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
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/22—Secondary treatment of printed circuits
  • H05K3/28—Applying non-metallic protective coatings
  • H05K3/285—Permanent coating compositions
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/06—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • 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
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/22—Secondary treatment of printed circuits
  • H05K3/28—Applying non-metallic protective coatings
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/46—Manufacturing multilayer circuits
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2274/00—Thermoplastic elastomer material
• • 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
  • B32B2305/00—Condition, form or state of the layers or laminate
  • B32B2305/30—Fillers, e.g. particles, powders, beads, flakes, spheres, chips
• • 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
  • B32B2305/00—Condition, form or state of the layers or laminate
  • B32B2305/55—Liquid crystals
• • 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
  • B32B2307/202—Conductive
• • 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/51—Elastic
• • 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
  • B32B2377/00—Polyamides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2457/00—Electrical equipment
  • B32B2457/08—PCBs, i.e. printed circuit boards
• • 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
  • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
  • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
  • H05K2203/1194—Thermal treatment leading to a different chemical state of a material, e.g. annealing for stress-relief, aging
• • 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
  • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
  • H05K2203/13—Moulding and encapsulation; Deposition techniques; Protective layers
  • H05K2203/1377—Protective layers

Definitions

• the present disclosure relates to a method for manufacturing a laminate, a film, a thermosetting film, and a wiring board.
• Patent Document 1 describes a resin composition containing a styrene-based polymer, an inorganic filler, and a curing agent, which The 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, and the content of the inorganic filler is , 20 to 80 parts by mass based on 100 parts by mass of the styrenic polymer, and the resin composition satisfies the following formulas (A) and (B) in the form of a film having a thickness of 25 ⁇ m.
• the 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 content of the inorganic filler is , 20 to 80
• 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, in which a cured product obtained by heating the above thermosetting adhesive sheet at 180° C. for 1 hour has the following properties (i) to (iv):
• a thermosetting adhesive sheet is described that satisfies the following.
• 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
• problems to be solved by the embodiments of the present invention is to provide a laminate that has excellent step followability and suitability for laser processing. Further, problems to be solved by other embodiments of the present invention are a film and a thermosetting film that are excellent in step followability and suitability for laser processing, and a method for manufacturing a wiring board using the above film or thermosetting film. The goal is to provide the following.
• Means for solving the above problems include the following aspects. ⁇ 1> It has a layer A, a layer B on at least one surface of the layer A, and a conductive pattern in contact with at least a part of the layer B, and has a dielectric loss tangent at 28 GHz of 0.01 or less, and has the above-mentioned A laminate in which the value obtained by subtracting the mass residual rate at 900°C from the mass residual rate at 440°C of layer B is 40% by mass or more.
• the layer B contains a resin having at least one group selected from the group consisting of a maleimide group, an allyl group, and a vinyl group.
• ⁇ 3> The laminate according to ⁇ 1> or ⁇ 2>, wherein the layer B contains a thermoplastic elastomer.
• ⁇ 4> The laminate according to any one of ⁇ 1> to ⁇ 3>, wherein the layer B contains an inorganic filler.
• ⁇ 5> The laminate according to any one of ⁇ 1> to ⁇ 4>, wherein the layer A contains a liquid crystal polymer.
• ⁇ 6> The laminate according to any one of ⁇ 1> to ⁇ 5>, wherein the layer A contains an aromatic polyesteramide.
• ⁇ 7> It has a layer A and a layer B on at least one surface of the layer A, the dielectric loss tangent at 28 GHz is 0.01 or less, and the elastic modulus of the layer B at 160° C. is 0.
• the layer B contains a thermosetting resin.
• the thermosetting resin has at least one group selected from the group consisting of a maleimide group, an allyl group, and a vinyl group.
• the layer B further contains a thermoplastic elastomer.
• the layer B contains an inorganic filler.
• the layer A contains a liquid crystal polymer.
• ⁇ 12> The film according to any one of ⁇ 7> to ⁇ 11>, wherein the layer A contains an aromatic polyesteramide.
• An overlaying step of overlaying the film according to any one of ⁇ 7> to ⁇ 12> on the wiring pattern of the wiring patterned base material from the layer B side, and the wiring patterned base material A method for manufacturing a wiring board, including a heating step of heating the film in a stacked state to obtain a wiring board.
• the heating temperature in the heating step is 240° C. or lower.
• thermosetting film containing a thermosetting compound and a thermoplastic elastomer, wherein the thermosetting compound has at least one group selected from the group consisting of a maleimide group, an allyl group, and a vinyl group.
• thermosetting film according to ⁇ 16> having an elastic modulus at 160° C. of 0.5 MPa or less.
• thermosetting film according to ⁇ 16> or ⁇ 17> which has a dielectric loss tangent of 0.01 or less at 28 GHz.
• thermosetting film according to any one of ⁇ 16> to ⁇ 18> which contains at least one selected from the group consisting of polyimide, liquid crystal polymer, fluorine-based polymer, and inorganic filler.
• thermosetting film according to any one of ⁇ 16> to ⁇ 19> further comprising an aromatic polyesteramide.
• thermosetting film according to any one of ⁇ 16> to ⁇ 20> on the wiring pattern of the substrate with the wiring pattern
• a method for manufacturing a wiring board comprising: heating the base material with a wiring pattern and the thermosetting film in a superposed state to obtain a wiring board.
• Substrate manufacturing method comprising: heating the base material with a wiring pattern and the thermosetting film in a superposed state to obtain a wiring board.
• thermosetting film that are excellent in step followability and suitability for laser processing, and a method for manufacturing a wiring board using the above film or thermosetting film. Can be done.
• 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 laminate according to the present disclosure includes a layer A, a layer B on at least one surface of the layer A, and a conductive pattern in contact with at least a part of the layer B, and has a dielectric loss tangent of 0.01 at 28 GHz. and the value obtained by subtracting the mass residual rate at 900°C from the mass residual rate at 440°C of the layer B is 40% by mass or more.
• the present inventors have discovered that conventional films and laminates have difficulty in achieving both step followability and laser processing suitability.
• 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 dielectric loss tangent at 28 GHz is 0.01 or less, and the value obtained by subtracting the mass survival rate at 900°C from the mass survival rate at 440°C of the layer B is 40% by mass or more.
• the dielectric loss tangent of the laminate according to the present disclosure at 28 GHz is 0.01 or less, preferably 0.008 or less, and 0.005 or less from the viewpoints of dielectric constant, laser processing suitability, and step tracking ability. It is more preferable that it is, it is still more preferable that it is 0.004 or less, and it is especially preferable that it is more than 0 and 0.003 or less.
• 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 using a resonance perturbation method at a frequency of 28 GHz.
• a 28 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. When measuring each layer, an unnecessary layer may be scraped off with a razor or the like to prepare a sample for evaluation of only the desired layer.
• 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 carried out according to the method for measuring the dielectric loss tangent described above, using a powdered sample of the polymer to be measured after specifying or isolating the chemical structure of the polymer constituting each layer. do.
• the dielectric loss tangent of the laminate may be determined by weighted average from the dielectric loss tangent and film thickness of layer A and layer B, respectively.
• the value obtained by subtracting the mass residual rate at 900 °C from the mass residual rate at 440 ° C of the layer B is 40% or more, and from the viewpoint of laser processing suitability and step followability, It is preferably 40% to 95%, more preferably 45% to 90%.
• the value obtained by subtracting the mass residual rate at 900° C. from the mass residual rate at 440° C. of the layer B can be adjusted by the amount of the thermosetting compound, the amount of the inorganic filler, etc., which will be described later.
• the method for measuring the value obtained by subtracting the mass survival rate at 900°C from the mass survival rate at 440°C of layer B in the present disclosure is as follows. Layer B was cut from the film, 5 mg was added to a platinum pan, and heated using a differential thermal balance (TG-DTA) (TG-8120 manufactured by Rigaku Co., Ltd.) at a heating rate of 10°C/min and a measurement temperature of 25°C to Measure at 900°C.
• the mass residual rate shall be the following value.
• Mass residual rate (%) of layer B mass residual rate (%) at 440°C - mass residual rate (%) at 900°C
• the laminate according to the present disclosure has layer A. Furthermore, methods for detecting or determining the layer structure in the film, 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 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.
• 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 laminate 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 followability. , 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 a polymer with a dielectric loss tangent of 0.01 or less is determined from the viewpoints of the dielectric loss tangent of the film, adhesion to metals (e.g., metal layer, metal wiring, etc.), and heat resistance.
• the temperature is preferably 200°C or higher, more preferably 250°C or higher, even more preferably 280°C or higher, and particularly preferably 300°C or higher. Although there is no particular restriction on 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 the polymer having a dielectric loss tangent of 0.01 or less is preferably 150° C. or higher, and preferably 200° C. or higher from the viewpoints of the film's dielectric loss tangent, adhesion with metal, and heat resistance. More preferably, the temperature is 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 viewpoints of the film's dielectric loss tangent, adhesion to metals, 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 laminate according to the present disclosure preferably contains a liquid crystal polymer from the viewpoints of the film's dielectric loss tangent, laser processing suitability, and step followability.
• 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 group polyester amides.
• 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 acid and aromatic dicarboxylic acid can be replaced with aromatic hydroxycarboxylic acid anhydride and aromatic dicarboxylic acid anhydride.
• 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 referred to as formula (1)) from the viewpoints of liquid crystallinity, dielectric loss tangent of the film, and adhesion to metals. 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-2 - a structural unit derived from naphthoic acid) or a 4,4'-biphenylylene group (a structural unit derived from 4'-hydroxy-4-biphenylcarboxylic acid).
• 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).
• the amount equivalent to the substance amount (mol) of the structural unit is determined and the sum thereof is preferably 30 mol% or more, more preferably 30 mol% to 80 mol%, and 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). Further, the liquid crystal polymer may have structural units other than structural units (1) to (3), but the content thereof is preferably 10 mol% or less, more preferably 10 mol% or less based on the total amount of all structural units. Preferably it is 5 mol% or less.
• the liquid crystal polymer has a structural unit (3) in which at least one of X and Y is an imino group, that is, the structural unit (3) has an aromatic It is preferable to have at least one of a structural unit derived from hydroxylamine and a structural unit derived from an aromatic diamine, and more preferably only a structural unit (3) in which at least one of X and Y is an imino group.
• the liquid crystal polymer is preferably produced by melt polymerizing 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, even more preferably 250°C or higher, and the upper limit of the flow start temperature is preferably 350°C, 330°C. is more preferable, and 310°C is even more preferable.
• the solubility, heat resistance, strength and rigidity are excellent, and the viscosity of the solution is appropriate.
• the flow start temperature is also called the flow temperature.
• the flow temperature is also called the flow temperature.
• a capillary rheometer under a load of 9.8 MPa (100 kg/cm 2 ), the liquid crystal polymer is melted while increasing the temperature at a rate of 4°C/min. This is the temperature at which a viscosity of 4,800 Pa ⁇ s (48,000 poise) is exhibited when extruded from a nozzle with a diameter of 1 mm and a length of 10 mm. Polymers - Synthesis, Molding, Applications'', CMC Co., Ltd., June 5, 1987, p. 95).
• the weight average molecular weight of the liquid crystal polymer is preferably 1,000,000 or less, more preferably 3,000 to 300,000, 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 viewpoints 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.
• fluoropolymers examples include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxyfluoropolymer, tetrafluoroethylene/hexafluoropropylene copolymer, and ethylene/tetrafluoropropylene copolymer.
• fluoropolymers include chloroethylene copolymers, ethylene/chlorotrifluoroethylene copolymers, 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 - CH 3 and n is 1-4.
• 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: thermoplastic resins, which 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 an aromatic compound having an ethylenically unsaturated bond such as a chain olefin or a vinyl group.
• a polar group may be introduced into the polymer of a compound having a 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 cycloaliphatic hydrocarbon group include a cyclopentane ring, a cyclohexane ring, a cyclooctane ring, an isophorone ring, a norbornane ring, and a dicyclopentane ring.
• the compound having a 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 1 to 3.
• the number of hydroxyl groups or the number of phenolic hydroxyl groups of polyphenylene ether can be found, 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 the adhesion with metal. It is preferably 100% by mass, more preferably 20% by mass to 100% by mass, even more preferably 30% by mass to 100% by mass, particularly 40% to 100% by mass. preferable.
• the content of the polymer having a dielectric loss tangent of 0.01 or less, preferably a liquid crystal polymer, in the film is 20% by mass to 100% by mass based on the total mass of the film, from the viewpoint of the dielectric loss tangent of the film and adhesion with metal. It is preferably 30% by mass to 100% by mass, even more preferably 40% to 100% by mass, and particularly preferably 50% to 100% by mass. Note that 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.
• -Filler- Layer A may contain a filler from the viewpoint of thermal expansion coefficient and adhesion to metal.
• the filler may be in the form of particles or fibers, and may be inorganic or organic filler. It is preferable that In the laminate according to the present disclosure, it is preferable that the number density of the filler is larger inside the film than on the surface from the viewpoint of thermal expansion coefficient and adhesion to metal.
• 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 in the depth direction from the most surface, 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 organic filler material include polyethylene, polystyrene, urea-formalin filler, polyester, cellulose, acrylic resin, fluorine-based polymer, hardened epoxy resin, crosslinked benzoguanamine resin, crosslinked acrylic resin, liquid crystal polymer, and two types of these. Materials including the above may be mentioned.
• the organic filler may be in the form of fibers such as nanofibers, or may be hollow resin particles.
• organic fillers include fluorine-based polymer particles, polyester-based resin particles, polyethylene particles, liquid crystal polymer particles, or cellulose-based resin nanofibers from the viewpoint of film dielectric loss tangent, laser processing suitability, and level difference followability.
• 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.
• the material of the inorganic filler include BN, Al 2 O 3 , AlN, TiO 2 , SiO 2 , barium titanate, strontium titanate, aluminum hydroxide, calcium carbonate, and materials containing two or more of these. It will be done.
• the inorganic filler is preferably metal oxide particles or fibers, more preferably silica particles, titania particles, or glass fibers, from the viewpoint of thermal expansion coefficient and adhesion to metals, and silica particles, Alternatively, glass fiber is particularly preferred.
• 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. Further, the average particle size of the inorganic filler is preferably 5 nm to 20 ⁇ m, more preferably 10 nm to 10 ⁇ m, and 20 nm to 1 ⁇ m from the viewpoint of thermal expansion coefficient and adhesion to metal. is more preferable, and 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 filler content in layer A is preferably lower than the filler content in layer B from the viewpoint of adhesion to metal.
• the content of the filler in layer A is preferably 10% by mass to 90% by mass, and 30% to 80% by mass, based on the total mass of layer A, from the viewpoint of suitability for laser processing and adhesion with metal. Mass% is more preferred.
• 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 0.5 to 10 from the viewpoint of dielectric loss tangent of the film and adhesion to metal. It is preferably from 0.5 to 5, even more preferably from more than 0.6 to 3 or less, and particularly preferably from more than 0.6 to 2 or less.
• the average thickness of layer A is not particularly limited, but from the viewpoint of the dielectric loss tangent of the film and the adhesion with metal, it is preferably 5 ⁇ m to 90 ⁇ m, more preferably 10 ⁇ m to 70 ⁇ m, Particularly preferred is 15 ⁇ m to 60 ⁇ m.
• the method for measuring the average thickness of each layer in the laminate 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 laminate according to the present disclosure has layer B on at least one surface of layer A.
• the layer B preferably contains a cured product obtained by curing a thermosetting compound, and preferably contains a cured product obtained by curing a thermosetting resin, from the viewpoints of suitability for laser processing and step followability. More preferred.
• the layer B preferably contains a thermoplastic resin, and more preferably contains a thermoplastic elastomer.
• thermosetting compound examples include compounds having a maleimide group, an allyl group, a vinyl group, an epoxy group, an oxetanyl group, a cyanate group, a benzoxazine group, and the like.
• the thermosetting compound is at least one group selected from the group consisting of a maleimide group, an allyl group, a vinyl group, a cyanate group, and a benzoxazine group, from the viewpoint of laser processing suitability and level difference followability. From the viewpoint of dielectric loss tangent, it is more preferable to include a resin having at least one group selected from the group consisting of a maleimide group, an allyl group, and a vinyl group.
• the thermosetting compound is preferably a compound with a weight average molecular weight (Mw) of 100 or more, more preferably a compound with a weight average molecular weight of 200 or more, and a compound with a weight average molecular weight of 300 or more, from the viewpoint of laser processing suitability and step followability. Particularly preferred are compounds.
• the weight average molecular weight of the thermosetting compound is preferably 100,000 or less, more preferably 200 to 50,000, and more preferably 300 to 50,000, from the viewpoint of laser processing suitability and step followability. It is more preferably 30,000, and particularly preferably 300 to 10,000.
• thermosetting compound examples include bismaleimide resin, allyl group-containing polyphenylene ether resin, allyl group-containing polyarylate resin, vinyl group-containing polyphenylene ether resin, and the like.
• Layer B may contain only one type of thermosetting compound, or may contain two or more types of thermosetting compounds.
• the content of the cured product obtained by curing the thermosetting compound in layer B is 10% by mass to 80% by mass with respect to the total mass of layer B, from the viewpoint of suitability for laser processing and step followability. is preferable, and 15% to 50% by weight is more preferable.
• thermoplastic resins mentioned above include polyurethane resins, polyester resins, (meth)acrylic resins, polystyrene resins, fluorine-based polymers, polyimide resins, fluorinated polyimide resins, polyamide resins, polyamideimide resins, polyetherimide resins, and cellulose acylate resins.
• polyurethane resin for example, polyethylene resin, polypropylene resin, resin consisting of a cyclic olefin copolymer, alicyclic polyolefin resin), polyarylate resin, polyether sulfone resin, polysulfone resin, Examples include 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 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
• 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 thermoplastic resin from the viewpoint of dielectric loss tangent, laser processing suitability, and step tracking ability, and preferably contains a polystyrene-based elastomer. More preferably, it contains a styrene-butadiene-styrene block copolymer or a hydrogenated styrene-ethylene-butylene-styrene block copolymer.
• thermoplastic resin a polystyrene-based elastomer or a hydrogenated polystyrene-based elastomer is preferable from the viewpoint of dielectric loss tangent, laser processing suitability, and level difference followability.
• Layer B may use only one type of thermoplastic compound, or may use two or more types of thermoplastic compounds.
• the content of the thermoplastic resin in layer B is not particularly limited, but from the viewpoint of dielectric loss tangent of the film, suitability for laser processing, and adhesion to metal, the content of the thermoplastic resin in layer B is 10% by mass to 10% by mass based on the total mass of layer B.
• the content is preferably 95% by weight, more preferably 20% to 90% by weight, and particularly preferably 50% to 85% by weight.
• layer B contains a filler from the viewpoints of dielectric loss tangent, suitability for laser processing, adhesion to metal, 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 preferably includes an inorganic filler from the viewpoints of dielectric loss tangent, suitability for laser processing, and step followability. Among these, silica particles are particularly preferred.
• the filler used in layer B preferably contains polymer particles having a dielectric loss tangent of 0.01 or less from the viewpoints of dielectric loss tangent, laser processing suitability, and level difference followability. Preferred examples of the polymer particles having a dielectric loss tangent of 0.01 or less include liquid crystal polymer particles or fluororesin particles.
• Layer B may contain only one type of filler, or may contain two or more types of filler.
• the content of filler in layer B is preferably 5% by mass to 70% by mass, and 10% by mass to 50% by mass, based on the total mass of layer B. Mass% is more preferred.
• Layer B may contain a leveling agent.
• hydrocarbon-based, silicone-based, or fluorine-based compounds may be mentioned, and hydrocarbon-based, silicone-based, or fluorine-based surfactants are preferably mentioned.
• fluorine-based surfactants include the Megafac series manufactured by DIC Corporation such as Megafac F-444, the Surflon series manufactured by AGC Seimi Chemical Co., Ltd. such as Surflon S-221, and the Surflon series manufactured by AGC Seimi Chemical Co., Ltd. such as Ftergent 100.
• Neos Futergent series is an example.
• the surfactant may be a polymer, such as an acrylic polymer containing a monomer containing a fluorinated alkyl group as an essential component, or a siloxane polymer whose chain skeleton is composed of Si--O bonds.
• Layer B may contain other additives other than those mentioned above. Preferred embodiments of other additives used in layer B are the same as those of other additives used in layer A, except as described below.
• the average thickness of layer B is not particularly limited, but from the viewpoint of the dielectric loss tangent of the film, suitability for laser processing, and level difference followability, it is preferably 1 ⁇ m to 90 ⁇ m, more preferably 5 ⁇ m to 60 ⁇ m.
• the thickness is preferably 10 ⁇ m to 40 ⁇ m, particularly preferably.
• the laminate according to the present disclosure has a conductive pattern in contact with at least a portion of the layer B.
• the conductive pattern is preferably a conductive pattern of metal (for example, gold, silver, copper, iron, etc.), and more preferably a conductive pattern of copper.
• the surface roughness Rz of the conductive pattern on the side in contact with the layer B 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 conductive pattern is, the better, so the lower limit is not particularly set, but for example, it is 0 or more.
• 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 the conductive pattern is measured by the following method. Using a non-contact surface/layer cross-sectional shape measuring system VertScan (manufactured by Ryoka System Co., Ltd.), 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 (conductive pattern) and the above. Create an average line for the roughness curve. Extract a portion corresponding to the standard length from the roughness curve.
• the maximum value of the peak height i.e., the height from the average line to the peak
• the maximum value of the valley depth i.e., the height from the average line to the valley bottom
• the average thickness of the conductive pattern is not particularly limited, but is preferably 0.1 nm to 30 ⁇ m, more preferably 0.1 ⁇ m to 20 ⁇ m, and even more preferably 1 ⁇ m to 18 ⁇ 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 from 5 ⁇ m to 100 ⁇ m, more preferably from 10 ⁇ m to 50 ⁇ m.
• the conductive pattern has 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.
• 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.
• groups capable of interacting include the groups listed as functional groups in the above-mentioned compounds having functional groups. 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 conductive pattern in the laminate according to the present disclosure may be a circuit pattern.
• a method for manufacturing the conductive pattern in the laminate according to the present disclosure a preferred example is a method of processing a metal layer into a desired circuit pattern by etching.
• the etching method is not particularly limited, and any known etching method can be used.
• the laminate according to the present disclosure preferably further has a layer C, and from the viewpoint of adhesion to metal, it is more preferable to have the layer B, the layer A, and the layer C in this order.
• Layer C is preferably an adhesive layer. Further, as the layer C, a layer similar to the above-mentioned layer B may be provided separately. That is, layer B may be provided on both sides of layer A, respectively.
• Layer C 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.
• 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 B is 10% by mass to 99% by mass based on the total mass of the film, from the viewpoint of the dielectric loss tangent of the film and the adhesion with metal. It is preferably 20% by mass to 95% by mass, even more preferably 30% to 90% by mass, and particularly preferably 40% to 80% by mass.
• layer C preferably contains a polymer having an aromatic ring, and is a resin having an aromatic ring and an ester bond and an amide bond. In addition, it is more preferable to include a polymer having a dielectric loss tangent of 0.01 or less. Moreover, it is preferable that the layer C contains an epoxy resin from the viewpoint of adhesiveness.
• the epoxy resin is preferably a crosslinked product of a polyfunctional epoxy compound.
• a polyfunctional epoxy compound refers to a compound having two or more epoxy groups. The number of epoxy groups in the polyfunctional epoxy compound is preferably 2 to 4.
• layer C contains a leveling agent.
• hydrocarbon-based, silicone-based, or fluorine-based compounds may be mentioned, and hydrocarbon-based, silicone-based, or fluorine-based surfactants are preferably mentioned.
• fluorine-based surfactants include the Megafac series manufactured by DIC Corporation such as Megafac F-444, the Surflon series manufactured by AGC Seimi Chemical Co., Ltd. such as Surflon S-221, and the Surflon series manufactured by AGC Seimi Chemical Co., Ltd. such as Ftergent 100.
• Neos Futergent series is an example.
• the surfactant may be a polymer, such as an acrylic polymer containing a monomer containing a fluorinated alkyl group as an essential component, or a siloxane polymer whose chain skeleton is composed of Si--O bonds.
• polyfunctional epoxy compound examples include a polyfunctional epoxy compound having a glycidyl ether group, a polyfunctional epoxy compound having a glycidyl ester group, and a polyfunctional epoxy compound having a glycidylamino group.
• polyfunctional epoxy compounds having a glycidyl ether group examples include ethylene glycol diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A diglycidyl ether, and trimethylol.
• Examples of the polyfunctional epoxy compound having a glycidyl ester group include phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, and dimer acid diglycidyl ester.
• Examples of compounds having a glycidylamino group include N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane and 4,4'-methylenebis(N,N-diglycidylaniline). .
• Examples of the polyfunctional epoxy compound having a glycidyl ether group and a glycidylamino group include N,N-diglycidyl-4-glycidyloxyaniline.
• the epoxy resin is preferably a crosslinked product of a polyfunctional epoxy compound having a glycidylamino group, and N,N-diglycidyl-4-glycidyloxyaniline. and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane.
• layer C preferably contains an aromatic polyesteramide and an epoxy resin from the viewpoints of the dielectric loss tangent of the film, suitability for laser processing, and adhesion to the metal layer.
• 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 content of filler in layer C is not particularly limited and can be set arbitrarily, but when providing metal layers on both sides of the film, from the viewpoint of adhesion with metal, the content of filler in layer A It is also preferable that the amount is also small.
• the filler content in layer C is either no filler or 0% by volume based on the total volume of layer C, from the viewpoint of adhesion with metal.
• 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 the layer C is preferably thinner than the average thickness of the layer A from the viewpoint of the dielectric loss tangent of the film and the adhesiveness with 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 adhesion with metal. It is preferably from 2 to 100, even more preferably from 2.5 to 20, particularly preferably from 3 to 10.
• 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 adhesion with metal.
• the average thickness of layer C is preferably 0.1 nm to 20 ⁇ m, more preferably 0.1 nm to 5 ⁇ m, and 1 nm to 5 ⁇ m, from the viewpoint of dielectric loss tangent of the film and adhesion to metal. More preferably, the thickness is 1 ⁇ m.
• the average thickness of the laminate 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. is more preferable, and particularly preferably 20 ⁇ m to 80 ⁇ 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 method for manufacturing the laminate according to the present disclosure is not particularly limited, and known methods can be referred to.
• Preferred methods for producing the laminate according to the present disclosure include, for example, a co-casting method, a multilayer coating method, a co-extrusion method, and the like.
• the co-casting method is particularly preferable for forming a relatively thin film
• the co-extrusion method is particularly preferable for forming a thick film.
• layer A is formed by dissolving or dispersing components of each layer, such as a polymer or liquid crystal polymer with a dielectric loss tangent of 0.01 or less and a compound having a functional group, in a solvent. It is preferable to perform a co-casting method or a multilayer coating method as a composition for forming a layer B, a composition for forming a layer B, a composition for forming a 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 less 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 lower.
• the laminate according to the present disclosure may have a support when manufactured by a manufacturing method such as the above-mentioned co-casting method, multilayer coating method, or co-extrusion method.
• 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.
• 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, fluorine-based polymer, 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 laminate according to the present disclosure can be appropriately combined with stretching 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 without stretching by utilizing self-shrinkage due to drying. Stretching is particularly effective for improving elongation at break and strength at break when film brittleness is reduced due to addition of inorganic fillers or the like.
• the method for manufacturing a laminate according to the present disclosure preferably includes a step of curing the curable compound with heat.
• heat application means there are no particular limitations on the heat application means, and known heat application means such as a heater can be used. There are no particular restrictions on the conditions for applying heat, and heating can be performed at a desired temperature and time and in a known atmosphere.
• the method for manufacturing a laminate according to the present disclosure preferably includes a step of heat-treating (annealing) layer B when bonding it to the conductive pattern.
• the heat treatment temperature in the above heat treatment step is preferably 240°C or less, and preferably 120°C to 220°C, from the viewpoint of dielectric loss tangent, adhesion, laser processing suitability, and step followability.
• the temperature is more preferably 140°C to 200°C, even more preferably 150°C to 200°C.
• the heat treatment time is preferably 15 minutes to 10 hours, more preferably 30 minutes to 5 hours.
• the method for manufacturing a laminate according to the present disclosure preferably includes a step of heat-treating (annealing) layer A before forming layer B.
• 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 particularly 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 laminate according to the present disclosure may include other known steps as necessary.
• the laminate according to the present disclosure can be used for various purposes, and among them, can be suitably used for electronic components such as printed wiring boards, and can be suitably used for flexible printed circuit boards.
• 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 has a dielectric loss tangent of 0.01 or less at 28 GHz, and an elastic modulus of the layer B at 160°C. is 0.5 MPa or less, and the layer B contains a thermosetting resin.
• Preferred embodiments of the layer A in the film according to the present disclosure and the layer B other than the cured product obtained by curing the thermosetting resin are the same as the preferred embodiments of the layer A and the layer B of the laminate in the present disclosure described above. Each is similar.
• the laminate according to the present disclosure is obtained by pasting a conductive pattern on the film according to the present disclosure and curing layer B, and regarding the aspect that does not change before and after curing, the preferred aspect of the film according to the present disclosure is , is the same as the preferred embodiment of the laminate according to the present disclosure.
• it is preferable that the film according to the present disclosure does not have a conductive pattern.
• the film according to the present disclosure has a dielectric loss tangent of 0.01 or less at 28 GHz, an elastic modulus of the layer B at 160° C. of 0.5 MPa or less, and the layer B contains a thermosetting resin.
• Layer B which has a low elastic modulus at 160°C and contains a thermosetting resin, has excellent step followability, and can be thermally cured during and after lamination of conductive patterns, etc., and both. As a result, the heat resistance of layer B is improved, so that it is possible to provide a film that is excellent in both step followability and laser processing suitability.
• the elastic modulus of layer B at 160°C. in the film according to the present disclosure is 0.5 MPa or less, and from the viewpoint of laser processing suitability and step tracking ability, it is preferably 0.45 MPa or less, and 0.40 MPa or less. More preferably, it is 0.01 MPa to 0.35 MPa.
• the elastic modulus in the present disclosure shall be measured by the following method. First, a cross section of a film or a laminate is cut with a microtome or the like, and layer A or layer B is identified from an image observed with an optical microscope. Next, 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 is performed by unloading at a loading rate of 0.28 mN/sec.
• a microhardness tester product name "DUH-W201", manufactured by Shimadzu Corporation
• Layers other than layer A and layer B are also measured in the same manner. Moreover, when measuring each layer, an unnecessary layer may be scraped off with a razor or the like to prepare a sample for evaluation of only the desired layer. Furthermore, if it is difficult to take out a single film because the layer is thin, etc., the layer to be measured may be scraped off with a razor or the like, and the resulting powdered sample may be used.
• the layer B in the film according to the present disclosure includes a thermosetting resin, and from the viewpoint of laser processing suitability and step followability, the thermosetting resin is selected from the group consisting of a maleimide group, an allyl group, and a vinyl group. It is preferable to have at least one selected group.
• Layer B may contain only one type of thermosetting resin, or may contain two or more types of thermosetting resin. Further, the content of the thermosetting resin in layer B is preferably 10% by mass to 80% by mass, and preferably 15% by mass to 80% by mass, based on the total mass of layer B, from the viewpoints of suitability for laser processing and step followability. 50% by mass is more preferred.
• thermosetting film includes a thermosetting compound and a thermoplastic elastomer, wherein the thermosetting compound is at least one group selected from the group consisting of a maleimide group, an allyl group, and a vinyl group. has.
• thermosetting film according to the present disclosure are the same as the preferred embodiments of layer B of the film in the present disclosure described above, except as described below.
• thermosetting film according to the present disclosure is made of at least one material selected from the group consisting of polyimide, liquid crystal polymer, fluorine-based polymer, and inorganic filler from the viewpoints of electrostatic tangent, laser processing suitability, and step followability. , and more preferably at least one selected from the group consisting of polyimide particles, liquid crystal polymer particles, fluorine-based polymer particles, and inorganic fillers. Furthermore, from the viewpoints of electrostatic tangent, laser processing suitability, and step followability, the thermosetting film according to the present disclosure preferably contains aromatic polyesteramide, and more preferably contains aromatic polyesteramide particles. .
• thermosetting compound is preferably a compound (resin) having a weight average molecular weight (Mw) of 100 or more, more preferably a compound having a weight average molecular weight of 200 or more, from the viewpoint of laser processing suitability and step followability.
• Mw weight average molecular weight
• the weight average molecular weight of the thermosetting compound is preferably 100,000 or less, more preferably 200 to 50,000, and more preferably 300 to 50,000, from the viewpoint of laser processing suitability and step followability. It is more preferably 30,000, and particularly preferably 300 to 10,000.
• Layer B may contain only one type of thermosetting compound, or may contain two or more types of thermosetting compounds. Further, the content of the thermosetting compound in layer B is preferably 10% by mass to 80% by mass, and preferably 15% by mass to 80% by mass, based on the total mass of layer B, from the viewpoints of suitability for laser processing and step followability. 50% by mass is more preferred.
• the elastic modulus at 160° C. of the thermosetting film according to the present disclosure is preferably 0.5 MPa or less, more preferably 0.45 MPa or less, from the viewpoint of laser processing suitability and step followability, It is more preferably 0.40 MPa or less, and particularly preferably 0.01 MPa to 0.35 MPa.
• the dielectric loss tangent of the thermosetting film according to the present disclosure at 28 GHz is preferably 0.01 or less, more preferably 0.008 or less, from the viewpoints of dielectric constant, laser processing suitability, and level difference followability. It is preferably 0.005 or less, more preferably 0.004 or less, and most preferably more than 0 and 0.003 or less.
• the method for manufacturing a wiring board according to the present disclosure is not particularly limited as long as it is a method using the film according to the present disclosure or the thermosetting film according to the present disclosure.
• the overlapping step and the heating step may be performed simultaneously.
• the method for manufacturing a wiring board according to the present disclosure can refer to the above-described method for manufacturing a laminate according to the present disclosure as appropriate.
• the base material with a wiring pattern is not particularly limited, and any known material can be used.
• Preferred materials for the wiring pattern include the same materials as those for the conductive pattern described above.
• the heating means in the heating step is not particularly limited, and any known heating means such as a heater can be used. Heating conditions are not particularly limited, and heating can be performed at a desired temperature and time and in a known atmosphere.
• the heating temperature in the above heating step is preferably 240°C or less, more preferably 120°C or more and 220°C or less, and 140°C or more from the viewpoint of dielectric loss tangent, laser processing suitability, and step followability.
• the temperature is more preferably 200°C or lower, and particularly preferably 150°C or higher and 180°C or lower.
• the value obtained by subtracting the mass residual rate at 900°C from the mass residual rate at 440°C of the layer B or the thermosetting film after the heating step is 40% or more from the viewpoint of laser processing suitability and step followability. It is preferably 40% to 95%, particularly preferably 45% to 90%.
• the method for manufacturing a wiring board according to the present disclosure may include other known steps as necessary.
• Aromatic polyesteramide A1a is heated under a nitrogen atmosphere from room temperature to 160°C over 2 hours and 20 minutes, then from 160°C to 180°C over 3 hours and 20 minutes, and held at 180°C for 5 hours.
• aromatic polyesteramide A1b was 220°C.
• Aromatic polyesteramide A1b is heated under a nitrogen atmosphere from room temperature to 180°C over 1 hour and 25 minutes, then from 180°C to 255°C over 6 hours and 40 minutes, and held at 255°C for 5 hours.
• the mixture was cooled to obtain a powdery aromatic polyesteramide P1.
• the flow initiation temperature of aromatic polyesteramide P1 was 302°C. Further, the melting point of the aromatic polyesteramide P1 was measured using a differential scanning calorimeter and was found to be 311°C.
• the solubility of the aromatic polyesteramide P1 in N-methylpyrrolidone at 140° C. was 1% by mass or more.
• acetic anhydride (1.08 molar equivalent to the hydroxyl group) was further added. While stirring under a nitrogen gas stream, the temperature was raised from room temperature to 150°C over 15 minutes, and the mixture was refluxed at 150°C for 2 hours. Next, the temperature was raised from 150° C. to 310° C. over 5 hours while by-product acetic acid and unreacted acetic anhydride were distilled off, and the polymer was taken out and cooled to room temperature. The temperature of the obtained polymer was raised from room temperature to 295°C over 14 hours, and solid phase polymerization was performed at 295°C for 1 hour.
• the liquid crystal polymer particles PP-1 had a median diameter (D50) of 7 ⁇ m, a dielectric loss tangent of 0.0007 at 28 GHz, and a melting point of 334°C.
• reaction solution was neutralized with hydrochloric acid, reprecipitated in 5 L of methanol, taken out by filtration, washed three times with a mixture of methanol and water in a mass ratio of 80:20, and then heated at 80°C for 24 hours. It was dried for hours to obtain allyl group-containing polyphenylene ether resin T3.
• reaction solution was neutralized with hydrochloric acid, reprecipitated in 5 L of methanol, taken out by filtration, washed three times with a mixture of methanol and water in a mass ratio of 80:20, and then heated at 80°C for 24 hours. It was dried for hours to obtain vinyl group-containing polyphenylene ether resin T4.
• ⁇ P1 Aromatic polyesteramide P1 (produced by the above method)
• ⁇ PP-1 Liquid crystal polymer particles PP-1 (produced by the above method)
• ⁇ PP-2 Liquid crystal polymer particles PP-2 (produced by the above method)
• ⁇ P6 S202A, manufactured by Asahi Kasei Chemicals Co., Ltd., polyphenylene ether resin
• ⁇ P2 Tuftec M1913, manufactured by Asahi Kasei Chemicals Co., Ltd., hydrogenated styrene-ethylene-butylene-styrene block copolymer
• ⁇ P3 Tufprene 912, manufactured by Asahi Kasei Chemicals Co., Ltd., styrene-butadiene-styrene block copolymer
• ⁇ P4 Epofriend AT501, manufactured by Daicel Corporation, styrene-butadiene-styrene block copolymer
• PTFE Polytetrafluoroethylene
• thermoplastic resin, thermosetting resin, initiator/catalyst, and additives listed in Table 1 are mixed in the mass part ratio listed in Table 1, and toluene is added to adjust the solid content concentration to 25% by mass.
• a coating liquid for layer B was obtained.
• a laminator product name: Vacuum Laminator V-130, manufactured by Nikko Materials
• lamination was performed for 1 minute at 140°C and a lamination pressure of 0.4 MPa to form a precursor to double-sided copper-clad laminates. I got a body.
• a thermocompression bonding machine product name "MP-SNL", manufactured by Toyo Seiki Seisakusho Co., Ltd.
• the obtained double-sided copper-clad laminate precursor was bonded for 10 minutes at 300°C and 4.5MPa.
• a double-sided copper-clad laminate was produced by thermocompression bonding for a minute.
• the copper foils on both sides of the double-sided copper-clad laminate were etched and patterned to produce a base material with a wiring pattern including a ground line and three pairs of signal lines on both sides of the base material.
• the length of the signal line was 50 mm, and the width was set so that the characteristic impedance was 50 ⁇ .
• the obtained undercoat layer coating liquid was applied using an applicator to copper foil (manufactured by Fukuda Metal Foil & Powder Industries Co., Ltd., CF-T4X-SV-18, thickness 18 ⁇ m, surface roughness of the pasting surface (treated surface) Rz0. .85 ⁇ m) on the treated surface and dried with air at 150° C. for 1 hour.
• the thickness of the undercoat layer after drying was 3 ⁇ m.
• the coating liquid for layer A was applied onto the obtained undercoat layer using an applicator and dried with air at 50° C. for 3 hours. Thereafter, an annealing treatment was performed at 300° C. for 3 hours under nitrogen.
• the copper foil of the obtained film was dissolved in an aqueous ferric chloride solution to obtain a layer A film.
• the obtained undercoat layer coating liquid was applied using an applicator to copper foil (manufactured by Fukuda Metal Foil & Powder Industries Co., Ltd., CF-T4X-SV-18, thickness 18 ⁇ m, surface roughness of the pasting surface (treated surface) Rz0. .85 ⁇ m) on the treated surface and dried with air at 150° C. for 1 hour.
• the thickness of the undercoat layer after drying was 3 ⁇ m.
• the coating liquid for layer A was applied onto the obtained undercoat layer using an applicator and dried with air at 50° C. for 3 hours. Thereafter, an annealing treatment was performed at 300° C. for 3 hours under nitrogen.
• the thickness of layer A was as shown in Table 1. Further, on the obtained layer A, a coating liquid for layer B was applied using an applicator and dried with air at 90°C for 1 hour to obtain a polymer film having a copper layer (single-sided copper-clad multilayer film). .
• the obtained undercoat layer coating liquid was applied using an applicator to copper foil (manufactured by Fukuda Metal Foil & Powder Industries Co., Ltd., CF-T4X-SV-18, thickness 18 ⁇ m, surface roughness of the pasting surface (treated surface) Rz0. .85 ⁇ m) on the treated surface and dried with air at 150° C. for 1 hour.
• the thickness of the undercoat layer after drying was 3 um.
• the coating liquid for layer A was applied onto the obtained undercoat layer using an applicator and dried with air at 50° C. for 3 hours. Thereafter, an annealing treatment was performed at 300° C. for 3 hours under nitrogen.
• the thickness of layer A was as shown in Table 1.
• the layer B single layer film produced above was placed on the obtained layer A, and the substrate with the wiring pattern produced above was further superimposed on the layer B, and the film was heated at 160° C. and 4 MPa for 1 By performing hot pressing for a period of time, a laminate with a wiring pattern was obtained.
• the resulting laminate had a wiring pattern (ground line and signal line) buried therein, and the thickness of the wiring pattern was 18 ⁇ m.
• the elastic modulus of layer B of the single-sided copper-clad multilayer film 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 dielectric loss tangent was measured using a resonance perturbation method at a frequency of 28 GHz.
• a 28 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 was measured from the change in resonance frequency before and after insertion for 96 hours in the environment.
• the dielectric loss tangent of Layer A was measured using the Layer A film produced above.
• the dielectric loss tangent of Layer B was measured using the Layer B single layer film produced above.
• the dielectric loss tangent of the laminate was determined by weighted average of the dielectric loss tangent and film thickness of layer A and layer B, respectively.
• Step tracking ability (wiring tracking ability)
• the laminate with the wiring pattern was cut along the thickness direction using a microtome, and the cross section was observed using an optical microscope.
• the length L1 of the gap created in the in-plane direction between layer B and the wiring pattern was measured.
• the average value at 10 locations was calculated.
• the films, laminates, or thermosetting films of Examples 1 to 24 were superior to the film of Comparative Example 1 in step followability and laser processing suitability.

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