Classifications

• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
  • H05K1/036—Multilayers with layers of different types
• • 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
  • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/022—Mechanical properties
• • 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
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/01—Dielectrics
  • H05K2201/0137—Materials
  • H05K2201/0141—Liquid crystal polymer [LCP]
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/01—Dielectrics
  • H05K2201/0137—Materials
  • H05K2201/0145—Polyester, e.g. polyethylene terephthalate [PET], polyethylene naphthalate [PEN]

Definitions

• the present disclosure relates to a film, a laminate, and a method for manufacturing the same.
• Patent Document 1 describes a resin composition containing a styrene polymer, an inorganic filler, and a curing agent.
• the styrene polymer is an acid-modified styrene polymer having a carboxyl group
• the inorganic filler is silica and/or aluminum hydroxide
• the particle size of the inorganic filler is 1 ⁇ m or less
• the inorganic filler is silica and/or aluminum hydroxide.
• the content of the filler is 20 to 80 parts by mass based on 100 parts by mass of the styrene polymer, and the resin composition has the following formulas (A) and (B) in the form of a film having a thickness of 25 ⁇ m. It is stated that the following requirements are met.
• X ⁇ 50...(A) Y ⁇ 40...(B) (In the formula, X represents the absorption rate (unit: %) of light with a wavelength of 355 nm, and Y represents the haze value (unit: %).)
• Patent Document 2 describes a thermosetting adhesive sheet containing a binder resin and a curing agent, and a cured product obtained by heating the thermosetting adhesive sheet at 180° C. for 1 hour satisfies (i) to (iv).
• a thermosetting adhesive sheet is described.
• the dielectric constant is 1.5 to 3.0 at a frequency of 10 GHz and 23°C.
• the dielectric loss tangent is 0.0001 to 0.01 at a frequency of 10 GHz and 23°C.
• the linear expansion coefficient ⁇ 1 at 0°C to glass transition temperature is 100 to 500 ppm/°C.
• Patent Document 1 Japanese Patent Application Publication No. 2019-199612
• Patent Document 2 Japanese Patent Application Publication No. 2022-17947
• the problem to be solved by the embodiments of the present disclosure is to provide a film that has excellent step followability and suitability for laser processing.
• Another problem to be solved by other embodiments of the present disclosure is to provide a laminate that has excellent step followability and suitability for laser processing, and a method for manufacturing the same.
• Means for solving the above problems include the following aspects. ⁇ 1> It has a layer A and a layer B on at least one surface of the layer A, and the ratio of the elastic modulus of the layer A at 160° C. to the elastic modulus of the layer B at 160° C. is 1.2. A film in which the layer A has a thermal conductivity of 0.05 W/(m ⁇ K) or more. ⁇ 2> The film according to ⁇ 1>, wherein the layer A has an elastic modulus of 100 MPa to 2,500 MPa at 160°C. ⁇ 3> The film according to ⁇ 1> or ⁇ 2>, wherein the layer A has a dielectric loss tangent of 0.01 or less.
• ⁇ 4> The film according to any one of ⁇ 1> to ⁇ 3>, wherein the layer A contains a liquid crystal polymer.
• ⁇ 5> The film according to any one of ⁇ 1> to ⁇ 4>, wherein the layer A contains an aromatic polyesteramide.
• ⁇ 6> The film according to any one of ⁇ 1> to ⁇ 5>, wherein the layer A contains a filler having a thermal conductivity of 0.05 W/(m ⁇ K) or more.
• ⁇ 7> The film according to any one of ⁇ 1> to ⁇ 6>, wherein the layer B has a dielectric loss tangent of 0.01 or less.
• ⁇ 8> The film according to any one of ⁇ 1> to ⁇ 7>, wherein the layer B contains a liquid crystal polymer.
• ⁇ 9> The film according to any one of ⁇ 1> to ⁇ 8>, wherein the layer B contains an aromatic polyesteramide.
• the layer B contains a thermoplastic resin having a structural unit having an aromatic hydrocarbon group.
• a laminate comprising the film according to any one of ⁇ 1> to ⁇ 10> and a metal layer or metal wiring disposed on at least one surface of the film.
• ⁇ 12> It has a layer A, a layer B, and a metal layer or metal wiring in this order, and the ratio of the elastic modulus of the layer A at 160° C. to the elastic modulus of the layer B at 160° C. is 1.
• a method for manufacturing a laminate comprising: step B of applying composition B containing composition B to form layer B on at least one surface of layer A.
• the present disclosure it is possible to provide a film that has excellent step followability and suitability for laser processing. Further, according to other embodiments of the present disclosure, it is possible to provide a laminate that is excellent in step followability and suitability for laser processing, and a method for manufacturing the same.
• 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 as a concept that includes both acrylic and methacrylic
• (meth)acryloyl is a term used as a concept that includes both acryloyl and methacryloyl. It is.
• process in this specification refers not only to an independent process, but also to the term “process” when the intended purpose of the process is achieved, even if the process cannot be clearly distinguished from other processes. included.
• mass % and “weight %” have the same meaning
• mass parts and “weight parts” have the same meaning.
• a combination of two or more preferred embodiments is a more preferred embodiment.
• the weight average molecular weight (Mw) and number average molecular weight (Mn) in this disclosure are determined by gel permeation chromatography using a column of TSKgel SuperHM-H (trade name, manufactured by Tosoh Corporation).
• PFP pentafluorophenol
• chloroform 1/2 (mass ratio)
• GPC GPC
• the film according to the present disclosure has a layer A and a layer B on at least one surface of the layer A, and the ratio of the elastic modulus of the layer A at 160°C to the elastic modulus of the layer B at 160°C is , 1.2 or more, and the thermal conductivity of the layer A is 0.05 W/(m ⁇ K) or more.
• laser processing suitability in the present disclosure refers to suitability for laser cutting. Specifically, it is a property that can reduce excessive laser cutting, especially when through-hole processing is performed. If the above characteristics are excellent, it can be said that the workability of the cut portion into a desired shape in laser processing is excellent.
• the present inventors have discovered that in conventional films provided with a low elastic modulus layer, there is a problem in that the low elastic modulus layer is cut excessively when laser processing is performed.
• the film according to the present disclosure has a layer A and a layer B on at least one surface of the layer A, and the ratio of the elastic modulus of the layer A at 160°C to the elastic modulus of the layer B at 160°C is , 1.2 or more, the layer B has a low elastic modulus at 160° C., so it has excellent step followability, and the thermal conductivity of the layer A is 0.05 W/(m ⁇ K) or more. This improves the thermal conductivity coefficient of layer A and suppresses overheating of layer A, thereby suppressing the temperature rise of layer B, providing a film with excellent step tracking ability and laser processing suitability. can do.
• the ratio of the elastic modulus MD A of layer A at 160° C. to the elastic modulus MD B of layer B at 160° C. is 1.2 or more.
• the ratio of MD A /MD B is preferably from 5 to 2,000, more preferably from 100 to 1,500, and from 350 to 1,000, from the viewpoint of laser processing suitability and step followability. It is particularly preferable that
• the elastic modulus of layer A at 160° C. in the film according to the present disclosure is preferably 100 MPa to 5,000 MPa from the viewpoint of laser processing suitability and step followability, It is more preferably 500 MPa to 4,000 MPa, even more preferably 800 MPa to 3,000 MPa, and particularly preferably 1,000 MPa to 2,500 MPa.
• the elastic modulus at 160° C. of layer B in the film according to the present disclosure is preferably 100 MPa or less, more preferably 10 MPa or less, and 0.001 MPa to It is more preferably 10 MPa, and particularly preferably 0.5 MPa to 5 MPa.
• the elastic modulus in the present disclosure is measured by the following method. First, a cross section of a film or a laminate is cut using a microtome or the like, and layer A or layer B is identified from an image obtained by observing the vicinity of the wiring using an optical microscope. Next, the elastic modulus of the specified layer A or layer B is measured as an indentation elastic modulus using a nanoindentation method. The indentation modulus was measured using a microhardness tester (product name "DUH-W201", manufactured by Shimadzu Corporation) at 160°C with a Vickers indenter at a loading rate of 0.28 mN/sec, with a maximum load of 10 mN.
• a microhardness tester product name "DUH-W201", manufactured by Shimadzu Corporation
• the measurement is performed by unloading at a loading rate of 0.28 mN/sec.
• an evaluation sample of only the desired layer may be prepared by scraping off unnecessary layers with a razor or the like.
• the layer to be measured may be scraped off with a razor or the like, and the resulting powdered sample may be used.
• the film according to the present disclosure has layer A. Furthermore, methods for detecting or determining the layer structure of the film, the thermal conductivity of layer A, the thickness of each layer, etc. include the following methods. First, a cross-sectional sample of the film is cut out using a microtome, and the layer structure and the thickness of each layer are determined using an optical microscope. If it is difficult to determine with an optical microscope, the determination may be made by morphological observation using a scanning electron microscope (SEM) or component analysis using time-of-flight secondary ion mass spectrometry (TOF-SIMS).
• SEM scanning electron microscope
• TOF-SIMS time-of-flight secondary ion mass spectrometry
• the thermal conductivity of the layer A is 0.05 W/(m ⁇ K) or more, and from the viewpoint of the film's dielectric loss tangent, laser processing suitability, and step followability, it is 0.1 W. /(m ⁇ K) or more, preferably 0.2W/(m ⁇ K) or more, and 1.0W/(m ⁇ K) to 500W/(m ⁇ K) is more preferable, and 2.0 W/(m ⁇ K) to 50 W/(m ⁇ K) is particularly preferable.
• the method for measuring the thermal conductivity of layer A or filler in the present disclosure is as follows.
• the thermal diffusivity of layer A in the thickness direction is measured by the laser flash method using "LFA467" manufactured by NETZSCH.
• layer A preferably contains a filler having a thermal conductivity of 0.05 W/(m ⁇ K) or more.
• filler materials with a thermal conductivity of 0.05 W/(m K) or higher include inorganic nitrides, inorganic oxides, inorganic carbides, metal titanates, metals, alloys, diamonds, carbon fibers, graphite, etc. It will be done.
• Examples include nickel, iron, platinum, tin, alloys of these metals, diamond, carbon fiber, graphite, and the like.
• fillers with a thermal conductivity of 0.05 W/(m ⁇ K) or higher include boron nitride particles, aluminum nitride particles, silicon nitride particles, silicon carbide particles, diamond particles, carbon fibers, It preferably contains at least one type of particle selected from the group consisting of alumina particles and silica particles, and is composed of boron nitride particles, aluminum nitride particles, silicon nitride particles, silicon carbide particles, diamond particles, and carbon fibers.
• the volume average particle diameter of the filler having a thermal conductivity of 0.05 W/(m K) or more is preferably 5 nm to 50 ⁇ m, more preferably 5 nm to 20 ⁇ m, from the viewpoint of suitability for laser processing. More preferably, the thickness is 100 nm to 10 ⁇ m.
• the volume average particle size of the particles is measured by a light scattering method, or by taking an electron micrograph of the particles, measuring the particle size of a total of 5,000 particles on the photo, and determining the average value. shall be calculated.
• the equivalent circle diameter of the particle in the photograph is used. Note that the average particle size of particles in the present disclosure is a volume average particle size unless otherwise specified.
• Layer A may contain one type of filler having a thermal conductivity of 0.05 W/(m ⁇ K) or more, or may contain two or more types.
• the content of the filler with a thermal conductivity of 0.05 W/(m K) or more is 5% by mass to 90% by mass based on the total mass of layer A from the viewpoint of the dielectric loss tangent of the film and suitability for laser processing. It is preferably 10% by mass to 90% by mass, even more preferably 20% to 85% by mass, and particularly preferably 50% to 85% by mass.
• the dielectric loss tangent of layer A is preferably 0.01 or less, more preferably 0.005 or less, and even more preferably 0.004 or less, from the viewpoints of the film's dielectric loss tangent, laser processing suitability, and step tracking ability. , 0.003 or less is particularly preferable.
• the lower limit value is not particularly set, but may be, for example, greater than 0.
• the dielectric loss tangent in the present disclosure shall be measured by the following method.
• the measurement of the dielectric loss tangent 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.) was connected to a network analyzer (“E8363B” manufactured by Agilent Technology), a test piece was inserted into the cavity resonator, and the temperature was 25°C and the humidity was 60% RH.
• the dielectric loss tangent of the film is measured from the change in resonance frequency before and after insertion for 96 hours in the environment.
• an evaluation sample of only the desired layer may be prepared by scraping off unnecessary layers with a razor or the like.
• the layer to be measured may be scraped off with a razor or the like, and the resulting powdered sample may be used.
• the measurement of the dielectric loss tangent of a polymer in the present disclosure is performed by identifying or isolating the chemical structure of the polymer constituting each layer, and using a powdered sample of the polymer to be measured, according to the method for measuring the dielectric loss tangent described above. do.
• Layer A preferably contains a polymer having a dielectric loss tangent of 0.01 or less from the viewpoint of the dielectric loss tangent of the film and suitability for laser processing. Further, from the viewpoint of the dielectric loss tangent of the film and suitability for laser processing, layer A preferably contains a polymer having an aromatic ring, and contains a polymer having an aromatic ring and a dielectric loss tangent of 0.01 or less. It is more preferable.
• layer A preferably contains a polymer and polymer particles, and preferably contains a polymer having a dielectric loss tangent of 0.01 or less, and a polymer having a dielectric loss tangent of 0.01 or less. It is more preferable to include particles of a polymer having a particle size of 0.01 or less.
• the dielectric loss tangent of the polymer contained in layer A of the film according to the present disclosure is preferably 0.01 or less, more preferably 0.005 or less, from the viewpoints of the film's dielectric loss tangent, laser processing suitability, and step tracking ability, It is more preferably 0.004 or less, particularly preferably 0.003 or less.
• the lower limit value is not particularly set, but may be, for example, greater than 0.
• the melting point Tm or 5% weight loss temperature Td of the polymer having a dielectric loss tangent of 0.01 or less is preferably 200° C. or higher, and 250° C. from the viewpoint of the film's dielectric loss tangent, step followability, and heat resistance.
• the temperature is more preferably 280°C or higher, even more preferably 300°C or higher, and particularly preferably 300°C or higher.
• the upper limit for example, it is preferably 500°C or lower, more preferably 420°C or lower.
• the melting point Tm in the present disclosure shall be measured using a differential scanning calorimetry (DSC) device.
• the 5% mass reduction temperature Td in the present disclosure is measured using a thermal mass spectrometry (TGA) device. That is, the mass of the sample placed in the measurement pan is taken as an initial value, and the temperature at which the mass decreases by 5% by mass with respect to the initial value due to temperature increase is taken as the 5% mass loss temperature Td.
• TGA thermal mass spectrometry
• the glass transition temperature Tg of a polymer with a dielectric loss tangent of 0.01 or less is 150°C or higher from the viewpoints of the dielectric loss tangent of the film, adhesion to metals (for example, metal layers, metal wiring, etc.), and heat resistance.
• the temperature is preferably 200°C or higher, more preferably 200°C or higher, and particularly preferably 200°C or higher.
• the upper limit is not particularly limited, but is preferably less than 350°C, more preferably less than 280°C, more preferably 280°C or less.
• the glass transition temperature Tg in the present disclosure shall be measured using a differential scanning calorimetry (DSC) device.
• DSC differential scanning calorimetry
• 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 0.01 or less is preferably 50,000 or less, more preferably 20,000 or less, and particularly preferably less than 13,000. .
• the type of polymer having a dielectric loss tangent of 0.01 or less is not particularly limited, and known polymers can be used.
• polymers having a dielectric loss tangent of 0.01 or less include liquid crystal polymers, fluorine-based polymers, polymers of compounds having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, polyether ether ketone, polyolefin, Thermoplastic resins such as polyamide, polyester, polyphenylene sulfide, aromatic polyether ketone, polycarbonate, polyether sulfone, polyphenylene ether and its modified products, polyetherimide; Elastomers such as copolymers of glycidyl methacrylate and polyethylene; Phenol resins , thermosetting resins such as epoxy resins, polyimide resins, and cyanate resins.
• liquid crystal polymers, fluorine-based polymers, and compounds having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond are preferred from the viewpoint of film dielectric loss tangent, adhesion with metal, and heat resistance. It is preferably at least one polymer selected from the group consisting of polymers, polyphenylene ethers, and aromatic polyether ketones, and more preferably at least one polymer selected from the group consisting of liquid crystal polymers and fluorine-based polymers. preferable. From the viewpoint of film adhesion and mechanical strength, a liquid crystal polymer is preferable, and from the viewpoint of heat resistance and dielectric loss tangent, a fluorine-based polymer is preferable.
• the -Liquid crystal polymer- Layer A in the film according to the present disclosure preferably contains a liquid crystal polymer from the viewpoints of the dielectric loss tangent, laser processing suitability, and step followability of the film.
• the type of liquid crystal polymer is not particularly limited, and any known liquid crystal polymer can be used.
• the liquid crystal polymer may be a thermotropic liquid crystal polymer that exhibits liquid crystallinity in a molten state, or may be a lyotropic liquid crystal polymer that exhibits liquid crystallinity in a solution state.
• the liquid crystal polymer is a thermotropic liquid crystal polymer, it is preferably a liquid crystal polymer that melts at a temperature of 450° C. or lower.
• liquid crystal polymers examples include liquid crystal polyester, liquid crystal polyester amide in which an amide bond is introduced into a liquid crystal polyester, liquid crystal polyester ether in which an ether bond is introduced into a liquid crystal polyester, and liquid crystal polyester carbonate in which a carbonate bond is introduced into a liquid crystal polyester.
• the liquid crystal polymer is preferably a polymer having an aromatic ring, more preferably an aromatic polyester or an aromatic polyester amide, and an aromatic polyester or an aromatic polyester amide. Particular preference is given to polyesteramides of the group polyesteramides.
• the liquid crystal polymer may be a polymer in which isocyanate-derived bonds such as imide bonds, carbodiimide bonds, and isocyanurate bonds are further introduced into aromatic polyester or aromatic polyester amide. Further, the liquid crystal polymer is preferably a wholly aromatic liquid crystal polymer using only an aromatic compound as a raw material monomer.
• liquid crystal polymers include the following liquid crystal polymers. 1) (i) aromatic hydroxycarboxylic acid, (ii) aromatic dicarboxylic acid, and (iii) at least one compound selected from the group consisting of aromatic diol, aromatic hydroxyamine, and aromatic diamine; Something made by polycondensation. 2) A product obtained by polycondensing multiple types of aromatic hydroxycarboxylic acids. 3) A product obtained by polycondensing (i) an aromatic dicarboxylic acid and (ii) at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxyamine, and an aromatic diamine.
• a product obtained by polycondensing (i) a polyester such as polyethylene terephthalate and (ii) an aromatic hydroxycarboxylic acid.
• a polyester such as polyethylene terephthalate
• an aromatic hydroxycarboxylic acid the aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic hydroxyamine, and aromatic diamine may each be independently replaced with a polycondensable derivative.
• aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid esters and aromatic dicarboxylic acid esters.
• aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid halides and aromatic dicarboxylic acid halides.
• aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid anhydrides and aromatic dicarboxylic acid anhydrides.
• polymerizable derivatives of compounds having hydroxy groups such as aromatic hydroxycarboxylic acids, aromatic diols, and aromatic hydroxyamines include those obtained by acylating a hydroxy group to convert it into an acyloxy group (acylated products) can be mentioned.
• aromatic hydroxycarboxylic acids, aromatic diols, and aromatic hydroxyamines can each be replaced with acylated products.
• polymerizable derivatives of compounds having an amino group such as aromatic hydroxyamines and aromatic diamines include those obtained by acylating an amino group to convert it into an acylamino group (acylated product). For example, by acylating an amino group to convert it into an acylamino group, aromatic hydroxyamine and aromatic diamine can each be replaced with an acylated product.
• liquid crystal polymers are composed of structural units represented by any of the following formulas (1) to (3) (hereinafter, represented by formula (1)). It is preferable to have a structural unit represented by the following formula (1), and it is more preferable to have a structural unit represented by the following formula (1). It is particularly preferable to have a structural unit represented by the following formula (2), and a structural unit represented by the following formula (3).
• Ar 1 represents a phenylene group, a naphthylene group, or a biphenylylene group
• Ar 2 and Ar 3 each independently represent a phenylene group, a naphthylene group, a biphenylylene group
• the following formula (4) represents a group represented by, X and Y each independently represent an oxygen atom or an imino group, and the hydrogen atoms in Ar 1 to Ar 3 are each independently substituted with a halogen atom, an alkyl group, or an aryl group. It's okay.
• Ar 4 and Ar 5 each 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, 2-ethylhexyl group, Examples include n-octyl group and n-decyl group.
• the number of carbon atoms in the alkyl group is preferably 1 to 10.
• aryl group examples include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 1-naphthyl group and 2-naphthyl group.
• the number of carbon atoms in the aryl group is preferably 6 to 20.
• the number of substitutions in Ar 1 , Ar 2 or Ar 3 is preferably 2 or less, more preferably 1, each independently.
• alkylene group examples include a methylene group, a 1,1-ethanediyl group, a 1-methyl-1,1-ethanediyl group, a 1,1-butanediyl group, and a 2-ethyl-1,1-hexanediyl group.
• the alkylene group preferably has 1 to 10 carbon atoms.
• Structural unit (1) is a structural unit derived from aromatic hydroxycarboxylic acid.
• the structural unit (1) includes an embodiment in which Ar 1 is a p-phenylene group (a structural unit derived from p-hydroxybenzoic 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 a 4,4'-biphenylylene group (a structural unit derived from 4'-hydroxy-4-biphenylcarboxylic acid) is preferred.
• the structural unit (2) is a structural unit derived from an aromatic dicarboxylic acid.
• the structural unit (2) includes an embodiment in which Ar 2 is a p-phenylene group (a structural unit derived from terephthalic acid), an embodiment in which Ar 2 is a m-phenylene group (a structural unit derived from isophthalic acid), and an embodiment in which Ar 2 is a m-phenylene group (a structural unit derived from isophthalic acid).
• Ar 2 is a diphenyl ether-4,4'-diyl group (diphenyl ether-4,4'- structural units derived from dicarboxylic acids) are preferred.
• the structural unit (3) is a structural unit derived from aromatic diol, aromatic hydroxylamine, or aromatic diamine.
• the structural unit (3) includes an embodiment in which 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 a m-phenylene group (isophthalic acid). ), or an embodiment in which Ar 3 is a 4,4'-biphenylylene group (derived from 4,4'-dihydroxybiphenyl, 4-amino-4'-hydroxybiphenyl or 4,4'-diaminobiphenyl); structural units) are preferred.
• the content of the structural unit (1) is determined by dividing the total amount of all structural units (the mass of each structural unit (also referred to as "monomer unit") constituting the liquid crystal polymer by the formula weight of each structural unit). Calculate the amount equivalent to the substance amount (mol) of the structural unit, and calculate the sum of them), preferably 30 mol% or more, more preferably 30 mol% to 80 mol%, even more preferably 30 mol% to 60 mol %, particularly preferably from 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%, even more preferably 20 mol% to 35 mol%, especially Preferably it is 30 mol% to 35 mol%.
• the content of the structural unit (3) is preferably 35 mol% or less, more preferably 10 mol% to 35 mol%, even more preferably 20 mol% to 35 mol%, especially Preferably it is 30 mol% to 35 mol%.
• the ratio between the content of structural unit (2) and the content of structural unit (3) is expressed as [content of structural unit (2)]/[content of structural unit (3)] (mol/mol).
• the ratio is preferably 0.9/1 to 1/0.9, more preferably 0.95/1 to 1/0.95, and still more preferably 0.98/1 to 1/0.98.
• the liquid crystal polymer may each independently have two or more types of structural units (1) to (3). Furthermore, the liquid crystal polymer may have structural units other than structural units (1) to (3).
• the content of structural units other than structural units (1) to (3) is preferably 10 mol% or less, more preferably 5 mol% or less, based on the total amount of all structural units.
• the liquid crystal polymer preferably has a structural unit (3) in which at least one of X and Y is an imino group. That is, the structural unit (3) preferably has at least one of a structural unit derived from an aromatic hydroxylamine and a structural unit derived from an aromatic diamine, and a structural unit in which at least one of X and Y is an imino group ( It is more preferable to have only 3).
• the liquid crystal polymer is preferably produced by melt polymerizing raw material monomers corresponding to the structural units constituting the liquid crystal polymer.
• Melt polymerization may be carried out in the presence of a catalyst.
• catalysts include metal compounds such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide, and metal compounds such as 4-(dimethylamino)pyridine and 1-methylimidazole.
• metal compounds such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide
• metal compounds such as 4-(dimethylamino)pyridine and 1-methylimidazole.
• nitrogen-containing heterocyclic compounds and nitrogen-containing heterocyclic compounds are preferred.
• the melt polymerization may be further carried out by solid phase polymerization, 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, and still more preferably 250°C or higher.
• the upper limit of the flow start temperature is preferably 350°C, more preferably 330°C, and even more preferably 310°C.
• the flow start temperature is also called the flow temperature or flow temperature, and the liquid crystal polymer is melted using a capillary rheometer while increasing the temperature at a rate of 4°C/min under a load of 9.8 MPa (100 kg/cm 2 ). This is the temperature at which it exhibits 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.
• the flow start temperature is a guideline for the molecular weight of liquid crystal polymers (see Naoyuki Koide, ed., "Liquid Crystal Polymers - Synthesis, Molding, Applications", CMC Corporation, 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, even more preferably 5,000 to 100,000, A range of 5,000 to 30,000 is particularly preferred.
• the film after heat treatment has excellent 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 fluorine-based polymer from the viewpoint of heat resistance and mechanical strength.
• the type of fluoropolymer used as a 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 fluoropolymer may be used. be able to.
• fluorine-based polymers include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxy fluororesin, tetrafluoroethylene/hexafluoropropylene copolymer, ethylene/tetrafluoride
• fluorine-based polymers include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxy fluororesin, tetrafluoroethylene/hexafluoropropylene copolymer, ethylene/tetrafluoride
• examples include ethylene copolymer, ethylene/chlorotrifluoroethylene copolymer, and the like. Among them, polytetrafluoroethylene is preferred.
• the fluoropolymer also includes a fluorinated ⁇ -olefin monomer, that is, an ⁇ -olefin monomer containing at least one fluorine atom, and optionally a non-fluorinated ethylene reactive with the fluorinated ⁇ -olefin monomer.
• a fluorinated ⁇ -olefin monomer that is, an ⁇ -olefin monomer containing at least one fluorine atom, and optionally a non-fluorinated ethylene reactive with the fluorinated ⁇ -olefin monomer.
• Homopolymers and copolymers containing structural units derived from sexually unsaturated monomers are included.
• vinyl ether eg, perfluoromethyl vinyl ether, perfluoropropyl vinyl ether, perfluorooctyl vinyl ether.
• Non-fluorinated monoethylenically unsaturated monomers include ethylene, propylene, butene, ethylenically unsaturated aromatic monomers (eg, styrene and ⁇ -methylstyrene), and the like.
• the fluorinated ⁇ -olefin monomers may be used alone or in combination of two or more. Further, the non-fluorinated ethylenically unsaturated monomers may be used alone or in combination of two or more.
• fluorine-based polymers include polychlorotrifluoroethylene (PCTFE), poly(chlorotrifluoroethylene-propylene), poly(ethylene-tetrafluoroethylene) (ETFE), poly(ethylene-chlorotrifluoroethylene) (ECTFE), Poly(hexafluoropropylene), poly(tetrafluoroethylene) (PTFE), poly(tetrafluoroethylene-ethylene-propylene), poly(tetrafluoroethylene-hexafluoropropylene) (FEP), poly(tetrafluoroethylene-propylene) (FEPM), poly(tetrafluoroethylene-perfluoropropylene vinyl ether), poly(tetrafluoroethylene-perfluoroalkyl vinyl ether) (PFA) (e.g., poly(tetrafluoroethylene-perfluoropropyl vinyl ether)), polyvinyl fluoride ( PVF), polyvinylidene fluoride (PVDF),
• the fluorine-based polymer is preferably at least one of FEP, PFA, ETFE, or PTFE.
• FEP is available from DuPont under the trade name TEFLON FEP or from Daikin Industries, Ltd. under the trade name NEOFLON FEP;
• PFA is the product name of NEOFLON PFA (NEOFLON PFA) from Daikin Industries, Ltd., the product name of Teflon (registered trademark) PFA (TEFLON (registered trademark) PFA) from DuPont, or Solvay Solexis. It is available from Solexis under the trade name HYFLON PFA.
• the fluorine-based polymer contains PTFE.
• the PTFE can include a PTFE homopolymer, a partially modified PTFE homopolymer, or a combination including one or both of these.
• the partially modified PTFE homopolymer contains less than 1% by weight of constitutional units derived from comonomers other than tetrafluoroethylene, based on the total weight of the polymer.
• the fluoropolymer may be a crosslinkable fluoropolymer having a crosslinkable group.
• the crosslinkable fluoropolymer can be crosslinked by conventionally known crosslinking methods.
• One representative crosslinkable fluoropolymer is a fluoropolymer having (meth)acryloxy groups.
• R is a fluorine-based oligomer chain having two or more structural units derived from a fluorinated ⁇ -olefin monomer or a non-fluorinated monoethylenically unsaturated monomer
• R' is H or -CH3
• 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 by exposing a fluoropolymer having (meth)acryloxy groups to a free radical source to initiate a radical crosslinking reaction via the (meth)acryloxy groups on the fluoropolymer.
• the free radical source is not particularly limited, but suitable examples include photoradical polymerization initiators and organic peroxides. Suitable radical photoinitiators and organic peroxides are well known in the art.
• Crosslinkable fluoropolymers are commercially available, such as Viton B manufactured by DuPont.
• Polymer of a compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be a polymer of a compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond.
• Examples of polymers of compounds having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond include a structural unit formed from a monomer consisting of a cyclic olefin such as norbornene or a polycyclic norbornene monomer; Examples include thermoplastic resins having the following, and are also called thermoplastic cyclic olefin resins.
• Polymers of compounds having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond can be obtained by hydrogenation of a ring-opening polymer of the above-mentioned cyclic olefin or a ring-opening copolymer using two or more types of cyclic olefins. It may be an addition polymer of a cyclic olefin and a chain olefin or an aromatic compound having an ethylenically unsaturated bond such as a vinyl group. Further, a polar group may be introduced into the polymer of the compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond. The polymer of a compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be used alone or in combination of two or more.
• the ring structure of the cyclic aliphatic hydrocarbon group may be a single ring, a condensed ring of two or more rings, or a bridged ring.
• Examples of the ring structure of the cyclic aliphatic hydrocarbon group include a cyclopentane ring, a cyclohexane ring, a cyclooctane ring, an isoborone ring, a norbornane ring, and a dicyclopentane ring.
• the compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be a monofunctional ethylenically unsaturated compound or a polyfunctional ethylenically unsaturated compound.
• the number of cyclic aliphatic hydrocarbon groups in the compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be one or more, and may have two or more.
• the polymer of a compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond is obtained by polymerizing a compound having at least one kind of cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond. It may be a polymer of compounds having two or more types of cycloaliphatic hydrocarbon groups and a group having an ethylenically unsaturated bond, or it may be a polymer having no cycloaliphatic hydrocarbon groups. It may also be a copolymer with other ethylenically unsaturated compounds. Further, the polymer of a compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond is preferably a cycloolefin polymer.
• layer A contains polyphenylene ether.
• the weight average molecular weight (Mw) of polyphenylene ether is preferably from 500 to 5,000, preferably from 500 to 3,000, from the viewpoint of heat resistance and film forming properties when it is thermally cured after film formation. It is more preferable that there be. Further, in the case of not being thermally cured, it is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, although it is not particularly limited.
• the average number of phenolic hydroxyl groups per molecule at the end of the molecule is preferably 1 to 5 from the viewpoint of dielectric loss tangent and heat resistance, and 1.5 More preferably, the number is from 1 to 3.
• the number of hydroxyl groups or phenolic hydroxyl groups of polyphenylene ether can be determined, for example, from the standard values of polyphenylene ether products.
• the number of terminal hydroxyl groups or the number of terminal phenolic hydroxyl groups includes, for example, a numerical value representing the average value of hydroxyl groups or phenolic hydroxyl groups per molecule of all polyphenylene ethers present in 1 mole of polyphenylene ether.
• One type of polyphenylene ether may be used alone, or two or more types may be used in combination.
• polyphenylene ether examples include polyphenylene ether consisting of 2,6-dimethylphenol and at least one of bifunctional phenol and trifunctional phenol, or poly(2,6-dimethyl-1,4-phenylene oxide).
• examples include those containing polyphenylene ether 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 having 1 to 3 carbon atoms or a single bond
• m represents an integer of 0 to 20
• n represents an integer of 0 to 20
• the combination of m and n The sum represents an integer from 1 to 30.
• Examples of the alkylene group in the above X include a dimethylmethylene group.
• 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 any known aromatic polyetherketone can be used.
• the aromatic polyetherketone is a polyetheretherketone.
• Polyetheretherketone is a type of aromatic polyetherketone, and is a polymer in which bonds are arranged in the order of ether bond, ether bond, and carbonyl bond (ketone). It is preferable that each bond is connected by a divalent aromatic group.
• One type of aromatic polyetherketone may be used alone, or two or more types may be used in combination.
• aromatic polyetherketones examples include polyetheretherketone (PEEK) having a chemical structure represented by the following formula (P1), and polyetherketone (PEK) having a chemical structure represented by the following formula (P2). , polyetherketoneketone (PEKK) having a chemical structure represented by the following formula (P3), polyetheretherketoneketone (PEEKK) having a chemical structure represented by the following formula (P4), and the following formula (P5) Examples include polyetherketoneetherketoneketone (PEKEKK) having the chemical structure shown below.
• n in each of formulas (P1) to (P5) is preferably 10 or more, and more preferably 20 or more.
• n is preferably 5,000 or less, more preferably 1,000 or less. That is, n is preferably 10 to 5,000, more preferably 20 to 1,000.
• the 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 include N-methylpyrrolidone, N-ethylpyrrolidone, dichloromethane, dichloroethane, chloroform, N,N-dimethylacetamide, ⁇ -butyrolactone, dimethylformamide, ethylene glycol monobutyl ether at 25°C. and ethylene glycol monoethyl ether in an amount of 0.1 g or more dissolved in 100 g of at least one solvent selected from the group consisting of ethylene glycol monoethyl ether.
• Layer A 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 loss tangent of 0.01 or less, preferably a liquid crystal polymer, in layer A is 10% by mass based on the total mass of layer A, from the viewpoint of the dielectric loss tangent of the film and adhesion to metal. It is preferably ⁇ 90% by mass, more preferably 15% by mass to 85% by mass, even more preferably 15% to 80% by mass, particularly 15% to 50% by mass. preferable.
• the content of the polymer having a dielectric loss tangent of 0.01 or less includes a particulate polymer having a dielectric loss tangent of 0.01 or less, which will be described later.
• the -Filler- Layer A may contain a filler from the viewpoint of thermal expansion coefficient and step followability.
• the filler may be in the form of particles or fibers, and may be inorganic or organic filler. It is preferable that In the film according to the present disclosure, the number density of the filler is preferably larger inside the film than on the surface from the viewpoints of thermal expansion coefficient and step followability.
• the surface of the film refers to the outer surface of the film (the surface in contact with air or the substrate), and the range of 3 ⁇ m from the most surface in the depth direction, or 10% of the total thickness of the film from the most surface. The smaller of the following ranges is defined as the "surface".
• the inside of the film refers to parts other than the surface of the film, that is, the inner surface of the film (the surface that does not contact the air or the substrate), and includes, but is not limited to, the area within ⁇ 1.5 ⁇ m from the center of the film in the thickness direction.
• the smaller value of the range or the range of ⁇ 5% of the total thickness from the center in the thickness direction of the film is defined as "inside".
• organic filler known organic fillers can be used.
• the material of the organic filler include polyethylene, polystyrene, urea-formalin filler, polyester, cellulose, acrylic resin, fluororesin, hardened epoxy resin, crosslinked benzoguanamine resin, crosslinked acrylic resin, liquid crystal polymer, and two or more of these.
• materials include:
• the organic filler may be in the form of fibers such as nanofibers, or may be hollow resin particles. Among them, from the viewpoints of dielectric loss tangent of the film, suitability for laser processing, and step tracking ability, organic fillers include fluororesin particles, polyester resin particles, polyethylene particles, liquid crystal polymer particles, or cellulose resin nanofibers.
• the liquid crystal polymer particles refer to, but are not limited to, those obtained by polymerizing a liquid crystal polymer and pulverizing it with a pulverizer or the like to obtain a powdered liquid crystal.
• the liquid crystal polymer particles are preferably smaller than the thickness of each layer.
• the average particle diameter of the organic filler is preferably from 5 nm to 20 ⁇ m, more preferably from 100 nm to 10 ⁇ m, from the viewpoints of the dielectric loss tangent of the film, suitability for laser processing, and step tracking ability.
• the inorganic filler a known inorganic filler can be used.
• Materials for the inorganic filler include, for example, those mentioned above as fillers with a thermal conductivity of 0.05 W/(m ⁇ K) or higher, as well as glass fiber, aluminum hydroxide, calcium carbonate, and materials containing two or more of these. can be mentioned.
• the average particle size of the inorganic filler is preferably about 20% to about 40% of the thickness of layer A, and may be selected to be, for example, 25%, 30% or 35% of the thickness of layer A. . When the particles or fibers are flat, the length in the short side direction is shown.
• the average particle size of the inorganic filler is preferably 5 nm to 20 ⁇ m, more preferably 10 nm to 10 ⁇ m, and 20 It is more preferably nm to 1 ⁇ m, particularly preferably 25 nm to 500 nm.
• Layer A may contain only one type of filler, or may contain two or more types of filler.
• the content of filler in layer A is preferably lower than the content of filler in layer B from the viewpoint of step followability.
• the content of filler in layer A is preferably 10% by mass to 50% by mass, and 20% by mass to 40% by mass, based on the total mass of layer A, from the viewpoints of suitability for laser processing and step followability. is more preferable.
• the content of fillers such as polyethylene and olefin elastomers is preferably 50% to 90% by volume, more preferably 75% to 85% by volume.
• the filler content in layer A is preferably 55% to 90% by mass, more preferably 80% to 85% by mass, based on the total mass of layer A.
• -Other additives- Layer A may contain other additives other than the above-mentioned components.
• additives known additives can be used. Specifically, examples thereof include curing agents, leveling agents, antifoaming agents, antioxidants, ultraviolet absorbers, flame retardants, colorants, and the like.
• layer A may contain other resins than the above-mentioned polymers and polymer particles as other additives.
• other resins include thermoplastic resins such as polypropylene, polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone, polyphenylene ether and its modified products, and polyetherimide; combinations of glycidyl methacrylate and polyethylene.
• Elastomers such as polymers; thermosetting resins such as phenol resins, epoxy resins, polyimide resins, and cyanate resins.
• the total content of other additives in layer A is preferably 25 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the polymer having a dielectric loss tangent of 0.01 or less.
• the amount is more preferably 5 parts by mass or less.
• the average thickness of layer A is preferably thicker than the average thickness of layer B from the viewpoint of the dielectric loss tangent of the film and the adhesion with metal.
• the value of T A /T B which is the ratio of the average thickness T A of layer A to the average thickness T B of layer B, is 0.8 to 10 from the viewpoint of the dielectric loss tangent of the film and the adhesion with metal. It is preferably from 1 to 5, even more preferably from more than 1 to 3 or less, and particularly preferably from more than 1 to 2 or less.
• the average thickness of layer A is not particularly limited, but from the viewpoint of the film's dielectric loss tangent and step tracking ability, it is preferably from 5 ⁇ m to 90 ⁇ m, more preferably from 10 ⁇ m to 70 ⁇ m, and from 15 ⁇ m to Particularly preferred is 50 ⁇ m.
• the method for measuring the average thickness of each layer in the film according to the present disclosure is as follows. Cut the film with a microtome, observe the cross section with an optical microscope, and evaluate the thickness of each layer. Cut out the cross-sectional sample at three or more locations, measure the thickness at three or more points on each section, and use the average value as the average thickness.
• the film according to the present disclosure has layer B on at least one surface of layer A.
• the dielectric loss tangent of layer B is preferably 0.01 or less, more preferably 0.005 or less, and even more preferably 0.004 or less, from the viewpoints of the film's dielectric loss tangent, laser processing suitability, and level difference followability. , 0.003 or less is particularly preferable. Any lower limit value is not particularly set, but may be, for example, greater than 0.
• the layer B preferably contains a polymer having a dielectric loss tangent of 0.01 or less, from the viewpoint of the film's dielectric loss tangent and step followability.
• Preferred embodiments of the polymer having a dielectric loss tangent of 0.01 or less used in layer B are the same as preferred embodiments of the polymer having a dielectric loss tangent of 0.01 or less used in layer A, except as described below.
• the polymer having a dielectric loss tangent of 0.01 or less contained in layer B may be the same as or different from the polymer having a dielectric loss tangent of 0.01 or less contained in layer A. From the viewpoint of adhesion between layer A and layer B and suitability for laser processing, it is preferable that layer A contains the same polymer having a dielectric loss tangent of 0.01 or less.
• Layer B 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 ratio of the polymer having a dielectric loss tangent of 0.01 or less in layer B is preferably equal to or higher than the content ratio of the polymer having a dielectric loss tangent of 0.01 or less in layer A.
• the content of the polymer having a dielectric loss tangent of 0.01 or less in layer B is 20% by mass to 100% by mass based on the total mass of layer B, from the viewpoint of the dielectric loss tangent of the film, laser processing suitability, and step tracking ability. %, more preferably 30% to 100% by weight, particularly preferably 40% to 100% by weight.
• layer B may contain, as a binder polymer, a polymer other than the polymer having a dielectric loss tangent of 0.01 or less.
• a polymer other than the polymer having a dielectric loss tangent of 0.01 or less Preferred examples of other polymers include thermoplastic resins including thermoplastic elastomers from the viewpoints of the film's dielectric loss tangent, laser processing suitability, and level difference followability.
• the elastomer refers to a polymer compound that exhibits elastic deformation. That is, a polymer compound that has the property of deforming in response to an external force when an external force is applied, and recovering its original shape in a short time when the external force is removed.
• Thermoplastic resins include polyurethane resin, polyester resin, (meth)acrylic resin, polystyrene resin, fluororesin, polyimide resin, fluorinated polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, cellulose acylate resin, and polyurethane.
• Resin polyetheretherketone resin, polycarbonate resin, polyolefin resin (for example, polyethylene resin, polypropylene resin, resin consisting of cyclic olefin copolymer, alicyclic polyolefin resin), polyarylate resin, polyethersulfone resin, polysulfone resin, fluorene ring
• polyetheretherketone resin for example, polyethylene resin, polypropylene resin, resin consisting of cyclic olefin copolymer, alicyclic polyolefin resin
• polyarylate resin polyethersulfone resin, polysulfone resin, fluorene ring
• modified polycarbonate resin alicyclic modified polycarbonate resin, and fluorene ring modified polyester resin.
• Thermoplastic elastomers are not particularly limited, and include, for example, elastomers containing repeating units derived from styrene (polystyrene elastomers), polyester elastomers, polyolefin elastomers, polyurethane elastomers, polyamide elastomers, polyacrylic elastomers, and silicones. elastomers, polyimide elastomers, and the like. Note that the thermoplastic elastomer may be a hydrogenated product.
• polystyrene-based elastomers examples include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), polystyrene-poly(ethylene-propylene) diblock copolymer (SEP), and polystyrene.
• SBS styrene-butadiene-styrene block copolymer
• SIS styrene-isoprene-styrene block copolymer
• SEP polystyrene-poly(ethylene-propylene) diblock copolymer
• polystyrene-based elastomers examples include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), polystyren
• SEPS Poly(ethylene-propylene)-polystyrene triblock copolymer
• SEBS styrene-ethylene-butylene-styrene block copolymer
• SEEPS polystyrene-poly(ethylene/ethylene-propylene)-polystyrene triblock copolymer
• SEEPS polystyrene-poly(ethylene/ethylene-propylene)-polystyrene triblock copolymer
• layer B preferably contains a thermoplastic resin having a structural unit having an aromatic hydrocarbon group as the other polymer, from the viewpoint of the film's dielectric loss tangent, laser processing suitability, and level difference followability.
• the elastomer contains a hydrogenated styrene-ethylene-butylene-styrene block copolymer.
• a hydrogenated polystyrene elastomer is preferable from the viewpoint of the dielectric loss tangent of the film, suitability for laser processing, and ability to follow steps.
• the content of other polymers other than the liquid crystal polymer is not particularly limited, but from the viewpoint of the dielectric loss tangent of the film, laser processing suitability, and level difference followability, it is 20% by mass to 100% by mass based on the total mass of layer B. It is preferably 30% by mass to 95% by mass, and particularly preferably 40% by mass to 90% by mass.
• layer B contains a filler from the viewpoint of the dielectric loss tangent of the film, suitability for laser processing, and step followability.
• Preferred embodiments of the filler used in layer B are the same as those of the filler used in layer A, except as described below.
• the filler used in layer B the above-mentioned thermoplastic resin particles are also preferably mentioned.
• at least one of the binder polymer and filler contained in layer B should be a polymer having a dielectric loss tangent of 0.01 or less.
• a liquid crystal polymer is more preferable.
• layer B preferably contains inorganic particles as a filler, and at least one kind selected from the group consisting of silica particles and alumina particles. It is more preferable that the silica particles be included, and it is particularly preferable that the silica particles be included.
• Layer B may contain only one type of filler, or may contain two or more types of filler.
• the content of the filler in layer B is preferably 1% by mass to 80% by mass, and 5% by mass to 50% by mass, based on the total mass of layer B, from the viewpoint of suitability for laser processing and ability to follow steps. is more preferred, and 20% by mass to 40% by mass is particularly preferred.
• Layer B preferably contains a compound having a functional group from the viewpoint of adhesion to metal.
• the functional group is at least one group selected from the group consisting of a group capable of covalent bonding, a group capable of ionic bonding, a group capable of hydrogen bonding, a group capable of dipolar interaction, and a group capable of curing reaction. It is preferable that It is estimated that the compound having a functional group contained in layer B interacts with or bonds with the metal or a group present on the metal surface, thereby improving the adhesion with the metal. Further, the compound having the above functional group may interact with, bond with, or form entanglements with the polymer contained in layer B.
• Entanglement refers to a mode in which a continuous phase of a compound having a functional group and a continuous phase of a polymer with a dielectric loss tangent of 0.01 or less interpenetrate with each other, or a mode in which the coefficient of friction increases due to the morphology of each continuous phase. etc.
• a functional group that can interact with or bond with a group present on the surface of the metal is preferable.
• the compound having a functional group may be a low-molecular compound or a high-molecular compound.
• the compound having a functional group is preferably a low-molecular compound from the viewpoint of the compatibility of the compound having a functional group with a polymer having a dielectric loss tangent of 0.01 or less and the dielectric loss tangent of the film. From the viewpoint of heat resistance and mechanical strength, a polymer compound is preferable.
• the number of functional groups in the compound having a functional group may be 1 or more, and may be 2 or more, but preferably 2 or more. From the viewpoint of reducing the dielectric loss tangent, it is preferably 10 or less.
• the compound having a functional group may have only one type of functional group, or may have two or more types of functional groups.
• the low molecular weight compound used as a compound having a functional group preferably has a molecular weight of 50 or more and less than 2,000, more preferably a molecular weight of 100 or more and less than 1,000, from the viewpoint of adhesion to metal. It is particularly preferable that the molecular weight is 200 or more and less than 1,000.
• the content of the compound having a functional group is 10% by mass based on the total mass of layer B, in order to narrow the spread of the compound and increase the probability of contact between the functional groups. It is preferable to include the above.
• the polymer compound used as the compound having a functional group is preferably a polymer having a weight average molecular weight of 1,000 or more from the viewpoint of adhesion to metal, and a polymer having a weight average molecular weight of 2,000 or more. It is more preferably a polymer, more preferably a polymer with a weight average molecular weight of 3,000 or more and 1,000,000 or less, particularly a polymer with a weight average molecular weight of 5,000 or more and 200,000 or less. preferable.
• the polymer having a dielectric loss tangent of 0.01 or less and the compound having a functional group are compatible with each other.
• being compatible means that no phase separation is observed inside layer B.
• the difference between the Hoy method SP value of a polymer with a dielectric loss tangent of 0.01 or less and the Hoy method SP value of a compound with a functional group is the difference between a polymer with a dielectric loss tangent of 0.01 or less and a compound with a functional group.
• the pressure is 5 MPa 0.5 or less. Note that the lower limit value is 0 MPa 0.5 .
• the SP value (solubility parameter value) according to the Hoy method is calculated from the molecular structure of the resin by the method described in the Polymer Handbook fourth edition. Further, when the resin is a mixture of multiple types of resins, the SP value of each constituent unit is calculated respectively.
• the functional group in the compound having a functional group is selected from the group consisting of a group capable of covalent bonding, a group capable of ionic bonding, a group capable of hydrogen bonding, a group capable of dipole interaction, and a group capable of curing reaction. Preferably, it is at least one type of group. From the viewpoint of adhesion to metal, the functional group is preferably a group capable of covalent bonding or a group capable of curing reaction, and more preferably a group capable of covalent bonding. Moreover, from the viewpoint of storage stability and handleability, it is preferable that the functional group is a group capable of ionic bonding, a group capable of hydrogen bonding, or a group capable of dipolar interaction.
• -Covalently bondable group- Groups that can be covalently bonded are not particularly limited as long as they can form a covalent bond, such as epoxy groups, oxetanyl groups, isocyanate groups, acid anhydride groups, carbodiimide groups, N-hydroxyester groups, and glyoxal groups. , an imidoester group, a halogenated alkyl group, a thiol group, a hydroxy group, a carboxy group, an amino group, an amide group, an isocyanate group, an aldehyde group, a sulfonic acid group, and the like.
• the surface of the metal to be bonded has a group that pairs with the functional group of the compound having a functional group.
• a combination of groups that can be covalently bonded a combination of a functional group of a compound having a functional group and a group on the surface of a metal
• the other is an epoxy group or an oxetanyl group.
• examples include a hydroxy group and an amino group.
• the other group may be an amino group.
• the cationic group is preferably an onium group.
• the onium group include ammonium group, pyridinium group, phosphonium group, oxonium group, sulfonium group, selenonium group, and iodonium group.
• an ammonium group, a pyridinium group, a phosphonium group, or a sulfonium group is preferable, an ammonium group or a phosphonium group is more preferable, and an ammonium group is particularly preferable.
• the anionic group is not particularly limited and includes, for example, a phenolic hydroxyl group, a carboxy group, -SO 3 H, -OSO 3 H, -PO 3 H, -OPO 3 H 2 , -CONHSO 2 -, -SO 2 NHSO 2 - etc.
• a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfonic acid group, a sulfinic acid group or a carboxy group are preferable, and a phosphoric acid group or a carboxy group is more preferable. More preferably, it is a carboxy group.
• ionically bondable groups a combination of a functional group of a compound having a functional group and a group on the surface of a metal
• a combination of ionically bondable groups a combination of a functional group of a compound having a functional group and a group on the surface of a metal
• examples include sexual groups.
• the acidic group include a carboxy group, a sulfo group, a phosphoric acid group, and a carboxy group is preferred.
• examples of the group capable of ionically bonding with the carboxy group include a tertiary amino group, a pyridyl group, a piperidyl group, and the like.
• the group capable of hydrogen bonding include a group having a hydrogen bond donating site and a group having a hydrogen bond accepting site.
• the hydrogen bond donating site may have any structure having an active hydrogen atom capable of hydrogen bonding, but preferably has a structure represented by XH.
• X represents a heteroatom, and is preferably a nitrogen atom or an oxygen atom.
• the hydrogen bond donating moieties include hydroxy group, carboxy group, primary amide group, secondary amide group, primary amino group, secondary amino group, primary
• the structure is preferably at least one selected from the group consisting of a class sulfonamide group, a secondary sulfonamide group, an imide group, a urea bond, and a urethane bond, and a hydroxy group, a carboxy group, and a primary amide group.
• a secondary amide group, a primary sulfonamide group, a secondary sulfonamide group, a maleimide group, a urea bond, and a urethane bond a class sulfonamide group, a secondary sulfonamide group, an imide group, a urea bond, and a urethane bond.
• a carboxy group a primary amide group, a secondary amide group, a primary sulfonamide group, a secondary sulfonamide group, and a maleimide group. More preferably, it is particularly preferably at least one structure selected from the group consisting of a hydroxy group and a secondary amide group.
• the hydrogen bond-accepting site preferably has a structure containing an atom with a lone pair of electrons, preferably a structure containing an oxygen atom with a lone pair of electrons, and a carbonyl group (carboxy group, amide group, imide group).
• a sulfonyl group including a carbonyl structure such as a urea bond, a urethane bond, etc.
• a sulfonyl group including a sulfonyl structure such as a sulfonamide group
• a carbonyl group is particularly preferred.
• the group capable of hydrogen bonding is preferably a group having both the above hydrogen bond donating site and hydrogen bond accepting site, such as a carboxy group, amide group, imido group, urea bond, urethane bond, or sulfonamide group.
• the group preferably has a carboxy group, an amide group, an imide group, or a sulfonamide group.
• a combination of groups capable of hydrogen bonding (a combination of a functional group of a compound having a functional group and a group on the surface of a metal), specifically, when one of the groups has a group having a hydrogen bond donating site, The other group includes a group having a hydrogen bond-accepting site.
• the groups when one of the groups is a carboxyl group, examples thereof include an amide group and a carboxyl group.
• the other is a phenolic hydroxyl group.
• the group capable of dipolar interaction has a polarized structure other than the structure represented by Any group may be used, and preferred examples include groups in which atoms having different electronegativities are bonded.
• the combination of atoms with different electronegativities is preferably a combination of a carbon atom and at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.
• a combination of at least one kind of atom selected from the group consisting of sulfur atoms and a carbon atom is more preferable.
• a combination of groups capable of dipole interaction (combination of a functional group of a compound having a functional group and a group present on the surface of the metal)
• a combination of the same groups capable of dipole interaction is preferably mentioned.
• one is a cyano group the other is a cyano group.
• one is a sulfonic acid amide group for example, the other is a sulfonic acid amide group.
• layer B contains a curable compound, it is preferable that layer B contains a curable compound and a curing aid.
• the curable compound is a compound that is cured by irradiation with heat or light (for example, visible light, ultraviolet rays, near infrared rays, far infrared rays, electron beams, etc.), and may require a curing aid as described below.
• examples of such curable compounds include epoxy compounds, cyanate ester compounds, vinyl compounds, silicone compounds, oxazine compounds, maleimide compounds, allyl compounds, acrylic compounds, methacrylic compounds, and urethane compounds. These may be used alone or in combination of two or more.
• the content of the curable compound in layer B is preferably 10% by mass or more and 90% by mass or less, and more preferably 20% by mass or more and 80% by mass or less, based on the total mass of layer B.
• curing aid examples include polymerization initiators such as photoreaction initiators (photoradical generators, photoacid generators, photobase generators).
• curing aids include onium salt compounds, sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, triazine compounds, nitrobenzyl compounds, Examples include benzylimidazole compounds, organic halides, octylic acid metal salts, disulfones, and the like.
• curing aids may be used alone or in combination of two or more, regardless of the type.
• the content of the curing aid in layer B is preferably 5% by mass or more and 20% by mass or less, and more preferably 5% by mass or more and 10% by mass or less, based on the total mass of layer B.
• the functional groups in the compound having a functional group include an epoxy group, an oxetanyl group, an isocyanate group, an acid anhydride group, a carbodiimide group, an N-hydroxyester group, a glyoxal group, an imidoester group, a halogenated alkyl group, Thiol group, hydroxy group, carboxy group, amino group, amide group, isocyanate group, aldehyde group, sulfonic acid group, ammonium group, pyridinium group, phosphonium group, oxonium group, sulfonium group, selenonium group, iodonium group, phosphoric acid group, Phosphonic acid group, phosphinic acid group, sulfuric acid group, sulfonic acid group, sulfinic acid group or carboxy group, hydroxy group, carboxy group, primary amide group, secondary amide group, primary amino group, secondary amino It is preferable to include at least
• epoxy groups oxetanyl groups, isocyanate groups, acid anhydride groups, carbodiimide groups, N-hydroxyester groups, glyoxal groups, imidoester groups, halogenated alkyl groups, or thiol groups are more preferred.
• the compound having a functional group is preferably a polyfunctional epoxy compound or a polymer of a polyfunctional epoxy compound from the viewpoint of the dielectric loss tangent of the polymer film and the adhesion to metal, and is preferably a difunctional epoxy compound or a polymer of a polyfunctional epoxy compound.
• a polymer of a difunctional epoxy compound is more preferable, and a difunctional epoxy compound is particularly preferable.
• Layer B may contain only one kind of compound having a functional group, or may contain two or more kinds of compounds.
• the content of the compound having a functional group in layer B is preferably 0.1% by mass to 20% by mass based on the total mass of layer B, from the viewpoint of dielectric loss tangent of the film and adhesion with metal. It is preferably 1% by mass to 10% by mass.
• Layer B may contain other additives other than those mentioned above. Preferred embodiments of other additives used in layer B are the same as preferred embodiments of other additives used in layer A, except as described below.
• the average thickness of layer B is not particularly limited, and from the viewpoint of the dielectric loss tangent of the film, suitability for laser processing, and step followability, it is preferably 1 ⁇ m to 90 ⁇ m, more preferably 5 ⁇ m to 60 ⁇ m. , 10 ⁇ m to 30 ⁇ m is particularly preferred.
• the film according to the present disclosure has excellent adhesion to metal.
• layer A has a filler
• layer B is preferably a surface layer (outermost layer).
• the film is used as a laminate (a laminate with a metal layer) having a layer configuration of metal layer/layer A/layer B, another metal layer or a laminate with a metal layer is further placed on the layer B side. There are things to do. In this case, interface destruction between layer B and another metal layer in the laminate is suppressed, and step followability is improved.
• the polymer contained in layer B contains a polymer having higher breaking strength (toughness) than the polymer contained in layer A.
• the breaking strength shall be measured by the following method. A sample made of the polymer to be measured was prepared, and the stress against elongation was measured using a universal tensile tester "STM T50BP" manufactured by Toyo Baldwin Co., Ltd. at a tensile rate of 10%/min at 25°C and 60% RH, and Find the breaking strength.
• the film according to the present disclosure preferably further has a layer C, and from the viewpoint of step tracking ability, it is more preferable to have the layer B, the layer A, and the layer C in this order. Furthermore, when a metal layer is present apart from the above-mentioned layers, layer C is preferably a surface layer (outermost layer). Layer C preferably contains a polymer having a dielectric loss tangent of 0.01 or less, from the viewpoint of the film's dielectric loss tangent and step followability.
• Preferred embodiments of the polymer having a dielectric loss tangent of 0.01 or less used in layer C are the same as preferred embodiments of the polymer having a dielectric loss tangent of 0.01 or less used in layer A, except as described below.
• the liquid crystal polymer contained in layer C may be the same as or different from the polymer having a dielectric loss tangent of 0.01 or less contained in layer A or layer B. From the viewpoint of adhesion, it is preferable that the layer A contains the same polymer having a dielectric loss tangent of 0.01 or less.
• the content of the polymer having a dielectric loss tangent of 0.01 or less in layer C is preferably equal to or less than the content of the polymer having a dielectric loss tangent of 0.01 or less in layer A, from the viewpoint of adhesion to metal.
• the content of the polymer having a dielectric loss tangent of 0.01 or less in layer C should be 10% by mass to 100% by mass based on the total mass of layer C, from the viewpoint of the dielectric loss tangent of the film and the ability to follow steps. It is preferably 20% by mass to 99% by mass, even more preferably 50% to 98% by mass, and particularly preferably 70% to 98% by mass.
• Layer C preferably contains a compound having a functional group.
• Preferred embodiments of the compound having a functional group used in layer C are the same as preferred embodiments of the compound having a functional group used in layer B, except as described below.
• the compound having a functional group contained in layer C may be the same as the compound having a functional group contained in layer B, or may be different.
• Layer C may contain only one kind of compound having a functional group, or may contain two or more kinds of compounds. It is preferable that the content ratio of the compound having a functional group in layer C is higher than the content ratio of the compound having a functional group in layer A.
• the content of the compound having a functional group in layer C should be 0.1% by mass to 20% by mass based on the total mass of layer C, from the viewpoint of dielectric loss tangent of the polymer film and adhesion to metal. It is preferably 1% by mass to 10% by mass.
• Layer C may contain filler. Preferred embodiments of the filler used in layer C are the same as those of the filler used in layer B, except as described below.
• the filler content in layer C is not particularly limited and can be set arbitrarily.
• the filler content is preferably lower than the filler content in layer A from the viewpoint of step followability.
• the content of filler in layer C is either no filler or more than 20% by volume based on the total volume of layer C, from the viewpoint of step tracking ability. It is preferable that the filler is not more than 10% by volume, and it is more preferable that the amount is more than 0 volume% and 10% or less with respect to the total volume of the layer C.
• the amount is more than 0 volume % and 5 volume % or less with respect to the total volume of C, and it is particularly preferable that no filler is included.
• the filler content in layer C is preferably 0% to 15% by mass, more preferably 0% to 5% by mass, based on the total mass of layer C.
• the content of fillers such as polyethylene and olefin elastomers is preferably 50% to 90% by volume, more preferably 75% to 85% by volume. In this case, the filler content in layer C is preferably 55% to 90% by mass, more preferably 80% to 85% by mass, based on the total mass of layer C.
• Layer C may contain other additives other than those mentioned above. Preferred embodiments of other additives used in layer C are the same as preferred embodiments of other additives used in layer A, except as described below.
• the average thickness of layer C is preferably thinner than the average thickness of layer A from the viewpoint of dielectric loss tangent of the film and adhesion to metal.
• the value of T A / TC which is the ratio of the average thickness T A of layer A to the average thickness T C of layer C, is preferably larger than 1 from the viewpoint of the dielectric loss tangent of the film and the step tracking ability, It is more preferably from 2 to 100, even more preferably from 2.5 to 20, and particularly preferably from 3 to 15.
• the value of T B / TC which is the ratio of the average thickness T B of layer B to the average thickness T C of layer C, is preferably larger than 1 from the viewpoint of the dielectric loss tangent of the film and the step tracking ability, It is more preferably from 2 to 100, even more preferably from 2.5 to 20, particularly preferably from 3 to 10.
• the average thickness of layer C is preferably 0.1 ⁇ m to 20 ⁇ m, more preferably 0.5 ⁇ m to 15 ⁇ m, and preferably 1 ⁇ m to 10 ⁇ m, from the viewpoint of dielectric loss tangent of the film and step followability. It is particularly preferable that there be.
• the average thickness of the film according to the present disclosure is preferably 6 ⁇ m to 200 ⁇ m, and preferably 12 ⁇ m to 100 ⁇ m, from the viewpoint of strength and electrical properties (characteristic impedance) when formed into a laminate with a metal layer.
• the thickness is more preferably 20 ⁇ m to 60 ⁇ m.
• the average thickness of the film is measured at five arbitrary locations using an adhesive film thickness meter, for example, an electronic micrometer (product name "KG3001A", manufactured by Anritsu Corporation), and is taken as the average value.
• an adhesive film thickness meter for example, an electronic micrometer (product name "KG3001A", manufactured by Anritsu Corporation), and is taken as the average value.
• the dielectric loss tangent of the film according to the present disclosure is preferably 0.008 or less, more preferably 0.005 or less, even more preferably 0.004 or less, and 0. It is particularly preferable that it exceeds 0.003 or less.
• the method for producing the film according to the present disclosure is not particularly limited, and known methods can be referred to. Suitable methods for producing the film according to the present disclosure include, for example, a co-casting method, a multilayer coating method, a co-extrusion method, and the like. Among these, the co-casting method is particularly preferable for forming a relatively thin film, and the co-extrusion method is particularly preferable for forming a thick film.
• a composition for forming layer A When produced by a co-casting method and a multilayer coating method, a composition for forming layer A, a composition for forming layer B, in which components of each layer such as a polymer having a dielectric loss tangent of 0.01 or less are dissolved or dispersed in a solvent, respectively; It is preferable to perform a co-casting method or a multilayer coating method for the composition for forming layer C, etc.
• solvents 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 Carbonates such as carbonate and propylene carbonate; Amines such as triethylamine; Nitrogen-containing heterocyclic aromatic compounds such as pyridine; Nitriles such as acetonitrile and succinonitrile; N,N-dimethylformamide,
• the solvent preferably contains an aprotic compound (particularly preferably an aprotic compound without a halogen atom) because it has low corrosivity and is easy to handle.
• the proportion of the aprotic compound in the entire solvent is preferably 50% to 100% by weight, more preferably 70% to 100% by weight, particularly preferably 90% to 100% by weight.
• amides such as N,N-dimethylformamide, N,N-dimethylacetamide, tetramethylurea, N-methylpyrrolidone, etc. or ⁇ -butyrolactone etc. It preferably contains an ester, and more preferably N,N-dimethylformamide, N,N-dimethylacetamide, or N-methylpyrrolidone.
• the solvent preferably contains a compound having a dipole moment of 3 to 5 because it easily dissolves the above-mentioned polymers such as liquid crystal polymers.
• the proportion of the compound having a dipole moment of 3 to 5 in the entire solvent is preferably 50% to 100% by mass, more preferably 70% to 100% by mass, particularly preferably 90% to 100% by mass. be.
• a compound having a dipole moment of 3 to 5 is preferably used as the aprotic compound.
• the solvent preferably contains a compound having a boiling point of 220° C. or less at 1 atm, since it is easy to remove.
• the proportion of the compound having a boiling point of 220° C. or lower at 1 atm in the entire solvent is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, particularly preferably 90% by mass to 100% by mass. It is.
• the aprotic compound it is preferable to use a compound whose boiling point at 1 atmosphere is 220° C. or less.
• a support may be used when producing the film by the above co-casting method, multilayer coating method, coextrusion method, or the like. Furthermore, when a metal layer (metal foil) or the like used in a laminate described later is used as a support, it may be used as it is without being peeled off. Examples of the support include a metal drum, metal band, glass plate, resin film, or metal foil. Among these, metal drums, metal bands, and resin films are preferred.
• Examples of the resin film include polyimide (PI) films, and examples of commercially available products include U-Pyrex S and U-Pyrex R manufactured by Ube Industries, Ltd., Kapton manufactured by DuPont Toray Co., Ltd., and Examples include IF30, IF70, and LV300 manufactured by SKC Kolon PI.
• a surface treatment layer may be formed on the surface of the support so that it can be easily peeled off.
• hard chrome plating, fluororesin, etc. can be used.
• the average thickness of the support is not particularly limited, but is preferably 25 ⁇ m or more and 75 ⁇ m or less, more preferably 50 ⁇ m or more and 75 ⁇ m or less.
• the method for removing at least a portion of the solvent from the cast or applied film-like composition is not particularly limited, and any known drying method may be used. .
• the film according to the present disclosure can be stretched as appropriate from the viewpoint of controlling molecular orientation and adjusting linear expansion coefficient and mechanical properties.
• the stretching method is not particularly limited, and known methods can be referred to, and stretching may be carried out in a state containing a solvent or in a dry film state. Stretching in a state containing a solvent may be carried out by gripping and stretching the film, or may be carried out by utilizing self-shrinkage due to drying without stretching. Stretching is particularly effective for improving elongation at break and strength at break when film brittleness is reduced by addition of inorganic fillers or the like.
• the method for producing a film according to the present disclosure may include a step of polymerizing with light or heat, as necessary.
• the light irradiation means and heat application means are not particularly limited, and known light irradiation means such as a metal halide lamp, and known heat application means such as a heater can be used.
• the light irradiation conditions and the heat application conditions are not particularly limited, and can be performed at a desired temperature and time and in a known atmosphere.
• the method for manufacturing a film according to the present disclosure preferably includes a step of heat-treating (annealing) the film.
• the heat treatment temperature in the above heat treatment step is preferably 260°C to 370°C, more preferably 280°C to 360°C, and 300°C to 350°C from the viewpoint of dielectric loss tangent and peel strength. It is more preferable that The heat treatment time is preferably 15 minutes to 10 hours, more preferably 30 minutes to 5 hours.
• the method for manufacturing a film according to the present disclosure may include other known steps as necessary.
• the film according to the present disclosure can be used for various purposes, and among them, can be suitably used as a film for electronic components such as printed wiring boards, and can be suitably used for flexible printed circuit boards. Further, the film according to the present disclosure can be suitably used as a metal adhesive film.
• the laminate according to the present disclosure may be a laminate of the films according to the present disclosure, and includes the film according to the present disclosure and a metal layer or metal wiring arranged on at least one surface of the film.
• a laminate is preferred.
• the laminate according to the present disclosure has a layer A, a layer B, and a metal layer or metal wiring in this order, and the elastic modulus of the layer A at 160°C is relative to the elastic modulus of the layer B at 160°C. It is preferable that the ratio is 1.2 or more, and the thermal conductivity of the layer A is 0.05 W/(m ⁇ K) or more.
• the laminate according to the present disclosure preferably includes the film according to the present disclosure and a metal layer or metal wiring arranged on the surface of the layer B side of the film, and the metal layer or metal wiring comprises: More preferably, it is a copper layer or copper wiring.
• the metal layer or metal wiring arranged on the layer B side surface is preferably a metal layer or metal wiring arranged on the surface of the layer B.
• the laminate according to the present disclosure includes a film according to the present disclosure having layer B, layer A, and layer C in this order, and a metal layer or metal disposed on the surface of the layer B side of the film.
• metal layer or metal wiring arranged on the surface of the layer C side of the film It is preferable to have wiring and a metal layer or metal wiring arranged on the surface of the layer C side of the film, and it is more preferable that both the metal layer or metal wiring are copper layers or copper wiring.
• the metal layer or metal wiring arranged on the surface on the layer C side is preferably a metal layer or metal wiring arranged on the surface of the layer C, and the metal layer or metal wiring arranged on the surface on the layer B side
• the metal wiring is a metal layer or metal wiring placed on the surface of the layer B, and the metal layer or metal wiring placed on the layer C side is a metal layer or metal wiring placed on the surface of the layer C.
• metal wiring is more preferable.
• the metal layer disposed on the layer B side surface and the metal layer disposed on the layer C side surface may be made of different materials and have different thicknesses. and shaped metal layers.
• 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 only on one side of layer B or layer C.
• an embodiment in which a metal layer is laminated on one side of layer B or layer C and another film is laminated on the other side is also preferably mentioned.
• the above-mentioned metal layer and metal wiring are not particularly limited and may be any known metal layer and metal wiring.
• they are preferably a silver layer, silver wiring, copper layer or copper wiring, It is more preferable that Moreover, it is preferable that the metal layer and the metal wiring are metal wiring.
• the metal in the metal layer and metal wiring is preferably silver or copper, and more preferably copper.
• the peel strength between the film and the copper layer is preferably 0.5 kN/m or more, more preferably 0.7 kN/m or more, It is more preferably .7 kN/m to 2.0 kN/m, and particularly preferably 0.9 kN/m to 1.5 kN/m.
• the peel strength between a film and a metal layer shall be measured by the following method.
• a peel test piece with a width of 1.0 cm was prepared from the laminate of the film and the metal layer, the film was fixed to a flat plate with double-sided adhesive tape, and the peel test piece was peeled at 50 mm/min by the 180° method according to JIS C 5016 (1994).
• the strength (kN/m) is measured when the film is peeled off from the metal layer at a speed of .
• the surface roughness Rz of the metal layer on the side in contact with the film is preferably less than 1 ⁇ m, more preferably 0.5 ⁇ m or less, particularly preferably 0.3 ⁇ m or less, from the viewpoint of reducing transmission loss of high-frequency signals. Note that the lower the surface roughness Rz of the metal layer is, the better, so the lower limit is not particularly set, but for example, 0 or more can be mentioned.
• surface roughness Rz refers to a value expressed in micrometers of the sum of the maximum height of the peak and the maximum value of the depth of the valley observed in the roughness curve at the reference length. means.
• the surface roughness Rz of a metal layer shall be measured by the following method. Using VertScan (manufactured by Ryoka System Co., Ltd.), a non-contact surface/layer cross-sectional shape measurement system, a square area of 465.48 ⁇ m in length and 620.64 ⁇ m in width was measured to determine the roughness curve on the surface of the object to be measured (metal layer) and the above. Create an average line for the roughness curve.
• the metal layer is preferably a silver layer or a copper layer, and more preferably a copper layer.
• the copper layer is preferably a rolled copper foil formed by a rolling method or an electrolytic copper foil formed by an electrolytic method.
• the average thickness of the metal layer is not particularly limited, but is preferably from 2 ⁇ m to 20 ⁇ m, more preferably from 3 ⁇ m to 18 ⁇ m, and even more preferably from 5 ⁇ m to 12 ⁇ m.
• the copper foil may be a carrier-attached copper foil that is removably formed on a support (carrier).
• carrier known carriers can be used.
• the average thickness of the carrier is not particularly limited, but is preferably 10 ⁇ m to 100 ⁇ m, more preferably 18 ⁇ m to 50 ⁇ m.
• the metal layer is provided with a known surface treatment layer (for example, a chemical treatment layer) on the surface in contact with the film to ensure adhesive strength with the resin. It is preferable to have.
• the above-mentioned interacting group is preferably a group corresponding to a functional group of a compound having a functional group contained in the above-mentioned film, such as an amino group and an epoxy group, or a hydroxy group and an epoxy group. Examples of the group capable of interacting include the groups listed above for the functional group in the compound having the functional group. Among these, from the viewpoints of adhesion and ease of processing, a group capable of covalent bonding is preferred, an amino group or a hydroxy group is more preferred, and an amino group is particularly preferred.
• the metal layer in the laminate according to the present disclosure may be a metal layer having a circuit pattern. 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 any known etching method can be used.
• the method for producing a laminate according to the present disclosure includes a step A of forming a layer A by applying a composition A containing a liquid crystal polymer, a filler having a thermal conductivity of 0.05 W/(m ⁇ K) or more, and a solvent. and a step B of applying a composition B containing a liquid crystal polymer and a solvent to form a layer B on at least one surface of the layer A. It is more preferable that the ratio of the elastic modulus at 160° C. of the layer A to the elastic modulus at 160° C. is 1.2 or more, and the liquid crystal polymer and the filler have a thermal conductivity of 0.05 W/(m K) or more.
• the method for manufacturing a laminate according to the present disclosure it is preferable that the above step A and the above step B are performed simultaneously, and the above step A and the above step B are performed simultaneously by a co-casting method or a multilayer coating method. It is more preferable that the Furthermore, it is preferable that the method for manufacturing a laminate according to the present disclosure produces a laminate according to the present disclosure.
• the method for manufacturing the laminate according to the present disclosure can be performed using any known method, and the method for manufacturing the film described above and the method for attaching the film and metal layer or metal wiring according to the present disclosure may be suitably used. I can do it.
• the dielectric constant measurements were performed using a resonance perturbation method at a frequency of 10 GHz.
• a 10 GHz cavity resonator (CP531, manufactured by Kanto Electronics Applied Development Co., Ltd.) was connected to a network analyzer (“E8363B” manufactured by Agilent Technology), and a sample (width: 2 mm x length: 80 mm) was inserted into the cavity resonator.
• the dielectric constant and dielectric loss tangent of the sample were measured from the change in resonance frequency before and after insertion for 96 hours under an environment of a temperature of 25° C. and a humidity of 60% RH.
• the metal layer was laminated
• the cross section of the film was cut using a microtome or the like, and layer A or layer B was identified from the image observed using an optical microscope.
• the elastic modulus of the specified layer A or layer B was measured as an indentation elastic modulus using a nanoindentation method.
• the indentation modulus was measured using a microhardness tester (product name: DUH-W201, manufactured by Shimadzu Corporation) at 160°C with a Vickers indenter at a loading rate of 0.28 mN/sec, with a maximum load of 10 mN. After holding for 10 seconds, the measurement was performed by unloading at a loading rate of 0.28 mN/sec.
• the liquid crystal polyester (A1) obtained above was heated under a nitrogen atmosphere from room temperature to 160°C over 2 hours and 20 minutes, then from 160°C to 180°C over 3 hours and 20 minutes, and at 180°C. After solid-phase polymerization was carried out by holding for 5 hours, the mixture was cooled, and then pulverized using a pulverizer to obtain a powdery liquid crystal polyester (A2).
• the liquid crystal polyester (A2) obtained above was heated under 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. After solid phase polymerization was carried out by holding at °C for 5 hours, the mixture was cooled to obtain powdery liquid crystal polyester P-1.
• P-2 Commercially available liquid crystal polymer (Vectra A950, manufactured by Polyplastics Co., Ltd.)
• F-1 Silica particles with an average particle size of 0.5 ⁇ m (SC2050-MB, manufactured by Admatex Co., Ltd.)
• F-2 Boron nitride particles with an average particle size of 2 ⁇ m (HP-P1, manufactured by Mizushima Ferroalloy Co., Ltd., thermal conductivity is 0.05 W/(m ⁇ K) or more)
• F-3 Liquid crystal polymer particles produced according to the manufacturing method below, thermal conductivity of 0.05 W/(m ⁇ K) or more
• Liquid crystal polyester (C1) was ground using a jet mill (KJ-200 manufactured by Kurimoto Iron Works Co., Ltd.) to obtain liquid crystal polyester particles F-3.
• the average particle size of the liquid crystal polyester particles was 9 ⁇ m.
• F-4 Aluminum nitride powder (average particle size 1 ⁇ m, H grade (manufactured by Tokuyama Corporation), thermal conductivity 0.05 W/(m ⁇ K) or more)
• E-1 Carboxyl group-modified hydrogenated styrene-ethylene-butylene-styrene block copolymer (Tuftec M1913, manufactured by Asahi Kasei Chemicals Co., Ltd.)
• E-2 Elastomer particles produced according to the following manufacturing method
• Elastomer E-1 was pulverized using a jet mill (KJ-200 manufactured by Kurimoto Iron Works Co., Ltd.) to obtain elastomer particles E-2.
• the average particle size of the elastomer particles E-2 was 5 ⁇ m.
• M-1 Condensation polycondensation epoxy resin (jER YX8800, manufactured by Mitsubishi Chemical Corporation)
• M-2 Aminophenol type epoxy resin (jER 630LSD, manufactured by Mitsubishi Chemical Corporation)
• a polymer film (laminate) having layers was obtained.
• heat treatment was performed under the conditions of 200°C for 30 minutes, 300°C for 20 minutes, and 360°C for 5 minutes.
• a film (laminate) having layers was obtained.
• the obtained pellets were fed into a cylinder from the same feed port of a twin-screw extruder with a screw diameter of 50 mm, and heated and kneaded at 340° C. to 350° C. to obtain a kneaded product. Subsequently, the kneaded materials for layer A and layer B were each sent to a T-die having a multi-manifold structure, and the molten film-like kneaded materials were discharged and solidified on a chill roll. The obtained film was peeled off from the chill roll and tenter stretched to adjust the anisotropy of elastic modulus (MD/TD) to 2 or less to obtain a film.
• MD/TD anisotropy of elastic modulus
• the material for layer B listed in Table 1 was added to toluene and stirred to obtain a surface layer varnish (resin composition).
• the obtained resin composition was applied to the release surface side of a PET film having a thickness of 38 ⁇ m and subjected to a release treatment on one side, and dried until it became a semi-cured state, to obtain a layer B transfer film.
• the transfer film of layer B is placed on the layer A side of the film (laminate) having the copper layer described in Tables 1 and 2, which serves as the adherend, and is laminated.
• the release PET film was peeled off.
• the treated side of a copper foil (manufactured by Fukuda Metal Foil & Powder Industry Co., Ltd., CF-T9DA-SV-18, thickness 18 ⁇ m, surface roughness of the pasting surface (treated surface) Rz 0.85 ⁇ m) was placed on layer B. They were bonded together and heated and pressed at 160° C. and 4 MPa for 60 minutes to obtain a film (laminate) having copper layers on both sides.
• thermocompression bonding process The obtained copper-clad laminate precursor was thermo-compressed at 300°C and 4.5 MPa for 10 minutes using a thermo-compression bonding machine (“MP-SNL” manufactured by Toyo Seiki Seisakusho Co., Ltd.) to form a single-sided copper-clad laminate. A laminate or a double-sided copper-clad laminate was produced.
• MP-SNL manufactured by Toyo Seiki Seisakusho Co., Ltd.
• a flexible wiring board having a four-layer stripline structure including an outer layer plane (ground layer) was manufactured using the metal-clad laminate described above.
• wiring base material The copper foil of the double-sided copper-clad laminate was patterned using a known photofabrication method to produce a wiring base material including three pairs of signal lines.
• the length of the signal line was 100 mm, and the width was set so that the characteristic impedance was 50 ⁇ .
• a flexible wiring board was produced by laminating layers at a press temperature of 160° C. using a vacuum press device.
• Step tracking ability (wiring distortion)>
• the flexible wiring board was cut with a microtome, the cross section was observed with an optical microscope, and the distortion of the wiring was evaluated based on the following evaluation criteria.
• the films of Examples 1 to 10 which are films according to the present disclosure are superior to the films of Comparative Examples 1 and 2 in step followability and laser processing suitability. Furthermore, from the results shown in Tables 1 and 2, the films of Examples 1 to 10, which are films according to the present disclosure, have low dielectric loss tangents.

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• Engineering & Computer Science (AREA)
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• 2023
  • 2023-03-30 JP JP2024512875A patent/JPWO2023191012A1/ja active Pending
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• 2024
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