient.
  • the liquid crystal polymer may be a polymer in which an imide bond, a carbodiimide bond, an isocyanate-derived bond such as an isocyanurate bond, or the like is further introduced into an aromatic polyester or an aromatic polyester amide. Further, the liquid crystal polymer is preferably a total aromatic liquid crystal polymer using only an aromatic compound as a raw material monomer.
  • liquid crystal polymer examples include the following liquid crystal polymers. 1) (i) an aromatic hydroxycarboxylic acid, (ii) an aromatic dicarboxylic acid, and (iii) at least one compound selected from the group consisting of aromatic diols, aromatic hydroxyamines and aromatic diamines. It is made by polycondensing. 2) Polycondensation of multiple types of aromatic hydroxycarboxylic acids. 3) A polycondensation of (i) an aromatic dicarboxylic acid and (ii) at least one compound selected from the group consisting of aromatic diols, aromatic hydroxyamines and aromatic diamines. 4) (i) Polyester such as polyethylene terephthalate and (ii) aromatic hydroxycarboxylic acid are polycondensed.
  • the aromatic hydroxycarboxylic acid, the aromatic dicarboxylic acid, the aromatic diol, the aromatic hydroxyamine and the aromatic diamine may be independently replaced with a polycondensable derivative.
  • the aromatic hydroxycarboxylic acid and the aromatic dicarboxylic acid can be replaced with the aromatic hydroxycarboxylic acid ester and the aromatic dicarboxylic acid ester by converting the carboxy group into an alkoxycarbonyl group or an aryloxycarbonyl group.
  • the aromatic hydroxycarboxylic acid and the aromatic dicarboxylic acid can be replaced with the aromatic hydroxycarboxylic acid halide and the aromatic dicarboxylic acid halide.
  • the aromatic hydroxycarboxylic acid and the aromatic dicarboxylic acid can be replaced with the aromatic hydroxycarboxylic acid anhydride and the aromatic dicarboxylic acid anhydride.
  • polymerizable derivatives of compounds having a hydroxy group such as aromatic hydroxycarboxylic acids, aromatic diols and aromatic hydroxyamines, are those obtained by acylating a hydroxy group and converting it into an acyloxy group (acylated product). Can be mentioned.
  • the aromatic hydroxycarboxylic acid, the aromatic diol, and the aromatic hydroxyamine can each be replaced with an acylated product.
  • polymerizable derivatives of compounds having an amino group such as aromatic hydroxyamines and aromatic diamines, include those obtained by acylating an amino group and converting it into an acylamino group (acylated product).
  • aromatic hydroxyamines and aromatic diamines can each be replaced with acylated products by acylating the amino group to convert it to an acylamino group.
  • the liquid crystal polymer is a structural unit represented by any of the following formulas (1) to (3) from the viewpoint of liquid crystal property, dielectric loss tangent of the polymer film, and adhesion to the metal layer (hereinafter, formula (1). ) Is preferably referred to as a constituent unit (1) or the like, more preferably a constituent unit represented by the following formula (1), and the following formula (1). ), A structural unit represented by the following formula (2), and a structural unit represented by the following formula (3) are particularly preferable.
  • Ar 1 represents a phenylene group, a naphthylene group or a biphenylylene group
  • Ar 2 and Ar 3 independently represent a phenylene group, a naphthylene group, a biphenylylene group or the following formula (4).
  • Ar 4 and Ar 5 independently represent a phenylene group or a naphthylene group, and Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group or an alkylene group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-hexyl group and 2-ethylhexyl group. Examples thereof include an n-octyl group and an n-decyl group.
  • the alkyl group preferably has 1 to 10 carbon atoms.
  • aryl group examples include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 1-naphthyl group and a 2-naphthyl group.
  • the aryl group preferably has 6 to 20 carbon atoms.
  • the number of substitutions is independently, preferably 2 or less, and more preferably 1 in Ar 1 , Ar 2 or Ar 3 , respectively.
  • alkylene group examples include a methylene group, a 1,1-ethanediyl group, a 1-methyl-1,1-ethanediyl group, a 1,1-butandyl group and a 2-ethyl-1,1-hexanediyl group.
  • the alkylene group preferably has 1 to 10 carbon atoms.
  • the structural unit (1) is a structural unit derived from an aromatic hydroxycarboxylic acid.
  • Ar 1 is a p-phenylene group (a structural unit derived from p-hydroxyacousic acid) and an embodiment in which Ar 1 is a 2,6-naphthylene group (6-hydroxy-).
  • a structural unit derived from 2-naphthoic acid) or an embodiment having a 4,4'-biphenylylene group (constituent unit derived from 4'-hydroxy-4-biphenylcarboxylic acid) is preferable.
  • the structural unit (2) is a structural unit derived from an aromatic dicarboxylic acid.
  • Ar 2 is a p-phenylene group (constituent unit derived from terephthalic acid)
  • Ar 2 is an m-phenylene group (constituent unit derived from isophthalic acid)
  • Ar 2 Is a 2,6-naphthylene group (a structural unit derived from 2,6-naphthalenedicarboxylic acid)
  • Ar 2 is a diphenyl ether-4,4'-diyl group (diphenyl ether-4,4'-.
  • a structural unit derived from a dicarboxylic acid) is preferable.
  • the structural unit (3) is a structural unit derived from an aromatic diol, an aromatic hydroxylamine or an aromatic diamine.
  • Ar 3 is a p-phenylene group (a structural unit derived from hydroquinone, p-aminophenol or p-phenylenediamine) and an embodiment in which Ar 3 is an m-phenylene group (isophthalic acid).
  • the structural unit to be used) is preferable.
  • the content of the structural unit (1) is determined by dividing the total amount of all the structural units (the mass of each structural unit (also referred to as “monomer unit”) constituting the liquid crystal polymer by the formula amount of each structural unit.
  • the amount of substance equivalent (mol) of the constituent unit is determined, and the total value thereof) is preferably 30 mol% or more, more preferably 30 mol% to 80 mol%, still more preferably 30 mol% to 60 mol. %, Especially preferably 30 mol% to 40 mol%.
  • the content of the structural unit (2) is preferably 35 mol% or less, more preferably 10 mol% to 35 mol%, still more preferably 20 mol% to 35 mol%, particularly, with respect to the total amount of all the structural units.
  • the content of the structural unit (3) is preferably 35 mol% or less, more preferably 10 mol% to 35 mol%, still more preferably 20 mol% to 35 mol%, particularly, with respect to the total amount of all the structural units. It is preferably 30 mol% to 35 mol%.
  • the larger the content of the structural unit (1) the easier it is to improve the heat resistance, strength and rigidity, but if it is too large, the solubility in a solvent tends to be low.
  • the ratio between the content of the constituent unit (2) and the content of the constituent unit (3) is expressed by [content of the constituent unit (2)] / [content of the constituent unit (3)] (mol / mol). It is preferably 0.9 / 1 to 1 / 0.9, more preferably 0.95 / 1 to 1 / 0.95, and further preferably 0.98 / 1 to 1 / 0.98.
  • the liquid crystal polymer may have two or more types of constituent units (1) to (3) independently. Further, the liquid crystal polymer may have a structural unit other than the structural units (1) to (3), but the content thereof is preferably 10 mol% or less with respect to the total amount of all the structural units. It is preferably 5 mol% or less.
  • the liquid crystal polymer has a structural unit (3) in which at least one of X and Y is an imino group as a structural unit (3), that is, an aromatic as a structural unit (3). It is preferable to have at least one of the structural unit derived from hydroxylamine and the structural unit derived from aromatic diamine, and it is more preferable to have only the structural unit (3) in which at least one of X and Y is an imino group.
  • the liquid crystal polymer is preferably produced by melt-polymerizing a raw material monomer corresponding to a constituent unit constituting the liquid crystal polymer.
  • the melt polymerization may be carried out in the presence of a catalyst.
  • catalysts include magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, metal compounds such as antimony trioxide, 4- (dimethylamino) pyridine, 1-methylimidazole and the like.
  • metal compounds such as antimony trioxide, 4- (dimethylamino) pyridine, 1-methylimidazole and the like.
  • nitrogen heterocyclic compounds and nitrogen-containing heterocyclic compounds are preferably mentioned.
  • the melt polymerization may be further solid-phase polymerized, if necessary.
  • the lower limit of the flow start temperature of the liquid crystal polymer is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, still more preferably 250 ° C. or higher, and the upper limit of the flow start temperature is preferably 350 ° C. or higher, 330 ° C. or higher. Is more preferable, and 300 ° C. is even more preferable.
  • the solubility, heat resistance, strength and rigidity are excellent, and the viscosity of the solution is appropriate.
  • the flow start temperature also called the flow temperature or the flow temperature, melts the liquid crystal polymer using a capillary leometer while raising the temperature at a rate of 4 ° C./min under a load of 9.8 MPa (100 kg / cm 2 ). It is a temperature that shows a viscosity of 4,800 Pa ⁇ s (48,000 poise) when extruded from a nozzle with an inner diameter of 1 mm and a length of 10 mm, and is a guideline for the molecular weight of the liquid crystal polymer (edited by Naoyuki Koide). , "Liquid Liquid Polymer-Synthesis / Molding / Application-", CMC Co., Ltd., June 5, 1987, p.95).
  • the weight average molecular weight of the liquid crystal polymer is preferably 1,000,000 or less, more preferably 3,000 to 300,000, still more preferably 5,000 to 100,000. It is particularly preferably 5,000 to 30,000.
  • the film after heat treatment is excellent in thermal conductivity, heat resistance, strength and rigidity in the thickness direction.
  • the polymer having a dielectric loss tangent of 0.01 or less is preferably a fluoropolymer from the viewpoint of heat resistance and mechanical strength.
  • the type of the fluorine-based polymer used as the polymer having a dielectric loss tangent of 0.01 or less is not particularly limited as long as the dielectric loss tangent is 0.01 or less, and a known fluorine-based polymer is used. be able to.
  • fluoropolymer examples include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxy fluororesin, ethylene tetrafluoride / propylene hexafluoride copolymer, and ethylene / tetrafluoride.
  • fluoropolymer examples include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxy fluororesin, ethylene tetrafluoride / propylene hexafluoride copolymer, and ethylene / tetrafluoride.
  • examples thereof include an ethylene copolymer and an ethylene / chlorotrifluoroethylene copolymer. Among them, polytetrafluoroethylene is preferable.
  • the fluoropolymer is a fluorinated ⁇ -olefin monomer, that is, an ⁇ -olefin monomer containing at least one fluorine atom, and, if necessary, a non-fluorinated ethylene that is reactive with the fluorinated ⁇ -olefin monomer.
  • fluorinated ⁇ -olefin monomer that is, an ⁇ -olefin monomer containing at least one fluorine atom, and, if necessary, a non-fluorinated ethylene that is reactive with the fluorinated ⁇ -olefin monomer.
  • Examples include homopolymers and copolymers containing building blocks derived from sex unsaturated monomers.
  • Examples thereof include perfluoro (alkyl having 2 to 8 carbon atoms) vinyl ether (for example, perfluoromethyl vinyl ether, perfluoropropyl vinyl ether, perfluorooctyl vinyl ether) and the like.
  • tetrafluoroethylene CF 2
  • (perfluorobutyl) ethylene vinylidene fluoride
  • CH 2 CF 2
  • hexafluoropropylene CF 2 ).
  • At least one monomer selected from the group consisting of CFCF 3 ) is preferred.
  • the non-fluorinated monoethylene unsaturated monomer include ethylene, propylene, butene, and an ethylenically unsaturated aromatic monomer (for example, styrene and ⁇ -methylstyrene).
  • the fluorinated ⁇ -olefin monomer may be used alone or in combination of two or more.
  • the non-fluorinated ethylenically unsaturated monomer may be used alone or in combination of two or more.
  • fluoropolymer examples include polychlorotrifluoroethylene (PCTFE), poly (chlorotrifluoroethylene-propylene), poly (ethylene-tetrafluoroethylene) (ETFE), poly (ethylene-chlorotrifluoroethylene) (ECTFE), and the like.
  • the fluoropolymer may be used alone or in combination of two
  • the fluoropolymer is preferably at least one of FEP, PFA, ETFE, or PTFE.
  • FEP is available under the trade name of Teflon (registered trademark) FEP (TEFLON (registered trademark) FEP) from DuPont, or the trade name of NEOFLON FEP from Daikin Industries, Ltd .
  • PFA is the trade name of NEOFLON PFA from Daikin Industries, Ltd., the trade name of Teflon (registered trademark) PFA (TEFLON® PFA) from DuPont, or Solvay. It is available from Solexis) under the trade name of HYFLON PFA.
  • the fluoropolymer preferably contains PTFE.
  • the PTFE can include a PTFE homopolymer, a partially modified PTFE homopolymer, or a combination comprising one or both of these.
  • Partially modified PTFE homopolymers preferably contain less than 1% by weight of building blocks derived from commonomers other than tetrafluoroethylene, based on the total weight of the polymer.
  • the fluoropolymer may be a crosslinkable fluoropolymer having a crosslinkable group.
  • the crosslinkable fluoropolymer can be crosslinked by a conventionally known crosslinking method.
  • One of the typical crosslinkable fluoropolymers is a fluoropolymer having a (meth) acryloxy group.
  • R is a fluorinated oligomer chain having two or more structural units derived from a fluorinated ⁇ -olefin monomer or a non-fluorinated monoethylene unsaturated monomer, and R'is H or-. It is CH 3 and n is 1 to 4.
  • R may be a fluorine-based oligomer chain containing a structural unit derived from tetrafluoroethylene.
  • Forming a crosslinked fluoropolymer network structure by exposing a fluoropolymer having a (meth) acryloxy group to a free radical source in order to initiate a radical crosslinking reaction via the (meth) acryloxy group on a fluoropolymer.
  • the free radical source is not particularly limited, but a photoradical polymerization initiator or an organic peroxide is preferable. Suitable photoradical polymerization initiators and organic peroxides are well known in the art.
  • Crosslinkable fluoropolymers are commercially available and include, for example, DuPont Byton B.
  • the polymer having a dielectric tangent of 0.01 or less may be a polymer of a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond.
  • a polymer of a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond a structural unit formed of a monomer composed of a cyclic olefin such as, for example, norbornene or a polycyclic norbornene-based monomer is used.
  • thermoplastic resin having the above examples are also referred to as a thermoplastic cyclic olefin resin.
  • the polymer of the compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond is the hydrogenation of the ring-opening polymer of the above cyclic olefin or the ring-opening copolymer using two or more kinds of cyclic olefins. It may be a product, or it 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.
  • 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 isovoron ring, a norbornane ring, a dicyclopentane ring and the like.
  • 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 cyclic aliphatic hydrocarbon groups in the compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be 1 or more, and may be 2 or more.
  • a polymer of a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond polymerizes a compound having at least one cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond.
  • the polymer may be a polymer of a compound having two or more kinds of cyclic aliphatic hydrocarbon groups and a group having an ethylenically unsaturated bond, or may not have a cyclic aliphatic hydrocarbon group. It may be a copolymer with another ethylenically unsaturated compound.
  • the polymer of the compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond is preferably a cycloolefin polymer.
  • the polymer having a dielectric loss tangent of 0.01 or less may be a polyphenylene ether.
  • the weight average molecular weight (Mw) of the polyphenylene ether is preferably 500 to 5,000, preferably 500 to 3,000, from the viewpoint of heat resistance and film forming property when thermosetting after film formation. It is preferable to have. When it is not heat-cured, it is not particularly limited, but is preferably 3,000 to 100,000, and preferably 5,000 to 50,000.
  • the average number of phenolic hydroxyl groups at the molecular terminal per molecule is preferably 1 to 5 from the viewpoint of dielectric loss tangent and heat resistance, and is preferably 1.5. More preferably, the number is 3 to 3.
  • the number of hydroxyl groups or phenolic hydroxyl groups of the polyphenylene ether can be found, for example, from the standard value of the product of the polyphenylene ether. Examples of the number of terminal hydroxyl groups or the number of terminal phenolic hydroxyl groups include numerical values representing the average value of hydroxyl groups or phenolic hydroxyl groups per molecule of all polyphenylene ethers present in 1 mol of polyphenylene ether.
  • the polyphenylene ether may be used alone or in combination of two or more.
  • polyphenylene ether examples include polyphenylene ether composed of 2,6-dimethylphenol and at least one of bifunctional phenol and trifunctional phenol, poly (2,6-dimethyl-1,4-phenylene oxide) and the like.
  • examples thereof include those containing the polyphenylene ether of the above as a main component. More specifically, for example, a compound having a structure represented by the formula (PPE) is preferable.
  • X represents an alkylene group or a single bond having 1 to 3 carbon atoms
  • m represents an integer of 0 to 20
  • n represents an integer of 0 to 20
  • m and n The sum represents an integer from 1 to 30.
  • alkylene group in the X include a dimethylmethylene group and the like.
  • the polymer having a dielectric loss tangent of 0.01 or less may be an aromatic polyetherketone.
  • the aromatic polyetherketone is not particularly limited, and known aromatic polyetherketones can be used.
  • the aromatic polyetherketone is preferably a polyetheretherketone.
  • Polyetheretherketone is a kind of aromatic polyetherketone, and is a polymer in which bonds are arranged in the order of ether bond, ether bond, and carbonyl bond (ketone). It is preferable that each bond is linked by a divalent aromatic group.
  • the aromatic polyetherketone may be used alone or in combination of two or more.
  • aromatic polyether ketone examples include a polyether ether ketone having a chemical structure represented by the following formula (P1) (PEEK) and a polyether ketone having a chemical structure represented by the following formula (P2) (PEK).
  • P1 polyether ether ketone having a chemical structure represented by the following formula (P1)
  • P2 polyether ketone having a chemical structure represented by the following formula (P2)
  • P3 Polyether ether ketone ketone
  • PEEKK polyether ether ketone ketone
  • P5 examples thereof include polyether ketones and ether ketone ketones (PEKEKK) having the represented chemical structure.
  • n of the formulas (P1) to (P5) is preferably 10 or more, more preferably 20 or more, from the viewpoint of mechanical properties.
  • n is preferably 5,000 or less, more preferably 1,000 or less, in that an aromatic polyetherketone can be easily produced. That is, n is preferably 10 to 5,000, more preferably 20 to 1,000.
  • the polymer having a dielectric loss tangent of 0.01 or less is preferably a polymer soluble in a specific organic solvent (hereinafter, also referred to as “soluble polymer”).
  • the soluble polymers in the present disclosure are N-methylpyrrolidone, N-ethylpyrrolidone, dichloromethane, dichloroethane, chloroform, N, N-dimethylacetamide, ⁇ -butyrolactone, dimethylformamide, ethylene glycol monobutyl ether at 25 ° C.
  • ethylene glycol a polymer that dissolves 0.1 g or more in 100 g of at least one solvent selected from the group consisting of monoethyl ether.
  • the polymer film may contain only one kind of polymer having a dielectric loss tangent of 0.01 or less, or may contain two or more kinds of polymers.
  • the content of the polymer having a dielectric positive contact of 0.01 or less in the polymer film is 20% by mass with respect to the total mass of the polymer film from the viewpoint of the dielectric positive contact of the polymer film and the adhesion to the metal foil or the metal wiring. It is preferably ⁇ 99% by mass, more preferably 30% by mass to 98% by mass, further preferably 40% by mass to 97% by mass, and particularly preferably 50% by mass to 95% by mass. preferable.
  • the polymer film according to the present disclosure preferably contains a curing inhibitor from the viewpoint of controlling the curing state and suppressing wiring distortion.
  • the curing inhibitor include a polymerization inhibitor, a heat stabilizer, and the like, and known ones can be used.
  • the polymerization inhibitor include p-methoxyphenol, quinones (eg, hydroquinone, benzoquinone, methoxybenzoquinone, etc.), phenothiazine, catechols, alkylphenols (eg, dibutylhydroxytoluene (BHT), etc.), alkylbisphenols, dimethyldithiocarbamine.
  • Zinc acid copper dimethyldithiocarbamate, copper dibutyldithiocarbamate, copper salicylate, thiodipropionic acid esters, mercaptobenzimidazole, phosphites, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), Examples thereof include 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl (TEMPOL) and tris (N-nitroso-N-phenylhydroxylamine) aluminum salt (also known as cuperon Al).
  • TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyl
  • TMPOL 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl
  • tris N-nitroso-N-phenylhydroxylamine aluminum salt
  • heat stabilizer examples include tris (2,4-di-tert-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphite, and Tetrakiss (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite and bis (2,4-di-tert-butylphenyl) pentaerythritoldi Phosphite and other phosphorus-based heat stabilizers, and lactone-based heat stabilizers such as the reaction product of 8-hydroxy-5,7-di-tert-butylfuran-2-one and o-xylene can be mentioned.
  • the curing inhibitor one type may be used alone, or two or more types may be used in combination.
  • the content of the curing inhibitor is not particularly limited, but is preferably 0.0001% by mass to 2.0% by mass with respect to the total amount of the polymer film.
  • the polymer film preferably contains a filler from the viewpoint of the coefficient of linear expansion and the adhesion to the metal foil or the metal wiring.
  • the filler may be in the form of particles or fibers, and may be an inorganic filler or an organic filler.
  • the number density of the filler is larger inside than the surface of the polymer film from the viewpoint of the linear expansion coefficient and the adhesion to the metal foil or the metal wiring.
  • the inorganic filler a known inorganic filler can be used.
  • the material of the inorganic filler include BN, Al 2 O 3 , Al N, TiO 2 , SiO 2 , barium titanate, strontium titanate, aluminum hydroxide, calcium carbonate, and a material containing two or more of these. Be done.
  • metal oxide particles or fibers are preferable, and silica particles, titania particles, or glass fibers are more preferable, and silica particles or fibers are preferable from the viewpoint of adhesion to a metal foil or metal wiring. Glass fiber is particularly preferred.
  • the average particle size of the inorganic filler is preferably about 20% to about 40% of the thickness of the layer A, and for example, those having an average particle size of 25%, 30% or 35% of the thickness of the layer A may be selected. .. When the particle or fiber is flat, it indicates the length in the short side direction.
  • the average particle size of the inorganic filler is preferably 5 nm to 20 ⁇ m, more preferably 10 nm to 10 ⁇ m, and further preferably 20 nm to 1 ⁇ m from the viewpoint of adhesion to the metal foil or metal wiring. It is preferably 25 nm to 500 nm, and particularly preferably 25 nm.
  • the organic filler a known organic filler can be used.
  • the material of the organic filler include polyethylene, polystyrene, urea-formalin filler, polyester, cellulose, acrylic resin, fluororesin, cured epoxy resin, crosslinked benzoguanamine resin, crosslinked acrylic resin, and a material containing two or more of these.
  • the organic filler may be in the form of fibers such as nanofibers, or may be hollow resin particles.
  • the organic filler is preferably fluororesin particles, polyester-based resin particles, or cellulose-based resin nanofibers from the viewpoint of adhesion to a metal foil or metal wiring, and polytetrafluoroethylene particles. Is more preferable.
  • the average particle size of the organic filler is preferably 5 nm to 20 ⁇ m, more preferably 10 nm to 1 ⁇ m, still more preferably 20 nm to 500 nm, from the viewpoint of adhesion to the metal foil or metal wiring. It is particularly preferably 25 nm to 90 nm.
  • the polymer film may contain only one kind of filler or two or more kinds of fillers.
  • the content of the filler in the polymer film is preferably 5% by volume to 80% by volume, preferably 10% by volume to 70% by volume, based on the total volume of the polymer film, from the viewpoint of adhesion to the metal foil or metal wiring. It is more preferably 15% by volume to 70% by volume, and particularly preferably 20% by volume to 60% by volume.
  • the polymer film according to the present disclosure preferably has a three-dimensional crosslinked structure from the viewpoints of dielectric positive contact of the polymer film, adhesion to a metal foil or metal wiring, heat resistance, and mechanical strength.
  • Examples of the method for forming the three-dimensional crosslinked structure include a method of polymerizing a polyfunctional reactive compound (polyfunctional monomer) to form a cured product of the polyfunctional reactive compound.
  • the polymer film may contain other additives other than the above-mentioned components.
  • additives known additives can be used. Specific examples thereof include leveling agents, antifoaming agents, antioxidants, ultraviolet absorbers, flame retardants, colorants and the like.
  • the polymer film may contain other additives other than the polymer having a dielectric loss tangent of 0.01 or less and the compound having a functional group as other additives.
  • other resins include thermoplastic resins such as polypropylene, polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone, polyphenylene ether and its modifications, polyetherimide, etc .; Elastomers such as polymers; thermocurable resins such as phenolic resins, epoxy resins, polyimide resins, cyanate resins and the like can be mentioned.
  • the total content of the other additives in the polymer film is preferably 25 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of the polymer having a dielectric loss tangent of 0.01 or less. Yes, more preferably 5 parts by mass or less. Further, the total content of other additives in the polymer film is preferably smaller than the content of the compound having a functional group.
  • the polymer film according to the present disclosure may have a multilayer structure.
  • the polymer film according to the present disclosure preferably has a layer A and a layer B on at least one surface of the layer A.
  • the polymer film according to the present disclosure includes a layer A containing a polymer having a dielectric positive contact of 0.01 or less from the viewpoint of the dielectric positive contact of the polymer film and adhesion to a metal foil or metal wiring, and at least the above layer A. It is preferable to have a polymer having a dielectric positive contact of 0.01 or less and a layer B containing the curable compound A on one surface.
  • the layer A may contain only a polymer having a dielectric loss tangent of 0.01 or less, or may contain a polymer having a dielectric loss tangent of 0.01 or less and a curable compound. Further, the layer A may contain the curable compound A, but it is preferable that the layer A does not contain the curable compound A. Further, the layer A preferably further contains a filler.
  • the layer B preferably contains a polymer having a dielectric loss tangent of 0.01 or less and the curable compound A, and is more preferably a layer composed of the polymer having a dielectric loss tangent of 0.01 or less and the curable compound A. preferable.
  • the polymer film according to the present disclosure preferably has a layer C in addition to the layer A and the layer B, and preferably has the layer B, the layer A, and the layer C in this order.
  • the layer C preferably contains a polymer having a dielectric loss tangent of 0.005 or less and the curable compound A, and is more preferably a layer composed of the polymer having a dielectric loss tangent of 0.01 or less and the curable compound A. preferable.
  • the average thickness of the layer A is not particularly limited, but is preferably 5 ⁇ m to 90 ⁇ m, preferably 10 ⁇ m to 70 ⁇ m, from the viewpoint of the dielectric loss tangent of the polymer film and the adhesion to the metal foil or the metal wiring. More preferably, it is particularly preferably 15 ⁇ m to 50 ⁇ m.
  • the method for measuring the average thickness of each layer in the polymer film according to the present disclosure is as follows.
  • the polymer film is cut with a microtome and the cross section is observed with an optical microscope to evaluate the thickness of each layer.
  • the cross-section sample is cut out at three or more places, the thickness is measured at three or more points in each cross-section, and the average value thereof is taken as the average thickness.
  • the average thickness of the layers B and C is preferably thinner than the average thickness of the layer A independently from the viewpoint of the dielectric loss tangent of the polymer film and the adhesion to the metal foil or the metal wiring.
  • the value of TA / TB which is the ratio of the average thickness TA of the layer A to the average thickness TB of the layer B , is determined from the viewpoint of the dielectric loss tangent of the polymer film and the adhesion to the metal foil or the metal wiring. It is preferably larger than 1, more preferably 2 to 100, further preferably 2.5 to 20, and particularly preferably 3 to 10.
  • the value of TA / TC which is the ratio of the average thickness TA of the layer A to the average thickness TC of the layer C , is determined from the viewpoint of the dielectric loss tangent of the polymer film and the adhesion to the metal foil or metal wiring. It is preferably larger than 1, more preferably 2 to 100, further preferably 2.5 to 20, and particularly preferably 3 to 10. Further, the value of TC / TB , which is the ratio of the average thickness TC of the layer C to the average thickness TB of the layer B , is determined from the viewpoint of the coefficient of linear expansion and the adhesion to the metal foil or the metal wiring. It is preferably 0.2 to 5, more preferably 0.5 to 2, and particularly preferably 0.8 to 1.2.
  • the average thickness of the layers B and C is preferably 0.1 ⁇ m to 20 ⁇ m, preferably 0.5 ⁇ m, independently from the viewpoint of the dielectric loss tangent of the polymer film and the adhesion to the metal foil or the metal wiring. It is more preferably ⁇ 15 ⁇ m, further preferably 1 ⁇ m to 10 ⁇ m, and particularly preferably 3 ⁇ m to 8 ⁇ m.
  • the average thickness of the polymer film according to the present disclosure is preferably 6 ⁇ m to 200 ⁇ m, preferably 12 ⁇ m to 100 ⁇ m, from the viewpoints of strength, dielectric positive contact of the polymer film, and adhesion to a metal foil or metal wiring. It is more preferably 20 ⁇ m to 60 ⁇ m, and particularly preferably 20 ⁇ m to 60 ⁇ m.
  • the average thickness of the polymer film is measured at any five points using an adhesive film thickness meter, for example, an electronic micrometer (product name "KG3001A", manufactured by Anritsu Co., Ltd.), and is used as the average value thereof.
  • an adhesive film thickness meter for example, an electronic micrometer (product name "KG3001A", manufactured by Anritsu Co., Ltd.), and is used as the average value thereof.
  • the dielectric loss tangent of the polymer film according to the present disclosure is preferably 0.02 or less, more preferably 0.01 or less, further preferably 0.005 or less, and 0. It is particularly preferable that it exceeds 0.003 and is 0.003 or less.
  • the coefficient of linear expansion of the polymer film according to the present disclosure is preferably ⁇ 20 ppm / K to 50 ppm / K, more preferably ⁇ 10 ppm / K to 40 ppm / K, and 0 ppm / K to 35 ppm / K. It is more preferably 10 ppm / K to 30 ppm / K, and particularly preferably 10 ppm / K to 30 ppm / K.
  • the method for measuring the coefficient of linear expansion in the present disclosure shall be as follows. Using a thermomechanical analyzer (TMA), apply a tensile load of 1 g to both ends of a polymer film with a width of 5 mm and a length of 20 mm or a measurement sample of each layer, and raise the temperature from 25 ° C to 200 ° C at a rate of 5 ° C / min. Then, the coefficient of linear expansion is calculated from the slope of the TMA curve between 30 ° C. and 150 ° C. when the temperature is cooled to 30 ° C. at a rate of 20 ° C./min and the temperature is raised again at a rate of 5 ° C./min.
  • TMA thermomechanical analyzer
  • the layer to be measured may be scraped off with a razor or the like to prepare a measurement sample. If it is difficult to measure the coefficient of linear expansion by the above method, it shall be measured by the following method.
  • the film is cut with a microtome to prepare a section sample, set in an optical microscope equipped with a heating stage system (HS82, manufactured by Polymer Toledo), and subsequently from 25 ° C to 200 ° C at a rate of 5 ° C / min. After raising the temperature, the polymer film or the thickness of each layer (ts30) at 30 ° C. and the thickness of each layer (ts30) at 30 ° C. when the temperature was cooled to 30 ° C.
  • HS82 heating stage system
  • the thickness (ts150) of the polymer film or each layer was evaluated, the value obtained by dividing the dimensional change by the temperature change ((ts150-ts30) / (150-30)) was calculated, and the linear expansion coefficient of the polymer film or each layer was calculated. calculate.
  • the ratio Es / Ec of the surface elastic modulus Es and the internal elastic modulus Ec at 160 ° C. of the polymer film is preferably 0.05 to 10 and preferably 0.1 to 10 from the viewpoint of suppressing wiring strain. Is more preferable, 0.1 to 1 is even more preferable, and 0.1 to 0.5 is particularly preferable. Further, the ratio Es / Ec of the surface elastic modulus Es and the internal elastic modulus Ec at 300 ° C. of the polymer film is preferably 0.01 to 10 and preferably 0.05 to 10 from the viewpoint of suppressing wiring strain. It is more preferably present, more preferably 0.05 to 1, and particularly preferably 0.05 to 0.5. Unless otherwise specified, the elastic modulus in the present disclosure is the storage elastic modulus.
  • the surface elastic modulus Es is the elastic modulus of the layer existing on at least one surface, and the elastic modulus of the surface of the two surfaces having the lower elastic modulus is lower. It is an elastic modulus, and the internal elastic modulus Ec is the elastic modulus of the layer existing in the central portion in the thickness direction of the polymer film.
  • the surface elastic modulus Es is the elastic modulus of the portion within 5 ⁇ m from the surface of the polymer film, and is the elastic modulus of the surface of the two surfaces having the lower elastic modulus.
  • Internal elastic modulus The inside in Ec is the elastic modulus of the central portion in the thickness direction of the polymer film.
  • the loss tangent at 160 ° C. in the layer containing the curable compound A of the polymer film is preferably 0.01 or more, more preferably 0.03 or more, and 0. It is particularly preferably 0.05 to 0.2. Further, the loss tangent at 300 ° C. in the layer containing the curable compound A of the polymer film is preferably 0.03 or more, more preferably 0.1 or more from the viewpoint of suppressing wiring strain. , 0.1 to 0.6 is particularly preferable.
  • the method for measuring the elastic modulus and the loss tangent in the present disclosure is shown below.
  • the polymer film is embedded in UV resin and cut with a microtome to prepare a sample for cross-section evaluation. Subsequently, observation was performed in VE-AFM mode using a scanning probe microscope (SPA400, manufactured by SII Nanotechnology Co., Ltd.), and the surface and internal storage elastic moduli at the measured temperature, as well as the loss positive contact (loss elasticity). Rate / storage modulus) is calculated.
  • SPA400 scanning probe microscope
  • the method for producing the polymer film according to the present disclosure is not particularly limited, and known methods can be referred to.
  • a method for producing a polymer film according to the present disclosure for example, a casting method, a coating method, an extrusion method and the like are preferably mentioned, and among them, the casting method is particularly preferable.
  • the polymer film according to the present disclosure has a multi-layer structure, for example, a co-flow spreading method, a multi-layer coating method, a co-extrusion method and the like are preferably mentioned. Of these, the coextrusion method is particularly preferable for relatively thin film formation, and the coextrusion method is particularly preferable for thick film formation.
  • a layer A forming composition, a layer B forming composition, and a layer C in which the components of each layer such as a liquid crystal polymer are dissolved or dispersed in a solvent, respectively, are used. It is preferable to carry out a co-flow spreading method or a multi-layer coating method using a forming composition or the like.
  • the solvent examples include 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; ethylene Phenols such as carbonates and propylene carbonates; amines such as triethylamine; nitrogen-containing heterocyclic aromatic compounds such as pyridine; nitriles such as acetonitrile and succinonitrile; N, N-dimethyl
  • an aprotic compound particularly a solvent containing an aprotic compound having no halogen atom as a main component is preferable because it is low in corrosiveness and easy to handle, and the ratio of the aprotic compound to the whole solvent is It 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.
  • an amide such as N, N-dimethylformamide, N, N-dimethylacetamide, tetramethylurea, N-methylpyrrolidone, or ⁇ -butyrolactone may be used. Esters are preferred, with N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone being more preferred.
  • a solvent containing a compound having a dipole moment of 3 to 5 as a main component is preferable because the liquid crystal polymer is easily dissolved, and the ratio of the compound having a dipole moment of 3 to 5 in the whole solvent is preferable. Is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass.
  • the aprotic compound it is preferable to use a compound having a dipole moment of 3 to 5.
  • a solvent containing a compound having a boiling point of 220 ° C. or lower at 1 atm as a main component is preferable because it is easy to remove, and the ratio of the compound having a boiling point of 220 ° C. or less at 1 atm to the whole 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 atm.
  • a support when the polymer film is produced by the above-mentioned casting method, co-casting method, coating method, multi-layer coating method, extrusion method, co-extrusion method or the like, a support may be used. good. Further, when a metal layer (metal foil) or the like used for the laminate described later is used as a support, it may be used as it is without peeling. Examples of the support include a metal drum, a metal band, a glass plate, a resin film or a metal foil. Of these, metal drums, metal bands, and resin films are preferable.
  • the resin film examples include a polyimide (PI) film, and examples of commercially available products include U-Pylex S and U-Pylex R manufactured by Ube Kosan Co., Ltd., Kapton manufactured by Toray DuPont Co., Ltd., and Examples thereof include IF30, IF70 and LV300 manufactured by SKC Koron PI.
  • the support may have a surface treatment layer formed on the surface thereof so that the support can be easily peeled off.
  • the surface treatment layer hard chrome plating, fluororesin or the like can be used.
  • the average thickness of the resin film support is not particularly limited, but is preferably 25 ⁇ m or more and 75 ⁇ m or less, and more preferably 50 ⁇ m or more and 75 ⁇ m or less.
  • the method for removing at least a part of the solvent from the cast or applied film-like composition is not particularly limited, and a known drying method can be used.
  • the polymer film according to the present disclosure can be appropriately combined with stretching from the viewpoint of controlling the molecular orientation and adjusting the coefficient of thermal expansion and the mechanical properties.
  • the stretching method is not particularly limited, and a known method can be referred to, and the stretching method may be carried out in a solvent-containing state or in a dry film state. Stretching in a state containing a solvent may be carried out by grasping and stretching the film, or by utilizing self-shrinkage due to drying without stretching. Stretching is particularly effective for the purpose of improving the elongation at break and the strength at break when the brittleness of the film is reduced by the addition of an inorganic filler or the like.
  • the method for producing a polymer film according to the present disclosure may include a step of polymerizing by light or heat, if necessary.
  • the light irradiating means and the heat applying means are not particularly limited, and known light irradiating means such as a metal halide lamp and known heat applying means such as a heater can be used.
  • the light irradiation conditions and the heat application conditions are not particularly limited, and can be carried out at a desired temperature and time, and in a known atmosphere.
  • the method for producing a polymer film according to the present disclosure preferably includes a step of heat-treating (annealing) the polymer film.
  • the heat treatment temperature in the above heat treatment step is the glass transition of the polymer having a dielectric positive contact of 0.01 or less from the viewpoint of the mechanical strength of the web during the manufacturing process, the dimensional change of the manufactured polymer film, the breaking strength, and the like.
  • the temperature is preferably Tg or higher, or preferably less than the melting point Tm.
  • the heat treatment temperature in the heat treatment step is preferably 260 ° C. to 370 ° C., more preferably 310 ° C. to 350 ° C. from the viewpoint of breaking strength.
  • the annealing time is preferably 1 minute to 5 hours, more preferably 5 minutes to 3 hours.
  • the method for producing a polymer film according to the present disclosure may include other known steps, if necessary.
  • the polymer film according to the present disclosure can be used for various purposes, and above all, it can be suitably used for a film for electronic parts such as a printed wiring board, and can be preferably used for a flexible printed circuit board. Further, the polymer film according to the present disclosure can be suitably used as a polymer film for metal adhesion. Further, the polymer film according to the present disclosure can be suitably used as a base film. When used as a base film, the polymer film according to the present disclosure preferably has the layer A and the layer B. Furthermore, the polymer film according to the present disclosure can be suitably used as a bonding sheet (interlayer adhesive sheet). When used as a bonding sheet, the polymer film according to the present disclosure preferably has the layer A, the layer B, and the layer C.
  • the laminate according to the present disclosure may be a laminate of the polymer films according to the present disclosure, but the polymer film according to the present disclosure and a metal layer or metal wiring arranged on at least one surface of the polymer film. It is more preferable to have the polymer film according to the present disclosure, and it is more preferable to have a copper layer or a copper wiring arranged on at least one surface of the polymer film. Further, the laminate according to the present disclosure preferably has a metal layer or metal wiring, a polymer film according to the present disclosure, and a metal layer or metal wiring in this order, and the copper layer or copper wiring and the present disclosure. It is more preferable to have the polymer film according to the above and the copper layer or the copper wiring in this order.
  • the polymer film according to the present disclosure, the copper layer or the copper wiring, the polymer film according to the present disclosure, the metal layer or the metal wiring, and the polymer film according to the present disclosure are used. It is preferable to have them in order.
  • the two polymer films according to the present disclosure used for the laminate may be the same or different.
  • the metal layer and the metal wiring are not particularly limited and may be a known metal layer and metal wiring, but for example, a silver layer, a silver wiring, a copper layer or a copper wiring is preferable, and the copper layer or the copper wiring is preferable. Is more preferable. Further, the metal layer and the metal wiring are preferably metal wiring.
  • the metal in the metal layer and the metal wiring is preferably silver or copper, and more preferably copper. Since the polymer film according to the present disclosure can be further cured, for example, after the metal layer or the metal wiring is attached, the laminate according to the present disclosure contains the above-mentioned curable compound A from the viewpoint of durability. It is preferable to include a cured product obtained by curing. Further, the laminate according to the present disclosure includes a polymer film according to the present disclosure having a layer B, a layer A, and a layer C in this order, and a metal layer arranged on the surface of the polymer film on the layer B side.
  • the metal layer arranged on the surface on the layer B side is preferably a metal layer arranged on the surface of the layer B.
  • the metal layer arranged on the surface on the layer C side is preferably a metal layer arranged on the surface of the layer C, and the metal layer arranged on the surface on the layer B side is the surface of the layer B. It is more preferable that the metal layer arranged on the surface of the layer C and the metal layer arranged on the surface of the layer C is a metal layer arranged on the surface of the layer C.
  • the metal layer arranged on the surface on the layer B side and the metal layer arranged on the surface on the layer C side are different materials and thicknesses even if they are metal layers having the same material, thickness and shape. And may be a metal layer of shape. From the viewpoint of characteristic impedance adjustment, the metal layer arranged on the surface on the layer B side and the metal layer arranged on the surface on the layer C side may be metal layers of different materials and thicknesses. A metal layer may be laminated on only one side of B or layer C.
  • the method for attaching the polymer film and the metal layer or the metal wiring according to the present disclosure is not particularly limited, and a known laminating method can be used.
  • the peel strength between the polymer film and the copper layer is preferably 0.5 kN / m or more, more preferably 0.7 kN / m or more, and 0.7 kN / m to 2.0 kN / m. It is more preferably 0.9 kN / m to 1.5 kN / m, and particularly preferably 0.9 kN / m to 1.5 kN / m.
  • the peel strength between the polymer film and the metal layer shall be measured by the following method.
  • a 1.0 cm wide peeling test piece was prepared from the laminate of the polymer film and the metal layer, the polymer film was fixed to a flat plate with double-sided adhesive tape, and 50 mm by the 180 ° method according to JIS C 5016 (1994).
  • the strength (kN / m) when the polymer film is peeled from the metal layer at a rate of / minute is measured.
  • the metal layer is preferably a silver layer or a copper layer, and more preferably a copper layer.
  • a rolled copper foil formed by a rolling method or an electrolytic copper foil formed by an electrolytic method is preferable, and a rolled copper foil is more preferable from the viewpoint of bending resistance.
  • the average thickness of the metal layer, preferably the copper layer, is not particularly limited, but is preferably 2 ⁇ m to 20 ⁇ m, more preferably 3 ⁇ m to 18 ⁇ m, and even more preferably 5 ⁇ m to 12 ⁇ m.
  • the copper foil may be a copper foil with a carrier formed on a support (carrier) so as to be peelable.
  • a carrier a known carrier can be used.
  • the average thickness of the carrier is not particularly limited, but is preferably 10 ⁇ m to 100 ⁇ m, and more preferably 18 ⁇ m to 50 ⁇ m.
  • the metal layer preferably has a group capable of interacting with the polymer film on the surface on the side in contact with the polymer film.
  • the interoperable group is preferably a group corresponding to a functional group of a compound having a functional group contained in the polymer film, such as an amino group and an epoxy group, and a hydroxy group and an epoxy group. ..
  • the interactable group include the groups listed as functional groups in the above-mentioned compound having a functional group. Among them, from the viewpoint of adhesion and ease of processing, a covalently bondable group is preferable, an amino group or a hydroxy group is more preferable, and an amino group is particularly preferable.
  • etching it is also preferable to process the metal layer in the laminate according to the present disclosure into a desired circuit pattern by etching, for example, to form a flexible printed circuit board.
  • the etching method is not particularly limited, and a known etching method can be used.
  • the loss tangent at 160 ° C. in the layer containing the curable compound A is preferably 0.01 or more, preferably 0.03 or more, from the viewpoint of suppressing wiring strain. It is more preferably 0.05 to 0.2, and particularly preferably 0.05 to 0.2. Further, in the laminate according to the present disclosure, the loss tangent at 300 ° C. in the layer containing the curable compound A is preferably 0.03 or more, preferably 0.1 or more, from the viewpoint of suppressing wiring distortion. It is more preferable, and it is particularly preferable that it is 0.1 to 0.6. When the polymer film is a single layer, the layer containing the curable compound A is the polymer film itself.
  • the method for producing the laminate according to the present disclosure is not particularly limited, but in the case of half-cure, for example, in a polymer having a dielectric tangent of 0.01 or less and a polymer film containing a curable compound, the above-mentioned curing is performed. It is preferable to include a partial curing step of forming the curable compound A in which a part of the sex compound is cured, and a bonding step of bonding the film to the copper layer or the copper wiring to form a laminated body in this order. ..
  • the curable compound A obtained by curing a part of the curable compound is used in a polymer having a dielectric loss tangent of 0.01 or less and a polymer film containing a curable compound. It is preferable to include a partial curing step of forming. Further, the method for producing a laminate according to the present disclosure is a partial curing step of forming the curable compound A in which a part of the curable compound is cured in a liquid crystal polymer and a polymer film containing a curable compound. It is preferable to include.
  • the curing method in the partial curing step may be appropriately selected depending on the curable compound to be used, but it is preferable to use a polymerization initiator, and it is more preferable to use a thermal polymerization initiator. Further, in the partial curing step, it is preferable to use a curing inhibitor. By using a curing inhibitor, the progress of curing can be controlled, and a layer in a partially cured state, that is, a so-called B-stage layer can be easily formed. Further, as the polymer having a dielectric loss tangent of 0.01 or less, the curable compound, and the curable compound A, those described above can be preferably used.
  • the method for producing a laminated body according to the present disclosure preferably includes a bonding step of bonding the film to a metal layer or metal wiring to form a laminated body. Further, in the above bonding step, it is preferable to bond the metal wiring.
  • the laminating method in the laminating step is not particularly limited, and a known laminating method can be used.
  • the bonding pressure in the bonding step is not particularly limited, but is preferably 0.1 MPa or more, and preferably 0.2 MPa to 10 MPa.
  • the bonding temperature in the bonding step can be appropriately selected depending on the film or the like used, but is preferably 150 ° C. or higher, more preferably 280 ° C. or higher, and 280 ° C. or higher 420. It is particularly preferable that the temperature is below ° C.
  • the content of the curable compound A after the bonding step is 30% by mass with respect to the total mass of the curable compound. It is preferably ⁇ 100% by mass, more preferably 50% by mass to 100% by mass, and particularly preferably 70% by mass to 100% by mass.
  • the method for producing a laminated body according to the present disclosure can be suitably used for a method for forming through holes.
  • the method for manufacturing a laminate according to the present disclosure includes a preparation step for preparing a polymer film according to the present disclosure, a bonding step for bonding a metal layer or a metal wiring to the polymer film to form a laminate, and a bonding step.
  • the preparation step is not particularly limited, and the polymer film according to the present disclosure may be prepared. Further, the polymer film according to the present disclosure may be produced.
  • the bonding step is the same as the bonding step described above, and the preferred embodiment is also the same.
  • through holes are provided for mounting electronic components or connecting multilayer printed wirings, and conductive plating of a predetermined thickness is applied to the through holes.
  • Ru conductive plating of a predetermined thickness.
  • the method for producing a laminated body according to the present disclosure preferably includes a through hole forming step of forming a through hole in the layer containing the curable compound A in the laminated body. When the layer containing the curable compound A is formed, it is preferable that at least a part of the surface of the through holes is cured in the through hole forming step.
  • the layer containing the curable compound A can further cure the curable compound A by the heat and pressure at the time of forming the through holes, although it depends on the conditions for forming the through holes.
  • the hole diameter and shape of the through hole are not particularly limited and can be appropriately selected as desired.
  • the method for forming the through hole is not particularly limited, and a known method can be used. For example, a method using a laser or a router, a method by dry etching, and the like can be mentioned. Above all, since heat is generated during the formation of through holes by the laser, the vicinity of the inner wall surface of the through holes to be formed is hardened by using the polymer film according to the present disclosure, and the mechanical strength is further improved. It is preferable because it can be made to.
  • the method for producing the laminate according to the present disclosure preferably includes a post-curing step of curing the curable compound A after the through-hole forming step. ..
  • the layer containing the curable compound A can be further cured after the formation of through holes, and the strength and durability can be improved.
  • the method for producing a laminate according to the present disclosure may include other known steps. Examples of other steps include a cleaning step and the like.
  • the film was cut with a microtome to prepare a sample for cross-section evaluation. Subsequently, using a micro-infrared spectroscopic analysis (micro-IR) device, measurements were taken every 2 ⁇ m from the surface with a 5 ⁇ m ⁇ 20 ⁇ m aperture, and the characteristics derived from polymers with a dielectric constant of 0.01 or less and those derived from curable compounds. The content of the curable compound on the surface and inside of the polymer film was evaluated using the absorption spectral intensity.
  • micro-IR micro-infrared spectroscopic analysis
  • LC-A Liquid crystal polymer produced according to the following manufacturing method
  • the liquid crystal polyester (A1) obtained above is heated in 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 at 180 ° C. By holding for 5 hours, solid-phase polymerization was carried out, the mixture was cooled, and then the mixture was pulverized with a pulverizer to obtain a powdery liquid crystal polyester (A2).
  • the flow start temperature of this liquid crystal polyester (A2) was 220 ° C.
  • the liquid crystal polyester (A2) obtained above is heated in a nitrogen atmosphere from room temperature (23 ° C.) to 180 ° C. over 1 hour and 25 minutes, and then from 180 ° C. to 255 ° C. over 6 hours and 40 minutes. After solid-phase polymerization by holding at 255 ° C. for 5 hours, the mixture was cooled to obtain powdery liquid crystal polyesters (A) (LC-A).
  • the flow start temperature of the liquid crystal polyester (A) was 302 ° C. Further, the melting point Tm of this liquid crystal polyester (A) was measured using a differential scanning calorimetry apparatus and found to be 311 ° C.
  • LC-B Liquid crystal polymer produced according to the following manufacturing method
  • the liquid crystal polyester (B1) obtained above is heated in 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 at 180 ° C. By holding for 5 hours, solid-phase polymerization was carried out, the mixture was cooled, and then the mixture was pulverized with a pulverizer to obtain a powdery liquid crystal polyester (B2).
  • the liquid crystal polyester (B2) obtained above was heated in a nitrogen atmosphere from room temperature (23 ° C.) to 180 ° C. over 1 hour and 20 minutes, and then from 180 ° C. to 240 ° C. over 5 hours to 240.
  • the liquid crystal polyester (C) (LC-B) in the form of powder was obtained by solid-phase polymerization by holding at ° C. for 5 hours and then cooling.
  • M-1 A commercially available low-dielectric adhesive (SLK (manufactured by Shin-Etsu Chemical Co., Ltd.) varnish containing mainly a polymer-type curable compound) was used so that the solid content was as shown in Table 1.
  • SK synthetic low-dielectric adhesive
  • M-2 A commercially available aminophenol type epoxy resin (jER630LSD, manufactured by Mitsubishi Chemical Corporation) was used so that the solid content was the amount shown in Table 1.
  • ⁇ Filler> F-1 Commercially available hydrophobic silica with an average primary particle size of 20 nm (NX90S (surface treated with hexamethyldisilazane, manufactured by Nippon Aerosil Co., Ltd.) is used so that the solid content is as shown in Table 1. board.)
  • NX90S surface treated with hexamethyldisilazane, manufactured by Nippon Aerosil Co., Ltd.
  • F-2 Liquid crystal polymer particles produced according to the following manufacturing method
  • Liquid crystal polyester (LC-C) was pulverized using a jet mill (“KJ-200” manufactured by Kurimoto Iron Works Co., Ltd.) to obtain liquid crystal polyester particles (F-2).
  • the average particle size of the liquid crystal polyester particles was 9 ⁇ m.
  • F-3 Commercially available silica particles having an average particle size of 0.5 ⁇ m (SO-C2, manufactured by Admatex Co., Ltd.) were used so that the solid content was the amount shown in Table 1.
  • F-4 Commercially available hollow powder with an average particle size of 16 ⁇ m (Glass Bubbles iM30K, manufactured by 3M Japan Ltd.)
  • F-5 Boron nitride particles (melting point> 500 ° C., HP40MF100 (manufactured by Mizushima Alloy Iron Co., Ltd.), dielectric loss tangent 0.0007)
  • a film was formed according to the following flow.
  • a sintered fiber metal filter having a nominal pore diameter of 10 ⁇ m was passed, and then a sintered fiber metal filter having a nominal pore diameter of 10 ⁇ m was also passed to obtain each polymer solution.
  • a polymer solution was prepared without adding the additive, passed through the sintered fiber metal filter, and then the additive was added and stirred.
  • a sintered fiber metal filter having a nominal pore diameter of 10 ⁇ m was passed, and then a sintered fiber metal filter having a nominal pore diameter of 10 ⁇ m was also passed to obtain each polymer solution.
  • a liquid crystal polymer solution was prepared without adding the additive, passed through the sintered fiber metal filter, and then the additive was added and stirred.
  • a copper foil of a double-sided copper-clad laminate using the film of Comparative Example 1 was patterned to prepare a wiring base material containing three pairs of signal lines.
  • the length of the signal line was set to 100 mm, and the width was set so that the characteristic impedance was 50 ⁇ .
  • the single-sided copper-clad laminate / wiring base material / single-sided copper-clad laminate is formed so that the film side of the single-sided copper-clad laminate is in contact with the wiring substrate.
  • the curable compound was sufficiently cured by crimping for 60 minutes at the temperature shown in Table 1 and under the conditions of 4.5 MPa using a vacuum press device to prepare a flexible wiring board.
  • the flexible wiring substrate was cut with a microtome, the cross section was observed with an optical microscope, and the inhibitory property of wiring distortion was evaluated based on the following evaluation criteria.
  • Example 1 As shown in Table 1, in Examples 1 to 9, it was found that the dielectric loss tangent was 0.01 or less, and the surface was excellent in followability of unevenness, so that the distortion of the wiring was suppressed. Further, the flexible wiring boards of Examples 1 to 4 were excellent in durability because the curing reaction was sufficiently performed in the laminating step. On the other hand, it was found that when the single-sided copper-clad laminate of Comparative Example 1 was used, the surface unevenness followability was inferior and wiring distortion occurred.
  • the polymer film of Example 4 was further used for the evaluation of through-hole processability described later, and the polymer film of Example 5 was used for the film lamination evaluation described later without performing the wiring strain evaluation.
  • the through-hole portion of the obtained laminate was cut with a microtome, and the surface roughness Rz of the through-hole plating was observed using a scanning electron microscope. As a result, it was 5 ⁇ m when the film of Comparative Example 1 was used. On the other hand, when the film of Example 4 was used, it was as good as 1 ⁇ m.
  • thermocompression bonding machine (“MP-SNL” manufactured by Toyo Seiki Seisakusho Co., Ltd.), the obtained copper-clad laminate precursor was thermocompression-bonded at 300 ° C. and 4.5 MPa for 10 minutes. A double-sided copper-clad laminate was produced.
  • the peel strength of the obtained double-sided copper-clad laminate was 9 kN / m, and it was confirmed that sufficient strength was secured.

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  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne : un film polymère comprenant un polymère ou un polymère à cristaux liquides ayant un facteur de dissipation diélectrique inférieur ou égal à 0,01 et un composé durcissable, ledit composé durcissable comprenant un composé durcissable A qui est un oligomère ou un polymère ; un stratifié dans lequel le film polymère est utilisé ; et un procédé de production associé.
PCT/JP2021/047403 2020-12-21 2021-12-21 Film polymère, stratifié et son procédé de production WO2022138665A1 (fr)

Priority Applications (3)

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KR1020237019478A KR20230107302A (ko) 2020-12-21 2021-12-21 폴리머 필름, 및, 적층체 및 그 제조 방법
JP2022571517A JPWO2022138665A1 (fr) 2020-12-21 2021-12-21
CN202180084326.5A CN116600986A (zh) 2020-12-21 2021-12-21 聚合物膜以及层叠体及其制造方法

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JP2020-211785 2020-12-21
JP2020211785 2020-12-21

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WO2022138665A1 true WO2022138665A1 (fr) 2022-06-30

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JP (1) JPWO2022138665A1 (fr)
KR (1) KR20230107302A (fr)
CN (1) CN116600986A (fr)
TW (1) TW202239833A (fr)
WO (1) WO2022138665A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024048729A1 (fr) * 2022-08-31 2024-03-07 富士フイルム株式会社 Film, son procédé de fabrication et stratifié
WO2024048727A1 (fr) * 2022-08-31 2024-03-07 富士フイルム株式会社 Stratifié, film, film thermoducissable et procédé de production de substrat de câblage
WO2024095641A1 (fr) * 2022-10-31 2024-05-10 富士フイルム株式会社 Film polymère et stratifié

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019054334A1 (fr) * 2017-09-15 2019-03-21 Jsr株式会社 Stratifié de circuit à haute fréquence, son procédé de fabrication, et feuille d'état b
JP2020026474A (ja) * 2018-08-10 2020-02-20 住友化学株式会社 液晶ポリエステルフィルム、液晶ポリエステル液状組成物及び液晶ポリエステルフィルムの製造方法
JP2022018372A (ja) * 2020-07-15 2022-01-27 昭和電工マテリアルズ株式会社 積層フィルム及び導体基板

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019054334A1 (fr) * 2017-09-15 2019-03-21 Jsr株式会社 Stratifié de circuit à haute fréquence, son procédé de fabrication, et feuille d'état b
JP2020026474A (ja) * 2018-08-10 2020-02-20 住友化学株式会社 液晶ポリエステルフィルム、液晶ポリエステル液状組成物及び液晶ポリエステルフィルムの製造方法
JP2022018372A (ja) * 2020-07-15 2022-01-27 昭和電工マテリアルズ株式会社 積層フィルム及び導体基板

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024048729A1 (fr) * 2022-08-31 2024-03-07 富士フイルム株式会社 Film, son procédé de fabrication et stratifié
WO2024048727A1 (fr) * 2022-08-31 2024-03-07 富士フイルム株式会社 Stratifié, film, film thermoducissable et procédé de production de substrat de câblage
WO2024095641A1 (fr) * 2022-10-31 2024-05-10 富士フイルム株式会社 Film polymère et stratifié

Also Published As

Publication number Publication date
CN116600986A (zh) 2023-08-15
JPWO2022138665A1 (fr) 2022-06-30
KR20230107302A (ko) 2023-07-14
TW202239833A (zh) 2022-10-16

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